Advances in X-Ray Analysis - Volume 33 - 1989

ADVANCES IN
X-RAY ANALYSIS
Volume 33
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ADVANCES IN
X-RAY ANALYSIS
Volume 33
Edited by
Charles S. Barrett
University of Denver
Denver, Colorado
John V. Gilfrich
Sachs/Freeman Associates
Washington, D.C.
Ting C. Huang
IBM Almaden Research Center
San Jose, California
Ron Jenkins
JCPDS-International Centre
for Diffraction Data
Swarthmore, Pennsylvania
and
Paul K. Predecki
University of Denver
Denver, Colorado
Sponsored by
University of Denver Department of Engineering
and
JCPDS - International Centre for Diffraction Data
PLENUM PRESS • NEW YORK AND LONDON

The Library of Congress cataloged the first volume of this title as follows:
Conference on Application of X-ray Analysis.
Proceedings 6th- 1957 - [Denver]
v. iIIus. 24-28 cm. annual.

No proceedings published for the first 5 conferences.
Vols. for 1958- called also: Advances in X-ray analysis, v. 2-
Proceedings for 1957 issued by the conference under an earlier name: Conference on
Industrial Applications of X-ray Analysis. Other slight variations in name of con-
ference.
Vol. for 1957 published by the University of, Denver, Denver Research Institute,
Metallurgy Division.
Vols. for 1958- distributed by Plenum Press, New York.
Conferences sponsored by University of Denver, Denver Research Institute.
1. X-rays - Industrial applications - Congresses. I. Denver University. Denver
Research Institute II. Title: Advances in X-ray analysis.
TA406.5.C6 58-35928
ISBN 978-1-4613-9998-8 ISBN 978-1-4613-9996-4 (eBook)

DOI 10.1007/978-1-4613-9996-4
Proceedings of the Thirty-eighth Annual Conference on

Applications of X-Ray Analysis, held July 31-August 4, 1989,
in Denver, Colorado
© 1990 University of Denver

Softcover reprint of the hardcover 1st edition 1990
Plenum Press is a Division of Plenum Publishing Corporation

233 Spring Street, New York, N.Y. 10013
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted

in any form or by any means, electronic, mechanical, photocopying, microfilming,
recording, or otherwise, without written permission from the Publisher
FOREWORD
The 38th Annual Denver Conference on Applications of X-Ray Analysis

was held July 31 - August 4, 1989, at the Sheraton Denver Technical Center,
Denver, Colorado. The conference alternates emphasis between x-ray
diffraction and x-ray fluorescence, and this being an odd year the emphasis
was on diffraction. Thus the Plenary Session was slanted toward diffraction
in general and thin film analysis in particular.
The Plenary Session on x-ray analysis of thin films did not just
happen this year but really began four years ago with Paul Predecki
suggesting a special session devoted to thin film techniques. The session
generated a great deal of interest, so Paul suggested that a workshop on
thin films should be slated for the 1987 conference. A full day was devoted
to the workshop, which was split into a half day on epitaxial thin films and
the other half day on polycrystalline thin films. The workshop attendance
indicated a great deal of interest in this topic, leading to this year's
Plenary Session.
The first two speakers of the Plenary Session (B. Tanner and K. Bowen)
have been key throughout the thin film activities. They were invited
speakers for the 1985 special session on thin films and instructors for the
1987 workshop on epitaxial thin films.
Brian Tanner, University of Durham, England, opened the session with a

talk on "High Resolution X-Ray Diffraction for the Characterization of
Semiconducting Materials." This talk described various multiple reflection
methods of examining epilayers. Keith Bowen, University of Warwick,
England, followed with a talk on x-ray topography of epitaxial films. Keith
explained how the topography complements the high resolution techniques
discussed in the first paper and went on to discuss single and double
crystal and section topography of thin films.
The third talk, by Professor Jerome Cohen of Northwestern University,

dealt with residual stresses in thin films. Jerry reviewed the recent
techniques for stress measurement and analysis and gave specific examples
including some work on aluminum alloy films that show surprisingly high
stresses.
The next talk was on the topic of thin film characterization by

grazing incidence asymmetric Bragg diffraction by T. C. Huang of IBM
Research. This paper described diffraction at or near the critical angle
for total reflection which limits the x-ray depth of penetration to the top
lOOA or less. A specific example of the GIAB analysis was shown in which a
magnetically dead iron oxide magnetic thin film was caused by a surface
layer of 90A of alpha iron oxide. The final talk in this session was on
x-ray fluorescence characterization of thin films by James Willis of Data
Acquisition and Control. Jim described recent advances in the fundamental
v
vi FOREWORD
parameters technique' which has extended the range of analysis to include the
determination of single and mUltiple layer unknown films without the need
for similar types of standards.
The "Denver Conference," as it is generally known, is successful

because of the efforts and cooperation of the participants. I have never
had anyone say "no" when asked to be a keynote speaker or a workshop
instructor. This has made it a pleasure to participate in the x-ray thin
film characterization over the past several years and see the increase in
interest in this topic. I hope that the interest will continue and I look
forward to seeing the advances that will occur over the next few years.
Charles Goldsmith
East Fishkill, NY
December 1989
PREFACE
This volume constitutes the proceedings of the 1989 Denver Conference

on Applications of X-Ray Analysis and is the 33rd in the series. The
conference was held July 31 - August 4, 1989, at the Sheraton Denver Tech
Center, Denver, Colorado. The general chairmen were: J. V. Gilfrich,
Sachs/Freeman Associates, NRL; and P. K. Predecki, University of Denver;
with C. S. Barrett of the University of Denver as honorary chairman. The
conference advisory committee this year consisted of: C. S. Barrett -
University of Denver; V. E. Buhrke - The Buhrke Company; J. V. Gilfrich -
Sachs/Freeman Associates, NRL; T. C. Huang - IBM Almaden Research Center;
R. Jenkins - International Centre for Diffraction Data; G. J. McCarthy -
North Dakota State University; M. C. Nichols - Sandia National Laboratories;
and P. K. Predecki - University of Denver. We take this opportunity to
thank the advisory committee for their active participation, tireless
efforts and able guidance which made this conference successful.
The conference plenary session was organized and chaired by C. C.

Goldsmith, IBM, Hopewell Junction, NY, and was entitled: "APPLICATIONS OF
X-RAY METHODS TO THIN FILMS."
The invited papers on the program are listed below.
"High Resolution X-Ray Diffraction for the Characterization of Semiconducting

Materials," B. K. Tanner
"X-Ray Topography of Surface Layers and Epitaxial Films,"
D. K. Bowen
"Stresses in Films,"
J. B. Cohen
"Surface and Ultra Thin Film Characterization by Grazing Incidence Asymmetric
Bragg Diffraction," T. C. Huang
"Characterization of Thin Film Samples Using X-Ray Fluorescence,"
J. E. Willis
"Quantitative Defect Mapping in Polycrystalline Materials by X-Ray Rocking
Curve Analysis," C. F. Lo, W. E. Mayo and S. Weissmann
"The Use of Field-Portable X-Ray Fluorescence Technology in the Hazardous
Waste Industry," G. A. Raab
"Rietveld Crystal Structure Analysis,"
R. L. Snyder
"Problems in the Derivation of d-Values from Experimental Digital XRD
Patterns," R. Jenkins and M. Nichols
"Derivation of d-Values from Digitized X-Ray and Synchrotron Diffraction
Data," T. C. Huang, W. Parrish, M. Hart, N. Masciocchi, H. Toraya,
R. Cernik, B. Gilles and P. W. Wang
"Investigations of the Linear Paracrystalline Model for Polymer Fibres using
Small-Angle X-Ray Scattering," I. H. Hall and B. H. Hussain
"Scattering from Rigid-Rod Polymer Fibers,"
W. W. Adams
vii
viii PREFACE
In addition to the Plenary Session, the following Special Sessions

were held:
o APPLICATION OF X-RAY METHODS TO THIN FILMS, chaired by C. C. Goldsmith,

IBM, Hopewell Junction, NY
o ANALYSIS OF DIGITAL DIFFRACTION DATA, INCLUDING RIETVELD, chaired by
C. A. Peck, General Motors, Warren, MI; and M. C. Nichols, Sandia
National Labs, Livermore, CA
o CHARACTERIZATION AND ANALYSIS OF CRYSTAL DEFECTS AND EPITAXIAL FILMS,
chaired by S. Weissmann, Rutgers University, Piscataway, NJ
o POLYMER APPLICATIONS OF XRD, SMALL ANGLE SCATTERING, chaired by
R. Barton, DuPont, Wilmington, DE
o OTHER APPLICATIONS OF XRD, INCLUDING SOME AT HIGH TEMPERATURES,
chaired by C. R. Hubbard, Oak Ridge National Lab, Oak Ridge, TN
o XRF TECHNIQUES FOR HAZARDOUS WASTES AND ENVIRONMENTAL APPLICATIONS,
chaired by S. Piorek, Princeton Gamma-Tech, Princeton, NJ
Tutorial workshops on various XRD and XRF topics were held during the
first two days of the conference. These are listed below with the names of
the workshop organizers and instructors.
WD-l X-RAY CHARACTERIZATION OF EPITAXIAL THIN FILMS I, D. K. Bowen,

University of Warwick, U.K. (chair); B. Tanner, University of Durham,
U.K. (chair); and M. Halliwell, British Telecom Research Labs, U.K.
WD-2 MAINTENANCE AND OPTIMUM USE OF DIFFRACTOMETERS, R. Jenkins, JCPDS-ICDD,
Swarthmore, PA (chair); and T. G. Fawcett, Dow Chemical Co., Midland,
MI (chair).
WD-3 X-RAY CHARACTERIZATION OF EPITAXIAL THIN FILMS II
- Continuation of WD-l -
WD-4 CALCULATION OF XRD PATTERNS, D. K. Smith, Penn State University, PA
(chair); Q. C. Johnson, Lawrence Livermore National Lab, Livermore, CA
(chair); K. L. Smith, Siemens Analytical X-Ray Instruments, Madison,
WI; and G. J. McCarthy, North Dakota State University, Fargo, ND
WD-S XRD CHARACTERIZATION AND ANALYSIS OF LATTICE DEFECTS, S. Weissmann,
Rutgers University, Piscataway, NJ (chair); and W. E. Mayo, Rutgers U.
WD-6 DERIVATION OF d-VALUES FROM DIGITAL XRD PATTERNS, R. Jenkins,
JCPDS-ICDD, Swarthmore, PA (chair); M. C. Nichols, Sandia National
Labs, Livermore, CA (chair); C. A. Peck, General Motors Research,
Warren, MI (chair); T. C. Huang, IBM Almaden Research Center, San
Jose, CA; and W. N. Schreiner, Katonah, NY
WD-7 XRD CHARACTERIZATION OF POLYCRYSTALLINE THIN FILMS, C. Goldsmith, IBM,
Hopewell Junction, NY (chair); T. N. Blanton, Eastman Kodak Co.,
Rochester, NY; T. Nunes, IBM Corp., Hopewell Junction, NY; and
J. Angilello and A. Segmuller, IBM Corp., Yorktown Heights, NY
WD-8 OPEN SESSION ON PROBLEMS IN POWDER DIFFRACTION, R. Jenkins,
JCPDS-ICDD, Swarthmore, PA (chair); and Ben Post, Polytechnic
University of New York
WF-l XRF CHARACTERIZATION OF THIN FILMS, J. E. Willis, Data Acquisition and
Control (chair); J. Criss, Criss Software, Largo, MD; and T. C. Huang,
IBM Almaden Research Center, San Jose, CA.
WF-2 QUANTITATIVE XRF SOFTWARE, R. M. Rousseau, Geological Survey of Canada,
Ottawa (chair).
WF-3 SPECIMEN PREPARATION FOR XRF ANALYSIS I, V. E. Buhrke, The Buhrke Co.,
Redwood City, CA (chair); Ron Corbett, AMAX R&D, Golden, CO; Howard
Kanare, Construction Tech Labs, Skokie, IL; Joe Taggert, US Geological
Survay, Denver, CO; Larry Creasy, Axel Johnson Metals, Exton, PA; and
John Croke, Philips Electronic Ins., Mahwah, NJ.
WF-4 SPECIMEN PREPARATION FOR XRF ANALYSIS II
- Continuation of WF-3 -
PREFACE ix
The total number registered for the conference was 415, over 225 of whom
registered for one or more workshops. We are particularly indebted to the
workshop organizers and instructors who gave unselfishly of their time and
experience to make the workshops an outstanding part of the conference.
The conference dinner attendance was 170. Prof. Sigmund Weissmann of

Rutgers University presented an outstanding and most enjoyable piano recital
after the dinner.
On behalf of the organizing committee, I would like to sincerely thank

the plenary session chairman, the invited speakers, the special session
chairmen, the contributed session chairmen (J. V. Gilfrich, H. Ebel, T. C.
Huang, R. J. Cernik, I. C. Noyan, M. Kurita, J. A. Anzelmo, T. K. Smith,
P. A. Pella and D. S. Urch) , the poster session chairmen (C. S. Barrett and
G. A. Raab) and the authors for their contributions. The exceptional efforts
of all these people made the sessions a great success.
My special thanks to the conference staff: Louise Carlson, John Getty,

Brenda Ziegler, Anis Gopalani, Sam Eber, Shyam Mariwala, and to the conference
secretary, Lynne Bonno, all of whom worked long and unusual hours to make the
Conference successful.
Paul K. Predecki
for the Organizing Committee
January 1990
UNPUBLISHED PAPERS
The following papers were presented at the conference but are not
published here for various reasons.
"Scattering from Rigid-Rod Polymeric Fibers," W. Wade Adams, Wright-

Patterson Air Force Base, OH.
"Computer Aided XRF Analysis (CAX/CAA)," John A. Anzelmo, Applied Research
Laboratories, Dearborn, MI.
"The NIST Digital SAXS Camera," John D. Barnes, NIST Polymers Div.,
Gaithersburg, MD.
"Solid State Structure of Mesogenic Azomethine Ether Polymers," Amit Biswas,
K. H. Gardner and P. W. Wojtkowski, DuPont Experimental Station, Wilmington, DE
"Rapid Qualitative Classification of Unknown Materials using WDXRF and a
8036 Based Microcomputer," Bardley W. Boyer, Applied Research Laboratories,
Dearborn, MI.
"High Temperature Oxidation of Stainless Steel," o. B. Cavin, Oak Ridge
National Laboratory, TN; and J. S. Wolf, Clemson University, Clemson, SC.
"X-Ray Diffraction of Papers - A Forensic Approach," V. S. Chincholkar,
Forensic Science Laboratory, Bombay, India.
"Residual Strain in Tungsten Carbide/Cobalt: An Evaluation of Instrument
Parameters," S. J. Brownell and C. Crowder, The Dow Chemical Co., Midland, MI
"A Channeled X-Ray Beam Extracts Energy from Free Electrons," Kamal Das
Gupta, Texas Tech University, Lubbock, TX.
"Small Angle X-Ray Analysis using Area Detector," Ashok G. Dhere, DuPont,
Chattanooga, TN.
"Phase Transitions in Undoped and Doped AMPL," W. Ding and D. Chandra,
University of Nevada, Reno, NV; and J. Tomlinson, Oak Ridge National Lab, TN.
x PREFACE
"Rocking Curves and 'Rocking Curves' for the Analysis of Quaternary

Structures on InP Substrates," M. Downey and G. Hamill, GTE Laboratories,
Waltham, MA.
"Substrate Asymmetry Effects on Interface Misorientation and Defects in
GaAs/Si and Related Heterostructures," M. Fatemi and A. Christou, U.S. Naval
Research Laboratory, Washington, DC.
"Fiber Diffraction Data Collection on a Nicolet Area Detector: A
Redetermination of the Crystal Structure of Poly(ethylene Terephthalate),"
Kenn H. Gardner, DuPont Experimental Station, Wilmington, DE.
"XRF Analysis of Elemental Concentrations in Small Mass Particulate Matter
from Samples Taken Aboard an Aircraft," R. L. Gunter, U.S. Dept. of Commerce,
Boulder, CO; C. Crouch, University of Denver and CIRES, Denver, CO; and
H. Sievering, University of Colorado at Denver and CIRES, Denver, CO.
"Investigations of the Linear Paracrystalline Model for Polymer Fibres using
Small-Angle X-Ray Scattering," Ivan B. Hall and B. Huddin Hussain, University
of Manchester Inst. of Science & Technology, Manchester, U.K.
"X-Ray Fluorescence, XANES and EXAFS at Trace Levels Using Synchrotron
Radiation," P. J. Harget, C. K. Saw and D. P. Karim, Hoechst Celanese Corp.,
Summit, NJ.
"X-Ray Fractographic Approach to Composite Ceramics," Yukio Hirose, Kanazawa
University, Japan; Z. Yajima, Kanazawa Institute of Technology, Japan; and
K. Tanaka, Kyoto University, Japan.
"Anisotropic Thermal Expansion of Delta-Yttrium Disilicate and Yttrium
Nitrogen Apatite by High-Temperature X-Ray Diffraction," C. R. Hubbard and
O. B. Cavin, Oak Ridge National Laboratory, TN; D. Devlin and N. Corbin,
Norton Company, Northboro, MA.
"Special Problems in High Temperature X-Ray Diffraction of Ceramic
Materials," Lois A. Johnson and V. A. Greenhut, Rutgers University,
Piscataway, NJ.
"High Temperature X-Ray Diffraction on Bulk Material," Gerhard Klaus, Schott
Glaswerke, Mainz, W. Germany.
"Quantitative Representation of Texture Development in Rolled Polyethylene
with 2-D Gaussian Distributions," Stephen J. Krause, Arizona State U., Tempe,
AZ.
"Determination of Stress in Electrodeposited Chromium Layer," Makoto
Kuramoto, The Institute of Vocational Training, Kanagawa, Japan; Y. Kobayashi
and J. Nagasawa, Yokico Ltd. Research Laboratory, Kanagawa, Japan.
"Quantitative Analysis of Mineral Ores by XRD," J. J. Lee, D. H. Lee and
J. C. So, Research Institute of Industrial Science and Technology, Pohang,
Korea.
"Characterization of Epitaxial Films by X-Ray Diffraction," Hung-Yu Liu,
Yung-Chung Kao and Roland Koestner, Texas Instruments Inc., Dallas, TX.
"X-Ray Diffraction Based Stress Measurements on Integrated Circuit
Metallization," Lynn E. Lowry, Jet Propulsion Laboratory, Pasadena, CA;
James A. Van Den Avyle and Bruce Draper, Sandia National Laboratories,
Albuquerque, NM.
"Use of Portable X-Ray Fluorescence for the Analysis of Metals in Complex
Matrices at a Hazardous Waste Site," Charles R. Lytle and Gary N. Bigham,
PTI Environmental Services, Bellevue, WA.
"Quantitative Defect Mapping in Polycrystalline Materials by X-Ray Rocking
Curve Analysis," William E. Mayo, Chi-Fung Lo and Sigmund Weissmann, Rutgers
University, Piscataway, NJ.
"Wide Angle Scattering Measurements of Fiber Orientation in Multiple Fiber
Bundles and Single Filaments Using an Area Detector," Thomas F. McNulty,
J. M. Quigley, J. L. Radtke, A. J. Wauchope, Siemens Analytical X-Ray
Instruments Inc., Madison, WI; and B. Chu, State University of New York at
Stonybrook, Long Island, NY.
PREFACE xi
"Integration Methods for Analyzing X-Ray Polymer and Powder Diffraction

Patterns from a Two-Dimensional Position-Sensitive Detector," Thomas F.
McNulty, J. M. Quigley and A. J. Wauchope, Siemens Analytical X-Ray
Instruments Inc., Madison, WI.
"A New Method for Quantitative EDXRF Analysis Without Standards," Medhat
W. Mickael, Applied Research Associates, Raleigh, NC.
"Nylon 66 Carpet Fiber Morphology, A Function of Heat-Setting," Richard W.
Miller, J. H. Southern, N. P. C. Chao, S. Belyeu and M. Engel, Monsanto
Chemical Company, Pensacola, FL.
"Automated Separation and Preconcentration Methods for XRF Analysis of
Trace Elements," Peter A. Pella and G. Sleater, NIST, Gaithersburg, MD.
"Characterization of Ultra-Thin Epitaxial Layers Using a Five-Crystal
Diffractometer," Tom W. Ryan, Philips Analytical, Almelo, Netherlands; and
M. A. G. Halliwell, British Telecom Research Labs, Ipswich, U.K.
"An X-Ray Diffraction Study of the Crystal Quality of (100) and (111)
Oriented CdTe on GaAs," Tom W. Ryan, E. J. Fantner, Philips Analytical,
Almelo, Netherlands; A. Pesek, K. Lischka and H. Sitter, Universitat Linz,
Austria.
"Real Time X-Ray Diffraction Experiments with Polymers," C. K. Saw and
P. J. Harget, Hoechst Celanese Corp., Summit, NJ.
"Application of Geochemical Aqueous Speciation-Solubility Program EQ3/6 to
the Preparation of Multi-Element Liquid Standards for X-Ray Fluorescence and
Other Analytical Methods," W. N. Sawka and W. L. Bourcier, Lawrence Livermore
National Lab, Livermore, CA.
"Rietveld Crystal Structure Analysis (Review of the Petten Workshop),"
Robert L. Snyder, Alfred University, Alfred, NY.
"Accurate d Values using Zero Background Sample Holders," Robert L. Snyder
and M. Bijak, Alfred University, Alfred, NY.
"A High-Resolution, High-Brilliancy Primary Beam Laboratory X-Ray Optical
System for HRPD, SAXS, Thin-Film, PSD and Imaging Plate Applications -
Siroflux", Stephen Wilkins and Andrew Stevenson, CSIRO, Victoria, Aus~ralia.
"An Investigation of the Morphology of Amorphous/Semicrystalline Nylon
Blends using Small Angle X-Ray Scattering (SAXS)," Andrew M. Wims and Mark
E. Myers, General Motors Research Labs, Warren, MI; and John Barnes, NIST,
Gaithersburg, MD.
PRESENTATION OF THE 1989 BARRETT AWARD TO JEROME B. COHEN
"For his fundamental and wide-ranging work on the application of

diffraction methods to materials science and through his lectures, books
and publications for his pivotal role in the education of a generation of
diffraction-literate materials scientists."
In photo, left to right:

Jerome B. Cohen, Northwestern University, Evanston, IL,
recipient of the 1989 Barrett Award in X-Ray Diffraction.
Charles S. Barrett, University of Denver, Denver, CO.
xiii
CONTENTS
I. CHARACTERIZATION OF EPITAXIAL THIN FILMS

AND CRYSTAL DEFECTS BY X-RAY DIFFRACTION
High Resolution X-Ray Diffraction for the Characterization

of Semiconducting Materials 1
B. K. Tanner
X-Ray Topography of Surface Layers and Epitaxial Films 13

D. K. Bowen
Stresses in Thin Films 25

J. B. Cohen
Deformation, Recovery and Stress Corrosion Cracking of Nickel-Base

Alloy 600 by X-Ray Rocking-Curve Measurements 33
C. F. Lo, G. Feng, W. E. Mayo and S. Weissmann
X-Ray Characterisation of Residual Surface Strains after Polishing

of Silicon Wafers . 55
L. Hart, D. K. Bowen and G. R. Fisher
Measurement of Relaxation in Strained Layer Semiconductor Structures 61

M. A. G. Halliwell
Characterization of Structural Inhomogeneities in GaAsjA1GaAs

Superlattices 67
P. C. Huang, S. R. Stock, A. Torabi and C. J. Summers
X-Ray Diffraction Analysis of SiGejSi Superlattices 75

M. Fatemi, S. Prokes, B. V. Shanabrook, Jr., and K. L. Wang
High Resolution Measurement of Surface Misorientation in

Single Crystal Wafers 83
M. Fatemi
II. XRD CHARACTERIZATION OF POLYCRYSTALLINE THIN FILMS
Surface and Ultra-Thin Film Characterization by Grazing-Incidence

Asymmetric Bragg Diffraction 91
T. C. Huang
Study of Thin Films and Multilayers using Energy-Dispersive

Diffraction of Synchrotron Radiation 101
R. J. Cernik, S. M. Clark and P. Pattison
xv
xvi CONTENTS
Effects of Refraction and Reflection on Analysis of Thin Films

by the Grazing-Incidence X-Ray Diffraction Method 109
T. Takayama and Y. Matsumoto
Enhanced Range of Measurable Thickness of Thin Crystalline Layers

Using 8/28 Decoupled Powder X-Ray Diffraction 121
G. Kimmel and W. Kaplan
X-Ray Diffraction of Plasma Nitrided Ti-6Al-4V . 129

A. Raveh, G. Kimmel, R. Avni and A. Grill
A Comparative Study of Stress Determination Techniques in

Polycrystalline Thin Films 137
I. C. Noyan and C. C. Goldsmith
X-Ray Line Broadening Analysis of TI-Superconducting Films . 145

M. O. Eatough, D. S. Ginley and B. Morosin
Stress Analysis of Thin-Film SmS using a Seemann-Bohlin Diffractometer. 153

F. E. Moore
Residual Stresses and Differential Deformation of Electroplated

Structures 161
G. Sheikh and I. C. Noyan
X-Ray Residual Stress Analysis of Zn-Ni Alloy Electroplating Layers . 171

T. Sasaki, M. Kuramoto and Y. Yoshioka
XRD Characterization of Titanium/Copper Thin Films Heat Treated in

Vacuum and Hydrogen 177
M. J. Sullivan, C. Goldsmith and P. Ficalora
III. X-RAY SPECTROMETRIC CHARACTERIZATION OF THIN FILMS
Characterization of Thin Films Using XRF . 189

J. E. Willis
The Determination of Elemental Composition, Thickness and Crystalline

Phases in Single and Multi-Layer Thin Films 197
R. A. Brown, K. Toda and R. L. Wilson
Near-Surface Chemical Characterization Using Grazing Incidence

X-Ray Fluorescence 205
K. Sakurai and A. Iida
Basic Studies of Multi-Layer Thin Film Analysis Using Fundamental

Parameter Method 213
Y. Kataoka and T. Arai
Application of Multi-Layer Thin Film Analysis by X-Ray Spectrometry

Using the Fundamental Parameter Method . 225
Fundamental Parameter-Based X-Ray Fluorescence Analysis of Thin

and Multilayer Samples 237
D. K. G. de Boer and P. N. Brouwer
CONTENTS xvii
Non-Destructive Chemical-State Analysis of Thin Films and Surface

Layers (1-1000 nm) by Low-Energy Electron-Induced X-Ray
Spectroscopy (LEEIXS) 247
A. K. Gyani, P. McClusky, D. S. Urch, M. Charbonnier,
F. Gaillard and M. Romand
IV. ANALYSIS OF DIGITAL DIFFRACTION DATA INCLUDING RIETVELD
Structure Refinements in Chemistry and Physics. A Comparative

Study Using the Rietveld and the Two-Step Method 261
G. Will, E. Jansen and W. Schafer
X-Ray Powder Diffraction QPA by Rietveld Pattern-Fitting - Scope

and Limitations 269
B. H. O'Connor, L. Deyu, B. Jordan, M. D. Raven and P. G. Fazey
Application of Position Sensitive Detectors for Neutron Diffraction

Texture Analysis of Hematite Ore . 277
G. Will, P. Merz, W. Schafer and M. Dahms
Problems in the Derivation of d-Values from Experimental Digital

XRD Patterns 285
R. Jenkins and M. Nichols
Derivation of d-Values from Digitized X-Ray and Synchrotron

Diffraction Data 295
T. C. Huang, W. Parrish, N. Masciocchi and P. W. Wang
The Optimization of Step Size While Collecting a Digitized Diffraction

Pattern at a Constant Total Scan Time 305
J. R. Burleson
XRD Acquisition Parameters for Detection of Weak Peaks 313

P. W. Seabaugh, D. B. Sullenger, C. R. Hudgens, M. C. Nichols
and D. R. Boehme
V. X-RAY STRESS ANALYSIS
X-Ray Examination of Fracture Surfaces of Silicon Nitride Ceramics 319

Z. Yajima, Y. Hirose and K. Tanaka
X-Ray Residual Stress Measurement on Fracture Surface of Stress

Corrosion Cracking 327
M. Tsuda, Y. Hirose, Z. Yajima and K. Tanaka
Time-Resolved X-Ray Stress Measurement During Cyclic Loading 335

S. Ohya and S. Ohta
Determination of Rolling Contact Stress Distribution by X-Ray

Diffraction 341
D. L. Milam
Residual Stress Distribution of Ceramic-Metal Joint 353

M. Kurita, M. Sato, I. Ihara and A. Saito
Diffraction Plane Dependence of X-Ray Elastic Constants of Alumina 363

M. Kurita, I. Ihara and A. Saito
xviii CONTENTS
VI. DETERMINATION OF CRYSTALLITE SIZE AND STRAIN
The Importance of Consistent lid Scans in Determining Size and Strain

by Powder Diffraction Profile Analysis . 373
Y. Zhang, J. M. Stewart, C. R. Hubbard and B. Morosin
The Comparison of Several Standard Materials and Techniques for

the Warren-Averbach Determination of Microstructure
Characteristics of Calcium Hydroxide Sorbent Materials 383
F. E. Briden
The Use of 2-D Detector Utilizing Laser-Stimulated Luminescence

for X-Ray Diffraction Studies on Mechanical Behaviour of
Materials . . 389
Y. Yoshioka, T. Shinkai and S. Ohya
Correction of X-Ray Diffraction Profiles Measured by PSPC System . 397

S. Ohya and Y. Yoshioka
Strain and Particle Size of Palladium Metal Powders by Time-of-Flight

Neutron Diffraction 403
A. C. Lawson, J. W. Conant, C. L. Talcott, M. A. David,
J. Vaninetti, J. A. Goldstone, A. Williams, R. B. Roof,
R. B. Von Dreele, R. L. Hitterman, J. W. Richardson, Jr.,
and J. Faber, Jr.
Numerical Resolution Enhancement of X-Ray Diffraction Patterns 409

K. Ohno, H. Harada, T. Yamagata and M. Yamazaki
VII. PHASE IDENTIFICATION, STRUCTURAL AND

QUANTITATIVE ANALYSIS BY DIFFRACTION
Standard Database Format for the Dissemination and Storage of

Diffraction Data - Task Group Progress Report on JCAMP-DX 417
G. P. Hamill, R. Jenkins and W. N. Schreiner
X-Ray Analysis of the Structure of Wholly Aromatic Copolyamides

and Copolyester Carbonates . 423
A.-I. Schneider and J. Blackwell
Polymorphism in Syndiotactic Polystyrene 433

B. G. Landes, M. T. Malanga and B. P. Thill
Phase Diagram Studies on Neopentylglycol and Pentaerythritol-Thermal

Energy Storage Materials 445
D. Chandra, R. A. Lynch, W. Ding and J. J. Tomlinson
Crystal Chemistry and Phase Equilibria of the BaO-R203-CuO Systems 453

W. Wong-Ng, B. Paretzkin and E. R. Fuller, Jr.
Measurement of the Phase Composition of Partially Stabilized Zirconia

(PSZ) Test Parts by X-Ray Powder Diffraction 467
R. A. Newman
X-Ray Mass Absorption Coefficients: Measurements and Uses in the

Quantitative Diffraction Analysis of Pyrite in Coals 475
D. L. Wertz, C. B. Smithhart and S. L. Wertz
CONTENTS xix
An Overview of the Use of XRD as a Tool in the Total Analysis of

Powdered Household Laundry Detergents 485
M. M. King and E. M. Sabino
The Determination of Quartz in Perlite by X-Ray Diffraction 493

R. D. Hamilton and N. G. Peletis
VIII. X-RAY SPECTROMETRY DATA ANALYSIS
The Concept of Pathlength Distributions Applied to Fundamental

Parameter Approach 499
H. Ebel, C. Pohn, R. Svagera, M. Mantler, M. Wernle and M. F. Ebel
A Versatile Fundamental Alphas Program for Use with Either Tube

or Secondary Target Excitation 509
L. Feng, P. A. Pella and B. J. Cross
Absorption Corrections via Backscattered Radiation in Polychromatic

Excitation Energy-Dispersive X-Ray Fluorescence Spectrometry. 515
F. Araujo, F. He, P. Van Espen and R. Van Grieken
Intensity and Distribution of Background X-Rays in Wavelength

Dispersive Spectrometry III 521
T. Arai and T. Shoji
An Artificial Intelligence System for XRF Data on a Personal Computer 531

E. P. Wittig and C. E. Rechsteiner
SPC: What is It and Why should You Use It in Your X-Ray Analytical
Laboratory? 537
P. B. DeGroot
SPC Analysis of Optimal Strategies for Restandardization of X-Ray

Fluorescence Analyses 543
P. B. DeGroot
Analytical Errors from Electronic Instability in the Counting Chain

of a Wavelength-Dispersive XRF Spectrometer 549
T. K. Smith and M. N. Ingham
Corrections for the Effect of Scattering on XRF Intensity 553

J. E. Fernandez, V. G. Molinari and M. Sumini
XRFPC: A Program and Data Base for XRF Computations 567

J. E. Fernandez
Theoretical Estimation of the Fourth-Order XRF Intensity 573

J. E. Fernandez and V. G. Molinari
IX. XRF INSTRUMENTATION
TXRF Spectrometer for Trace Element Detection 581

F. HegedUs, P. Winkler, P. Wobrauschek and C. Streli
A Compact On-Line XRF Analyzer for Chemical and Petrochemical Processes. 585
D. J. Kalnicky, A. I. Ahonen, M. J. Hietala and K. J. Kauhanen
xx CONTENTS
XRF Macroprobe Analysis of Geologic Materials 593

N. L. Gilfrich, D. E. Leyden and E. A. Erslev
Qualitative XRF Analysis with Pattern Recognition 603

L. I. Yin and S. M. Seltzer
Design of High Performance Soft X-Ray Windows 615

R. T. Perkins, D. D. Allred, L. V. Knight and J. M. Thorne
X-Ray Capillary Microbeam Spectrometer 623

S. Larsson, P. Engstrom, A. Rindby and B. Stocklassa
X. XRF TECHNIQUES FOR HAZARDOUS WASTES AND OTHER APPLICATIONS
The Use of Field-Portable X-Ray Fluorescence Technology in the

Hazardous Waste Industry 629
G. A. Raab, C. A. Kuharic, W. H. Cole III, R. E. Enwall
and J. S. Duggan
XRF Technique as a Method of Choice for On-Site Analysis of Soil

Contaminants and Waste Material 639
S. Piorek
Application of Field Mobile EDXRF Analysis to Contaminated Soil

Characterization 647
A. R. Harding and J. P. Walsh
Screening of Hazardous Waste with an Energy Dispersive X-Ray

Fluorescence Spectrometer 655
N. C. Jacobus
X-Ray Fluorescence Analysis of Trace Metals in the Annual Growth

Layers of Freshwater Mussel Shells 665
W. E. Maddox, L. Duobinis-Gray, D. A. Owen and J. B. Sickel
Application of PIXE Method for Environmental Protection in Poland 671

T. Zoltowski, W. Ratynski, M. Jaskola, J. Parus and L. Wawrzonek
Microvolume Analysis of Fly Ash by Synchrotron Radiation X-Ray

Fluorescence (SRXRF) and Electron Microprobe X-Ray
Microanalysis (EPXMA) 673
Sz. Torok, Sz. Sandor and H. Rausch
X-Ray Fluorescence Analysis of Zeolites for the Determination of

Silica:Alumina Ratio and Soda:Alumina Ratio 679
P. A. Gokhale and M. R. Wuensche
Alumina Characterization by XRF 685

F. R. Feret
Author Index 691
Subject Index 695

HIGH RESOLUTION X-RAY DIFFRACTION FOR THE CHARACTERIZATION
OF SEMICONDUCTING MATERIALS
B K Tanner
Department of Physics, University of Durham

South Road, Durham, DHl 3LE, U.K
Abstract
Use of a reference crystal to condition the beam in the double-axis diffractometer
permits the Bragg peak width to be reduced to the correlation of the two crystal
reflecting ranges. Some recent applications of double axis diffractometry to the study
of heteroepitaxial layers are discussed. The advantages of multiple reflections for
beam conditioning and the four reflection DuMond monochromator are examined.
Glancing incidence and exit diffractometry permits the study of very thin layers, down
to a few tens of nanometres in thickness and both synchrotron radiation and skew
reflections can be used to tune the glancing angle close to the critical angle. Recent
applications of triple-axis diffraction, where an analyzer crystal is used after the
specimen, to the study of very thin single epitaxial layers and multi quantum well
structures are reviewed.
Introduction
The width of the Bragg peaks, and hence the angular resolution, in single-axis
diffractometry is determined by the collimator geometry, the source size and the
spectral width of the characteristic lines in the X-ray spectrum. In practice, this
means that the Bragg peaks from a substrate and a nearly lattice-matched epitaxial
layer cannot be resolved. The requirement to determine non-destructively the
composition of heteroepitaxial layers grown for electro-optic applications has
stimulated the widespread use of high resolution diffraction over the past decade. By
simulation of rocking curves of model structures and seeking a best match with
experiment, a very great deal of structural information can be acquired. Indeed,
although not discussed here, simulation is essential for the interpretation of very thin
and multiple layer structures. While standard geometries are well suited to quality
control of wafers for commercial device fabrication and the characterization of many
research systems, there is an unrelenting drive toward the exploitation of very thin
layers where quantum confinement effects give rise to totally new physics from
which novel electronic devices can be devised. This challenge to characterize
nanometre-thick layers at the Angstrom level has been met by precision diffraction
techniques. The methodology of determining structural parameters of epitaxial layers
from the X-ray data has recently been surveyed 1,2. Extensive bibliographies are also
contained in these papers 1-3. Here, an attempt is made to compare the information
available from different settings and clarify the criteria to be used when designing
Advances in X-Ray Analysis, Vol. 33

Edited bv C.S. Barrett el al.
Plenum Press, New York, 1990
2 I. CHARACTERIZATION OF EPITAXIAL THIN FILMS BY X-RAY DIFFRACTION
experiments. Throughout the paper, the term high-resolution diffraction is taken to

mean diffraction experiments in which one or more additional Bragg reflecting
elements are used to condition the X-ray beam.
Double-Axis Diffractometry
The (+n, -n) setting

The most widely used high-resolution diffraction setting is that where the reference
crystal is chosen to be of the same material as the specimen and the reflection
geometry is chosen such that the X-rays from the source are first diffracted from the
(hkl) planes of the reference crystal and subsequently the (-h-k-l) planes of the
specimen (Fig. l(a». If the crystals are not curved and care has been taken to set the
Bragg planes perpendicular to the incidence (scattering) plane 4,5, then the rocking-
curve width from ideally perfect crystals is just the mathematical correlation of the
two plane-wave reflecting ranges, which may be calculated using dynamical
diffraction theory. The rocking-curve is thus symmetric, even though the plane-wave
reflecting curves may be asymmetric due to absorption. Rocking-curve widths are a
function of material, reflection and wavelength band selected by the reference crystal
but are typically 5-10 arc seconds for strong reflections (Fig l(b».
As the (+n,-n) setting is non-dispersive in wavelength, if the collimator angular

aperture is greater than about an arc minute, the KO(l and K0(2lines will usually both
be diffracted by the reference crystal when this IS set for maximum diffracted
intensity as a function of angle. When the specimen and reference are parallel both
will be diffracted from the specimen, but from different points across its surface. If
the crystal is non-uniform, then rocking-curve broadening results. The intermediary
aperture between reference and specimen crystal may be used to limit the area of
sample sampled and in doing so, remove one of these components. For perfect
crystals, the intermediary aperture does not affect the rocking-curve width. However,
Reference E~~~
Source ~ (a)
~ Collimator Specimen
camt•• t.
1720 1725 1730 1735 17040 1745 1750 17&5 1750 17&5 1770 1775
Fig 1. (a) The (+n,-n) double-crystal diffraction geometry. (b) Silicon 004, 004
reflection rocking curve with CuK radiation.
B. K. TANNER 3
for strained-layer epitaxial systems such as GaAs on Si, CdHgTe on CdTe, or GejSi
on Si, the mismatched layer results in very significant wafer bowing. Unless the area
of the specimen sampled by the beam is quoted, results of different investigations
cannot hope to be compared in a meaningful manner. An example of good practice is
the correlation of dislocation density and rocking-curve full width at half-height
maximum (FWHM) in CdxHgl_xTe on GaAs by Brown et aZ 6 in a volume containing
a number of high-resolution diffraction papers. While it is standard practice to use an
open detector, it should also be noted that use of a slit before the detector to
improve signal to noise can lead to a change in the FWHM of the rocking curves in
imperfect crystals.
The (+ n,-n) double-crystal setting is capable of a signal-to-noise ratio of at least

104:1, provided that care is taken to shield the scatter from the reference crystal with
a substantial enclosure, that a small aperture is used between reference and
specimen crystals, that there is no line of sight between detector and collimator and a
proportional counter is used in place of a scintillation detector. When such
precautions are observed the low intensity Pendellosung or thickness fringes from
thin epitaxial layers become visible far from the Bragg peak 7. These are particularly
important in multiple-layer structures where interference fringes from each layer and
sums of layers can be distinguished. The fringe period ~ep is independent of
scattering power and varies with the layer thickness t as;
(1)
where 8 B is the Bragg angle, ).. is the X-ray wavelength and 'lJ h is the the cosine of
the angle between the diffracted beam and the inward surface normal. Although
direct measurement of fringe period in multiple-layer structures cannot be used to
determine t 7 due to beating of the fringe systems, Fourier analysis will yield
thicknesses directly 8. Note that it is important to Fourier-analyze the rocking curve
plotted on a logarithmic scale as otherwise the Bragg peak totally dominates the
spectrum. A major importance of this technique is that it fixes the layer thicknesses.
In mu1tiple-Iay~r structures, very different structures can give rise to very similar
rocking curves and there is danger that in least-squares minimization methods with
many variables, one may end up at a local minimum which does not correspond to
the experimental structure.
The (+n, om) setting

When the Bragg-plane spacings of reference and specimen differ, then a broadening
of the rocking-curve results, which is given by
(2)
where 8 1 and 8 2 _are the Bragg angles of reference and specimen and ~" is the
bandwidtb of the -X-ray spectrum passed by the collimator. In most experimental
situatio,!ls this will approximate to the splitting of the Koc. 1 and K(){2 lines. Thus, the
004, 004 rocking curve of InP and GaAs is broadened by about 25 secs which may be
quite acceptable for the study of strained-layer systems such as InGaAs or GaAsSb
on GaAs. Similarly, the mismatch between Si and GaAs results in a peak broadening
which is small compared with the rocking-curve FWHM of GaAs grown epitaxially
on Si 10. As the lattice parameters of Ge and GaAs are very nearly equal, it follows
that the double crystal setting is also satisfactory for the study of SixGe1_x on Si 11.
However, with InP and Si, the mismatch is so large that, in the 004, 004 reflection,
the Kot 1 and Koc 2 lines are resolved (Fig 2). The reason can be readily seen from the
25000
(a) 8000 (b)
7000
20000
6000
ISOOO 5000
4000
10000
3000
2000
SOOO
1000
6600 66SO 6700 67SO 6800 -140 -120 -100 -80 -60 -40 -20 -j) 20 40
Fig 2 Rocking curves in the (+n,-m) setting where the lattice parameters are not
equal; 004 reflection using CuKc:t radiation with (a) InP and GaAs. The GaAs peak is
additionally broadened to 44 secs due to an epitaxial InGaAs layer which curves the
wafer. (b) Si and InP. The two peaks are the resolved Kc:t1 and lines. K«z
DuMond diagram 1 or by ray tracing. In the (+n,-m) setting the Kl)(l and Kit. rays in
Fig 1 are no longer diffracted when the second crystal is parallel to the firs!. When
the difference in angular setting of the specimen to satisfy these two rays significantly
exceeds the correlation of the two reflecting ranges, then a split peak results.
Fortunately, lattice mismatches in current strained-layer systems is such as to
broaden, not split the peaks.
The four-reflection DuMond monochromator

The way to avoid the broadening due to mixing of crystals is to limit the bandwidth
passed in the system by using a crystal as a true monochromator. To do this, one
needs to use a (+n,+n) pair of reflections at the reference crystal (Fig 3(a». As
evident in the Dumond diagram (Fig 3(b)), there is only a very small overlap range in
both angle and wavelength for a given setting of the crystals. [Although this has a
very low angular sensitivity to strain, this is a true monochromator]. If the specimen
crystal is in the -m setting, the region of overlap of the reflecting ranges of the three
crystals is very small (Fig 3(c». A small angular misorientation of the specimen with
respect to the reference-crystal pair will lead to total loss of diffracted mtensity. It is
clear, that the angular sensitivity is preserved when the slope of the specimen-crystal
line in the DuMond diagram changes, and thus the beam conditioner can be used to
give high angular resolution rocking-curves for an arbitrary lattice parameter of the
specimen.
The ( + n, + n,-mJ setting is a little inconvenient experimentally as, for Bragg angles of
the order of 30 , the diffractometer body has to be at an angle of 1200 with respect
to the X-ray tube housing. A way of avoiding this is to use an extra reflection on the
reference crystal to give a (-n,+n,+n,-m) setting (Fig 4(a)). The first pair of
reflections can be conveniently made for a single-grooved, or channel-cut, crystal and
the diffractometer is now aligned at the same angle as for a single reference
reflection in the ( + n,-m) setting.
In 1935 DuMond 12 described a monochromator which used one further reflection

giving a (-n,+n,+n,-n,-m) setting (Fig 4(b». This has the attraction that the
conditioned beam is always collinear with the incident beam, independent of the
B. K. TANNER 5
(a)
(b) (c)
Fig 3 (a) The (+n, +n,-m) setting showing true beam monochromatization (b) The
DuMond diagram for the first two reflections (c) The DuMond diagram for all three
reflections. The dotted line 3' corresponds to the specimen crystal angularly
displaced. No overlap, and hence diffracted intensity, results from a very small
rotation as in the ( + n,-n) setting 1
Bragg angles. One may therefore change monochromator reflection or the

wavelength of the conditioned beam without realignment of the sRecimen. The
setting was used by Beaumont and Hart 13 and Bowen and Davies 1 for use with
synchrotron radiatIOn and subsequently re-examined by Bartels 15. Bartels exploited
the high intrinsic scattering power of germanium and the use of a pair of channel-cut
crystals to turn the design into one which was useful as an analytical tgol rather than
a laboratory curiosity. His design was subsequently patented 1 and is now
commercially available. While the four-reflection monochromator has the great
advantage of removing the broadening due to dispersion when the lattice parameter
of specimen and reference differ, it is important to stress that it does not eliminate
the rocking curve broadening due to specimen curvature.
(a)
Specimen
(b)
Fig 4 (a) The (-n, +n, +n,-m) setting giving a convenient beam geometry and high,
dispersion-free, sensitivity to lattice strain (b) The four reflection (-n, + n, + n,-n,-m)
setting giving collinear incident and conditioned beams.
Asymmetric reflections
Symmetric reflections only provide data on the Bragg plane spacing normal to the
surface and thus give no information on the degree of relaxation in a strained layer.
Even when relaxation does not occur, serious errors can be incurred if it is not
appreciated that epilayers can be, and often are, tilted with respect to the substrate.
Provided that the layer is not sufficiently thin that interference effects lead to peak
shifts (typically < 0.5 pm) 19, the measured peak splitting A8 between layer and
substrate is
L:l.8 = - m* cot e B + ~ jV [3]

where ~f is the tilt component in the Bragg planes between substrate and layer, and
m'" is the effective mismatch. In the case of G<lxAll_xAs on GaAs where the lattice
mismatch between AlAs and GaAs is small, neglect of the tilt can lead to a major
error in the determination of the Al concentration 20,21. Rocking curves taken with at
least three orientations of the specimen rotated about the surface normal are
necessary for complete characterization and two rocking curves are needed simply to
determine mismatch and hence composition.
Deduction of composition from effective mismatch is also unreliable when relaxation

takes place due to the creation of misfit dislocations at the interface between
substrate and layer. The layer is no longer coherent and the real mismatch in
unconstrained materials cannot be deduced from the mismatch measured normal to
the surface. Two asymmetric reflections are required in addition and it is normally
most convenient to use two such asymmetric reflections with the beam paths reversed
but the same Bragg planes. From the two splittings, one may deduce independently
the Bragg plane spacing and the tilt between the epitaxial layer and substrate planes.
In combination with the s~mmetric reflection data, the c and a parameters for the
layer can be extracted 1, . A study of the relaxation of multilayer structures of
Si:SixGel_x has recently been reported by Halliwell et a1 22. In this situation, it proves
again possIble to extract individual a and c parameters of the component layers from
asymmetric reflections. Pietsch and Marlow 23 have exploited asymmetric reflections
to measure the lattice parameters of quaternary layers on InP as a function of
temperature. They find that the thermal expansion coefficient is 30% greater than
that expected from cubic relaxed material.
Multiple-reflection beam conditioners

The four-reflection monochromator has an additional advantage in that the extra
reflections added to the basic monochromating reflection illustrated in Fig 3 serve
not only to steer the beam but also to reduce the tails of the rocking curves. Thi~
effect is most dramatic when viewed on a logarithmic scale. Bonse and Hart 1
exploited the effect in the design of a very high-resolution small-angle scattering
camera, and with the intensity available from synchrotron radiation sources, interest
in this technique has recently been rekindled, particularly amongst the biological
science community.
If a channel-cut crystal is used as a reference crystal on a standard double-axis
diffractometer, it may provide, for example, four reflections to give the (-n, + n,-n,
+n,-n) setting (Fig 5). The reflectivity from the beam conditioner for any angular
setting will be R4 where R is the reflectivity of a single Bragg reflection. Clearly
when R is nearly unity, the multiple reflection has little effect, but the tails of the
Bragg reflection are reduced by the fourth power. When the specimen is rotated with
respect to the reference crystal to form the rocking curve, the correlation of the
reference and specimen is between an effectively square function from the ~efe!ence
crystal and the intrinsic reflectivity of the specimen. Diffuse scatter appeanng ill the
B. K. TANNER 7
Fig 5 Multiple-reflection beam conditioner to reduce the tails of the Bragg peak for
study of diffuse scatter.
wings of the Bragg peak can then be readily distinguished. For example, the diffuse
scatter arising from silicon wafer polishing processes can be distinguished 18.
Grazing incidence or exit asymmetric reflections

The depth penetration of an X-ray beam into a crystal is limited by two factors,
photoelectnc absorption and extinction. It is easy to see that in the case of grazing
mcidence, the path length of the X-ray beam to reach a given depth will be increased.
Thus the depth t at which the intensity is reduced to 90% of the incident intensity is
given by
[4]
where ¢ is the angle between Bragg planes and the crystal surface and u is the linear
photoelectric absorption coefficient. This formula may be used to determine the
depth sensitivity of X-ray topographs. However, at the Bragg reflection, the
extinction distance determines the depth to which the X-ray wave penetrates. Even in
the case of zero photoelectric absorption, the depth reached by the X-ray wave will,
for strong reflections, usually be only of the order of microns due to the dynamical
diffraction effects occurring. The extinction distance h is given by
h = l6'h ~ 0 11/2/ C (XhX_h)1/2 [5]
where X h is the Fourier component of susceptibility, C is the polarization factor

and 'If 0 ana )f h are the cosines of the angles between incident and diffracted beams
and tile inward-surface normal. In the Bragg (reflection) geometry
[6]
Thus, in either glancing-incidence or glancing-exit geometry, the layer thickness
ds
,,
,,
.
,,
----- ... _-_ ...... "
---.:......._..
,
Fig 6 Bragg cones (a) unembedded reflection (b) embedded reflection

(a)
IDIID
(b)
are sees
.....
..Il00
(c) (d)
'''''''''
'''''''''
Fig 7. Simulated and experimental rocking curves taken with CuK radiation and 333
reflection of a 100 nm thick GalnAsP layer on InP [28]. An&le between incident
beam and surface of (a) 1.15 0 , (b) 20 (c)11.4° (d)46.9 (glancing exit)
corresponding to a reflectivity of unity is reduced and the experiment becomes more

surface sensitive. This is extremely important for the study of very thin layers where,
in the symmetric geometry, the peak intensity becomes low and the peak width
simultaneously becomes very broad. The peak height thus goes down much faster
than the layer thickness and although in GaAsSb on GaAs, which has a large
mismatch, rocking curves of layers as thin as 160 Angstroms have been recorded in
the 004 reflection with CuK radiation 24, for near-matched layers, the tails of the
Bragg peak from the substrate mask the layer peak. Use of a glancing reflection,
where (fo or ~b approach zero, leads to enhanced scattered intensity from the layer.
Down to glancmg angles of 1.5 0 no deviation from the predictions of the Takagi-
Taupin equations are found 25.
Glancing incidence can be achieved by varying wavelength 25,26 and this is most
appwpriate to synchrotron radiation work. In the laboratory, in order to maintain the
intensIty afforded by the characteristic X-ray lines, skew reflections are used. SARCA
(Skew Asymmetric Rocking Curve Analysis) 27 involves the use of a reflection in
which the Bragg cone is embedded in the crystal surface (Fig 6).
Rotation of the specimen about the diffraction vector thus tunes the angle between
the incident beam and the surface, from a minimum at glancing incidence to a
maximum at glancing exit. As evident from Fig 7, the layer peak intensity varies
systematically with azimuthal angle and the ~reement between simulated rocking
curve and experiment is at all points excellent . The ratio of layer to substrate peak
intensity reaches 53%, in comparison with 14%. which is the highest value in a non-
B. K. TANNER 9
-- & (a)
Speci men
(b)
AllnAs InP(substrate)
(0,4'0025,4074) (0,4,4074) (0,4,4'017) (044) (0,4,3926)
(0,39973,4074)
Fig 8 (a) Basic triple-axis diffraction geometry (b) Map of the scatter in reciprocal
space around the 440 reciprocal lattice point from a 20nm thick InAlAs layer on InP
capped by 3 nm of GaAs 34. Flat Ge (111) crystals were used as beam conditioner
and analyzer; 1.54 A radiation.
skew geometry (using the 044 reflection). It should be noted however, that the peak
intensity for a given reflection goes down as the glancing angle is reduced, and there
is thus a balance to be achieved between peak shape and intensity. Also, the peak
widths narrow in the glancing-exit case as the FWHM w is given by
[7]
However, the substrate and layer peaks move together (Fig 7), thus offsetting the
gain in angular resolution.
The method has been exploited by Pietsch and Borchard 29 for the study of lattice
matched C~Sr1_xF2 grown on GaAs. Although for high angle reflections, the Bragg
peaks of substrate and layer overlap, at extreme grazing incidence the effect of
refraction is sufficiently large to separate the two peaks. The magnitude of the shift
depends not only on the incidence angle but also the atomic numbers of substrate
and layer. For 1.35 micron band gap InGaAs on InP the shift for the 333 reflection at
glancing angle of 10 is 16 secs 28 which is rather small in comparison with the rocking
curve peak widths.
Triple-Axis Diffractometry
In the double-axis geometry, the scattering is integrated along a line in reciprocal

space. Use of an analyzer crystal after the specimen (Fig 8(a» permits the scattering
to be mapped in a plane in reciprocal space (Fig 8(b» and thus diffuse scatter can
readily be distinguished from coherent scatter. Even more importantly for
semiconductor characterization, the method allows Bragg plane tilts and dilations to
be determined independently and thus the effect of wafer curvature is eliminated.
Ryan et al 3D and Lucas et al 31 demonstrated that with glancing incidence geometry
at the specimen and single-crystal beam conditioner and analyzer, single quantum
wells of thickness of less than 20 nm were readily visible, and structural data on
layers as thin as 2 nm could be deduced from rocking-curve fitting. Interface
roughness must be included in order to obtain good fits to the data.
Fewster 32 has elegantly combined the advantages of the four-reflection

monochromator with the triple-crystal method to characterize an all-binary
AlAs/GaAs laser structure which contained 1517 layers and was significantly curved.
When the four-reflection monochromator was used with the specimen in the double-
crystal geometry, two broad peaks were observed but when an analyzer crystal was
included after the specimen to remove the effects of the wafer curvature, complex
interference fringe~ were seen between the peaks from which the multilayer structure
could be refined 3 . Fewster has also shown that use of a channel-cut crystal as an
analyzer giving a total of 8 reflections from the three axes 33 removes much of the
parasitic scatter inherent in the instrument function of the single-reflection triple-axis
system. Very clean maps of the specimen scatter in reciprocal space can then be
obtained.
Triple-axis diffractometry is thus applicable not simply to the most highly perfect
crystals. Indeed it is most appropriate for the study of such systems as GaAs on Si
where it is extremely difficult in the double-axis mode to distinguish between tilts and
dilations. In the triple-axis mode a rocking curve recorded by scanning only the
specimen will provide a measure of the tilts only. A so-called e ~ scan, in which the
analyzer is stepped around the specimen for each angular position of the specimen,
permits a map of the scattering to be reconstructed in reciprocal space. (Note that,
once set up, the angular setting of the analyzer about its own axis remains
e
unchanged.) The ideal method of data collection is one in which the and1 setting
are chosen to give a grid in reciprocal space and it is straightforward to program an
instrument to perform this operation. Integration along a line in reciprocal space
recovers the tilt-free, quasi-double-axis rocking curve 34. Apart from increased
complexity of setting up the apparatus, the only disadvantage of the triple-axis mode
is the increased data collection time but this is of course offset by the increased data
collected! Careful thought to experimental design, such as use of a strong scattering
analyzer, and the size of the area element in reciprocal space from which scattering is
measured can minimize data collection times. A channel-cut InP analyzer crystal
works very well for example and has an acceptance range well matched with
optimum step on the analyzer. Because of the additional Bragg-reflecting elements,
fluorescence from the specimen is eliminated and the signal-to-noise is much better
than in the do~rle-axis diffractometer. A value of 106:1 has been reported by
Zaumseil et al in their study of ion implantation in silicon. They were able to
determine the depth profiles of strain and static lattice disorder. Their measurement
technique was to scan the analyzer at a fixed setting of the specimen and determine
the value of the maximum scattered intensity. This was then plotted as a function of
specimen angular setting.
Fornard Projection
High resolution diffraction has been performed since the 1920s but has only become
widely exploited within the past decade. Double-axis diffraction is now regarded by
many crystal growers as an llltegral part of their analytical armoury. However, most
workers have not exploited fully the variety of geometries or beam conditioners
available. It is clear that, with the recent commercial availability of a triple-axis
diffractometer, this mode of high-resolution diffraction is likely to develop rapidly
and become of comparable importance to double-axis diffraction in the 1990s.
References
1. B. K. Tanner, Electrochem. Soc. Symp. Proc. 88-20: 133 (1988).

2. B. K. Tanner,1 Electrochem. Soc. (in press).
3. B. K. Tanner, J Crystal Growth (in press).
4. P. F. Fewster, 1. AQpt. Cryst. 18: 334 (1985)
5. B. K. Tanner, X. Chu and D. K. Bowen, Mater. Res. Soc. Symp. Proc. 69: 191
(1986).
B. K. TANNER 11
6. G. T. Brown, A. M. Keir, M. 1. Gibbs, 1. Gless, S. J. C. Irvine and M. G. Astles, in:

"Heteroepitaxial Approaches in Semiconductors: Lattice Mismatch and its
Consequences", Electrochem. Soc. Symp. Proc. 89-5: 171 (1989).
7. B. K Tanner and M. A. G. Halliwell, Semicond. Sci. Tech. 3: 967 (1988).
8. A. T. Macrander, S. Lau, K Strege and S. N. G. Chu, ADpl. Phys. Lett. 52: 1985
(1988).
9. B. K Tanner, G. S. Green, S. Cockerton and S. J. Miles, 1. Crystal Growth (in
press).
10. J. W. Lee, D. K Bowen and J. P. Salerno, Mater. Res. Soc. SymD' Proc. 91: 193
(1987).
11. S. 1. Barnett, G. T. Brown, D. C. Houghton and J-M. Baribeau, ADD!. Phys. Lett.
54: 1781 (1989).
12.1. DuMond, Phys. Rev. 52: 872 (1937).
13.1. H. Beaumont and M. Hart, 1. Phys. E: Sci. Inst. 7: 823 (1974).
14. D. K Bowen and S. T. Davies, Nucl. Inst. Meth. 208: 725 (1983).
15. W. 1. Bartels, 1. Vac. Sci. Teelmo!. Bl: 338 (1983).
16. W. 1. Bartels, US Patent No. 4567605 (1986).
17. U. Bonse and M. Hart,ADDI. Phys. Lett. 7: 238 (1965).
18. L. Hart, D. K Bowen and G. R. Fisher, Adv. X-ray Anal. 33: (1990) this volume.
19 P. F. Fewster and C. J. Curling,!. ADDI. Phys. 62: 4154 (1987).
20. B. K Tanner, S. J. Miles, G. G. Peterson and R. N. Sacks, Materials Letts. 7: 239
(1988).
21. P. Auvray, M. Baudet and A. Regreny, 1. Crystal Growth 95: 288 (1989).
22. M. A. G. Halliwell, M. H. Lyons, S. T. Davy, M. Hockly, C. G. Tuppen and C. 1.
Gibbings, Semicond. Sci. Techno!' 4: 10 (1989).
23. U. Pietsch and D. Marlow, Phys. Stat. Sol. (a) 93: 143 (1986).
24. M. Brozel, K Singer and W. S. Truscott (private communication)
25. B. K Tanner and M. 1. Hill, 1. Phys. D: ADDI. Phys. 19: L229 (1986).
26. H-G. Bruhl, U. Pietsch and B. Lengeler, 1. ADD1. Cryst. 21: 240 (1988).
27. M. H. Lyons and M. A. G. Halliwell, Inst. Phys. Cant Ser. 76: 10 (1985).
28. S. J. Miles, PhD Thesis, Durham University, (1989).
29. U. Pietsch and W. Borchard, 1. Appl. Cryst. 20: 8 (1987).
30. T. W. Ryan, P. D. Hatton, S. Bates, M. Watt, C. Sotomayor-Torres, P. A. Claxton
and J. S. Roberts, Semicond. Sci. Teelmol. 2: 241 (1987).
31. C. A. Lucas, P. D. Hatton, S. Bates, T. W. Ryan, S. Miles and B. K Tanner, l.
ADDI. Phys. 63: 1936 (1988).
32. P. F. Fewster,Electrochem. Soc. Symp. Proc. 89-5: 278 (1989).
33. P. F. Fewster, 1. Appl. Cryst. 22: 64 (1989).
34. S. Bates, P. D. Hatton, C. A. Lucas, T. W. Ryan, S. J. Miles and B. K. Tanner,
Adv. X-ray Anal. 31: 155 (1988).
35. P. Zaumseil, U. Winter, F. Cembali, M. Servidori and Z. Sourek, Phys. Stat. Sol.
(a) 100: 95 (1987).
X-RAY TOPOGRAPHY OF SURFACE LAYERS AND EPITAXIAL FILMS
D. Keith Bowen
Department of Engineering
University of Warwick
Coventry CV4 7AL, UK
ABSTRACT
The techniques of X-ray topography are reviewed, with special reference to

their application to the study of surface layers and thin films. The
methods of section topography, white radiation topography and double and
triple crystal topography are shown to be the most appropriate, with
grazing or glancing incidence methods assuming special importance.
Applications to the questions of epilayer mismatch and dislocation
content, process-induced defects and surface damage are discussed.
INTRODUCTION
The methods of high precision X-ray diffractometryl have undergone

considerable development in recent years, driven by the requirement of the
electronics industry for the characterization of novel device materials.
Techniques for the measurement of strain and composition profiles, normal
to the surface, in layers less than 50 nm thick are available, and the
method is applied widely in research and quality control in industry. The
closely-related topographic imaging methods have also grown in
importance, although to a lesser degree, because of the need to study the
areal variation of structure, such as the dislocation density in strained
or relaxed layers, defect generation in device processing and surface
damage due to wafer polishing and other treatment. As devices become
smaller, and utilise a shallower surface layer, such effects increase in
importance, and it is timely to review the X-ray topographic methods for
materials characterization. Historically, the techniques were developed
primarily for the study of the perfection of bulk crystals, whether by
transmission or reflection methods, but we shall concentrate upon their
application to the study of thin layers j we choose the figure of 10
microns to define this region of interest.
All methods of X-ray topography result in an 'image', that is, a map of

the diffracted X-ray intensity across the X-ray exit surface of the
crystal. Contrast in this image is produced by strain variations, and the
strain around a single dislocation gi ves quite strong contrast.
Superficially, the images can appear quite similar to electron
Advances in X-Ray Analvsis, Vol. 33 13

Edited by C.S. Barrett el at.
micrographs, but the scales are quite different. X-ray images are,
roughly, 1000 times more sensi ti ve to strain, cover 1000 times larger
diameter specimens but have 1000 times poorer spatial resolution. The
methods are complementary, and, for example, one should use electron
microscopy for details of interface structure but X-ray topography (XRT)
for strain mapping in whole wafers (or large portions of them) before or
after device processing.
TECHNIQUES AND INSTRUMENTATION FOR TOPOGRAPHY OF THIN LAYERS
Singlecryst.almetnQ.ds
In these methods there are no beam-conditioning optics between the X-ray
source and the specimen. The intrinsic reflectivity of the crystal must be
correlated with the properties of the source (e.g. its divergence), so
these methods do not have the highest strain sensitivity. They can,
however, reveal individual dislocations and other short-range strains and
are relatively undemanding on alignment and other experimental techniques.
The Berg-Barrett method 2 was the earliest topographic method to enjoy

substantial popularity, and it is still very useful for the study of
surface layers. The principle is illustrated in figure la. A broad,
monochromatic source is used to illuminate the specimen at a grazing
angle, and an asymmetric reflection geometry is used to give a relatively
undistorted diffraction map of the specimen. As discussed in the next
section, this geometry gives the Berg-Barrett method very good surface
sensitivity.
Spatial resolution is determined in the Berg-Barrett and in any

topographic method by two factors 3. In the incidence plane (the plane
containing the incident and diffracted beams and hence also the
diffraction vector) the resolution di is determined by the divergence of
the beam leaving a point on the specimen. This is controlled by the
wavelength spread dA/X of the X-ray beam used:
d i = b dA/X tan (J (1)
where (J is the Bragg angle and b is the specimen-film distance.

Perpendicular to the incidence plane the resolution d p is determined by
the demagnification of the source:
dp = hb/a (2)
to a good approximation 4 , where a is the source-specimen distance and h is

the source height perpendicular to the incidence plane. In the Berg-
Barrett method, b can be as little as I mm. Taking typical values (for a
sealed tube, line focus) of a = 200 mm and h = 0.04 mm we obtain a
resolution d p = 0.2 microns. However, both Kal and KaZ lines diffract, and
for a typical case (CuKa GaAs specimen with 440 reflection) the incidence
plane resolution di with the same b value is 3 microns.
In the section topography and Lang methods (figure lb and lc), a point
source is used and the divergence controlled with slits, so that only the
Kal line is used. It is difficult to make b<10 mm in these cases, but
parameters may now be chosen so that d p - d i - I micron. The specimen
must be scanned through the beam to build up the image for the Lang method
(in reflection or transmission) but if left stationary in transmission the
D. K. BOWEN 15
method is that of section topography. Note that the latter provides depth
information, since it gives diffraction effects in a slice through the
crystal, and can thus yield near-surface information.
Figure Id illustrates the white radiation methodS, used on synchrotron

radiation sources. These have an intense, broad-band spectrum, a small
source and long collimation lengths. The specimen selects the appropriate
wavelength from the source, as in the traditional Laue method, but the
parameters are such that 1 micron resolution is quite easily achieved in
either plane. If the specimen is elastically or plastically curved, image
distortion will result but the image can still be obtained and analysed 6 •
ImagecQutrast.andpeuetratiQudepth in.. sindecrystal ..methQds

The contrast in single - crystal transmission X-ray topography has been
worked out in considerable detail (see e.g. 7 ). However, this technique is
of very limited use for thin layer and surface characterization. A free
thin layer will normally only give useful contrast for defects such as
dislocations if it is thicker than about one-third of the dynamical
extinction distance for the radiation and reflection used. Whilst in
principle this need not be a restriction if strongly scattering materials
and/or very soft radiations are used, extinction distances are typically
tens of microns for semiconductor materials and available wavelengths and
I Plate
r-~~-~-rc-e--"I-~
(a) (b)
Traverse
point _ _ _ _ _ _ _ _ _ _-:-_ _ ~
source
(c)
synchrotron
:-=--urce
I
_-Iaf--~~
Plate
It I~
(d)
Figure 1. (a) Berg-Barrett method, (b) Section topography (if the specimen
and film are translated this becomes the Lang transmission method) (c)
Lang method in reflection geometry, (d) white radiation method.
it is usually not possible to see contrast in thin isolated layers in

transmission. Contrast may be seen if the layer is coherent with its
substrate, but the information from a micron-scale layer in transmission
is usually swamped by that from the millimetre-scale substrate.
In section topography, however, the information is taken from a slice

across the crystal. All the X-ray wavefields generated at defects give
rise to contrast in the diffracted beam, after complex interference
effects, and the limitation on surface-related information is simply the
spatial resolution (multiplied by 2sinB, for a symmetrical reflection, to
account for the projection angle). Defects such as dislocations or oxygen
precipitates may therefore be localised to a few microns in depth. A
further advantage of the section topographic method is that the images may
be accurately simulated by means of digital solution of the Takagi-Taupin
equations, following the work of Epelboin 8 • The appearance of a single
defect can be very sensitive to the depth; this provides a positive
identification of the defect and also of its depth in the crystal.
The reflection methods are much more suitable for thin layer analysis. The
X-ray beam is confined to typically 10 microns of the surface by both
extinction and absorption effects, and thus only thin layers are probed.
Contrast arises primarily through kinematic scattering of X-rays from the
distorted regions around defects in comparison with dynamic scattering in
perfect regions, provided that the defects have a strong enough strain
field (which is the case for precipitates and dislocations). Single
crystal images are 'integrated' images, that is, they may utilise all
angular and spectral components of the incident beam that they can
diffract. Under these conditions, dynamical scattering is proportional to
the structure factor but kinematic scattering to its square, hence
contrast is strong. There must still be sufficient crystal thickness as in
the transmission method for this difference to be appreciable.
How thin a layer can be imaged? This depends upon the absorption, the
extinction and the defect structure of the specimen. If the specimen is
perfect, hence scattering according to dynamical theory, the incident wave
intensity is reduced to lie of its value at the surface in a depth equal
to the extinction distance 9 • In the symmetric Bragg case this is
proportional to sinBIAF, where A is the wavelength and F the structure
factor of the reflection. For an asymmetrical reflection, sinB is replaced
by {sin(B-tlplsin(8-tpl}l12 where 4> is the angle between the diffracting plane
and the surface. For example, taking a GaAs (001) wafer, with CuKa.
radiation, the extinction distance for a symmetrical 004 reflection is 7.1
microns, whilst that for a 224 reflection using a slice cut 4° off the
exact (001) orientation (so that the glancing angle is reduced to 2.6') is
4.2 microns. The effect does not become large until glancing incidence
angles near the critical angle for total reflection are achieved. This may
be achieved in two ways: by use of synchrotron radiation, which allows
arbitrary wavelength and hence Bragg angle selection, and by the use of
skew asymmetric reflections l , in which the crystal is rotated about the
diffraction vector until the glancing angle is sufficiently low.
Extinction distances below 0.5 microns may be achieved in this way,
permitting topography of layers down to about 0.1 microns.
Where the specimen is cut slightly off the exact 001 orientation, one may
use diffraction off planes nearly - but not quite - perpendicular to the
surface, and obtain grazing incidence and grazing exit beams, reducing the
extinction distance dramatically. This was first exploited by Afanasiev 1o ,
to obtain images of features in layers some tens of nanometres in
D. K. BOWEN 17
thickness. The method is also called 'grazing Laue-Bragg geometry' since a

very small change of specimen angle converts the case from Bragg
(reflection) to Laue (transmission). The method has been shown to be very
suitable for synchrotron radiation by Dudley, Wu and Yao l l • Note that
extreme grazing exit geometries also produce extreme foreshortening of the
image, which results in a serious loss of spatial resolution.
In the case of an imperfect specimen, in which the scattering is best

described by kinematic theory, the incident intensity is reduced to l/e of
its incident value at a thickness t given by:
t = p[cosec(6++} + cosec(6-+)]-l (3)
where p is the linear absorption coefficient for the material and

wavelength concerned. Note that for the dynamical case this effect
generally occurs as well as the extinction effect, reducing the
penetration. Again, with grazing incidence/exit (GIE) methods the
penetration may be reduced below 0.1 micron.
What is the boundary between perfect and imperfect for the calculation of
penetration depth? Dudley et al. demonstrated that dynamic and kinematic
si tuations can coexist in the salle experiment. Whi 1st scattering re.ote
from a dislocation is dynamic, the local scattering and penetration near a
dislocation is always kinematic. However, the GIE method allows the
dynaaical extinction distance to be reduced so that contrast can be
achieved in submicron layers.
Double and triple~rystal .llIe.t.hods
Double crystal methods 12 , both symmetric and asymmetric, are illustrated

in figure 2. In triple crystal methods an 'analyser' crystal is used
before the detector, giving for example a (+,-,+) geometry. The alignment
procedures are identical to those for the corresponding diffractometric
methods 1 except that broad beams are used to cover substantial specimen
areas, and 6" wafers may be imaged in one exposure. The setting for
exposure is normally on the steepest part of the flank of the rocking
curve, since this provides maximum strain sensitivity and also sensitivity
to the sign of the strain or dilatation. With narrow rocking curves, < 1
arc second, a strain sensitivity below 10- 6 is quite readily achieved
although servo control of the Bragg angle will probably be needed.
Exposures are typically of the order of several hours with a sealed tube
generator, and as with all topographic methods a rotating anode generator
or synchrotron radiation source is most useful. A standard double-crystal
diffractometer is normally suitable for topography.
In simple substrate/layer specimens the layer peak is often located at a

clearly different angular setting from that of the substrate. If the
camera is set on this peak, then the image will be exclusively of the
layer, whatever the penetration depth. In such cases, the topograph may be
taken in either reflection or transmission with similar results for thin
layers. Superlattice peaks may also be used, to image the superlattice
independently of the substrate 13 , although synchrotron radiation
intensities are strongly preferred for this experiment. If no such
splitting is observed, or if the specimen is complex, then the penetration
depth must be carefully considered in image interpretation.
A substrate with an epitaxial overlayer is normally under some stress, and

18 L CHARACTERIZATION OF EPITAXIAL THIN FILMS BY X-RAY DIFFRACTION
detector
plate or film
X-ray beam
line
source
Jr--
~
(a)
detector
plate or film
X-ray beam
(b)
Figure 2. Double crystal topography with (a) symmetric setting, (b)

asymmetric setting to increase specimen coverage.
will be macroscopically concave or convex. With a planar first crystal, a

band only of the specimen will be in the reflecting position, thus
seriously limiting the area imaged. The specimen may be scanned in angle
during the exposure to integrate over its area; although some strain
sensitivity is lost in this process, defects such as dislocations are
still clearly imaged. Jenichen et al. 14 have recently developed a double
crystal method using an elastically bent first crystal whose curvature is
made to match that of the specimen, utilising the fact that specimen
curvature in such cases is rather uniform. Large area topographs may then
be taken with reasonably short exposure times. If a triple crystal
arrangement is used it is possible to record separately the tilt and
dilatation maps, though exposures are long even using synchrotron
radiation (Ishikawa, Kitano and Matsui 1S ).
Imagecontra§t and.penetra.tiondepth in multiple crystal methods

The contrast in double crystal topography is essentially due to
orientation differences between the specimen and reference crystals.
Kinematic contrast is absent, because there are no angular or spectral
components of the beam incident on the specimen other than those that
diffract only at the perfect-crystal dynamical angle; in other words,
I. CHARACTERIZATION OF EPITAXIAL THIN FILMS BY X-RAY DIFFRACTION 19
these are not integrated images. The rate of change of intensity with
strain is therefore given simply by the (local) slope of the rocking
curve. Both short- and long- range strain fields are imaged.
The dynamical penetration depth is determined by the extinction and

absorption distances as for single crystal methods. It is likewise
probable, though not yet tested, that local penetration is increased at
defective regions even though kinematic contrast is largely absent. In
such regions, the incident beam is attenuated only by absorption and not
by extinction. Knowledge of the extinction distance is therefore
insufficient to determine the maximum depth of defects that are imaged,
and absorption lengths should also always be calculated. Again, grazing
incidence/exit methods are very important for studying thin layers.
It must once more be emphasized that topographic methods image the strain
fields of defects, not their central positions. This is significant in the
imaging of dislocations in coherent or semi-coherent epilayer materials.
Whether the dislocations are exactly in the interface, or just above or
just below it, the strain field of a dislocation will extend in both the
substrate and the epilayer. An image taken of the layer alone - that is,
with the diffractometer set on the flank of the layer peak - will still
give contrast from dislocations in the substrate, though with decreasing
contrast as their distance from the interface increases. Image simulation
is a powerful tool in this connection 16 but has not yet been sufficiently
widely applied.
(a) (b)
Figure 3. Interface dislocations in Si-Ge epilayers immediately after MBE

growth. (a) 12% Ge, 0.5 micron thickness, double crystal synchrotron
radiation topograph, 004 reflection, Si 004 reference crystal, 1 A
wavelength, (b) 12% Ge, 1. 5 m~crons ~thickness, white radiation
transmission topograph, 040 reflectIOn, 1 A wavelength. Courtesy D. K.
Bowen, D. Gordon-Smith, C.R. Thomas, M.A. Capano and M.A.G. Halliwell.
Figure 4. FET device structures on a GaAs wafer. 224 reflection, double

crystal glancing incidence synchrotron radiation topograph at 1.5 A.
Courtesy B.K. Tanner.
EXAMPLES OF APPLICATIONS
EpilaYf;)r mismatch
In strained-layer heteroepitaxial systems it is important to confirm the
absence of an interfacial dislocation network, and in relaxed or
partially-relaxed structures it is necessary to measure the degree of
relaxation and its detailed structure. Whilst the average relaxation may
be measured accurately with X-ray diffractomet ry 17 and in some cases
considerable detail may be revealed by etching 18 , only XRT will provide
large-area defect mapping of both layers and bulk, with the potential for
quantitative measurements such as Burgers vector analysis. Figure 3 shows
interface dislocation generation in an Si-Ge alloy. In the thin layer,
just above the critical thickness, nucleation has begun but the
dislocations are still confined near their initiation points and have not
spread far. In the thicker layer, the dislocation density is near the
limit of resolution yet the inhomogeneity can still be seen. Dislocation
nucleation and kinetics may thus be studied by this means (in this
material it is also known that the dislocations extend throughout the
crystal to form a relatively uniform net at device processing
temperatures).
D. K. BOWEN 21
PrQcess:::-relateddef.ects
Defects are inevitably introduced into the material during device
processing, and XRT is a powerful tool for process development and
troubleshooting. X-rays can also penetrate surface layers that are opaque
to other methods such as photoluminescence. Figure 4 is an image of a GaAs
wafer containing an array of FET devices. The long-range strain field,
substrate dislocations near the surface, the devices themselves and even
scratches on the metallisation are clearly seen.
Various doping and thermal treatments are now in use in silicon-device
fabrication with CZ silicon in order to produce a surface zone, around 20
microns thick, which is denuded of oxygen precipitates. Characterization
of this feature during process development and control is a difficult
problem by other methods, but figure 5 shows how the penetration depth may
be tuned in a topograph to examine this surface layer.
Further details of precipitates may be seen by the use of section

topography together with image simulation. Figure 6 shows an oblique
section through a silicon wafer containing spherical precipitates together
with the simulations. The latter were performed assuming the same
precipitate strain field at all depths, and the sensitivity of image
detail to the depth of the defect is clear.
Figure 5. Device structures in Si, double crystal synchrotron radiation t

glancing incidence 115 reflection, first crystal Si 333. (a) 1.5 A
wavelength, total penetration depth < 20 microns. (b) 1. 3 A wavelength,
giving greater absorption length and revealing oxygen precipitation below
the denuded zone. Courtesy G.S. Green, B.K. Tanner and P.J. Halfpenny.
111
- 9
. "I
u
I
Figure 6. Spherical precipitate strain fields revealed by section
topographs. 422 reflection, MoKa, field width 520 microns. The simulations
are shown opposite the appropriate part of the images. Courtesy Cui, Green
and Tannerl9.
As device layers become thinner, so the quality of the surface upon which
they are grown becomes more important; moreover, the application of modern
'machining' methods such as chemi-mechanical polishing, ultraprecision
machining, laser and ion milling and reactive ion etching depends upon the
residual damage that they introduce. Surface-sensitive characterization
methods are important and the sensitivity of the double-crystal X-ray
methods in diffractometry have been shown by Abdul Gani et al. 20. A
section topograph of laser-drilled holes in silicon is shown in figure 7.
The Pendellosung fringe system is highly sensitive to strain, and the
distortion of the fringes around the hole clearly shows the near-surface
strains, even in the section taken over 2 mm away from the edge of the 200
micron hole.
The use of grazing incidence beams with short wavelengths can reveal
astonishingly small strains. Topographic contrast has recently been
observed on high quality silicon wafers polished with silica chemi-sol -
the standard silicon device material - using 880 or 886 reflections with
Mo Ka in which the intrinsic rocking curve width is 0.5 arc seconds. The
strains involved have been found by precision diffractometry to be a few
parts in 10' and are largely confined to the top 20 nm 2l .
D. K. BOWEN 23
Figure 7. Section topographs near a 200 micron laser-drilled hole in

silicon. Synchrotron radiation white beam, 333 reflection, 0.6 A. The
upper topograph shows a section 0.15 mm from the edge of the hole, and the
middle and lower topographs are from sections displaced respectively 1 and
2 mm from the upper topograph. Courtesy S.R. Stock, Y.H. Chung and Z.U.
Rek 22 •
REFERENCES
B.K. Tanner, this volume.

2 C.S. Barrett, Trans. AIME, 161:15 (1945)
3 J. I. Chikawa, in Characterization of Crystal Growth Defects by X-ray
~lethods, (eds. B.K. Tanner & D.K. Bowen) Plenum, New York, 1980
4 D.K. Bowen & C.R. Hall, Microscopy of Materials, MacMillan, London,
1975.
5 J. Miltat, in Characterization of Crystal Growth Defects by X-ray
~1ethods, (eds. B.K. Tanner & D.K. Bowen) Plenum, New York, 1980
6 A.B. Hmelo, J.C. Bilello, S.T. Davies & D.K. Bowen, Mats. Letts. 2:6
(1983) .
7 B. K. Tanner & D. K. Bowen (eds.) Charactel'iztltion of Crystal Growth
Defects by X-ray ;\f(,thods, Plenum, New York, 1980; see in particular the
chapters by A.R. Lang, J.I. Chikawa, J. Miltat & R.W. Armstrong.
8 Y. Epelboin, J. Appl. Crystallogr., 7:372 (1974).
9 B.W. Batterman & H. Cole, Rev. mod. Phys. 36:681 (1964).
10 A.M. Afanasiev, P.A. Aleksandrov, R.M. Imamov, E.M. Pashaev & V.I.
Polovinkina, Phys. Status Solidi, (a)90:419 (1985).
11 M. Dudley, J. Wu & G.D. Yao, Nucl. Instrum. & Methods in Phys. Res.,
B40/41:388 (1989).
12 B.K. Tanner D.K. Bowen (eds.) Characterization of Crystal Growth
&
Plenum, New York, 1980; see in particular the
Defects b.y X-l'a.Y Methods,
chapters by E.S. Meieran, J.I. Chikawa, M. Hart & M. Sauvage.
13 S. Bensoussan, Ph.D. thesis, University of Paris VI, 1986.
14 Bernd Jenichen, Rolf Kohler & Werner Mohling, J. Phys. E: Sci.
Instrum., 21:1062 (1988).
15 T. Ishikawa, T. Kitano and J. Matsui, J. Appl. Crystallogr. 20, 344
( 1987) •
16 P. Riglet, M. Sauvage, J.F. Petroff & Y. Epelboin, Phil. Mag. 42:339
(1980) .
17 M.A.G. Halliwell, this volume.
18 C.G. Tuppen, C.J. Gibbings & M. Hockley, J. Cryst. Growth, 94:392
(1989).
19 S.F. Cui, G.S. Green & B.K. Tanner, Proc. M.R.S. (1989) in press.
20 S.M. Abdul Gani, B.K. Tanner, H.T. Hingle, T.G. McKenny & D.K. Bowen,
J. Appl. Crystall., 17:111 (1984).
21 L. Hart, G.R. Fisher & D.K. Bowen, this volume.
22 S.R. Stock, Y.H. Chung and Z.U. Rek, J. Appl. Cryst., 22:70 (1989).
STRESSES IN THIN FILMS
Jerome B. Cohen
Department of Materials Science and Engineering

Robert R. McCormick School of Engineering and Applied Science
The Technological Institute
Northwestern University, Evanston, IL 60208
INTRODUCTION
While any subject associated with films evokes immediate thoughts about
solid-state devices, there are other much more mature areas where it is impor-
tant, such as coatings, and yet work on this entire subject is only in its in-
fancy. Residual stresses are not only important because of their well-known
effect on corrosion and mechanical properties, they can also lead to other
severe problems. For example, it is now believed that stress gradients can
lead to void formation and subsequent failure in metallization in electronic
devices 1 • Thus, it is not only the level of stress that can be important, but
gradients across a surface of a thin stripe, or through the thickness.
There are really three classes of problems associated with this topic:
1) films that extend across an entire substrate,

2) stripes,
3) stresses in multilayers, for example, a stripe on a substrate
covered with a passivation layer.
In all three areas, the stress in the substrate may be of interest, as

well as in the film.
In this very brief paper we can only review techniques, as well as some
recent results. There have been two excellent re~ent publications that can
serve to bring the reader up-to-date in this area ,3.
Techniques
The various techniques can be placed in three categories:
1) Bending or Curvature, for example, determining stress via the deflec-

tion or a cantilever beam 4 , or from the radius of curvatures. X-rays can be
used, curvature being obtained from the shift in sample tilt (omega) to main-
tain diffraction as the sample is translated past a beam. However, using
focussed light beams is much more rapidS.
2) Peak Shifts. This is a return to our normal ., d" spacing determina-

tions, one way or another, either just simply by comparing the measured spac-
Advances in X-Ray Analysis. Vol. 33 25

Edited by C.S. Barrett et al.
ing to an unstressed sample or unstressed substrate 6 , or by applying the usual

"d" vs sample tilt (i.e. vs. sin2~). If the film is thin enough, the sub-
strate peaks can appear, which has advantages and disadvantages. The ad-
vantage is that it is then relatively easy to measure the stress in the sub-
strate, (although this has only recently been done) but its peaks can be very
close to those of the film. Rocking curves can then be employed, with a per-
fect crystal monochromator to provide good energy and angular resolution. (Of
course, the films must be highly perfect for this to prove fruitful.)
3) Peak Shapes. Basically, a gradient is assumed for this purpose to

calculate peak shape i - 10 However, gradients can occur across the stripe as
well as through it and to the best of my knowledge, this has not yet been at-
tempted. Some information on gradients could be obtained by measuring "d" at
various grazing angles of incidence and from the curvature of "d" vs sin2~1l.
Because this is an x-ray conference - and because that is my interest as

well - we will not comment too much further on the first class of methods, and
concentration on number 2. But first, it is necessary to say, at least, that
methods in category one rely on the fact there there is no local plastic defor-
mation associated with the curvature. While it is possible to correct for
this, considerable detail on the dislocation arrangement is needed, and this
can be difficult to obtain; the film itself must be destroyed, to examine it
via TEM.
Returning to x-ray peak shifts, more often than not, we are dealing with
either single crystal films, or highly textured polycrystalline films. This
poses special problems, because the normal "d" vs sin2~ technique for stress
measurement can be difficult if you can't find the peak!
However, even for highly textured films, adequate intensity can often be
obtained, either with a synchrotron source, or with a rotating anode genera-
tor. For example, in our own laboratory, we've found that a 12 kW rotating
1.1HOC)
1.18l16O
1.18860
"Uz 1.18840
~
Vl
6 1.111820
Sample 4
1.18l1OO
Stress - 71 +/- 1 MPa
1.18780
1,16760 c....L.J...L.J...L.J...L.J....u...u........................I...L..............................w...L.L..L.L..L.L..&..L.w...&..L..&..L..&..L..&..L.J
0,0 0.2 0.4 0,11 0,11 1.0
SIN SQUARED PSI
FIG 1: Stress determination; continuous highly textured

AI-Cu film on Si single crystal measured with Cr
radiation. The Cr was plated on a Cu rotating anode
target. Peak positions found by fitting Pseudo-
Voight functions.
J. B. COHEN 27
FIG 2: The axial system.
anode generator is adequate for work on thin AI-alloy films. And it is par-
ticularly simple to pick the radiation you wish to have by plating a narrow
strip around the demountable target, masking the rest of the target with plat-
ing tape. We·ve had good experience (long life) for example, with hard
chromium plating 2~m thick on a copper target 12 . The chromium can be removed
by light polishing, with the target in a lathe.
When the peaks are weak, better precision for the peak position can be ob-
tained by fitting with pseudo-Voight functions, than with parabolae. This
also permits using a functional form for the background, especially important
if the weak peak is in the tail of a much stronger one. One example of our
results, on a highly textured Al-2 wt pct. Cu film on Si, is given in Fig. 1.
While it is often possible to measure peaks at various ~ tilts with the

available strong sources, there are cases where the preferred orientation is
so well developed that ~ tilts are not possible. A number of years ago 13 we
developed a technique for such situations, but buried it in an Appendix to our
paper. With the increased interest in such films, it is worth repeating here.
Consider the determination by diffraction of the three-dimensional stress

tensor for a single crystal, a grain in a coarse grained specimen, or a highly
textured film. The orthonormal co-ordinate system is illustrated in Fig. 2;
the Si define the sample, with Sl' S2 in the surface and S3 normal to the sur-
face, whereas the measurement for an hkl plane is made along L3. (The axis L2
is in the plane defined by Sl and S2 and the axis L1 is the vector cross
product L2 and L3.) Strains in the Li axial system will be primed, those in
the Pi' unprimed. The direction cosines that link the axes Si to Li' (that is
the axes Li in terms of Si) form a matrix, a ij :
S. S~ SJ
(L 1) xf cos~cosX sin¢Cosx cos(900+X)
(L 2) xci> cos(90° +¢) cos¢ cos 90° (1)
(L3) xci> cos¢Cos(900-X) cos(900-¢) cos X
As the strains (€ij) are a rank 2 tensor:
(2)
Therefore:
2,;..... 2 2 2
X+ X+E))cos X.
Co • Co .,;.....
+<'22 s l. n 'l"'l.n <'2)sl.n'l"'l.n (3)
FIG 3: A cubic crystal with [Ill] normal to its face.
With six or more independent reflections for which X,¢ can be calculated
(or experimentally measured since stress may cause them to change), the six un-
known E., can be obtained. These can then be referred to the crystal axes
using Eq~. 2 and the direction cosines between the axes Si and the crystal
basis. The stresses in the crystal axial system can be obtained from:
a ij = Cijk1 Ekl · (4)
These may be referred back to the axes Si by the inverse of Eqn. 2 (with
a ij replacing Eij ).
In cases where a 13 = a 23 = a 33 = 0, that is, there are stresses only in

the surface plane, assuming that the co-ordinates Si are along the principal
axes; and
(5)
and to obtain the S' from S" in the crystal axial system:
S'ijk1 (6)
Also:
(7)
Employing Eqn's 5 to 7 for this special case:
C33' = Aa u + Ba 22 , (8)
where
A S' 31 cos 2¢CoS 2X - (S'34/2)sin 2¢CosX + (S'3si2)COs 2qx,in2X
+ S'32sin2¢ - (S'34/2)sin 2¢ sinX+S'3s12)cos 2qx,in 2x,

(9)
and
As a practical example, consider a Si wafer with a (Ill) plane as the sur-

face. A stereographic projection is shown in Fig. 3. The "d" spacing of the
513 reflection is - 0.918 ~ and, with CoKa 20 = 154°, so that the diffraction
peak occurs at high angles where precision is good. In fact, this angle is
very similar to the value employed for steel. The 513 and 153 reflections are
57.1° apart and a simple tilt suffices to cause either reflection.
J. B. COHEN 29
Some Examples
Strains throughout a single crystal copper oxide film on Cu have been

determined, using analysis of peak shapes 14 . There has also been a measure-
ment reported on the stresses in the substrate below a 100~m plasma sprayed
A1 20 3 coating 15 , where it was found that the residual stress produce by shot
blasting was reduced 50% by the hot plasma flare.
In Fig. 4, we show the stresses in Al-2wt pct Cu evaporated films used

for interconnects 16 These stresses arise primarily due to differential ther-
mal contraction of the metal and the Si substrate, (thermally oxidized before
deposition) or the metal coated with a sputtered quartz passivation layer. In
fact, for an isotropic continuous film17
da = ~ ((Xf - (Xs) (10)

dT 1 - II f
Where subscripts f and s represent film and substrate and the (X are coeffi-
cients of expansion. For a stripe, with a passivation layer:
da ~ ((Xf - (Xs) (11)

dT 1 - 2 II f
For Al on Si, Eqn. 10 gives - 2 MPa/oC, whereas Eqn. 11 gives 4.4 MPa/oC.
The films used in this study were continuous and sputtered at - 150°C and the
passivation layer was produced at 350°C and then thermally cycled at 125°C.
Without passivation, Eqn. 10 predicts a possible residual stress of - 380

MPa for a unpassivated film, 770 MPa after passivation, but the values are
much less than this, indicating that relaxation has occurred or that there is
little bonding between the two materials. In fact, the instantaneous stresses
~ higher, Fig. 5, and relaxation occurs, rather rapidly. (When the different
time scales are considered both alloy and Al films appear to be recovering at
about the same rate.) Also, for the 2~m sample there was considerable peak
sharpening after passivation. This could be evidence for this relaxation, (or
for the development of more uniform stress due to encapsulation). In fact,
one of the surprising things about these results is the magnitude of the ac-
tual stresses. These are much larger than the yield stress of wrought AI-Cu
250 ** * * * Unpassivated. Before Cycling

00000 Passivated. Before Cycling
OQPQP Un passivated. Cycled
61'0 6-1' Passivated. Cycled
200
o
~ 150
(fJ
(fJ
~ 100
V;
50
O+nTITrrnTITrrnTITrrnTITrrnTITTIT~TITrrnTn
0.000 0.500 1.000 1.500 2.000 2.500
Film Thickness (microns)
FIG 4: Residual stresses in AI-Cu films on Si single crystals,
after long term storage (solid lines) or after cycling to
125°C for 1015 cycles and 1 month storage.
20000
16000
o
CL
::;; , '
120.00
Ifl
Ifl
Q)
U)
8000
40000 -f0~0~~~~5.~0-r0 ' , , '1 0.00' , , ii'i

15.00
I
Time (days)
FIG Sa: Stress relaxation at room temperature after deposition

of 1 micron AI-Cu film on to 200°C silicon substrate
(unpassivated film).
250 00
20000
I
~:::::l
(f)
Stress versus Time for l micron AI-Cu film on
S, during heat treatment at 350°C and after
quench to room temperature
~ 50,00
U)
000
-50.00
J T=350'C
-10000 ~Tn-rTTn"Tn-rTTn"Tnn-rTnn-r~n-r~n-r"n-r"n
0.00 5.00 1 0.00 15.00 20.00 25.00
Time (Hr.)
FIG 5b: Stress vs. time in unpassivated Al-2wt% Cu film.
alloys (which is - 60MPa), and close to the ultimate tensile strength. In ef-
fect, the film takes on some of the mechanical character of the substrate,
which is somewhat surprising at these film thicknesses. In fact, in a bend
test of one of these films on its substrate, the Si fractured when the applied
stress in the outermost layer (the film) was - 70 MPa. During this test we
followed the "d" spacing, looking for a change in slope vs strain, indicating
plastic rather than elastic deformation; the film was still behaving elasti-
cally at fracture. We could perhaps better define a film, as that layer that
has different properties than the bulk, rather than by its thickness, and/or
perhaps these layers in which a biaxial stress state prevails.
The Future
Work in this area is really just in its infancy and much more is needed:
1) We need to know more about gradients, with depth, and, with stripes,
across the face.
J. B. COHEN 31
2) More measurements are needed of the stress in the substrate as well

as in the film.
3) Studies of relaxation effect could be very fruitful, as they might

lead to an understanding of the mechanisms throufth the activation energy. To
my knowledge there has been only one such study for pure Al films on Si,
and the energy was of the order of that for grain boundary diffusion (but some-
what lower) and different for compressive and tensile residual stresses.
4) Eqn. 10 (or 11) can be used to test how strongly a film is bonded to
its substrate; measurements of stress (or just "d") vs temperature should fol-
low this equation, if the bonding is strong ?1er the temperature range, as has
been demonstrated by Vreeland and co-workers .
Unfortunately, while there are now adequately intense sources for work on
actual devices, the grain size in the stripes is probably too coarse to work
at this level. We will have to be content with model systems, such as a col-
lection of parallel strips.
ACKNOWLEDGEMENTS
Our research on Al films is being supported by IBM at Hopewell Junction,

NY. We thank Dr. Dexter Jeanotte for his help and advice - as well as our col-
leagues in this effort, Profs. M. E. Fine, Y. W. Chung and L. M. Keer. All of
the results on stresses in Al alloy interconnect material (Figs. 4 and 5) are
those of Ms. Carla Shute a Ph.D. candidate at Northwestern University. Prof.
P. Georgopoulos demonstrated to us the usefullness of plating rotating anode
targets.
REFERENCES
1. F. G. Yost, A. D. Romig, Jr. and R. J. Bourger, "Stress Driven

Diffusive Voiding of AI-Conductor Lines: A Model for Time
Dependent Failure", SAND 88-0946-UC-25-Sandia National
Laboratory (1988).
2. A. Segmuller, I. C. Noyan and V. S. Speriosu, "X-ray Diffraction
Studies of Thin Films and Multilayer Structures", Progress
in Crystal Growth and Characterization, 18, 21-66 (1989)
3. J. C. Bravman, W. D. Nix, D. M. Barnett and D. A. Smith, (eds.)
"Thin Films: Stresses and Mechanical Properties", MRS Soc.
Proc., 130, Pittsburgh, PA (1989).
4. T. P. Weihs, S. Hong, J. C. Bravman and W. D. Nixon, "Measuring
the Strength and Stiffness of Thin Film Materials by
Mechanically Deflecting Cantilevers", in MRS Soc. Proc.,
130, pg. 87, Pittsburgh, PA (1989).
5. P. A. Flinn, "Principles and Applications of Wafer Curvature
Techniques for Stress Measurements in Thin Films"
in MRS Soc. Proc., 130, pg. 41, Pittsburgh, PA (1989).
6. T. Vreeland, Jr., A. D. Dommann, C.-J. Tsai and M. -A. Nicolet,
in MRS Soc. Proc., 130, Pittsburgh, PA (1989).
7. B. Borie and C. J. Sparks, "Analysis of Thin Films", in "Local
Atomic Arrangements Studied by X-ray Diffraction, (J. B.
Cohen and J. E. Hilliard, eds.), Materials Science
Conferences,36, pg. 341, Gordon Beach, NY (1966).
8. C. B. McDowell and T. C. Pilkington, "X-ray Diffraction Method
for Determining Strain Distributions in Thin Metallic Films
with Application to Gold Films", J. Appl. Phys., 42,1958
(1971).
9. C. R. Houska and T. M. Smith, "Least Squares Analysis of X-ray
Diffraction Line Shapes with Analytical Functions", J. Appl.
Phys., 52, 748 (1981).
10. M. Murakami, "Residual Strains of Pb Thin Films on to Si

Substrates", Acta Metal1., 26, 175 (1978).
11. H. DOlle and J. B. Cohen, "Determining Stress
Analysis from Powder Diffraction Patterns", pg. 1453, in NBS
Special Publication #567 (1980).
12. Metals Handbook, 9th Edition, 2, 176 (1982).
13. E. Kula and V. Weiss (eds.) "Residual Stress and Stress Relax-
ation", pg. 1, in Sagamore Arms Materials Research
Conference Proc., 28, Plenum Press, New York (1982).
14. B. Borie, C. J. Sparks and J. V. Cathcart, "Epitaxially Induced
Strains in Cu 20 Films on Copper Single Crystal - I", Acta
Metall., 10, 691 (1962).
15. P. Georgopoulos, J. B. Cohen and H. Herman, "Residual Stress
Measurements of a Plasma Sprayed Coating System Using
Synchrotron X-Radiation", Mat. Sci. & Eng., 480, 41 (1986).
16. C. J. Shute, J. B. Cohen and D. A. Jeanotte, "Residual Stress
Analysis of Al Alloy Thin Films by X-ray Diffraction as a
Function of Film Thickness, in MRS Soc. Proc., 130, pg. 29,
Pittsburgh, PA (1989).
17. R. E. Jones, Jr., M. L. Basehope, "Stress Analysis of Encap-
sulated Fine-Line Aluminum Interconnect", Appl. Phys.
Letters, 50, 725 (1987).
18. M. Hershkovitz, I. A. Blech and Y. Komem, "Stress Relaxation in
Thin Al Films", Thin Solid Films, 130, 87 (1985).
19. G. Bai, M.-A. Nicolet, T. Vreeland, Jr., Q. Ye, Y. C. Kao and K.
L. Wang, "Thermal Strain Measurements in Epitaxial CoSi 2 /Si
by Double Crystal X-ray Diffraction, in MRS Soc. Proc.,
130, pg. 35, Pittsburgh, PA (1989).
DEFORMATION, RECOVERY AND STRESS CORROSION CRACKING OF
NICKEL-BASE ALLOY 600 BY X-RAY ROCKING-CURVE MEASUREMENTS
Chi Fung Lo, Gajiang Feng, William E. Mayo and

Sigmund Weissmann
Department of Mechanics and Materials Science

Rutgers University
P.O. Box 909
Piscataway, NJ 08855-0909
ABSTRACT
The aim of this investigation was the establishment of a quantitative

link between micro and macrodeformation and kinetic recovery of nickel-base
Alloy 600 as well as the early detection of microcracks in this alloy when
exposed to stress corrosion. To reach these objectives, X-ray rocking-
curve measurements were carried out using the method known by its acronym
CARCA (computer-aided rocking-curve analysis). Supported by transmission
electron microscopy, a calibration curve was established relating disloca-
tion density, X-ray rocking-curve halfwidth and strain. Applying CARCA,
deformation levels and work-hardening characteristics of the alloys were
measured by quantitative characterization of the induced defect structure.
By correlating the analysis of the defect structure to the kinetic recovery
of the alloys, including determination of the activation energies, it was
possible to infer from the thermal stability of the alloys the dislocation
obstacles responsible for hardening at different strain levels. It was
shown that the recovery of the alloys was conditioned by their low stacking-
fault energy and that it depended on the strain level. Rapid recovery
associated with grain boundary diffusion occurred at very small plastic
strains up to about 0.7% with measured activation energies of recovery of
about 25.6 Kcal/mol. At higher strains bulk diffusion was necessary to
overcome the obstacles by dislocation climb with Q - 67 kcal/mol. The
CARCA method proved itself to be a valuable research tool for assessing
quantitatively the defect density and the mechanically and thermally in-
duced changes. Relaxation effects, recorded by CARCA in the apex region of
stressed C-rings exposed to a caustic medium, may open a path for early
nondestructive detection of microcracks in stress-corrosion cracking.
INTRODUCTION
There exists a fundamental recurring problem in materials science

which refers to the correlation between micro and macrodeformation and
micro and macro thermal stability of a technological material. The ques-
tions that frequently resurface and are being asked can be simply stated as
follows: to what extent do the details of a microstructure explain and
determine the macro behavior of a material, viz. the workhardening of an
Advances in X·Ray AnalYSIS, Vol. 33 33

Edited by C.S. Barrett el al.
alloy? Can one deduce and predict the macrodeformation response and ther-
mal stability of an alloy from the deformation characteristics of its
microstructure? The dilemmas that one usually faces in answering these
questions are inextricably linked to the investigative methods applied.
Although one can well characterize the induced dislocation structure of the
grains by optical metallography and electron and scanning microscopy, the
cooperative behavior of large dislocation populations, conditioned by the
inhomogeneous distribution of deformation encountered in macrodeformation,
cannot be revealed by these methods. X-ray powder diffractometry, sampling
a large strain population, is capable of giving information of group ef-
fects on macroplasticity and on residual elastic strains. The former can
be deduced from the broadening and the latter from the peak shifts of the
X-ray lines. These investigative methods, however, lose sight of the
deformation characteristics of the individual grains and of local in-
homogeneity and severity of deformation which may disrupt the integrity of
the alloy and cause it to fail. This paper represents one aspect of a
series of studies which made it its goal to establish a link between micro-
and macro-mechanics [1-8). It will focus on the workhardening and recovery
characteristics as well as on aspects of stress corrosion cracking of the
nickel-base Alloy 600. This alloy is a solid solution alloy of Ni-Cr con-
taining chromium carbide precipitates and because of its low stacking fault
energy deforms by planar slip mode into a Taylor type of lattice. The al-
loy has considerable technological importance and has been the subject of
many studies for steam generator tubing in pressurized water reactors and
ensuing problems of stress corrosion cracking [19). In the present study
the link between the micro and macro aspects of deformation, recovery and
stress corrosion cracking is sought by characterizing quantitatively the
dislocation structures of the individual grains of a numerous grain popula-
tion via X-ray rocking curve measurements using the CARCA method as
principal research tool [13), supported by TEM measurements [8). The un-
derlying reason for linking recovery studies to the preceding deformation
process is to obtain information on the thermal stability of immobile-
dislocation obstacles, such as sessile and forest dislocations and Lomer-
Cottrell locks. These are invariably generated during the deformation of a
Taylor type lattice and can be removed by controlled isothermal anneals.
By determining the activation energies of recovery a clue can be obtained
as to what type of deformation microstructure is associated with the ther-
mal response of the microstructure.
EXPERIMENTAL METHODS
Alloy 600 tubing was investigated with the composition 0.03 wt. % C,
76.2 wt. % Ni, 15.4 wt. % Cr, 7.6 wt. % Fe, 0.25 wt. % Mn, 0.2 wt. % Si,
0.37 wt. % Al, 0.26 wt. % Ti, 0.26 wt. % Cu, 0.001 wt. % S, 0.009 wt. % P
and 0.003 wt. % B. Tensile samples were prepared by cutting longitudinal
strips from the tubes and annealing at 704°C for 15 hr. Prior to deforma-
tion, the samples were electropolished to remove a thin ground surface
layer and any residual oxide layer. The grain size of the material ranged
between 10 and 100 ~m. Deformation was carried out on samples to which
precision resistance (120 0) strain gages were attached and after which the
samples were strained to various amounts between 0.3% and 2.4% plastic
strain.
The rocking-curve me,1surements were performed non-destructively on the

gauge length of the speciH.en after which the samples were sectioned by
electrospark cutting for the transmission electron-microscopy (TEM)
studies. The computer-aided rocking-curve method (CARCA) is based on the
double crystal diffractometer in the parallel arrangement (+n, -n). A
monochromatic beam impinges on the test specimen in which individual grains
are considered to function independently as the second crystal in the
C. F. LO ET AL. 35
double crystal diffractometer. By rotating the specimen in discrete an-

gular intervals, the grains are rotated (or rocked) through their
reflecting ranges and the diffracted intensities versus angular position
are recorded. The diffracted beam is intercepted by a position-sensitive
detector (PSD) placed tangent to the Debye arc and parallel to the rotation
axis of the diffractometer. As a result, each grain in the sample (or at
least a representative proportion) can be individually analyzed to provide
a measure of the lattice misalignment. The specimen under investigation is
mounted on the two-dimensional microscope stage which enables precise
selection of the region of interest. The diffracted beam from the sample
is detected by the PSD and the X-ray spectra are collected and displayed by
a multichannel analyzer before being transmitted to an on-line computer.
By this automated procedure, rocking-curves of a numerous grain population
are rapidly obtained from which the important parameter, namely the average
halfwidth, p, of all the grains, can be determined to an accuracy of a few
minutes of arc. This high accuracy in angular halfwidth is made possible
by a combination of low instrumental broadening « 1 min of arc) combined
with small incremental rotations of the specimen «< 1 min of arc).
Sampling a numerous grain population of 100-500 grains, this method

sensitively and rapidly measures the microdeformation range of the in-
dividual grains through its rocking curve halfwidth.
The samples for the TEM analysis were prepared by jet polishing with
an electrolyte of 7% perchloric acid and 93% methanol at -27°C. The ex-
amination was then carrieo out on a JEM-lOO CX microscope.
The dislocation density was measured by two sets of grid lines using
the expression derived by Smith and Guttman [14]. The average dislocation
density p can be expressed by the equation
p (1)
where n l and n 2 are the average number of intersections of dislocation

lines wlth the two sets of grid lines; 11 and 12 are the lengths of the two
sets of grid lines and E is the thickness of the TEM film. Applying trace
analysis, the film thickness was found to be 1600-3200 A with a mean thick-
ness of 2000 A which was used for the dislocation-density calculations.
By relating the macroscopic strain levels, €,of control samples to the

average rocking-curve halfwidth, p, of the sampled-grain populations, as
analyzed by CARCA, and relating the strain levels to the dislocation den-
sity, p, as measured by T[~, calibration curves were obtained. These es-
tablish the interrelation1:hip of €-p-~ and when combined with a conven-
tional stress-strain curv!-', it is possible to relate the nondestructive X-
ray rocking-curve measurements via € to the local stress, 0, on the sample
[8] .
To perform the study of the recovery kinetics, two sets of deformed

samples were investigated, based on induced strain. One set contained 0.3%
plastic strain and the other set contained 2%-3.5% total strain. Samples
with 0.3% plastic strain were strained in C-ring samples to 0.45% total
strain prior to annealing at S93-704°C for short times (0-30 min). Higher-
strained samples (2%-3.5% total strains) were prepared as tensile specimens
onto which strain gauges were cemented. The deformed samples were annealed
at SOO-980°C for various times up to 2800 min. Both of the two sets of
samples have been annealed at 704°C for 15 hr prior to the deformation
process. At predetermined intervals, samples were removed for the X-ray

rocking-curve analysis to ascertain the level of recovery.
RESULTS
Strain Dependence of Disl'!cation Arran~ements
TEM observations of the undeformed annealed alloy disclosed straight-

line dislocations which wege r~2domly arranged. The average dislocation
density was about 2.2 x 10 cm . After a small amount of plastic strain,
the original straight dislocations were replaced by grouped dislocations
with pronounced dipole characteristics. The dislocations had a coplanar
arrangement and formed mosaic block walls which originated from the grain-
boundaries and extended towards the center of the grains, as shown in Fig.
1. The coplanar dislocation arrangement of Alloy 600 is typical of a
Taylor lattice and is attributed to the low stacking fault energy of this
nickel-base alloy. Because the grain boundaries and associated carbides
were the primary dislocation sources, in agreement with the in-situ high
voltage TEM studies of Bruemmer and Heneger [15,16], the dislocation den-
sity near the grain boundary was distinctly higher than that in the grain
interior. When the deformation was increased the dislocation density in-
creased rapidly and at about 2.4% total strain a high density of
dislocation networks was formed in the grain interiors which resulted from
the interaction of intersf,cting slip planes (Fig. 2).
It will be demonstrated shortly that this transformation of disloca-

tion arrangement from about 0.7% plastic strain upward is accompanied by
significant changes of the corresponding X-ray measurements and that both
are intimately related to the macroscopic workhardening response of the
alloy. Conversely, it will be also shown that if the deformed alloy is
subject to isothermal annealing, the dislocation arrangements pertaining to
small and increased applied strains have a marked effect on the respective
activation energies for plastic strain recovery.
Fig. 1. Coplanar dislocation arrays generated near grain boundaries

and grain boundary carbides (total strain 0.6%)
C. F. LO ET AL. 37
Fig. 2. Dislocation structure of Alloy 600 at a strain of 2.4%
Correlation of Strain-Hardenin~ Characteristics in Microdeformation and

Macrodeformation
Figure 3 exhibits the stress-strain plot of Alloy 600 with small and
large grain size and that of pure copper having a grain size of 20~m.
Polycrystalline copper was selected as a model material to contrast the
work-hardening behavior of Alloy 600 because it is well known that copper
develops upon deformation 3 pronounced cell structure which in Alloy 600,
due to its low stacking fault energy, is totally absent.
500
ALLOY 600
400 ( 1O\Jm)
'@
a. 300
6
(jJ ALLOY 600
(jJ
w (110\Jm)
a: 200
I-
(jJ
100
o o~--------~--------~--------~--------~-
0.01 0.02 0.03 0.04
STRAIN, C
Fig. 3. Stress-strain curves for Alloy 600 with different grain

sizes:o, grain size of 10 ~m; 0 , grain size of 110 ~m.
Shown for comparison is the corresponding curve for pure
copper (A).
The stress-strain relation can be expressed by an empirical equation

which is frequently employed in engineering application and which has the
form
(2)
where a is the stress, a the yield stress, € the strain, A the material
constant, € the strain Xt elastic limit and n the strain-hardening ex-
ponent. y
It is of particular interest that Alloy 600 with a small grain size

exhibits a more complex deformation response than Alloy 600 with a larger
grain size. In the former, two zones of work-hardening can be distin-
guished, one that extends from 0.2% strain to approximately 0.7%, and
another from 0.7% to 1.7% strain with n values of 0.109 and 0.343, respec-
tively. The immediate task is now to investigate the microdeformation
behavior and to see whether the workhardening characteristics disclosed in
the microdeformation plot of Fig. 3 finds corresponding expression in the
microdeformation response.
Figure 4 shows the average normalized X-ray rocking-curve halfwidth,

~/~ , as a function of applied strain, obtained by sampling a numerous
gra~n population with the CARCA method; ~ refers to the average X-ray
rocking-curve halfwidth of the initial st~te of the grains prior to strain-
ing. It is evident that there is a greater increase in dislocation density
for the larger-grained sample. This observation is not entirely unexpected
since it can be explained on the basis of dislocation mobility since the
mean free path for mobile dislocations is greater in the large grained
sample.
10
6
i3 /
/
i3 0 ./ \
ALLOY 600
( 11Ollm)
4
....
.-' . " '\
,
,,
ALLOY 600
2 ( 1Ollm)
o
o 0.01 0.02 0.03
STRAIN. t
Fig. 4. Normalized plot for ~/~ vs. € for Alloy 600 of grain size
10 ~m (-----), for Al18y 600 of grain size 110 ~m (---), for
pure copper ( ).
C. F. LO ET AL. 39
Of special interest in relating microplastic deformation to macroplas-

tic deformation and strain-hardening characteristics is the dependence of
the incremental microplasticity parameter ~, on the strain £, shown in Fig.
5. This parameter, defined by ~ =o(~/~ )/0£, is an indicator of the varia-
tion in dislocation density per incremegtal strain variation and as such
has a direct bearing on the macroscopic hardening response. If, for ex-
ample, upon increased strain, the dislocation density p increased and ~
declined, the implication emerges that the rate at which the dislocation
density increased has declined. This constitutes a hardening effect. With
the aid of Figs. 4 and 5 one can now attempt to correlate the features of
microdeformation to those of macrodeformation. Figure 4 shows that the
dislocation density increased for all strain levels investigated. This
feature is expected, of course, when plastic deformation takes place. The
important aspect, however, is the rate by which the dislocation density
increased. Consequently, focusing the attention on Fig. 5, it will be
noted that for copper there is a rapid increase of ~ reaching a maximum at
€ = 0.025. Significantly, this strain level corresponds to the estab-
lishment of a cell structure, and the decline of ~ at higher strain levels
indicates hardening of the metal. The rapid increase of ~ up to its maximum
value is in accord with the propensity of copper for profuse cross-slip.
For Alloy 600 with grain size 10 ~m, the microdeformation plot of Fig.
5 exhibits shape changes that reflect those of the macroscopic workharden-
ing curve of Fig. 3. There is an inflection point at £ = 0.007, designated
by I in Fig. 5, above which the increase of ~ diminished. The segment
below € = 0.007 corresponds to that of the macrodeformation plot having the n
value of 0.109. The increase of workhardening above £ = 0.007 to n = 0.343
(Fig. 3) is reflected in the microdeformation plot of Fig. 5 in much
greater detail. The diminished increase of ~ reaches a maximum at € =
0.015and at larger strains it reverses its course, and goes downward. The
C'
>
I-
4
(3
i=
(j)
«
...J
a. "-
0
a:
u 3
,
,I, ALLOY 600(110Ilm)
~
...J
«
I-
,,
"
Z
,--,
UJ
~
I ,' ... ...
+,'
2 ... ...
UJ
a:
u ,, ......
....
~ ,, i . ··
-- ALLOY 600(1Ollm)
0
0 0.01 0.02 0.03
STRAIN, (;
Fig. 5. Plot of incremental microplasticity (~=o(~/~ )/0£) vs. strain
for Alloy 600 of grain size 10 ~m (-----), f8r Alloy 600 of
grain size 110 ~:1 (- - -) and for pure copper ( - - ) .
fine resolution of the successive workhardening stages in the microdeforma-

tion plot of Fig. 5 is achieved because of the sensitively-resolved group
effects of the sampled-grain population by CARCA. These effects get
smeared out in the macrodeformation plot which characterizes the hardening
effects merely by an overall n value of 0.343.
For Alloy 600 with grain size 110 ~m the break in the stress-strain
curve can be seen at strain level € = 0.0125 when the initial parabolic
shape of the curve transforms gradually into a linearly-ascending segment
(Fig. 3). This hardening effect is manifested in the microdeformation plot
by a pronounced downward turn of~. It is of interest to note that the
strength increase of the fine-grained Alloy 600, manifested on a macro-
scopic scale by the higher a vs. € curve, is reflected on a microscopic
level in Fig. 5 by the trend of ~ values which consistently lies below that
of the large-grained alloy.
Recovery Kinetics of Alloy 600 with Small Plastic Strain
One of the most important aspects in correlating the properties of

microdeformation and micro recovery to the corresponding properties of the
macrostructure is the inhomogeneity of deformation which occurs at all
deformation levels. It occurs because the grains which lie in or close to
positions of maximum stress undergo a more severe deformation than those
further removed. Conversely, upon annealing, they recover also at an ear-
lier stage. Figure 6 may serve to clarify this point. It shows the
statistical distribution of the lattice misalignment in Alloy 600 as deter-
mined by the CARCA method for an annealed and a 0.3% plastically deformed
sample. These curves are based on a normal distribution about the mean
halfwidth value and they illustrate graphically how important it is to
examine the entire strain jistribution instead of just the mean value.
Thus it will be seen that while the mean value increased from the annealed
value of 12 to 20 minutes of arc subsequent to the small deformation, ex-
amination of the entire profile of the distribution curve reveals
significantly that one third of all the grains in the deformed material
25
20 NO STRAIN
~
rn 0.3% PLASTIC STRAIN
~
a:
(!)
15
....
0
UJ
z~
10
UJ
u
a:
UJ
~ 5
0
0 10 20 30 40 50 60 70
HALFWIDTH. B (MIN OF ARC)
Fig. 6. Microstrain distribution for Alloy 600: , annealed

sample; - - - , sample with 0.3% plastic strain.
C. F. LO ET AL. 41
30
0.3% PLASTIC STRAIN (APEX POSITION)
593°C ANNEALED
ANNEALING TIME
25 (MINUTES)
o
~ 20 5
a: 10
(!)
15
~ 15 NO STRAIN
w
(!)
<{
I- 10
Z
W
()
a:
w
Il. 5
o 10 20 30 40 50 60 70
HALFWIDTH (MIN OF ARC)
Fig. 7. Microstrain distribution as a function of annealing time
at an annealing temperature of 593°C for 0.3% plastic
deformation: - - - , 0 min; - - -, 5 min;
10 min; - . -, 15 min; ...... , no strain.
have halfwidths above 30. Virtually no grains of the undeformed material

have such higher values. Isothermal anneals were carried out at 593, 649
and 704°C for timeq between 0 and 30 min. As may be seen from Fig. 7,
strain redistributions took place with the mean reverting towards the
original distribution. Based on the approach of Johnson and Mehl [17] and
of Avrami [18], the thermal recovery of strained specimens can be expressed
in the form
k
X = l-exp( -Bt ) (3)
where X is the fraction representing degree of recovery, t is the isother-

mal annealing time, and Band k are material and process parameters.
With the aid of these micros train distribution curves, a much greater
precision in determining ,he recovery of the residual strain was possible
than is obtainable by con'entional X-ray methods. As shown in Fig. 8, the
residual strain was obtained by calculating the ratio of the area AB be-
tween the micros train distribution curves of a certain annealing time
(upper limit) and the unstrained state (lower limit) to the area AA between
the distribution curves of deformed samples prior to recovery annealing
(upper limit) and the unstrained state (lower limit). Thus
X (4)
The resulting curves of fraction In{l/(l-x)) of recovery vs. time are shown
in Fig. 9. A good straight-line fit was obtained except at the highest
temperature where the recovery process reached a saturation level very
quickly. By replotting these data for constant values of X, it was pos-
sible to calculate the activation energy of the recovery process. Thus,
Fig. 10 shows three curves representing time and temperature combinations
(A) FRACTION OF RECOVERY X=1-(B/A)
0.3% PLASTIC STRAIN

10
_. + 643°C/5MIN ANNEALING
~~
B' ~.
~ ......
o 20 40 60
HALFWIDTH. B (MIN OF ARC)
Fig. 8. Process for determining degree of recovery from
micros train distribution curves.
X: FRACTION OF STRAIN RELEASE
1.0 ff//
0/
: " ~,,,oc
/ ~ --0-- 649°C
- 0 - 704°C
10 100
TIME (MINUTES)
Fig. 9. Isothermal annealing response of Alloy 600 deformed to
0.3% plastic strain: '" , 593°C: 0 , 649°C; 0, 704°C.
C. F. LO ET AL. 43
TEMPERATURE ('C)
I I
STRAIN RELEASE
- t : . - 30% ~
O~
0UJ
1000 ::=~~~ ~D~
O~ ~~
~o~:~O
~
UJ
::E
i=
............ D~ ~ 0 30 %25.52 kcal/mole
~ 0 50 %:25.64 kcal/mole
100 ............ t:. 0 70 %:25.74 kcal/mole
I I
1.00 1.05 1.10 1.15 1.20
l/Tx 10 3 (oK')
Fig. 10. Calculation of activation energies for various levels of

rec~yery in deformed Alloy 600: 6 , 30~1(Q30% = 25.52 kcal
mol ); 0 , 50~1(Q50% = 25.64 kcal mol ); 0, 70% (Q70% =
25.74 kcal mol ).
to achieve 30%, 50% and 70% recovery. The slope of each line represents
the activation energy for the recovery process to that particular point.
The following activation energies were obtained:
-1
25.52 kcal mol_ l
25.64 kcal mol_ l
25.74 kcal mol
The good agreement between the three measured values indicates that only a
single atomistic process is operating during the l~y-strain recovery of
Alloy 600. The value obtained here, 25.6 kcal mol ,is in fairly good -1
agreement with the value obtained by Smidoda et al. [19) of 26.9 kcal mol
for nickel grain-boundary self-diffusion. This process as a controlling
recovery mechanism would be consistent with the results of the high voltage
TEM studies by Bruemmer and coworkers and this study, and also with the
fact that grain boundary carbides were the primary source of dislocations
generated during low strain deformation, and the fact that the dislocations
were arranged in a planar low-energy dislocation Taylor-type of lattice
adjacent to the grain bounjaries.
Recovery Kinetics with 2%-3% Plastic Strain
Figure 11 shows the micros train distribution of a 3%-strained specimen

when subjected to an isothermal anneal at 500°C from 0 to 2800 min. At
this annealing temperature the peak values of the distribution curves moved
toward higher values and the spread of the distribution curve became nar-
rower with an increase in holding time. As a result, the specimen could
not be recovered to the unstrained state, for which the peak ~ value was
12.5'. Focusing attention on Fig. 11, it will be noted that, gt the an-
nealing temperature of 500°C (a temperature which is slightly below 0.5 T
and at which dislocation climb usually begins), nearly 20% of the grain- m
population investigated retained a lattice misalignment of 30' and a con-
siderable percentage of the population exceeded this value. When the
deformed specimens were isothermally annealed at 920-980°C, significant
recovery took place. An example is shown in Fig. 12. The specimen was
plastically deformed and was annealed at 950°C for 0-30 min. It will be
seen that the peak value of the micros train distribution shifted toward the
ALLOY 600
20 3% PLASTIC STRAIN
/", 500°C ANNEALING
(/l
Z
/ \.
<
a:
(!)
15
! \ / 2 8 0 0 MIN
u.
o .I
. ,.,
.......
''1''\
'..,.......670 MIN
w
(!)
10 j~-... ~ .~ 200 MIN
<
I- /-;~ ..... '~~40 MIN
Z
W ;' / / i .('\:\'"
t)
a: 5 ;": ,~,
w
Q. / . ..I
./
"",~ ,
...... .
.......~
o .-/ '.. ' .....
o 10 20 30 40 50 60 70 80
ROCKING CURVE HALFWIDTH (MIN OF ARC)
Fig. 11. Microstrain distribution as a function of time at

anneal1ng temperatures of 500°C for 3% plastic
deformation: - ,40 min; ---, 200 min; - . -
670 min; -"-, 2800 min.
ALLOY 600
40 2% PLASTIC STRAIN
950°C ANNEALING
35
30
(/l
~ ~
<!
25 .:
a: c
t'J •
~
u.
0 20
W
t'J
<!
I-
z 15
w
u
a:
w
0-
10
20 40 60 80 100 120
ROCKING CURVE HALFWIDTH (MIN OF ARC)
Fig. 12. Microdeformation distribution as a function of time at

annealing temperature of 950°C for 2.0% plastic
deformation: , 0 min; -'-, 5 min; -"-, 10 min;
--, 20 min; - - -, 30 min; .... , no strain.
C. F. LO ET AL. 45
TEMPERATURE (oG)
980 950 920

I
STRAIN RELEASE 2.2% STRAIN

- 6 . - 20%
- 0 - 40%
- 0 - 50% 0/
~ ~O/
~O~t/';'
1000
CIJ
/o~O~
w
~
I-
100
~'"' 073.00 ""Imo"
0 40 % :67.58 kcal/mole
0 50 % :64.08 kcal/mole
7.9 8.1 8.3 8.5

l/Txl0' (OK-1)
Fig. 13. Calculation of activation energies for various levels of

recovery _for Alloy 600 deformed 2.0%: 6., 20~l (Q20% ~ 73.00
kcal mol ); 0 , 491 (Q40% = 67.58 kcal mol ); 0, 50% (Q30%
= 64.08 kcal mol ).
unstrained state very rapidly. For an anneal at 950°C, the deformed state
was virtually fully recovered without any recrystallization taking place.
Following the same procedures for determining the activation energy as

that previously outlined, a plot of fraction In{l/(l-x)} of recovery vs.
time was made and a good straight-line fit was obtained except for the
920°C anneal where the recovery process reached a saturation level at about
50% recovery. At the higher temperatures, however, the recovery went to
completion. By replotting the data of holding time vs. the inverse of the
annealing temperature for constant values of X, it was possible to calcu-
late the activation energies for the various stages of the recovery
process. Figure 13 shows three straight lines for the time and temperature
combinations to achieve 20%, 40% and 50% recovery. From the slope of the
respective lines, the following activation energies were obtained:
-1
73.00 kcal mol_ l
67.58 kcal mOl_ l
64.08 kcal mol
The results shown above indicated that the activation energy decreases as
the recovery proceeds. This implies that more energy was required for
strain release at the earliest stages of the recovery process.
Strain Relaxation in Stress-Corrosion Crackin~ (SCC)
Using the CARCA method it was observed that relaxation of plastic

strains took place in strained, unnotched C-rings of Alloy 600 when exposed
to caustic environments. The C-rings are widely used as convenient models
for simulation studies of tubes and pipes subjected to stress with or
without a hostile environment. Confirming previous, detailed CARCA studies
of the strain distribution of C-rings as a function of gap closure [8],
Fig. 14 shows that the strain maximum was generated at the apex region and
HEAT#2609 1070°C/60 MIN 00

50 DC-RING CLOSURE
U
a:
« • C-RING CLOSURE +
u. 40 1000 HOURS IN 10% CAUSTIC
~~
0
i 30
"
C!l
:i
b 20
f--f--'~~.
~
u.
«
-J
J: 10
--.0
o 10 20 30 40 50
DEGREES FROM APEX
Fig. 14. Microstrain relaxation on the surface of an Alloy 600
C-ring following SCC exposure. The sample was heat
treated to produce no GB carbides.
that the strains decreased along the periphery as the angular position from
the apex increased. Prior to straining,the sample was heat treated at
1070°C for 60 minutes and water quenched to maximize the potential for
stress-corrosion cracking (sensitized condition). When the strained C-ring
was exposed to a 10% mixture of NaOH and KOH for 1000 hrs, the CARCA
measurements disclosed a total strain relaxation over the range of 0 to 0
20 0 from the apex (Fig. 14).
Beyond this point, there was no measurable change in the strain as a

result of the 10% caustic exposure. Metallographic examinations of this C-
ring, shown in Figs. 15 and 16 show pronounced SCC cracking from the apex
Fig. 15. Micrograph of apex region of Alloy 600 with extensive SCC
cracking. Sample was heat treated to produce no GB
carbides and,exposed to 10% caustic for 1000 hours.
C. F. LO ET AL. 47
1MM
Fig. 16. Composite micrograph of transverse section of Alloy 600

C-ring heat treated to produce no GB carbides and exposed
to 10% caustic for 1000 hours. SCC cracks can be seen out
to 30% from the apex.
region out to approximately 25°_30°. More importantly, it appears that the

region showing the greatest extent of cracking also showed the greatest
strain relaxation. This may be more clearly seen in Fig. 17 in which the
total crack length over an angular region of 10° is plotted as a function
of the strain relaxation. Thus at the apex region, the total crack length
was found to be 8.2 mm and resulted in a drop of the rocking-curve
o
~,--------------------------------------------------------,
HEAT# 2609
o 10700 C/60MIN +704° C/15HR

cD
o
N
o
ci~----------r----------.-----------r----------r---------~
0.0 5.0 10.0 15.0 20.0 25.0
DIFFERENCE OF HALFWIDTH (MIN OF ARC)
Fig. 17. Relationship between cracking severity, as measured

by total crack length, and decrease in X-ray rocking
curve halfwidth.
' .. ' )
..
__ ... I
,
~
., :~ -~'
.
~ -. _ V ' ._
- " .... \
r I'-,-".
oJ
...- ; • yr '
.~ ,
,.
.... , • i
-- ·O.2mm
Fig . 18. Micrograph of apex region of Alloy 600 with no observable
SCC cracking. Sample was heat treated (704°C/1S hr) to
contain a significant number of GB carbides .
halfwidth of 21.5 min of arc. Further away from the apex there was much
less cracking with a concomitant decrease in the ~~ . In the region of 20°-
30°, the total crack length was only 2.4 mm with a ~ decrease of 2.5 min of
arc. Thus, there appears to be a mechanism operative whereby crack growth
promotes strain relaxation . A second sample was prepared to explore more
fully the above effect. l~is sample, however, was heat treated at 704°C
for 15 hr to produce a substantial number of grain boundary carbides. In
this heat treated condition the alloy is known to be much more resistant to
SCC than the sample described above . In fact no microcrack could be
detected in the metallograph of Fig. 18 when the strained sample was ex-
posed to the caustic solution. The X-ray results of Fig. 19, however, gave
clear evidence that significant microstructural changes have occurred even
though no visible cracks have been initiated . There was a substantial drop
I-EAT#2609
1070·C/2OMN + 704°C/1SHR
50 '" C-RNG CLOSURE
• C·RNG CLOSlH: +
1000 ~ IN 10% CAUSTIC
O'--~--'L.---'---L-""""-"""'-
o 10 20 30 40 50
DEGREES FROM APEX
Fig. 19. Microstrain relaxation on the surface of an Alloy 600
Coring following SCC exposure. Sample was heat treated
(704°C/1S hr) to contain a significant number of GB
carbides .
C. F. LO ET AL. 49
in the rocking-curve halfwidth in the region extending from the apex to

30°. It is tempting to attribute this decline in halfwidth value to the
formation of microcracks which were too small to be resolved met-
allographically.
DISCUSSION
Correlation of Workhardening Characteristics with Micro and Macrostructure
To obtain a useful correlation between the observed microstructural

properties of an alloy, sl~h as deformation and recovery, and those of the
macrostructure, it is imp0rtant to consider the inhomogeneity of lattice
defects introduced by the deformation process. It results from the loca-
tion of the grains relative to the stress field and from the concomitant
impact of induced strains on neighboring grains so as to preserve the in-
tegrity of the material. It has been shown that even for as small as 0.3%
plastic strain many grains of the sampled population exhibited various de-
grees of plasticity while others remained totally unaffected (Fig. 6).
Unlike the conventional X-ray powder method where the specimen is

rotated or prepared in such a way that a smeared-out diffraction line of
the sampled grain population is obtained, the CARCA method retains the in-
dividual grain reflections and analyzes them. It is, therefore, possible
to obtain group information of the grain population whereby the criteria
for group identification are the comparable lattice defects, characterized
by the X-ray rocking-curve halfwidth. This group identification by non-
destructive means offers a path from micro to macrodeformation and becomes
particularly effective when supported by TEM metallography. It has been
shown that complex features of the macroscopic stress-strain curve of Alloy
600 (Fig. 3) can be directly related to the microstructure whereby the in-
cremental plasticity paraI.,eter 1'/, as indicator of the variation in
dislocation density per incremental-strain variation, functions as an im-
portant link (Fig. 5). Thus the low workhardening rate of the fine-grained
Alloy 600 up to about € = 0.7%, characterized by the low value of n = 0.109
(Fig. 3) could be related to the rapid (unimpeded) increase of the disloca-
tion density up to the inflection point I of Fig. 5 as manifested by the
rapid increase of 1'/. This spread of dislocations at small strains without
the generation of dislocation obstacles could be related to the coplanarity
of dislocation arrays generated near grain boundaries and grain-boundary
carbides shown by TEM in Fig. 1. The coplanarity of dislocation arrange-
ment is typical for low-stacking-fault material (Taylor lattice) and is
retained until dislocation obstacles are generated by intersecting slip
planes (Fig. 2). This switch in deformation mode appears to be initiated
at about € = 0.7% and coincides with the inflection point I of the 1'/ plot
of Fig. 5. The activation of intersecting slip-planes in low-stacking-
fault alloys does not obey the Schmidt criterion of resolved shear stress
and is referred to in the literature as "unpredicted glide" [20]. In light
of the inhomogeneity of strain distributions which exist even in a slightly
deformed grain population, as demonstrated in this study (Fig. 6), there
undoubtedly will be generated what Ashby terms compatibility stresses [21]
by neighboring grains. These trigger off intersecting slip activity which
by interaction with the primary slip results in a strain-hardening effect.
Although the dislocation density increases constantly with increased strain
over the range investigated, as shown in Fig. 4, the micros train hardening
occurs in successive stages (Fig. 5) since it depends on the successive
group hardening of the grain population in encountering accrued obstacles
to dislocation mobility. Several important consequences are associated
with the group effect of micros train grain hardening which, as will be dis-
cussed later, has also an impact on the recovery kinetics.
If one compares the features of the workhardening characteristics of

the macrostructure (Fig. 3) with those of the microstructure (Fig. 5) it
will be seen that the slOF~S of the stress-strain curve for the fine-
grained Alloy 600 changes slightly after € = 0.7% and subsequently leads
gradually over from n = 0.109 to n = 0.343. The '1-plot of Fig. 5 however
is more explicit on the course of hardening with strain increase. By its
precipitous plunge after € = 1.5%, it shows that a stage of increased hard-
ening has occurred and that the hardening rate decreased at higher strains.
In the stress-strain curve of the macrostructure, on the other hand, the
successive group effects of microstructural grain hardening are averaged
out. If indeed one were able to resolve these effects the stress-strain
curve would have serrated features.
Especially instructive are the deformation characteristics of copper.

It is well documented in the literature that the stress-strain curve of
polycrystalline copper does not exhibit at small strains any conspicuous
shape features which would reveal the onset and formation of the disloca-
tion cell structure. Yet the organization of dislocations into cell walls
is expected to result in a hardening effect. The '1 maximum at € = 0.025 of
Fig. 5, corroborated by the TEM micrographs showing the development of a
cell structure at 2% strain, gives support to the concept that the workhar-
dening effect associated with cell-wall formation is real. The reason why
the stress-strain curve of the macrostructure does not reveal any special
shape feature is due to the inhomogeneity of deformation which causes
microstructural grain harJening to develop in successively overlapping
stages that cannot be resolved by the macroplot.
Role of Dislocation Obstacles in Recovery Process
If the trend of increased deformation transforms a low-energy disloca-

tion structure into high-energy dislocation structures, the reverse is true
for recovery. The essence of recovery analysis by the CARCA method con-
sisted of measuring the return of the broadened X-ray rocking curve of the
deformed grains to that of their original shape, by isothermal annealing
In an analogous but reverse manner to the deformation analysis, the
greatest precision is obtained by measuring only the changes of the X-ray
halfwidth of those grains of the sampled population which exceeded the
values of the original, undeformed distribution (Fig. 8). The measurement
of the return of the broadened X-ray line to its original shape is of
course also the essence of X-ray recovery studies by the conventional
method. For small plastic strains, however (often comprising the range of
technological importance), the broadening to be measured is often larger
than or about equal to th,~ instrumental broadening. Consequently the
results obtained by conveltional methods are very inaccurate and mislead-
ing. Isothermal annealing at different temperatures, coordinated to
structure analysis by the CARCA method made it possible to identify dis-
location arrangements by their structural stability. Thus, this study
showed that the planar dislocation arrangement of the Alloy 600 strained
0.3% could not contain a significant number of immobile obstacles; this
conclusion was reached from the_~bservation that the activation energy for
recovery was only 25.6 kcal mol and that the strained alloy could be com-
pletely recovered by the low-energy process of grain-boundary self-
diffusion. In addition, the TEM micrograph of Fig. 1 corroborated the con-
clusion that internal barriers to dislocation mobility were absent, such as
forest dislocations and dislocation configuration with sessile locks. When
the alloy was plastically deformed 2%-3% it was concluded that a large num-
ber of obstacles containing immobile, sessile dislocations were generated
(Fig. 2) since complete recovery could not be reached at temperatures when
dislocation climb near 0.5 T becomes operative (Fig. 11). To overcome
these obstacles massive bulkmdiffusion was necessary and annealing had to
be carried out at 950°C to obtain complete recovery (Fig. 12). Just as in
the deformation analysis (Fig. 6) the CARCA analysis of recovery took ad-
vantage of the group identification of the deformed grains which is not
C. F. LO ET AL. 51
accessible at all to conventional X-ray line broadening studies. By "group

identification" is again meant grains of equal ~ values (lattice misalign-
ment or, via calibration dislocation density). Thus the distribution
curves of Figs. 7, 8, 11 and 12 can be viewed as mapping of group lattice
defects and their kinetic variations resulting from annealing.
Ouest of Early Detection of Microcracks in Stress-Corrosion Crackin& (SCC)
The early detection of microcracks by nondestructive (ND) methods has

great technological significance particularly in connection with the
decision-making process of retiring structure-members without a cause.
Microcracks in C-rings are difficult to detect by ND methods because they
are held in compression and frequently become only visible when cross sec-
tions of the specimen are metallographically investigated.
It appears that the CARCA method offers some hope, at least on a

laboratory scale, that microcracks can be detected by plastic-strain
release, manifested by a decrease of rocking-curve halfwidth, such as that
shown in the apex region of the C-ring of Alloy 600 in the sensitized con-
dition (Fig. 14) and to a much lesser degree in the unsensitized condition
(Fig. 19).
SCC of Alloy 600 in caustic environment is always intercrystalline and

also the path of crack propagation is intercrystalline (Fig. 15). In the
unsensitized (thermally treated) condition, the fine, continuous distribu-
tion of carbide precipitates in the grain boundaries has a beneficial
effect by making the alloy more resistant to SCC. One of the theories pos-
tulates that the grain boundary carbides strengthen the boundaries and
blunt crack propagation [16]. Under stress, the grain boundary carbides
become the primary dislocation source so that the greatest dislocation den-
sity of the grain is situated near the grain boundary. This has been
verified also in this study. Because Alloy 600 abides by the deformation
mode typical of a Taylor lattice it never develops a cell structure.
Wilsdorf and coworke~s [22,23] carrying out in-situ deformation of

various metals in the high-voltage electron microscope have shown that
microcracks were initiated at sites of high dislocation densities, such as
cell walls, and at high-stress centers, even in the absence of second-phase
particles. The microcracks lying ahead in the path of an advancing larger
crack will assist its propagation by coalescence. Applying the CARCA
method to fracture studies of binotched, tensile-deformed silicon crystals,
it was shown that lattice regions with large ~ maxima are preferred sites
where crack initiation starts and it was furthermore demonstrated that
crack propagation followed the path of greatest lattice misalignment, that
is, largest dislocation density [5]. It is now argued that in the absence
of cell walls in deformed Alloy 600, the accumulation of dislocations near
the grain boundary represent the most likely sites for microcrack forma-
tion. Thus to minimize the strain energy, microcracks will form in such
highly strained regions as the apex region of a deformed C-ring when ex-
posed to caustic media. The microcracks will be intergranular, being
generated from the excess dislocation density located at grain-boundary
sites. Because of emissicn and redistribution of these dislocations, the ~
values of these grains are expected to decrease as observed in Figs. 14 and
19.
In the nonsensitized condition, Alloy 600 when exposed to a caustic

medium shows improved stress-corrosion resistance but succumbs nevertheless
to caustic attack when the exposure is very long and it fails by inter-
granular cracking. It is tempting to ascribe the drop of the ~ value in
the highly stressed apex region of Fig. 19 to microcracks in grain bound-
aries, cracks too minute Lo be detected by electro or light metallography.
ACKNOWLEDGMENTS
The authors are grateful to Elsevier for their kind permission to use
several of the figures in this paper. The authors are also grateful to
EPRI for financial support of this work.
REFERENCES
[1] Z.H. Kalman and S. Weissmann, Determination of Strain Distribution in

Elastically Bent Materials by X-ray Intensity Measurements, ~
~ ~rystallogr. 12:209 (1979).
[2] Z.H. Kalman, J. Chaudhuri, G.J. Weng and S. Weissmann, Determination

of Strain Concentration by Microfluorescent Densitometry of X-ray
Topography: A Bridge Between Microfracture and Continuum Mechanics,
~ Appl. Crystallogr., 13:290 (1980).
[3] J. Chaudhuri, Z.H. Kalman, G.J. Weng and S. Weissmann, Determination

of the Strain Concentration Factors Around Holes and Inclusions in
Crystals by X-ray Topography, J. Appl. Crystallogr. 15:423 (1982).
[4] H.Y. Liu, G.J. Weng and S. Weissmann, Determination of Notch-Tip

Plasticity by X-ray Diffraction and Comparison to Continuum
Mechanics, J. Appl. Srystallogr. 15:594 (1982).
[5] H.Y. Liu, W.E. Mayo and S. Weissmann, Mapping and Analysis of
Microplasticity in Tensile-Deformed Double-Notched Silicon Crystals
by Computer-Aided X-ray Double-Crystal Diffractometry, Mat. Sci. and
Eng., 63:81 (1984).
[6] W.E. Mayo and S. Weissmann, Nondestructive Failure Prediction in

Cycled Commercial Alloys by CARCA, in: "Fatigue-84", C.J. Beevers,
ed., Eng. Mat. Advisory Servo Ltd., Birmingham (1984).
[7] S. Weissmann, X-ray Failure Prediction Based on Plasticity Response

to Microcrack, in: "Fatigue-87", 3:1459, Emas Eng. Mat. Advisory
Servo Ltd., Birmingham (1987).
[8] C.F. Lo, H. Kamide, G.F. Feng, W.E. Mayo and S. Weissmann, X-ray
Determination of Stress-Strain Distribution in Unnotched C-rings: A
Link from Micro- to Macromechanics, Acta. Metall. 36:3069 (1988).
[9] D. Van Rooyen, Review of the Stress Corrosion Cracking of Inconel

600, Corrosion J. 31:327 (1975).
[10] D. Lee and D.A. Ven,ilyea, The Initiation of Intergranular Failure in

Inconel 600, Metall. Trans. 2:2565 (1971).
[11] C.L. Blanchet, H. Corion, L. Grall, C. Mathieu, C. Otter and G.

Turluer, Influence de la contrainte, des traitments thermiques et des
couplaques sur la fissuration intergranulaire des alliages Inconel
600 et X750, J. Nucl. Mater. 55:187 (1975).
[12] C.L. Briant and S. Banerji, Intergranular Failure in Steel: The Role
of Grain Boundary Composition, Int. Metall. Rev. 23:164 (1978).
[13] R. Yazici, W.E. Mayo, T. Takemoto and S. Weissmann, Defect Structure

Analysis of Polycrystalline Materials by Computer-Aided
Diffractometer with Position-Sensitive Detector, J. Appl. Cryst. 16:
89 (1983).
C. F. LO ET AL. 53
[14] C.S. Smith and L. Guttmann, Measurement of Internal Boundaries in

Three-Dimensional S,-ructures by Random Sectioning, Trans. AIME, 197:
81 (1953).
[15] S.M. Bruemmer and C.H. Henager, High Voltage Electron Microscopy
Observations of Microdeformation in Alloy 600 Tubing, Scr. Metall.,
20:909 (1986).
[16] S.M. Bruemmer, L.A. Charlot and C.H. Henager, Microstructure and
Microdeformation Effects on IGSCC of Alloy 600 Steam Generator
[17] W.A. Johnson and R.F. Mehl, Reaction Kinetics in Processes of
Nucleation and Growth, Metals Technology 6:5 (1939).
[18] M. Avrami, Kinetics of Phase Change I - General Theory, J. Chern.

Phys. 7:1103 (1939).
[19] K. Smidoda, C. Gottschalk and H. Gleiter, Grain-Boundary Diffusion in

Migrating Boundaries, Met. Sci. 13:146 (1979).
[20] D. Kuhlman-Wilsdorf, Theory of Plastic Deformation, Properties of

Low-Energy Dislocation Structures, (Penny Lectures) Int. Conf. on Low
Energy Dislocation ~tructures, University of Virginia,
Charlottesville, VA (1989).
[21] M.F. Ashby, The Deformation of Plastically Non-Homogeneous Material,

Phil. Mag. 21:399 (1970).
[22] H.G.F. Wilsdorf, The Ductile Fracture of Metals: A Microstructure

Viewpoint, Mat. Sci and Eng. 59:1 (1983).
[23] K. Jagannadham and H.G.F. Wilsdorf, Low Energy Dislocation Structures

Associated with Cracks in Ductile Fracture, Mat. Sci. and Eng. 81:283
(1986).
X-RAY CHARACTERISATION OF RESIDUAL SURFACE
STRAINS AFTER POLISHING OF SILICON WAFERS
Linda Hart, D. Keith Bowen, Graham R. Fisher
Department of Engineering
University of Warwick, UK
ABSTRACT
Detailed x-ray double-axis rocking-curve analysis has been made of a series of

silicon wafers, polished using various colloidal silicas with a number of different
conditions. Significant differences, attributable to the polishing conditions, were
observed in the tails of the rocking curves, using a four-reflection, non-dispersive
beam conditioner. These have been compared with theoretical simulations in order to
deduce the strain profile near the surface.
INTRODUCTION
Many current semiconductor-device processes require extremely high quality of the

surface and near-surface regions of semiconductor wafers. This requirement becomes
more stringent as device packing densities increase and it is relevant to investigate even
today's highest-quality wafer production methods in order to assess the resultant
material quality and to identify paths for its further improvement.
Double-axis x-ray diffraction methods may be used to detect strains in the range
to- 5 to to- 6 , with depth resolution down to "- 50 nm, near the surface of single-
crystal semiconductor materials.
It is well known (Manas'ev, 1984) that information on very thin sub-surface

layers (down to 10 nm) may be found in the tails of the Bragg reflection curve. By
using a four-reflection, non-dispersive beam conditioner to give a tailless reflection
curve (Bonse and Hart, 1965; Iida and Kohra, 1979), information on surface scattering
from the sample may be obtained from the tails of the double-axis rocking curve. A
strong reflection must be used to give enough intensity in the tails (with a
conventional x-ray source) and a long wavelength for low extinction depth. Surface
symmetric reflections give information on strains perpendicular to the surface, while
asymmetric reflections also give information on strains parallel to the surface.
X-ray double-axis rocking-curve analysis has been used to characterise the

residual strain after mechanical-chemical polishing of the surface of high-quality silicon
wafers.
Advances in X-Ray Ana/ysis, Vol. 33 55

The effect of using different silica colloids and changing the polishing conditions is
also being investigated and silicon wafers from various manufacturers are being
compared.
EXPERIMENTS
Silicon wafers go through a number of processes: cutting with an inside diameter

saw; lapping flat; etching to remove damage and, finally, polishing and cleaning.
There are two main stages in the polishing process: a rough polish for stock removal
and a final polish for surface finish. The wafers are typically polished on one side
using an alkaline colloidal silica on a polyurethane pad. This combines free abrasive
lapping with chemical polishing so that the silica particles abrade the native oxide, the
alkali attacks the silicon underneath, the oxide regrows and the cycle repeats itself
until the surface becomes flat and highly reflective.
To determine whether there was significant strain or damage induced in the

polishing process, rough polished and full polished wafers were compared, before and
after etching in steps of 1 pm in 1% HF (40%): 99% HNO 3 (70% ). To find
whether any improvement could be made, silicon wafers which had been repolished a
number of times, or polished under different conditions were compared.
Double-axis rocking curve analysis
The experiments were performed using a Bede Scientific Instruments model 450
diffractometer mounted to give a vertical dispersion plane. The smallest obtainable
step size of the diffractometer fine axes was 0.05 arc seconds. This was confirmed
experimentally by measurement of silicon 880 rocking curves of intrinsic width 0.5 arc
seconds. The x-ray generator was a Hiltonbrooks model DG2 run at 45 kV, 35mA
with a copper target.
The 400 reflection was used with CuKQ! 1 radiation, gIVIng a surface symmetric
reflection with Bragg angle 8 = 34.56·. The four-reflection beam conditioner was
channel cut from a single block of silicon, with a strain-relief cut for mounting, and
etched to remove sawing damage. The experiment was set up in the (+, -, +, -, +)
parallel geometry (figure 1) which is non-dispersive in wavelength. A 0.5 mm diameter
collimator was used, which gave a beam size of 0.5 x 4 mm 2 at the sample, due to
horizontal beam divergence. Care was taken to reduce the background as much as
possible without intercepting the beam, by placing narrow slits and lead perspex
shielding between the two axes.
four reflection slits

beam conditioner
collimator
x-ray
source
Fig. 1. Double axis diffractometry. Experimental set-up.
L. HART ET AL. 57
0.8
............ 0.6
°5
~... 0.4
0.2
0
-40 -20 0 20 40
arc seconds
Fig. 2. Instrument function measured using two
four-reflection beam conditioners.
Theory - Experiment ..
The auto-correlation instrument function was measured by placing an identical

four-reflection beam conditioner in the sample position. This gave a tailless rocking
curve of width 4 arc seconds, which is close to the theoretical (figure 2), and has no
contributions in the tails.
The silicon wafer samples were mounted kinematically to prevent unnecessary

strains. The Bragg peak was scanned up to 150 arc secs on either side, in steps of
0.5 arc secs, with total data collection times up to 8 hours to give good counting
statistics in the tails.
Figure 3 shows rocking curves from a rough - polished wafer which was then
etched to depths of 1 pm and 2 pm to remove strain and damage. There is no
significant difference in the rocking curve shapes produced by the 1 pm and 2 pm
etching treatments, which implies that most of the residual strain is in the top micron
below the surface. The residual strain level is greatly reduced in fully-polished wafers.
A rocking curve from such a wafer is shown in figure 4 which compares rough
polished, fully -polished and etched -wafer rocking curves. The plots are shown on a
semi-logarithmic scale.
101~--~----~----~----~ 101~--~~--~----~----~
-100 -50 o 50 100 -100 -50 o 50 100
arc sec arc sec
Rocking curves from polished silicon wafers - 400 reflection.
Fig. 3. Rough polish - Fig. 4. Rough polish -
1 11m etch Full polish
2 11m etch .. 1 11m etch ..
Most of the scattering in the tails appears between 5 and 60 arcs secs, i.e. 1 to
15 rocking-curve widths from the Bragg peak maxima, with more intensity on the low
angle side of the peak, implying a lattice dilation at the surface.
ANALYSIS AND DISCUSSION
Rocking-curve simulations were made using the software package developed by

Hill (1985) and Halliwell, Lyons and Hill (1984), based on the solution of the Takagi-
Taupin equations (Takagi, 1962, Taupin, 1964). To simulate the reflection curve from
the four-reflection beam conditioner, a perfect crystal curve was raised to the fourth
power. This was then cross-correlated with the reflection curve from the model
sample to give a simulation of the rocking curve.
Experimental data from an etched silicon wafer was compared with a theoretical
simulation of a perfect silicon crystal rocking curve, shown in figures 5 and 6. A
background of 0.001, chosen by matching the background at 100 arc seconds away
from the peak, has been added to the theoretical simulation. This is ascribed to
Compton and thermal diffuse scattering.
A number of different strain profiles was simulated in order to find any possible
agreements with the experimental data. A positive mismatch was assumed, due to the
asymmetrically increased intensity on the low- angle side of the rocking curve.
Mismatch may be defined as follows:
'experimental' mismatch m* = a-
lia
=
lid
~ = - lie cot e
'true' or 'relaxed' mismatch m = (al - as) = m*[l-v] = m*

as l+v 2
where al and as are the lattice parameters of the layer and substrate, e is the Bragg
angle, and v is the Poisson ratio. In the simulations, lattice mismatch was varied
between 3 and 20 parts per million, with total layer thicknesses from 0.5 to 20
microns, assuming maximum strain at or near the surface.
In the first instance, comparisons were made with data from rough-polished wafers.
The best fit was given by a non-linear graded mismatch of 8 ppm near the surface,
decreasing to zero at 1 pm below the surface (figure 7). This was divided into 20
layers of 50 nm each, assuming a constant strain across each layer. The model shows
10°
0.8 10-1
;;., ;;.,
.1:: .1::
.=>
0
0.6
.=>
~ 0.4 ~
~ ~
0.2
0 10-4
-100 -50 0 50 100 -100 -50 0 50 100
arc seconds arc seconds
Comparison of experiment with theory for a perfect silicon crystal.
Theory - Experiment ..
Fig. 5. Linear scale Fig. 6. Logarithmic scale
L. HART ET AL. 59
w
U
0-
~ Z
-'
O~--~ __ ~ __ ~~~~
~o ~z ~. ~. ~. ~o
DEPTH BELDU SURFACE ~m
Fig. 7. Strain profile model used in simulation.
a very low strain profile at the surface, nsmg to a maximum about 50 nm below.
Models with maximum strain at the surface itself consistently showed poorer agreement
with experiment. The resulting simulation is shown in figure 8, compared with a
perfect-crystal simulation. The low-angle tail of the curve shows increased intensity,
while the high-angle intensity is reduced. This asymmetrical shape was typical of all
the simulations tried, assuming a positive mismatch at the surface. Other effects
which change the peak shape include sample curvature, surface orientation and surface
roughness. These effects were eliminated by comparing rocking curves from the same
point on the sample before and after etching. Initial comparisons for fully- polished
wafers place an upper bound for the strain level at 4 ppm, with similar depth profiles.
A good fit to the experimental data may be obtained by adding intensity to both
tails of the theoretical strained -layer curve. This could be explained by diffuse
scattering from atom disorder or defects near the surface, which would increase the
intensity at the rocking curve tails on both sides of the peak (Thomas, Baldwin,
Dederichs, 1971; Dederichs, 1971).
It was therefore concluded that a combination of lattice dilation and disorder or

defects must be present near the surface in order to give an asymmetric peak shape
with both tails higher in intensity than for a perfect crystal. We are currently
100 ~----.---~.----,----~
10-1
10-3
104L---~~--~----~------'
-100 -50 o 50 100
arc seconds
Fig. 8. Theoretical simulations comparing perfect crystal
with model strained crystal.
Perfect crystal - Strained crystal --
investigating theoretical models to explain the mechanism by which these effects are
produced.
It has been shown (Andrews and Cowley, 1985; Robinson, 1986) that diffuse
scattering may arise from an abrupt truncation of charge density at a crystal surface
and this has been measured from polished (111) silicon wafers (Harada et ai, 1983,
1987). An asymmetry, implying lattice dilation, was also measured, in agreement with
the results presented here.
CONCLUSIONS
Double-axis x-ray diffractometry may be used to detect very small strains (mis-
matches of a few parts per million) down to - 50 nm below the surface.
The mechanical-chemical polishing process used to produce high-quality silicon

wafers leaves residual strain at the surface, which may be removed by etching.
Comparison with theoretical simulations enables strain-depth profiles to be determined.
A probable strain profile is a very low lattice mismatch just at the surface, rising to
between 4 and 8 ppm at about 50 nm depth, decreasing non-linearly to zero at 1 Iffil
below the surface. There is also disorder or defects near the surface, which give
extra diffuse scattering in the rocking curve tails.
This technique may be used to evaluate various stages in the silicon wafer
polishing process.
REFERENCES
1. Manas'ev, A.M., Aleksandrov, P.A., Imamov, R.M., Lomov, A.A.,

Zavyalova, AA, Acta Cryst. A 40, 352-355 (1984).
2. Bonse, U., Hart, M., Appl.Phys.Lett. 7, 238-240 (1965).
3. Iida, A, Kohra, K., Phys.stat.Sol. (a) 51, 533-542 (1979).
4. Hill, M.J., PhD Thesis, Durham University, (1985).
5. Halliwell, M.AG., Lyons, M.H., Hill, M.J., 1.Cryst.Growth 68, 523-531 (1984).
6. Takagi, S., Acta Cryst. 15, 1311-1312 (1962).
7. Taupin, D., Bull.Soc.Fr.Min.Crist. 87, 469-511 (1964).
8. Thomas, J.E., Baldwin, T.O., Dederichs, P.H., Phys.Rev.B3, 1167-1173 (1971).
9. Dederichs, P.H., Phys.Rev. B 4, 1041-1050 (1971).
10. Andrews, S.R., Cowley, R.A, 1.Phys.C. Solid State Phys. 18, 6427-6439 (1985).
11. Robinson, I.K., Phys.Rev. B 33, 3830-3836 (1986).
12. Kashiwagura, N., Harada, J., Ogino, M., 1.AppI.Phys. 54, 2706-2710 (1983).
13. Harada, J., Kashiwagura, N., Sakata, M., Miyatake, H., 1.AppI.Phys. 62,
4159-4162 (1987).
14. Kashihara, Y., Kawamura, K., Kashiwagura, N., Harada, J., lapan.J.AppI.Phys.
26, Ll029-Ll031 (1987).
MEASUREMENT OF RELAXATION
IN STRAINED LAYER SEMICONDUCTOR STRUCTURES
Mary A G Halliwell
British Telecom Research Laboratories

Martlesham Heath
IPSWICH IPS 7RE, United Kingdom
INTRODUCTION
Many advanced semiconductor device designs require the growth of

heteroepitaxial layers with lattice parameters differing by. up to a few percent with
respect to the substrate. X-ray diffraction offers a nondestructive method of
determining the extent of relaxation. This paper discusses the sensitivity of x-ray
techniques to small amounts of relaxation, describes how relaxation is measured in cubic
materials for layer on (001) substrates and suggests nomenclature for the case of
asymmetric relaxation.
THE RELAXATION MECHANISM
A heteroepitaxial layer is said to be relaxed if mismatch dislocations have been

introduced into the structure (usually near the heteroepitaxial interface) as a result of
the lattice parameter difference between the layer and substrate being sufficiently great
for the elastic limit to have been exceeded. Below the elastic limit the unit cells in a
heteroepitaxiallayer grown on a (001) substrate have tetragonal symmetry; the cia ratio
of the tetragonal cell being dependent on the lattice-parameter mismatch and the elastic
constants of the layer material. This tetragonal distortion decreases as dislocations are
introduced and the layer unit cell relaxes back towards its cubic form as shown in Fig 1,
layer
a unit cell
~
U substrate
unit cell
bulk or strained partially

fully relaxed relaxed
Fig 1 Relaxation of the layer unit cell (ideal case)
Advances in X-Ray Analysis, VoL 33 61

Edited by c.s. Barrett et al.
which depicts a layer with bulk lattice parameter ar grown on a substrate with lattice
parameter a . In the ideal case illustrated it is assumed that the layer unit cell remains
tetragonal w?th cell edges parallel to those of the substrate unit cell. Then the fractional
relaxation is defined by:
(1)
where a is the lattice parameter of the partially relaxed layer unit cell parallel to the
interface.
R equal to zero indicates that the layer unit cell is strained to exactly match the
substrate unit cell parallel to the interface. R equal to unity implies total relaxation with
the layer unit cell acquiring cubic symmetry. This is rarely achieved in practice. When
the lattice parameter difference between the layer and substrate is large, complete
relaxation can occur during growth at an elevated temperature. Measurements made at
room temperature frequently show a small residual strain which results from the
difference in thermal expansion of layer and substrate as the sample is cooled. This will
lead to a measured relaxation greater than unity for a layer which has a higher
expansion coefficient and higher lattice parameter than its substrate.
R can be determined if the dimensions of the partially relaxed unit cell are
measured. This can be done by recording rocking curves from reflecting planes which
are inclined to the (001) substrate surface. Measurement of a number of partially
relaxed samples has indicated that relaxation is seldom ideal. As will be described
below, all three axes of the layer unit cell may be tilted with respect to the axes of the
substrate unit cell.
Electron microscopy examinations show that mismatch dislocations which cause

relaxation at (001) interfaces are predominantly of the 60° type. These dislocations glide
in the inclined {111} slip planes to form long segments lying along the < 11 0> directions
parallel to the interface. The result is a mismatch dislocation network at or close to the
interface. Fig 2 indicates the orientations of the {l1l} slip planes on which the mismatch
dislocations glide. The assumption that the layer unit cell retains tetragonal symmetry
after relaxation (ideal relaxation) is equivalent to assuming that there is an equal
distribution of dislocations on each of the four sets of slip planes.
H we are considering III-V semiconductor materials, then the upward facing
surfaces of one pair of the slip planes are terminated with group III atoms while the
other pair are terminated with group V atoms. The ease with which dislocations glide
can be different for these two cases (Nagai, 1981) leading to a unit cell in which the two
< 110> vectors lying in the plane of the interface have different lengths. In this case the
[100] and [010] vectors in layer and substrate will no longer be parallel.
Fig 2 Orientations of the four {Ill} slip planes

M. A. G. HALLIWELL 63
The [001] vectors in the layer and substrate may also be non-parallel. A possible
mechanism for both group IV and group III-V semiconductor materials is the case of a
substrate surface slightly tilted with respect to the (001) plane. The substrate surface will
then have atomic steps which could preferentially favour the nucleation of dislocations
along one of a pair of slip planes rather than the other. An assumption which can still
reasonably be made in circumstances when there are possible differences in dislocation
densities on the four {Ill} slip planes is that the [110] and [110] directions in the
layer and substrate remain parallel. This assumption is used in the next section to
develop a general method of deriving the layer unit cell dimensions from diffraction
data.
DETERMINATION OF THE LAYER UNIT CELL DIMENSIONS

In order to determine the dimensions of the layer unit cell, the unit cell
dimensions of the substrate material are assumed known. X-ray rocking curves are
recorded from which the angular separation between layer and substrate diffraction
peaks can be determined and hence the relative positions of the reciprocal lattice points
of the layer and substrate. Because the [110] and [110] zone axes are assumed to be
parallel for the layer and substrate, the measurement of the relative positions of the
layer and substrate reciprocal lattice points will be most straightforward in these zones.
Fig 3 shows the Ewald sphere construction for the hhZ reflections with low (L) and high
(H) angles of incidence. 0 is the origin of the reciprocal lattice, R is the hhZ reciprocal
lattice point and P is the OOZ reciprocal lattice point. For beam path L, represented by
the triangle LOR, the angle of incidence with respect to the (001) plane is i and that for
beam path H, represented by the triangle HOR, is e. For the substrate, i is equal to the
difference between the Bragg angle and the tilt between the (hhZ) and the (001) plane
and e is equal to the sum of the Bragg and tilt angles. The angles i and e can be
calculated for the substrate from its known lattice parameter and cubic symmetry. The
separation of the layer and substrate peaks in a rocking curve is a measure of the change
of angle of incidence required to move the Ewald sphere from a position where it
intercepts the substrate reciprocal lattice point to the position where it intercepts the
layer reciprocal lattice point. By adding or subtracting the measured peak separation to
the known angle of incidence for the substrate we have a value for the angles of
incidence with respect to the (001) substrate plane corresponding to strong diffraction
from the layer. If we take x and z axes as indicated, two dimensional co-ordinate
geometry can be used to obtain an equation for the point of intersection of the two
Ewald spheres in terms of the angles of incidence for the Land H beam paths. It is thus
possible to determine the position of the reciprocal lattice point for the layer. If the
procedure is repeated to obtain the liliZ reciprocal lattice point position, the position
(001)
substrate
Fig 3 Ewald sphere construction for hhZ reflection

TABLE 1
NB all values in seconds of arc for Copper K.a radiation
Reflection Substrate Material
hkl Si Ge GaAs InP

S dS S dS S dS S dS
002 1058 5 1047 5 1106 5 1095 5

004 2455 10 2410 11 2531 12 2477 12
113H 159 10 92 9 87 10 13 10
113L 2950 15 2982 19 3141 21 3165 22
224H 579 14 502 13 451 16 313 14
224L 3992 20 3947 21 4183 23 4163 24
115H 2624 4 2506 4 2552 5 2376 4
115L 4528 23 4411 23 4636 26 4526 26
335H 3305 18 2563 16 2459 16 1872 16
335L 6807 18 6174 20 6358 23 5894 29
444H 4147 57 1879 42 1758 40 961 35
444L 7540 24 5345 7 5467 3 4786 3
117H 17484 91 13007 48 8902 35
117L 18718 105 14736 64 10679 51
of the 001 point can be calculated. From these points it is possible to calculate dx and dz
(=c), the d spacings of the (110) and (001) planes for the layer. If the procedure is
repeated for the hlil and 11hl reflections a second value for dz can be obtained
together with a value for dV' the d spacing for the (110) planes for the layer. Thus the
complete symmetry of the unit cell can be determined from a minimum of eight rocking
curves. The measurement can be repeated for different hhl reflections to reduce the
experimental error. The next section considers the best choice of reflections for
determining relaxation.
Before the relaxation can be calculated, the bulk lattice parameter of the layer,
ar , is required. This will be known if the layer is silicon, germanium or a binary III-V
semiconductor. Otherwise the lattice parameter of the layer in bulk form will have to be
calculated from the distorted unit cell dimensions using elastic theory.
CHOICE OF REFLECTION
Table 1 shows the peak separations (S) which would be observed in rocking
curves recorded from unrelaxed layers with lattice parameters differing by 1% from
their substrate~ (normally referred to as a 1% mismatch), together with the change in
peak separation (dS) which occurs for a relaxation of 1% as given by equation (1). Data
is given for four of the most common substrate materials - silicon, germanium, gallium
arsenide and indium phosphide. The S value for a particular reflection is proportional to
the value of (c-a) for the tetragonally distorted layer cell while dS is P!opprtional to
R(c-a). For silicon and germanium the data are for silicon_germanium alloy layers with
the appropriate mismatch. For the III-V substrates the data are for gallium indium
arsenide heteroepitaxial layers. Because Poisson's ratio is smaller for Si and Ge than
for the III-Vs (Brantley, 1973) there is a significant difference in the S values for
germanium and gallium arsenide even though the lattice parameters of the two
materials are very close.
The 002 and 004 reflections have been included in the table for completeness.
However since they only involve the c parameter of the unit cell they cannot be used to
determine relaxation unless the layer is of known lattice parameter, as for example in
the case of a layer of GaAs on Si. The change of separation with relaxation is small but
the reflections are much simpler experimentally and may be appropriate to use in some
circumstances. In this case four rocking curves should be recorded with the x-ray beam
M. A. G. HALLIWELL 65
parallel to [011] directions, with 90° rotation about the surface normal between each. In
this way the presence of a tilt between the layer and substrate can be revealed. It will not
be possible to determine if there is a difference between dx and dy for the layer.
The reflections which are most useful for determining relaxation are those for
which the ratio dS/S is greatest. The 113 reflection appears a good choice for all
materials. However for InP the value of i for the L beam path is less than 10 and its use
is not straightforward. In this case, and for other substrates with larger lattice
parameters the 224 reflection is the best choice. The minimum relaxation that can be
measured will depend on the minimum peak movement that can be determined. This
will be instrument dependent. A well-aligned double-a.xis diffractometer can give typical
peak widths of 10 to 20 seconds of arc. It should be straightforward to measure peak
shifts of one half the peak width and hence a 1% relaxation in a layer with 1% mismatch
should be measurable on a routine basis. Because the peak movement is proportional to
(c-a)R, or the product of mismatch and relaxation, this means that 0.5% relaxation
should be measurable in a layer with 2% mismatch. The relaxation is equivalent to a
lattice parameter difference of 100 ppm (parts per million) parallel to the interface.
This method can also be used for measuring the relaxation occurring in
superlattice stacks consisting of alternating layers of two semiconductor materials. In
this case the relaxation is defined in terms of the mean lattice parameter of the stack. By
averaging over several reflections it was possible to measure relaxations equivalent to a
difference in lattice parameter of 20 ppm parallel to the interface (Halliwell et aI, 1989).
DEFINITIONS OF RELAXATION
The only established definition of relaxation is given in equation (1). This only
applies to the ideal case. Two possible definitions for the non·ideal case should be
considered:
Strain relief parallel to the < 110> directions in the inteiface. This would be the preferred
method when the asymmetry is large, particularly in circumstances where special efforts
have been made to achieve uniaxial distortion (Tuppen et aI, 1989). In this case if the
bulk lattice parameter of the layer is '!T and the d spacing parallel to the two < 110>
directions are dx and dy then the two values of the relaxation could be expressed as:
Rx = (2°.5dx-ao)/(~-ao) and Ry = (20.5dfao)/(ar-ao) (2)

Note that ~ and Rv equal implies tetragonal distortion and equation (1) can be used. If
R is equal to unity 1ll only one of the < 110> directions then the layer is strain free in
that direction, but is still strained in the other < 110> direction and the c parameter
could be larger or smaller than the bulk value. If ~ and R are nearly equal, then the
deviation from tetragonal distortion is small. The r€laxatiort could be expressed as the
average of Rx and Ry-
Strain relief calculated from the change in c parameter. Alternatively when
~ and Ry are
nearly equal the relaxation could be derived from the change in c parameter of the layer
unit cell. For layers of known bulk lattice parameter (ar ) this method would have the
advantage of being derived from the experimentally simple 001 reflections. If ~ and c
are known the a parameter can be calculated from the elastic equation for tetragonal
distortion (Halliwell,1981), where v is Poisson's ratio:
ar = a + (c-a)(l-v)/(l+v) (3)
The approximation involved in assuming tetragonal distortion should be small. The a
parameter obtained can then be substituted into equation (1) to give a value for the
extent of relaxation. In this case an R value of unity does not necessarily imply a strain-
free layer. It does imply that the c parameter of the layer is equal to the bulk lattice
parameter but the layer could still be in compression parallel to one < 110> direction
and in tension parallel to the other < 110> direction in the plane of the layer.
For the case of binary group IV, or ternary or quaternary group III-V
heteroepitaxiallayers where the composition, and hence ar' is not precisely known, then
asymmetric reflections will have to be used so that all three layer unit cell parameters
can be determined. In this case a=(d}+d})O.5 can be substituted into equation (1)
together with ar to obtain a mean value lor die relaxation.
SUMMARY
X-ray diffraction can be used to fully characterise the state of relaxation of

heteroepitaxiallayers. The smallest relaxation which can be measured is instrument and
sample dependent. For a well aligned diffractometer and a good quality sample,
relaxations which give lattice parameter differences of 100 parts per million parallel to
the interface should be readily measurable. This is equivalent to 1% relaxation for a
layer with a 1% lattice parameter difference with respect to the substrate. Smaller
relaxations should be measurable if values are averaged over several reflections.
Methods for defining non-ideal relaxation are suggested.
ACKNOWLEDGEMENTS
Thanks to my colleagues at BTRL, Chris Tuppen and Michael Lyons for many
discussions, and in particular to Mark Hockly who also supplied the electron microscopy
results. Acknowledgement is made to the Research and Technology Board of British
Telecom for permission to publish this paper.
REFERENCES
Brantley, W.A., 1973, Calculated elastic constants for stress problems associated
with semiconductor devices, J. App!. Phys. 44:534
Halliwell, M.A.G. 1981, X-ray measurements of lattice mismatch in
heteroepitaxiallayers, Inst. Phys. Conf. Ser. 60:271
Halliwell, M.A.G., Lyons, M.H., Davey, S.T., Hocldy, M., Tuppen, e.G., and
Gibbings, C.J., 1989, Estimation of percentage relaxation in Si/Si1_ Ge x
strained-layer superlattices, Semicond. Sci. Technol. 4: 10 x
Nagai, R., 1981, Dislocation velocities in indium phosphide, lpn. J. App!. Phys.
20:793
Tuppen, e.G., Gibbings, C.J., Rockly, M. and Halliwell, M.A.G., 1989,
Asymmetric strain distribution produced by the preferential nucleation of
misfit dislocations, submitted to Appl. Phys. Lett.
CHARACTERIZATION OF STRUCTURAL INHOMOGENEITIES IN
GaAs/AlGaAs SUPERLATTICES
P. C. Huang*, S. R. Stock*, A. Torabi ** and C. J. summers**

.
* School of Materlals Eng., * *.
Georgla Tech Research Inst.,
and *'**Microelectronics Research Center
Georgia Institute of Technology, Atlanta, GA 30332
ABSTRACT
Thin films containing periodic chemical or strain

modulation (e. g. artificial superlattices or SL) are often
characterized nondestructively by X-ray double-axis
diffractometry. The satellite peaks from the modulated
structure allow analysis of layer structure, elemental
concentration and strain profile. This paper focuses on the
effect of layer uniformity on the rocking curves of (001)
GaAs/Al xGa 1 _xAS SL. Double-axis diffractometry for results from
MBE samples with 800 A SL periods and x=0.35 are compared for
GaAs/AlGaAs layer thicknesses of 350/450, 400/400 and 450/350
A. Symmetric (004) and asymmetric (315) diffraction planes are
used to measure parallel and perpendicular misfit strains,
layer periodicity and aluminum concentration. A modified
kinematical scattering model, correcting for absorption and
extinction, is used to calculate the satellite peak intensities
and spacings. The relative thicknesses of GaAs and AIGaAs and
the aluminum elemental concentration are optimized by matching
with experimental results. The effect of nonuniform layer
thickness on SL peak intensities is also investigated. The
experimental results, the modified kinematical scattering
calculations and dynamical theory agree closely for the 3-4 ~m
thickness layers studied.
INTRODUCTION
Superlattices are a class of epitaxial materials with

modulated composition. 1 The alternating layers form a new,
intentionally-imposed periodic potential and quantized energy
structure. 2 such superlattices behave as man-made
semiconductor materials with properties that can be greatly
influenced by the choice of the superlattice potential. 3
The characteristics of SL such as layer structure,
Advances in X-Ray Analysis, Vol. 33 67

elemental concentration and strain profile are frequently

determined by x-ray double~axis diffractometry which precisely
measures the pattern of diffraction peaks. The SL structure
dictates the spacing, intensity and width of a fundamental peak
and associated satellite peaks.
Kinematical diffraction models 4-7 and dynamical diffraction
formulations 8-10 have all been used to model the structure of
SL rocking curves. The review by Tanner in this volume
summaries much of the work which has been done in rocking curve
simulation." In general, use of dynamical diffraction is to
be preferred for simulating rocking curves, but the lengthy
computations make use of kinematical diffraction results very
attractive for certain applications.
In this paper a modified kinematical diffraction model,
containing corrections for absorption and extinction, is used
to simUlate double axis rocking curves of (GaAs/Al xGa 1 _xAs) n SL
on (001) GaAs. Comparison of experimental and calculated
rocking curves is used to determine the average thickness of
GaAs and Al xGa 1 _xAs. The effect of varying sublayer thicknesses
is examined, and the SL peak intensities and widths are found
to be very sensitive to these variations.
DIFFRACTION MODEL
Kinematical diffraction theory is an approximation of
dynamical theory and is an adequate model when the maximum
reflecting power is low (i.e. for relatively thin layers). The
treatment of Speriosu and Vreeland,4 for example, is quite
successful for SL analysis, and it provides the basis for the
model used here. Each period of the SL is assumed to diffract
independently, and the transition between the sublayers is
assumed to be sharp. The intensity calculated for any given
orientation is, therefore, the sum of the intensities
diffracted from each layer. The modified kinematical
diffraction model used in this paper extends the earlier
approach by correcting for normal absorption and extinction
(e.g. Batterman and cole 12 ) . Note that diffracted intensity
from both the substrate and buffer layers are explicitly
included. The accuracy of the modified kinematical diffraction
model should be comparable to that of dynamical diffraction
treatments for total layer thicknesses considerably greater
than 2 J.4m. It should be noted, however, that dynamical
diffraction must be used for more complex layered structures
where large lattice-parameter gradients are present or where
layers reach 5-10 J.4m total thickness. Another experimental
feature which should not be expected to be reproduced by the
kinematical model is the set of subsidiary maximum associated
with each satellite reflection.
EXPERIMENTAL PROCEDURES
The undoped superlattices of GaAs/AIGaAs were grown in a
VARIAN GEN II system on two degrees-off (001) GaAs substrates.
The nominal Al concentration in the AIGaAs layers was x=O.35,
P. C. HUANG ET AL. 69
and surface conditions during growth were monitored with RHEED.

Three SL structures were produced with 40 periods of nominal
thickness of 800 A: 350/450, 400/400 and 450/350 A thicknesses
of GaAs/AIGaAs. A thin, short-period SL and a bulk AIGaAs
layer (x=0.35, 0.5 ~m thick) separated the 800 A period SL and
substrate to block extension of substrate defects.
Double-axis diffractometry was used to characterize the
structure of SL. The diffractometer was a prototype of Bede's
Model 150, with Bede goniometers and computer control. A (004)
GaAs monochromator, Cu Ka radiation and a 1 mm diameter
collimator (before the monochromator) were used. Rocking
curves for the (004) symmetric and (315) asymmetric diffraction
planes were used to determine misfit strain parallel to and
perpendicular to the sample's surface.
RESULTS AND DISCUSSION

Al Composition of SL
The SL diffracts as an alloy which has an average
composition defined by the compositions of the sublayers and
their relative thicknesses. The SL main peak position relative
to that of the substrate is defined by:4
where ek and eM are the perpendicuiar and parallel misfit

strains in the SL, defined by (M/a) = (a!lt.-a s ) las and (~a/a)1I
= (a~l-as) las' respecti'lely, and where as is the lattice parameter
of free substrate, a SL is the SL's average lattice parameter
perpendicular to the surface and a~t is that parallel to the
surface. In this model, the substrate is assumed to be so
thick compared to the SL that it is rigid. The angle 8 8 is the
exact Bragg angle for the substrate, and the asymmetry angle,~,
is the angle between the normals of the diffracting plane and
the crystal surface. The first term of Eq. (1) arises from the
difference of interplanar d-spacings of the SL and substrate.
The latter term accounts for the different inclinations of the
diffracting planes of the SL and sUbstrate 13 ; the difference
results from the unequal perpendicular and parallel lattice
parameters of the SL. The "+" and "_,, signs denote the angle
of the incident beam relative to the surface normal 8 = 8 8 - ~
and 88+ ~, respectively. This equation implicitly assumes that
no interface dislocations are present which might produce a net
rotation between the SL and substrate. Both e*and eMof the SL
were determined by measuring the 004 and 315 rock1ng curves
for which ~ =0· and 32.3·, respectively. The values of ~8o
show that eM'" 0 for all three SL's, and these values are
consistent w1th coherent layers.
1.
The measured value of (~a/a) needs to be converted to a
"relaxed" value 13-14 in order to determine the average aluminum
content of the SL as a whole and from this the aluminum content
of the Al xGa 1_xAs sublayers. The "relaxed" value lies between
the lattice constants of AlAs and GaAs, and linear
interpolation between these endpoints yields the average

aluminum content of the SL. If the SL periodicity t and the
thickness of the individual sublayers are known, the value of
x is straight-forward to calculate. The simple formula relating
the average aluminum content of the SL to the angular
separation of the SL fundamental and substrate peaks, X SL =-
2.65*10- 3 MJ o ' can be used to convert peak spacing data directly
to composition, but this shortcut must be used cautiously
because apparent compositions in layers with thicknesses less
than 1 J-Lm can be quite different from the actual
composition. 15-16 This value of X SL assumes that the misfit
between AlAs and GaAs is 0.149%17 and that the substrate is
rigid. Non - rigid substrates require a tiny correction. 18
Periodicity of SL
In the kinematical treatment, l::.0p' the angular spacing

between adjacent peaks from the layer (fundamental and
satellites) is related to the SL periodicity t by:4
~Irhl
(2)
where t1 and t2 denote the thicknesses of GaAs and Al xGa 1_xAs

sublayers, respectively, and r h is the direction cosine of the
diffraction planes relative to the surface normal. Unless one
is absolutely sure of the sense of the asymmetric planes in an
off-axis orientation sample, measurements should be conducted
for ¢ = 0·,90·, 180· and 270·, where ¢ is measured about the
axis normal to the sample surface and in the plane of
dispersion and the angle is defined relative to one of the
edges (e.g. cleavage planes) of the substrate.
simulations of SL
The sublayer thicknesses t1 and t2 cannot be determined from

the positions of the peaks in the rocking curve. Calculation
of the intensities of the superlattice peaks produced by
different pairs of t1 and t2 is required to identify the
sublayer thicknesses. The composition x of the Al xGa 1_xAs
sublayer is fixed, therefore, by t2 and the average Al
concentration of the SL. Diffusion of Al is very slow at the
growth temperature 600·-700·C,19 and interdiffusion can be
ignored. The simulation thus assumes sharp interfaces, and
the best match is determined from simulations of the rocking
curve for valves of t2 between 0 and t and increments of l::.t2 =
0.01 t. Two criteria are used to select the optimum match
between simulation and experiment. The first is that the
simulation must predict correctly which peak has the largest
intensity, which is second largest, etc. If this condition is
met, the simulation coming closest to the experimental results
is selected. Different residual factors are being evaluated
for quantifying the goodness-of-fit. We estimate that the
selected t2 are within ±O.Olt of the optimum value.
Figure 1 shows the experimental rocking curves paired with

the simulated rocking curves showing the closest agreement.
The agreement between the calculated and observed curves is
good. Dynamical diffraction simulations of these rocking

curves are very close to the results obtained with the
kinematical model. 2o The differences between the three samples'
structure are clearly seen by comparing the even-order
satellite peaks. In Fig. 1a the +2 and +4 peak intensities are
much higher than that of the +3 peak, whereas they are smaller
10'
100
10-'
1;-
.iii 10- 2
C
2
..£ 10-3
Q)
>
:p
0
Q)
0:::
10-5
10--6
b
10- 7
-1500.0 -500.0 500.0 1500.0 -2000.0 -666.7 666.7 2000.0
W, (are seconds) W, (are seconds)
10'
10--6 E-_-~
C
10-7~------~--------~------~
-1500.0 -166.7 1166.7 2500.0
W, (are seconds)
Figure 1. Rocking curves which are best fit by the following

GaAs/AlxGa'_xAS sublayer thicknesses and compositions. a.
360/500 A, x=0.33i b. 324/262 A, x=0.5 and c. 423/286 A,
x=0.38. The sublayer thicknesses were intended to be
400/400, 350/450 and 450/350 A, respectively, with x=0.35.
than the +3 peak in Fig. 1b and are virtually absent in Fig.

1c. The nominal sublayer thicknesses and aluminum
concentration are different, therefore, from the values
determined from the rocking curves and simulation. This is not
surprising in that the SL were grown during commissioning of
the MBE system. The accuracy of the experimental results and
of the simulation has been checked by measurements on other MBE
AIGaAs/GaAs SL's whose growth had been followed by RHEED
oscillations and whose periodicity had been measured by high
resolution, cross-sectional TEMi all agree within 2%.
As illustrated in Fig. 2a, the intensities of the higher-

order satellites are much more sensitive to the relative
thickness of GaAs and Al xGa 1 _xAs. This figure shows peak
intensities as a function of Al xGa 1_xAs layer thickness for
constant SL period and composition. variation of satellite
peak intensity with aluminum concentration for constant
sublayer thicknesses is quite small (Fig. 2b) and indicates
that the sublayer structure is much more important in
determining superlattice peak intensity.
Period Variation of SL
The effect of nonconstant SL periodicity on the intensities

of the satellite peaks can be quite SUbstantial. 4,21 In these
earlier kinematical simulations, the standard deviation of SL
period is used in the form of a Debye-Waller factor. This
o (+1)
t:.. (+2)
-.-(+4)
o (+6)
a b
10~~------------~----------------~--------~~------------~----------------~------------~
0.00 333.33 666.67 1000.00 0.00000 0.33333 0.66667 1.00000
Thickness of AIGaAs Layer, W AI Cone. of AIGaAs Layer
Figure 2. Simulated satellite peak intensity for 40 period

SL's as a function of a. AIGaAs sublayer thickness for 800 A
periodicity and average SL concentration of 0.175; and b. Al
concentration for 400/400 A sublayer thicknesses.
40.0 r----------.....,
• expo • expo
A cal.&O"=O.% A cal.&0"=O.2%
10° ------------- -------------
c cal.&0"=1.%
o cal.&O"=O.5% r0-
~ cal.&0"=2.% t> 30.0
.....>.
Q)
'00 10-
1 C/l
c ~
.....Q) S
.£ 10-2 2 20.0
Q)
I
>
:,::; 3:
0 LL
V 10-
3
~
a: o
Q) 10.0
0...
10- 4
a 0.0 _b_ _ _10....._ _-"'_ _ _.....

10-5
-2.0 2.0 6.0 0.0 2.0 4.0 6.0
Peak order Peak order
Figure 3. Measured and calculated SL peak a. intensities and
b. widths (full width at half maximum, FWHM) for non-constant
SL period. Only the 11+11 SL peaks for Fig. 1b are shown.
approach, however, is inadequate for the rocking curves shown

in Fig. 1. Instead, a set of specific layer thicknesses, with
an average period equal to that from the data, with the
composition of the Al xGa 1 _/<As sublayer kept constant and with a
standard deviation optim1zed to match the experimental data,
is used for investigating SL peak intensities.
The thickness of the successive layers must be specified
in the simulation and could influence the results. A large
number of layer arrangements yield similar SL peak intensities,
and typical results (Fig. 3a) show that a better fit of the
experimental intensities is obtained with a standard deviation
in periodicity between of 0.5% and 2.0% than with perfect
periodicity. The calculations indicate that peak intensities
drop with increasingly-variable SL period and that the effect
is largest for the higher-order peaks. This observation could
explain why it is frequently difficult to find many orders of
satellite peaks and why this effect might be more pronounced
for equal-magnitude fluctuations in short-period SL's.
The distribution of peak widths is a second indication of
the SL's uniformity. According to the kinematical model, the
FWHM of main and the satellite peaks is uniform if the
periodicity of SL is constant. The presence of variations in
FWHM indicates that the period varies. Fig. 3b shows FWHM as
a function of satellite order for the data and for two values
of period variation (some of the intensities were too low for
accurate FWHM measurement). These results are consistent with
the results of the simulations of the peak intensities, but
agreement is not perfect. Details of the peak profile, however,
can be treated adequately only by using dynamical diffraction.
CONCLUSIONS
A modified kinematical model, which corrects for normal
absorption and extinction, is used to interpret the rocking
curves of GaAI/AlGaAs SL's of moderate thickness. The
experimental results could be matched closely using a two-
sublayer structure with sharp interfaces and slightly varying
periodicity. The difference between expected structure and
that from the rocking curves and simulations illustrates the
importance of x-ray diffraction during commissioning of MBE and
other thin film growth apparatus.
ACKNOWLEDGEMENTS
The authors wish to thank Polaroid Corporation for their
support of the MBE growth runs and Mr. Kenneth Maloney for his
support and encouragement of this work.
REFERENCES
1. L. Esak, IEEE J Electronics, 22: 1611 (1986).
2. N. Ho1onyak, Jr., R.M. Kolbas, W.O. Laidig and B.H.
Vojak, J ~ Phys, 51: 1378 (1980).
3. W.T. Tsang, ~ Phys Lett, 38: 204 (1981).
4. V.S. Speriosu and T. Vreeland Jr., J ~ Phys, 56: 1591
(1984) .
5. P. Auvray, M. Baudet and A. Regreny, J ~ Phys, 62: 456
(1987) .
6. J.M. Vandenberg, M.B. Panish, H. Temkin and R.A. Hamm,
~ Phys Lettr, 53: 1920 (1988).
7. J.M. Baribeau, Song Kechang and K. Munro, ~ Phys
Lettr, 54: 323 (1989).
8. P.F. Fewster, J ~ Cryst, 21: 524 (1988).
9. A.T. Macrander, G.P. Schwartz, and G.J. Gualtieri, J
~ Phys , 64: 6733 (1988).
10. S.J. Barnett, G.T. Brown, D.C. Houghton and J.M.
Baribeau, ~ Phys Lettr, 54: 1781 (1989).
11. B.K. Tanner, this volume
12. B.W. Batterman and H. Cole, Rev Mod Phys, 36: 681 (1964).
13. W.J. Bartels and W. Nijman, J Cryst Growth, 44: 518
(1978) .
14. J. Hornstra and W.J. Bartels, J Cryst Growth,44: 513
(1978) .
15. P.F. Fewster and C.J. Curling, J ~ Phys, 62: 4154
(1987) .
16. C.W. Wie, J ~ Phys, 66: 985 (1989).
17. M. Ettenberg and R.J. Paff, J ~ Phys, 41: 3926 (1970).
18. E. Estop, A. Izrael and M. Sauvage, Acta Cryst, A32: 627
(1976) •
19. M.C. Joncour, M.N. Charasse, and J. Burgeat, J ~ Phys,
56: 1591 (1984).
20. P.C. Huang and S.R. Stock, simulation similar to C.W. Wie,
T.A. Tombrello and T. Vreeland, Jr., J ~ Phys, 59: 3743
(1986) •
21. D. Chrzan, J ~ Phys, 59: 1504 (1986).
X-RAY DIFFRACTION ANALYSIS OF SiGe/Si SUPERLATIICES
M. Fatemi, S. Prokes and B. V. Shanabrook, Jr.
U.S. Naval Research Laboratory

Washington, DC 20375-5000
and K.L. Wang
University of California at Los Angeles

Los Angeles, CA 90024
IN1RODUCfION
It is well known that x-ray diffraction techniques provide one of the most
direct means of analyzing superlattice periodicity, layer thickness, strain, and
defect structure. This suitability of x-rays is a consequence of the fact that most
superlattice periods are in the range of 10 to 50 times the typical wavelength
(CuKa 1 =1.54 A) and are hence measurable by x-ray diffraction, and also that x-
rays are non-destructive within the energy and dosage ranges needed for these
studies. Applications of x-ray techniques to superlattices have been discussed in
many publications in the open literature. 1- 8
A number of physical and device-structural parameters can be investigated

with superlattices of proper composition. For example, the diffusion coefficient
of Si in Ge or Ge in Si can be obtained by examining the annealing effects of
SiGe/Si superlattices. Similarly, AlAs/GaAs superlattices can be studied both for
their familiar buffering effect in the epitaxial growth of III-V compounds on Si,
and for examination of roughness at the AlAs/GaAs interfaces as a function of
growth parameters. Interface roughness, whose effect is magnified by the pres-
ence of multiple superlattice layers is useful in the studies of bonding in strained-
layer systems.
The experimental techniques used for these measurements are single-

crystal diffractometry on powder diffractometers and double-crystal rocking
curve methods. The former technique increases the recorded intensity, and the
latter increases the resolution. The intensities recorded on the double-crystal
diffractometer are in practice obtained under proper crystal tilts and orienta-
tions, and the related errors of measurement are thus minimized. However, the
same degree of accuracy cannot be expected from "single crystal" measurements
on the powder diffractometer. This instrument has only limited degrees of
freedom so that the integrated intensity from a single crystal may show
considerable variation depending on its orientation in the beam. As these
intensities are used in calculating important physical parameters such as the

Edited by C.S. Barrett el 0/.
diffusion coefficient, it is essential that the measurements be free from large

random errors and also from any systematic errors which might not be subtracted
out in data processing. We will show that in addition to the physical condition of
the crystal itself, there are several other factors such as the beam alignment, the
crystal mounting procedure, extraneous surface coating on the crystal, and
variations in the x-ray output with time that can affect the measured intensities.
Hence the associated random variables from these sources must be made as small
as appropriate in order to determine the physical parameter under investigation.
In general, the validity of experimental data rests upon two broad groups of
factors, namely (a) the superlattice and sample preparation procedure, and (b)
the instrumental and physical constraints of the diffraction technique employed.
These two sets of factors will be considered in the following sections, and
comments and observations will be provided on obtaining interpretable data, free
from ambiguities.
TYPICAL DIFFRACTION PATTERNS
A reasonably accurate measure of the superlattice parameters may be ob-

tained from powder diffractometer scans which often show several satellite peaks
near the characteristic (002) or (004) peaks of the substrate. The satellite
intensities are enhanced by the same mechanism as the peaks of the substrate,
that is, the structure factors associated with those lines are large enough to yield
detectable intensities. For the same reason, the satellite intensities decrease as the
angular separation from the main superlattice line increases. Clearly there is no
requirement for symmetrical intensity distributions around the main peak of the
superlattice. Figs. 1 and 2 show the diffraction patterns obtained from AlAs/GaAs
on GaAs and SiGe/Si on Si, respectively. It can be seen that the distribution of the
satellite peaks in the former system is more symmetrical than in the latter. The
appearance of Ka doublets in the SiGe/Si system is due both to better growth
conditions and to larger diffraction angles which increase the dispersion. We
note, however, that superlattices grown from alternate thin layers of amorphous
materials such as W-C and V-C and deposited on another amorphous substrate,
such as glass, do not follow the same arrangement as SiGe/Si on Si or AlAs/GaAs
M. FATEMI ET AL. 77
Si(400)
(Si-Ge):(Si) on Si
_ 4 SG35V2H
CI SLiOOL)
.9
1++++++++++++~~~~r-~~~~~~~~++++~
60 62 64 66 68 70
ANGLE 28, (degrees)
Fig. 2 Superiattice peaks about the Si(004) Bragg reflection in the SiGe-
Si/Si system.
on GaAs, and would hence require direct low-angle Bragg reflection measurement
appropriate to their periodicity starting, typically, with order n=1.
The angular positions of the satellites enable the periodicity of the super-
lattice to be calculated and compared with the epitaxial growth parameters. Com-
putational methods can also be used to fit the experimental data in terms of rela-
tive chemical composition and interface roughness (see below).
It is generally assumed that the average SL peak coincides with the main
substrate peak, since the two peaks cannot be resolved on a single crystal
diffraction pattern. Using high resolution x-ray double-crystal diffractometry,
however, the small but finite separation between the two peaks becomes more
easily detectable. This angular separation can be used for an estimate of the aver-
age composition of Al in AIAs/GaAs or Ge in SiGe/Si superlauices. 4
PROBLEM AREAS
Sample Preparation
In general, there are variations across the wafer in the superlattice pa-
rameters including the periodicity, composition and layer thickness caused by
flux variations during the epitaxial deposition. These variations introduce addi-
tional broadening and spurious detail in the x-ray diffraction profile, which in
turn may complicate the analysis. For this reason alone the choice of smaller
samples over the larger ones is preferred. However, as described below there are
also other considerations for choosing smaller samples.
Sample Mounting and Geometry Problems
The fact that strained-layer depositions produce bending stresses in most

epitaxial growths, is well known. These stresses cannot generally be removed
from the sample during x-ray measurements, and sample mounting presents a
particular source of difficulty in obtaining consistent results and interpreting
the intensities. Sample bending strongly influences the shape of the diffraction
profile, and the effect is more apparent with the powder diffractometer than the
I
I,
,
I
,
(B)
PLATE
Fig. 3 Demonstration of the effect of bending strain in single crystal

diffraction measured by powder diffractometry. In position A, the
system is set to receive the diffracted beam from the lower part of
the crystal; the upper part does not diffract. In B, the sample holder
has moved by ~9=9z-91' as the detector angle moves by 2~9. Although
the upper part now diffracts, the detector cannot receive the
diffracted beam since it is no longer at the proper 29B.
double diffractometer simply because the former uses a much larger beam size
and sample area. Associated with this problem is the manner in which the sample
is affixed to the mount several times during the course of the investigation. It has
been found that practically any adhesive causes some degree of strain and may
unpredictably change the relative alignment of the beam with respect to the
sample. Fig. 3 shows a sketch of such an occurrence for a sample which for
simplicity has been assumed to have been bent into two flat regions so that either
one or the other may be oriented at the proper diffraction angle with the detector
set at the angle 29 B .
"'I:::=' 6E5
0 SG35/ l2xl2mm
i:l Original paraffin mount
...
~=
<Il
5E5 Paraffin remelted
&
~ 4E5
U
6
i-
.;;:: 3E5
J 2E5
l
4)
>
.~
<l 1E5
Il:::
0
J
1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0
Detector Angle, 29, degrees -+
Fig. 4 Powder diffractometer scan of the first superlattice peak about the
(000) reflection. The measurements were taken on a 12mm x 12mm
sample, as a function of wax mounting.
M. FATEMI ET AL. 79
6E5~--------------------------------,
SG35/ Sample size: 12x12~

5E5 8 - scan
Original paraffin mount
o
.;;)
4E5 ..... Paraffin remelted
c
] 3E5
d)
>
.~ 2E5 I'
~
1E5
0.5 0.6
j
0.7 0.8
~"
0.9 1.0 1.1 1.2 1.4
1.3
Specimen Angle 8, degrees
Fig. 5 Powder diffractometer 8 -scan of the first superlattice peak about
(000). The sample and mounting are identical to those of Fig. 4, but
the detector angle 28 is fixed.
To reduce the strain caused by mounting, several substances were tested as

possible adhesives. Paraffin wax was found earlier to be unsatisfactory due to its
unusual and spontaneous change (possibly crystallization) after settling over a
period of approximately 24 to 48 hours.9 A comparison of two different profiles
obtained by remounting a sample with paraffin is shown in Fig. 4. The change in
the intensity is mostly due to the extent to which the crystal is aligned in the
beam. A more descriptive picture of this alignment problem is seen in Fig. 5
where the same sample has been scanned with respect to the angle 8 alone,
keeping the detector angle fixed at the proper 29. A much better choice was found
to be petroleum jelly which remains relatively stable over long periods and also
possesses just enough surface tension to support the weight of the crystal without
introducing additional stresses of its own.
Another important effect is the scattering of thin metallic layers which

are sometimes deposited on a sample surface by sputtering, etc. Particularly in
the case of low-angIe scattering where the contribution of the surface layer is
'80 2.8E5 Ni-Capped

~ 2.4E5
'".... Uncapped
8- 2.0E5
~
8 1.6E5
.~ 1.2E5
c
.s
..s
d)
8.0E4
>
~
';:l 4.0E4 SG35
~ t-- '.
( ...
0.0
1.0 2.0 3.0 4.0 5.0
Detector Angle, 29, degrees ~
Fig. 6 Low-angle 9-29 scans (about (000» of the first three harmonics of
the SiGe/Si superlattice, showing the effect of a 100A Ni cap on the
scattering in tensi ties.
8E3 I,
II
"
OJ
I
-g 6E3 I
0 I I
~ I I
...'" ,
I I
I
8. I I
j I
II
I
I
I
20 arc-sec
1------1
U I
.~ 4E3 Before Anneal I
I
I
j
I
I I
I
I
0
I After Anneal
.~
os 63toC/30 min
'il
~
2E3
I
\
I
\
\
\
" 20
60 40 20 0 40 60
.6.e - arc-sec
Fig. 7 (004) rocking curve from the substrate in the SiGe/Si superlattice
system (004) before and after an anneal at 631°C.
amplified. the shape of the superlattice harmonic may be significantly altered by

this component. An example of this effect is shown in Fig. 6 for the first har-
monic of the SiGe/Si system. The contribution of the surface layer is seen here to
be quite serious. and the additional component to the intensity should thus be
corrected through any reasonable procedure available. or the data be taken using
an uncoated sample.
Variations in the X-Ray Power
A third equally important source of error is the vanatlOn of x-ray output

particularly during the warm-up period. and also during periods of extreme
change in the atmospheric pressure. Typical warm-up periods of approximately 1
hour are necessary to ensure that the x-ray tube output is stabilized.
TYPICAL RESULTS AND DISCUSSION
Effect of Annealin& on the Substrate (400) Diffraction Line
Assuming that the "errors" in intensity due to differences in sample

mounting and orientation have been eliminated. it is then necessary to ascertain
that other observed variations in intensity are related specifically to the physical
parameter being examined. Thus. intensity calibration becomes an important
issue. A natural tendency is to use the (004) diffraction line from the substrate of
the sample itself as an internal calibrator. tacitly assuming that this quantity
M. FATEMI ET AL. 81
remains unchanged over the course of investigation. However, we have observed

a significant difference between pre-anneal and post-anneal intensity profiles of
the substrate which we report here. While the integrated intensity based on both
powder diffractometer and double-crystal diffractometer is greatly increased, Fig.
7 shows that after the anneal the double crystal peak intensity is reduced, and the
tails of the diffraction profile are significantly enhanced. Along with the
relatively small broadening in the rocking curve after anneal, this behavior, ob-
served for anneal temperatures from 600°C to 700°C, suggests a process similar to
the scattering of point defects and clusters in single crystals. An earlier example
of this effect has been observed in the rocking curves of neutron-irradiated
copper crystals showing broad tails and reduced peak intensity compared to the
unirradiated material. 10 The clustering in the SiGe/Si system may be represented
by the formation of small, nearly independent regions of slightly different ori-
entation or spacing due to relative changes in Ge concentration at the SiGe-Si
interface, thus becoming somewhat incoherent with the bulk of the substrate.
The peak intensity is reduced while the tails of the diffraction peak are extended
due to scattering from the clusters.
Numerical Calculations
X-ray diffraction profiles of superlattices can be calculated from basic

principles of optical diffraction theory II. The relative phases of the waves
scattered from various atomic planes are added to give an expression for the total
diffracted amplitude, then squared to yield the intensity. These calculations have
been applied to the superlattices used in the present work with excellent
agreement (Fig.8). The satellite intensities are affected by "interface roughness,"
which may be defined as a fluctuation of atomic layers of one component (e.g.,
AlAs) into the other (GaAs). Adjustments in this parameter may be made in the
calculation, and very good agreement with the experimental data can be obtained.
CONCLUSIONS
In this paper, several aspects of superlattice studies using x-ray diffraction

techniques were discussed. It was shown that proper care in sample handling and
diffractometer alignment is essential in obtaining reliable measurements. Sev-
eral examples were given in which significant variations in intensity resulted
IE7 SiGe:SiJSi
#SG3S simulation
IE6
.~
c:
£ IES
oS.,
>
·w
lFA
U"
II::
IE3
IE2
S9 61 63 6S 67 69 71
Detector Angle, 2&, degrees
Fig. 8 Computer simulation of the SiGe/Si superlattice powder diffraction

pattern.
under otherwise proper measurement conditions. The change in the substrate

integrated intensity after anneal was explained in terms of a "clustering" model,
consisting of small regions of varying composition or alignment in the neigh-
borhood of the superlattice/substrate interface. A typical computational method
was described and an outline of its application to interface roughness was pre-
sented.
REFERENCES
1. L.L. Chang, L.Esaki, W.E. Howard, and R. Ludeke, J. Vac. Sci. lQ., (1973) 11.
2. A. Segmiiller, P. Krishna, and L. Esaki, 1. Appl. Cryst. N, (1977) 1.
3. R.M. Fleming, D.B. McWhan, A.C. Gossard, W. Weigman, and R.A. Logan, J.
Appl. Phys. n, (1980) 357.
4. J. Kervarec, M.Baudet, J. Caulet, P. Auvray, J.Y. Emery, and A. Regreny, J.

Appl. Cryst. 11., (1984) 196.
5. V.S. Speriosu and T. Vreeland, J. Appl. Phys. ~, (1984) 159.
6. M.C. Joncour, M.N. Charasse, and J. Burgeat, 1. Appl. Phys. 58, (1985) 3373.
7. Y. Kashihara, T. Kase, and J. Harada, Jap. 1. Appl. Phys . .6., (1986) 1834.
8. M. Quillec, Springer Proceedings in Physics 13, (1986) 121.
9. M. Fatemi, J. Cryst. Growth 2.6., (1989) 316.

10. lE. Thomas, T.O. Baldwin, and P.H. Dederichs, Phys. Rev. B3, (1971) 1167.
11. M. Born and E. Wolf "Principles of Optics," 6th Ed., Pergamon Press. New
York (1980).
mGH RESOLUTION MEASUREMENT OF SURFACE MISORIENTATION IN
SINGLE CRYSTAL WAFERS
M. Fatemi
Electronics Science and Technology Division

U.S. Naval Research Laboratory
Washington, DC 20375-5000
ABSTRACT
A simple method for high-resolution measurement of surface misorienta-

tion in electronic materials is introduced. The technique combines laser optical
alignment with double-crystal x-ray diffraction to yield a typical sensitivity of
better than 1-2 arc sec. The technique can also be used to make corrections in
spectrometric measurements in which commonly ignored rocking - curve errors
may be significant.
INTRODUCTION
Recently there has been considerable interest in the microelectronics

industry to grow relatively perfect layers of III-V compounds on Si substrates, in
order to combine materials of different electronic properties into one package. It
has been proposed that an "off-axis" Si wafer in which the (001) planes are at a
small misorientation of 2-4 degrees with respect to the surface might yield more
perfect epitaxial layers compared to the well aligned wafer!. Hence, experimental
studies of the effect of misorientation on the epitaxial growth of GaAs on Si have
been undertaken, including several at NRL. In these studies, wafers with known
misorient at ions ranging from 0.010 to several degrees would be subjected to dif-
ferent growth conditions, the results to be analyzed for defect structure through'
destructive and non-destructive techniques.
Several methods for the precise measurement of misorientation angles

were investigated. The simple technique using the double-crystal diffractometer
described in this paper is the outcome of our efforts to streamline the measure-
ments on a large number of wafers, at the same time to improve the capabilities of
commercially available instruments for spectrometric applications. We describe
the fundamental concept, the details of the modification of a commercially avail-
able instrument and the role of each component in the measurement process. An
actual example of the measurement on a Si wafer will also be given.
EXPERIMENTAL CONCEPr
Consider a Si wafer whose (100) planes are misoriented with respect to the
surface at an angle cp, oriented in such a way that the incident beam and the

normal vectors to the surface and to the diffracting planes are co-planar. The
(004) rocking curve from the wafer can thus be obtained and the peak angle
recorded. If the crystal is rotated in its own plane by 180° and the process is
repeated, the position of new rocking curve peak will be displaced from the old by
twice the misorientation, and the angle </l is, therefore, immediately obtained,
even though the exact diffraction angle itself is not known. The basic reversal
concept has been used in several applications by various workers. 2 - 4 For
example, Fewster 3 has applied a related technique to the determination of lattice
parameters of epitaxial layers on substrates of similar composition. In that
application, however, the surface misorientation was subtracted out, and only the
difference between the substrate and epilayer peaks was needed. In the present
application laser alignment is used to define the direction of the crystal surface,
while x-rays are used to determine the direction of the diffracting planes.
In order for the concept to be correctly applied to the present problem, two
important conditions must hold. First, it is essential that the azimuthal rotation of
the crystal in its own plane (the 0)- motion) be reproducible within a few arc-
mins, even after several rotations about the azimuth axis. Second, the O)-axis must
be centered on the region of the crystal illuminated by the x-rays so that the same
area of the crystal remains in the beam at all azimuths. The most detailed part of
instrumental preparation, a one-time process, deals with the initial permanent
adjustment of the omega axis and the tilt mechanisms as required for all double-
crystal instruments. This alignment also removes ambiguities that often arise
when the diffractometer is used for spectrometric studies.
The exact direction of misorientation is generally not known in advance,

even in those cases in which an off-axis angle has been specified. Also, with the
crystal mounted in an arbitrary direction, the vector normals to the surface and
to the diffracting planes are not co-planar with the incident beam. Hence, two
components of the misorientation vector along orthogonal directions will be
needed. The total misorientation can then be calculated from the Pythagorean
formula.
INSTRUMENTAL MODIFICATIONS
The measurement of misorientation is accomplished by requiring that the

0)- axis intersect at the same point with the diffractometer 9 -axis, the crystal tilt
axes, and the x-ray beam. The difference in the rocking curve peak positions is
measured for two orthogonal directions in the crystal surface, one for the pair
0)=0° and 0)=180°, the other for the pair 0)=90° and 0)=270°. The measurements are
preceded with a one-time alignment of the 0) -axis in the horizontal plane which is
perpendicular to the diffracting planes of the first crystal. With this arrange-
ment, the vertical tilt of the second crystal, once set, say, for either 0) =0° or
0) = 180°, will not require further readjustment.
Fig. 1 is a sketch of the modified instrument showing all the components on

the second stage of the double-crystal diffractometer. The exploded view shows
the relationship among various translation and rotation devices incorporated in
the NRL instrument. The completed assembly is shown in Fig. 2.
The design of the second stage (Fig. 1) was based on the premise of opera-
tional simplicity without introducing misalignment errors due to mechanical
instability. It is for this reason that the crystal translations in both lateral and
vertical directions are controlled by the first and the last mechanisms, i.e., the
main lateral translation (part #1) and the vertical sample translation (part #8),
respectively. The lateral translation stage supports the entire weight of the
second stage and can be used to select various test points of the sample along a
horizontal strip in line with the x-ray beam. On the other hand, translation along
the vertical line is accomplished by the manually-operated micrometer (part #7).
M. FATEMI 85
Fig. 1 Exploded diagram of the components controlling the motion and align-
ment of the second crystal. See text for a description of each part.
Attached to the main lateral stage is the main vertical slide (part #2). This mech-
anism is used in the preliminary alignment of the instrument to compensate for
changes in the height of the crystal during the adjustments in the tilt of the 00-
axis. Next, the foreaft translation stage, part #3, controls the position of the
crystal surface in the x-ray beam. The main 00- axis control, part #4, is carried by
the fore-aft slide and supports, in turn, the motor-driven 00 rotation mechanism
(part #5). The sample-centering translation slides (part #6) and sample tilt
controls (part #7) are part of a commercially-available eucentric goniometer.
Since the axes of the sample tilt controls must lie in the sample surface,
appropriate spacers are needed to compensate for the extra distance between the
outer face of the goniometer and the tilt axes. Some of this space is taken up by
Fig. 2 Completed second crystal stage installed on a Blake double crystal

diffractometer.
the mounting plate and micrometer used to vary the sample height (part #8). It is
absolutely essential that prior to any of the alignment steps described below,
spacers of correct thickness are used with each wafer. We also assume that the
vertical a-axis of the second crystal stage has already been determined, that the
incident x-rays (from the first crystal) intersect this axis horizontally, and that
the tilt center, i.e. the intersection of the two tilt axes (part #7) is in line with the
co-axis. This last operation can usually be performed "on the bench" and requires
an iterative adjustment of sample translations (part #6) and rotation about the co-
axis.
Component Calibration
Prior to any alignment, the interaction among the three critical compo-
nents, i.e. the co - axis tilt control, the main height control, and the sample
goniometer tilt mechanisms must be determined and calibrated. The calibration
process, taking advantage of both x-rays and laser optics, is as follows.
Any change in the tilt of the crystal using the co - axis tilt mechanism
affects the height of the test area. The resultant shift must then be corrected
using the main height control. The change in the sample height as a function of
variations in the co -axis tilt may be calibrated by passing the incident x-rays
directly through a narrow slit at the sample position. The beam intensity is kept
constant by adjusting the height, while the co -axis tilt screw is turned in regular
increments. The height-vs-main tilt calibration can, therefore, be easily made.
However, since adjusting the main height does not change the crystal tilt, this tilt
may be reset to the original value using the sample tilt controls (on the eucentric
goniometer). In this fashion the readings of the sample tilt help calibrate the
angles associated with the co-axis tilt mechanism.
In larger wafers the effect of warping becomes particularly obvious with

visible distortions in the laser image, making it difficult to focus the beam on
cross-hairs (see below). In order to reduce the effect of the surface curvature on
2ND CRYSTAL 2ND CRYSTAL
.-J.----. LASER BEAM
( a) (b)
• w
c=:I7--. ~
.~
LASER SOURCE
CROSS HAIRS CB-.
FRONT-SURFACE
MIRROR
2ND CRYSTAL
CB--,--~
Fig. 3 Initial laser optical alignment of the co-axis with respect to the second
crystal. (a) co =0° orientation. The laser spot is focused at point A on
"distant" cross-hairs. (b) With a rotation of the crystal to co=180°, the
laser spot moves to point B. (c) The beam is brought to the half-way
point C by readjusting the sample tilt goniometer.
M. FATEMI 87
the measurements, It IS important to limit the test area of the crystal to within 2-3
mm, using a ring of opaque material surrounding the region, centered on both
the co and the tilt axes. A fine laser beam is centered in the ring and is reflected
toward a front-surface mirror at a distance several meters away. For the optical
alignment described later, the beam is focused on "cross-hairs" mounted on the
wall at a convenient location as close to the crystal as possible. The double
reflection increases the sensitivity of optical alignment to changes in the crystal
position. It is also necessary to ensure that the laser beam remains within the
specified area on the crystal for all rotations about the co- axis. Thus, if the angle
co is changed by 180°, and a significant shift in the position of the laser spot with
respect to the ring is noted, the alignment of the region with respect to the co-axis
must be rechecked, as well as the position of the laser beam on the crystal.
Optical Alignment
In this step the co - axis is brought to a direction perpendicular to the crystal

surface (Fig. 3). The tilt controls of part #6 are used to place the reflection of the
laser spot on the cross-hairs. The crystal is rotated about the co-axis by 180°, and
the shifted spot is returned to a position halfway between the old and the new,
using the same mechanism. The remaining half is aojusted by repositioning the
direction of the incoming beam and changing the angle e by an appropriate
amount. Note that the actual value of e is unimportant. By repeating this process
several times, a point will be reached when the laser spot will remain nearly sta-
4
(a 1 (b1
DIFFRACTING PLANES
¢-o:
n1
----j,::::,CX'
w=o I w=180· I
2ND CRYSTAL TILT: 2ND CRYSTAL TILT:
¢+o: DOWN ¢. a. UP
FOR ROCKING CURVE FOR ROCKING CURVE
~ (c 1
1 LOWER W.ASSEMBLY 2 RAISE 2ND CRYSTAL

BY ANGLE 0: . ASSEMBLY BY HEIGHT h.
Fig. 4 X-ray alignment of the co-axis with respect to the spectrometer plane.
The horizontal dashed line is parallel to the direction of incoming x-
rays arriving from the right. The solid line below it denotes the co-axis.
(a) Rocking curve for co=O° is obtained with the crystal tilted downward
by cp+ a. (b) For the rocking curve at co = 180° the crystal tilt is corrected
upward by cp-a. (c) The main tilt is lowered by a = 1/2 the total
difference between (a) and (b). The entire assembly is then raised by
the amount of sample drop (h).
2ND CRYSTAL 1ST CRYSTAL
tP"'
<l>Vj
w=oo
.. n1
U
jf="' ..
U
"1
r<l>v
\=::,Q,
A
.", U
Fig. 5 When the x-ray alignment is complete, the diffracting planes remain
normal to the 00- axis at both azimuths of 0° and 180° with only one tilt
adjustment.
tionary on the cross-hairs, except for possibly a deviation on the order of 10-20
arc-sec which may be difficult to remove by this procedure. However, as seen
below, as long as the shift in the laser beam is visible, one may correct for its
effect with a simple analysis.
X-Ray Alignment
The oo-axis should also be made "parallel" to the horizontal plane of the
diffractometer. To perform the x-ray alignment the motorized crystal tilt controls
are adjusted to obtain a rocking curve from the test area. The azimuth is then
changed to 180 0 and the process repeated. The vertical tilt angle for 00=0° is
compared with that of 00 = 180°. One-half the total change is compensated by an
appropriate adjustment of the oo-axis tilt control. The sample tilt control is next
set at the average tilt reading for the two azimuths, and the change in the crystal
height is corrected as in Fig. 4. As before, the procedure is repeated to remove
possible residual errors. When this stage of alignment is complete, the crystal tilt
will be properly set for rocking curves at both 00=0° and 00=180° (Fig. 5).
Correction of Residual Misalignment
As noted earlier, the laser-optical alignment of the oo-axis may reach a

point where the residual shift of the laser spot from the cross-hairs cannot, due to
mechanical limitations of the oo-control, be further removed. When this happens,
the following analysis can be used to correct the data.
Fig. 6 shows a simplified picture in which the laser source is first directed
at the crystal, oriented at "00=0°." For this configuration (A), the surface is drawn
perpendicular to the beam so that the reflected beam returns directly to the
source. In the actual process the reflected beam for 00 =0° is adjusted for the
center of cross-hairs; that is, the incident beam will not be perpendicular to the
crystal surface. Assuming that the 00- axis is shifted with respect to the crystal by
a small angle 0, a 180° azimuthal rotation causes a shift of 40 on the cross-hairs.
Were it possible to remove the misalignment, the crystal would be rotated
clockwise by an angle 0 into the oo-axis. The reflected beam in turn would shift by
M. FATEMI 89
CRYSTAL SURFACE
w=180°
\
(B)
A
B
B
+ LASER
SOURCE
Fig. 6 Correction of residual misalignment of the second crystal with respect

to the co-axis following laser-optical alignment (see text).
20, to the midway position (point C in the Figure), and remain there for both co=O°
and co=180° positions. In the absence of that capability, however, one may still
accurately measure the angle of shift by observing the distance the laser spot
moves using the calibrated a -drive. Clearly, the angular shift of the x-ray
diffraction peaks follows a similar pattern. Hence, in configuration B the angular
reading of the a-scale would be too low by 1/2 the observed shift in the laser spot,
namely, by 20. The factor 2 should not be misleading, since the diffraction angles
at the two azimuths are averaged, thus only adding /) to the correction.
THE MEASUREMENT
With the co-axis aligned and the tilt axes contained in the sample surface,
the area to be examined is outlined using an opaque material such as photoresist.
The mounted sample generally is in the form of wafers whose front and back sur-
faces are nearly parallel. Hence, only small corrections in the surface orienta-
tion need be made. The laser beam will again be used to define the direction of the
surface. When first mounted on the sample plate, the wafer will shift the laser
beam both laterally and vertically with changing azimuth. The object is to adjust
the wafer so as to keep the spot laterally stationary on the cross-hairs. Vertical
deviations above or below the cross-hairs are not critical. In this mode, two
rocking curves at co =0° and co = 180° are obtained from the wafer. The peak sepa-
ration gives twice the component of the misorientation angle (4)h) in the horizon-
tal direction. The wafer is next rotated to the azimuth co=90°, and the procedure is
repeated, again obtaining two rocking curves after centering the laser beam lat-
erally. The new difference in the peak positions is twice the misorientation
component (4)u) in the vertical (90-270) direction. It is known that for small
(commuting) rotation angles the total misorientation angle is given by
In a typical case, a 75-mm Si wafer specified as "on axis to within ±0.5°" was
measured by this technique. The components -Ph and CPu were found to be +1260
and +330 arc-sec, respectively, with the primary flat of the wafer placed verti-
cally on the right. Both numbers were within ± 10 arc-sec. Hence, the total angle
cP was calculated to be 1300 arc-sec in the direction of 14.7° from the x-axis. Note
that an accuracy of 1-2 arc-sec could have been obtained with only a 1/2-hour
additional effort. To check the reproducibility, the wafer was rotated by 15°
clockwise in order to bring the misorientation vector in the horizontal plane.
The measurement was repeated, and a total misorientation of l300 arc-sec was
obtained along the new horizontal line.
CONCLUSIONS
In this paper a fast and simple double diffractometer method to measure

surface misorientation in single crystal wafers was described. The alignment
process for important motions in the double crystal diffractometer and spectrom-
eters, e.g. sample tilt and co-rotation, was discussed in detail, and a method to
eliminate persistent errors of alignment caused by instrumental limitations was
presented. Finally, an example was given to demonstrate the quality of results
attainable with this technique.
ACKNOWlEDGEMENTS
The author thanks Mr. M.C. Geiger for assistance in the x-ray measure-
ments, Mr. D.F. Peters for his skillful fabrication of parts for the modified second
stage, and Ms. Mary Daley for typing the manuscript.
REFERENCES
1. K.C. Hsieh, M.S. Feng, and G.E. Stillman, Proc. Materials Research Soc., 116,
261 (1988).
2. S. Kikuta, K. Kohra, and Y. Sugita, lap. 1. Appl. Phys. l 1047 (1966).
3. P.F. Fewster, l. Appl. Cryst. II 275 (1982).
4. M. Fatemi, 1. Cryst. Growth 2.Q. 316 (1989).

SURFACE AND ULTRA-THIN FILM CHARACTERIZATION BY
GRAZING-INCIDENCE ASYMMETRIC BRAGG DIFFRACTION
T. C. Huang
IBM Research Division, Almaden Research Center

650 Harry Road, San Jose, CA 95120-6099
ABSTRACT
An effective technique using grazing-incidence X-rays and asymmetric-Bragg diffraction

(GIABD) for the characterization of crystalline phases on surfaces and structural depth-
profiles in thin films is described. The application of the GIABD using both X-ray and
synchrotron radiation sources for the analysis of an iron-oxide magnetic thin film previ-
ously reported to have an unexpected magnetically-dead layer is disc1..ssed. The X-ray
diffraction analysis using the GIABD and the conventional 0-20 scanning techniques de-
tected an anti-ferromagnetic hexagonal a-Fe203 on the surface and a ferromagnetic
tetragonal y-Fe203 in the bulk of the film, respectively. The synchrotron diffraction anal-
ysis using incident angles below and above the critical angle of total reflection
quantitatively determined the structural depth-profiles of a-Fe203 and y-Fe203 in the film.
The a-Fe203 surface layer was found to be 90±15A thick on the average with an
a-Fe 20 3 to y-Fe 20 3 transition width of no more than ±60A.
I:\,TRODUCTIO~
The study of surfaces and ultra-thin films is a growing and important application of the
X-ray diffraction technique (XRD). The conventional 0-20 scanning or symmetric
Bragg-diffraction geometry is not suitable for characterizing this type of materials because
the X-ray path lengths through a surface layer or ultra-thin film are too short to produce
adequate diffraction intensities relative to the bulk or the substrate. The path length in
a film can be increased or the penetration depth of the X-rays-can be decreased by an
order of magnitude using a fixed incident angle of a few degrees such as that used in the
Seemann-Bohlin geometry.1 To further limit the incident X-rays to the top surface layer,
a grazing-incidence geometry with an incident angle of less than one degree is required.
Several techniques which utilize grazing incident X-rays for studying surfaces and thin
films have been reported. For example, the reflectivity/interference technique has been
used successfully for determining density, smoothness, and thickness of thin films.2-4 The
grazing-incidence diffraction method has been used to study the in-plane crystallography
of epitaxial films.s The grazing-incidence scattering technique has been used extensively
for the surface structure determination of two-dimensional solids. 6 ,7 The grazing-incidence

92 II. XRD CHARACTERIZATION OF POL YCRYST ALLINE THIN FILMS
geometry has also been used for surface and near-surface X-ray spectroscopic studies of
trace elements (in the ng!g range),8-IO elemental depth-profiling,II.12 short range order /
local atomic structure,13 surface oxidation and corrosion,14 etc.
Recently, a GIABD technique has been developed for the determination of crystalline
phases on surfaces and structural depth-profiles in thin films. IS -18 In this paper, the basic
principles, the experimental techniques, and the results of characterizing iron-oxide thin
films are discussed.
THEORETICAL BACKGROUND
For X-rays, the refractive index of most materials IS slightly smaller than one, the
refractive index of air, and can be calculated from
n = 1 - t5 - iP = 1- (1 ),
where No is the Avogadro's number, e the electronic charge, me the electronic mass, c the
velocity of light, Z the atomic number, A the atomic mass, p the density, ,.! the X-ray
wavelength, and J-t the X-ray linear absorption coefficient.
When an X-ray beam incident from air onto a material with an index of refraction less
than one, there is a critical angle (a c = j2i) below which X-ray total reflection occurs.
Typical values for the critical angle are in the 0.2° - 0.6° range for"! = 1.54A. At incidence
angles less than a c' the incident X-ray beam is evanescent within the material and pene-
trates only the top 100A or thinner layer. As the incident angle a increases and ap-
proaches a c' the penetration depth increases rapidly and reaches that expected from
normal absorption at a»a c (i.e., D(a)= sina/Il)' The lie penetration d<!pth is given by
D(a) = ("!/4n) {[ )(a 2 - a~)2 + 4p2 + a~ - a 2]/2}-1/2 (2).
The penetration depth in Fe2 0 3 as a function of IX calculated from Eq. (2) is plotted in
Fig. 1.
6000
~ 4000
o
A = 1.54 A
J1 = 1175/cm
3 4 5
a (0)
Fig. 1. The X-ray penetration depth normal to the surface of Fe 20 3 as a function of a.

The full line is calculated from Eq. (2), and the broken line from D( a) = sinal J-t.
T. C. HUANG 93
The diffracted beam, which originates from this region of variable depth, can be used
for crystalline phase and structural depth-profile determination of surfaces and ultra-thin
films. The diffracted intensity of the reflection i from material j can be calculated by
Iji cx ) = Cjj I E~(cx) I f ~(t)

o
tf
ex p [ 0(:) ] dt (3)
where
IE~(cx) I = 4cx 2/[(p + cx)2 + q2] (4)
P = J [J(cx 2 - cx~)2 + 4[12 - cx~ + cx 2 ]/2 (5)
q=J[J(cx2-cx~)2+4fP +cx~-cx2]/2 (6)
C ij is a proportional constant for reflection i of material j, Eo the normalized electric field

at the surface, t f the film thickness, and ~(t) the structural depth-profile of material j.
Thin films that consist of more than one phase with depth-dependent concentrations
will produce diffraction patterns with intensities varying with the incident angle. Using
equation (3), the diffraction intensities Ij(cx) can be calculated for an assumed structural
depth model. These calculated intensiti6s can then be least-squares fitted to the exper-
imental diffraction intensities obtained at different incident angles to determine
quantitatively the parameters of the profile ~(t) of the phases.
EXPERIMENTAL TECHNIQUE
The geometry of GIABD is shown in Fig. 2. The thin-film specimen is fixed at a grazing
angle with respect to the incident X-ray beam. The detector is scanned along the 28 circle
in the vertical plane of a diffractometer to record the asymmetrically Bragg-diffracted X-
rays from crystal planes that are inclined to the specimen surface.
Incident X-Rays \
~ ____ ~~~~~-=~====~~~
a(fixed)
Monochromatic ,
f
Thin Film
Substrate
Fig. 2. Schematic representation of the G IAIlD geometry.

94 II. XRD CHARACTERIZATION OF POL YCRYSTALLINE THIN FILMS
The GIABD measurement can be obtained using either a conventional rotating-anode

X-ray or a synchrotron radiation source. The former can be used for routine structural
identification of surfaces. The latter with its parallel and tunable X-rays is most suitable
for structural depth-profiling of surfaces and thin films.
APPLI CA TI 01\S
The G IABD technique has been used successfully for characterizing single- and multi-
layer thin filmsY-18 An example of using GIABD for surface and depth-profile analysis
of iron-oxide thin films are given below.
Thin y-Fe203 films with good magnetic and mechanical properties suitable for high
density magnetic recording application can be prepared in a number of ways. One of the
most effective methods involves an initial formation of an intermediate iron-oxide,
Fe304, in an as-deposited film by reactive sputtering of an Fe target in a carefully con-
trolled Ar-02 atmosphere, and then followed by a high-temperature post-oxidation in air
to complete the conversion to y-Fe203.19 In 1986, a polarization neutron-reflection
depth-profile analysis of sputtered iron-oxide thin films revealed a previously unreported
magnetic behavior of a post-oxidized film.2o A thin magnetically-dead layer was detected,
the top 150A layer of the post-oxidized film, whereas the as-deposited film had uniform
magnetic properties throughout its 2600A depth. A structure analysis of the surface and
the bulk of the films is thcreforc important for the understanding of the observed but
unexplained magnetically-dead layer.
The oxidation of face-centered cubic Fe304 to tctragonal y-FC203 is a complicated

process, and a detection of an intermediate phase with a simple cubic structure was re-
ported. 21 XRD patterns taken at successive stages of oxidation showed that the original
face-centered cubic spinel structure of Fe304 transformed into a simple cubic structure
when the Fe2+ cation content was reduced from 33% to below 22~/o of the total Fe cation
content. Further oxidation caused more conversion of Fe2+ into Fe3+, and a tetragonal
y-Fe203 was eventually formed when Fe 2 + was reduced to below 8.5'%. Computer-
simulated diffraction patterns of these three iron-oxides are plotted in Fig. 3.
(311)
33-22% Fe 2+
Fe 3 0 4 -fcc
1311)
:0
OJ 22-8.5% Fe 2+ Fig. 3. Computer simulated Cu
.~ Simple Cubic Ka XRD patterns: top, face-
co 1220)
E centered cubic spinel Fe3 0 4 ;
0c 5;::
o~ middle, simple cubic iron-
~£'l
oxide; and bottom, tetragonal
1313) y- Fe20 3.
8.5-0% Fe 2+
'Y-Fe203-Tetragonal
1220)
20 30 40 50 60
'2e
T. C. HUANG 95
Apart from small shifts and some intensity changes, the transformation from a face-
centered cubic spinel to a simple cubic or a tetragonal structure has generated several
weak "superlattice" reflections, such as the (300) and (310) peaks of the simple cubic and
the (214) peak of the tetragonal phases. The presence or absence of these "superlattice"
peaks can be used to distinguish these phases.
The application of G IABD to the characterization of the iron-oxide films was done
using both Cu-target X-ray and synchrotron radiation sources; the results are discussed
below.
Analysis Using Conventional Cu-KG( X-Rays
The basic structure of the post-oxidized film was first identified using the conventional
8-28 scanning technique. The XRD pattern, plotted in Fig. 4, shows a set of relatively
broad thin-film peaks superimposed on a sharp and intense Si(lll) substrate peak at
28.4°. The presence of the strong (214) peak at 28° and seven other weak peaks allow for
a positive identification of the y-Fe203 phase in the film. Because of preferred orientation,
the relative intensities of these peaks are different from those of a randomly oriented
powder specimen. ;\10 second phase was detected in the pattern, probably because the
X-ray path lengths through the surface layer are too short to produce surface diffraction
with adequate intensities relative to the bulk of the film. Therefore, it was necessary to
use the G IABD technique for a surtace-structure determination of the film.
The GIABD pattern of the post-oxidized film was obtained using a modified Rigaku
thin-film goniometer. To increase intensities, a 12-kW rotating Cu anode X-ray source
was used. A bent graphite incident-beam monochromator was placed btfore the specimen
to remove the Cu KP and unwanted radiations. The specimen was fixed at an incident
angle ofO.3±O.2SO. A data collection time of over 15 hours was used to obtain a GIABD
pattern with intensities sufficient for surface structure identification. The GIABD pattern
is predominately by an usually high backgrounJ superimposed on top of a relatively weak
surface-diffraction pattern .. The background intensity decreases monotonically with in-
creasing 28 and was caused by the air scattering and/or the Fe fluorescence from the film.
y(214) Si(111)
y(113)
IX1QQ
-0
<1l
.~
ro
E
a
c
20 30 40 50 60
"28
Fig. 4. 8-28 scanning Cu Ka XRD pattern of the post-oxidized iron-oxide thin film.
The net surface diffraction pattern after background is subtracted numerically is plotted
at the top of Fig. 5. It shows a new polycrystalline diffraction pattern; the y-Fe203 peaks
previously observed in Fig. 4 are absent. The new diffraction peaks match those of a
hexagonal IX-Fe2 0 3 shown at the bottom of Fig. 5. It is worth noting that the relative
intensities of the GIABD peaks also match those of the JCPDS standard pattern (PDF
#33-664) indicating a randomly oriented material (see Fig. 5).
In summary, the GIABD technique has successfully detected IX-Fe203 on the surface,
while the conventional 8-28 scanning technique has identified y-Fe203 in the bulk of the
film. The formation of an anti-ferromagnetic IX-Fe203 layer on the surface caused the
magnetically-dead layer, which had previously been observed by polarized neutron re-
flection. 2o
Analysis Using Synchrotron Radiations
To determine the structural depth-profile quantitatively, it is necessary to use a parallel

incident beam with negligible divergence. A synchrotron radiation source is most suitable
for this purpose because of its unique characteristics of parallel-beam optics, high inten-
sities, easy wavelength selection, etc.
The synchrotron diffraction analysis was performed at the eight-pole Wiggler station
VIJ-2 of the Stanford Synchrotron Radiation Laboratory.22 A Si{lll) double-crystal
monochromator was used for the selection of a proper wavelength from the continuous
synchrotron radiation source; 1.38A radiation was used initially, and a long X-ray wave-
length (i.e., 1 = 1.83A) was subsequently selected for the analysis. The GIABD patterns
were obtained using a Huber six-circle goniometer.
(104)
a-Fe 2 03
(110)
(024) (116)
(012)
(113) iii
I I
(0061 (202)
I I
~I I
20 30 40 50 60
°2{)
Fig. 5. GIABD pattern of the post-oxidized iron-oxide thin film with background
subtracted (top), and computer simulated XRD pattern of an IX-Fe203 standard (bottom).
T. C. HUANG 97
a(104)
a=O.12°
D=30'&'
"0
OJ
.~
co
E
....
o y(313)
c
a=8.0°
D=3pm
y(226)
y(213+220)
y(400)
20
Fig. 6. Synchrotron diffraction patterns of the post-oxidized film (A = l.38A).
The synchrotron diffraction patterns obtained initially with ). = l.38A and at ex = 0.12°
and 8.0° are plotted in Fig. 6. The synchrotron data positively confirm the results previ-
::msly obtained from conventional Cu-Kex X-rays by detecting ex-Fe203 0'1 the surface and
y-Fe203 in the bulk of the film .. The peak-to-background ratios, especially the pattern
obtained at ex=O.12°, where the entire incident beam was limited to the top surface of the
film, were also low because of the Fe fluorescence caused by the 1.38A radiation.
To eliminate the Fe fluorescence and to improve the peak-to-background ratios, a long

wavelength of 1.83A beyond the Fe K absorption edge was used for the structural
depth-profile analysis. Synchrotron diffraction patterns obtained with ex::;; 1.0° were re-
corded. In this region, the synchrotron penetration depth increases with ex from total re-
flection at the top 25-50A layer to a normal absorption condition with X-rays penetrating
deep into the bulk of the film. Selected diffraction patterns obtained at ex~exc (i.e.,
ex=0.312°, 0.319°, and 0.325°) are plotted in Fig. 7. At ex=0.312°, the ex(l04) peak at
40° is significantly higher than the y(313) peak at 46°. As ex increases by o.oor to
0.319°, the y(313) peak grew to approximately equal to the ex (104) peak. The increase in
the y-Fe203 intensities made it possible to detect a third weak y(220) peak at 36°.
Another 0.006° increase in ex from 0.319° to 0.325° shows a further increase in y-Fe203
intensities, and the appearance of a fourth y(300) peak at 39°. \1eanwhile, the decrease
in ex-Fe203 intensities with an increasing ex has led to a gradual disappearance of the weak
ex(l13) peak at 49°. The reverse in relative intensities of these two phases reveals clearly
a transition from ex-Fe 20 J to y-Fe203 as the synchrotron radiation penetrated deeper and
deeper into the film.
The transition and the structural depth-profiles of ex-Fe203 and y-Fe203 were deter-
mined quantitatively from the intensities of the ex(104) and the y (313) peaks obtained at
a(104) a==O.312°
D==90A
,),(213)
~ a(113)
1J
III a==O.319°
.~ D==120A
C1l
E
.... ,),(220)
o
c ~
a==O.325°
D==20oA
30 40 50
°28
Fig. 7. Synchrotron diffraction patterns of the post-oxidized film (tl == uuA and ex ~ ex c )'
ex:S: 1.0°. I t should be noted that the ex(llO) peak is buried under the y(313) peak, and only
the net intensities of the y(313) peak were used in the least-squares refinement analysis.
The two models of the structural depth-profiles used in the least-squares refinement are:
(I) a step distribution function with a constant depth d~ at the surface for ex-Fe203, and
(2) a linear distribution function, with an average depth da and a linear width d w ' (Details
of the refinement has been given elsewhere and will not be repeated here. IS)
The best fit was obtained by a step profile and da == 90A. The observed and calculated
diffraction intensities with a da == 90A step surface of ex-Fe203 are plotted in Fig. 8. The
refinement with the linear distribution profile, however, showed that the fit is insensitive
to a small variation of d w' The maximum value of dw was found to be l20A. Combining
the results obtained from these two models, the ex-Fe203 surface was found to have an
average depth of90±ISA and a transition width of no more than ±60A.
._--1----...:-::1 ')'-Fe 20 3
10,000 25,000 Fig. 8. Plot of the experimental
intensities of the (104) re-
.~ 8,000 20,000
c: flection of ex-Fe203 (open cir-
'" cles) and the (313) reflection
:§ 6,000 15,000
-c of y-Fe203 (solid dots) as a
~
~ 4,000 10,000
function of the incident angle
c: ex. The solid curves are the
5,000 least-square fitted results ob-
tained using a step profile and
o d~ == 90A.
0.2 0.3 0.4 0.5 0.6
a (deg.)
T. C. HUANG 99
a=O.2S0
D=40~
-a
OJ
.~
co
E
o
c a=S.O°
D=2Jlm
(220)
30 40 50
°29
Fig. 9. Synchrotron diffraction patterns of the as-deposited film.
GIABD analysis of the as-deposited film has also been conducted. Synchrotron
diffraction data were recorded with (X from 0.25 to 5.0
0
Selected diffraction patterns
0
•
obtained at (X = 0.25 and 5.0 are plotted in Fig. 9. Unlike those of the post-oxidized film,
0 0
practically the same synchrotron diffraction patterns have been obtained for all (X angles
which indicate no structural change in the as-deposited film. The presence of a weak and
broad "superlattice" (300) peak at 37" of the (X = 5.0 pattern shown in Fig. 9 indicates
0
that the film is not Fe304, but has converted into a simple cubic and/or a tetragonal
iron-oxide. In terms of the degree of oxidation and the iron-cation content, the results
indicates that the film has been oxidized beyond Fe304, and has less than 22% Fe2+ and
more than 78% Fe3+.
CONCLUSION
Is has been shown that the GIABD technique can be used for the structural identification
and depth-profiling analysis of surfaces and ultra-thin films. The successful application
of GIABD using conventional X-ray and sync!lrotron radiation sources for the charac-
terization of the as-deposited and post-oxidized iron-oxide films demonstrates the effec-
tiveness of the technique.
ACKNOWLEDGMENTS
The author would like to thank S. S. P. Parkin for providing the iron-oxide films; B. R.
York for collecting the GIABD data using a rotating anode X-ray source; S. Brennan, Z.
Rek, and M. Toney for the GIABD experiments preformed at SSRL; and M. Toney for
the least-squares refinement analysis.
REFERENCES
1 R. Felder and B. S. Berry, J. App!. Cryst. 3,372 (1970).

2 H. Kiessig, Ann. Physik 10, 769 (1931).
3 N. Wainfan and L. G. Parratt, J. App!. Phys. 31, 1331 (1960); and references therein.
4 A. Segmi.iller, Thin Solid Films 18,287 (1973).
5 A. Segmi.iller, Adv. X-Ray Ana!. 29,353 (1986); Thin Solid Films 154,33 (1987).
6 P. Eisenberger and W. C. Marra, Phys. Rev. Lett. 46, 1081 (1981).
100 II. XRD CHARACTERIZATION OF POLYCRYSTALLINE THIN FILMS
7 R. Feidenhans'l, Surface Science Report 10, 105 (1989); and references therein.
8 Y. Yoneda and T. Horiuchi, Sci. Instr. 42,1069 (1971).
9 P. Wobrauschek and H. Aiginger, Spectrochim. Acta, B35, 607 (1980).
10 C. T. Yap, R. E. Ayala, and P. Wobrauschek, X-Ray Spectrom. 17, 171 (1988).
11 1. M. Bloch et aI., Phys. Rev. Lett. 54, 1039 (1985).
12 A. Iida, K. Sakurai, and Y. Gohshi, Adv. X-Ray Anal. 31,487 (1987).
13 S. M. Heald, E. Keller, and E. A. Stern, Phys. Lett. J03A, 155 (1984).
14 G. N. Greaves et aI., Daresbury Laboratory Technical Report DLjSCIjP586E, SERC,
Daresbury Laboratory, Daresbury, Warrington WA4 4AD, U.K.
15 B. R. York and A. B. Austin, Proc. APIE, X-Rays in Materials Analysis: Novel
Applications and Recent Developments, edited by T. W. Rush, Vol 690, P. 135 (1986).
16 T. C. Huang and B. R. York, Appi. Phys. Lett. 50,391 (1987).
17 T. C. Huang, M. F. Toney, S. Brennan, and Z. Rek, Thin Solid Films 154,439 (1987).
18 M. F. Toney, T. C. Huang, S. Brennan, and Z. Rek, 1. Mat. Res. 3, 351 (1988).
19 Y. Ishii, A. Terada, 1. Ishii, S. Ohta, S. Hattori, and K. Makino, IEEE Trans. Magn.
MAG-16, 1114 (1980).
20 S. S. P. Parkin, R. Sigsbee, R. Felici, and G. P. Felcher, Appi. Phys. Lett. 48, 604
( 1986).
21 K.l. Gallagher, W. Feitknedht, and U. Mannweiler, Nature 217, IllS (1968).
22 D. E. Moncton and G. S. Brown, Nuci. Instrum. Methods, 208, 579:1983).
STUDY OF lHIN FILMS AND MULTILAYERS USING ENERGY-DISPERSIVE
DIFFRACTION OF SYNCHROTRON RADIATION
R J Cemik, S M Clark and P Pattison
Daresbury Laboratory
Warrington WA4 4AD
England
ABSTRACT
We present the results of a preliminary study of the use of
polychromatic synchrotron radiation in energy-dispersive mode for the rapid
characterization of thin film and multilayer materials. This technique takes
advantage of the high intensity and excellent collimation properties of white
beam synchrotron radiation. The glancing angle diffraction geometry allows
structural depth probing as well as enhanced signal-to-noise by suppressing
substrate contributions. The technique was successfully applied to metallic
films a few hundred Angstroms thick, and to W-C multilayers.
INTRODUCTION
The technique of using a glancing incidence angle to enhance surface
SenSltlVlty in X-ray diffraction experiments is well established both for
studying single crystal surfaces (Marra et al 1979 and 1982) and thin
polycrystalline films (reviewed recently by Wagner et al 1988). When using a
divergent beam from an X-ray tube, a focussing geometry imposes severe
constraints on the range of glancing angles which can be accessed without
introducing defocussing errors and consequent line broadening. Although the
Seemann-Bohlin parafocussing geometry has been used with some success in
characterizing thin films, the poor angular resolution is a serious
limitation (York and Austin, 1986). It is evident that a parallel beam
geometry offers the possibility of improved angular resolution, and the
advantages of this arrangement for studying thin films have been demonstrated
by Lim et al (1987). The ease and versatility of the parallel beam geometry
for powder diffraction applications, particularly when using synchrotron
radiation, has been extensively documented by Parrish et al (1986 and 1987)
and Hart and Parrish (1986 and 1989). In this arrangement, the angle of the
beam diffracted by the specimen is defined by a set of long, parallel foils
positioned between specimen and detector. In this way, the specimen and
detector may be coupled or uncoupled during a scan without distorting or
broadening the reflections. For enhanced surface sensitivity, the decoupled
mode is used, and a fixed incident or glancing angle (typically less than
1°) is selected. For a given wavelength in the incident monochromatic beam,
the choice of glancing angle will determine the penetration of the radiation
into the sample (Lim et al 1987).
As an alternative to angle scanning, the sample and detector can be

fixed and energy-dispersive diffraction data can be obtained by scanning the
monochromator energy (Hart and Parrish, 1986 and 1989). The scanning of the
monochromator produces energy dispersive data at far higher resolution than
can be achieved with the usual solid state detector arrangement. However, we
wish to explore the possibilities of rapid sample characterization which can
be achieved by using the parallel beam geometry at glancing angle in
conjunction with a solid state detector. After describing the experimental
arrangement, we will present data collected under various conditions on
examples of thin metallic films and multilayers. These experiments cover a
range of lattice spacings from about lA to 50A, with data collection times of
a few minutes per spectrum.
INSTRUMENTATION
The general experimental layout is sketched in Fig.I. The incident

white beam is produced by the 5 Tesla Wiggler insertion device on beamline 9
of the SRS Daresbury. The front end of Station 9.7 consists of an evacuated
beam-pipe in which an interchangeable tungsten carbide pin-hole can be
positioned. The white beam emerges through a Be window into air. A set of
4-jaw slits positioned after the Be window define the beam cross-section
falling onto the sample. In our case, the chosen beam dimensions were 4mm
horizontal x O.1mm vertical. The sample was placed on a pair of motor-driven
precision arcs, which in turn were supported on a motor-driven XYZ-stage.
In this way, both the height and inclination of the sample relative to the
incident beam could be controlled from outside the experimental hutch.
Behind the sample, an assembly of parallel molybdenum foils of thickness
O.lmm, length 50mm and spacing O.lmm served to define the diffraction angle
and divergence of the beam reaching the solid state detector. Both detector
and foil assembly were mounted on a heavy-duty rotary table, allowing the
diffraction angle to be selected by hand before commencing the experiment.
Additional slits positioned immediately in front of the detector define the

horizontal and vertical cross-section of the diffracted beam. The incident
white beam has an intrinsic vertical divergence of about 0.1 mrad FWHM, while
the diffracted beam is constrained by the parallel foils to have a maximum
vertical divergence of 0.2 mrad. Station 9.7 is in routine use for the
collection of energy-dispersive powder diffraction data, and a more detailed
description of the station equipment and controls can be found elsewhere
(Clark, 1989).
solid state
detector
~",~t" «O,2.mdl ,[,.
28
------
t""
~--------------~---
~ .
sample ,<fJ ~ inCident white beam
(-<1 0,1 mrad)
glanCing a~gle
Fig. I Experimental layout

R. J. CERNIK ET AL. 103
3
Inllde.nt white beam spectrum
m
(throuyh 1mm2 aperture I
0~ x108
0
u
5
-
QJ
VI
.c::
-x
Cl.
:J
LL
o
o 20 40 60 80 100
Energy (keY)
Fig.2 Incident flux spectrum
The range of d-spacings which can be observed in an energy-dispersive

diffraction pattern depends upon both the chosen Bragg angle and the e
spectral distribution of the source:
dhkl = 6.199 / (E. sin e)
where E is the incident beam energy in keY and dhkl is the interplanar
lattice spacing in Angstroms. The range of energies available in the
incident white beam is shown in Fig.2. Although useful flux is present up to
about 80 keY, experiments are usually designed so that sufficient powder
peaks fall between about 15 keY and 45 keY. A typical powder pattern from an
NBS Si sample is shown in Fig.3, which was collected at a Bragg angle of 15°.
Although this is an appropriate choice of Bragg angle for a typical
polycrystalline specimen, we will see that much smaller angles are needed
when studying multilayers. It is also clear that the broad widths of the
Bragg peaks shown in Fig.3 limit this technique to crystallographic systems
of fairly high symmetry, otherwise excessive peak overlap will complicate the
interpretation of the pattern. Fortunately, most thin film polycrystalline
materials possess a suitable high symmetry (often being simple metals or
oxides).
Energy dispersive powder

16
diffraction (NBS Si)
12
VI
§ B
o
LJ
o-~
-'I--~----~I---'----'---~
10 20 30 40
Energy (keY)
Fig.3 Energy-dispersive powder pattern of Si NBS 640b

TABLE 1
Critical angle cl>c (mrad)
Energy (ke V) Cu Au
10 5.94 8.70
20 2.97 4.35
30 1.98 2.90
40 1.48 2.17
50 1.19 1.74
60 0.99 1.45
70 0.85 1.24
80 0.74 1.09
90 0.66 0.97
100 0.59 0.87
RESULTS
It is not our intention at this stage to present a detailed analysis of

any particular sample, but rather to illustrate with a few examples the way
in which this technique allows us to characterize rapidly the degree of
crystallinity of a thin film or the quality of a multilayer. In each case,
the data presented here took only a few minutes of measuring time per
spectrum during single-bunch operation of the SRS. Since beam currents in
multi-bunch operation are typically an order of magnitude higher, we will
show that it should be possible to characterize a sample with a thickness of
a few hundred Angstroms in less than a minute.
The first example is a sputtered metallic film on a glass substrate.

The film consists of a 3soA layer of eu on a 1000A layer of Au. We chose a
bilayer sample in order to illustrate the way in which depth probing can also
be achieved in an energy-dispersive experiment. It is useful to consider the
critical angles for eu and Au as a function of the energy of the incident
beam. Table 1 shows that the critical angles in the energy range between 10
(II (] SOAI I Au 11000AI on glass

lSOO
lOOO 2u _ 8~o
f = 1.7. 3,4 & 5 mrad
;><,00
7000
:J
0
u
10;00 -
1000
~oo
I~ 20 7~ 10 lS
Energy I keVI
Fig.S eu on Au bilayer at a scattering angle 28 of 20°

collected at various glancing angles
29 =20·
( u 1350},) I Au (l000'\) on glass
f = 1.2.3. 4&5
2500
mrad
o ......
...,
o
...
2000 « i
,
.. U
,
'" ' SOC

C ,
M
:::I
o c
...... .
0
..,'"
U ~
o ~
......
o ...
,UU, , ,
N ~
' 000
o "''''
...,
o
" "
U
soo
'5 2S JO lS 40
Energy (keV)
FigA Cu on Au bilayer at a scattering angle 28

of 8.5 0 collected at various glancing angles
keV and 50 ke V are of the order of a few rnrad. A glancing angle of 1 rnrad,
say, should limit the penetration of the X-ray beam to approximately the
uppermost 50A of the Cu layer. FigA shows spectra collected at a scattering
angle of 8.5 0 at various glancing angles. At a glancing angle of 1 rnrad only
the Cu(111) peak can be observed in the energy range between 15 keY and 45
keY. As the glancing angle is increased, the Au peaks rapidly become
dominant. Above 3 rnrad, the beam penetrates through both the Cu and Au
layers into the amorphous glass substrate, producing a broad hump of
scattered radiation centred around 30 keY. Increasing the scattering angle
to 20° brings many more powder peaks into the region of interest, as shown in
Fig.5. Once again, the contribution from the Au remains very small until the
glancing angle is large enough for the beam to penetrate through the Cu
layer. It is interesting to note the strong Cu(222) and, at larger glancing
angles, the Au(222) peaks in this pattern. This confirms the high degree of
texture in these sputtered films. Each of the spectra shown in Figs. 4 and 5
was collected in a measuring time of 600 seconds.
The next two examples are W-C multilayers deposited on a Si single
crystal substrate. Both multilayers consist of 30 bilayers with ad-spacing
of 28A in one case and 56A in the other. At the chosen scattering angle of
2°, the first order Bragg peaks should appear at 12.7 keY and 6.35 keY for
the 28A and 56A multilayers, respectively. The results are shown on a log-
scale in Figs. 6 and 7, where the various orders of Bragg reflections are
labelled. Again, the measuring time per spectrum was 600 seconds during
single-bunch operation of the SRS. It should be remembered that the
intensity of the incident beam beyond about 50 keY has fallen dramatically
(see Fig.2), and no correction for the incident spectral distribution has
been made. Nevertheless, diffraction peaks up to about 6th or 7th order can
be seen in the raw data shown in Fig.7. It should also be pointed out that
these spectra were collected in asymmetrical grazing incidence geometry. If
measurements are made in symmetrical geometry (ie the glancing angle is set
equal to the Bragg angle, in this case 1°), very high reflectivities can be
10 w-( multi layer

I N= 30 . d : 28 A I
29 : 2°. f : 2 mrad
o ~ ro ~ ~ ~ ~ ~ ~ ~ ~
Ener gy (keY I
Fig.6 Energy-dispersive diffraction pattern of a W-C multilayer

with a d-spacing of 28A
achieved. We have deliberately chosen the asymmetric case, in order to avoid

saturating the detector with the strong 1st order diffraction peak.
DISCUSSION
We have shown that the parallel beam energy-dispersive glancing angle

geometry offers the possibility of rapidly characterizing thin film or
multilayer materials. By appropriate choice of the diffraction angle, a wide
range of d-spacings can be accessed. It is also possible to select a
glancing angle which allows a degree of depth probing to be achieved. It
should also be noted that the radiation above 20 ke V used in these
experiments is highly penetrating. Therefore, it will be possible to
investigate surfaces which are covered by a liquid (for example, an
11
w- ( multilayer
10
IN: 30 . d: 56 AI
9
29 : 2°. 4J : 2 mrad
8
.
~ 6
::>
o
!! 5
c
- 4
o~ __________________~~~~~~
o 10 ro ~ ~ W ~ ~ ~ ~
Energy I keY I
Fig.? Energy-dispersive diffraction pattern of a W-C multilayer

with a d-spacing of 56A
electrolyte) in order to observe the formation of a film deposited onto an

electrode. Alternatively, a pressure cell could be constructed in order to
introduce a reactive gas over a surface. The hard radiation used in this
experiment would have no difficulty penetrating through the walls of such
cells, while the glancing angle geometry would constrain the radiation to the
uppermost 100A or so of the diffracting material.
Because of the very short data co~lection times referred to above, it

will be possible to study kinetic effects using this technique. These could
be catalytic or electrolytic reactions using the cells mentioned above.
Alternatively, the performance of a multilayer material, for example, could
be monitored during annealing. It would even be possible to use the
synchrotron radiation itself to induce radiation damage on the surface of the
sample, and to measure the degree of damage using this technique. Finally,
it is worth considering some other systems whose 2-dimensional character
could lend itself to the glancing angle geometry, such as liquid crystals.
The degree of ordering in such a system could be studied as a function of
applied field.
ACKNOWLEDGEMENTS
The authors wish to express their gratitude to the SERC for use of the
Daresbury Laboratory facilities, and special thanks to Mr A Neild for his
technical support.
REFERENCES
Clark, S.M., 1989 "Energy-dispersive powder diffraction at the SRS", Nucl.

Instrum. Methods, A276:381.
Hart, M., and Parrish, W., 1986 "Parallel beam powder diffractometry using
synchrotron radiation", Materials Science Forum, 9:39.
Hart, M., and Parrish, W., 1989, "Polycrystalline diffraction and synchrotron
radiation", Mat. Res. Soc. Symn. Proc., 143:185.
Lim, G., Parrish, W., Ortiz, C., Bellotto, M., and Hart, M., 1987, "Grazing
incidence synchrotron X-ray diffraction method for analysing thin films", L.
Mater. Res., 2:471.
Marra, W.e., Eisenberger, P., and Cho, A.Y., 1979, "X-ray total external
reflection Bragg diffraction : A structural study of the GaAs-AI interface"
1. Annl. Phys., 50:6927.
Marra, W.C., Fuoss, P.R., and Eisenberger, P., 1982, "X-ray diffraction
studies: Melting of Pb monolayers on Cu(1lO) surfaces", Phys. Rev. Lett.,
49:1169.
Parrish, W., Hart, M., Erickson, e.G., Masciocchi, N., and Huang, T.C., 1986,
"Instrumentation for synchrotron X-ray powder diffractometry ", Advances in X-
ray Analysis, 29:243.
Parrish, W., Hart, M., Huang, T.e., and Bellotto, M., 1987, "Lattice
parameter determination using synchrotron powder data", Advances in X-ray
Analysis, 30:373.
York, B.R., and Austin, A.B., 1986, "Structural depth probing by glancing
angle X-ray diffraction", SPIE, 690:135.
Wagner, C.N.I., Boldrick, M.S., and Keller, L., 1988, "Microstructural
characterization of thin polycrystalline films by X-ray diffraction",
Advances in X-ray Analysis, 31:129.
EFFECTS OF REFRACTION AND REFLECTION ON ANALYSIS OF THIN
FILMS BY THE GRAZING-INCIDENCE X-RAY DIFFRACTION METHOD
Toru Takayama and Yoshiro Matsumoto

Research and Development Division
Sumitomo Metal Industries, Ltd.
Nishinagasu-Hondori, Amagasaki, 660 Japan
ABSTRACT
The grazing-incidence X-ray diffraction (GIXD) method
was employed to analyze two-layer thin films, which were the
samples of 100A Au/500A Cu/Si0 2 (substrate) and 250A Cu/500A
Au/Si0 2 (substrate), which were prepared by the evaporation
technique under the condition that the Si0 2 substrate was
at room temperature. Diffraction profiles were obtained at
various glancing angles (a) and the data were analyzed as a
function of a. The results were as follows: 1) Diffraction
peaks were shifted to larger diffraction angles, because of
the refraction of the incident X-ray beam. The a2gular2s~}~t
has been approximated by the equation, a-( a - ac ) ,
where ac is the total reflection critical angle of the
material. 2) As a result of the correction of angular shift,
the stress of the evaporated films was estimated to be nUll.
3) The broadening of the Cu diffraction peak and the
enhancement of the Cu diffraction intensity occurred at
angles near a c of CU,due to the reflection of the X-ray beam
at the Cu/Au interface. The angular ~hift2 ~y~ to the
reflection has been approximated by a+( il' - a c ) , where
il'c is the critical angle of the upper-layer, Cu. 4) Below
the critical angle, small angular shifts were also observed.
The shift was thought to be caused by the roughness of the
sample surface. 5) In order to calculate the crystallite size
from FWHM (full width at half maximum) obtained by GIXD, a
somewhat higher glancing angle than the critical angles of
both the upper- and the lower-layers should be adopted. 6)
The X-ray penetration depth for the multilayer sample has
been calculated as a function of the glancing angle and the
calculated results agreed with the experimental results. 7)
The intenSities of diffracted X-ray beams were also
calculated as a function of glancing angle. In consideration
of the interface-reflection, the calculated results for the
Cu in the Cu/Au sample were consistent with the experimental
values.
Advances in X-Ray Ana/ysis. Vol. 33 109

Edited by C.S. Barrett et at.
I. INTRODUCTION
Recently several surface analyses have been performed in
several fields by many investigators. In analyses by
employing X-ray beams, the methods with the technique of
grazing-incidence are particularly noteworthy for surface-
and near-surface-analysis ; for example, the total-reflection
X-ray flyorescence method for elemental analysis of trace
amounts, the grazing-incidence X-ray ~Jattering for
structural analysis of near-surface layers , etc. The
grazing-incidence X-ray diffraction CGIXD) method is a
similar surface-analytical technique. There are two kinds
of GIXD methods. One of them is to analyze a three-
dimensional structure Cpolycrystalline)3) The other is to
analyze a two-dimensional structure by employing both grazing
incidence and grazing observation, for determining the atomic
arrangeme~} on the surface; for example, the InSb(lll) 2 X 2
structure . The former GIXD is well suited for the near-
surface measurement, i.e., a thin film near gyrface, and
has gyen applied to the study of a nitride layer ,an oxide
film '7)etc. This GIXD is also called the Seemann-Bohlin
method .
In the present study, the former GIXD was employed for
three-dimensional structure analysis. Au/Cu and Cu/Au two-
layer thin films were analyzed by the GIXD and the phenomena
of refraction and reflection at the surface and the interface
were observed. Effects of these phenomena on the angular
shifts, the penetration depth, and the diffraction intensity
due to the very small angle of the incident X-ray were
discussed.
II. EXPERIMENTAL
The GIXD measurements were carried out using a
Geigerflex Rad-B spectrometerCRigaku Corporation) attached to
the thin-film measuring systemCModel 2655Al). The geometry of
instrument is shown in Figure 1. A rotating cobalt anode was
operated at 30kV and
100mA, and a flat
graphite monochromator
(0002) was used a
Measurement conditions
were an incident
slit width of 0.2mm
and a ~ranning speed
of 2°min . Values of
the symbols in Fig.l
are shown in Table I. X-ray
The flat-surface Source Slit
samples of two-layer SI
thin films were
prepared by the
evaporation technique,
i.e., Au and Cu were
evaporated onto an
optical flat surface
an amorphous quartz Fig.! Geometry of GIXD instrument
T. TAKAYAMAANDY. MATSUMOTO 111
Table I. The values of symbols in Fig.l
length (mm) 0.1 0.2 30 10 25 10 95 90 145 ca.33
substrate at room temperature.
III. RESULTS AND DISCUSSION

III-I. Intensity of X-rays Reflected at the Mirror-Surface
On the analysis of three-dimensional structure by GIXD,
the incident X-ray path should be investigated. Reflection
intensities were measured to learn the behavior of the
incident X-ray beam. The results are shown in Figure 2. T~~
calculated critical angles of the X-ray total reflection
Q:'c(Au), Q:'c(Cu), and Q:'c(Si0 2 ) are 0.663° (11. 57mrad) , 0.481°
(8.40mrad), and 0.275° (4.80mrad), respectively. The marks (X)
shown in Fig.2 indicate the
experimental critical angles
on the abscissa axis. Under a
condition of total reflection,
the reflection intensity at a SOOA Au/SOOACu
high incident angle is larger
than that at a low angle, 100A Au/SOOA Cu
. .-....;
because more flux of the
incident beam is effectively
reflected at the sample
~ (a)
surface. For this reason, the X 2.5

are marked at the half :i SOOA Cu/SOOA Au
positions of the maximum
~I ( b)
-
intensities.
In Fig.2, the >. X1.7
-
I I)
t:
are almost consistent with C1>
the calculated angles. t:
However, in Fig.2(b), the (c)

experimental Q:' (Au) of the >.
lIS X1
100X Au/500A cu/§i0 2 sample '-
I
was somewhat smaller than the X
calculated Q:'c(Au) and the 2S0ACu
slope of the curve near /SOOAAu
Q:' c(Au) is gentler than the / (d)
others. We presumed that the 1
surface of 100X Au film layer X5
was rougher than the others.
In Fig.2(c) and (d),
oscillations of intensi ties are (e) X 10
shown between Q:' c (Cu) and Q:' o 0.5 1.0
(Au). Parratt reported that Incident Angle (degrees)
the oscillation of intensi ty
was caused by the reflection Fig.2 Intensity of reflected
at the interface between the X-ray vs. incident angle
, '2 II. XRD CHARACTERIZATION OF POL YCRYST ALLINE THIN FILMS
upper-layer of copper oxide and the lower-layer of CuB). It

is judged that the oscillations of intensities shown in
Fig.2Cc) and Cd) occur by the reflection at the interface.
Consequently, the amplitude of the oscillation in Fig.2Cd)
is larger than that in Fig.2Cc), because the
attenuation of the X-ray beam in the 250~ Cu-Iayer is smaller
than that in the 500~ Cu-Iayer. In our GIXD measurements,
the samples of 100X Au/500X Cu/Si0 2 and 250A Cu/500A
Au/Si0 2 were used.
111-2. Shift of Diffraction Angle by Refraction
Changes of the
/1
GIXD profiles were
investigated in detail Au(lll) Au 100;"
at the glancing-angle I Cu(111) ~cu 500A
range 0 f O. 1° to 2. 0° . .......___ \' , Si0 2 100~~1s
The GIXD profiles
obtained at some of Au(200) I
the glancing angles I Cu(200)
are displayed in I
Figure 3, where each
peak pOSition
indicates the value
c=
I
from JCPDS. The ~I
diffraction peaks tend X
to shift to higher
diffraction angles at
small glancing angles.
The integral peak
positions were
determined after data
treatment with Co K a2 40 50 60
stripping and
smoothing. Figure 4
Au(lll) Cu 250A
shows the diffraction- ( b)
angle differences ~Au500A J
between the Cu(ll1) ~ 1000cfsl
experimental peak 8-28 I x 112
positions and the
JCPDS positions I
plotted as a function Cu(200)
of glancing angle.
At a< a c ' total
I
reflection occurs at
the sample surface;
the diffraction peaks ~I
appear in Fig.3. One X
of the causes was
thought to be
divergence of the
incident beam the
divergence of the
incident beam 40 50 60
was geometrically 28 I degrees
calculated to be below
0.02°). Another of Fig.3 GIXD profiles and 9-29
causes was thought diffraction profiles
to be the roughness of the sample surface. These possible

causes suggest that the incident beam was slightly deviated
from an angular condition of total reflection. Therefore, the
angular shift of the diffraction peak decreases, as the
glancing angle decreases below the critical angle as shown
in Fig.4(a). That is, the measurement under the above
condition is scarcely influenced by total reflection, such as
a powder X-ray diffraction method.
At a > a c ' total
reflection does not
occur at the sample
surface and an
incident beam Au
til
penetrates into the QJ
QJ
sample. The angular 0,

shift due to ~0.5
refraction caused by ,......
q::,
the penetration of X- N
ray beam is
approximately given by ~O.O --e-
the following equation
,H2 (J):::: a-( a 2 0.0
2)112
•
_ a
c '
1.0 (b) Cu
(1)
derived from Fresnel's

simple formulae 3)
The calculated angular
shifts are shown in
Fig.4. The calculated
result for Au in Fig.
4(a) agrees wi th the
experimental values,
but for Cu it is not
appreciably consistent
with experimental
values as is seen in Fig.4 Shifts [ ~(2 (J)] of
Fig.4(b). The angular diffraction peaks from JCPDS
shift of the values as a function of U'
diffraction peaks for
(111) (220) (311) (222)

4.10
~~~~
corrected -11- - - - - - - - - -
4.05
_______ J--------.JJ! (l- - - - - - -
'--a:=0.7°
uncorrected
0.135 0.140 0.380 0.385 0.525 0.530 0.570 0.575

sin 2 ¢
Fig.5 Calculated lattice constant (aO) of Au vs. sin2~

Cu will be discussed in the next section.

The lattice constant (aO) of gold was calculated from
the real Bragg's angle, obtaIned by the 2 O-correction of Eq.
(1) at a> a c . The angle ¢ between the reciprocal-lattice
vector and the vector normal to the sample surface is given
by
¢= °obs- a + M20 )/2, (2 )
where 00bs is the observed Bragg's angle. L~ttice constants

obtained by Eq.(l) were plotted against sin ¢ , for
determining lattice strain. The results are shown in Figure
5. If the angular shifts by refraction were not corrected,
the calculated lattice constant was dependent on the glancing
angle and the diffraction plane (diffraciion angle). In Fig.
5, the line of uncorrected aD versus sin ¢ is also displayed
at a= 0.7° (dashed line). This line indicates that the film
had a tensile stress. But the stress of the evaporated film
was estimated to be null after the 2 O-corrections by Eqs.(1)
and (2) were applied.
111-3. Diffraction Peaks Produced by X-rays Reflected

at Interface
The angular shifts of the diffraction peaks of Cu phases
could not be sufficiently accounted for by the refraction at
the Cu surface as mentioned above. As shown in Fig.2(d),
reflection at the Cu/Au interface of the 2S0A Cu/SOOA Au/Si0 2
sample was observed. If a diffraction peak appears by the X-
ray beam being reflected at the interface at angle a , with
ac(CU)<11'<ac(Au), the angular shift is approximated by
.1(2 0 )rl c:1. a+( 11'2_ 11'/)1/2, (3)
identical to Eq. (1). Figure 6(a) is a schematic diagram of the

shifts of the diffraction peaks caused by the refraction at
the surface and the reflection at the interface. The Cu(lll)
peak positions calculated by Eqs.(I) and (3) are shown in
Fig.6(b). The peak positions calculated by Eq.(3) are in fair
agreement with the positions of discernible shoulders at
higher diffraction angles.
Conventionally, the full width at half maximum (FWHM) of
a diffraction peak is used to compute crystallite size. The
FWHM is dependent on crystallite size and ununiform
dist6Jtion. This relation is given by Scherrer's formula,
etc. In GIXD, the X-ray glancing angle also took part in
the FWHM. In the investigation of FWHM as a function of
glancing angle, the FWHM wi th ac(CU)< 11'< ac(Au) is larger
than that with a > a (Au), because diffraction peak
shoulders appear due to the X-ray beam being reflected at the
interface. Therefore, in order to calculate the crystallite
size from FWHM, a ~omewhat higher glancing angle than
the critical angles of all materials of the sample should be
employed.
Stokes and Wilson 10 ) derived a new experimental formula
from Scherrer's formula, assuming that the crystallites were
spherical. At the glancing angle of 1.5°, the crystallite
sizes calculated by the formula of Stokes and Wilson with Eq.
Table II. Calculated crystallite size (f) in A at

glancing angle of 1.5 0
material plane .8i /rad 6/degrees f /.1.
111 0.0175 22.36 111
Au 220 0.0205 38.38 111
311 0.0274 46.78 95
Cu 200 0.0198 29.76 104
(1) are shown in Table II, where 6 is the real Bragg's angle
obtained by Eq.(I), .8i is the integral FWHM (integral
breadth), and f is the average crystallite size. Although
the formula does not contain the instrumental correction
coefficient term, the calculated crystallite sizes of the
(a)
reflected
X-ray
interface +------"--:-,---=::::,...,:::::.....---1---_\_
Au 500A
I
(b)
I250c/s
a
Z' It
'iii ~--""""' 0.7 0
-
c
<I>
"""""""--0.65 0
.....C
::- :::~ :==~:~;o

50 52 54
2 () / degrees
Fig.6 (a)Schematic diagram of angular shifts and (b) GIXD

profiles of 250.1. Cu/sooA Au/Si0 2 near Cu(111)
diffraction peak. Solid and dashed arrows indicate
calculated peak positions by refraction and
reflection, respectively.
evaporated gold corresponded to the thickness of 100X.

As previously described, at a> a c ' the 28-correction
to calculate the lattice constant was possible and in
computing the crystallite size the FWHM was not influenced by
the glancing angle. Consequently a somewhat higher glancing
angle than the critical angles should be employed in order to
calculate lattice constants and crystallite sizes.
111-4. X-ray Penetration Depth
g-ray penetration depth is dependent on the glancing
angle) ; equations of X-ffY ~enetration depth have been
proposed by some researchers ,12. In the present work, the
penetration depth in multilayer samples with mirror-surface
and interfaces is considered.
The intensity at a distance t from the sample surface
can be directly derived by application of the requirement for
the continuity of tangential electric and magnetic fields
across the surface. To a good app roximation'13) the wave
intensity at small glancing angles is given by
= 10 T(a) exp[-t{a(a)+,ucosec,Ll}]' (4 )
where 10 is the intensity of the incident beam, ,u is the

linear absorption coefficient, ,Ll is the take-off angle of the
diffracted beam shown in Fig.I, a( a) is the linear
absorption function for the glancing angle a , and T( a) is
the transmission function of the electromagnetic beam through
the surface for glancing angle a. Describing the index of
refraction for a matter with n:I- 0I- i 02'
a(a) = 47l"Im(F)/.-t, (5)
and
(6)
where the function F is given by
F = (7 )
And, in the exponential term

i n Eq. (4), the fir s t t e r m
concerns the incident beam incident
and the second term is X-ray
concerns the diffracted beam.
Because ,Ll is very large, the
: : :h
refraction phenomenon is
ignored in Eq.(4).
The attenuation model
of the incident X-ray
considered for the multilayer
is
(j-l)th layer ~
""~'-'-t' t
*tj-l
sample as indicated in Figure
7. Analogous to Eq.(4), the (j)th layer ----~_~tl
wave intensity diffracted at
depth t' in the (j)th layer Fig.7 Attenuation model of
of the multilayer sample is X-ray beam in multilayer
given by sample
j-l j-l
= 10 IT Ti(a) exp[- r ti{ai(a)+,ui cosec/d Tj(a)
i=l i=l
x exp[-t' {a j (a)+ ,uj cosec (J }], (8)
. 1
where i denotes the (i)th layer and t'= tp- rt:lt i . Assuming
that the decaying rate of X-rays reaching the surface after
being diffracted in the (j)th layer is y %, which is the
mInImum rate-value of the detected intensity, the X-ray
penetration depth tp is given by
j j-l
tp = [-In{(1-0.01y)/ IT Ti (a )}- r ti {ai (a )-a j ( a)
i=1 i=1
fro m Eq. (8) .

At y values from 90 to 99% for the two samples, the
X-ray penetration depths were calculated by Eq. (9).
The resul ts are shown in Figure 8. At a < 2 and 0
20 <1000 , the penetration

depths are almost
i ndependen t 0 f 2 0 • The
determination of the
appearing angle a of the
diffraction peak ior lower-
layers is very difficult.
However the y values from 95
to 99% are thought to be
adequate for two-layer
samples, as shown in Fig.2.
111-5. Intensity of
Diffracted X-ray Au
Dependent on o 0.5 1.0 1.5
Glancing Angle
For powder X-ray
diffraction analysis, Peiser
et al. has given an
equation of diffraction
intensity14). However, this
equation can not be applied
to practical measurements,
because a sample with enough
or infinitely wide surface
is needed, and refraction
and reflection are not o
considered in this equatio~5 a/ degrees
BruneI and de Bergevin
have given the equation of Fig.8 Calculated X-ray
X-ray intensity for mirror- penetration depth
surface samples. In this vs. glancing angle( a)
section, the diffraction intensity of a multilayer sample

with a mirror-surface and interface is discussed.
The total intensity of diffraction at the (j)th layer
is derived by the integration of Eq.(8) as a function of t'.
If the effective area Z( a) irradiated by the incident beam
is considered, the total intensity Id is given by
j j-1
Id = 10 Z(a) IT T i ( a ) exp[- r t.{a.(a)+,ui coseCjl}]
i=l i=l I I
I-exp[-tj{a j ( a)+ ,uj cosec,} }]

{a j ( a)+ ,uj cosec jl } (10)
where Z ( a ) is the minimum value within the width

irradiated to sample plane is S cosec a, the width of
the sample is SO' and the width of detection at the
sample plane is
SMsinOMcoseCjl if
the X-ray beam dispersion
normal to the scanning plane
of the detector is ignored ; 7.5 (a)
ct'c(Au)
S, SO' and SM are shown in ,.....
Fig .1.
On the IooA Au/500A Cui
I!!
u
'b 5.0
~
Si0 2 sample, Figure 9(a)
~C1
~
shows that the several ....>.

calculations by Eq.OO) .~ 2.5
indicate good agreement ....Qj X5
between the experimental and -=
calculated results for Au, 0 1.0 2.0
supposing that the Au-layer
thickness is 120A, in spite
of the real mass thickness
of IOOA. This could be
,.....
~ 10.0
(b)
d pc(AU)
Au(111)
'-' ct'C<Cu)A • ~ Q
induced by roughness of the ~ 7.5 :.. 500A Q
surface, as shown in the .~
.,
.;tJ.... 800.4
section III-I. In Fig.9(a),
the thickness of the Cu-
....
Qj
.5 5.0
~.;..
:::----
----
layer in the 100A Au/500A Cu "C
Q)
/SiO~ sample was not "Iii

consIdered, because the Cu- ~ 2.5
layer also had rough ....c:
interfaces, i.e., Au/Cu and
Cu/Si0 2 . In Fig.9(b), the o 0.5 1.0 2.0
calculated intensities from ct'/ degrees
the Au-layer in the 250~ CU
/500A Au/Si0 2 sample Fig.9 Comparison with
correspond with the experimental and
experimental values, calculated intensities
supposing the thickness to as a function of a
be sooA. This result dashed curves :
indicates that the substrate in consideration of
surface also had roughness. interface-reflection
As shown in sections 111-1 and 111-3, total reflection

occurred at the Cu/Au interface in the 250X Cu/500X Au/Si0 2
sample at ac(Cu)< a < ac(Au). Therefore the total intensi ty
from the Cu-Iayer should be calculated with consideration
of this phenomenon. Similarly to Eq.(lO), the intensity of
diffraction caused by the interface-reflection is given by
I dr = 10 Z(a) Tl(a) R2 (a) exp{- 2a l(a) t l }
l-exp[-{,ul cosecjl -ale a )}tl]
x-----------------------------
,Ill cosec fJ -al ( a ) (11)
where R2 ( a) is the reflection function for Au, that is,

R2 ( a) ~ [( a-Re(F)}2+{lm(F)}2]/[{ a +Re(F)}2+{lm(F)}2]. (12)
In fact, the Cu total intensities [ I d +l dr : dashed curves]

correspond with the experimental values, In consideration of
the interface-reflection, as seen in Fig.9(b).
IV. CONCLUSION
The grazing-incidence X-ray diffraction (GIXD) method

was employed to analyze two-layer thin films, which were
prepared by an evaporation technique. Diffraction profiles
were obtained at various glancing angles and the data were
analyzed as a function of glancing angle. The results were as
follows:
At glancing angles above the critical angle,
(1) Diffracted peaks were shifted to larger diffraction
angles. The shift was caused by the refraction of the
incident X-ray beam. T2e an~uI'2 shift has been approximated
by the equation, a -( a - a c ) .
(2) As a result of the correction for angular shift, the
stress of the evaporated films was estimated to be nUll.
(3) The broadening of the eu diffraction peak and the
enhancement of the Cu diffraction intensity occurred at
angles near a c of Cu due to reflection of the X-ray beam at
the Cu/Au interface. The an gula 2 Shi~t 1~e to the reflection
has been approximated by a+( a - ac)l .
(4) In order to calculate the crystallite size from FWHM
obtained by GIXD, a somewhat higher glancing angle than
the critical angles of both the upper- and the lower-
layers should be adopted.
(5) Small angular shifts were also observed at glancing
angles below the critical angle. These shifts were thought to
be caused due to the roughness of the sample surface.
(6) The X-ray penetration depth in the multilayer sample
could be calculated as a function of the glancing angle and
the calculated results agreed with the experimental results.
(7) The intensities of the diffracted X-ray beams were also
calculated as functions of the glancing angles. In
consideration of the interface-reflection, the calculated
results for Cu of Cu/Au sample were consistent with the
experimental values.
ACKNOWLEDGMENT
The authors wish to express their gratitude to Mr. Y.
Matano and Mr. H. Tamura for assistance in part of the
experiment.
REFERENCE
1) P. Wobrauschek, H. Aiginger : Spectrochim. Acta, 35B, 607
(1980).
2) E. Matsubara et al. : Z. Naturforsch. 43A, 181 (1988).
3) M. BruneI, F. de Bergevin: Acta Cryst. A42, 299(1986).
4) J. Bohr et al. : Phys. Rev. Lett. H, 1275(1985).
5) N. Moncoffre et al. : Surf. Interface Anal. ~, 139(1986).
6) G. Lim et al. : J. Mater. Res. £.471(1987),
7) R. Feder, B. S. Berry: J. Appl. Cryst. ~, 327(1970).
8) L. G. Parratt : Phys. Rev. ~. 359(1954).
9) H. F. Quinn, P. Cherin : Adv. X-ray Anal. Q, 94(1961).
10) W. H. Hall: J. Inst. Met. 75, 1127(1950).
11) R. Khanna et al. : Nucl. Instrum. Methods Phys. Hes. B15,
752(1986).
12) M. Katayama, M. Shimizu: Adv. X-ray Chern. Anal. Jpn. ~,
281(1988),
13) M. F. Toney et al. : J. Mater. Res. ~, 351(1988).
14) H. S. Peiser et al. : " X-ray Diffraction by Polycrystal-
line Materials" Inst. Phys., London. p.159 (1955).
ENHANCED HANGE OF MEASURABLE THICKNESS OF THIN CRYSTALLINE
LAYERS USING 8/28 DECOU PLED POWDER X-RAY DIFFRACTION
G. Kimmel and W. Kaplan
Dept. of Materials Engineering

Technion - Israel Institute of Technology
Haifa, 32000 ISRAEL
INTRODUCTION
X-ray diffraction is one of the most useful methods for

the characterization of thin crystalline layers or coatings 1 • 2 .
The most interesting techniques are: the identification of
phases and their relative quantities, texture analysis, and
residual stress measurements.
Thin layers which are transparent to the x-ray beam (in

the diffracted wavelength) yield different intensities as
compared with a bulk sample. This modification is expressed by
the term l1-exp(-~·u·t·csc8)] for a flat sample in the
Bragg-Brentano geometry, where u is the linear absorption
coefficient and t is the thickness. If U is known, the
thickness can be measured, in principle, by comparing the
intensities of a bulk sample with a transparent one. However,
this method is difficult to use because thickness and density
are only part of the many factors which govern the absolute
diffraction intensity.
This problem can be resolved by using relative

intensities instead of absolute intensities. For random samples
the best way to determine the ut value using relative
intensities is through the refinement of ut from the entire
diffraction spectrum, but in principle we can use a pair of
reflections in two Bragg angles 8 1 and 8 2 , comparing their
intensity ratio: i(t) = 11/12 to i(m) of bulk 3 . Thus we obtain:
i(t)
Y [1]
i(co) 1-exp(-2·U·t·csc~)
The function Y vs. ut shows that in the usual 28 range, Y

is sensitive to ut only in the range of ut = 0.01 up to 0.5.
This limits the use of this method to a certain range of
thickness for a given material. By tilting the sample around
Advances in X·Ray Ana/ysis, Vol. 3;3 121

Edited by C.S. Barrett et 0/.
the 9-axis, causing asymmetric 9/29 reflections, it is possible

to expand the range of measurable thickness and increase the
sensitivity.
In this work we will present expected relative-intensity
distributions along Bragg angles for thin layers during
asymmetric 9/29 reflections, modified by the absorption
correction. Since many diffractometers are not equipped with a
decoupled 9/29 goniometer, we constructed a special sample
holder allowing us to present experimental data.
MODEL
Taking the expression for the diffracted intensity from a
unit volume of material and introducing the correct. ion for a
sample tilt of a degrees, we obtain the following equation:
dI = K-A(9) -dx-exp [ -~-x-csc(9 + a) - ~-x-csc(9 - a)] (2]
where K is a function of the sample reflectivity, beam

brightness, focal length, general angular intensity
distribution, structure factors, multiplicity, and Lorentz
polarization for the specific diffractometer. This factor also
includes unknown systematical and non-systematical errors. A(9)
is the effective illumination area at a given 9 angle.
If we define
S(9,a) csc(9 + a} + csc(9 - a) (3]
then
dl (4J
and finally we have:
t
K-A(9) [ ]
let) 1 - exp(-~-t-S) (5J
~-S
o
In a similar manner, the factor which modifies the intensity
ratio between two diffraction lines 291 and 292 is:
1 - exp(-~-t-S(91,a»
y (6]
1 - exp(-~-t-S(92,a»
and the thin layer thickness can be determined as described

earlier-"" .
The expected influence of the tilt angle a on the ratio Y

is shown in Figure 1. The angle a has a direct effect upon the
G. KIMMEL AND W . KAPLAN 123
lI": TA I- IO rtf'TnZ-OO
1.2 r------ - - - - --
IIlPIl Il - r J -
1-
IIlPI1II - S - ---
~ 1.r) -~;.':":1.;"~~;-:: ~ ... _ "7"' __
IIU'I III - 7 - -
1\1 r'~ ~9 -.
I- "
'.
II.A
IU
1-
'r n.G
•..1
UJ
(1
n n.~
II I
r I
..J
':1 n.;::
tt:
---.--_._._ ...
4
f€ ".
11.1I--- - - -y- o
UJ' ,( 'J t ) 10'
Fig. 1: The expected influence of the tilt angle a on

the normalized relative intensity.
sensitivity of the method, and allows for a wider range of thin

layer thickness to be measured.
EXPERIMENTAL METHOD
The data were collected by a commercial Philips PW-1820

automatic powder-diffractometer including a long fine-focus Cu
X-ray tube powered by a PW-1730 generator and routinely
operated at 40 kV, 40 mA, fixed 1 deg divergence and scatter
slits, a 0.2 mm receiving slit followed by a curved graphite
monochromator.
The counting electronics chain consisted of the standard

Philips PW-1710 system, which compensates for pulse-height
shifts up to about 500,000 counts per second. The system was
operated by a PDP 11/53 microcomputer.
The integrated intensities were measured by accumulation

of the counts between two background points using straight-line
background subtraction.
A special sample holder was constructed in order to

provide 9/29 asymmetric data collection (see Fig. 2). The
sample holder consists of two sections connected in a
swallowtail fashion, where the inner part is locked to the
goniometer, and the outer section holds the sample. The sample
itself consisted of 20~m - sized MgO particles mixed with
vaseline and spread over a constant area upon a polycrystalline
Silicon standard. The Si standard resided in a plexiglass
holder in such a manner that it could be lowered or raised to
change the thickness of the upper MgO layer .
Fig. 2: Sample holder which provides 9/29 asymmetric

diffraction.
Data were collected for a varying thickness and at tilt

angles of 0°, S°, and 10°; ~t of the MgO layer was determined
both by the attenuation of the Si reflections 4 , and through the
use of the multiple line method 2 • 3 • .
DISCUSSION AND CONCLUSIONS
Figure 3 shows the integrated intensities collected for

the Si standard substrate upon which were applied MgO layers of
2000
o Si Free I 11]0 U. IITm i!!I MgO O .4rrm
c'n
:~ I51JO
c
:~ leno
:no
Ill-L-l-"-----'--
HI<L S i 1=-1 I O~8
Fig. 3: Integrated intensities collected from the

Silicon standard with varying thickness layers of MgO.
G. KIMMEL AND W. KAPLAN 125
varying thickness. A range of values from transparent to bulk

were observed, and these data were used to calculate the MgO
thickness using the attenuation method. The values will be
compared later to those determined using the multiple-line
method combined with sample tilting.
Figures 4a and 4b demonstrates integrated intensities

observed for the MgO reflections for absolute and relative
intensities, respectively. Figure 4a shows that absolute
intensities do not yield reliable information for ut due to a
variety of factors; including sample surface area,
inconsistency of aperture positions, and tube brightness
variations. On the other hand, when relative intensities are
used, highly accurate results can be obtained (Fig. 4b).
4000
3ffiO
o 'VJ THI~~ • 'VJ O.an. tt;Poerm
3200
3' 2fn) (a)

OJ
~ 2t1OO
c
- 2U'ln
0
a H.W
<I>
\.
0>
:!! 1200
oS
1.01
<100
a
HI<.L r l l)n8
150
1<10 o r-tJl THIN • tt;P O.2nm tt;P o.an ..
130
J>
~ 120
~ 110
c IOU
0 00
~ 80
0 ( b)
\.
01 7U
:!! GO
oS
50
0
01
N 40
-
:JO
~\.
0 20
z: In
n
HI<L p lone
Fig. 4; (a) Absolute MgO integrated intensities.

(b) Relative MgO integrated intensities.
///
:1 . 0 r - - - - - - - - -- - - -- -- - - -/---...
~~::-
.3 2.4
o 2.2
¥ 2.0
e
E I.B
1.6 -
•. / / /
_
//
. ~
1.4
ill
L
1. 2 '
1.0 ./
ft ,,'
J
(ij
a
+
0.8-
III
:L 0.6'
..... 04 ~
~O"I/ O.O~~~~-~~-~~--~~~~-~~~~
0.0 0 .2 0.4 0.6 0.8 1.0 1. 2 1.4 1.6 1. 8 2.0 2.2 2.4 2.6 2.8 3.0
Fig. 5: A comparison of ~t values collected from the

MgO layer vs. attenuation from the Si standard.
Figure 5 shows results of ~t measurements of the MgO

layer, both from the Si standard and from the ratios of MgO
reflections. A wide combination of MgO planes were used to
enhance the statistics. A good agreement between ~t calculated
from MgO and Si is evident. Figure 5 also demonstrates optimal
accuracy when data is collected from the highest sensitivity
range of Y vs. a (see Fig. 1).
In this experiment values of a=0°,5°,100 were used and as
such the lower and upper ~t vs. sensitivity limits were not
examined. Only the ability to enhance the measurable range and
improve the statistics of the measurements was detailed.
However, the existence of an increased sensitivity range and
its fit to the mathematical model presented have been
determined, and the accuracy of the multiple-line method has
been demonstrated.
ACKNOWLEDGEMENTS
This research was supported by Technion V.P.R. Fund -

Steiner Research Fund.
REFERENCES
1. H. Hejdov and M. Cermak, "A New X-ray Diffraction

Method for Thin Films Thickness Estimation",
Phys. Stat. Sol. 72:K95-K98 (1982).
2. C. G. Brandt and G. H. van der Vliet, "Quantitative
Analysis of Thin Samples by X-ray Diffraction", Adv.
X-ray Anal. 29:203-209 (1985).
G. KIMMEL AND W. KAPLAN 127
3. G. Kimmel,G. Shafirstien, and M. Bamberger, "Fast

Thickness Measurement of Thin Crystalline Layers By
Relative Intensities XRPD Method, Adv. X-Ray Anal.,
32:293-301 (1988).
4. W.N. Schreiner, G. Kimmel, "Observed and Calculated
XRPD Intensities for Single Substance Specimens," Adv.
X-Ray Anal .. 30:351-356 (1986).
X-RAY DIFFRACTION OF PLASMA NITRIDED Ti-6AI-4v
A. Raveh * , G. Kimmel+, R. Avni * and A. Grill
Materials Eng:. Dept., Ben-Gurion University of the Negev,

P.O.Box 653, Beer-Sheva, ISRAEL. * also at NRC-Negev,
P.O.Box 9001, Beer-sheva 84190, ISRAEL. + Dept. of Mater.
Eng., Technion, Haifa 32000, ISRAEL
ABSTRACT
Ti-6AI-4v alloy has been nitrided in plasmas of N2-H 2-Ar. The

structure has been characterized by X-ray diffraction (XRD) for the
determination of the products formed. The information was supported by
elemental analysis with Auger Electron Spectroscopy (AES).
Three phases were identified as follows: o-TiN, E-Ti 2N and a'-Ti

(solid solution of nitrogen in titanium). The' gas-feed composition affects
the nitriding process as found from phase orientation and relative
concentration of the products.
1. INTRODUCTION
X-ray diffraction (XRD) is widely used in studies of microstructures

of TiN coatings l - 2 • This analysis determines the amount of phases, their
lattice parameters, crystal size, residual stresses etc.
In the present study we deal with titanium alloy (Ti-6AI-4V) nitrided

in an inductive rf plasma of N2 and H2 . Both external layers formed by the
reaction between plasma and substrate, and changes in the substrate due to
solubility of nitrogen in titanium were characterized.
Since mechanical properties (e.g. wear resistance) strongly correlate

with phase distribution along the depth from the surface, their
composition, orientation and thickness, XRD is an important tool to study
these properties.
In contrast to the depOSition of conventional Ti-N coatings formed in

a Ti-N binary system, nit riding Ti-6AI-4v, a multi-component system, is
more complicated because of the possible formation of nitrides and
hydrides of Ti and AI. The optimal purpose of titanium ni triding is to
form a continuous layer of o-TiN on the surface. The accomplishment of

Edited by CS. Barrett et 0/.
this goal is not simple and the formation of TiN on the surface depends
strongly on the nitriding conditions.
This paper presents and discusses the identified phases in the

treated Ti-6AI-4v as analysed by XRD.
2. EXPERIMENTAL
The nitriding process was carried out on polished Ti-6AI-4v surfaces,

by rf plasma as described elsewhere 3 . 4. Ni triding was performed in low-
pressure (7 mbar) , inductive rf plasma of N2-H 2 , N2 -Ar and N2 -H 2 -Ar
mixtures. The plasma was sustained by inductive coupling to a 0.5 MHz
generator operating at 1.1 kVA or a 13.56 MHz generator operating at 300
Watt. The sample was placed at the center of the rf coil in the plasma
reactor. Nitriding time was 10 min to 5 h and temperature of the sample
during the process was 550±50°C.
Concentration of N2 in the films was determined by Auger Electron

Spectroscopy (AES) and film thickness by metallographic section using
Scanning Electron Microscopy (SEM), as reported previously3. 4 •
The X-ray diffraction was done on a Bragg-Brentano Philips

diffractometer, with a fixed beam divergence of 1°. Cu-Ka radiation was
used and the KR> was removed by a graphite monochromator. The data was
obtained by stepscanned measurements with step size 0.03° and 3 sec time
steps.
3. RESULTS AND DISCUSSION
The untreated Ti -6AI-4v alloy was a mixture of hP2 magnesium type

alloy with lattice parameters a=4.67{l') A and c=2.92(1) A. (different
from the lattice parameters of pure titanium, a=2.951 A; c~4.685 A).
The (110) line of R>-Ti (cI2 tungsten type) was also present (Fig. 1a).
As seen from Fig. 1, the diffraction patterns, after the process, show
different modifications for different gas mixtures. The common feature for
all spectra is the disappearance of the R>-phase and the appearance of only
three crystalline phases: at, 6-TiN and E-Ti 2N phases.
From Fig. 1 it can be seen that the formation of TiN is enhanced by

hydrogen and depressed by argon additions to the plasma. In addition, the
formation of 6-phase is accompanied by the appearance of E-phase.
Although the' nitrided alloy showed sharp at lines (Figs. 1b-1d),

their modification was different for each condition. For example, as shown
in Fig. 2 and Table 1 the lattice parameters of the identified phases (at,
E and 6) varied with the N2:H2 ratio in the gas feed.
Since the thickness of the layers was beyond the penetration depth of
the Cu-Ka beam (8 J.1m at 29=40°), diffractograms of several samples were run
with Mo-Ka radiation and the (110)R> line appeared. For this line, the
penetration depth is 30 J.1m (Mo-Ka) and this diffractogram was received
from both the nitrided zone and the untreated bulk. From these results, we
came to a conclusion that the nitrided zone is composed of titanium at ,
E and 6 phases.
A. RAVEH ET AL. 131
3.1 The 6-phase
The thickness of the TiN layer measured by SEM. and the ni trogen
concentration determined by AES are correlated with the XRD results.
Figure ~ shows the I(200}!I(111} ratio as calculated by the XRIC computer
program vs. film thickness for randomly oriented 6-TiN. while Fig. 4
shows values as measured in this work. As shown in Fig.3. the
a-(Ti.N) N
0
~
E-Ti2N
0-
~
• I)-TiN
0-
§
~ (a)
N
'"
0
~
N2+H2 (80:20)
(b)
N2+H2+Ar (80:10:10)
(e)
N2+Ar (80:20)
(d)
80 70 60 50 40 30
Diffraction angle (2e)
Figure 1 X-ray diffractograms of plasma-nitrided samples at
0.5 MHz. rf power=1.1 kVAj gas pressure=7 mbarj total
feed=150 sccmj nitriding time=5 h. (a) untreatedj
(b) N2 :H2 =80:20 (c) N2 :H2 :Ar=80:10:10 (d) N2 :Ar=80:20.
2.95 4.685
0$ 2.94
."
~ 2.93
4.680
..
'"
-.:
OJ
OJ
.."
S
4.675
..
~
"CI.
OJ
2.92 "CI.
OJ
~ ~
"
...l 2.91
4.670 "
...l
2.90
0 10 20 30 40 50 60
92 Concentration (vol. %)
Figure 2 Lattice parameters (a and c) of a'-Ti-6Al-4v as a

function of hydrogen concentration in the N2-H2 plasma.
TABLE 1 : Lattice parameters* of identified phases as function

of gas feed composition. 1) 100vol.%N2 , 2) N2 :H2=80:20,
3) N2:H2:Ar= 80:10:10, 4) N2 :Ar=80:20.
Gas a-TiN E-Ti 2N a'-Ti

Composition a a c cia a c cia
(iq ($.)
0
(A) (A) (A)
1) N2 4.2328 4.9340 3.0369 0.6150 2.9073 4.6763 1. 6085

2) N2-H2 4.2419 4.9442 3.0407 0.6143 2.9228 4.6820 1.6019
3) N2-H 2-Ar 4.2408 4.9421 3.0350 0.6141 2.9217 4.6747 1. 6000
4) N2-Ar 4.2392 4.8143 3.1318 0.6505 2.9229 4.6720 1. 5985
Ti# 2.9510 4.6855 1.5878
Ti-6Al-4v 2.9239 4.6710 1. 5975
; average error ±0.0005A.

data from Pearson 5 •
4
B
1.8
52at.%N
1.6 ;;- 3
....
;;-
.... 1.4
:j
'-----::oN g
8eo
.----
t:: --------::oN
8<: 1.2 --. ~
~
• .... 2 II
.... 1.0 35at.%N B

II EI
.....
B
II
0.8 B
0.6 1 "
0 2 4 6 8 0 2 4 6 8
Film Thickness (J.!m) Film Thickness (J.!m)
Figure 3 (left) Calculated I(200)/I(111) ratio for TiN vs.

thickness and nitrogen percentage 6 •
Figure 4 (right) Measured I(200)/I(111) ratio of a-TiN phase vs.
film thickness.
A. RAVEH ET AL. 133
4.246
z ~
...1= 4.244 +
'eu"
... + ~
.!l 4.242 ~
"e
...eueu + +
Q. 4.240
~
+
~"
-=
....l
4.238
~ +
4.236
30 35 40 45 50 55
Nitrogen Content (at. %)
Figure 5 Lattice parameter of o-TiN vs. atomic percent of nitrogen

in the nitrided films measured at 0.1 pm depth.
1(200)/1(111) ratio is expected to increase with nitrogen content and film

thickness. However, Fig. 4 shows no such dependence of the 1(200)/1(111)
ratio. Only thin films showed a strong (200) texture.
Figure 5 shows the lattice parameter of o-TiN phase as function of

the nitrogen content measured at 0.1 pm depth in the nitrided film.
Although it is reported that the stoichiometric TiN phase has a lattice
parameter of 4.240A 8 , our results (Fig. 5) show that the lattice
parameter increases for over-stoichiometric o-phases. The expansion of
the lattice parameter can be explained by the incorporation of nitrogen
interstitially in the lattice at tetragonal positions. Similar behaviour
was observed by Sundgren et al. 8 and by Noel et al. 9 during
non-equilibrium growth conditions.
Figures 3 - 5 indicate that the strong (200) texture of thin films

("'1 pm) is governed by over-stoichiometry, while TiN was close to the
stoichometry (N:Ti"'1:1 ratio, 1(200)/1(111)"'1.5), for films thicker than
1 pm.
3.2 The E-phase

The E-phase was found in all samples. The amount of the E-phase
reached a maximum after nitriding with a plasma of pure N2 . In this case
w (,()
~ ~
50
I I 40
40
E E
'"' 30
C "
C
.'"
0 0
U U 211
20
'"'"'"'
.&: III '"
.c
c.. 0-
CJ ()
0 10 20 50
G:lS Composition H2 Concentration (vol. %)
Figure 6 Phase content vs. gas-feed composition.

(a) as function of hydrogen concentration in the N2-H2 plasma;
(b) at different plasmas.
lOO
~ 80
Q
.... 60
Q
"
.......,
tl 40
N
e
Q
~
20
Film Thickness (l.lIn)
Figure 7 Relative intensity of 1(200) line of E-phase vs. film

thickness.
the amount of a-phase was only one third of that of E-phase. The amount
of E-phase decreased with decreasing N2 concentration in the plasma
(Fig. 6a), or when the hydrogen was replaced by argon (Fig. 6b). The
E-phase was found to have a strong texture with the c axis normal to the
surface. The preferred orientation is a function of the overall film
thickness as seen from Fig. 7. The variation of the texture for several
conditions is also shown in Fig. 1.
3.3 The a'-phase

The lines of a'-phase in the diffractograms (Fig. 1b-1c), are
interpreted as resulting from a thick layer of almost uniform solid
solution of nitrogen in Ti. Based on the lattice parameters of pure Ti and
untreated Ti-6Al-4v, it can be seen that adding hydrogen to the plasma,
depleted the nitrided zone from at least one of its components, Al or V,
as shown from the modification of the lattice parameters of a' -phase
(Fig. 2). Hydrogen in the plasma causes a systematic change of the lattice
parameters towards increasing the unit cell volume (Fig. 2). Thus we
suggest that hydrogen enhances the purity of the titanium during nitride
formation. The AES analysis shows an almost constant nitrogen content
under the nitride layer. We can conclude that the a' is a solid solution
of a-titanium.
The disappearance of the ~-phase is explained by the phase diagram of

Ti-N 10 showing that nitrogen is an a stabilizer and no ~-phase exists when
nitrogen concentration is above 12 at%. The extent of lattice parameter
modification is not necessarily proportional to the percentage of the
nitrogen in the plasma. Figure 2 shows that in N2 -H 2 mixtures it is even
inversely proportional. It should be noted that no titanium hydride was
formed. This is in agreement with the disapearance of the ~-phase which is
stabilized by hydrogen.
Summarizing the experimental data, the nitriding process occurs along

several paths as follows:
(a) Solution of nitrogen in the a-phase. This solubility occurs by
penetration of nitrogen assisted and enhanced by H2 if present.
(b) Formation of over-stoichiometric TiN a-phase with a thickness of less
than 1 pm and with a strong (200) texture.
A. RAVEH ET AL. 135
(c) The reaction between active nitrogen species and the titanium
depleted of Al and V forms a compound layer of E and a phases. In this
layer, the E-phase has a strong (001) orientation parallel to the
surface, but the a-phase is randomly oriented. Similar texture was
found by Rie and Lampe 11 •
REFERENCES
1. R.R. Manory and G. Kimmel, Thin Solid Films 150, 277 (1987) .
2. V. Valvoda, R. Cerny, R. Kuzel,Jr., L. Dobiasova, J. Musil, V. Poulex
and J. Vyskocil, Thin Solid Films 170, 201 (1989).
3. A. Raveh, G. Kimmel, U. Carmi, A. Inspektor, A. Grill and R. Avni,
Surface and Coatings Technology, 36, 183 (1988).
4. A. Raveh, R. Avni and A. Grill, to be publ. in Thin Solid Films (1989).
5. W.B. Pearson, Handbook of Lattice Spacing and Structure of Metals and
Alloys (Vol.4), Pergamon Press, 1965.
6. G. Kimmel, "Program XRIC (X-Ray Intensities Computations)", Rep #878,
Philips Lab. Briarcliff Manor, NY, 1986.
7. L.E. Toth, Transition Metal Carbides and Nitrides, Academic Press,
New York 1971.
8. J.E. Sundgren, B.O. Johansson, H.T.G. Hentzell and S.E. Karlsson,
Thin Solid Films 105, 385 (1983).
9. J.P. Noel, D.C. Houghton, G. Este, F.R. Shepherd and H. Plattner,
J. Vac. Sci. Technol. A2, 284 (1984).
10. Metals Handbook, 8th ed. (American Society of Metals, 1973), Vol.8,
pp 322 and 369.
11. K.T. Rie and Th. Lampe, Metallberflaeche 31, 1003 (1983).
A COMPARATIVE STUDY OF STRESS DETERMINATION
TECHNIQUES IN POLYCRYSTALLINE THIN FILMS
I. C. Noyan and C. C. Goldsmith
Thomas.l. Watson Research Center

IBM Research Division
Yorktown Heights, NY
IBM General Technology Division

I1opewell.lunction, NY
Abstract
A review of the literature has shown that two major techniques are used to determine
stress/strain in thin film structures: curvature measurement technique and internal stress measure-
ment by the traditional sin 2t/J technique. However, to date, there is no published comparison of the
results from both techniques when they are applied to a given specimen.
In this paper we compare hoth methods theoretically and experimentally. We show that,
while in some cases similar information is obtained from both techniques, there are cases where the
two measurements give different results. We will show that, in such cases, the two methods can be
complementary. Thus, they can be used to yield a more complete description of the total
stress/strain tensor in the material.
Definitions and Theoretical Analysis
Stresses and strains are almost always present in thin films deposited on substrates. These
stresses may be intrinsic to the film, caused by defect distributions in the film volume, such as im-
purity, void and/or dislocation distributions. I - 3 They may also arise from morphology changes
within the film, such as partial grain growth, recrysta11ization or phase change. These intrinsic
strcsses may be affected by the presence of the substrate; however, they would be present even if
the film was "free-standing". The intrinsic stress field, if integrated over the entire film volume,
will average to zero. Another type of residual stress field may form solely due to the presence of the
substrate, in response to the differences of material parameters in the film/substrate interface. These
residual stresses can be called exlriflSi<' residual stresses. For example, a film deposited at elevated
temperature will have residual stresses at room temperature if its coefficient of thermal expansion
is different from that of its substrate. In epitaxial films, differences in plane spacing between the film
and the substrate may also cause an appreciable residual stress field at any temperature. "Extrinsic

Edited by C.S. Barrett el 01.
Figure 1: The sample coordinate system Xi and the direction of the measured x-ray stress ".p.
stresses" will have finite values when integrated over only the film or the substrate, but will yield a
zero average if integrated over the total film + substrate volume. 4
The total stress in the film is the sum of the stresses from all the different causes. Interactions
between materials, deposition parameters, etc., can result in complex stress/strain distributions
within the film-substrate composite. Thus, even though theoretically one can calculate the stress
distribution for some cases, experimental measurement of strain/stress distributions is the preferred
approach.
There are two methods that enjoy wide spread usage in stress measurements on
polycrystalline thin films. If the thin film has sufficient thickness to yield a good diffracted beam,
one can use the traditional d vs. sin 2if; technique4 : In this method *, the plane spacing of a family
of planes d hk, are used as an internal strain gage. If dhk, are measured along various directions I1¢\I
in the film (fig. I), where the angles ,p, if; are set on a powder diffractometer, the stress in the surface
direction S+ is given by the formula:
d</>, >/1 - do (1 + v) . 2 v
d = {--
•.- } "A. sm 1/1 - (-,. )"kk (I)
o "hkl 'I' \
Thus, from the slope of the d¢~ vs. sin 2if; plot, one can obtain the stress "¢, if the elastic constant
term {I + v/Ehkl and the unstressed lattice spacing do are known. For routine analysis, one may
use the intercept of the d¢~ vs. sin 21/1 plot at if; = 0 for do. For most cases, the error due to this term
will be negligible compared to the instrumental errors4 • This method of stress analysis requires
largely untextured or weakly textured films and assumes linear variation of d¢jI with sin2if;. When
these conditions are fulfilled, one can obtain stress values to =+= IOMpa with reasonable attention to
experimental detail. The errors associated with the measurement have been studied extensively and
formulas describing them are available in the literature. 4 ,S
The stress a¢ obtained from equation (1) is the total average stress in the grains diffraeting
during the measurement. Because of the selective nature of the diffraction process, only a partieular
set of grains will diffract at any if; tilt and, thus, the strain data is from incomplete, local subsets of
*This method was originally proposed for use on bulk samples and has been in use for over 70
years. In its original form, it was applicable to bi-axial stress distributions. In the last decade or
so,this method has been modified and extended to triaxial stress distributions. For most routine
thin film deposition techniques, the bi-axial analysis is adequate. We will review this method here.
For more detailed analysis techniqllcs, the reader is referred to reference 4.
I. C. NOYAN AND C. C. GOLDSMITH 139
the total irradiated volume. Such incomplete averaging can result in fmite values for certain strain
fields that would integrate to zero over large, continuous volumes of the film. Consequently, 11~
determined from the sin 2t/1 technique may contain extrinsic and intrinsic components as well as
interaction stresses, depending on the actual stress distribution in the irradiated volume. Further-
more, 11~ is an average over the depth of penetration. Any stress gradient within the irradiated vol-
ume will be averaged over.
The second method widely used in stress detennination from thin films is the measurement
of bending. It is well known that, when a substrate is coated with a film on one side, the composite
bends. 6 This is due to the unbalanced moments caused by the asymmetric residual stress distrib-
ution. The radius of curvature R uniquely represents the internal stress distribution, and a large
body of literature exists for the formulas linking R to l1R. I • 2• 6 - 12 Por a substrate with a single film
layer on it, the relationship between Rand O"R in the film is given by+:
(2)
Here, to, tJ, Eo, EJ, VO, VI, are the thicknesses, Young's moduli and Poisson's ratio of the substrate
and the film, respectively. The term,) is the Davidenkov deltaR and describes the shift of the neutral
axis from (to + t l){2:
(3)
If olle assumes that the film and the substrate have the same elastic moduli, and that the film
thickness is much smaller that the substrate thickness; (tl < < to), equation (2) becomes:
Eo t~
(l1¢)R = (1- vo) 6Rt l ' (4)
which is the extended Stoney equation applicable to this case.
A large number of the papers also treat multiple films on substrates. I - 3,9·- 11 None of these
approaches, on the other hand, can rigorously analyze the case where ollly the total radius of cur-
vature R, and thickness of each layer t i , i ~ IN are known. The best approach in such cases is to se-
quentially deposit the films and measure R after each deposition step. One can, then, use equation
(4) for stress analysis as long as the total thickness of the films is much smaller than that of the
substrate. One can see from equations (2-4) that thickness information for all the layers on the
substrate must be known accurately for bending analysis. When such information is not available,
measurement of R by itself yields little, if any, information on the state of stress.
X -ray diffraction can be used to measure the radius of curvature R if the substrate is a single
crystal. The technique is straightforward and has been described in detail in the literature. I ,2,13,14
Because diffraction is used to determine peak positions from which the radius of curvature R is later
calculated, there will be a statistical error associated with R. Thus, the errors associated with the
bending method depend on the accuracy of the radius of curvature R and on the errors associated
with the ti. The standard deviation in (TR calculated from equation (4) can be determined from
standard error propagation I.,: ..!..
Eo to 2 t62 t~22
SO' = (I _ vo) 6Rt l {4S Io + 7 St l + R2 SR} (5)
I
*Details of the derivation are givcn in reference (12).

Table I. Specimen Descriptions
Specimen # Film I (adhesion layer) Pilm 2 (evaporated Film 3 (eleetroless Cu)

Cu)
KRI Cr-Cu (t::;500 i\) - (\.94 Jim)
KR2
N
0.80 Jim -
KR3
N
0. 93 ,lm 1.56 Jim
KR5 - 2 Jim -
KR7 Polyimide (lO,lm) \.9 Jim (electroplated) -
KR8
N
- -
KR9
N
2.72 11m (electroplated) -
--
NI Cr (~400i\) I Jim 1.48 Jim
-----
N2 2.8 Jim
N N
N3
N N
-
~-
N4
N N
-
c--------- - -- -
N5 Cr (1.7 11m) on both 3 Jim -
sides!
'-------------- - - - - - - - - ~-
--
Where Sj denotes the standard deviation of the ith variable. It can be seen from this equation that
the film and substrate thicknesses must be known very accurately. SR will contribute less to the
overall uncertainty because of the multiplier t~/R2. For most practical cases, S. will be around 4-15
MPa.
The stress (l'R obtained from equations (2, 4) is, by defInition, an extrinsic stress, since it -rc-
suIts from the asymmetric moments in the film-substrate couple. Thus, if there are intrinsic stresses
in the film as wen, the stress determined from equations (I), (2, 4) may not agree. In such a case,
the difference, if any, may be due to the presence of such intrinsic stresses. Thus, the two methods
are complementary and may be used to fully determine the stress state in such materials. In the
following, the results of such an analysis, carried on Cu films deposited on Si substrates is reported.
Experimental Details
Thin Cu films were deposited on (100) Silicon wafers by electroplating, electro less plating,
vapor deposition or by a combination of the three methods. Three other specimens (KR7-KR9)
were prepared by spin coating 10 micrometers of polyimide on Si wafers. i\ thin film of Cu was
subsquently deposited on the polyimide by a combination of electro less and electroplating tech-
niques. Film thicknesses were measured by surface profilometry, or weight gain. In table I, perti-
nent data about the specimens used in this study are summarized.
After the specimens were prepared, residual stress measurements were carried out using both
sin 21j, and radius of curvature methods. Por the sin21j1 measurements, the 420, 220, 222 and 311 re-
flections were used, with eu radiation for the 420 reflection, Cr radiation for the 220 reflection and
Fe radiation for the 222, 311 reflections. Data collection for 420 (eu X.) and 222 , 311 (Pe K. )
was carried out using P filtered radiation, with the x-ray tube operated at 40kV-45mA. Por these
measurements the goniometer was a Rigaku powder diffractometer using normal parafocussing
optics and a scintillation detector. Por data collection from the 220 planes (CrK.) a vacuum path
II>
~
o
~~'--~--~~--~--~~--~
o 0 0.2 sinzt/l 0.4 0.6
figure 2: ;\ typical d"" vs. sin 21/' plot. The plot shows no psi-splitting
and is qllasi-linear (420 reflection from specimen KR2).
goniometer was used, in which the entire diffractometer (source, goniometer, and detector) was
enclosed in a vacuum chamber pumped down to rough pump vacuum. For this measurement,
parallel beam optics were utilized with unfiltered radiation and a flow proportional detector. For
all cases, the specimens exhibited partial texture, with quasi-linear d4>!1 vs. sin2'" plots. A typical plot
is shown in figure 2. For stress analysis, x-ray elastic constants, calculated from single crystal
compliances in tpe Kroner limit, were employed. A summary of the applicable elastic constants is
given in table 2.
The wafer bending measurements were carried out on a modified Lang topography camera,
with Mo radiation diffracted in transmission from the Si (220) planes. The center 60 mm of the
wafer was scanned, using step sizes ranging from 2 to 20 mm depending on the amount of curva-
ture. A typical plot of rotation vs. translation is shown in figure 3. In this figure, since the rotation
vs. translation is quite linear, the wafer is bent uniformly, with a constant radius of curvature across
the distance scanned. The intensity vs. translation, on the other hand, shows some non-linearity,
with one fairly large peak at the begining. This may indicate some thickness non-uniformity near
the edge. For the stress calculations, the elastic constant E/(l - vo) for Si (100) wafers was used
from Brantley16 and UR was calculated using both equations (2) and (4).
Table 2. Elastic Constants for Cu (xI012Pa)

Reflection Voigt Limit Reuss Limit Hill Value Kroner Limit
220 9.17 10.31 9.74 9.31
311 9.17 14.39 11.79 11.44
222 9.17 6.65 7.91 7.39
420 9.17 14.26 11.72 11.37
Elastic Compliances used in calculation l
Sll = l.5xlO- ll , S12 = -6.3xlO- l2 , S44 = 1.33xlO- ll (Pa- l)
0.20 19000
0.15
...,...,
<f)
~ Z
-<
17000
z 0.10 '~z""
-< 16000
tS -<
~ 0.05
15000
10 20 30 40 50 6d 4OOO
POSITION IN IIILLlIIETERS
Figure 3: A typical rotation (omega) vs. position plot for measurement of curvature.
Here w is the rotation to keep the diffraction peak at its maximum intensity in
a fixed detector. R is obtained from the slope of this plot 1.
Results and Discussion
Stress results from the sin 21/! and radius of curvature methods are summarized in table 3. As
indicated in the table, all results are + 15MPa or better, at three standard deviations, as calculated
from scatter around the linear model. At ftrst glance, one can make the following observations:
I. Stresses measured from the 311, 222 and 420 reflections seem to agree within experimental er-
ror.
2. In general, stresses measured using the 220 reflection differ signiftcantly from stresses obtained
using the above reflections.
Table 3. Summary of Stress Analysis Results (in MPa)

Method: sin2.jt Technique Curvature Technique
Specimen 0"220 0"311 0"222 0"420 O"R(eq.2) O"R(eq.4)
#
KR1 ·47 -10 -2 -4 -10 -8
KR2 47 81 70 93 117 110
KR3 54 64 77 76 94 78
KR5 25 27 7 39 13 11
KR7 68 76 110 - 136 117
KR8 (polyirnide film only) 15 8
KR9 77 75 75 90 134 109
NI -34 -IS -2 -13 7 8
N2 -65 --7 9 -9 9 7
N3 30 22 . 31 102 94
N4 9 31 13 19 85 77
N5 154 187 160 - 422 338
All data with three standard deviation::;; +15MPa
3. The stress calculated from equations (2, 4) using experimentally measured R values exceeds the
stress from sin 2'" measurement in most cases.
4. Even for the thin films used in this study, there can be significant differences between the
modified Stoney formula, eqt. (4), and the more general fonnula, eqt (2).
One may obtain further infOlmation from table III, if it is analyzed in conjunction with table
II. Consider specimens KR7, KR8, KR9: These specimens have 10 /-lm of 5878 PIon them. The
PI was spun on and oven cured (80-400 °C, with 40 min at 400 0C). Then, a thin layer (2000A
or so) of electroless Cu was plated on the PIon specimens KR7, KR9. A thin film of Cu was,then,
electroplated on this "strike layer". Diffraction data was obtained from this final Cu layer. Specimen
KR8 was kept as a reference sample for the detennination of stresses due to PI deposition. It can
be seen that the bulk of the stresses are due to the Cu plating operation. For these specimens, the
differences between the stresses from bending and from the sin2'" measurements were significant,
but not very large ( ~ 30MPa.)
Specimens KRI- KR5 and NI-N4 demonstrate the effect of different Cu plating methods on
the residual stress distribution. The data indicates that electroless Cu plating (KR I) has signif-
icantly less stress than Cu evaporation(KR2, N3, N4). On the other hand, KR5, which is evapo-
rated Cu on Si without an adhesion layer shows low stresses from all the measurements, indicating,
possibly, a weak interface. Specimens KR3, NI, N2 are composite Cu structures. Here Cu was
evaporated on an adhesion layer and e1ectroless Cu plated on the evaporated layer. Thus, there are
two layers of Cu with different stress distributions. In such a case, one would expect the total stress
to be a weighted average of these distributions, since the entire Cu volume will contribute to the
diffraction peaks in the sin 2YI method. Since we measure the composite R in the radius of curvature
measurement, "R from this method will also be an average. Specimen KR3 meets these expecta-
tions, even though the average stresses are higher than expected. On the other hand, NI, N2 have
very low stresses, indicating that the average was dominated by the electroless plating. The cause
of this effect is unknown at this time.
Specimens N3, N4 present another puzzling case. N3, N4 have the same Cu that was evap-
orated on KR2 and all three specimens yield similar stresses from the radius of curvature method.
On the other hand, both N3 and N4 have low stresses if analyzed by the sin2'" method. One can
not simply ascribe such differences to the intrinsic stress distribution, because KR2 does not behave
the same way as N3, N4.
Specimen N5 is different from all the above specimens in that it has symmetric evaporated
Cr films on both sides of the Si wafer and an evaporated Cu film on the top of the Cr film on one
side. Thus, we would expect bendIng to be representative of the Cu film only. However, this spec-
imen has the smallest radius of curvature and the highest stress among the specimens presented
here. The stress from the sin 2'" method is significantly smaller than the bending stress. Again, fur-
ther experimentation is needed to determine the cause of the disagreement.
Conclusions
It may be seen from the results presented so far that the stress results from the two most-common
techniques of stress detennination do not always agree. The reasons they do not agree are not clear
at this time. One may make the argument, made here in the theoretical analysis section , that the
disagreement is due to intrinsic and/or interaction stress components. It may also be due to error
in the f!lm thickness. In any case, however, the results of this study indicate a need for combined
usage of the sin2'" and radius of curvature methods·. Even for well-characterized specimens, the
It must be noted here that the conclusions discussed above are valid irrespective of the method used
to measure R.
scatter in the data is significant enough to preclude anyone method from claiming the "correct"
stress value. If only the sin2'" method is available, data should be obtained from more than one
reflection as a check.When multi-layer ftlms arc present, stress from as many layers as possible must
be obtained before one can claim to "know" the stress in the structure.
References
1. "X-Ray Diffraction Studies of Thin Films and Multilayer Structures", A. SegmuUer, I. C.

Noyan, V. S. Spcriosu, Prog. Crystal Growth and Charact. 18,21-66 (1989).
2. i\. Segmul\er, and M. Murakami, "Characterization of Thin Films by X-Ray Diffraction," in
Thin Films from Free Atoms and Particles, K. J. Klabunde, Ed., Academic Press, New York
(1985), 325-351.
3. S. N. G. Chu, i\. T. Macrander, K. E. Strege, and W. D. Johnson, Jr., "Misfit Stresses in
InGaAs/InP IIeteroepitaxial Structures Grown by Vapor Phase Epitaxy," J. Appl. Phys. 57,
249-257 (1985).
4. I. C. Noyan and J. B. Cohen, Residual Stress, Measurement by Diffraction and Interpretation,
Springer, New York (1987).
5. J. B. Cohen, II. Dolle, M. R. James, "Determining Stresses from X-ray Powder Patterns",
NBS Special Publication 567, 453-477 (1980).
6. G. G. Stoney, "The Tension of Metallic Films Deposited by Electrolysis", Proc. Roy. Soc.
London A 82 , 172-175 (1909).
7. S. Timoshenko, "Analysis of Bi-metal Thermostats, 1. Opt. Soc. Am., 11,233-255 (1925).
8. N. N. Davidenkov, "Measurement of Residual Stresses in Electrolytic Deposits," Sov. Phys.-
Solid State 2,2595-2598 (1961).
9. K. Roll, "Analysis of Stress and Strain Distribution in Thin Films and Substrates," J. Appl.
Phys. 47, 3224-3229 (1976).
10. J. Vilms and D. Kerps, "Simple Stress Formula for Multilayered Thin Films on a Thick
Substrate", 1. Appl. Phys. 53, 1536-1537 (1982).
11. P. Townsend, D. M. Barnett, T. A. Brunner, "Elastic Relationships in Layered Composite
Media with Approximation for the Case of Thin Films on a Thick Substrate", J. Appl. Phys.
62,4438-4444 (1987). .
12. I. C. Noyan and L. T. Nguyen, "Residual Stresses in Polymeric Passivation and Encapsulation
Materials," J. Poly. Sci. Eng., 28,1026-1034 (1988). .
13. "Automatic X-Ray Diffraction Measurement of the Lattice Curvature of Substrate Wafers for
the Determination of Linear Strain Patterns," J. Appl. Phys. 5t, 6224-6230 (1980).
14. C. Goldsmith, P. Geldermans, F. Bedetti, G. A. Walker, "Measurement of Stresses in Cured
Polyimide Films" J. Vac. Sci.& Techn. At, 407-409 (1983).
15. H. D. Young, Statistical treatment of Experimental Data McGraw-Hill, New York (1962).
16. W. A. Brantley, "Calculated Elastic Constants for Stress Problems Associated with Semicon-
ductor Devices," J. Appl. Phys. 44, 534-535 (1973).
X-RAY LINE BROADENING ANALYSIS OF TI-SUPERCONDUCTING FILMS
M. O. Eatough, D. S. Ginley, and B. Morosin

Sandia National Laboratories
Albuquerque, New Mexico 87185
Abstract
Superconducting thin films (0.3-0.7Ilm) in the TI-Ca-Ba-Cu-O system have been
prepared on various single crystal substrates by sequential electron beam
evaporation followed by appropriate sintering and annealing. Oxygen-annealed films
show Tc as high as 11 OK and critical current densities to SOO,OOO A/cm 2. X-ray
diffraction analyses of these films show predominantly the TI2Ca2Ba2Cu301 0 phase
(c-parameter near 3SA), but some also contain up to 50 at% of the TI2CaBa2Cu208
phase (c-parameter near 30A). The complete absence of hkl reflections other than
001 demonstrates the highly oriented nature of the films as well as the absence of
other TI phases. The diffraction peaks are noticeably broader for the 3sA phase than
for the 30A phase. For a 0.71lm film such broadening is consistent with coherent sizes
along the c-axis of 1200 - 1400A and sooA, respectively, for the 30A and 3sA phases,
and of strain values near 1.4 - 1.8 x1 0-3 for both phases.
Introduction
The discovery of superconducting ceramics with transition temperatures (Td
above liquid nitrogen temperatures has stimulated development of superconducting
thin films. The materials which have generated the most interest recently are those in
the TI-Ca-Ba-Cu-O system. These are tetragonal perovskite-like structures with a-axis
dimensions near 3.8SA and c-axes of different lengths characteristic of each
phase 1-4. Tc for these phases are as high as 12SK1-4.
The quaternary nature of this system as well as the volatility of TI make thin-film
production more difficult 5. For this study samples prepared using a sequential
electron beam evaporation technique were analyzed S. These samples were
prepared using a starting stoichiometry of TI2Ca2Ba2Cu301 0, hereafter refered to as
Advances in X·Ray Analysis, Vol. 33 145

2223, which was deposited on single crystal SrTi03 and Y-Zr02. The 2223 phase
has been shown to have Tc up to 125K1.
Our experience has shown that in bulk ceramics 2223 is difficult to form as a phase
-pure superconductor, suggesting that a phase transition mechanism exists between
2223 and other TI-superconductor phases. X-ray diffraction (XRD) was used to check
the phase purity of these films, as well as to determine orientation of the crystallites.
Line broadening analysis was used to determine strain vs crystallite size
relationships. In this paper we detail this XRD study.
Sample preparation
Films were depOSited on single crystal substrates of SrTi03 and Y-Zr02 using
sequential electron beam evaporation as described by Ginley et al 5. Cleaned
substrates were mounted into a Leybold-Hereaus ESV-6 e-beam evaporator loaded
with a four-pocket crucible containing metallic TI, Ca, Ba, and Cu. Sequential layers
of Cu-Ba-Ca-TI were deposited so as to start and end with Cu. Film thickness was
predetermined by varying the number of layers deposited. The net stoichiometry of
the deposit was near that of 2223. Chamber pressure was maintained at 1.5 X1 0- 5
mbar using a controlled oxygen leak. Film thickness for this study was 0.7I1m.
The materials were calcined at 850°C for 15 minutes in air followed by a 3O-minute
oxygen anneal at 750°C. A TI vapor overpressure was maintained by bulk 2223
ceramic during calcination and annealing in order to prevent loss of TI. The films with
I
a=2223
b=2122
I .
;;
0.0 '"
0
-'"0 ~
o~
0 '" en
E
en
e.
.!t
'"
0
e. .
co
0
e. .!t
'"
'"
e.
0
.0
.0
N . ;;
0
e.
8J
:E.~
0
.0
[ AlA
0
0-
~~ ~ T 0
J: V\
000
I. -d"-
4 18 32 46 E o
Two Theta (degrees)
Figure 1. Diffraction pattern of film on SrTi03 showing c-axis orientation

of 2223 (peaks labeled a) and 2122 (peaks labeled b).
M. O. EATOUGH ET AL. 147
I a=2223
b=2122
.0
c;;-
.i?:' o
e.
'iii
c .llt '"
~
~
.E '"e.
0 0
e.
Q)
.0
> c;;-
"iU o
'iii e.
a: III
<0'.0
.0 (; ;¢
_o 0~
<0'
0
e.", Q '" e.
N
<0
1l
0
4
1.11 118
1JJ
32 46 E o
Two Theta (degrees)
Figure 2. Diffraction pattern of film on Zr02 demonstrating a higher

concentration of 2122 than shown in figure 1.
the best superconducting properties had Tc to 111 K and critical current densities
above 600,000 Ncm 2 as detailed by Ginley et a1 5.
X-ray Diffraction
XRD analyses were done using a Siemens D500 automated powder diffractometer
in a standard Bragg configuration using Cu radiation. The detector was a scintillation
counter preceded by a diffracted beam monochromator. The samples were mounted
onto a custom sample holder to insure alignment with the focusing circle. Data were
collected and analyzed using Siemens Diffrac 500 software.
Figure 1 shows a typical diffraction scan of a film on SrTi03. Several observations

were made from the pattern. First the lowest'two diffraction peaks, 5.0ao 29 (d=17.4A)
and 6,13 28 (d=14.4A), are consistent with a two-phase system containing 2223 as
well as TI2CaBa2Cu20a (2122). Further, diffraction peaks represent only 001 type
reflections for both phases. A least squares fit of the peak positions indicate c-axis
dimensions of 35.5A and 29.19A (±.01), respectively, for the two phases.
In figure 1, 2223 is the dominate phase, but in many other films 2122 appears to be
in equal abundance. An example is shown in figure 2 for a film depOSited on Zr02,
Finally, in films containing both phases, the diffraction peaks for the 2223 phase
are broader than those for 2122. Figure 3 more clearly shows this point. This
observation was made regardless of the substrate material or dominant phase. This
precipitated a study to determine the cause of line broadening.
148 II. XRD CHARACTERIZATION OF POLYCRYST ALLINE THIN FILMS
4 5 6 7
Degrees (two-theta)
Figure 3. This enlargement of the low angle region from figure 2 clearly
shows that the diffraction peaks for 2223 are broader than those for 2122
(left to right respectively).
Line broadening analysis

When diffraction peaks are broadened there are generally two major causes:
non-uniform strain and/or small crystallite sizeS. However, in the TI-Ca-Ba-Cu-O
system stacking-faults and inhomogeneity due to solid solution are common and can
also contribute to broadened diffraction peaks. Therefore the excess broadening of
the 2223 peaks could result from any combination of the above.
Various authors7 have examined contributions leading to broadening due to strain
and crystallite size. Strain effects are a function of diffraction angle while crystallite
size affects all the line profiles equally. Broadening caused by stacking faults and
inhomogeneity are also a function of diffraction angle. Separating the broadening
contribution due to strain and crystallite size effects can be done by methods such as
the Warren- Averbach procedure or more classical methods such as the
Gauss-squared or Hall Williamson methods7. The quantitative precision of these
methods is dependent on how well the diffracted peaks are profiled to obtain proper
widths as well as how well instrumental broadening is subtracted. In order to use our
software based on the Warren-Averbach method, very accurate peak profiles are
required with information collected far into the tails as well as a standard with peaks
near those of the sample 8. In the case of this two-phase system numerous peak
overlaps exist and multiple isolated peaks were not available. Therefore a
less-stringent Gauss-squared method was chosen for our analysis. With the
Gauss-squared relationship,
where B is the broadening of the peak less the instrumental breadth, e is the
diffraction angle and A is the wavelength of the x-rays used (Cu Ka1 = 1.540SA). DG
10 .,----_ _ _ _ _ _ _ _- - ,
-<
~
8
(0
b
~ 6 q, = 490A
X
C\J
2'
<D
4
'"o() 2
~
O+-~-.~_.,----~-.~~
0.00 0.02 0.04 0.06 0.08
(sin 8/')..)2
Figure 4. Plotting of the Gauss-squared function shows that the 2122

and 2223 phases in films deposited on SrTi03 are similarly
strained and that the crystallite size of 2122 is much larger
than 2223
is the size value, and eG is the strain value. Thus the slQpe of the least-squares line
through the breadth function in each phase determines the strain (16eG 2) while the
intercept is the crystallite size functiQn ((1/DG)2).
Because of the peak overlaps a pseudo Voight function 9 was used to profile all
sets of peaks in each pattern. Instrumental brQadening was removed by subtracting
the peak breadths calculated from a well characterized, recently identified general
reference of LaB61 0 measured just priQr to. sample data cQllectiQn.
Figure 4 gives the plQtted data frQm a film deposited Qn SrTi03. It clearly shQWS
that broadening is due to both crystallite size and strain. Strain values for 2122 and
2223 are very similar ( eG = 1.4-1.5 x 10-3 ). This is cQnsidered a significant strain
value 7. Crystallite size, however, is very different fQr each with the size Qf 2122 abQut
3x that Qf 2223 (-500A vs -1400A respectively). The result for films Qn Y-Zr02
(Figure 5) are nearly identical to those fQr films Qn SrTi03. Strain values are slightly
higher for these films.
Because broadening due stacking faults and/Qr inhQmogeneity are a function of

diffractiQn angle their presence WQuid give an upward influence on the strain values.
However, very little change in slQpe exists between the plQtted breadth functions fQr
2122 and 2223. Since it is unlikely that effects frQm stacking fault and/or
inhomogeneity are always identical between 2122 and 2223 we feel there is very little
contributiQn from stalking faults Qr inhQmQgeneity and that the excess broadening is
due to. crystallite size differences.
10,-__________________,
<
<0
8
b
~ 6
X
C\J
2"
(j)
4
8'" 2
23:
0.02 0.04 0.06 0.08

(sin 8f},,j2
Figure 5. Results for film deposited on Zr02 are similar to those in figure
4 for films deposited on SrTi03'
Conclusions
The present studies show that even with a starting stOichiometry of 2223, 2122
often forms in abundance. Synthesis protocol appears to be very important. Ginleyet
al. 5 have shown that the configuration of the experiment contributes toward the ability
to form polycrystalline C-axis oriented films or randomly oriented films. The substrate
may also contribute by influencing epitaxial-like growth. Both substrate materials
(SrTi03 d1 00=3.905A, Y-Zr02 d11 0=3.60A) have dimensions near those of the
a-parameter (3.85A) for the TI-superconductor materials. Whether this mismatch of
lattice parameters causes the formation of dislocations that lead to nonuniform strain
is not yet proven.
The fact that 2122 grows to a much larger grain size than 2223 might indicate that
the films are first oxidized and calcined to the 2223 form, appearing as many relatively
small crystallites separated by dislocation boundaries, but still c-axis oriented. The
2122 phase is then nucleated at a few points and grows to larger crystallites through
a more gradual, "phase transition" driven mechanism.
Acknowledgements
The authors gratefully acknowledge the technical advice and review given by
Martin J. Carr. They also acknowledge the help with XRD work by R. G. Tissot and R.
D. Lujan. This work supported by the U. S. Department of Energy under contract
number DE-AC04-76DP00789
References
1. S. S. Parkin, V. Y. Lee, E. M. Engler, A. I. Nazzal, T. C. Huang, G. Gorman, R.
Savoy, and R. Beyers, Bulk Superconductivity at 125K in TI2Ca2Ba2Cu30x,
Phys. Rev. Lett., 60:2539 (1988)
2. C. C. Torardi, M. A. Subramian, J. C. Calabrese, J. Gopalakrishnan, K. J.

Morrissey, T. R. Askew, R. B. Flippen, U. Chowdhry, and A. W. Sleight, Crystal
structure of TI2Ba2Ca2Cu301 0, Science, 240:631 (1988)
3. B. Morosin, D. S. Ginley, P. F. Hlava, M. J. Carr, R. J. Boughman, J. E. Schirber,
E. L. Venturini, and J. F. Kwak, Structural and compOSitional characteristics of
polycrystals and single crystals in the Bi- and TI-superconducting systems:
Crystal structure of TICaBa2Cu207, Physica C, 152:413 (1988)
4. B. Morosin, D. S. Ginley, J. E. Schirber, and E. L. Venturini, Crystal structure of
TICa2Ba2Cu309, Physica C. 156:587 (1988)
5. D. S. Ginley, J. F. Kwak, R. P. Hellmer, R. J. Baughman, E. L. Venturini, and B.
Morosin, Sequential electron beam evaporated films of TI2CaBa2CU20y with
zero resistance at 97K, Agpl. Phys. Lett., 53:406 (1988)
6. B. D. Cullity, "Elements of X-Ray Diffraction," Addison-Wesley Publishing Co.,
Inc, Reading, Mass (1978)
7. B. Morosin, X-ray diffraction line broadening of shock-modified ceramic
powders, in "High pressure explosive processing of ceramics," R. A. Graham
and Akira B. Sawaoka, ed., Transtech publications (1987)
8. Diffrac 500, v 1.1, Siemens Analytical X-Ray Systems, Madison, WI (1988)
9. Siemens Application Note No. 75, Siemens Analytical X-Ray Systems,
Madison, WI (1986)
10. T. G. Fawcett, C. E. Crowder, S. J. Brownell, YZhang, C. R. Hubbard, W.
Schreiner, C. P. Hamill, T. C. Huang, E. Sabino, J. I. Langford, R. Hamilton, and
D. Louer, Establishing an instrumental peak profiling calibration standard for
powder diffraction analyses: International round robin conducted by the
JCPDS-ICDD and the U. S. National Bureau of Standards, Powder Diffraction,
3:209 (1988)
STRESS ANALYSIS OF THIN-FILM SmS
USING A SEEMANN-BOHLIN DIFFRACTOMETER
Fergus E. Moore
LTV Missiles and Electronics Group

P. o. Box 650003, Dallas TX 75265-0003
ABSTRACT
X-ray diffraction is especially useful in analyzing the phase-

transition response of thin-film SmS to strain impressed by the two-
dimensional constraints of the substrate. A biaxi.al-stress model 1 ,2 is
applied and extended to a randomly-oriented crystalline film. The changes
in macrostress, the compliance tensor and effective Poisson's ratio are
evaluated near the bulk phase transition. An analysis of crystallite size
and microstrain broadening is also presented including broadening effects
due to biaxial macrostrain on the randomly-oriented crystallites. These
results illustrate the effect of a constraining, biaxial-stress field on the
unusual elastic character of samarium monosulfide. It is demonstrated that
the thin-film geometry suppresses the first-order phase transition allowing
only linear changes between the semiconducting and metallic states.
INTRODUCTION
Samarium monosulfide and its alloys with other rare-earth monosulfides

transform from a semiconductor to a metal under hydrostatic pressure. The
change in phase alters the crystalline elastic parameters and includes an
effectively negative Poisson's ratio near the transition. The first-order
semiconductor-to-metal phase transition in bulk SmS and Sml_xRxS (R = tri-
valent lanthanide or yttrium) has been studied by a number of investiga-
tors 3 - 6 , particularly for its metallic-state mixed valence of 2.7. The NaCl
crystal structure of semiconducting SmS has a lattice parameter of 5.97A at
ambient conditions which collapses isostructurally to 5.67A in the metallic
state at 6 kbars of hydrostatic pressure. The transition is accompanied by
large changes in optical reflectivity at wavelengths greater than 6000A7.
The pressure required for the metallic state is reduced for alloyed SmS,
e.g. Sml_xGdxS is metallic at ambient pressure for x > Xc = .17. 8 An ultra-
sonic study of Sml_xYxS elastic parameters indicates that for x > Xc
Poisson's ratio is effectively negative. 9
Sm1_xGdxS thin films are produced in our laboratories by coevaporating

Sm and Gd into -lx10- 4 torr of H2S and depositing the reaction product on
multiple substrates held at 400°C. A single-phase, polycrystalline film

SmS
JCPDS 26-1479
\ 11
1'1
IJ"
RELATIVE
INTENSITY
21 31 41 51 101 111 121

29 (DEGREES)
Fig. 1. Diffraction pattern for 2000 A SmS thin film on fused quartz with
JCPDS powder standard 26-1479.
with random orientation is produced which can be seen in Figure I by

comparing diffraction intensities with those of the JCPDS standard file. In
order to analyze the elastic properties of the film, one may use the stress
induced through the difference between thermal expansion coefficients of the
film and the substrate upon cooling from 400°C to 2SoC.
EXPERIMENTAL
The data for stress analysis are collected using a Seemann-Bohlin

,diffractometer in a low incident-angle configuration. 10 Figure 2
1\
L
+
DETECTOR
-;_; ::0~THIN
INTERFACE
FILM
/
/
///
/ /
~
L
l ."'"ACnOH 'UN,.
-L THIN-FILM PLANE
/; 'i~
/ ~
Fig. 2. Diffraction geometry for low incident-angle Seemann-Bohlin
thin-film diffractometer.
F. E. MOORE 155
illustrates the geometry where ~ =So and the Bragg condition selects those
crystallites whose d·iffraction planes have an angle qI with the thin-film
plane. Following the methodology of Segmuller and Murakami,2 expressions
for the change in d-spacing caused by lattice strain may be developed with
the strain tensor, E, related to the stress tensor, d, by £ij = Sijkl okl
or £'ij = S'ijkl O'kl. While the compliance tensor, S, is most simply
expressed in the crystalline coordinates (unprimed), the stress tensor is
most simply expressed in the thin-film coordinates (primed). The stress
model, in which a constant stress field is applied in the film plane, is
given by 0'11 = 0'22 = s, 0'33 = 0, and o'kl = 0 for k + 1. The stress
tensor is expressed in the crystalline coordinate system by applying
rotational transformations to the primed tensor. Briefly, the expressions
in dyadic form are d' = s (I - L' L') and d = s (I - L L) where in the
unit tensor I = Okl and the unit vector L is perpendicular to the
thin-film plane as shown in Figure 2. In order to determine L in the
crystal coordinates one may relate it to the unit vector M perpendicular
to the diffraction planes. In effect, L is rotated about M in the
crystal coordinate system with LoM = cosql. The following expression
for (8d/dlhkl per unit stress, s, is derived.
(M/d)/s cos2q1 1 1 2
+ sin 2q1 So fl(hkl) - cos 2q1 So f2(hkl)
+ cosql sin1ll So [ sinS f3(hkl) + cosS f4(hkl)
+ sin 2q1 So [ sin2S fS(hkl) + cos2S f6(hkl) 1
where So 544/2 - ( 511 - 512 )
fl(hkl) m1 2 m2 4 + m1 2 m3 4 + m2 2 m3 2 + m1 2 m2 2 m3 2 ) 1 m2
f2(hkl) 2 m1 2 m2 2 + m2 2 m3 2 + m3 2 m12)
f3(hkl) 2 ml m2 4 + ml m3 4 m1 3 m2 2 - m1 3 m3 2 ) / m
f4(hkl) 2 m2 3 m3 m2 m33 ) / m
fS(hkl) ml m2 3 m3 - ml m2 m33) / m2
f6(hkl) m2 2 m3 2 - m1 2 m2 4 - m1 2 m3 4 - m1 2 m2 2 m3 2 ) / m2
and m m2 2 + m3 2
h dhkl/a, m2 = k dhkl/a, m3 = 1 dhkl/a
For randomly-oriented crystallites the rotational angle S (Figure 2) about

M is uniformly distributed.
In the analysis which follows, each peak position is found by fitting

the raw data with a linear background and a pseudo-Voight or a split-
Pearson profile. Subsequently, the slope and intercept of a straight line
are least-square fit to the measured peak positions. Finally, appropriate
selected subsets of the model parameters, e.g. d, sand S, are adjusted
to obtain an equivalent fitted line for the modeled peak positions.
In Figure 3 where the thermal expansion coefficient of SmS is between

that of fused quartz and CaF2 (Table I), cooling from the 400°C deposition
imposes stress of opposite sign. The values of aO, the unstressed lattice
constant, and v, Poisson's ratio, are fitted using the compliances from
Hailing et al. 9 Note that ao and v are given by the intersection of the
6.00 r - - - - - - - - - - - - - - - - - - - - - - - , 6.00
ao = 5.9527 A
II = -0.27
5.98 5.98
LATTICE LATTICE
o PARAMETER
PARAMETER 5 96 5.96
0_-
(A) . ~_-cr (A)
• _- 0
CaF2 O_~o1f- o. 0 •
5.94 -- --
SUBSTRATE _ _
2.3 kbar
COMPRESSION
.90-
5.94
5.92 5.92
-1.0 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1.0
all COS (2~) a .1.
Fig. 3. Stress analysis of SmS thin films on fused quartz and CaF2 sub-
strates. Parameters shown are results of least-square fits.
two lines if So = 0 and substitutions 'for Young's modulus and Poisson's

ratio, Sll = lIE and S12 = -vIE, are made in the equation for (~d/d)/s.
Values of a are a L at cos(21jJ) - 1.0, and an at cos(21jJ) = -1.0.
Figure 4 illustrates the stress analysis results for a surface layer

which has been converted to the metallic state by polishing an SmS thin
film. 3 A large compressive stress caused by rearrangement of the
crystallites during polishing maintains the metallic surface layer.11
Tabulations of stiffness tensor, C = S-l, indicate that Cll and C44
remain relatively constant while C12 changes sign through the transition. 9
In order to fit the data using the previously determined aO, a negative C12
is required which results in a negative Poisson's ratio, v = -.70.
For Sm1_xGdxS with x ~ Xc = .17 where the thermal expansion coefficient

is small, one might expect the thermal contraction of CaF2 to induce a
metallic state. Figure 5 illustrates that a negative Poisson's ratio is
present in the film on the CaF2 substrate, otherwise the two linear fits
would intersect at an observable ~ angle corresponding to the unstrained
lattice parameter. One should note, however, the lattice parameter is not
that of a fully metallic state. The lattice parameter parallel to the
substrate (all) is constrained to a value determined by its value at the
400°C deposition minus the substrate contraction due to cooling from 400°C.
For x > Xc = .17 the effective Poisson's ratio is negative as shown in

Figure 6 since the fitted-lines do not intersect at an observable ~ angle.
Table I. Selected Thermal Expansion Coefficients
SmS 11. 7 x 10- 6 Ref. 6

Sm.S6 Gd .14S 1. x 10- 6 Ref. 3
Sm.S2 Gd .1S S 36. x 10- 6 Ref. 3
Fused Quartz .5 x'10- 6

Sapphire 5. x 10- 6
CaF2 lS.5 x 10- 6
F. E. MOORE 157
5.76 16.2 kbar COMPRESSION 5.76

p = -0.70
ao = 5.9527 A
5.74 5.74
LATTICE LATTICE
PARA~ETER 5.72
(AI
• 5.72
PARAMETER
(AI
5.70 5.70
5.68 5.68
-1.0 -0.8 -0.6 -0.4 1.0

all a.l
Fig. 4. Stress analysis of metal surface layer of polished SmS thin film.
Parameters shown are result of least-square fit with fixed aO'
In this case tension is generated in the films because Sml_xGdxS of this

concentration has a very large thermal expansion coefficient between the
400·C deposition and ambient temperatures (Table II due to the onset of the
phase transition at a critical temperature of -200·C. Although the
unstressed lattice constant, aO, has a metal-like value, note that the
parallel lattice parameter (an) is determined by the constraining planar
dimensions of the substrate. Since the average valence is proportional to
the average lattice parameter, the thin film should display an optical
reflectance between that of the semiconducting and metallic states. This
behavior has been verified by optical spectroscopy.
5.90,---,,---,I,---,----rI----r----rI- . - .I-.-.-I-,---.--
1-'--'---1'-'-1'---'1,---,---,5.90
Si02 SUBSTRATE
I
+
I- 0.67 kbar TENSION -
•
-.=-0-.04----___~·:!~~+L~T~-I~r__J
[
~ ~ ~
J.-9--~
5.88r 5.88
LATTICE
ao = 5.8797 A ~ ~_ (y- LATTICE
PARAMETER
PARAMETER
(AI
I-
-rr-- - - -
(AI
1----- _ - - - - - I
5.861- 5.86
CaF 2 SUBSTRATE
I- 1.36 kbar COMPRESSION -
p = -0.49
5.84 1 1 1 1 1 1 1 1 I 5.84
-1.0 -0.8 -0.6 -0.4 -0.2 o 0.2 0.4 0.6 0.8 _ 1.0
COS (2;(-1 a.l
Fig. 5. Stress analysis of Sm.86Gd.14S thin films on fused quartz and CaF2
substrates. Parameters shown are results of least-square fits.
ao = 5.7363 A
5.84 p = -0.49 5.84
10.4 kbar
5.82 TENSION 5.82
LATTICE • LATTICE
PARA~ETER 5.80 PARAMETER
5.80
(A) (A)
5.78
---
CaF;------_
SUBSTRATE
4.9 kbBr
5.76 TENSION
BJ.
Fig. 6. Stress analysis of Sm.82Gd.18S thin films on fused quartz and CaF2
substrates. Parameters shown are results of least-square fits.
Figure 7 illustrates results of a simple microstrain/crystallite-size

analysis using FWHM broadening of Cauchy-function profiles. 12 Line broaden-
ing due to random orientation of crystallites in the macrostrain field as
determined by peak-to-peak deviations of (~d/d)/s with varying 8 have been
removed from the 220 and 440 line widths. As can be seen from the slope of
the analysis line, SmS films have only slight microstrain whereas films
alloyed to a concentration greater than Xc have a large microstrain. The
change in slope occurs at xc' The exact origin of the phenomena and its
association with the phase transition has not been determined but may be
related to variations in x between crystallites. The extrapolated intercept
28
24
Sm.78 Gd .22 S
... 220,440
20
o .111,222
FWHM 16 o .200,400
x COS (e)
x 103 12 A,s
(2e RADIANS) 12
DEPOSITION RATE
345 A SmS
SIN (e)
Fig. 7. Microstrain/crystallite-size analysis of SmS and Sm.78Gd.22S showing

extrapolated crystallite size of 345 A.
F. E. MOORE 159
corresponds to a crystallite-size of 34SA which correlates well with 340A

determined by TEM analysis.
SUMMARY
We have demonstrated that x-ray diffraction is extremely useful in the

analysis of thin-films of SmS and Sm1_xGdxS which display intriguing elastic
behavior near the region of the phase transition. The first-order phase
transition observed in bulk material is suppressed due to substrate
constraints on the parallel lattice parameter which permit only a partial
phase transition between the semiconducting and metallic states.
The author acknowledges the support of A. M. Turner, W. E. Case, T. A.

Shafer, L. C. Coleman, C. L. Hawkins, A. J. Quinonez and M. G. Murley.
1. J. Hornstra and W. J. Bartels, ~ Crys. Growth, 44:513 (1978).

2. A. Segmuller and M. Murakami, in: "Analytical Techniques for Thin
Films," K. N. Tu and R. Rosenberg, Eds., Academic Press (1988).
3. A. Jayaraman et al., Phys. Rev. ~, 11:2783 (1975).
4. A. Jayaraman et al., High Temperatuers ~ High Pressures, 7:1 (1975).
5. I. A. Smirnov and V. S. Oskotskii, Sov. Phys. ~, 21:117 (1978).
6. Samarium Sulfides, in: "Gmelin Handbook of Inorganic Chemistry, e7,
Rare Earth Elements: Sc, Y, La-Lu: Sulfides, Oxide Sulfides, Alkali
Thiometallates," R. J. Meyer et. al., eds., Springer-Verlag (1983).
7. J. L. Kirk et al., Phys. Rev. ~, 6:3023 (1972).
8. V. I. Rashchupkin et al., Sov. Phys. Sol. ~, 20:1453 (1978).
9. T. Hailing et al., ~ Phys. ~: Sol. ~ Phys., 17:4564 (1984).
10. Huber 652 Guinier system with Siemens D500 control electronics.
11. B. I. Smirnovet al., Sov. Phys. Sol. ~, 25:305 (1983).
12. H. P. Klug and L. E. Alexander, "X-Ray Diffraction Procedures," John
Wiley and Sons (1974).
RESIDUAL STRESSES AND DIFFERENTIAL DEFORMATION
OF ELECTROPLATED STRUCTURES
G. Sheikh and r. c. Noyan
Dept. of Metallurgical Engineering,

Henry Krumb School of Mines, Columbia University
New York, NY
Thomas J. Watson Research Center

IBM Research Division
Yorktown Heights, NY
ABSTRACT
We report the results of a recent study where nickel substrates electroplated with chromium
were loaded in-situ on an x-ray diffractometer. This technique allows determination of lattice
spacings in the vicinity of the interface for both the film and the suhstrate as a function of the ap-
plied load. We used such lattice parameter data, SEM observations of the surface and x-ray peak
breadth data to study the partitioning of deformation hetween the film and the suhstrate. The data
indicates progressive loss of adhesion between the film and the substrate with increasing deforma-
tion. We observe significant effect of electroplating residual stresses on the mechanical behavior of
the system. The loss of adhesion between the film and the substrate coupled with the initial residual
strcss profile causes an apparent 'negative Poisson's ratio' for the film during initial stages of the
loading. This effect disappears with cyelie loading and unloading.
INTRODUCTION
Electroplated systems are used in many areas of engineering. They can be found in decorative
areas such as gold-plated jewelry, or in technical applications such as device interconnections in
micro-electronic circuits. As such, the mechanical response of plated systems to applied loads and
the integrity of the interface hetween the film and the suhstrate is a subject of significant techno-
logical importance. To characterize the interface and the mechanical response various tests are
used. These tests fall into two broad groups; (i) tests applied to the plated system (film plus the
suhstrate) and (ii) tests applied to free standing filmsl.
Signifieant among the tests applied to the plated system is the standard tensile tesP. In this
test, the applied load and total elongation of the plated system arc measured. Since the film is
usually very thin, the measured parameters arc dominated hy the response of the substrate. Little
is learned ahout the stress/strain distribution in the film or ahout the deformation concentration at
the interface. Interface integrity and strength can be determined hy the"peel" test 3 , whcre the load
required to peel thc film ofT the substratc is recorded. This test, however, is gcometry sensitivc and
is hcst used as a comparative technique. It can not he applied with ease to all specimens, especially
to hrittle films. Furthermore, stress/strain partitioning between the film and the substrate can not
he studied by this method. As a result of the complications associated with the tests described
ahove, significant research effort has gone into the determination of the mechanical properties of
free standing films4. These films are tested in uniaxial tension on thin-film testers, or in bi-axial
tension on bulge testers2,5. The properties measured by such methods will be only those of the film.
The interface between the film and the substrate, and its effects on the mechanical properties can
not be studied by these methods. Reconstructing the properties of the plated system from the
stand-alone properties of the film and substrate is not a trivial task. It requires, in addition to these
properties, information about the interface and its effects.
The fundamental parameters which influence the mechanical response of a plated structure
to an applied load are the elastic constants (Young's moduli and Poisson's ratio) of the substrate
and the film. In addition, configurational parameters, which depend on the past treatment and ge-
ometry of the structure, influence the mechanical response. These include the yield and fracture
stre~ses and the respective thickness's of the substrate and the deposit. Other configurational pa-
rameters that can strongly influence mechanical response arc the residual stress fields within the
system, defect types and distributions near the interface and interface geometry. Testing free-
standing films alters the residual stress field of the e1ectrodeposit6. It also bypasses the clastic
compatibility requirements imposed upon the system due to the presence of such an interface.
Hence the results obtained from the mechanical testing of free-standing deposits, uniaxial tensile
testing or biaxial bulge testing, may yield misleading information.
Thus it is necessary to be able to distinguish the elastic response of the individual components
of the plated structure to an applied load without interfering with the structure. The standard
method of x-ray elastic constant determination utilized routinely in x-ray residual stress analysis 7 is
an ideal testing method that can he applied to this problem. This application is demonstrated in the
current study.
THEORY
Assume that a homogeneous load F is applied along the XI direction to a plated system. The
strain at any point within the system (film or substrate) is given by:7
(I)
I lere e~ is the strain due to the applied load, eij is the residual strain in the system due to plating
residual stresses, and Eif is the incompatibility strain that arises because of the presence of the film-
sllh~trate interface. This term will be zero if the elastic constants of the film and substrate are equal
and if the interface is "perfect".
The strains given hy equation (I) will affect the atomic plane spacings along a given axis
by the relation:
(2)
where Ei,res is the resolved net strain along the axis i. The changes in d j can be detected by x-ray
diffraction. This forms the basis for the majority of x-ray stress/strain determination techniques.
In an x-ray diffraction experiment using the traditional sin 2 t/' technique, the plane spacing along a
given axis II (figure I), is given by:7
d<{lift - do 2 . 2 . 2
d = {Ell cos cP + E22 sm cP - En} sm tit + E.l3 (3)
o
In this equation, the shear terms Eij , iii arc assumed to be zero. In the cases of electroplating, this is
required by the equations of equilibrium and by symmetry considerations.
G. SHEIKH AND I. C. NOYAN 163
Figure I: The sample coordinate system Xij and the direction of the measured x-ray stress (T4>'
If equation (3) is written in terms of stresses, one obtains:
d"'I/t - do I- v . 2 v
do =~ (T", Sill '" - E (Tkk
(4)
Here the stress (T 4> is the stress in the S~ direction (figure I) and (Tkk = L(Tii' Again, as in equation
(I), (T ~ is the total stress and contains contributions from the applied, residual and interaction stress
fields;
(5)
~
Here the terms are analogous to those in equation (I). For a uniaxial load F applied to a plated
specimen along the XI direction, all (T~ are zero except (T~I' and all (Tij are zero except (TIl = (Th. The
interaction stresses (Tir depend on geometric factors as well as material parameters and all of these
tensor components may be locally finite'·8.
Equations (4) and (5) form the basis of x-ray tensile testing+. In this procedure, the load is
applied through a jig that is mounted on the diffractometer and the strain is read through the x-ray
measurement. This strain is an x-ray average of the microstrains in the diffracting volume of the
particular V' tilt. Since, because of diffraction, it is confined to either the film or the substrate, all
the data is obtained from a particular volume. Purthermore, because of absorption, the data can
be confined to the region around the interface in the substrate by choosing the fIlm thickness or the
wavelength of the incident radiation. Thus, this method can be used to study the strain effects in
the first couple of 11m of the substrate near the interface. Of course, with such radiation, one ob-
tains data from the entire thickness of the film.
EXPERIMENTAL PROCEDURE
In this study the chromium-nickel system was used. The nickel substrates were machined
into dog-bone type tensile specimens from commercially available rolled sheets (~99.2% pure). The
dimensions of the gage section were nominally (27.00 x 6.36 x 0.77) mm. The specimens were me-
chanically polished (240, 400, 600 grit paper, 6, 3 micron diamond paste and 0.05 micron alumina)
to a mirror finish. They were subsequently annealed at 600C for four hours in a reducing atmos-
phere (forming gas) amI furnace-cooled. The specimens at this point exhibited mild texture.
tOne can also plot the "slope" of the d~1l vs. sin 2V' data vs. the applied load (eqn. 4). This is the
traditional method of determining x-ray clastic constants. However, it can also be used to detect the
onset of micro - yielding'.
Chromium was, then, electroplated on the nickel substrates from a hexavalent chromium acid bath
(250 gil of er0 3 and 2.7 gil H2S04 ), Two separate plating conditions were used yielding bright
deposits·,ID. Plating at sse and 0.4 amps/em2 resulted in smooth deposits with no visible surface
defects even at high magnification (> 5k). Plating at room temperature and 0.08 amps/cm 2 resulted
in crazed deposits, where the surface had fme lines, or crazes separating large, smooth regions. The
deposit thickness's were in the range of 1-3 Ilm.
The plated specimens were, then, placed in a tensile device which, in turn, was mounted on a Picker
horizontal diffractometer. The load was applied step-wise and it was monitored by a load cell.
Applied Stress (MPc)

..,
~
ci
.
N
CII
....... 0
,. II!
EO
...e~o;
!fiio
Pl
c:
'0 b
co 0
~~
.... '
co 0
c:
co
e.
D
... 0
CII
01)
c: 01)
-ci
i
0u-__ ~ ____ ~ __ ~ ____ ~ __ ~ ____ ~ __ ~ ____ ~ __ ~ ____ ~~
o 50 100 150 200 250

Applied Stress (MPc)
Figure 2: Variation of the x-ray stress,O'~ (2-a) and the interplanar spacing at tit = 0; dhk',~~o
(2-b) with the applied load in the Ni substrate.
Filtered copper radiation, with the bcam centered in the gage length, was used. The 331 and 420
reflections of nickel at 20 Bragg = 1450 and 1560 respectively, and the 222 reflection of chromium
at 20 Bragg = 136° were examined during each step of the loading.
EXPERIMENTAl, RESUlTS
for each load, the complete sin 2 '" stress analysis was carried out for the Ni substrates. Represen-
tative data is shown in figure 2-a. It can be seen that Ni has compressive residual stresses at zero
applied load. This is quickly overcome by the applied tensile stress and the relationship between the
applied load and the x-ray stress is linear during load application. In addition, the d¢ll at '" = 0,
which is the (311) plane spacing in the direction of the surface normal x] was monitored (fig. 2-b).
This plane spacing dccreased monotonically with increasing applied (tensile) load along the XI di-
rection. This is expected, since Poisson's contraction must occur in all directions normal to the
tensile axis. Similar results were observed for the (420) planes. Thus, one can conclude that Ni is
behaving "normally" in its response to the applied load.
The x-ray analysis of the film was more complicated. The chromium deposits were highly
textured and the perfection of the (III) orientation increased with increasing thickness of the de-
posit. The chromium peak examined, 222, virtually disappeared at if/-tilts > 10°. llecause of the
limited if/ range, only the variation of the (222) plane spacing in the X3 direction ('" = 0) was mon-
itored as a function of the applied load. This data is shown in figure 3-a. It is seen that there are two
distinct regions: dm.~~o first decreases with applied load, showing the expected Poisson's con-
traction. Then, after a critical transition point (Ter it increases rapidly, showing effectively a negative
Poisson's ratio. All specimens examined exhibited similar behavior with the transition occurring
at applied stresses of 125-175 MPa. This behavior persisted regardless of the status of the deposits
(crazed or craze-free).
If these specimens are cycled in load; i.e, loaded, unloaded and loaded again, a ratcheting
mechanism is observed in this anomalous expansion (figure 3-b). The plane spacing does not relax
to its initial value after the first unloading step but relaxes to a higher value. If the film is loaded
again, we see some Poisson contraction until we reach a new transition load (Ter' However, in this
case, (Ter increases to approximately the highest load encountered by the specimen in the previous
loading cycle. After the transition point, we again observe some anomalous expansion of dm,~~o
with increasing tensile load. Upon unloading, the plane spacing dm.,H relaxes to value higher than
the prrvious cycle. At this point, further loading or unloading has no effect on the plane spacing
dm .,.-" from thc elcctrodeposited film.
The shapes and breadths of the x-ray diffraction peaks were also monitored during the x-ray
analysis. The peak breadth at half maximum intensity (1'.Il.lI.M.l.) of the chromium deposit re-
mains constant (within the margin of error) over the three cycles of loading. The Ni peak, however,
did show effects of plastic flow: Prior to deformation, the nickel substrate exhibited relatively 'sharp
and resolved peaks. The K." K.2 from the 311 and 420 reflections became broad and unresolved
when the load exceeded 150 MPa during the first loading cycle. This indicates some plastic flow
within the diffracting volume. However, towards the end of the second loading cycle, the peak was
resolved again, indicating some recovery.
The surfaces of the specimens were examined under scanning electron and optical micro-
scopes before and after each load cycle. After the transition point aen severe cracking was observed
in all Cr films. These cracks ran across the width of the specimen in the plane of the film, and were
normal to the tensile axis (Mode I cracks). In the crazed specimens, these cracks cut across the
craze-free regions. In addition, some crazes that were normal to the load axis enlarged considerahly
and hecame comparable in width to the cracks caused by the loading. Thc mode I cracks extended
over the edge anc! through the layer of chromium platcd on the sides. To check the interface,
transverse cross sections were prepared using an electron discharge machine. Cracks extending
parallel to the interface and occasional cracks parallel to the tensile axis were observed (Mode II
cracks). All cracks were limited to the gage length and ended at the grips of the tensile device.
DISCUSSION AND CONeI ,USIONS
The peak-breadth data indicates that the Ni suffers plastic flow in the range of 125-175 MPa,
whereas the Cr film docs not. The incompatibility in strain across the boundary causes cracking in
the Cr film. Microscopic examination of the surface reveals both Mode I and Mode II cracks.
Thus, we have delamination and cracking of the film when the Ni goes into plastic flow. The
Chromium Interplanar Spacing/Crazed Specimen
Ocr a
I
I
I
I
100 150
Applied stre•• (MPa)
Chromium Deposit Interplanar Spacing
2
+3
~OUL__ ~ __ ~ ____L-__ ~ __-L__ ~~ __ ~ __ ~ __-L__ ~~~~
o 200 250
Applied StreB. (MPo)
I'igure 3: Variation of dm,~-o with the applied load "~I in the Cr film. When the critical stress
"cr is exceeded, the lattice spacing normal to the applied tensile load starts expanding (3-a).With
cyclic loading, a ratcheting mechanism is observed in the anomalous expansion (3-b).
Figure 4: Surface of chromium eleetrodeposit after the transition point "cr'
anomalous expansion in the (222) plane spacing in the direction of the surface normal d 222 • \H' can
he explained hy the relaxation of plating residual stresses. If we re-arrange equation (4):
I -u r
(hkl,o/I=O = d0 + do( E ){ 11110 + "kk) (6)
The variation of dhkl.~~O with applied load, a~hkl'II=O, is given hy :

".pp.
(7)
For applied stresses larger than "eI' the observed variation in d hk, • ~ ~ o is possible if and only if
orrh/O(Tapp. < -I . Since the change in (Tapp. is positive, the change in the residual stress term must
be negative. Given the houndary conditions of this experiment, this is possible only by relaxing
ten~ilc rc~idual stresses in thc chromillm film.
It is possible to quantify the rate of this (residual stress) relaxation with the x-ray data. The
plot of d hk" ~=O vs. cr. pp. approximates a straight line for this specimen. If the experimentally measured
slope of this line is "M.", equation (7) can be written as:
-u aUkk
M<1=d o(T)(1 +-a-} (for "app. > "cr) (8)
, U app.
Thus, in the case of this specimen, the change in residual stresses is linearly related to the applied
load:
(for U apr. > u cr ) (9)
Here, (Ukk)'cr. is the total residual stress within the film hefore relaxation starts, C is a constant of
integration and K is given by:

-EM
K = _-,--(f_ + I. (for (Tapp. > O'er,) (10)
IJd o
Numerical analysis of the data using the above equations will be presented in a later article.
The analysis also permits qualitative evaluation of interface damage: The relaxation of the
residual stresses in the Cr film can be due to two possible causes;
I. Plastic flow in Cr.
2. Delamination of the interface.
Since x-ray data indicates negligible plastic flow in the Cr, most of the relaxation is due to the de-
lamination of the interface. In a recent study it was found that the cracking of brittle films may be
followed by delamination if the substrate possesed high yield strength (stainless steel) and if the
interface was not "clean". Low yield strength substrates (aluminum) enhanced film cracking tend-
ency but also inhibited delamination by blunting film cracks at the interface". Nickel lies on the
higher end of this spectrum and the lower fracture toughness of the interlayer may be due to the
presence of contaminating residues from the annealing process.
Assuming a homogeneous residual stress distribution in the film, as well as a homogeneous
distribution of deformation/damage due to the applied load, one can also conclude that delami-
nation is linear with the applied load. After the second loading cyc-le, delamination has reached
saturation and very little force is transmitted from the substrate to the film. Thus, no change at all
is seen in the d hk1 , H from the film in response to the applied load. The film is still attached to the
suhstrate in spots, since we did not observe any large scale spalling of the film. In such anchoring
spots, dhk1 , ,H mllst change. The fact that we do not see any change in the x-ray data indicates that
the total volume of such anchoring spots is much smaller than the delaminated regions·.
SUMMARY
Nickel substrates electroplated with Cr were loaded into the plastic deformation range on an
x-ray diffractometer. Plane spacing data as a function of load from the substrate and the film were
used to study the partitioning of deformation in the system. Progressive loss of adhesion was ob-
served above a critical load (Tn This loss of adhesion, coupled with plating residual stresses causes
an apparent "negative Poisson's ratio" in the film.
X-ray tensile testing is a novel and unique method which can be used to obtain qualitative and
quantitative information about the mechanical properties of plated interfaces. This technique can
be casily used as a non-destructive quality control tool in production.
ACK NOWI.EDGEMENTS
The authors would like to thank Dr. Dave Rath of IBM Yorktown for significant assistance
with plating theory and practice and many helpful discussions. Thanks are also due to Professor
Juan Sanchez of Columbia University for helping and encouraging us at all stages of this study.
REFERENCES
I. D. i\. Hardwick, The Mechanical Properties of Thin Films, Thin Solid Pilms, 154:109 (1987).
* The x-ray volume average is dominated by the larger volume.

2. T. D. Dudderar and F. B. Koch, Mechanical Property Measurements on Eleetrodeposited

Metal Foils, in: "Properties of E1ectrodeposits Their Measurement and Significance", R. Sard,
II. Leidheiser and F. Ogburn cds., vol. 187, The Electrochemical Society, Inc., Pennington,
NJ (1975).
3. D. S. Riekerby, A Review of the Methods for the Measurement of Coating-Substrate Adhe-
sion, Surf and Coating Tech, 36:541 (1988).
4. W. II. Safranek, 'The Properties of Electrodeposited Metals and Alloys", Elsevier, New York
( 1986).
5. R. RoIfT, Significance of Ductility and New Methods of Measuring the Same, in: 'Testing of
Metallic and Inorganic Coatings", W. B. IIarding and G. A Di Bari eds., vol. 947, ASTM,
Pairfield, PA (1987).
6. M. r. Doerner and W.D. Nix, Stresses and Deformation Processes in Thin Films on
Substrates, CRC Critical Reviews in Solid State and Materials Science vol. 14, issue 3 (1988).
7. I. C. Noyan and .T. B. Cohen, "Residual Stress Measurement by Diffraction and Interpreta-
tion", Springer-Verlag Inc., New York (1987).
8. A. Segmuller, J. C. Noyan and V. S. Speriosu, X-Ray Diffraction Studies of Thin Pilms and
Multilayer Structures, Prog. Crystal Growth and Charact., 18:21 (1989).
9. II. Fry, A Study of Cracking in Chromium Deposits, Trans. Inst. Met. Fininshing, 32:107
(1955).
10. M. McCormick and S. .T. Dobson, Characteritics and Properties of Electrodeposited
Chromium from Solutions with Varying Sulphate Ratios, Trans. Inst. Met. Finishing, 65:24
(1987).
II. M. S. I1u and A G. Evans, The Cracking and Decohesion of Thin Films on Ductile
Substrates, Acta metall., 37:917 (1989).
X-RAY RESIDUAL STRESS ANALYSIS OF Zn-Ni ALLOY ELECTROPLATING LAYERS
Toshihiko Sasaki*, Makoto Kuramoto* and Yasuo Yoshioka**
* The Institute of Vocational Training

Kanagawa, Japan
** Musashi Institute of Technology

Tokyo, Japan
INTRODUCTION
Zn-Ni-alloy electroplated steels are one of the surface-treated

materials with a high corrosion resistance and are mostly used for
automobiles. It is said that the corrosion resistance is more than four
times as great as that of Zn-plated steels.(l) Concerning x-ray stress
measurement,(2)(3) Kyono et al reported the result of measurement ony (552)
planes and showed that the sin 2 1jJ diagram was severely curved.
X-ray stress analysis in surface-treated materials will become more

important. Some problems, however, remain to be studied when we apply the
x-ray method to thin layers. For example, the effective x-ray penetration
depth may be different from that in ordinary materials. And complex
gradients of stresses and compositions may exist.
In this paper, the change in the sin 2 1jJ diagrams obtained from y(552)
planes in Zn-Ni-alloy electroplating layers under different conditions are
shown first. Next, some fundamental problems in the x-ray stress
measurement in thin layers are discussed.
Materials
Four kinds of samples of Zn-Ni-alloy electroplated steel were prepared

as shown in Table 1. The thickness of the substrate (rolled steel) is 0.8
mm; 12 wt% nickel is contained in the plating layer. This layer is said to
be composed of intermetallic compounds such as NiZn3 and Ni5Zn2l.(1)
The effect of heat treatment was examined on sample #4. Samples were
exposed to temperatures of 100, 200 and 300 oC, respectively, in vacuum for
two hours and a slow furnace cooling was applied.
X-Ray Instruments
Three types of x-ray instruments were used as shown in Table 2. They

differ from each other in respect of goniometer and x-ray optics.

Table 1. SAMPLES OF Zn-Ni-ALLOY ELECTROPLATED STEELS
Sample Plated Weight Thickness

Number Face of Plating of Plating
#1 Both Sides 20 (g/m2) 2.7 (]lm)

#2 One Side 20 2.7
#3 One Side 30 4.1
#4 One Side 40 5.4
Table 2. MAIN DIFFERENCES OF INSTRUMENTS
Instrument X-Ray Optics Goniometer
Type-A Para-Focussing 'l'-Type

Type-B Parallel \"I-Type
Type-C Parallel 'l'-Type
Sin 2 1/! Diagrams
Fig. 1 shows the sin2~diagrams obtained from Y(552) planes of a Zn-Ni

plating and different instruments and x-ray radiations used. Four specimens
were cut out from sample #1 and the measurements were carried out in both +~
and -~ directions. The averages of those were drawn in Fig. 1. We can see
that the sin2~ diagrams are curved and closely approximate a parabolic
shape. And the shape seems to be almost independent of instruments and
x-ray radiations. Fig. 2 shows an example of the distribution of the
diffraction intensity obtained by instrument C with Cr-Karadiation. It
appears difficult to explain the curvatures in the sin2~ diagrams by the
effect of texture alone.
~12,19r c, - JII j! II Cr-Ka PI

.;/: /1
K a FHa
~=f\ ~ 1:.
!: /
0
"'. ;' 0 B .' -
; .r." B ./ 0 "'~" \ 0
i \y
C \0 \.'. .... e,'
~O-A
c C aDa+--A
(a) (b) ( ) e...-- C
. 121 6'-:-_ _
a
---,,-=-__
.35
---'
.7 a
'"::-__--:~--~'-::-c---':::---~
.35 .7 a .35 .7
s i n2 1/J S i n2 I/J s i n2 I/J
Fig. 1. Sin2~ plot for the 552 reflection from Zn-Ni-alloy electroplating
layer obtained by (a) instruments A and B with Co-Ka, (b) instru-
ments A and B with Fe-Ka, and (c) instruments Band C with Cr-Ka.
T. SASAKI ET AL. 173
Fig. 2. Typical example of diffraction

intensity distribution for the
552 reflection in instrument C.
CO: 1/»0. .: 1/><0)
:i o
,
.35 .7
The effect of the thickness of the plating layer on the sin2~ diagram
was also examined with sample numbers 2, 3 and 4; we obtained the result
that the differences in the sin 2 ~ diagrams were very slight.
Effect of Heat Treatment
Figs. 3 and 4 show the diffraction profiles and the sin 2 ~ diagrams of
Zn-Ni plating after heat treatment. We can see that the sin2~ diagrams show
a complete change in shape, and a linear distribution is seen at 300 0 C; new
peaks emerge near 26=130 0 with an increase of temperature.
The elemental distribution of Zn, Ni and Fe in the plating layer was

examined by EPMA. It was found that: (1) Ni and Fe are distributed uniformly
before and after the heat treatment. (2) High concentrations of Zn near the
.122
r (552)
'-,..
7000
counts
e
,S
'c"
U e
...'"
co
100' e .1216
co
c
e !!
.,.'"
200'
300' e
300' e ~
e
500' e
.............. 600' e
======::::::=::::======~.~
120 130 140 150 700' e .7
28 (deg.) s i n2 1/J
Fig. 3. Diffraction profile for Zn-Ni Fig. 4. Sin2~ plot for the 552
alloy electroplating layer reflecting after heat
after heat treatment. treatment.
5°1
'"' 22°1 r (552) (a)
I a re(211)
oS
~ r~---\
;., 200
I;
. .
\\ ':"
\.:
-50
, , '\
: : A\
(I)
(I)
.......'"
Vl
'''~~/''''''\''
180 -1 5 0 !:-=---'------'="----'---,--,J
- 6 ~o0::----'----';;-0---'---'6:-::'0'0 - 600 0 600
Strain (X10- 6 ) Strain (X10- 6 )
Fig. 5. Stresses during bending process in (a): the plating layer
and (b): the substrate.
surface and the boundary to the substrate were observed before the heat
treatments; the distribution became uniform after the heat treatment at
300 0 C for two hours. Such a distribution of Zn may cause the sin2~ diagrams
to be parabolic.
Effect of Mechanical Loadin~
Fig. 5 shows the x-ray stresses in both the plating layer and the
substrate of sample #4 which was kept at 300 0 C for 2 hours while subjected
to a four-points bending. X-ray stresses in the substrate, aFe(2ll), are in
proportion to the applied strain. But x-ray stresses in the plating layer, y
(552), calculated by means of E=78 GPa, v=0.25, 8=70.5 0 are decreasing
during the tensile loading process and then change another way during the
stress releasing process. This result is thought to be caused by the
initiation or the growth of cracks in the plating layer. The residual
stress was released due to the removal of restriction.
The result suggests that we have to determine x-ray stress constants

when a non-heated sample shows a nonlinear sin2~ diagram. A method has
recently been developed by the authors but is not discussed in the present
paper.
CONCLUSIONS
(1) It was found that the sin2~ diagram for y (552) planes of the Zn-Ni-
alloy electroplated layer showed a parabolic shape.
(2) The change in the sin 2 ~ diagram due to changing the x-ray radiations
is very slight. This can be explained theoretically as being typical
of thin layers.
(3) High concentrations of Zn near the surface and the boundary to the
substrate were observed. These concentrations may be related to the
shape of the sin2~ diagram.
ACKNOWLEDGEMENTS
The authors are grateful to Dr. M. Katayama, Dr. K. Kyono and Dr. C.
Kato of Kawasaki Steel Co. for kindly supplying the samples and much helpful
T. SASAKI ET AL. 175
information. They are also grateful to Dr. T. Takebuchi and Dr. M.

Mochizuki of JUKI Co. for kindly co-operating with the experiment.
REFERENCES
(1) K. Yamato, T. Honjo, T. Ichida, H. Ishitobi and M. Kawai, Technical

Report of Kawasaki Steel, 16, 72 (1984).
(2) K. Kyono, K. Yamato and M. Katayama, The 24th Symposium on X-Ray
Studies on Mechanical Behavior of Materials, (1987), p. 31.
(3) M. Kurachi and K. Fujiwara, Trans. JIM, 11, 311 (1970).
XRD CHARACTERIZATION OF TITANIUM/COPPER THIN FILMS HEAT
TREATED IN VACUUM AND HYDROGEN
M. J. Sullivan, C. Goldsmith
International Business Machines

East Fishkill Facility
Hopewell Junction, NY
P. Ficalora
Rensselaer Polytechnic Institute

Troy, NY
INTRODUCTION
Thin film metallization is used on integrated circuit chips and

ceramic and/or organic substrates for a number of different purposes
[1]. On chips the metallization forms Ohmic and Schottky Barrier Diode
contact to the semiconductor and the electrical properties of these
contacts are strongly influenced by the metals used [2]. Interaction
of the metal and semiconductor during processing can result in major
variations in the electrical properties of the contacts [3-6]. Chip
metallization is also employed to provide electrical interconnection
between devices on a chip. The interconnections can all be made in a
single layer, or for more complex chips, a number of layers might be
employed using dielectric layers to separate metal layers and via
holes through the dielectric for layer-to-Iayer interconnection. Chip
metallization is also used to form the interconnections between the
chips and the substrate carrier [7]. These connections are usually
wire bonds or "solder bumps." On substrates the thin film
metallization is used for interconnections, wire bonds, solder bumps
and in some cases I/O pins are soldered or brazed to the metallization
to provide connection for the next level of packaging [8].
Since circuit delay times are directly related to metallization

resistance [9], it is important to choose a metallization system with the
lowest possible resistivity consistent with the many other constraints
imposed on metal system, i.e., good adhesion, process stability,
corrosion resistance, etc. Copper metallization provides excellent
electrical resistance and solderability, but copper exhibits poor
adhension to most chip and substrate insulators. In addition, the poor
corrosion resistance of copper makes it unsuitable as a wire bonding
Advances In X-Ray AnalYSIS, Vol. 33 177

material. The adhesion problem can be solved by providing a adhesion

layer such as chromium [10] or titanium [11] since these refractory
metals form very strong "oxide bonds" [12] to the substrates. Note
that the addition of the adhesion layer results in the formation of
another interface, i.e., adhesion layer-to-copper, and that
interactions at this interface are important. The corrosion problem
can be solved by covering the copper with a noble metal such as gold.
During integrated circuit package fabrication a number of high

temperature processing steps occur in the temperature range 300°C
to 450°C usually for times less than four hours. These steps could
include sputtered quartz deposition, curing of organics, contact
sintering to reduce oxides, soldering and brazing. During these high
temperature process steps, various atmospheres are employed such as
air, nitrogen, forming gas and hydrogen.
2.EXPERIMENTAL PROCEDURE
Thin films of titanium and titanium/copper were deposited on 82 rom

silicon wafers, <100> orientation, with 0.1 rom of thermally grown silicon
dioxide. The wafers were loaded into a Varian ele~6ron-beam evaporation
system, which was pumped to a pressure of 1.0 x 10 torr, and then
wafers were preheated to 150°C. The wafers were then R.F. sputter cleaned
for 20 minutes at 1.0 Kw using argon as the working gas. In order to
insure thickness uniformity, the wafer dome was rotated during metal
deposition. The titanium films were deposited at 1.0 nm/sec., as
determined by a quartz crystal rate monitor, and the as-deposited
thickness was 265 nm. Residual gas analysis (RCA) during titanium
deposition showed a decrease in the water peak and an increase in the
hydrogen peak. The titanium/copper films were deposited in a single
pump-down with a deposition rate of 1.0 nm/sec. for both titanium and
copper. The as-deposited film thicknesses were 240 nm titanium and 140 nm
copper.
Samples were heat treated in vacuum and in hydrogen using a hot-

stage furnace which was designed and built specifically for these
experiments. The samples were placed on a stainless steel hot stage
approximately 6 cm x 6 cm and 0.25 cm thick. Heat was supplied by
electrical resistance heaters obtained from the Tempco Electric Heater
Corp. The heaters consisted of nichrome wire imbedded in ceramic inside a
stainless steel tube with a glass seal around the power input wires. Two
iron-constantan thermocouples were placed in contact with the surface
of the hot stage. One thermocouple was attached to an Omega model
2176A digital thermocouple and was used to monitor the temperature.
The other thermometer was attached to an LFE model 216 temperature
controller which controlled the power input and also monitored the
temperature. The temperature variation across the hot stage was less
than 2°C and the temperature fluctuation due to the pulsed power input
was +3° C.
An ultra high vacuum system was used for these experiments. The
main pump was a Varian "Vac-Ion" pump capable of pumping 200 l/sec.
This unit was backed by two oil-free pumps used for rough pumping. A
venturi jet pump was used for light roughing and a Var~3n "Vac-Sorb"
sorption pump was used to attain pressures of 1.0 x 10 torr. Using
M. J. SULLIVAN ET AL. 179
this system work chamber pressures of 5 x 10- 9 torr were routinely

achieved. In ord~9 to make a run in hydrogen the system was first
pumped t05.0 x 10 torr vacuum and then back filled with hydrogen
(99.99% pure) to a pressure of 300 torr. as measured by an MKS
Baratron absolute pressure gauge (0 to 1000 torr, 0.01% of reading).
The sheet resistances of all samples were measured using a Magne-

Tron Instruments Model M-700 Resistivity-Conductivity Test System of
the in-line, four-point probe type. Each sample was measured at least
five times and as-deposited samples were remeasured periodically to
check calibration.
The RBS data was obtained using the instrument located at the IBM
Thomas J. Watson Research Center. Samples were first mounted on a
go~~ometer in a vacuum chamber and pumped down to approximately 1.0 x
10 torr. The samples were then bombarded with monoenergetic, singly
ionized helium ions at 2.3 MeV at current levels of 20-50 nA over a 2
mm x 2 mm area. The backscattered ions (170° take-off angle) were
analyzed using a silicon surface barrier detector which produces a
voltage pulse that is proportional to the energy of the individual
backscattered ions. This system has a sensitivity of 0.1 atomic % for
heavy elements.
The X-ray diffraction data was obtained using parallel-beam

optics in a diffractometer which was specially built by Rigaku
Industries. This diffractometer was built specifically for use with
thin films where the sample volume available for analysis may be very
small. This configuration results in a large increase sensitivity at
the expense of a small decrease in resolution. A point source of
chromium Ka radiation was used with a diffracted-beam graphite
monochromator. The beam then passed through Soller slits which were
rotated 90° with respect to the usual orientation found in the
Bragg-Brentanb configuration. The beam then impinged on the
sample at a 3° grazing angle in order to increase the volume of
material being sampled. The diffracted beam then passed through
another set of Soller slits which were rotated 90° to the usual
configuration to a flow proportional detector. The sample was not
rotated and the detector rotated through 28 directly. Also, the
diffracted beam does not focus at the diffractometer circle and
therefore some peak broadening occu~s. In order to minimize
scattering and absorption by air the_~iffractometer was evacuated to
a pressure of approximately 1.0 x 10 torr. Sixteen hours of data
collection time were required for a 2@ rotation from 20 to 150°.
Figure 1 shows that the thicknesses of the as-deposited

titanium and copper films are 240 nm and 140 nm, respectively. The
X-ray diffraction data [13, 14] in Table I shows that both titanium
and copper are present as crystalline phases. AES profiles (to be
published elsewhere), reveal the presence of oxygen in the titanium
layer and of oxide on the surface of the copper film. The X-ray data
indicates that the oxygen layer is in the form of crystalline CuO
[15]. This oxide layer is very thin, on the order of 10 nm, and
probably formed during cool-down in the evaporation and during storage
in room air.
100 200 soc
- ..... ' (2) " ' ' ' ' ' '
o
o
o
<D
V1
o
1-0
o
z"ot
:::J
o
U
o
o
o
N
1.2 1.6
Backscatiering Energy (MeV)
Figure 1 As-deposited titanium/copper RBSspectrum
The sheet resistance of the thin film couple is 0.208 ~/o and the
resistivity of the copper layer can be calculated assuming that the
titanium and copper layers are parallel resistors. The copper resistivity
is calculated to be 3.07 ~~-cm which is a factor of almost two greater
than the bulk value [16]. This is not unexpected since the resistivity of
copper is very sensitive to the presence of small amounts of impurities.
TABLE I
X-Ray diffraction results for
titanium/copper - time zero
d-sEacing (X) 1/10 (%) Ehase hkl
2.7521 2 CuD 110
2.5553 12 Ti 110
2.3440 43 Ti 002
2.2445 52 Ti 011
2.0834 100 Cu III
1. 8032 44 Cu 200
1.7262 22 Ti 012
1.4762 4 Ti 110
1. 3325 10 Ti 103
1.2775 70 Cu 220
1. 2472 45 Ti 112
1. 2307 22 Ti 201
1.0
0.8
00.6
"-
c
Q)
u
<=
III
~ 0.4
·M
Ul
Q)
p:;
....,
Q)
Q)
ti O. 2 ....:::<::::::::=:~->.~
o
o
Time (hrs)
Figure 2 Variation of sheet resistance with
heat treatment in vacuum
o
- - III$.lO
--l<>
tOO
(1 t) 511/1117
(1)2/1l1li
200
-
o
o
'"
(fl0
0
f- 0
z ~
::>
0
u
0
0
0
'"
0.4 0.8 1.2 1.6

Backscallering Energy ( MeV)
Figure 3 RBS spectrum of titanium/copper heat treated for

2 hrs at 425°C in vacuum with simulation
TABLE II
X-Ray diffraction results for
titanium/copper - 368°C/lhr/Vac
d-spacing (X) 1/10 (%) Phase hkl
2.7515 3 CuO 110
2.5475 7 Ti 010
2.3405 23 Ti 002
2.2402 55 Ti 011
2.2014 12 TiCu 3 020
2.1442 20 TiCu 102
2.0827 85 Cu 111
1. 8018 34 Cu 200
1. 7258 30 Ti 012
1.5564 7 TiCu 2 202
1.4737 5 Ti 110
1.3348 6 Ti 103
1. 2783 65 Cu 220
1.2502 100 TiCu 2 133
1.2339 26 Ti 201
Also, it has been shown that the impurities introduced during thin film
deposition can increase resistivity by factors of several hundred times
bulk values. Copper also forms a number of oxides and would be expected
to react with the residual gas during deposition. The amount of oxygen or
other impurities in the copper is, however, less than the AES sensitivity
of approximately 1.0%.
The change of sheet resistance with time at various temperatures in

vacuum is shown in Figure 2. The figure show~ that the sheet resistance
varies linearly with time. The RES spectra, Figure 3, show
interdiffusion of titanium and copper for all temperatures above 350°C
and for long times at 350°C. The X-ray diffraction data given in
Tables II and III reveal the presence of unreacted titanium and
copper and the surface oxide seen on the as-deposited samples.
The X-ray data also show the presence of three intermetalJic com-
pounds, Ti Cu [17], Ti CU 2 [18] and Ti CU 3 [19J. The general trend is
for the intermetallic compound X-ray peak intensity to increase while
the titanium and copper peak intensity decreases with increasing time
and/or temperature. The RBS spectra can be interpreted using the phase
identification provided by the X-ray diffraction data. Figure 3
shows, a simulated RBS spectra superimposed on the experimental
spectra. A number of points can be made concerning the RBS spectra
interpretation.
1) The precision of the layer thickness measurements is
approximately + 10 nm.
TABLE III
X-ray diffraction results for
titanium/copper - 450°C/0.75hrs/Vac
d-spacing (X) 1/10 (%) Ehase hkl
2.7548 6 CuO 110
2.2369 78 Ti 011
2.2022 73 TiCu 3 020
2.1432 100 TiCu 102
2.0841 27 Cu III
1. 9882 90 TiCu 3 021
1. 8022 15 Cu 200
1.7301 8 Ti 012
1. 6667 6 TiCu 103
1.5589 58 TiCu 2 202
1. 5072 4 CuO 113
1.4791 16 Ti 110
1.3587 4 TiCu 3 400
1. 3048 10 TiCu 2 033
1.2934 5 TiCu 3 230
1.2783 16 Cu 220
1.2638 57 TiCu 212
1. 2533 35 TiCu 2 133
1.2313 23 Ti 201
1.2192 29 Tieu 3 213
2) Although the titanium and copper films are planar

initially, the compound layers are not planar. This is apparent
in Figure 3 at the high energy edge of the titanium peak and the
low energy edge of the copper peak. The simulated spectra
energies drop off sharply at each layer interface while the drop-
off of the experimental data energies is more gradual. This is an
indication that the layers are not planar probably due to
diffusion and reaction along grain boundaries, see Figure 4.
Spectra were simulated to match the experimental data at the mid-
point of the energy decrease resulting an average layer thickness.
3) The film surface composition measured in a number of
spectra were modeled as "compounds, "TiCu 5 and TiCu S ' which do
not exist on the equilibrium binary phase diagram [20]. This
simulation represents a structure which consists of pockets
of unreacted copper surrounded by TiCu 3 which grew to the
surface along grain boundaries. The layer thicknesses were
calculated by assuming the presence of a planar layer of
Prior Copper Grain Boundaries
I ~ 1\\\)1
I I~I
Titanium Grain Boundaries
Figure 4 - Model of titanium/copper reaction in vacuum
4S0 o C
SO
42S o C
E
.5
til
til
60 0
OJ
c:
".
u 36S oC
°rl
.c:
.j.l
:l
U 40
°rl
8
3S0 o C
20
0
0"=1
0 1 2 3 4
Time (hrs)
Figure 5 - TiCu thickness as a function of time and temperature

unreacted copper over a planar layer of TiCu,' The simulation gives

another indication of non-planar compound grcrwth.
4) The presence of a thin layer of surface CuO is apparent
at the high-energy edge of the copper peak. The simulation
spectrumis shifted to slightly higher energies because the oxide
layer is not included in the simulation.
Although it is not the purpose of this work to establish
titanium-copper reaction kinetics in vacuum, the data can be used to
illustrate a number of points. Figure 5 shows thickness of TiCu
plotted as a function of time. As noted above, the sheet resistance is
also plotted as a function of time in Figure 2. In these figures, only
the data at 350°C and 368°C contain more than two points. The figures
show that these data appear to be linear in time, and regression
analyses confirm that the linear data fit is better than a parabolic
fit in all cases, including TiCu 2 and TiCu 3 formation and Cu
consumption. Linear kinetics inaicate interfacial reaction rate
control and are expected below a critical change-over thickness where
layer thicknesses are small and the diffusion of reactants is not rate
limiting.
At the interface an atom must surmount an energy barrier, ~Hn,

as it jumps from one phase of a given structure to another phase with a
different structure. Since this process is independent of reaction
product thickness, assuming that diffusion is rapid enough to provide
reactants, the reaction rate is constant at constant temperature.
There is no variation of titanium/copper resistance with heat

treatment in a hydrogen atmosphere. The X-ray diffraction data shown
in Table IV indicate that the only crystalline phases present are
copper [14] and TiH2 [21]. The RBS spectra also exhibit the count
reduction and width increase due to TiH2 formation.
The data discussed above show that the interdiffusion and

reaction behavior of titanium/copper thin film couples is completely
different in vacuum and hydrogen heat treatment ambients.
In hydrogen the reaction to form the hydride occurs and

titanium-copper intermetallic formation is suppressed due to the
TABLE IV
X-ray diffraction results for
titanium/copper - 360°C/1hr/H 2
d-SEacins ($.) IlIo (%) Phase hkl
2.5975 100 TiH2 III
2.2410 11 TiH2 200
2.0826 82 eu III
1.8003 38 eu 200
1. 5f.5 7 20 TiH Z 220
1.3353 19 TiH2 311
1.2779 93 eu 220
greater stability of the hydride. The standard free energy of

formation of TiH2 is -80.3 KJ/mole ~22]. The standard free energy of
formation of TiCu is -18.8 KJ/mole [23]. Formation engeries for TiCu~
and TiCu 3 were not found; however, values of the standard free energy~
of formation for TiCu 4 and Ti 2Cu are -22.6 KJ/mole and -26.3 KJ/mole
respectively. It is not unreasonable to assume that the formation
energies of TiCu 2 and TiCu~ are similar to those given for TiCu, TiCu2
and TiCu 4 based on the simllarities in melting temperatures. The free
energy relationships are the same at the reaction temperatures.
4. CONCLUSIONS
The effects discussed above can have significant consequences for

integrated circuit fabrication. As previously noted,copper conductors
have very low electrical resistivity but require an adhesion layer such as
titanium. A good adhesion layer must react with the copper and this
can result in a large increase electrical resistance, see Figure 2,
during subsequent heat treatments. The introduction of hydrogen into
the heat treatment ambient prevents the titanium/copper reaction,and
no increase in electrical resistance increase occurs. Also, the
titanium/hydrogen reaction results in the formation of TiH2 which has
a lower resistivity than the as-deposited titanium film.
5. REFERENCES
1. I. Blech, H. Sello and L. U. Gregor in Handbook of Thin Film

Technology, editors: L. I. Maissel and R. GIang, McGraW-Hill
Book Co., New York (1970), Chapter 23.
2. S. M. Sze, Physics of Semiconductor Devices, John Wiley & Sons; New

York (1981), 2nd Edition, Chapter 5.
3. M. J. Sullivan, T. M. Reith, M. Av-Ron, M. Shatzkes, J. Appl. Phys.

49 3574 (1978).
4. T. M. Reith and M. J. Sullivan, Appl. Phys. Lett. 32 177 (1978).
5. T. M. Reith and J. D. Schick, Appl. Phys. Lett. 25 524 (1974).
6. M. J. Sullivan, M. S. Thesis, Materials Eng. Dept., Syracuse

University, Syracuse, NY (1977).
7. C. A. Steidel in VLSI Technology, editor S. M. Sze, McGraw-Hill Book

Co., New York (1983), Chapter 9.
8. A. J. Blodgett, Scientific American, July (1983), Pgs. 86-96.
9. D. B. Fraser in VLSI Technology, editor S. M. Sze, McGraw-Hill Book

Co., New York (1983), Chapter 9.
10. B. S. Barry and I. Ames, LB.M. J. Res. and Dev., 13 (1969), pg. 286.
11. T. C. Tisone and J. Drobek, J. Vac. Sci. Technol. 9 271 (1971) .
12. A. G. Metcalfe in ComEosite Materials Vol. I, editor: A. G. Metcalfe,

Academic Press; New York (1974) , Chapter 3.
13. W. F. McCline, editor, Powder Diffraction Inorganic Phases, JCPDS

IntI. Center for Diffraction Data, Pa. (1982), File No.
05-0682.

IntI. Center for Diffraction Data, Pa. (1982), File No. 04-0836.
15. Ibid, File No. 05-0661.
16. T. Lyman, editor, Metals Handbook Volume I, ASM, Metals Park, Ohio
(1961), pg. 48.
17. W. F. McCline, editor Powder Diffraction Inorganic Phases, JCPDS

18. Ibid, File No. 20-0371.
19. Ibid, File No. 25-0316.
20. M. Hanson, Constitution of Binary Alloys, McGraw-Hill, New York

(1958), pg. 642.

22. D. D. Wagman, W. H. Evans, V. B. Parker, R. H. Schumm, I. Halow, S.

M. Barley, K. L. Churney and R. C. Nuttall, The NBS Tables of
Chemical Thermodynamic Properties, Vol. II, NBS, Washington,
D.C. (1982), pg. 209.
23. T. B. Massaliki, editor, Binary Alloy Phase Diagrams, ASM, Metals

Park, Ohio (1986).
CHARACTERIZA TION OF THIN FILMS USING XRF
James E. Willis
Data Acquisition and Control, Inc.

P.O. Box 779
Roswell, GA 30077
INTRODUCTION
Thin film samples represent ideal samples for analysis using X-ray fluorescence in that they
tend to be flat, smooth and homogeneous. However, before a sample can be characterized
using XRF, several questions must be answered. Some of these questions are:
• How thick is the sample to the incident X-ray beam?

• How thick is the sample to its own (analyte) X-rays?
• Is this sample within the analytical range of the technique?
• If the sample has more than one layer, will the X-rays from the inner
layer(s) be absorbed before reaching the surface?
• What must be done in order to calculate the thickness and composition of
the sample starting from the measured intensities?
SINGLE LAYER THIN FILMS

Figure 1 shows a schematic of the measurement of a single layer thin film sample. The
sample geometry is characterized by the incident angle '1'1' takeoff angle '1'2 and the layer
thickness t1•
Equation 1 relates the measured intensity versus thickness for a single layer thin film.
IJ (E )
[ 1 - exp ( _ ( 1 pr1 + (Eg. 1)
51n("'1)
"'lV"2
1
Figure 1-Schematic of the measurement of a single layer thin sample. The sample
geometry is defined in terms of the incident angle '1'1> takeoff angle '1'2 and the thickness t1.
Advances In X-Ray Analysis, Vol. 33 189

Edited by c.s. Barrett et 01.
190 III. X-RAY SPECTROMETRIC CHARACTERIZATION OF THIN FILMS
where
Rl is the relative intensity

PI tl is the thickness of the layer in [mg/cm2]
III (Epri) is the mass absorption coefficient in layer I for the primary
beam
III (Ei) is the mass absorption coefficient in layer I for the analyte X-rays
The relationship between the thickness and relative intensity of a single layer thin film
containing a single element is characterized by two fundamental parameters: (1) the mass
absorption coefficient for the incident X-rays and (2) the mass absorption coefficient for the
analyte X-rays. The sum is these two terms is the reciprocal of the lie thickness and has
units of [mg/cm2].
The reciprocal of the mass absorption coefficient for the incident X-ray beam is an
indication of the thickness of the sample for the incident beam. The reciprocal of the mass
absorption coefficient for the analyte X-rays is an indication of the thickness of the sample
to the analyte X-rays. The reciprocal of the sum of these two terms is an indication of the
analytical range of the technique.
Figure 2 shows the curve which relates the measured intensity versus thickness for a single
layer thin film. This curve is characterized by two parameters: (1) the intensity for a bulk
sample and (2) the thickness where the intensity reaches I-lie or 63% of the bulk.
Historically several terms have been used to describe the measurement of thin films in each
of three regions.
The thin region extends from zero thickness to a thickness where the film yields an
intensity of about 10% of the bulk. In this thickness region, the measured intensity is
proportional to the sample thickness and to the concentration of the analyte. This is another
way of saying there are no matrix effects. Samples in this thickness range are often
analyzed using empirical working curves established by measuring one or more similar
type standards.
...>
in
z
...w~
THICKNESS
Figure 2 - The curve of intensity vs. thickness is characterized by two parameters; the
intensity for a bulk sample of the same material and the thickness where the intensity
reaches 63% of the bulk (the lie thickness).
J. E. WILLIS 191
6
N
E
~ 5
§.
(f) 4
(f)
w
z
Q3
I
f--
o L-__ ~ __ ~ ____ ~ __ ~ __ ~ ____ ~ __ ~ __ ~ __ ~~
10 20 30 40 50 60 70 80
ATOMIC NUMBER
Figure 3 - The lie thickness versus atomic number for elements from sodium to uranium.
The curve on the left is for Ka lines, the curve on the right is for La lines.
The critical thickness is described as that thickness where a further increase in sample
thickness causes no corresponding increase in analyte intensity. Such a sample is also said
to be infinitely thick. Most matrix correction techniques and analysis programs were
developed for use in this thickness range.
Between the thin region and the critical thickness is the intermediate region, where
matrix effects are present in varying amounts and the analyte intensity is not linearly
proportional to thickness.
For a given acquisition condition, the lie thickness can be calculated as a function of atomic
number. Figure 3 shows the curve of lie thickness versus atomic number for elements
from Na to U. The curves are suprisingly flat, ranging from I [mg/cm2] for Na Ka lines to
10 [mg/cm2] for Mo Ka lines and from 0.5 [mg/cm2] for Sn La lines to 3 [mg/cm2] for U
La lines. The analytical range of the technique for single layer thin films is about twice the
range shown in the graph.
TWO LA YER THIN FILMS - Intensity from Layer Two

The intensity from the second layer of a two layer thin film depends on the thickness and
composition of the second layer as well as the thickness and composition of the first layer,
with the first layer acting as a transmission filter. Figure 4 shows a schematic of the
measurement of a two layer thin film sample. The sample geometry is characterized by the
incident angle '1'1> take-off angle '1'2 and the layer thickness tl and ~.
Figure 4 - Schematic of a two layer thin film system characterized by the incident angle '1'1>
take-off angle '1'2' thickness of the top layer tl and thickness of the bottom layer t2.
o
-"
u"
Au THICKNESS
Figure 5 - Measured intensity for eu Ka X-rays from a set of NBS Au on eu thin film
samples. In these samples the eu layer is infinitely thick.
The relationship between the relative intensity for the analyte present in layer 2 and the
thickness of the layers in a two layer thin film sample is given in Equation 2.
(Sq. 2)
The measured intensities for eu Ka X-rays from a set of NBS Au on eu thin film samples
are shown in Figure 5. In this example the Au in layer one ranges from 1.5 to 13
[mg/cm2], while layer two is an infinitely thick eu substrate. The measured intensity from
the eu layer as a function of the Au thickness is characterized by absorption of the primary
X-ray beam and the eu Ka (analyte) X-rays in the Au layer.
For this example, the top term in Equation 2, which represents the intensity from the eu
layer as a function of the eu layer thickness, is one, since the eu is infinitely thick.
MULTIPLE LAYER THIN FILMS
The relationship between the measured intensities and the thickness and composition of the
layers in a multiple layer thin film sample can be understood in terms of a simple working
model. In this model the measured intensities from the first layer depend only on the
thickness and composition of the first layer. The intensities from the second layer depend
on the thickness and composition of the second layer as well as the thickness and
composition of the first layer, where the first layer acts as a transmission filter. The
intensities from the Nth layer depend on the thickness and composition of the Nth layer as
well as the thickness and composition of the intervening layers.
The determination of the thickness and composition of multiple layer thin film samples is
not easily handled using empirical techniques. In this simplified model, which corrects
only for X-ray absorption, the calculation of an unknown sample is very complicated and
requires many linear and non-linear corrections. Empirical techniques can be used for
selected cases of only a few elements in a few layers, however, as the number of elements
J. E. WILLIS 193
and layers increases so does the number of similar type standards required for calibration.
Because of this requirement for many similar type standards, the calculation of the
thickness and composition of multiple layer unknown samples is best handled by a
fundamental parameters analysis program.
Fundamental parameter equations calculate theoretical intensities for hypothetical
samples when given the spectrometer geometry, X-ray tube operating conditions,
composition and thickness of any primary and secondary filters and thickness and
composition of the hypothetical sample.
Fundamental parameter analysis programs calculate the thickness and composition

of unknown samples using some iterative technique. A guess is made of the thickness and
composition of the first layer. The fundamental parameters equations are used to calculate
theoretical intensities for this layer. These theoretical intensities are compared with the
measured intensities and a new guess is made for thickness and composition. When this
process has converged, then this layer is used as a transmission filter for the second layer.
This process is repeated for each layer in the sample. If secondary fluorescence effects are
included in the calculation, then a second pass is made through the layers in the sample,
this time correcting for secondary effects.
SECONDARY FLUORESCENCE EFFECTS

Often elements present in the sample will enhance some of the analytes present. If
corrections are not made for these enhancements, significant errors in the analysis of
unknown samples will be introduced. In the following example, we will consider a two
layer system consisting of a layer of Fe and a layer of Ni. There are two possible cases:
(1) where the enhancing element is in a layer which is below the analyte and (2) where the
enhancing element is in a layer which is above the analyte.
Figure 6 shows the percentage of secondary intensity from the enhancement of Fe by the
Ni plotted as a function of thickness, when the Ni is below the Fe. In this hypothetical
case, the Fe layer and the Ni layer are the same thickness. The intensity due to the
enhancement of Fe from the Ni reaches a maximum of about 6% at a thickness of a few
[mglcm2J. If the secondary fluorescence contribution due to the Ni is neglected, the
measured thickness of the Fe would be about 6% high.
6
>-
f--
Cil
Z
W
f--
Z
o o~----------------------------------------~
20
THICKNESS (mglcm 2 )
Figure 6 - The secondary fluorescence intensity as a percentage of total Fe intensity versus

layer thickness in the Fe/Ni two layer system. In this case, the enhancer is in a layer which
is below the analyte.
194 III. X-RAY SPECTROMETRIC CHARACTERIZATION OF T:~IN FILMS
40 r---------------------------------------~
>-
t-
u;
Z
UJ
t-
Z
o ~______________________________________~
o THICKNESS (mglcm 2) 20
Figure 7 - The secondary fluorescence intensity as a percentage of total Fe intensity versus

layer thickness in the Fe/Ni two layer system. In this case, the enhancing element is in a
layer which is above the analyte.
Figure 7 shows the percentage of secondary intensity for Fe when the Fe is underneath the
Ni. In this case the fraction of Fe intensity due to enhancement by the Ni increases as a
function of thickness until it reaches about 30% at a thickness of about 16 [mglcm2]. If
secondary effects are neglected in the measurement of the Fe thickness for this sample, the
measurement could be more than 30% high.
This difference in the magnitude of enhancement of the Fe in these two examples is

explained by considering the absorption of the primary X-ray beam. In the second
example, the primary beam must pass through the Ni layer before reaching the Fe. As the
primary beam passes through the Ni layer most of the radiation above the Ni absorption
edge is removed. The primary X-ray spectrum appears to the Fe layer as a narrow band of
energies extending from the Fe absorption edge to the Ni absorption edge. Because of the
absorption of the primary beam in the case where the Ni is in a layer which is above the Fe,
the percentage of secondary fluorescence appears larger than in the case where the Ni is
below the Fe.
AN EXAMPLE WHERE THE INTENSITY FOR A THIN FILM EXCEEDS THE

INTENSITY FROM A BULK SAMPLE
Some unusual conditions can cause the intensity from a thin film sample to exceed that
from a bulk sample. In the example shown in Figure 8, a relatively thick layer of Ni is
applied to a bulk sample of Sn. The excitation conditions, 50 kV and a thick Cu filter,
provide relatively inefficient primary excitation for Ni.
// :: /////////////////////// +/:/
///////////////////////////////////
///////////////////////////////////
Figure 8 - Schematic of a Ni thin film on top of a bulk sample of Sn. This sample is
unusual in that the intensity from the Ni thin film layer exceeds the intensity from a bulk
sample of Ni.
J. E. WILLIS 195
140~--------------------------------------~
OL-______________________________________~
o THICKNESS (mglcm 2 ) 100

Figure 9 - Relative intensity of Ni Ka versus Ni layer thickness. The curve is unusual
since the intensity exceeds 100% relative and decreases with increasing thickness over
some range.
Because of the high energy of the primary beam, it is transmitted by the Ni to the Sn and
produces characteristic Sn X-rays. The Sn X-rays are then absorbed by the Ni and
produce secondary fluorescence. The graph of Ni intensity vs. thickness, shown in Figure
9, has two unusual characteristics: (1) it exceeds 100% relative (relative to a bulk sample
of Ni excited using the same conditions) and (2) the intensity decreases with increasing
thickness between about 20 and 100 [mg/cm2J.
CONCLUSION
A relatively simple model for understanding the X-ray production and absorption in single
and multiple layer thin film samples is useful for predicting the measured intensities from
thin film samples but may not provide adequate accuracy for characterization of samples if
secondary fluorescence effects are ignored. Because of the complexity of the problem and
number of standards that would be required for calibration of an empirical analysis
program, the calculation of unknown samples is best handled by a fundamental parameters
analysis program.
Acknowledgement
This work was supported in part by Tracor Xray, 345 E Middlefield Rd, Mountain View
CA 94043.
REFERENCES
1. G. Pollai, M. Mantler, H. Abel., Spectrochemica Acta, 26B : 747 (1971)
2. M. Mantler, Analytica Chirnica Acta, 188: 25 (1986)
3. T.e. Huang and W. Parrish, Adv. X-ray Anal., 29: 395 (1986)
4. I.E. Willis, Adv. X-ray Anal., 31: 175 (1988)

5. J.W. Criss, L.S. Birks and J.V. Gilfrich, Anal. Chern. 50 : 33 (1978)
6. J.E. Willis, X-ray Spectrometry, 18-#4: 143 (1989)
THE DETERMINATION OF ELEMENTAL COMPOSITION, THICKNESS AND
CRYSTALLINE PHASES IN SINGLE AND MULTI-LAYER THIN FILMS
R. A. Brown, K. Toda, and R. L. Wilson
Rigaku/USA, Inc.
Danvers, MA
INTRODUCTION
The purpose of this paper is to show how XRD and XRF can be
used as complimentary tools to determine multi-layer thin film
composition, both elemental and crystalline, as well as film
thickness.
FUNDAMENTAL PARAMETERS IN FLUORESCENCE
Using the Fundamental Parameters approach in XRF, the
thickness and composition of a multi-layer thin film can be
simultaneously determined for up to four layers. Conventional
XRF using an empirical method requires many standard samples
which must be of similar composition to the unknown. In the
case of multi-layered thin films, producing such standards can
be difficult. A large number of standards would be required
for a three or four layer film, making analysis impractical.
Using the Fundamental Parameter approach, one needs only to
produce a single-layer thin film, or have a pure metal of
"inf ini te thickness" as a standard. From these standards,
instrument sensitivity can be calculated. This in turn is used
to characterize multi-layered thin films for which no "matrix
matched" standards exist.
In order to obtain XRF data from lower layers in multi-
layered film, a high intensity source and a large incident/take
off angle are required. This geometry is achieved through the
close coupling of the end-window Rh tube, sample and detectors.
THIN FILM DIFFRACTOMETRY
Conventionally,e/2e XRD geometry is not very useful for the
study of thin multi-layered films because of poor sensitivity
and interference from the substrate.

Edited by C.S_ Barrett et al_
Table 1. Equipment
X-RAY DIFFRACTION
12 KW Rotating Anode
Thin Film Attachment
Horizontal Goniometer
21theta scans with theta fixed at: 0.5 degrees
2.0 degrees
4.0 degrees
8.0 degrees
IBM PS/2 Model 80 12.0 degrees
X-RAY FLUORESCENCE
3371 Sequential X-Ray Spectrometer
Data-flex Software with on-line Fundamental Parameters Program
IBM Model 70
Background and substrate contributions are minimized and

signal to noise ratio maximized with the XRD thin film attachment
which incorporates parallel optics, as well as a flat crystal
monochromator. As a result of fixing e at increasing angles,
each layer from the surface into the film can be analyzed. The
equipment used in the present research is described in Table
1.
COUPLED THETAl2THETA SCAN

3500
2800
~ 2100
~
Q
W
S
0
1400
::Ii
f/)
700
10 20 30 40 50 60 70 80
2 THETA
Figure 1. Standard powder diffraction geometry wherein
9/28 scan shows large broad hump from glass substrate as
well as not revealing the 100% relative peak for ZnO in
the ZnO/Ag sample.
R. A. BROWN ET AL. 199
350
280
~
a.. 210
It)
~
C
W
::&:
I-
0
0 140
::;
rn
70
10 20 30 40 50 60 70 80
2 THETA
Figure 2. Using the thin film attachment reduces

interference from substrate as well as four additional
peaks from the ZnO and Ag phases in the ZnO/Ag sample.
Figure 1 is a coupled 9/29 scan of a thin film consisting

of ZnO and Ag on a glass substrate. The thin film exhibits
preferred orientation and in the 9/29 coupled scan, the 100%
relative intensity peak for ZnO is missing. The peak for ZnO
appearing at 34.44° 29 is the 56% relative intensity peak. The
small peak at 38.11° 29 is the 100% peak for Ag. Also apparent
is a large broad hump which is the contribution from the
substrate. Configuring the system with the thin-film attachment,
Figure 2, setting 9 at 0.75° and scanning only 29, reveals the
100% line for ZnO at 35.96° 29, as well as additional peaks for
ZnO at 62.94°, Ag at 64.72° and 77.5° 29. Very little
interference appears from the substrate.
XRD analysis of Sample 1, Figure 3, with 9 set to 0.5 0, shows
four very small Au peaks (when vertical scale is set to 2500
cps). Setting 9 to 2°, Figure 4, shows a large increase in
intensities for Au peaks. Increasing the depth of penetration
where 9 = 4 0, Figure 5, reveals the presence of W. Scans, where
9 is set to 8° and 12°, did not reveal the presence of any other
phases. This indicates that this is a two-layer film.
TWO-LAYER FILM ASSUMPTION

The XRF qualitative scan of Sample 1 showed Au, Wand a small
amount of Ti. A thin-film analysis method was programmed to
analyze a two-layer thin film by Fundamental Parameters. Based
on the qualitative scan, the assumption was made that the first
layer was Au and the second was Wand Ti.
AU=GOLD 3000
2500
2000
iii
Ii:
It)
1500
C
III
:r
I-
0
0
:;; 1000
rn
499
AU
AU
AU
20 30 4D 50 60 70 80
2 THETA
Figure 3. Theta set to 0.5 0 for Sample 1. Reveals small
Au peaks.
AU=GOLD M=MOUNTING MEDIUM 3000
2500
AU
2000
AU
2 THETA
Figure 4. Theta set to 2 0 for Sample 1. Large increase
in Au peaks as well as appearance of a peak "M" due to
the mounting medium.
AU=GOLD W=TUNGSTEN AU M=MOUNTING MEDIUM 3000

2500
2000
AU
iii
I- 1500
11.
~
0 AU
UJ
:r
I-
0
0
::;: 1000
Ul
AU
500
W
20 30 40 50 60 70 80
2 THETA
Figure 5. Tungsten nwn peak when theta is set to 4° for
Sample 1.
Instrument sensitivities for Au, Wand Ti were obtained using

two single-layer Au standard samples with thicknesses of 2000A
and 3000A, one single-layer W standard of 1000A and one single
layer Ti standard of 1000A. Theoretical intensities were
calculated for Au, Wand Ti based on measured intensities of
single-layer thin films.
Measurements were made of unknowns and results are shown in
Table 2.
We assume, based on XRD and XRF qualitative scans, that the
Au layer is pure and the second layer is a mix of Wand Ti as
there was no evidence that the Wand Ti formed an alloy.
The calculation includes the thickness of the first and
second layer, as well as weight percent of Wand Ti in the
second layer.
From XRF we can see that the Ti concentration is of
insufficient quantity to produce a diffraction pattern. As a
result, Ti did not show up in the XRD data.
Table 2. XRF analysis of Sample 1
First Layer Second Layer (TiIW)
Au Thickness Thickness I Tiwt% I Wwt%
Analysis results 3161 1026 I 3.2 I 96.8
(Thickness: Angstrom)
AU=GOLD M=MOUNTING MEDIUM 1500

2500 AU
2000
.,~
1500
Q
W
i!:0
0 1Il00
::I!
In
500
M AU
20 30 40 50 60 70 80
2 THETA
Figure 6. Sample 2 with theta set to 0.5°. Au (gold)
and M (mounting medium).
AU=GOLD M=MOUNTING MEDIUM CU=COPPER 1500

2500 AU
2Il00
ui
I- 1500
Il.
on
~
Q
W
J:
I-
0
0 1Il00
::I!
In
CU AU
500 M AU AU
20 30 40 50 60 70 80
2 THETA
Figure 7. eu (copper) layer of Sample 2 becomes evident
when theta is set to 2°.
AU=GOLD M=MOUNTING MEDIUM CU=COPPER CR=CROMIUM 1500

2500 AU
CU
2000
iii
Ii: 1500
~
Q
W
j!: AU
0 U CR
0
::E
I/)
1000 R
M CU
CU AU
500
20 30 40 50 60 70 80
2 THETA
Figure 8. Increase in Cu peak intensity of Sample 2 when
theta is set to 4 0 • Cr (chromium) peaks overlap Au (gold)
peaks making identification difficult.
XRD analysis of Sample 2, Figure 6, with e fixed at 0.5 0 ,

shows four peaks for Au. By increasing the depth of penetration
by setting e to 2 0 , Figure 7, the Cu layer becomes evident.
Figure 8, where a = 4 0 , shows a large increase in the CU peak
intensity. XRF qualitative scan shows Au, Cu and a significant
amount of Cr. The Cr peaks, as indicated, lie directly on top
of two Au peaks. However, in checking intensities of those
peaks, it appears that the Cr does not add to the expected
relative intensities of the Au peaks. This indicates that Cr
is not present at this depth of penetration. Scans where e is
set to 8 0 and 12 0 did not reveal the presence of any other
phases.
THREE LAYER ASSUMPTION

From the above and the XRF qualitative scan, there are three
layers in which the first layer is pure AU, the second layer
is Cu and the third layer is Cr.
XRF instrument sensitivity was established using the same
Au standards as before. For Cu and Cr, standards that were used
were 5000A each.
Assuming there are three layers, the same instrument
sensitivities were used, but the Fundamental Parameters method
Table 3. XRF analysis of Sample 2.

Au-Cu-Cr
First Layer Second Layer Third Layer
Au Thickness Cu Thickness Cr Thickness
Analysis results 1310 4925 1132
Au-Cu/Cr
First Layer Second Layer (CulCr)

Au Thickness Cu/Cr Thickness I Cuwt% I Crwt%
Analysis results 1306 6073 I 85.6 I 14.4
(Thickness: Angstrom)
was used to analyze for three layers, Au, Cu and Cr. The
thickness of each layer was calculated and results are shown
in Table 3 as Au-Cu-Cr.
If no XRD data had been available, a second assumption could
have been made that there are two layers where the first layer
is pure Au and the second layer is a mix of Cu and Cr metal.
This assumption was tested by a method where thickness of
the first layer and both thickness and elemental composition
of the second layer can be found.
Results are shown in Table 3 as Au-Cu/Cr.
CONCLUSION
If we assume that there are two layers, with Cr as 14% of
the second layer, we should have seen an anomaly in peak
intensities for the XRD data on those peaks where Au and Cr
overlap. Since the XRF data indicates layer one and two in
excess of 6000A, one would not expect to see the third layer
through that thickness, especially through absorbers such as
Cu and Au.
NEAR-SURFACE CHEMICAL CHARACTERIZATION
USING GRAZING INCIDENCE X-RAY FLUORESCENCE
Kenji Sakurai and Atsuo Iida *
National Research Institute for Metals: 1-2-1, Sengen,

Tsukuba, Ibaraki 305, Japan
*Photon Factory, National Laboratory for High Energy
Physics: 1-1, Oho, Tsukuba, Ibaraki 305, Japan
INTRODUCTION
External X-ray total reflection occurs when collimated X-ray beams

impinge on a smooth, flat surface of matter at a small glancing angle,
typically a few mrad. 1 With respect to the X-ray fluorescence technique,
total reflection experiments have allowed the trace determination of
solution samples using an X-ray mirror as a sample support. 2- 5 The
grazing incidence X-ray fluorescence technique (GIF) is also suitable for
near-surface element analysis of the material, because the penetration
depth of X-rays is 10-1000 A around the critical angle. Besides the
trace determination of impurities localized near surfaces~ this technique
is capable of a non-destructive depth profiling analysis using the
angular dependence of the fluorescent X-ray intensity.7-10 Recent
studies show that synchrotron radiation (SR) is the most suitable X-ray
source for such experiments.
For the near-surface characterization of materials, information on

the chemical state is definitely as important as the identification/
determina tion of elements. While electron spectroscopic techniques are
very useful for surface characterization of less than several tens of
angstrom depth, it is very difficult to get reliable information on
deeper regions non-destructively. An ultra high vacuum environment is
sometimes inappropriate for practical samples.
One of the promising procedures for near-surface chemical character-

ization is the GIF technique used in conjunction with the selectively
induced X-ray emission ;:;pect.roscopy (SIXES) 11 ,12 which employs

absorption-edge shifts for chemical state analysis. The present paper

demonstrates that chemical nature of elements near the surface can be
analyzed clearly. separated from the bulk material information using an
extremely low glancing angle.
EXPERIMENTAL
The experime~t was carried out using SR at the Photon Factory on beam
line 4A. The apparatus for chemical state analysis by SIXES is
essentially the same as usual energy-dispersive X-ray fluorescence system
using SR as reported in our previous paper. 11 This technique measures
the X-ray absorption spectrum in terms of fluorescent X-ray intensity as
a function of the incident energy scanned around the absorption edge of
interest. In the present experiment, the GIF setup (Fig.1) was used for
the surface sensitive measurement.
SR beams were monochromatized by a Si (111) double -crystal sagittal

focusing monochromator. The energy resolution was about 1 eV at the
absorption edge of chromium. The intensities of incident and reflected
X-rays were measured by two ionization chambers. A Si(Li) detector was
employed for the measurement of Ka fluorescent intensity, and was set at
90 deg. to the incident X-rays with an inclination of about 10 deg. from
the horizontal plane. A slit was placed in front of the Si(Li) detector
to eliminate X-rays from the edges of the sample. Optical alignment was
optimized by the tranlational/rotational motion of the sample stage. The
measurement was done in air.
The sample used was Cr[200Al/Cr 203 [2000Al thin film. It was prepared
by vacuum evaporation with an electron beam gun and deposited on a flat,
~ lj:
Monochromatized
'-..... SR beams
'" ""---
Fluores~nt /
~----:JX_Rays
-~ ,,:
//,/'
Si(Li)detector
Fig.1 Schematic drawings of the experimental arrangement for

grazing incidence X-ray fluorescence (GIF) measurement.
Incident X-ray energy was scanned through the Cr K
absorption edg~.
K. SAKURAI AND A. IIDA 207
2 3 4 5 B
~'-'I---,'-..-~...,..L...-L.,-~~---.i-., ~~ I IP
,,
,
\
\
\
...>- \
'>
\
:;:
u 0
CI)
;:
CI)
rx:
,,
, Fig.2
,,
,
\ Angular dependence of the
reflectivity at lower (solid
line) and higher (dashed
line) energy side of the
absorption edge. Experimen-
5 10 15 tal (a) and calculated (b)
Glancing Angle (mrad) results are shown.
smooth synthetic quartz plate. Pure Cr and Cr 203 thin films of 2000l\.
were also prepared as reference samples.
Figure 2(a) shows the experimental results of reflectivity near the

Cr K absorption edge (5.9888 keV). The reflectivity calculation was
performed using simple Fresnel's theory1,13 for above (+41 eV) and below
(-22 eV) the edge and is shown in Fig.2(b). Anomalous dispersion factors
were taken from the table. 14 Reduced reflectivity in the experimental
curve for extremely low angles of less than 3 mrad. is due to the decrease
in the effective cross section of the sample. Below the absorption edge,
high reflectivity is observed due to small absorption in the film. The
curve also shows interference oscillations which can be mainly explained
as the effect of reflection at the Cr 203 /Si0 2 interface. Such a
structure has -been observed usually when a light loose layer is on top of
a heavy packed layer. However, it was confirmed that interference was
also observed even if the order of the layers was reversed, below the
absorption edge of the heavy element,as the present case. Good agreement
was obtained between the experimental and calculated data. In contrast,
above the absorption edge, strong absorption smears the angular
dependence of the reflectivity. The difference between the experimental
and calculated curves below the critical angle probably is due to the
uncertainty of the theoretical refractive index parameters.
Cr Ka fluorescent intensity was measured at various glancing angles

by scanning incident X-ray energy through the absorption edge. Figure 3
,.;
.5
GI
U
c::
GI
U
UI
I!!
o::::I
ii:
20
X·Ray Energy (eV)
Fig.3 Near-edge absorption spectra of Cr[200~]/Cr203[2000~] thin film

using the GlF setup. A: extremely small glancing angle,less
than 4 mrad. (See, Fig.2), B: ordinary 45 deg. incidence angle.
Standard spectra of chromium metal and its oxides measured at
45 deg. incidence angle are also shown as reference.
shows the near edge absorption spectrum measured at an extremely low

angle of less than 4 mrad. (A, See also Fig.2) and the one obtained at 45
deg. incidence angle (B). The standard spectra of Cr metal and Cr 203
thin films are also shown. Fluorescent X-ray intensity abruptly
increases as the incident energy crosses the absorption edge. The Cr 203
absorption curve locates higher energy side of the Cr curve, since the
position of the absorption edge shifts to a higher energy as the
oxidation number increases. The fine structure observed in the curve
also contains chemical information,as discussed elsewhere. 12
The curves A and B are clearly distinguished from each other, though
the sample is the same. For the 45 deg. incidence angle, the penetration
depth is in the order of ]Jm above the absorption edge. Therefore B
corresponds to information for the whole film, i.e., Cr metal 200 ~ layer
plus Cr 203 2000 ~ layer. From the quantitative analysis, it was found
that curve B was in good agreement with the synthesis spectrum of Cr and
Cr 203 in the layer thickness ratio of about 1:10. On the other hand, in
the grazing incidence condition, the penetration depth becomes extremely
shallow and is estimated to be less than 100 ~ for A. That is, curve A
indicates the chemical state of the near-surface layer of the sample.
Actually, it is close to the spectrum of Cr metal. The difference
between A and the Cr metal spectrum might be explained by considering the
formation of the surface Cr 203 layer by natural oxidation. Assuming that
curve A consists of two components,Cr and CrZ03 spectra, the thickness of
the surface Cr 203 layer can be calculated and was estimated to be about
40 A. From these results, it is concluded that we can analyze the near-
o 10 20
Fig.4 X-Ray Energy (eV)
Near - edge absorption spectra

around the critical angle. The
numbers in the drawing corre-
spond to the glancing angles
shown in Fig.2. (1: 5.05 mrad;
2: 8.12 mrad; 3: 9.33 mrad; 4:
14.18 mrad; 5: 5 deg.) A and B
are the same as in Fig.3.
(a) Reflectivity
4 (b) Surface Intensity
Fig.5
o ~------------------------~
The calculated angular depend- (c) Penetration Depth
ence of the reflecti vi ty (a),
surface X-ray intensity; (b),
and penetration depth; (c) for 10 3
pure chromium metal near the
absorption edge. Calculation
was made for +41 eV from the 10 2
absorption edge (broken line),
-22 eV (solid line), and +1 eV
(dot-dash line). Anomalous 10 ~------------------------~
scattering fa 1\ors were taken
5 10 15
from the table for the calcu-
lation of the refractive index. Glancing Angle (mrad)
surface layer separated from the bulk material information by using the
grazing incidence condition.
Generally, total - reflection experiments are affected by the

significant change in anomalous dispersion factors near the absorption
edge.'15 16 .
Flgure 4 shows a series of near - edge spectra around the
critical angle. They are strongly distorted from the real absorption
spectra. To understand the essentials of the situation, it is convenient
to consider a pure, homogeneous Cr metal sample. Figure 5 shows the
calculated results of the angular dependence of the reflectivity, surface
intensity and penetration depth for the three incident energies near the
edge. It is clearly seen that they have strong energy dependence
especially near the critical angle. Since the fluorescent intensity is
largely proportional to the product of the surface intensity and the
penetration depth, the low energy side of the absorption spectra is
relatively enhanced compared with the high energy side, consequently
deforming the shape of the spectra. Therefore, careful analysis is
needed when the absorption spectrum is measured near the critical angle.
SUMMARY
The GIF technique using SR is a promising tool for near-surface

characterization. Not only trace determination and depth profiling, but
also chemical state analysiS can be performed non-destructively. The
chemical nature of the near-surface is analyzed clearly separated from
the bulk-material information using an extremely low glancing angle.
ACKNOWLEDGF..MENTS
The authors would like to thank Prof. Y. Gohshi of the University of

Tokyo for his valuable discussion and encouragement. This work was
performed under the approval of the Photon Factory Program Advisory
Committee (Proposal No.89-072).
REFERENCES
1. L. G. Parratt, Surface Studies of Solids by Total Reflection of X-

Rays, Phys. Rev. 95:359 (1954)
2. Y. Yoneda and T. Horiuchi, Optical Flats for Use in X-Ray Spectro-
chemical Microanalysis, Rev. Sci. Instrum. 42:1069 (1971)
3. H. Aiginger and P. Wobrauschek, Total Reflectance X-Ray Spectrometry,
Adv. in X-Ray Anal. 28:1 (1985)
4. A. Iida and Y. Gohshi, Total-Reflection X-Ray Fluorescence Analysis
Using Monochromatic Beam, Jpn. J. Appl. Phys. 23:1543 (1984)
5. A. Iida, A. Yoshinaga, K. Sakurai and Y. Gohshi, Synchrotron
Radiation Excited X-Ray Fluorescence Analysis Using Total Reflection
of X-Rays, Anal. Chern. 58:394 (1986)
6. A. Iida, K. Sakurai, Y. Gohshi and S. Komiya, Analysis of
Contamination Layer of InP During LPE Process by Synchrotron
Radiation-Excited X-Ray Fluorescence, Jpn. J. Appl. Phys.

27:L1825 (1988)
7. J. M. Bloch, M. Sansone, F. Rondelez, D. G. Peiffer, P. Pincus, M. W.
Kim, P. M. Eisenberger, Concentration Profile of a Dissolved Polymer,
Phys. Rev. Lett. 54:1039 (1985)
8. J. M. Bloch, W. B. Yun, X. Yang, M. Ramanathan, P. A. Montano and C.
Capasso, Adsorption of Counterions to a Stearate Monolayer Spread at
the Water-Air Interface: A Synchrotron X-Ray Study, Phys. Rev. Lett.
61:2941 (1988)
9. A. Iida, K. Sakurai, A. Yoshinaga and Y. Gohshi, Grazing Incidence X-
Ray Fluorescence Analysis, Nucl. Inst. and Methods A246:736 (1986)
10. A. Iida, K. Sakurai, and Y. Gohshi, Near-Surface Analysis of
Semiconductor Using Grazing Incidence X-Ray Fluorescence, Adv. in X-
Ray Anal. 31:487 (1988)
11. K. Sakurai, A. Iida and Y. Gohshi, Chemical State Analysis by X-Ray
Fluorescence Using Shifts of Iron K Absorption Edge, Anal. Sci.
4:37 (1988)
12. K. Sakurai, A. Iida and Y. Gohshi, Chemical State Analysis by X-Ray
Fluorescence Using Absorption Edge Shifts, Adv. in X-Ray Anal. 32
(1989) (in press)
13. M. Born and E. 1>lolf, "Principles of Optics 6th ed.", Pergamon,
New York (1980)
14. S. Sasaki, Anomalous Scattering Factors for Synchrotron Radiation
Users: Calculated using Cromer and Liberman's Method, KEK Report
83-22 (1984)
15. G. Martens and P. Rabe, EXAFS Studies on Superficial Regions by Means
of Total Reflection, Phys. Stat. Sol(a) 58:415 (1980)
16. S. M. Heald, H. Chen and J. M. Tranquada, Glancing-angle extended x-
ray-absorption fine structure and reflectivity studies of interfacial
regions, Phys. Rev. B38:1016 (1988)
BASIC STUDIES OF MULTI-LAYER THIN FILM ANALYSIS USING FUNDAMENTAL
PARAMETER METHOD

Rigaku Industrial Corporation
Osaka, Japan
1. INTRODUCTION
X-ray fluorescence analysis is the most suitable method. for
the characterization of the thickness and the chemical
composition of thin film samples. It is non-destructive, rapid,
precise, and accurate for both metal and oxide samples.
X-ray spectrometry by the fundamental parameter method allows
determination of the thickness and composition of multi-Iarer
thin film simultaneously using a small number of standards. ,2,3
However, the process of generating fluorescent x-rays in a multi-
layer thin film is rather complex. The intensity is affected
by both the thickness and the composition of the film. it is
also affected by the upper and/or lower layer in the film.
This paper describes the basic studies of the fundamental
parameter method for multi-layer thin film analysis using an
IBM PC-based fundamental parameter software, Dataflex 270. The
software includes a theoretical intensity calculation for primary
and secondary excitations. The data reduction routines which
take the raw intensity and calculates the thickness and the
composition are described. The influence of the primary spectral
distributions on the analyzed results are also studied.
2. EXPERIMENTAL
A wavelength-dispersive sequential x-ray spectrometer (Rigaku
Model 3270) equipped with a Rh-target end-window tube was
employed for the measurements with a tube excitation voltage
of 50kV. The fundamental parameter software package was the
Dataflex 270 (DF 270) which runs on an IBM PC Personal System/2
connected directly to the spectrometer.
Advances in XRay Analysis, Vol. 33 213

3. FLUORESCENT X-RAY INTENSITY FROM MULTI-LAYER THIN FILM

(1) Theoretical fluorescent x-ray intensity
The derivation of the expression for theoretical fluorescent
x-ray intensity has evolved over the past several years. 1,4 The
equations shown below represent the theoretical expressions for
the primary and secondary excitations of the fluorescent x-ray
intensity from a single-layer film.
Absorption attenuation of primary X -rays 10 (;>, )exp \- ~ (;>,)- SI:~1 1
Absorption allenuation of fluorescent X - rays I (ip) exp l-~ (ip)- si; tzl
Excitation efficiency: 11 (AlWI - ( 1- i)-WI -Pi" Q(ip)
Primary excitation
IPO p) =
I
r f.~epQiP(~)lo(71)eXp \f_(~(_i\)fx+~(_iP!!X)}dX_d"=
t
to I-m
I
sin 1"1 hm _~_(A_) + _~(_ip_)

SInTZ
i
(~e_Q.,..,i.:,p_(A_)_lo-:-:(-;t.)~_ l-exp{-(-~_(-")t~_O_e!.\Pt} -d}.
sin'ti Slnti
sin'i'l sin f2
thickness term
Secondary excitation
~ 90'
l~ (ip)= iLl QJq (~)-Qip (jq)-lo(A)'\ tane
IQJAm Jo
x = ~- ~ Xz= p(iP)+ ~(jq) X3=~t~

I sin '/'1 cos e ' sin 9'Z cose SIn'!'1 SIn'r2
X=~+~ X=...H.i.!£l._J:!..!..igl
4 sinli', cose ' 5 sin \'2 cose
In the integral part of the secondary excitation, the

following equations are substituted for the values in the braces
for the angular integration when Xl or X5 is approximately equal
to 0:
where X,- 0
I - ( I + X 3ft) exp (- X31'1 ) + l-exp(-X3f'!) _exp(-X4f't)-exp(-X3ftJ
I 1= X~ X3 X4 X4 X5
where X5- 0
I ) = 1- exp (-Xz/'t) I-exp (-X3P!) 1- ( 1+ Xoft) exp (- X3ft)
l X, X2 X3X, + X~
The theoretical equations for multi-layer thin films include

corrections for inter-layer absorption and secondary excitation,
thus making the expressions more complicated.
Table 1 exhibits the abbreviations in the theoretical
equations. The chemical composition has unique parameters for
each sample which are usually unknown during the analysis. The
physical constants are common parameters which account for the
absorption and the excitation. All of the physical constants
are stored in master files within the software. The instrumental
factors are unique to each individual instrument. Some of the
terms, which include the primary beam distribution, incident
and take angles, are common for the same type of instrument.
The instrument's sensitivity for each element and condition
should be obtained.
Y. KATAOKA AND T. ARAI (1) 215
Table 1 Abbreviations in theoretical

intensity formulas
Chemical composition Chemical composition of measuring element : Wi
Chemical composition of co-existing element : W j
Density and thickness : p, t
Physical constants Total mass absorption coefficient : ~ (A)
Photo absorption coefficient: 7i (11)
Fluorescence yield : wi
Jump ratio : OJ
Transition probability : Pi
Wavelength of fluorescent X-ra ys

and absorption edge : Ai, A edge i
Instrument factors Primary beam distribution: 10 (M
Incident and take -off angle : cP I, '1'2

Instrument sensitivity : K
The secondary excitation can greatly influence the

fluorescent x-ray intensity. Figure 1 shows the Fe-Ka
intensities of primary and secondary excitations from a double-
layer film of Ni and Fe. The value of the arrow is the relative
calculated intensity of each excitation process. The first
layer is a binary phase of Ni and Fe while the second layer
contains only single atoms of Ni or Fe. There exists a strong
Fe -Koc Intensities
Primary Secondary
44.7192 Ip 1.8
/
NiFe(Fe20% 2000A
Fe m77t'7'7777/77;77?~-:+-;>77:m7'771 2000A
Primary Secondary
831 18.3 336 7.6
I I
/ I
.. "/<'. :/~ .
NiFe(Fe20%) -:'~ /1 : IO~m
Fe ~~~~~~~~~~2QCX)A
·1:'
Primary Secondary
44.7 1.0 16.8
MF,(::ro%JI A6 \~,(,/.
Figure 1 Fluorescent X-ray
intensities from double-layers
• Thin film
o Bulk
1.0r-------------j/
Ni-KO( P - i<o(
~ 0.1
Thin film samples 'iii Thin film samples
c
0.1 C/CoNi/Cr/NiP Q)
C/CoNi/Cr/NiP
NiP C Si02P2051Si
'C
~ Ni a1 0.01 NiP
11 0 .01 ~1
>
Q)
Bulk samples
Ni pure ~ 0.001
Sui k samples
Phosphate ro
Ni base alloy ~ Fe base alloy
~O.OOI Fe base alloy ;
~O.OOOI
~~0~.OO~I~~0~.071--~0~.I--~1.0 ~~~~--~~~~~
Relative t~etical intensity
Figure 2 Relationship between

measured and theoretical intensities
of bulk and thin film samples
excitation of the Fe-Ka lines by the Ni-K lines. In the first

case both layers are 2000 A. The primary excitation is 44.7
and the secondary excitation is 1. 0 for the first layer. There
is also secondary excitation from the second layer. The
secondary excitations are about 2% of the primary excitations
for both layers. In the second case the thickness of the NiFe
layer is 10 micrometers (/.Lm). The secondary excitation is about
40% of the primary excitation. In the third case 10 micrometer
Ni replaces Fe as the second layer. The secondary excitation
is about 40% of the primary excitation. As the data shows, the
secondary excitation can greatly influence many applications,
so the calculation of the secondary excitation can not be
ignored.
(2) Relationship between the measured and the theoretical
intensities
In analysis using the fundamental parameter method the linear
relationship between the measured and the theoretical
intensi ties is a basic requirement. Figure 2 shows the
relationships for both bulk and thin film samples. For the Ni-
Ka line the thin film samples measured were four-layer magnetic
disks (C/CoNi/Cr/NiP) and single-layer films of Nip and Ni.
The bulk samples measured were pure Ni, Ni-based alloys and Fe-
based alloys.
For the P-Ka line as a light element, the film samples

measured were magnetic disks, PSG films (Si0 2-P20s/Si) and Nip.
A NBS phosphate rock standard and Fe-based alloys were measured
for bulk.
4. FILM THICKNESS AND INTENSITY
Analyzing the. thickness is strongly dependent on the
wavelength of the measured line and the matrix of the film.
We calculated the thickness which gives 4% of the intensity
Excitation Absorption
1.0,---------------,
0:
H .....0:
.Q o
.~
t~~
~
C
... ...
~ .~0.5
.~ 1
III
H
~1
H
O~--~----~----~--~
5 20 o t05 10 20
Intensity Intensity ~ Thickness t
IR ~ I-e- pt IR~ e -pt
Thickness of IR Th ickness of I R
In{l-IR) InIR
tIR = In 0.96 ·to.04 tIR = InO.5 ·to.5
Intens ity of t Intensity of t
~ t
IR = I - 0.96 to.04 IR = 0.5 to.S
Figure 3 Relationship between film
thickness and intensity
ratio for excitation, and the thickness which reduces the

intensity from the lower layer to 50% for absorption as
illustrated in Figure 3. These thicknesses for eleven (11)
elements were calculated so that the analyzing thickness can
be estimated easily.
For excitation, the thickness giving 4% of infinite thickness
is one of the expressions as the boundary between the linear
and the curved ranges. The interelement effect can be ignored
Table 2 Film thickness at 4%

intensity of infinite thickness (Rh-
target 50 kV)
(Excitation) Analyzing element 10 % Matrix element 90%
Unit: IJm
Matrix C F AI S Ti Fe Cu Mo Sn Tb Pb
C - Ko< 0.048 0.021 0.0039 0.0032 0.0082 0.0034 0.0022 0.0015 0.0068 0.0036 0.0024
F - Ko< 0.021 0.15 0.031 0.021 0.0052 0.019 0.012 0.0036 00039 0.0079 0.0039
AI- Ko< 0.14 0.077 0.095 0.087 0.027 0.011 0.0076 0.011 0.012 0.0037 0.0071
S - 1<0< 0.32 0.19 0.047 0.11 0.066 0.028 0.019 0.QI8 0.027 0.010 0.012
Ti - Ko( 1.9 1.2 0.29 0.23 0.20 0.16 0.1 I 0.035 0.030 0055 0.023
Fe - Koe 3.8 2.9 0.71 0.56 0.12 0.18 0.26 0.082 0.067 0.090 0.053
Cu - Koe 6.0 5.1 1.3 1.0 0.23 0.093 0.23 0.15 0.12 0.077 0.097
Mo- Koe 15 19 7.1 6.6 1.5 0.61 0.43 0.41 0.81 0.34 0.14
Sn- Ka( 30 40 17 17 4.3 1.8 1.2 0.47 1.1 0.97 0.41
Tb- La( 2.2 2.1 0.60 0.51 0.12 0.17 0.21 0.078 0.064 0.081 0.051
Pb - Lo< 5.2 6.2 2.1 1.9 0.45 0.18 0.13 0.32 0.24 0.1 I 0.12
Density 2.25 1.50 2.71 2.0 4.60 7.874 8.94 10.22 7.29 8.272 11.34
Table 3 Film thickness for 50%

reduction in lower layer int~nsity
(Rh-target 50 kV)
(Absorption) Unit: IJm
Upper
C F AI S Ti Fe Cu Mo Sn Tb Pb
layer
C - Kc( - 0.33 0.053 0.046 0.11 0.041 0.025 0.016 0.087 0.044 0.026
F - K« 0.30 - OAO 0.28 0.065 0.20 0.12 0.034 0.043 0.083 0.035
AI- Kae 2.5 1.3 - 1.3 0.40 0.14 0.096 0.13 0.16 0.047 0.081
S - Kae 7.6 3.6 0.77 - 1.0 0.37 0.24 0.22 0.35 0.13 0.14
Ti - Koe 67 28 5.3 4.1 - 2.1 1.5 0.50 0.46 0.76 0.32

Fe-Kc.< 200 79 14 II 2.2 - 3.3 1.2 1.1 1.5 0.77
Cu -Kc.< 390 160 28 20 4.0 1.6 - 2.3 2.0 1.3 1.3
Mo-~ 2500 1300 240 170 31 I I 7.4 - 14 5.9 2.3

Sn - KO( 4300 3300 700 380 92 33 22 7.4 - 16 6.3
Tb-Lae 190 76 14 10 2.1 3.4 3.1 1.2 0.95 - 0.75
Pb-Lo( 880 370 64 46 8.7 3.2 2.2 4.7 4.3 1.8 -
Density 2.25 1.50 2.71 2.0 4.60 7.874 8.94 10.22 7.29 8.272 11.34
below the boundary. The thickness of a specific intensity ratio

or the intensity ratio of a specific thickness can easily be
estimated using the equations in Figure 3 .
Table 2 shows the film thickness at the 4% intensity. The

values on the diagonal line are for pure elements and the other
values are calculated with binaries of 10% of the analyte and
90% of the matrix element. For example, Fe in an aluminum
matrix gives 0.71 micrometer. A thickness of another element
not listed can be estimated using the value of a neighboring
element.
Table 3 shows the thickness which reduces the intensity

of the lower layer to 50%. This table can be used to determine
if the lower layer can be analyzed or to determine the amount
of absorption by the upper layer in multi-layer films. For
example, when the upper layer is Cu and the Fe-Ka line of the
lower layer is measured, the 50% absorption thickness of Cu is
3.3 micrometers.
5. CALCULATION PROCEDURE FOR THICKNESS AND COMPOSITION

DETERMINATION
The calculation procedure for thickness and composition
determination of multi-layer thin films should be different from
that of bulk samples. This is due to the relationship between
the intensity of an element and its concentration or thickness
(complicated in multi-layer films). Figure 4 illustrates
the calculation procedure of the DF 270. First, the measured
intensity is rescaled to match the theoretical intensity. The
I=ali + bIM +c
To. Wo (Optional input values )
Ir =Ip + Is
Calculate bT. llW using

'--_ _ _.--_ _ _--' difference equation
T"+I =T" + llT

wn+ 1 =W"+llW
Figure 4 Calculation procedure of

thickness and composition
determination of multi-layer film
initial values for thickness and composition are set for the
following iteration process. During the iteration the program
calculates the theoretical intensity of the thickness and
composition based upon the last iteration. It then calculates
the deviations for the thickness and concentrations, comparing
the theoretical intensities with measured intensities. A
difference equation is introduced in this part of the
calculation, after which new thickness and concentrations are
Table 4 Analyzed results of single

component films (Standards: bulk
standard materials)
Corrponent Spectrum wa(~e)ngth Std. value X - ray Deviation ReI. Dev.
(~g/crn2) (~g/cm2) (~g/crn2) (%)
Mg Mg-Kol 9.890 43 43.9 0.9 2.1
AI AI-Koe 8.339 67 67.3 0.3 0.4
SiO Si -Ko< 7.125 32 31.7 -0.3 -0.9
KCI K - Ko< 3.741 45 45.4 0.4 0.9
Mn Mn-Ko( 2.102 65 65.7 0.7 1.1
Fe Fe -Koe 1.936 33 32.7 -0.3 -0.9
Co Ca -Ko< 1.789 53 52.1 -0.9 -1.7
Ni Ni -Kd 1.658 50 50.2 0.2 0.4
CuS Cu - K« 1.541 61 61.3 0.3 0.5
CsBr Br -Kd 1.041 48.6 49.0 0.4 0.8
Ag Ag-Ka 0.559 59 58.4 -0.6 -1.0
Sn Sn -Kd 0.491 50 49.9 -0.1 -0.2
Pb Pb-Lp 0.983 55 54.9 -0.1 -0.2
SI S2 S3 TI T2
NigoFelo Cr 2cxx)A
Cu Cu 20001\.
Cr NigoFelO 2cxx)A
Si02 Si02
Figure 5 Sample models of single and

triple layer thin films
recalculated. The iterations proceed until the results

converge. This iteration process simultaneously determines the
thickness and compositions of all layers in multi-layer film
and gives results even for complicated multi-layer films, such
as a film which has the same component in different layers.
6. ANALYZED RESULTS FOR THIN FILMS
Table 4 contains the results for thirteen (13) single
component films coated on polymers. The elements measured cover
most of the analytical range. The standards used were pure
elements and pure compounds. The mass thickness of the samples
range from 32 to 67 micrograms/cm2 • The average of the relative
deviations is 0.9% and the deviations do not demonstrate any
dependence on the elements and their wavelengths.
Huang and Parrish3 reported on the analysis of single-layer

and triple-layer films using the LAMA-111 program. The sample
models are shown in Figure 5. The single -layers are NiFe,
Cu, and Cr. The thickness and the composition of each layer
in the triple-layer films should be identical to the single-
layer of the same component. The thickness of each layer is
roughly 2000 A. A comparison of the results obtained by the
LAMA-111 and the DF 270 using the reported intensities are
listed in Table 5. The overall differences of the results
between the two programs are 1% relative in the thickness and
0.2 wt% in concentration. As the data shows, the results are
essentially identical.
Table 5 Comparison of results using
LAMA-III and DF 270 for the analysis
of single and triple layer thin films
Sample Program NiFe(A) Niwt% Fewt% Cu(A) Cr (A)
Single layer
SI DF270 2092 89.77 10.23 - -
(NiFe) LAMA]! 2113 89.53 10,47 - -
S2 DF270 - - - 2400 -
(Cu) LAMA-][ - - - 2418 -
S3 DF270 - - - - 1675
(Cr) LAMA-II - - - - 1675
Triple layer
TI DF270 2096 90.04 9.96 2449 1635
(NiFe/Cu/Cr) LAMA-m 2123 89.76 10.24 2470 1653
T2 IDF270 2032 90.03 9.97 2433 1674
Cr/CulNiFeJ LAMA-m 2055 89.72 10.28 2462 1698
Y. KATAOKAANDT. ARAI (1) 221
Rh torget 50kV,90°,O.127mmBe
1.0 x Pella et 01.
o XRFII
Continuum o Ochietal.
• DF270
,.,
50.5
-CI)
c:
Characteristic lines .......... DF270
-XRFII
~
.~ RhL
.~ ~ RhK - Pella et 01.
.~
~
~
Q)
E 05
1 -Ochi et 01.
o0 1.0 20 3.0 4.0 5.0 6.0

- Wavelength (A)
O~ ____~~____~~____~__~~~____~~~~~
o 1.0 2.0 30
--~ Wavelength (A)
Figure 6 Comparison of primary

spectral distributions
7. PRIMARY SPECTRAL DISTRIBUTION AND ANALYZED RESULTS
The primary spectral distribution is one of the important

parameters in a fundamental parameter method. We compared the
results of mass thickness analyses using four different
calculations of the primary spectral distribution. The
distributions studied are the NBS algorithm by pella6 , XRF-11
by Criss software 7 , the distribution by Ochi 8 , and the one
developed by us as shown in Figure 6. In Ochi's distribution
the characteristic lines were obtained by experimentation and
they used the continuum reported by Tertian. 9 Our distribution
for the DF 270 ~ as shown in Figure 6 is obtained by a
theoretical calculation. The distributions are normalized at
the maximum of the continuum. Throughout the continuum our
distribution gives the highest intensities in the wavelength
range longer than the maximum. The intensities of the
characteristic lines have the same trend as the continuum.
The analyzed results of the single-component films in Table

4 were obtained by using the distribution in the DF 270. We
also calculated the mass thicknesses of the samples for the
other three distributions using the same intensity data. The
relative analytical errors of the results obtained from the four
distributions are shown in Figure 7 . The distribution of the
DF 270 shows consistent small errors over the entire range.
From Sn to Br the difference among the distributions is
approximately 1%. However, the difference increases for the
longer wavelengths. The error for K is 9% in Ochi's
distribution. For si to Mg where the Rh-L lines provide
excitation, the errors of Ochi's distribution are about 8%.
The reason for this error is the underestimation of the
continuum and characteristic lines.
(%)
Rh target
10 50KV
....
....
0
....
Q)
0
u 0
+=
>.
"0
c
0
-
0
.~
0 Ag
~ -5 x Pella et 01.
o XRFII
c Ochi et 01.
1 • DF270
-10
U5 2 3 4 5 678910
(AI
- - - Wavelength
Figure 7 Analytical errors in thin
film analysis using various kinds of
primary spectral distributions
(standards: bulk standard materials)
Table 6 Analyzed results of metal

foil thickness analysis using various
kinds of primary spectral
distributions (standards: bulk
standard materials)
Component Std. value Primary X-ray Deviation ReI. Dev.
( Spectrum) (mg/cm 2 ) distribution (mg/cin2) (mglcm2) ("!o)
(I) 8.01 0.03 0.4
( 2) 8.25 0.27 3.4
Fe 7.98
( 3) 8.15 0.17 2.1
( Fe-K.O
(4) 8.27 0.29 3.6
(I) 8.79 -0.04 -0.5
(2) 8.96 0.13 1.5
Ni 8.83
(3) 8.88 0.05 0.6
( Ni- Ko()
(4) 8.27 0.04 0.5
(I) 8.30 0.07 0.9
(2 ) 8.43 0.20 2.4
Cu 8.23
(Cu-KCl() (3 ) 8.36 0.13 1.6
(4) 8.31 0.08 1.0
(I) 4.51 -007 - 1.5
(2 ) 4.51 -0.07 -1.5
Sn 4.58
( 3) 4.49 -0.09 -2.0
(Sn-KoO
( 4) 4.48 -0.10 -2.2
Primary distribution (I) DF270 (3) XRFII

(2) Pellaetal (4) Ochi et al.
These results are in the microgram thickness range. We also

measured milligram thickness ranges using metal foil samples
whose intensities are 20% to 80% of infinite thickness. Their
results are in Table 6 . The standard values of the foil mass
thicknesses were measured using a micro-balance. As shown in
Table 6 , the results show the same trend of deviations among
the distributions.
8. CONCLUSIONS
The basic performance of the fundamental-parameter software
of the DF 270 has been evaluated and good linear relationships
between the measured and the theoretical intensities were
obtained for both bulk and thin film samples. We introduced
a difference equation in the iteration processing of thickness
and composition calculations, permitting the analysis of
complicated multi-layer thin films. The accuracies obtained
for single-component film analyses are approximately 1% over
most of the analytical elements by using pure element and pure
compound bulk standards. The analyzed results by four different
primary distributions were compared, with large differences
found among them. Our distribution gave the smallest average
analytical errors.
REFERENCES
1. D. Laguitton and M. Mantler, Adv. X-ray Anal., 20 (1977),
p.515
2. D. Laguitton and W. Parrish, Anal. Chem., 49 (1977), p.1152
3. T.C. Huang and W. Parrish, Adv. X-ray Anal., 29 (1986), p.395
4. T. Shiraiwa and N. Fujino, Japan J. Appl. Phys., 2 (1966),
p.886
5. K. Ohno J. Fujiwara and 1. Morimoto, X-ray Spectrum, .2.
(1980) p.138
6. P.A. Pella, L. Feng and J.A. Small, X-ray Spectrum, 14
(1985) p.125
7. J.W. Criss, Adv. X-ray Anal., 23 (1980), p.93
8. H. Ochi and H. Okashita, Shimazu Rev., 45 (1988), p.51
9. R. Tertian and N. BroIl, X-ray Spectrum, 13 (1984), p. 134
APPLICATION OF MULTI-LAYER THIN FILM ANALYSIS BY X-RAY
SPECTROMETRY USING THE FUNDAMENTAL PARAMETER METHOD

Osaka, Japan
1. Introduction
The fundamental parameter method for x-ray spectrometry
has been used most commonly for bulk samples, because it
permits an analysis utilizing a minimum number of standards,
even for samples with complicated matrices. The need for the
analysis of thin film materials, which includes multi-layer
films, has been increasing in recent years along with the rapid
progress of high technologies. However, there have been few
reports that deal with the application of fundamental parameter
methods to multi-layer thin films. 1,2,3,4 There may be two
situations in the analysis of thin films. In routine analysis
of quality control applications, they usually require precise
analysis. Fortunately, it is possible to prepare well
characterized standards similar to the unknowns. In the case
of research and development and service laboratories, there is
not limit to the type of samples they can see, nor can they
prepare adequate standards for each type of sample. We have
found that the fundamental parameter method to be described
fulfills the needs of both of these situations.
This paper describes some of the applications of the Rigaku
multi-layer thin film fundamental parameter program of the
DATAFLEX 270, including a standard less analysis method
utilizing a sensitivity library. 5,6
2. Experimental
A brief configuration of the spectrometer system including
the computer system used in this study is shown in Table 1.
The spectrometer system is a wavelength-dispersive type (Rigaku
sequential spectrometer Model 3270). The spectrometer can
analyze down to boron (Z=5) utilizing a Rh-target, end-window
x-ray tube and new analyzing devices, such as synthetic multi-
layer and total reflection devices. The analysis of ultra
light elements from boron to oxygen in thin films have broad

Table 1. Spectrometer and data processing system

configurations
Spectrometer R igoku sequentiol X - ray spectrometer
System 3270 I 3271
X-ray tube Rh target end-window type
Analytical range : 58 - 92U
Analyzing crystal: LiF, PET, Ge, TAP, Synthetic multi -layer
Total reflection device
Detector SC, F-PC
A ttenuator III, 1/10
Diaphragm 10 - 35 mm dia.
Data processing Software Rigaku Dataflex 270

Computer IBM PC PS/2
applications in electronic and other high-tech technologies. 7,B

The data processing system connected to the spectrometer is
an IBM PC Personal Systemj2 Model 70. The software is the
OATAFLEX 270 (OF 270) which includes bulk and multi-layer
fundamental parameter programs. The analyzed results shown in
this paper were obtained with the tube operating under 50kV
except when analyzing for carbon.
3. The fundamental parameter software of the OF 270

The fundamental parameter software of the DF 270 has various
functions which the operator can select to achieve the optimum
analysis method for each application. Figure 1 illustrates the
outline of the software. There are two programs for on-line
functions: Quantitative Analysis analyzes both bulk samples
and multi-layer films.
r1 Quantitative analysis r- Multi -layer fi 1m sample

(Thickness and composition)
On-line function- Bulk sample
Lj Semi-quantitative analysis Bulk sample
Off -line function Instrument sensitivity

calibration
Off-line
quantitative analysis
Theoretical intensity
co leulation
Theoreticol matrix correction

coefficient calculation
Figure 1. Outline of fundamental parameter program

(Dataflex 270)
Semi-quantitative Analysis is the method which combines both

qualitative and quantitative analysis in one routine. The data
acquisition, element identification and the quantification of
the elements found are performed sequentially as part of one
operation. This routine uses a sensitivity library for the
quantification, thus enabling the quantitative analysis of
completely unknown samples without standards.
In the off-line function, the instrument sensitivity
calibration is a way to calculate sensitivity factors. The
off-line quantitative analysis is identical to the on-line one
except that the operator inputs the intensities. It also
includes the calculation of theoretical intensities for multi-
layer film and bulk samples, plus the generation of theoretical
alphas for operator-defined compositions for bulk analysis.
4. !'1ulti-Iayer thin film analysis software
In the practical analysis of thin film samples there can
be many factors which complicate the solution, such as samples
which contain unmeasured elements. This software allows the
operator to select a data processing method for each component
from the options shown in Table 2. The operator can also
define any component to be either in its pure form or as a
compound, such as the oxide, and all calculations are performed
using stoichiometric relationships. since the compounds
defined are stored in a compound master file, the operator
simply enters the name of the compound desired. Either
thickness or mass thickness can be used for the unit of
thickness (i.e. Angstrom for thickness; mgjcm 2 for mass
thickness) . An empirical calibration method can also be
combined with the fundamental parameter method. The typical
applications of this method are the analyses of carbon and
boron whose physical constants have less reliability. The
operator can specify a fixed thickness or concentration, if the
value is known. During on-line analysis the value can be
entered during the analysis, and the concentration of any
unmeasured component can be determined by difference. This
technique is useful for the analysis of organic-based films.
Table 2. Data processing options in thin film analysis
Element or compound defined

Stoichiometric colculotion in compounds
Unit of thickness
moss thickness or thickness
Incorporotion of empirical col ibrat ion method

for th ickness or concentration
Fixed thickness or concentration
Manual input of thickness or concentration
Calculation of concentration by difference

Measuring conditions
Film st ructure
Spectral lines
Similar or'dissimilar
standards
Figure 2. Quantitative analysis operation procedure of

multi-layer thin films
There are many situations where no standards exist for a

particular matrix, especially in the research and development
environment. The standard less analysis method of the DF 270
uses a sensitivity library to make the analysis possible. If
good standards are available, the analysis is performed to
achieve the optimum accuracies using the sensitivity
calibration procedure. Figure 2 is the flowchart of the
analysis for thin film analysis. First, the operator presets
the measuring conditions, film structure and spectral lines to
be measured. If standards are present, the thickness and
concentrations of the standards are entered and then
intensities are collected. After that, the instrument
sensitivity factors are obtained and entered into the
sensitivity library. If no standards are available, the
operator selects the sensitivity library and simply measures
the unknowns. The sensitivity library can be used for any or
all elements.
5. Data library for the fundamental parameter method
The sensitivity library contains sensitivity factors for

any element from fluorine to uranium. In order to expand the
flexibility of the standardless analysis, the system also has
a sensitivity conversion library in addition to the sensitivity
library in its data library.
Figure 3 explains the data library and the data reduction

process in the standardless analysis. A plot of the pure
element intensities, measuring the Ka lines from titanium to
copper, against atomic numbers demonstrates a predictable
curve. So, if the sensitivities of selected elements are
Sensitivity canversian library
IntensiTy conversion
DI",hrogm
Diaphragm: 30mm dia.
Attenuator : III
ISensitivity I ibraryl
for all elements
Allenuator
>-/
51 yDB42
TI V Cr Mn Fe Co NI Cu
15 I I I I
Cu
,,
00933
Calculation af thickness and
.! tiD
.~
c concentrations with F. P.
method
r5~
22 23 24 25 26 27 26 29
--Atomic number
(Note) Arrow: Library sample
Figure 3. Data library for fundamental parameter method
measured and stored in the library, any element can be analyzed

by computing its sensitivity from the curve. The sensitivity
conversion library has the conversion factors for the
attenuators conditions and the diaphragm conditions which
correspond to the analyzing area on ~he samples. All
conversion factors are pre-stored in the library, so that any
type of sample can be analyzed without regard to its sample
size or sample matrix.
During data processing the measured intensities are

converted to standard condition intensities, which are for a
Spectrum : K«
Samples : Pure materials and compounds
X-ray tube: Rh-target
15
}I.O
\I)
~ ~c: Parabolic curve

'iii H
c:
II
~IO
H
8'
1 lO.5
5
Ti 0.0
Ti
o 20 30 40 0.5 1.0 1.5
- - Atomic number ----+ log E (Energy: keV)
Note: Intensities of compounds converted to the intensities of pure materials
Figure 4. Instrument sensitivity curve
30mm diaphragm and no attenuator. Then, the intensities are

converted to the theoretical intensity scale using the
sensitivity library. They are then used for the fundamental
parameter calculations. The data library can be used for both
multi-layer thin film and bulk samples.
Figure 4 shows the measured intensities of pure elements
and pure compounds from titanium to molybdenum. The
intensities of the pure compounds plotted were converted to the
intensities of the pure elements. The axes of the left chart
are intensity and atomic number, while the axes of the right
chart are log scales of intensity and energy of the spectral
lines. the parabolic curve fits very well in the log scales
and is simply another expression of the relationship.
6. Thin film analysis with the sensitivity library
The fundamental parameter analysis using the sensitivity
library can be applied to single-layer or multi-layer thin film
samples. Figure 5 shows the sample models and the analyzed
results obtained by using the sensitivity library. The samples
are a magneto-optical disk and a magnetic disk. No standards
were used for the analyses. The magneto-optical disk sample
has three layers on a polycarbonate substrate. The thickness
and composition of the FeTbCo layer were analyzed. The
measured lines are Fe-Ka, Tb-La and Co-Ka. In the magnetic
disk sample, the first layer is CoNi, and the second layer is
Cr. The Ka lines for all three elements were measured and the
thickness and composition were analyzed for both layers.
As shown in the tables, the results are satisfactory for
not using any standards. The deviations of the results are
from 2% to 5% relative in thickness and from 0.5% to 1.2% in
concentration.
7. Thin film analysis with similar standards
If there are similar standards to the unknowns, more
accurate analysis can be expected than in the analysis of pure
Magneto-optical disk Magnetic disk

(Test sample)
Si3N4 700 A CoNi 400A

FeTbCo 750A Cr 3030 A
Si3 N4 ~IOOOA
Gloss
PC
Result of Fe Tb Co layer Result of each layer
Component Chern. X-Ray Deviation Component Chern. X-ray Deviation
FeTbCo(A) 750 767 17 CoNHA) 400 410 10

Tb (At.%) 18.11 17.45 -0.66 Ni(wt%) 80.2 79.7 -0.5
Co (At%) 8.25 7.68 -0.57 Co( wl%) 19.8 20.3 0.5
Fe (At%) 73.64 74.87 1.23 CrlA) 3030 2883 -147
Figure 5. Thin film analysis with sensitivity library

Table 3. Instrument sensitivity calibration
Standards available Calibration fitting Remarks
Dissimilar standards Ratio Pure element standards, etc.
One similar standard Ratio Reduce errors in F.P. model
Several similar standards Ratio, Linear Reduce errors In F. P. model

Reduce errors In standord valutl
Many similar standards Ratio, Linear Improve accuracies of Irace elamenll
Quadratic as empirical method·
Calibration formula
Ie • a Ii+ bIM + c
Ie: calibrated intensity
1M: measured intensity
a. b,c : sensitivity constants
element bulk standards. The sensitivity calibration program

calculates the instrument sensi ti vi ty factors from measured and
theoretical intensities of the standards. It provides ratio,
linear, or quadratic calibration curves as shown in Table 3.
The calibration calculations are performed using a least
squares fit with the best fit selected using interactive
graphics routines. If there are dissimilar standards or one
similar standard, the ratio calibration method is used. If
there is more than one similar standard, the errors resulting
from the fundamental parameter model can be reduced. If there
are several or many standards available, the linear or
quadratic calibration models may be used. This will further
reduce the errors caused by standard values and improve the
accuracy for trace elements, like an empirical calibration
method.
Four layers of a magnetic disk is one of the applications
of multi-layer thin film analysis. The following represents
Rh target 4OKV-70mA Sample

Total reflection monochrometer r----::----, 0 - 900 A
IS 2.0
CoNi 400-1200A (Ni 20wl%J
:.: f---C-r ---I 400-3100A
I
u NiP 20.1-22.5~m ( P 12wt%J
"-
o
AI
°0~------~5~0~0--------~IOO~0--
Thickness of carbon (~)
Figure 6. Analysis of carbon on magnetic disks
Ni-Ka Co-Ka Cr-l«<
~20
'iii .£
c ~ 20
~ ~
.~ .~
"0
~IO
::> ~Vl 10
Vl
g 0
Q)
::?! ::?!
1 0 1 0
450 0 5 10 15 0 10 20 30
~ Theoreticol intensity ~ Theoretical intensity ~ Theoretical intensity
Figure 7. Relationship between measured and theoretical

intensities of magnetic disks
results of the magnetic disks analyzed using similar standards.

The samples have four layers on an aluminum substrate: the
layers consist of C, CoNi, Cr, and Nip. The analyzed thickness
ranges are shown in Figure 6. The compositions of the layers
should be constant among the samples. The carbon layer was
analyzed by an empirical calibration method with a total
reflection monochromator used to collect the carbon
intensities. A good calibration curve was obtained as shown
in Figure 6. For the other three layers the thicknesses were
analyzed by the fundamental parameter method. Figure 7 is the
plot of measured versus theoretical intensities of the magnetic
disk standards. A linear calibration was used to the Ni-Ka
lines, whereas, ratio calibrations were used for Co-Ka and Cr-
Ka lines. Table 4 is the list of the analytical accuracies
obtained from 12 magnetic disk standards. The carbon layers
were analyzed by the fundamental parameter method as stated
earlier. the thicknesses of all four layers were determined
simultaneously. The relative accuracy of each thickness is
from 2% to 3%, relative.
The analysis of magneto-optical disks is another typical
application of thin film analysis. The material of the
magneto-optical disks contain alloys of transition metals and
rare earth elements, and good spectral resolution is required
for the measurement of these samples. Figure 8 shows the
typical spectra of a Fe, Tb, and Co alloy measured by both a
wavelength-dispersive spectrometer (WDXRF) and an energy-
dispersive spectrometer (EDXRF). The sample measured is the
target material of a magneto-optical disk. The spectrum for
the WDXRF was obtained using a Rigaku sequential spectrometer
Table 4. Analytical accuracies of magnetic disks
Layer C (Al CoNi (AI Cr (Al NiP(~ml
Thickness 0 400 400 20.1

range ..,900 -1200 -3106 ---22.5
Accuracies 22 10 80 0.28
Note: Carbon was analyzed with empirical

calibration method
WDXRF EDXRF
LiF(220)
S.C. Si (Li) detector
Fine slit
4,---------------------,
;!?
:2
1
.~ 15 c If
c <1 ::> 3 '
::> ~
,
>.
.... u" c:-
g
QJ
E 1
:€IO .Q
- ....
0
_OJ 4 .3
...I
~7<1 1 >. N
.~ 5
§LF!T
N ..oN
OJ aJ
II)
c ,
.J
,u"'(l
f-<1
1...1
II)
c ,
...I
~ .0 .0' , 1 ~
c f- .0 C ~
H ~ ,
f- H
0 75 80 85 90 7.5
2 - Theta (deg.)
Figure 8. comparison of spectral resolution between

WDXRF and EDXRF Sample: FeTbCo metal (bulk)
Model 3270. The combination of a LiF (200) crystal,

scintillation counter, and fine slit collimator gives optimum
spectral resolution. As shown in the spectrum, all of the
analytical lines are clearly separated. In the spectrum of the
energy-dispersive spectrometer with a Si(Li) detector, the line
overlap poses a definite problem for the analysis. Figure 9
shows the analyzed result of a magneto-optical disk using
similar standards. The thickness of the silicon nitride layers
was measured simultaneously with the thickness and composition
High Resolution Loyer

Crystal: LlF 12201
Slit : Fine S i3N4 Pro lective Loyer h 1000 AI
Detector: S C
2 Fe TbCo Recording Loyer (~I 000 AI
3.0,--------..,
3 SI3N4 Protective Loyer (",1000 Al
m «
..,
~
8I
~
PC Substrate 1 I. 2 mm I
2.0 u" m
...J
Typical Analyzed Result

1.0
Loyer Component Chern. X-roy Deviation
I Si3N4 (A 700 718 18

0.07±5~7::':6:--::r77~78=---::l79.
--291degl 2 Loyer (A 750 753 3
Tb(At·/.I 18.11 18.08 -0.03
Co (At"!J a25 8.17 -0.08
Fe (At"!.1 73.64 73.75 0.11
3 Si3N4 (AI 750 733 -17
Figure 9. Analyzed results of magneto-optical disk

Table 5. Analytical parameters for thin film analysis

I. Measurement
· Spectral resolution
· Counting linearity
· Background substraction
· Sensi tivity and precision
2. Analytical technique
· Selection of analytical line
· Sensitivity calibration
3. Standards
· Pure materials or dissimilar standards
· Simi lor standards
4. Analytical problem
· Uniformity of thickness and composition
· Flatness of substrate
· Impurity in substrate
· Standard value errars
· Errors in physical parameter' and instrument factors
· Errors caused by density in thickness analysis
· Microscopic uniformity of film surface
of the FeTbCo layer. The lines measured were the Ka's of Si,
N, Fe and Co, and the Tb-La line. The spectrum shown in the
figure was obtained from one of the actual samples. The Co-Ka
line is clearly separated from the Tb-LB line. The thicknesses
of the two silicon nitride layers are determined by measuring
both silicon and nitrogen. Very accurate results were obtained
for the thickness and composition of the FeTbCo layer. The
errors of the silicon nitride thicknesses are from 2% to 3%,
relative. Similar results were also obtained by measuring the
Fe-La line instead of the N-Ka line to determine the
thicknesses of the silicon nitride layers.
8. Analytical parameters for thin film analysis
It is important to understand the impact the analytical

parameters have on thin film analysis in order to improve the
accuracy of the analysis and correctly evaluate the results.
Table 5 lists the analytical parameters for thin film analysis.
During the measurement the counting linearity is a basic
requirement of the fundamental parameter method. This is
particularly important when pure element standards, whose
intensities are often higher than unknown samples by more than
one order of magnitude, are used. For the selection of the
analytical lines the Dataflex 270 permits using both the K and
L lines for one element. This technique is useful when
different layers contain the same element. For most analytical
problems the sources of errors are understood and

straightforward. However, in thickness analysis a density has
to be entered for the calculations. If the specified density
is incorrect, this will lead to an error in the calculation of
the thickness.
9. Conclusion
The multi-layer thin film fundamental parameter program
which is part of the Rigaku Dataflex 270 software package was
described and its performance has been proven with practical
applications.
One of the features of the software is its sensitivity
library. The preparation of standards has been a major
obstacle of thin film analysis, especially in the research and
development environment. The sensitivity library feature
permits the analysis of any element capable of being measured
with reasonable accuracy, even if no standards are available.
If there are standards similar to the unknowns, optimum

accuracies can be obtained using a variety of data processing
options, such as the sensitivity calibration and its
combination with an empirical calibration method. This feature
meets the needs of routine analysis required for quality
control.
10. References
1. T. Shiraiwa and N. Fujino, Adv. X-ray Anal., ~ (1968),
p.446
2. T.C. Huang and W. Parrish, Anal. Chem., 49 (1977), p.1152
3.T. Arai, Adv. X-ray Anal., 30 (1987), p.315
4. J. Willis, Adv. X-ray Anal., 31 (1988), p. 175
5. H. Kohno, M. Murata, Y. Kataoka and T. Arai, Japan Adv.
X-ray Anal., 19 (1988), p.307
6. Y. Kataoka, Rigaku Journal, Q (1989), p.33
7. T. Arai, Adv. X-ray Anal., 30 (1987), p.213
8. R.L. White and T.C. Huang, in Proceedings of the 37th Denver
Conference, 36 (1988)
FUNDAMENTAL PARAMETER-BASED X-RAY FLUORESCENCE ANALYSIS
OF THIN AND MULTILAYER SAMPLES
D.K.G. de Boer and P.N. Brouwer
Philips Research Laboratories

P.O. Box 80000, 5600 JA Eindhoven, The Netherlands
Abstract
The Fundamental Parameter-based calculation of x-ray fluorescence intensities for thin and
multilayer samples is performed with new formulas. By the calculations it is shown that both illlra- and
inter-layer secondary fluorescence can cause significant enhancement. With a method based on the
discussed theory, it is possible to determine the composition and layer thicknesses of multilayer samples.
Analyses are discussed of samples from IC technology and magnetic recording. Furthermore, the angular
dependence of intensities is calculated, in good agreement with experiments performed with a novel
spectrometer.
Introduction
For the analysis of samples consisting of multilayers or thin layers on substrates, X-Ray
Fluorescence (XRF) is an attractive technique, as it enables both chemical composition and
layer thicknesses to be determined in a fast and in general nondestructive way. Examples
from our laboratory are: optical coatings (e.g. Ag/glass), protective coatings (e.g. WCfstecl),
magnetic recording material (e.g. CoCr/Ge/polyimid), optical recording material (e.g.
InShTe/PMMA), superconductive ftims (e.g. YBa2CuJO'-x/SrTiOJ), as well as sample~ from
Ie technology (e.g. metal/Si and BPSG/Si). Some of these examples will be discussed in detail
below.
Just as in the case of hulk samples, quantitative analysis can be accomplished using
calibration standards with composition close to that of the sample. lIowever, since the layer
thicknesses are additional unknown quantities, more standards arc needed than in the bulk
case, where it is difficult (if possible) to produce accurate thin-film standards. Thus, more
than in the case of bulk samples, Fundamental Parameter-based analysis is demanded for thin
and multi-layer samples where reference standards are only required to determine the
spectrometer sensitivity for an x-ray line, although the accuracy of the results may he
improved using standards close to the sample composition.
Theory
Here the formulas for the calculation ofXRF intensities J from multilayer samples 2 are
used in the closed form derived by De Boer3. Besides fluorescence caused directly by the
incident x-rays (primary fluorescence) cnhancement due to secondary fluorescence, caused
hy (primary) fluorescent radiation, will be considered. Tertiary and highcr effects are
neglected.
First the formulas are given for monochromatic irradiation with wavelength A. Thcy
will be extended to calculate the intensity for polychromatic irradiation. The symhols used

are defined in Table I. The primary fluorescence intensity of (the considered line with
wavelength A, of) element i in a homogeneous layer (I) with thickness d1 (rf fig. I) is
The factor between braces describes the intensity change as a function of layer thickness.
The last exponential accounts for absorption of radiation in layers a which may be prcsent
above the considered layer I. For more layers one has to sum over a in the exponent.
As for the secondary fluorescence, one has to distinguish betwecn intra-Iaycr and
inter-layer contributions. The intra-layer secondary fluorescence of i due to fluoresccnce
radiation fromj (i.e. within the same layer I) is
(2)
For bulk samples (dl ---> 00) the factor L is given by the well-known 1 formula
L =!.L In
/1/
II £L I
+
Ilj
+ I ~I
In I + Il) (J)
Table I. List of symbols

C, mass fraction of element i in the sample
dl mass thickness of layer I, containing analysed element
d2 . mass thickness of layer 2, containing element causing secondary fluorescence
d., db mass thickness of top layer a and intermediate layer b, respectively
G geometrical factor in XRF intensity accounting for detected irradiated sample area
g, relative emission rate for the considered line of i in preference to other lines originating from
the same shell
number of photons /second emitted (per unit solid angle) by x-ray source
detected number of photons /second emitted by element i in the sample
detected number of photons emitted by element i (per incident photon with wavelength A)
(x-ray line of) element to be analysed
} (x-ray line of) element causing secondary fluorescence of i
.1,(1.) absorption jump factor (at wavelength A) for creation of hole in considered shell of atom i
L factor describing secondary fluorescence within a layer
Mu,M d factor describing, respectively, upward and downward secondary fluorescence between layers
P,(A) detected number of photons emitted by primary fluorescence of element i per incident photon
with wavelength A
Sij(A) detected number of photons emitted by element i due to fluorescence radiation of J (per
incident photon with wavelength A)
A wavelength of incident radiation
Ao cut-off wavelength of incident spectrum
A" AI characteristic wavelength of fluorescence radiation from i and}, respectively
A,hs.' . absorption edge (belonging to the atomic level which forms the initial state for the fluorescence
radiation of wavelength A,)
/11> mass absorption coefficicnt of layer I (containing analysed element i) at wavelength A
111/ = fln I sin ,/I,
1111 mass absorption coefficient of layer I (containing analysed element /) at wavelength AI
11.1/ = lili I sin Ijl2
11..> , etc. mass absorption coefficient of layer a, etc. at wavelength A
flo/, etc.
/101 , etc.
"'I ,
= Ii., I sin etc.
mass absorption coefficient of layer a, etc. at wavelength A,
/-la/, elc. = Ii., I sin 1//2 , etc.
photoelectric part of mass absorption coefficient for element i at wavelength A
photoelectric part of mass absorption coefficient for element i at wavelength Aj
angle between incident and detected beam, respectively, and sample surface
fluorescence yield for the decay of the considered hole in atom i
D. K. G. de BOER AND P. N. BROUWER 239
a b
lda tda
d1 t d2 t j
tdb 1db
d2 t d1 t
Fig. I. Multilayer sample with in layer 1 atom i, emitting the detected x-rays, and in layer 2 atom j ,
emitting x-rays which can cause secondary fluorescence of i . One or more top layers a and one or more
intermediate layers b may be prescnt. (it) layer 1 above layer 2. (b) layer I below laycr 2.
For finite thickness one can write

(4)
where
(Ill +/12)f1j
1- C-(I'I +IJ 2 )d
D{('}j - 112) d} + (I ) D{(f11 + Ilj) d} ] +

112 (Ill + 112) /11 /11 + /12
PI (PI
I
+ 112)
In 11 + ~
Ii}
I +
112 (PI
I
+ P2 )
e-(I'I +112)d In II - f'~J~ I) (5)
Here
(6a)
and
EI(x) =' J OC! dy

-y C
-y
= 0.57721... - In Ixl -
2: -(-xt
00
-,- (6b)
n.n.
x n=l
Et(x) is the exponential-integral function and D(x) can be evaluated rapidly by a computer,
using fast converging series.
For the inter-layer secondary Ouorescence one has to distinguish the cases that the
radiation emitted hy j is directed upward (Fig. la) and downward (Fig. I b). The intensity
of the corresponding inter-layer secondary Ouorescence S./ CA.) and S'/ CA) can he written as
.1/ ()"J') t pc r ii
S..
lj
u,d
(A)= Y2
"
c.JJ.(A)w,gj
J.
--
.liU)
. M
'uI12i-. u,d
P (A)
/
(7)
where
Pl"+11 1,! 'd

MU = " f1-2j e- f1hl b X(flu , ,111/,
'd1,d)
2 (8)
C(I1I1'+ f1,,')d, -I
(9)
In Eqs. (8) and (9), if more than one intermediate layer is present, one has to sum over h.
The factor X in (8) and (9) is defined as
X(p,qA ,d2 ) = V( dl A) - V( dl ,0) - V(OA) + V(O,O) ( 10)
240 III. X-RAY SPECTROMETRIC CHARACTERIZATION OF THIN FILMS·
Ill} q
+ ----,----''-- lJ{(I--)(llIJA +llbidb+112id2)}
q (pIlI} + qll?,i ) 11 \j J"
- )q J) (,1 IjdJ + 11~idb + IJ?,id2)] (lla)
This general expression is not valid if dh = d, = d2 = °:

V(O,O) = -
PilI}
I
+q,J2j
_ . In
[1l7,i
P
I1 + -1l7,iPill
+ - I n I1 -
q
\j -q
II J}
I]
The total intensity of fluorescence from i (due to irradiation with wavelength A.) is given by
flU) = PI (A) + I SliP) (12)

J
where the summation is over the x-ray lines of aJl kinds of atoms with Aj < AabS.;, both within
and outside the layer with atom i. (Of course, if i is present in more than one layer, one has
to sum the contributions from the different layers.)
If the incident radiation is not monochromatic, but has an intensity distribution 10 (,1),
the total intensity of fluorescence from i is
(13)
With these formulas it is straightforward to calculate intcn~itics, if the numerical values of

the Fundamental Parameters are known. Ref. 4 discusses how these can be obtained from
literature. Pella's5 algorithm is used for the intensity distribution of the x-ray tube.
Calculation of intensities
As an illustration we will consider the calculation of Cr Ka intensities from
Coo.sCro.z/Ge films (analyses of which will be discussed in the following sections). In this
section we will use monochromatic irradiation with A = 0.2 A (and 1/" = 64°, "'Z = 400). In
general, the enhancement by secondary fluorescence is less for polychromatic irradiation.
Fig. 2a shows, on a double-logarithmic scale, the Cr Ka fluorescence intensity as a
function of the thickness of a Coo.sCro.z film on an infinitely thick Ge substrate. The dotted
curve indicates the primary contribution (Eq. I). The dashed curve includes the enhancement
due to intra-layer secondary fluorescence (Eq. 2) from the Co K lines (which grows, as a
function of thickness, from zero to the constant value given by Eq. 4). The full curve also
includes the enhancement due to inter-layer secondary fluorescence (Eq. 7) from the Ge K
lines (which decreases gradually as a function of thickness).
Fig. 2b shows the Cr Ka fluorescence intensity for a ca.235 nm thick Co o.SerO.2 film as a
function of Ge substrate thickness. For such a thin film the intra-layer secondary
f1uorescence (difference between dashed and dotted line) is only slight. The full curve
includes inter-layer secondary fluorescence (Eq. 7) due to Ge K lines, which incrcases as a
function of substrate thickness.
Fig. 2c shows the same, but now for back irradiation: Cr Ka intensity for a ca. 235 nm
thick Con.RerO.2 film as a function of the thickness of the Ge layer on top of it. The
pnmary contribution (dotted) is a simple exponential decrease. Again, dashed and full curve
include intra- and inter-layer seconclilry fluorescence, respectively.
"..
-'
.,'
.. '
, .'
".---:-:'. "
,.,.'
- - -.-
to-' to-' to-I to-' 10- 2

thickness (g/cm 2 ) thickness (II/cm 2)
Fig. 2. Calculated Cr Ka intensity for various CoCr/Ge samples. Dotted: primary fluorescence only,
dashed: primary + secondary fluorescence due to Co, full: primary + secondary fluorescence due to Co
+ secondary fluorescence due to Ge. (a) Cr Ka intensity as a function of coating thickness for a
COROCr20 coating on an infinitely thick Ge substrate. (b) Cr Ka intensity as a function of substrate
thickness for a 2 x 10 -4 g/cm 2-thick CO&OCr20 coating Oil a Ge substrate. (c) Cr Ka intensity as a function
of coating thickness for a Ge coating on a 2 x 10- 4 g/cm 2 thick COROCr20 substrate.
Examples of analyses
Of more practical interest than intensity calculations from known composItIon is the
calculation of sample composition (i.e. both concentrations and layer thicknesses) from
measured intensities. For this purpose a Fundamental Parameter-based (1'1') computer
prognun was written in which. for each x-ray line measured, (at least) one reference standard
is required (which could be a bulk sample). The program takes an initial estimate of the
composition from which the intensities (related to those of the reference) arc calculated, using
the formulas given above. Then the thicknesses and concentrations are updated (with the
condition that the sum of the concentrations equals one inside each layer) and this step is
repeated until the root-mean-square differencc between measured and computed intensities
is minimal.
In this section, some thin-layer analyses are considered (which, unless stated otherwise,
were done in a standard way using a Philips PWl404 spectrometer).
As a first example we will discuss CoCr films (on polymer substrates), which can be used
for perpendicular magnetic recording. The use of a Ge layer between CoCr and polymer
gives rise to a better crystallization of the CoCr layer, resulting in a higher perpendicular
magnetic anisotropy and better recording properties 6 • First a series of CoCr films sputtered
on a polyester substrate (without Oe interlayer) were analysed. The nominal composition
of all films, determined from the sputter target compo~ition, was 80.55 mass% Co, 19.45
mass% Cr. Neutron Activation Analysis of the films yielded 80.4 mass% Co, 19.6 mass%
Cr. The thicknesses d were determined from sheet resistance measurements.
The results of XRF measurements worked out with the FP program, using bulk Co and
Cr as standards, are as follows (assuming a density of 8.50 g/cm3 for the CoCr layer):
sheet resistance XRF

sample d(nm) d(nm) Co (mass%) Cr (mass%)
A 30 35 78.1 2\.9
B 300 320 78.0 no
C 750 790 78.4 21.6
D 1850 1910 78.9 21.1
As can be seen, about 2 mass'Yo too little Co is found, whereas the thicknesses are ca. 7%
higher than is found from sheet resistances. This may partly be due to a systematic error in
the assumed density. Another source of error is the uncertainty in the mass absorption
coefficients, which may amount to 5% relative 4 •
Next CoCr/Ge/polyimid samples were analysed. The results, using bulk Co, Cr and
Ge as standards are, (assuming that Ge has a density of 5.32 g/cm 3):
sample Co (mass%) Cr (mass%) deoc , (nm) d". (nm)
E 77.8 22.2 170 320
F 77.8 22.2 210 410
G 78.1 21.9 290 310
G* 78.0 22.0 270 290
Of course, instead of bulk standards, the CoCr/polyester samples could have been used as
standards, yielding higher (and probably more realistic) Co contents. The last sample,
marked G* , is sample G analysed from the back, with a polyimid film of 12 flm thickness
on top of the Ge layer. The agreement between the two measurements is good.
Many thin-layer samples which arc analysed by XRF in our laboratory originate from
Integrated-Circuit (lC) technology. Examples are metallization layers (e.g. AI, Ti, Co) on
Si wafers. We will consider (oxygen-contaminated) cohalt films on silicon. In advanced IC
technology silicide (in a self-aligned silicide process) is formed by the reaction of such a thin
metal film with the silicon substrate 1. The reaction is extremely sensitive for contamination
(C, N, 0) in the metal film. In order to study the inOuence of oxygen contamination in
sputter-deposited Co films on the silicide formation process, cobalt deposition was performed
not only in pure argon, but also in Ar/0 2 gas mixtures. The amount of 0 incorporated in
the deposited Co films (with a thickness of ca. 38 nm) was measured using XRF and the FP
method, with bulk quartz as a reference. It was found that the relative contribution of Si
substrate nuorescence to the 0 Koc signal is 21 % throughout the whole concentration range
of interest. In Fig. 3 the oxygen content in the Co layer is plotted against the O 2 content in
the argon during sputtering. The offset at the vertical axis corresponds to a native oxide layer
of 3.3 nm. At increasing O 2 content in the Ar/02 mixture the 0 content in the Co film
increases linearly up to 0.8% O 2 , At larger O 2 contents the oxygen incorporation in the Co
U
t
o
.!:
o
Cr tube
20
(60 keY)
~ Si detector
(width=50 pm)
10
o 2 . bent crystal
%02,nAr-
Fig. J. 0 content in sputter-deposited Co Fig. 4. Spectrometer used for measurement of

layer VS. O2 content of Ar during sputtering. angular dependence of intensities.
D. K. G. de BOER AND P. N. BROUWER. 243
layer increases rapidly. This is ascrihed to the fact that then, during the sputtering process,
the Co target surface is oxydized to such an extent that Co-O is sputtered instead of Co.
(Similar effects have been ohserved at Ti sputter deposition in M/N2 gas mixtures R .) The
discontinuity was also found in the formation of CoSi 2 from the sputtered films: at levels up
to 0.8% O 2 silicide formation occurs, whereas at higher levels hardly any continuous CoSi 2
film could he formed.
Another example from IC technology is the analysis of horophosphosilicate glass
(BPSG) planarisation layers on Si wafers. The properties of these layers, which mainly
consist of Si0 2 , strongly depend on their boron and phosphorus content. We will express
the last two as B20 3 and 1'2 0 5 (although some P may be trivalent). These measurements were
done with the Philips XRF Wafer Analyzer (which can handle whole wafers) using an Rh
end-window tuhe at 40 kV. The Band P contents were determined by Inductively Coupled
Plasma/Optical Emission Spectrometry (ICP/OES) and the thickness d was measured by a
taly-step method, ellipsometry or weighing before and after glass-layer removal 9 • (From these
measurements, the layer density was found to be 2.13 g/cm 3 .) With XRF, the intensities of
the B KIX, P KIX and Si Kf3 lines were measured and the results worked out by the FP method.
A selection of the results is as follows, using sample S as calibration standard:
sample mass% B20 3 mass% P2 0 S mass% Si02 d (nm)
ICP XRF IeI' XRF ICP XRF measured XRF
S 7.5 11.0 81.5 GOO
T 14.6 12.7 6.6 8.1 78.9 79.2 290 270
U 7.0 7.5 11.2 10.2 81.8 82.3 920 1020
V 7.1 6.4 12.9 12.1 80.0 81.5 590 620
W 7.4 6.6 13.6 12.4 78.9 81.0 590 610
The average relative deviation in both H20 3 and P20S content is about 10%; the average
relative deviation in layer thickness is ahout 5%. This probahly arises from the uncertainties
in the absorption coefficients and in the fluorescence yields (influencing the calculated
enhancement, cf C'q. (7». It was found that the elTect of enhancement due to substrate
fluorescence on the B K('( intensity is as high as 8%.
Angular dependence of intensities

The theory of section 2 can be used to calculate the dependence of XRF intensities on
the angle of incidence VtJ and the detection angle Vt2' To do that, however, one has to take into
account that the angular dependence of the geometrical factor Gin eq, (\) is different for the
various possible experimental arangements 10 •
In our laboratory a spectrometer was built (cf Fig. 4) in which "'I
and V/2 can be changed
simultaneously. The spectrometer uses focussing optics and a smal1 Si photodiode as a
detector. It can be shown 10 that, for such an arangement, G is proportional to
sin Vtt! sin V/2 , as long as V/2 is larger than half the aperture angle of the crystal (1ft, > 2.40 in
our instrument). The spectrometer is built in such a way that VII + V/2 = 150 + fI - <p , where
a b
o 30
Fig. 5. Intensity vs. detection angle for Ti Ket. measured with (113) reflection of an SiC 111) crystal. (a)
Ti layer on Si. (b) li bulk. +: measured (using a Cr tube at 60 kV) with q, > 0 (Vtl + V/2 = 42.57"), 0 :
measured (using a Cr tube at 50 kV) with <p < 0 (1//1 + V/2 = 101.56°). Full line: theory.
t I c)
I
.~
t front
en
c
\ ,Sl
I £;
I
\
\
x'\
t
CrKa
a) x\
COQ,e CrO,2 I
~
'iii Ge x\
c front y-back
,Sl polyimid
£; I
I
x
30
~
\x 1j>2(')-
\
+ I
+ + '\
+ +\~ ,,,
+'~')(
+ '<t~"'... x GeKa
/'+.....x
I
front ~if--.
I ~-;-if-~
o ~ 00 (0) o 30 60 1j>2(')_
1j>2 -
Fig. 6. Intensity V.f. detection angle for a CoCr/Ge/polyimid sample (see inset), measured (using a Cr tube
at 60 kV) with an Lifo(IOO) crystal. +: measured at front side, x : measured at the back, full curve:
calculated for front side, dashed: calculated for the back. (a) Co KG( intensity measured using (400)
reflection (VII + 1/12 = 77.69°). (b) Cr KG( intensity measured with an AI filter (0.1 mm) using (200)
reflection (V" + 1/12 = 49.65°). (e) Cie KG( intensity measured using (600) reflection (1/11 + 1/12 = 84.11°).
e isthe Bragg angle of the monochromatising crystal and 4> the asymmetry angle (i.e. the
angle between crystal surface and reOecting crystal planes), which can be positive or negative.
In FIg. 5 results are shown for the Ti KG( intensity of a titanium layer on silicon and of
bulk titanium as a function of 0/2 in two experimental configurations. Measured values are
shown, as well as values calculated with the for method (which are scaled in such a way that
they fit the experiments at intermediate 0/2)' As a general trend, it is seen that the intensity
decreases as a function of 0/2, due to the factor sin 0/1/ sin V/2 . For a thin layer (Fig. 5a) the
decrease is much greater than for a bulk sample (fig. 5b). So the surface sensitivity can be
increased by measuring at a small detection angle. As indicated above, for 0/2 below 2.4° the
experimental intensity decreases. for the bulk sample a deviation from theory is already seen
for slightly larger 0/2, because the (foil) sample was not completely flat.
Another example is shown in Fig. 6, giving both experimental and theoretical results for
a CoCr/Ge/polyimid tape (sample G of section 4), measured from both the front (CoCr) side
and the back (polyimid). It can be seen that for such a three-layer sample the results are also
good (except for small 0/2, because the sample was not completely flat).
Conclusions
For thin and multilayer samples, Fundamental Parameter-based calculation of XRF
intensities from the composition, and vice versa, is possible using the proposed method. In
many cases it is important to take into account enhancement due to inlra- and inter-layer
secondary Ouorescence. Also, the angular dependence of XRF intensities can be calculated
and agrees well with experiment.
Analytical results for both concentrations and layer thicknesses can be obtained with a
relative accuracy of at least 10%. It is expected that in the near future the accuracy can be
improved by the use of better values for the Fundamental Parameters, based for instance on
a comparison of many independent analytical results. Because of the high precision of the
XRF measurements, the method is already well suited to monitor changes in sample
composition.
Acknowledgments
We should like to thank O. Elgersma, J..J.M. Borstrok and C. Nieuwenhuizen for helpful
discussions and for providing results of analyses, TJ.M. Verspaget and M.G.M. Meulendijk
for performing analyses, J.P.c. Bernards for providing the CoCr layers and R. Wolters for
providing the data on Co(O)/Si.
References
\. 1. Sherman, Spectrochim. Acla 7 (1955) 283.
2. M. Mantler, Analytica Chimica Acta 188 (1986) 25.
3. D.K.G. de Boer, submitted to X-Ray Speclr.
4. D.K.G. de Boer, accepted by Spectrochim. Acta B.
5. P.A. Pella, L.Feng and 1.A. Small, XRay Spectr. 14 (1985) 125.
6. c.P.G. Schrauen, J.P.c. Bernards, RW. de Bie, GJ.I'. van Engelen, HI!. Stel, V. Zieren and S.B.
Luitjens, IEEE Trans. Magn. MAG-24 (1988) 1901; .T.I'.c. Bernards, c.P.G. Schrauwen, S.B.
I,uitjens, Appl. Phy,r., submitted for publication.
7. L. van den Have, R. Wolters, K. Maex, R.F. de Keersmaecker and G.J. Dcclerk, IEEE Trans.
Electron Devices ED-34 (J 987) 554.
8. R.C. Ellwanger and 1.M. Towner, Thin Solid Films 161 (1988) 289.
9. O. Elgersma and J..T.M. Borstrok, to be submitted to XRay. Spectr.
10. D.K.G. de Boer, X-Ray Spectr. 18 (1989) 119.
NON-DESTRUCfIVE CHEMICAL-STATE ANALYSIS OF THIN FILMS AND SURFACE
LAYERS (1-1000 NM) BY LOW-ENERGY ELECfRON INDUCED X-RAY
SPECTROSCOPY (LEEIXS)
Angeli K. Gyani, Phillip McClusky and David S. Urch
Chemistry Department, Queen Mary College,

Mile End Road, LONDON E1 4NS, U.K.
M. Charbonnier, F. Gaillard and M. Romand
Departement de Chimie appliquee et Genie chimique CNRS.

URA 417, Universite Claude Bernard-Lyon I, 43 Boulevard du 11
novembre 1918. F-69622 VILLEURBANNE, Cedex FRANCE
ABSTRACf
The penetration depth of 1-12 ke V electrons in most materials is less

than one micron and the characteristic soft x-rays that are produced can be
used to identify the elements present in the surface. Varying the energy of
the incident electron beam enables the depth of analysis to be controlled.
Soft x-rays often exhibit large 'chemical effects' (changes in peak

profile and peak position) which can be correlated with chemical changes.
A study of such effects for each element present in the sample surface, as a
function of electron -beam energy, can in some cases, permit changes in the
chemical state (valency - coordination number-spin state etc.) to be
determined as a function of depth.
Such analyses can be carried out either in a conventional x-ray

spectrometer in which the x-ray tube has been replaced by a gas-discharge
source, or in a spectrometer in which the sample is bombarded with
electrons from a normal electron gun. In this paper these techniques are
outlined and some applications reviewed:- the analysis of oxide layers on
aluminium and steel, the analysis of aluminium -nitride layers produced by
MOCVD on gallium arsenide, the analysis of silica films (with added boron and
phosphorus oxides) on silicon and the analysis of zinc-oxide films on glass.
1. INTRODUCTION
Electrons with kinetic energies of less than 12 ke V have penetration

depths in most materials of less than one micron. As a result of such
bombardment the sample surface emits characteristic x-rays from which its
elemental composition can be deduced. If the energies of the incident
electrons are controlled then the depth of analysis can also be controlled.

Low-energy electron-induced x-ray spectroscopy (LEEIXS) I is therefore a

technique for the non-destructive analysis of surface layers in the 1-1000
nm thickness range. As such it compliments other methods of surface
analysis such as Auger electron (AES), x-ray photoelectron (XPS) and
secondary-Ion Mass (SIMS)-spectroscopies (O.l - 5nm) and x-ray
spectroscopy via electron -beam microprobes (>500 nm). Whilst it is true that
XPS and AES can be adapted by the use of etching techniques for analysis of
surface layers in the nanometer range, these methods are, as is SIMS of
necessity, destructive. Also ion bombardment can seriously compromise
sharp layer boundaries, by promoting diffusion before and during analysis,
and can initiate chemical change. LEEIXS has therefore, certain distinct
advantages for the surface analysis of relatively thick films, provided that a
defocussed electron beam is used so as to keep sample damage to a minimum.
It is also possible in many cases to work with insulating samples) A further
potential advantage of LEEIXS is the possibility of being able to follow, for
certain elements, chemical state as a function of depth. This is because the
soft x-rays generated by low-energy electron bombardment often result
from valence shell ~ core level transitions. 'Soft' x-ray peaks of this type
often exhibit considerable fine structure which is a direct indication of the
electronic structure of the solid or the molecule, in the neighbourhood of the
emitting atom) Thus changes in peak shape, profile or position can be
correlated with a variety of chemical factors such as, oxidation state,4
coordination numberS and the nature of covalently-bound ligands. 6
'Chemical effects' can also be observed in transition -metal x-ray emission
spectra even in peaks that result from core-to-core transitions. In these
cases such effects appear to be due to interactions between vacancies in near
valence orbitals (e.g. Fe 3p) and partially-filled d shells. Correlations can be
made both with valence 7 and with spin states. 8 In this paper examples will
be given of the application of LEEIXS to a variety of different samples.
2. EXPERIMENTAL
Two different types of electron source have been used to excite x-ray
emission from surfaces, one novel and one quite conventional. The former
utilises the electron flux present in a gas-discharge plasma, the latter is an
ordinary electron gun. In both cases the analysis of the x-rays from the
sample is by standard procedures. In the experiments described in this
paper single flat crystals were used to disperse the x-rays which were then
detected in gas-flow proportional counters fitted with thin windows [~I 11m
polypropylene].
a) Gas-Discharge Electron Source
Figure 1 shows a diagram of this type of electron source. A discharge

occurs between the anode and the cathode in any suitable gas (air is quite
satisfactory) at about 10- 1 torr. A hole in the anode allows the electrons from
the discharge tube to escape. The energy (Eo) of the electrons in this beam
corresponds to the potential difference between the two electrodes. Typical
operating conditions are in the range 0.5 - 5.0 k V with a current of 0.1 - 0.5
mAo The stability of the discharge is maintained by controlling the pressure
which is, in turn, effected by means of an electronically -controlled needle
valve. This valve admits air at a rate that keeps the (pre-set) current in the
discharge constant. The diameter of the electron beam at the surface of the
sample is about Icm 2 , the precise value depending upon the size of the hole
in the anode.
A. K. GYANI ET AL. 249
A A
,
,,
I
,,
,,
I
,. I
I
r--, L--- "-
"-
~ [ HT
r-- "-
"'-
-L
Figure 1. Diagram of essential features of the gas-discharge source. A:
anode, C: cathode, hatched areas: insulators, dashed line: electron
beam.
This type of source has the great advantage that it can be used with
insulating samples. It is not necessary to have a conducting sample to
complete the electronic circuit. A further advantage is that the source can
be configured to replace an x-ray tube in a conventional x-ray spectrometer.
This means that ordinary x-ray fluorescence spectrometers, provided only
that they are capable of achieving a vacuum of a little better than one tenth
of a torr within the spectrometer chamber, can be easily adapted for this
type of surface analysis.
A more detailed discussion of the nature of the discharge and the

processes occurring within it has been given by Romand et al. l
b) Electron-Gun Source
The conventional electron gun in a Telsec 'Betaprobe' X-ray

spectrometer can be run satisfactorily in the voltage range 4-12 kV at O.lmA,
thus giving results complementary to those obtained with the gas-discharge
source.
c) X-ray Spectrometer
Whichever electron source was used the characteristic x-rays emitted

from the sample surface were analysed by conventional flat crystal X-ray
spectrometric procedures. In order to diffract the soft X-rays, the following
crystals were used:-
Eddt ethylenediamine D-tartarate : 2d, 0.881 nm

PE pen taerythritol : 2d, 0.875 nm
Rb AP rubidium acid phthalate : 2d, 2.621 nm
TlAP thallium acid phthalate : 2d, 2.571 nm
OHM octadeeyl hydrogen maleate : 2d, 6.25 nm
(}\() dioctadecyl adipate : 2d, 9.12 nm
No modifications need be made for the spectrometer to work at

wavelengths as long as 10 nm provided that a reasonable vacuum can be
maintained and that the proportional counter has a thin window, (one
micron or less). Pulses from the counter were amplified in the usual way
and data collection, handling and analysis were carried on microcomputers,
either Apple lIe or CBM 8000 series.
The angles of incidence of the electron beam on the sample and also the
take-off angles for the characteristic Xrays were different for the two
spectrometers so that both the penetration depth of the electron beam, as a
function of electron energy and also the importance of x-ray absorption
effects were different in the two systems. This means that a direct
comparison of results from the two spectrometers is not possible although
overall trends should show the same form (but perhaps at different beam
energies)
In this section results will be presented from a variety of different

systems starting with a comparison of the behaviour of observed x-ray
emission 'yields' with increasing electron - beam energy for very thin films
and for bulk samples. This will enable characteristic curves for the x-ray
yield as a function of beam energy, to be established for use in the discussion
of results from other systems.
a) Alumina/Aluminium
Fig. 2 shows how the oxygen Ka x-ray intensity varies with electron-
beam energy for the natural film of alumina which covers metallic
aluminium. In such a very thin film [5 nm or less] the absorption of oxygen
K a x-rays will be negligable so that the form of the curve in figure 2 should
be closely related to the variation of ionisation cross -section (cr) with energy.
That this is indeed so can be seen by comparing figures 2 and 3. Figure 3 is a
theoretical curve showing the ionisation cross-section as a function of
S 10
o 2. 4- kV Eo / EK
Figure 2. Variation of intensity of Figure 3. General curve 16 relating

oKa with bombarding the cross section for
electron energy from the ionisation (cr K) to the
'natural' oxide layer on incident energy (EO). EK
aluminium. is the ionisation threshold
energy.
Eo/EK. where EK is the threshold energy for ionisation. The maximum in

Figure 2 occurs at an energy a little greater than 3.EK [ -1.6 keY for oxygen].
where EK is the threshold for ionisation. For an 'infinitely-thick' sample the
relation between energy of excitation and observed intensity is more
complicated. even if it is assumed that self-absorption is absent. In this case a
curve describing the variation of x-ray 'yield' with beam energy would be
expected to increase as a function of electron beam energy from zero at EK to
a maximum rate of growth at around 3EK and then to continue to increase but
at a lower rate as the beam penetrates deeper into the sample. i.e. the curve
should have a roughly sigmoid shape. This is the form of curve observed for
oxygen Ka from a thick alumina sample. shown in figure 4 (i) but note that
the point of inflexion appears at a higher energy ( > 4 ke V) than in the very
thin oxide film (fig. 3). This increase in the energy at which the point of
inflexion is observed is mainly due to self-absorption effects. The
probability of x-rays being absorbed by the sample increases with the
thickness of sample to be traversed. Thus the attenuation of the x-ray 'yield'
x_ . _o-
.
•
x
,,-
.
_
.-/)( - )(
X
x/
/
•
/ >
/+ ----
)k
~
,;'
+
/
/
/
/T
y
/
-,
!o
2. 4
Figure 4. Variations with electron beam energy in the intensities of (i) OKa
(upper curves) and (ii) Al K (lower curves), X-rays from an
alumina sample. Open or solid circle data points (2-5 keY) were
obtained using the gas-discharge source. The other data. 4-11
ke V (x or +) were measured using the Telsec Betaprobe. As the
geometries of the two spectrometers are different, differences in
absorption effects can be expected and so the solid and dashed
curves have been displaced from each other. It should also be
noted that the solid circles are measurements of Al Ka intensity.
the crosses of Al K~; the change was made for experimental
convenience. Whilst absolute intensities are very different no
variation due to self-absorption is anticipated so that the form of
the curve should not be affected.
Figure 5. Aluminium X-ray emission in the KP-KP' region from, aluminium

metal (top), aluminium metal covered with a 120 nm thick oxide
layer (intermediate curves) and alumina (bottom). The
intermediate curves were measured with beam energies of 9,7,5
and 4.3 keY, in descending order.
will increase with bombardment energy which will, in tum, cause the
energy at which the point of inflexion is observed to increase.
The general applicability of these ideas is demonstrated in figure 4 (ii)

where the 'yield' of Al Ka or Al Kp from the sample is shown as a function of
beam energy. The form of the curve is the same as for 0 Ka but displaced to
higher energies; also the point of inflexion is found at a higher energy ( - 7
keY) than would be expected in the absence of self absorption (3 x l.566 '" 4.7
keY).
The above discussion shows that X-ray intensity vs. beam-energy

curves contain considerable information about film thicknesses and
composition and indicate that the generation of quantitative analytical data
will be both possible and complicated. The Feldman 9 equation has been used
by Charbonnier et al.,l0 and by SZ3 sz 11 to indicate how quantitative results
may be obtained from such data. The purpose of this paper is however to
consider the more qualitative aspects of LEEIXS and in particular to show how
the chemical effects that manifest themselves so clearly in many soft X-ray
spectra can be used analytically.
Figure 5 shows, at the bottom, the Al KP-KP' emISSIOn spectrum of

alumina and, at the top that of aluminium metal. The former spectrum shows
the well-known K~' low-energy satellite, which, at a separation of some 15 eV

from the main K~ peak, is indicative 12 of the presence of AI-O bonds. In the
latter spectrum this satellite is absent and the main peak is displaced slightly
to higher energies by 2.5 e V. These two spectra are sufficiently distinct to
allow them to be used to distinguish between metallic and oxidised
aluminium. This has been attempted for the other AI K~-KW spectra shown in
figure 5. which are all from a sample of aluminium covered with a 120 nm
thick surface layer of alumina. At the lowest energies the spectrum shows
considerable resemblance to that of Al20 3 but as the electron -beam energy
increases the relative intensity of the 'oxide' sateIlite decreases and the main
peak broadens. These changes are most easily understood as being due to the
electron bcam penetrating ever more deeply into the underlying substrate
of metallic aluminium. The observed spectra can be reproduced as the sums
of the AI K~ (oxide) and AI K~ (metal) spectra with the former a decreasing
percentage, and the latter an increasing percentage, with increasing beam
energy.
Z" La(
iI
500 510 520 e.V

Figure 6. X-ray emission spectra at various beam energies from a zinc-oxide
film on a glass substrate. The peak at 532 eV is due to the
potassium acid phthalate crystal used in the analysis.
M
3'-0 3go 400 e.1/
Figure 7. N Ka spectra at various beam energies from a film of aluminium

nitride. The peak at about 370 eV is due to Al Ka in the fourth
order. The increase in intensity with beam energy, is due to
gallium L emission (3rd order) from the gallium arsenide
substrate, at almost the same angle.
b) Zinc Oxide on Glass
A thin film of zinc oxide on a soda-glass cover slip was grown by low-
pressure metallo-organic vapour deposition using basic zinc acetate
(Zn40(CH3COO)6) as a precursor (ca. 0.4 Ilm, Shrs, 320°C, 10- 2 -10- 3 Torr). The
results of an examination of this film by LEEIXS are shown in figure 6. By a
happy circumstance it proved possible to study many of the X-ray lines of
interest over a small angle -range, because of the proximity of second -order
Zn La, ~ and Na Ka with first order oxygen Ka. As the beam energy is
increased from 4 through S to 7 ke V the corresponding increases in both Zn
La,~ and 0 Ka x-ray signals are consistent with increasing electron
penetration into the zinc-oxide layer. In going to 9 keY, however, striking
changes are seen in the intensities of both the oxygen Ka signal and the
sodium Ka (2nd order). This indicates that between 7 and 9 keY the electron
beam starts to penetrate the underlying glass to a significant extent. This
was confirmed by a direct measurement of the silicon Ka intensity which is
negligible up to 9 keY and then increased rapidly after 9 keY. The last
spectrum shown in fig. 6, at 11 keY is of interest in that not only is the
increase in Na Ka signal maintained but the Zn La,~ actually falls a little, as
would be expected once the exciting electrons can pass through the whole
film. It should also be noted that although a larger oxygen signal is found at
11 keY that at 9 keY the increase is slight. This is of course in keeping with
the behaviour seen in figure 4. (i). In this case of zinc oxide on glass both
film and substrate contain much oxygen : the OKa yield thus behaves as if it
came from a 'thick' sample.
A. K. GY ANI ET AL. 255
c) Aluminium Nitride on Gallium Arsenide
Films of aluminium nitride can be produced on a variety of different

substrates by MOCVD from dimethyl, diisopropylamine-aluminium dimer.
One such film, on gallium arsenide, was examined by LEEIXS. No signals, from
either gaIlium (Ga La, P) or arsenic (As La,p) were observed at electron beam
energies of less than 6 ke V indicating the presence of a surface layer of
some thickness. That this layer contains both aluminium and nitrogen is
shown in figure 7. where the N Ka and also AI Ka (4th order) signals can be
seen. These spectra also show the rapid increase of the gaIlium La,p signals
•
•
•
•
•
2- to KV
of- +
+
+
+
.-
0
+ 0
0
"
0
'0
ltv
2- 4 6
•
• •
2 4
Figure 8. Variation of X-ray intensities with electron beam energy from an
aluminium - nitride film.
i) top curve, nitrogen Ka
i i) middle curves, open circles Al Ka, crosses Al Kp.
The data points have been separated because they were
measured on different spectrometer. The
complementary nature of the curves is apparent.
iii) bottom curve, oxygen Ka.
I
1530 1!;7o
Figure 9. Aluminium KP-KP' spectra from aluminium nitride (top), an

aluminium -nitride film (intermediate curves) and alumina
(bottom). The intermediate curves were measured at different
beam energies 5.4,3 and 2.5 keY in descending order.
as an interfering peak in the 3rd- order 5.5 keY. This interference prevented
an extended study of the N Ka intensity as a function of beam energy. The
range 2-5 ke V is however shown in Figure 8 (i). Clearly a plateau is being
reached consistent with the notion of the nitrogen being confined to a
surface layer. A similar conclusion can be drawn from the curve shown in
figure 8 (ii), for aluminium x-rays. Note that the two curves [one for Al Ka,
at low beam energies, the other for Al Kp at higher beam energies] were
measured on different spectrometers. Thus a direct anion is not possible, as
explained above, however the form of the curves is clearly complementary.
Above 9 keY the intensity of the aluminium X-rays is effectively constant
showing that aluminium, too, is present only in a surface layer. Figure 8 also
shows (curve (iii» the behaviour of oxygen Ka. The rise and then dramatic
fall in intensity even at low beam energies indicates that oxygen is only
present very near the surface of this sample [which had been carried in the
air from the laboratory where it was made to the spectrometer].
A more detailed investigation of the aluminium KB -K B' peak profile as a

function of electron - beam energy enables a more thorough understanding
of the chemical nature of the surface films to be had. Figure 9 not only
shows Al KB-KB' for pure aluminium oxide and nitride but also the
corresponding spectra from the sample under investigation at energies
between 2.5 and 5 keY. As can be seen, at the highest energy the film
corresponds to aluminium nitride. The presence of the low -energy satellite
some 11 eV from the main peak in the Al K~-K~' spectrum from this sample
demonstrates 12 the presence of AI-N bonds and confirms that the MOCVD
procedure had, in fact, produced a film of aluminium nitride. At lower beam
energies, the satellite region is broadened to lower X-ray energies showing
that AI-O bonds are also being formed. These latter spectra therefore
indicate that the oxygen, whose presence was demonstrated in the very
surface of the film by the direct observation of 0 K a (figure 8 (iii)), is
chemically bound to aluminium. It seems reasonable to suppose that this
oxygen containing layer has resulted from the surface hydrolysis of
aluminium nitride.
J I I
170 1'ao 190
Figure 10. Boron Ka emission spectra from silica films on silicon (top three
curves), from B203 and [rom BP04 in descending order. Beam
energies for the silica films were 9,7 and 5 ke V.
e) Silica-Glass Film (with added oxides of boron and phosphorus) on Silicon
A film of silica approximately 500 nm thick can be produced on a silicon

substrate to provide an insulating layer. It is found that the mechanical
properties of this layer are enhanced by the presence of a few percent of the
oxides of boron and phosphorus. LEEIXS was used to study the composition of
such samples. Figure 10 shows that even low concentrations of boron can be
detected easily when OAO is used as the diffracting crystal. The figure also
shows that at higher electron beam energies 10th -order silicon Ka generates
an interference line which pulse -height selection was unable to totally
remove. This is not evidence that the Si : B ratio is increasing with probed
depth but is, rather, due to the differential rate of change of ionisation cross-
sections for B Is and Si Is levels as a function of electron energy. (cf. figures
4 (i) and (ii)). The form of the B Ka spectrum is especially interesting as it
shows not only the expected low energy satellite at 167eV [evidence for B-O
bonds] but also the high energy satellite at 193 eV. Preliminary results from
a wide range of boron-oxygen compounds have suggested 13 that this high-
energy satellite may be diagnostic for trigonal, as opposed to tetrahedral,
coordination of boron. Furthermore a comparison of the spectra shown in
figure 10 shows that B Ka from the glass closely resembles the spectrum from
boron C oxide and has little in common with that from boron phosphate.
Thus the x-ray spectra suggest that boron is not simply entering tetrahedral
hole sites in the silica -glass lattice [complemented by phosphorus replacing
silicon at other sites] but is initiating a structural change in the
neighbourhood of each boron atom.
CONCLUSIONS
The above examples show that considerable qualitative data about the
thickness and chemical structure of relatively thick surface films can be
obtained using low-energy electron-induced x-ray spectroscopy.
Comparable results can also be obtained, as Sza. sz 11 has shown at even longer
wavelengths using a grating spectrometer. It is also possible to carry out
non-destructive chemical state analysis of surface layers by x-ray-
fluorescence spectroscopy, using conventional x-ray sources
[Andermann ]14 and paper Willis presented at this conference .15 In the
former case the analysed depth is controlled by varying the angle at which
the exciting beam strikes the sample, at near-grazing incidence. As the
LEEIXS results described here can be obtained by the introduction of an
electron source into a conventional X-ray spectrometer it may be that this
will prove to be the simplest and most cost-effective solution for the analysis
of samples that range from tens to hundreds of nanometers in thickness.
ACKNOWLEOOEMENTS
The authors wish to thank the Royal Society, the Science and
Engineering Research Council [UK] and the Central Research Fund of
London University for their support of some of the research reported here.
They are also grateful to the European Economic Community for a 'twinning'
contract [it SJ2J -0282-C] which has facilitated the collaboration between the
London and Lyon Groups. They would also like to express their gratitude to
Dr. Elgersma, Philips Research, Eindhoven for the provision of the silica
samples discussed in section (e).
REFERENCES
1. M. Romand, R Bador, M. Charbonnier and F. Gaillard, Surface and Near-

Surface Chemical Characterization by Low-Energy Electron
Induced X-ray Spectrometry [LEEIXS]: A Review, ~
Spectrometry, 16: 7 [1987].
2. F. Gaillard and M. Romand, Applications de la spectrometrie d'emission
de rayons - X [LEEIXS] a I'etude des materiaux isolants. Cas de
quelques oxydes metalliques, Le Vide, les Couches Minces, supp. to
Vol 243: 231 [1988].
3. D.S. Urch, X-ray Emission Spectroscopy, in: 'Electron Spectroscopy-
Theory. Techniques and Applications', G.R. Brundle and A.D.
Baker, eds; Academic Press, London, 3: 1 [1979].
4. R Hom and D.S. Urch, Chemical Effects in the X-ray emission spectra of
sulphur, Spectrochimica Acta B, 42: 1177 [1987].
5. D.E. Day, Determining the Coordination Number of aluminium ions by X-
ray emission spectroscopy. Nature, 200: 649 [1963].
6. D.S. Urch, The origin and intensities of low energy satellite lines in X-
ray emission spectra : a molecular orbital interpretation, J, Phys.
C-Solid St. Phys., 3: 1275 [1970].
7. D.S. Urch and P.R Wood. The determination of the valency of
manganese in minerals by x-ray fluorescence spectroscopy, X-
ray Spectroscopy, 7: 9 [1978].
8. RA. Slater and D.S. Urch. The origin of the KW satellite peak in the X-
ray fluorescence spectra of iron compounds : a correlation with
magnetic susceptibility, J. Chern. Soc, Chern. Comm .. 564 1972].
9. C. Feldman, Range of 1-10 keV electrons in solids, Phys. Rev., 117: 2,455
[1960].
10. M. Charbonnier, M. Romand and F. Gaillard, Theoretical experimental
aspects of low energy electron induced spectroscopy, Analusis, 16
[supp to #9-10] : 17 [1988].
11. A. Szasz and J. Kojnok, 'Soft X-ray emission depth profile analysis :SXDA,
App. Surf. Sci., 24 : 34 [1985].
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by x-ray emission spectroscopy with use of low energy satellite
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elemental and chemical state analysis". Ph.D. Thesis. London
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STRUCTURE REFINEMENTS IN CHEMISTRY AND PHYSICS. A COMPARATIVE
STUDY USING THE RIETVELD AND THE TWO-STEP METHOD
G. Will, E. Jansen and W. Schafer
Mineralogical Institute of Bonn University

Poppelsdorfer SchloB, D-5300 Bonn, West Germany
INTRODUCTION
Two strategies are at present commonly used in studying and refining crystal
structures from powder diffraction data: the total pattern refinement proposed by
Rietveld (1969) and the two-step method originally proposed and applied by Will (Will
et aI., 1965). The latter one works by separating the intensity determination of the indi-
vidual peaks from the actual structure refinement, structure analysis or any structural
calculation (for example based on line broadening). Both methods have their merits,
and their drawbacks.
The merits of Rietveld's method are found especially in straight forward and con-
ventional structure refinements if we are dealing with i) single-phase substances; ii) a
simple and easy to be described background; iii) if the profile is known; iv) if the cell
metric is known approximately. The last two requirements are conditions sine qua non.
In the total pattern structure refinement a model must be presented to the program, and
this model then describes every data point in the diagram. This is useful and welcome
if the diagram is loaded with peaks, which becomes especially true if we have low-
symmetry materials or large unit cells. In other cases we have a great number of un-
necessary data points, basicly this is a ballast with no connection to the structure.
The two-step method has shown itself very usefu I and superior to total-pattern
methods if we have unconventional diffraction techniques with large amounts of con-
taminating peaks. This is found for example in in-situ high-pressure x-ray diffraction,
where there are always peaks from the sample holder, from the pressure marker and
from other containments. A second case is found when using position sensitive detec-
tors, especially in neutron diffraction, where there are quite commonly errors in the
linearity. Other fields of application and preference are cases where the background is
high and complex, where the profiles are not known and especially if the nonlinearity
disturbs peak positions. Also magnetic satellites fit into this list because such
incommensurate models are not implemented in Rietveld programs ..
The two-step method has been extended by sophisticated mathematical pattern-

decomposition procedures. Here the profiles are first analyzed on standard materials.
They can be complicated. This is followed by a profile-fitting procedure. Profile analysis
and profile refinement are independent of the structure information. In the two-step
method the profile-fitting or pattern-decomposition procedure yields integrated
intensities, besides position and halfwidth. From this list of data the structure-relevant

262 IV. ANALYSIS OF DIGITAL DIFFRACTION DATA INCLUDING RIETVELD
information, which means only the peaks belonging to the structure in question can be
sorted out and if needed, they can be varied specific to the problem (for example, if
there is a need to analyze for strain or stress; compare for example the presentation
by Delhez et al. (1989) at the Petten conference).
In the light of the progress made in powder diffraction it seems worthwhile to have
an unbiased comparison between the two methods on the same material. We have
therefore taken synchrotron diffraction data of quartz collected by Dr. W. Parrish, IBM,
at the Stanford Synchrotron laboratory, and in addition selected neutron diffraction data
from our daily measurements.
PROGRAMS USED FOR ANALYSIS
For Rietveld refinements we have used the program version DBW 3.2 (Wiles,
1982). This program is well documented and needs no further description. In the two-
step refinement we have used for the actual crystal structure refinements the program
POWlS-80 (Will, 1979; Jansen et aI., 1988) which also is widely used, well known and
well documented (Will et aI., 1983).
Attention is required, however, for acquiring integrated intensities for the POWlS
calcu lation. For a decomposition of the pattern, several programs are available world-
wide. One was published some time ago by Pawley (1981). In our laboratory we have
developed two programs, PROFAN and FUlFIT (Jansen et aI., 1988). PROFAN works
interactive, where we can tell the program by a crosshair on a graphic's terminal what
reflections we expect under an unresolved peak. Different profile functions, available
in a catalogue in the program, can be tried and the best one can be selected for final
analysis. If the peak function is known and we have an approximate knowledge of the
cell metric. e.g. cell constants and angles, it is convenient to use the program FUlFIT,
which is quite similar to the Rietveld program and stops just one step earlier after re-
finement of the peak positions, however, listing integrated intensities belonging to each
reflection (rather than positional parameters x y z). and a complete refinement of the
lattice constants.
ANALYSIS OF QUARTZ DIAGRAMS MEASURED BY SYNCHROTRON RADIATION
The samples were prepared from oscillator plate quality single crystals. After they
were sifted in a micro mesh sifter the final particle size used was 1-5 f.!. The sample
was rotated during the experiment around the normal to the sample plane. In a first
data set the wavelength was). = 1.0020 A, the step with ~(20) = 0.020 and the angu lar
range of the measurement 20 = 45 to 1350 (Smax = 0.92 A-1; S = sin 0/ ). ). The peak
halfwidth was 0.1r. All peaks could be analyzed and separated by profile fitting with
PROFAN. With this very short wavelength, 157 resolved peaks coming from, in many in-
stances,intrinsically overlapping 280 Miller planes of nonidentical intensities could be
obtained. (Due to the trigonal symmetry of quartz I(hkl) -+ I(khl).) Many of the peaks
were at high angles and had quite low intensities and consequently poor counting sta-
tistics; this necessarily affects the least squares calculations. Despite the low intensi-
ties these peaks are clearly visible in the diffraction diagram and well above the back-
ground.
The refinement calculation with POWlS was begun with only a limited data set to
20 = 75° (s = 0.47 A-1) with 31 peaks from 47 often intrinsically-overlapping planes.
We then proceeded in the refinement by extending the angular range, e.g. by increasing
the number of reflections to 20 = 45° to 105°, and finally to the full data set up to 20
= 135° (Table 1). All the results obtained are in excellent agreement with the results
from single crystal data by Levien et al. (1980), who used 602 reflections. The standard
deviations from the powder data are, as to be expected, about 3 times larger than the
ones from the single crystal data. For obtaining temperature factors, however, the high
G. WILL ET AL. (1) 263
Table 1: Positional parameters x. y, z, temperature factors Band R-values of quartz re-

finement calculations performed with the two-step and the Rietveld method for different
angular range extensions of synchrotron diffraction patterns recorded at two different
wavelengths.
FUlFITI
POWlS
Rietveld FUlFITI
POWlS
Rietveld FUlFITI
POWlS
Rietveld I
) (A) 2 Theta - sections (deg)
1.0020 45 - 135 45 - 105 45 - 75
x(Si) 0.4701 (2) 0.4699(1) 0.4701 (3) 0.4698(1) 0.4703(3) 0.4700(1)

x(O) 0.4106(7) 0.4118(3) 0.4105(8) 0.4119(3) 0.410(1) 0.4111(5)
y(O) 0.2658(6) 0.2666(2) 0.2658(6) 0.2666(2) 0.2657(7) 0.2665(4)
z(O) 0.2848(4) 0.2853(1) 0.2847(5) 0.2853(1) 0.2850(5) 0.2854(2)
B(Si) 0.45(1) 0.470(5) 0.44(2) 0.464(7) 0.51(4) 0.54(2)
B(O) 0.96(3) 0.96(1) 0.97(5) 0.97(2) 1.06(8) 1.07(4)
Rprof 0.0360 0.0459 0.0406 0.0504 0.0438 0.0524
RBragg 0.0446 0.0320 0.0402 0.0297 0.0248 0.0172
) (A) 2 Theta - sections (deg)

1.2823 15 - 115 15 - 90 15 - 60
x(Si) 0.4704(5) 0.4702(1) 0.4704(5) 0.4702(1) 0.471(1) 0.4708(1)

x(O) 0.4131(6) 0.4131(2) 0.4131(8) 0.4132(2) 0.413(1) 0.4133(3)
y(O) 0.2668(8) 0.2669(2) 0.2667(8) 0.2668(2) 0.267(1) 0.2675(3)
z(O) 0.2853(6) 0.2863(1) 0.2853(7) 0.2865(2) 0.285(1) 0.2875(3)
B(Si) 0.21(2) 0.281(6) 0.21(4) 0.281(6) 0.2(1) 0.33(2)
B(O) 0.68(6) 0.63(2) 0.65(9) 0.61(2) 0.2(2) -0.03(5)
Rprof 0.0347 0.1029 0.0316 0.1012 0.0218 0.1058
RBragg 0.0241 0.0263 0.0211 0.0259 0.0122 0.0189
angle data are needed, as can be seen very clearly when comparing results in Table
1.
Because in this first experiment the data below 20 = 45° were missing (due to a
failure in the electron accelerator), and also in order to increase the spatial resolution
and hence the separation of the peaks, we repeated the experiment with the same
sample a year later. Now the wavelength was set to A = 1.2823 A, the step width
t1(20) = 0.01 ° and the angu lar range of the measurement from 15 to 115°
(8 m" = 0.66 A-1). The halfwidth FWHM was 0.08°. This resulted in 72 well resolved
peaks. Large sections of well defined background were observed in this diagram with
only occasional small overlaps at the tails of some peaks. All peaks could be analyzed
and separated very well by profile fitting. The peak heights measured range from I(max)
= 35494for(101)/(011)tol(min) = 5 for (222), e.g. a range of 7000:1. (See Table 2). The
individual profile R-factors obtained with PROFAN are in the range of 1.4% to 2.0%,
except for the very weak peaks.
Also here we began the analysis with a smaller, low angle data set using only the
first 60 observations with 150 hkl-planes measured in the angular range up to
20=90°. The best results were obtained with 64 planes and 40 observations with
R = 1.41 % (Rw = 2.22%). (Not shown here). With 8 variables, the system is already 5 fold
overdetermined, therefore the limitation of the data set is well justified. This is clearly
demonstrated in Table 1. With the fu II data set up to 20 = 115° we have 72 observations
and 119 hkl planes and the system is 15 fold overdetermined. The R-values are
R = 1.68% and Rw= 3.21%.
The resu Its, e.g. the positional parameters, the temperature factors and even the
standard deviations did not change or improve, when we extended the data set to more
and finally all observations. In routine measurements for crystal structure refinements
.,
0
F ' L FIT
6
"C
-'
:J 4
c
u
2
-,. .
, , .. .', . .; " -,
M
,....
0
Ri e tveld
6
--
VI
C
;J 4
0
u
110 120 l3U

20
Fig. 1: Selected part of a quartz diffraction pattern measured with synchrotron radiation
(points). Profile refinements (lines) have been performed using the FUlFIT (above) and
the Rietveld routine (below) (A = 1.0020 A) .
it suffices from our experience to collect data out to s = sin 0/A = 0.7 A-1 or with our
wavelength out to 20 = 80-90°. (Remember the fu II Cu-sphere ranges only to s = 0.65
A-1).
In a subseqent analysis the same diagrams have also been refined a) with the
Rietveld method and b) with FUlFIT + POWlS. These are the values listed in Table 1.
The time spent for analysis was about the same for both methods, in real time approx-
imately one of the authors sitting one day in front of the terminal. Fig. 1 depicts the
quartz diagram after analysis by FUlFIT and by Rietveld. For the profile we used a
Pseudo-Voigt function, which gave the best Rpro/values. As can be seen from Fig. 1, we
have about the same quality in the difference diagram.
Table 1 summarizes the results, giving the structural parameters and the R-values
for both methods. We also demonstrate the influence of the size of the data set, where
we have refined the diagrams with different intervalls. There is no significant difference
in the actual values of the parameters. The real structural R-values (RsRAGG) are slightly
better with POWlS for the 1.2823 A data and with Rietveld for the 1.0020 A data. We
suspect that the differences originate from a different handling of the background with
regard to the R-value determinations. In both programs. Rp,o",. is slightly higher using
the Rietveld program, however, we have to keep in mind that this includes the struc-
tural constraints, whereas FUlFIT is run without structural constraints. For both wave-
lengths we can conclude that we get good and reliable atomic parameters already with
"short" diagrams, which means with a limited data set. On the other hand for reliable
Table 2: Comparison of observed and calculated quartz intensities according to a

POWLS refinement calculation
hkl lObs icalc hkl lObs Icalc hkl I.., , calc
100 7409 7161 311,131 1281 1263 106,016 119 109

101,011 35494 35834 204,024 146 163 412,142 494 433
110 3018 2995 222 5 18 305,035 116 128
102,012 2844 2750 303,033 130 182 323,233 8 12
111 1527 1345 312,132 1928 1940 500 1 0
200 2242 2341 400 333 368 116 148 120
201,021 1559 1409 105,015 803 839 501,051 87 73
112 5987 5776 401,041 615 690 404,044 80 61
003 121 120 214,124 980 999 206,026 612 660
202,022 1891 1837 223 868 904 413,143 786 789
103,013 723 736 402,042 175 182 330 282 248
210 106 119 115 551 559 502,052 696 716
211,121 5032 5024 313,133 385 387 225 300 291
113 879 886 304,034 215 200 331 299 304
300 269 257 320 492 496 420 614 587
212,122 3349 3304 205,025 37 26 315,135 375 333
203,023 3811 3775 321,231 1105 1050 421,241 206 213
301,031 2498 2505 410 98 57 324,234 1034 1022
104,014 1175 1202 322,232 396 374 216,126 313 325
302,032 1797 1784 403,043 704 749 332 16 11
220 1021 1004 411,141 910 926 422,242 484 507
213,123 1918 1830 224 322 312 503,053 8 10
221 534 535 006 104 82 414,144 420 449
114 1474 1450 215,125 591 620 510 173 169
310 1808 1826 314,134 534 544
temperature parameters we need reflections out to small d-values, e.g. data at

highscattering angles. Table 2 gives a comparison of observed and calculated intensi-
ties as derived by FULFIT (/Ob') and after the refinement form POWLS (/ealc). It seems
necessary to comment here, that those are real observed intensities, directly compa-
rable to single crystal data. And only such intensities can be used for so-called ab initio
structure determinations. If intensities are given after the Rietveld refinement, they are
artificially divided in overlapping peaks.
STRUCTURE REFINEMENT AND COMPARISON OF BOTH METHODS ON NEUTRON

DIFFRACTION DATA
Rietveld developed and published his method originally for neutron diffraction data
collected on polycrystalline samples. Because of the Gaussian peak shape the Rietveld
Table 3: Reference list of recent structure investigationsby neutron diffraction
Material Reference
CaMn(CO,), N. Jahrb. Mineral. Mh. 12, 539 (1989)
CsTaN, J. Less-Common Metals 146, 147 (1989)
DyFe,AI, Mat. Sci. Forum 27/28, 243 (1988)
ErFe.AI, Mat. Sci. Forum 27/28, 243 (1988)
HoFe,Al, Physica B 156/157, 751 (1989)
Li,CuO, Z. anorg. allg. Chemie, in print
Li,ZnCl, Mat. Res. Bull. 23, 1805 (1988)
NpCo,Ge, J. Less-Common Metals 149,243 (1989)
NpCu,Ge, J. Less-Common Metals 149, 243 (1989)
TbNiC, J. Magn. Magn. Mat., submitted 1989
TbFe,Al, Mat. Sci. Forum 27/28, 243 (1988)
ThFe,Al, J. Less-Common Metals 149,237 (1989)
T/- Fe - S J. Phys. Chem. Sol. 50, 297 (1989)
UFe,Al, J. Less-Common Metals 149,237 (1989)
YBa,Cu,O" Mat. Res. Bull. 23, 1439 (1988)
Table 4: Crystal structure data from three recent neutron diffraction measurements ac-
cording to Rietveld (R) and POWlS (P) refinement calculations
Li,CuO, UFe.AI, ThFe.AI, TbNiC,

Space group Immm 14/mmm 14/mmm Amm2
Site occupancy Li in 4(i) U in 2(a) Th in 2(a) Tb in 2(a)
Cu in 2(a) Fe in 8(f) Fe in 8(f) Ni in 2(b)
o in 4(j) All in 8(i) All in 8(i) C in 4(e)
AI2 in 8(j) AI2 in 8(j)
Free positions z(Li) x(All) x(All) z(Ni)
(R) 0.7144(9) 0.343(1) 0.3488(9) 0.612(1)
(P) 0.712(1) 0.338(3) 0.351(9) 0.605(2)
z(O) x(AI2) x(AI2) y(C)
(R) 0.6420(3) 0.281(1) 0.2790(9) 0.151(1)
(P) 0.6409(7) 0.279(2) 0.273(7) 0.155(2)
z(C)
(R) 0.302(1)
(P) 0.298(2)
No of hkl 70 138 145 70
RBragg (R) 0.082 0.076 0.063 0.097
(P) 0.053 0.084 0.115 0.072
routine works extremely well. We use the Rietveld technique on almost a daily basis,
and we have refined about 15 structures in the last 12 months. A list of some sub-
stances and references is given in Table 3. It is our experience that the Rietveld method
is superior in cases of structures with strongly overlapping peak clusters because of
the intrinsic structural constraints; as an example we may refer to a series of structure
refinements of the superconducting 1-2-3 compound (Schafer et aI., 1988).
For this presentation we have selected some recent diffraction patterns and re-
peated the analysis with both methods. Some results are listed in Table 4. But also in
neutron diffraction there are many cases where the two-step method is to be favoured.
One such case is when the position-sensitive detector technique is used, where we
have deviations in the linearity, where the observed and calculated positions of the re-
flections are not always where they should be according to calculations, C:'.nd which
therefore give necessarily errors in the Rietveld refinement.
DETERMINATION OF INCOMMENSURATE MAGNETC STRUCTURES BY THE TWO-STEP

METHOD
In the determination of magnetic structures the Rietveld method often fails com-
pletely, only the two-step method can lead to a solution. Such an example is TbAs0 4 ,
where we found an incommensurate magnetic structure below 1.5 K. The neutron
diffraction pattern is characterized by a complex scheme of sattelite reflections, which
cannot be interpreted by a simple spiral. A section of the low temperature diffraction
pattern is depicted in Fig. 2. The successful profile analysis of the satellite split re-
flections has been performed with PROFAN. The real incommensurate structure has not
been unscrambled at this date.
AB INITIO CRYSTAL STRUCTURE ANALYSIS
It is the aim of all researches in this field to push powder diffraction analysis to a
point where it is fully competitive with single crystal data, this means where unknown
crystal structures can be solved ab initio from the data. The way most wanted is of
course to have separated intensities for every reflection and then to go through the
common techniques like Patterson synthesis, heavy atom method, direct methods etc.
This can be done only if one refers to a two-step approach where the diffraction dia-
gram is first decomposed before crystallographic work begins.
G. WILLET AL. (1) 267
-.
'"o I I I I I I J
6 - r-
5 -
(f)
c:
2
::J
'c:"
4 -
.3
I
..: •...• .-~ .
I
.Ii ~<. ~
I
It
I
JI:,
"IJV~
I
J ,n
I I
l~.,. r-
5 10 15 20 25 .30 .35
2theto
Fig. 2: Low-temperature neutron diffraction pattern of TbAsO. (points) with magnetic

satellite splitting analyzed by FULFIT (lines).
There are, however, some rare cases where the old method of trial and error has
to be used. For such crystal structure determinations the Rietveld method is very use-
ful, simply because it it so easy to imagine a model, take the atomic parameter set and
have the program to refine iL We have done such a procedure on tetragonal NaPO•.
The Rietveld analysis of the neutron diffraction is based on space group P42 1c with a
= 10.80 and c = 6.81 A (Lissel et aI., 1989).
ACKNOWLEDGEMENT
This work has been funded by the Ger-man Federal Minister for Research and Tech-
nology (BMFT) under contract number 03-WI1BON.
REFERENCES
Delhez, R., de Keijser, Th.D., Langford, J.L, Lauer, D., Mittemeijer, E.J. and Sonneveld,
E.J., 1989, Crystal Imperfection Broadening and Peak Shape in the Rietveld Meth-
od, I nL Workshop on the Rietveld Method Petten, Netherlands Energy Research
Fou ndation.
Jansen, E., Schafer, W. and Will, G., 1988, Profile Fitting and the Two-Stage Method in
Neutron Powder Diffractometry for Structure and Texture Analysis, J. AppL CrysL
21:228.
Jansen, E., Schafer, W. and Will, G., 1989, Background and Reliability of Pattern Profile
Refinement in Powder Diffractametry, in: InL Workshop on the Rietveld Method
'Petten, Netherlands Energy Research Fou ndation.
Levien, L., Prewitt, C. and Weidner, D.J., 1980, Structure and elastic propertiesof quartz
at pressure, Am. Mineral. 65:920.
Lissel E., Jansen, E., Jansen, M. and Will, G. to be published
Pawley, G.S., 1980, Unit-cell refinement from powder diffraction scans, J. Appl. Cryst.
14:357.
Rietveld, H.M., 1969, A profile refinement method for nuclear and magnetic structures,
J. Appl. Cryst. 2:65.
Schafer, W., Jansen, E., Will, G., Faber Jr., J. and Veal, B., 1988, Crystal Structure Anom-
alies of YBa2Cu30S9 at the Superconducting Transition Temperature, Mat. Res. Bull.
23:1439.
Wiles D.B., 1982, "Program for Rietveld Analysis of X-ray and Neutron Powder Diffract-
ion Patterns: DBW 3.2." Georgia Institute of Technology, Atlanta, USA.
Will, G., 1979, POWlS: A powder least squares program, J. Appl. Cryst. 12:483.
Will, G., Frazer, B.C. and Cox, D.E., 1965, The crystal structure of MnS04 , Acta Cryst.
19:854.
Will, G., Jansen, E. and Schafer, W., 1983, "POWlS-80. Program for calculation and re-
finement of powder diffraction data." Report JOI-1867, KFA JOlich, F.R. Germany.
X-RAY J?CloIDER DIFFRACTlOO QPA BY RIF:IVEI.D PATl'ERN-FITl'm:i
- SCOPE AND LIMITATIClI."S
B.H. O'Cormor and Li. ~*

Curtin University of Teclmology
Perth, W A, Australia
B. Jordan
Deakin University, Geelong
Victoria, Australia
M.D. Raven and P.G. Fazey

CSIRO Division of Soils
Glen Osrrond, S A, Australia
* Pennanent address: Shanghai Institute of Ceramics,

Academia Sinica, Shanghai, China
The X-ray Analytical Science Group at Curtin University of

Technology has been developing and evaluating Rietveld pattern-fitting
for materials analysis since 1985. The results are reviewed with
particular reference to preferred orientation, crystallinity and phase
abundance.
INI'ROOOCTION
Rietveld pattern-fitting X-ray powder diffraction QPA is being

developed by va~ous workers 1 - 4 as an alternative'to conventional
discrete-peak QPA which pennits, at least in principle, the extraction
of descriptive data on speeiman microstructure (preferred orientation,
crystallinity, ionic substitution, crystallite size, residual strain) as
well as the phase carp::>sition results obtained in conventional QPA.
'!he Rietveld p:roredure involves optimisation of a pararretric nodel

of the speeiman and instrtmental factors by minimizing the residual
R = I Wi (Yi-Yci) 2 (1)
for intensity YLin the neasured diffraction pattern for profile point i,
Yci is the Rietveld-calculated intensity and Wi is the weighting
factor. '!he Yci are nodelled with the theoretical expression

Table 1. Rietveld characterisaticn descriptors
Descriptor Rietveld M:ldel Success at Curtin
l) Preferred March expression v

orientation for l'k
2) Crystallinity Volune fracticn Ck v
3) Ionic substituticn Site occ:upmcies, s.o. msults
cell paraneters poor
4) Phase aOOndance Volune fracticn Ck v *

(wlw) (nulti-~)
5) Residual stressl Profile functicn v

crystallite size ~ijk
* Potential problems due to poor crystallinity,
microabsorpticn, extincticn, etc.
Yci = (KJ~)~[Ljk·IFjkl 2 .0ijk(20ik-20jk),Pjk,Ck!Vk2 ]+Ybi (2)
for inst.rumant constant K, linear attenuation coefficient ~, lDrentz-

polarization-multiplicity factor Lik' structure factor Fik' profile
spread function 0i ik' preferred orier1tation factor Pjk' vollltle fraction
Ck , unit cell volurtE Vk and background carponent Ybi' Indices j and k
represent the Bragg peak j of ];tlase k.
In Equation (2), P ik contains the preferred orientation descriptor;

Ck provides the crystallinity of single-phase specinEns and the phase
abundances for multi-phase materials; F' k includes infonnation on ionic
site occupancies; and 0i'k yields ~llite size and residual strain
descriptors. Table 1 s~rises the descriptors and indicates the
progress made at Curtin so far. Progress with the ionic substitution,
residual stress and crystallite size descriptors is not reviewed in this
paper due to space limitations.
PREFERRED ORIENTATION
?he Rietveld software currently in use at Curtin6 arploys the March

m:::x:I.el of preferred orientation for uniaxially-oriented disk- or rod-
shaped crystallites with
IJc = (r2cos20CJc+r-lsin20CJc)-3/2 (3)
where 0CJc is the angle between the preferred orientation direction and
the relevant reciprocal lattice vector. Pararreter r is a measure of the
degree of preferred orientation according to the pole density
distribution ranging fran 1.00 (randon) to 0.00 (fully oriented).
Figure 1 shows an exanple8 involving texture characterisation of

gibbsite powder, Al(OH)3' The agreement between the measured and
calculated patterns improves dramatically when the March model is
erployErl with a highly-oriented spec:i1ren. GIB-BS for which r = 0.61.
Table 2 shows the improved agreemant between the Bragg intensities for
three gibbsites with substantially different degrees of preferred
orientation .
B. H. O'CONNOR ET AL. 271
2000 ,-~----------------------------------~
GIB.B5 : MEASURED
>
!::
III
Z 1000
W
I-
Z
CALCULATED (MARCH)
>
I-
iii
z
W
1000
I-
Z
CALCULATED (NON·MARCH)
~
iii
zW 1000
I-
~
1/i 25 35 45 55 6S 7S 85
Fig. 1. Measured X-ray powder diffraction patterns for GIB-BS (see

Table 2) and corresponding Rietveld-calculated patterns after
refinarents with the March and non-March m:xI.els.
Table 2. Con:ecti.cn of gi.J:bsite integrated intensities for

preferred orientaticn using the March m:xiel.
Intensities
h k la "'le(o) GIB-B P:"1(5) GIB-BS
(r=1.00) (r=O.76) (r=0.61)
0 0 2 0 41,400 (41,400)b (46,200)
91,BOO 191,100
1 1 0 B7.7 16,000 (14,BOO) (16,200)
10,000 B,OOO
2 0 0 B5.4 7,BOO (5,600) (6,700)
3,BOO 3,300
3 1 1 71.B B,100 (9,200) (B,OOO)
6,700 4,400
-3 1 3 54.B 6,BOO (6,200) (6,100)
5,700 4,700
a. Five IlDSt intense lines shown in table.
b. March--a>rrected intensities in parentheses.
1.01---1.-;:-=,...".-----------------,
[[
w
I-0.9
w
:;
oct
[[
oct
a.
Z
0
i=
oct 0.8
I-
Z
w
a:
0
c
w
[[
[[
W
"- 0.7 .GIB-A5
w
[[
a.
GIB-A1D
• GIB-A15
•
GIB-B5
0.6
•
5 10 15
MORPHOLOGICAL RATIO, MR
Fig. 2. '!heoretical relation between the Rietveld r par-

aneter and ratio MR. for gibbsite. Points show
results for gibbsite suite.
Fig. 2 shows the basis of a procedure for applying preferred

orientation corrections in conventional QPA. Correction factor
Pk is applied to each intensity according to 'morphology ratio'
which for gibbsite is defined as ~ = I 002 /I110 200 where I002 is the
intensity of the 002 line and I 110 .200 is' the intensity of the
110,200 doublet - see Table 2. MR. is' converted to Rietveld p paraneter
using the correlation-plot in Fig. 2, and then Fquation 3 is used to
calculate Pk . Note that the figure shows the neasured MR. and a
plot of the values calculated for a randan orientation roodel CO.K.
Smith, private corm.).
CRYSTALLINITY
'!he fractional cl:}'Stallinity in weight percent tenns, which may be

described as the canplarent of anorphous content, is evaluated with the
scale factor fran the Rietveld software used by the authors, i. e.
s = K Ck/J.!.. v~ (4)
using expression
(5)
Table 3. Rietveld aystallinity values for «-quartz am kaolinite

(refs 9,10).
Sanple We % Chanical CCJtp %
«--Q.!artz Si~
Fran quarry near Perth 99.s(0.8)a 99.7
NBS 1878 95.4(0.9) 99.8
lwst. standard quartz (~rksafe) 93.3(0.8) 99.5
MINUSIL-s standard 92.3(0.8) 99.6
Novaculite, Arkansas stale 78.3(0.7) 92.5
Kaolinite Al 203 ·2Si0 2 •2HiD
New Mexico, lEA 97.5(1.0) 94.3
Xuahua, China 96.2(1.1) 94.4
Korda, lwstralia 82.2(1.1) 91.6
a. Standard deviatioos in parentheses.
K being evaluated using an external standard of known crystallinity, e. g .

'OCAR--c conmdmn. '!he rrethod is of value when crystallinity is of
specific interest and for the evaluation of calibration standards and
standard ref~ materials. Table 3 shows a selection of results fran
two studies' . The results for oc-quartz show the appearanc~~~f
substantial anorphous content in the material as reported previously- .
The value for NBS1878 agrees with the value certified by NBS using
conventional rrethods.
PHASE .ABUNDAOCE
Equation 5 has been used in various equivalent fOllllS 2- 4 for QPA of

multi-phase materials. '!he procedure has various advantages - reduction
of line overlap problems; dealing with preferred orientation and lattice
pararreter variations; and perfonning calibration-free assays. However,
caution must be observed to ensure that sources of systenatic error which
cause problems in conventional QPA are also minimised - non-
• Actual values
• Actual values
• Rietveld, coarse Si02
80
• Rietveld values
80
o Rietveld, fine Si02
a
60 • 0c
60
N" N
..,e.
•
..,e.
40 40
20
• 20 o
20 40 60 80 100 20 40 60 80 100
% a-Si0 2
Fig. 3. Phase abundance assays for Fig. 4. Phase abundance assays for
oc-A1 20 3 /ZnO binaries. oc-Al 20 3 /oc-Si02 binaries.
100 100~---r-------....,
_ Actual values
• Rietveld, coarse Si02 I~ II-oActual values
Rietveld values,
80
o Rietveld, fine Si02
80 €)
coarse Si02 (constrained)
0'" 60 0'" 60
«'" ;f. «'" ;f.
• I
.
I
1j 40 1j 40
20 - 20
20 40 60 80 100 20 40 60 80 100
Fig. 5. Phase abundance assays Fig. 6. Amanded phase abundance

ZnO/~-Si02 binaries. assays for the ~-Al203/
~-Si02 (course) binanes
- total concentration
constrained to 100%.
reproducibility of intensities due to large particles, extinction,

surface ro~ghness, porosity, arrorphous content and microabsorption. Hill
and Howard have enphasised the value of using n,F,tron data to overcare
absorption-related pcoblems. Bish and Howard have highlighted the
severe bias in results which can result fran microabsorption.
In this pa.per we report trial analyses for three suites of binary

mixtures - canprising ~-Al203' Zno and ~-Si02 for which the volurretric
D50 sizes measured by laser scatter are 4. 5!LIl\, O. 9!LIl\ and 24 !LIl\ ,
respectively. Course grained ~-Si02 was used to enhance particle -
dependent errors. Figures 3-6 shOW" the results of experiments using a
Siemms D500 diffractareter with CuKcc radiation. For these conditions
the values of exp(-1ill50) are 0.94, 0.97 and 0.79 for the three materials.
Figure 3 shOW'S the resUlts for the ~-Al203/Zno binary suite using a pure
sample of the ~-Al203 for instrument calibration and Equation 5 to
canpute the phase abundances. The obvious systanatic errors in the assay
results are probably due to microabsorption. Figures 4 and 5 shOW" the
enhancarent in systanatic errors when coarse-grained ~-quartz is mixed
with the other ~ phases. The open circles in these figures shOW" the
inq;:>roverents in results when finer-grained ~-Si02 is E!l1ployed - 13!llll 0 50
povrler. Figure 6 shOW'S the dangers inherent in constraining the total
phase abundance to 100% - the results correspond to the un-nonnalised
values for the coarse-grained ~-Si02/ ~-Al203 detenninations in Figure 4.
It is concluded that Rietveld assay of phase abundance, like conventional
discrete-peak work, requires careful attention to pa.rticle-size related
errors. Possible strategies include optimisation of particle size,
choice of X-ray wavelength and use of neutron diffraction.
REFERENCES
1. B.H. O'Connor and M.D. Raven, XIV Meeting of Soc. of Cryst. in

Australia - 1Ide1aide. Abstracts Vol. (1985).
2. R.J. Hill and C.J. Howard, J. Appl. Cryst. 20:467 (1987).
3. B.H. O'Connor and M.D. Raven, Povrler Diffr. 3:2 (1988).

4. D.L. Bish and S.A. Howard, J. AWL Cryst. 21:86 (1988).
5. H.P. Klug and L.E. Alexander, "X-ray Diffraction Procedures", 2nd
00. P 531. Wiley and Sons, New York (1974).
6. R.J. Hill and. C.J. Howard, "A canputer program for Rietveld Analysis
of fixed wavelength X-ray and neutron powder diffraction
patterns :version IHPMl "Australian Atanic Energy Carmission (1986).
7. A. March, Zeit fur Kristallogr. 81:285 (1932).
8. Li Deyu, B.H. O'Connor, G.LD. Roach and J.C. Cornell, suhnittoo,
1989, to Povrler Diffr.
9. B. Jordan and B.H. O'Connor, suhnittOO, 1989, to Povrler Diffr.
10. M.D. Raven, MAppSc 'Ihesis. Curtin U. Tech. (1989).
11. S. Altree-Williams, G.J. Byrnes and M.B. Nonnan, Ann. Occup. Hygiene
24:347 (1981).
APPLICATION OF POSITION SENSITIVE DETECTORS FOR
NEUTRON DIFFRACTION TEXTURE ANALYSIS OF HEMATITE ORE
G. Will, P. Merz, W. Schafer and M. Dahms'
Mineralogical Institute, University Bonn, Poppelsdorfer SchloB

D-5300 Bonn, West Germany
• Forschu ngszentru m Geesthacht, D-2054 Geesthacht, West Germany
INTRODUCTION
Texture means the orientation distribution of the many crystallites in a

polycrystalline sample with respect to a reference system on the sample, for example
the rolling direction in steel. Texture has to be distinguished from preferred orientation
observed in laboratory-made powder samples. Preferred orientation is just a nuissance
in the experiment and must be corrected in the ensu ing analysis, for example by the
formula given by March 1 and published by Dollase 2. Preferred orientation we find
commonly in samples containing plate-like crystal flakes. This is again to be distin-
guished from a non-random particle distribution in the powder samples prepared for
diffraction experiments. This effect is always present, also for example in NBS silicon,
even if only to a very small degree (see for example Will et. al 3). It must and can easily
be corrected for in the final least-squares calculation.
Texture is a technical property, which carries importance in the every day pro-
duction processes in industry, for example of metals or ceramics. The anisotropy of
many physical properties originates from inhomogeneous orientation distributions of
the crystallites. X-ray diffraction is widely and commonly used for texture analysis. The
classical procedure is to keep the detector fixed at the 2,9 position of a possible Bragg
reflection and to turn the sample, positioned on an Eulerian cradle, stepwise through
the whole space about the two angles <p and X. With modern computer controlled tex-
ture goniometers and high-intensity X-ray tubes this procedure is fast. Nevertheless
only one pole figure is measured at a time, the procedure has to be repeated for each
hkl of which a pole figure is needed or wanted. For example if the three-dime.nsional
orientation distribution, called ODF (orientation distribution function) is requested there
are different modes of operation: equal-step scanning or equal-area scanning. We are
using equal-area scanning (in neutron diffraction) with generally more than 621 angular
positions <p and X.
Neutron diffraction for texture analysis is a comparatively new method 4. Only

very recently considerable progress has been made on the basis of both hardware and
software: A significant step forward is accomplished by using position sensitive de-
tectors, (PSD's), where several, or many pole figures can be measured simultaneously.
Position sensitive detectors have become operational in a reliable way. PSD's will
solve another serious problem, peak overlap or superposition. This problem is en-
countered to a very high extent for example in rocks. The second improvement comes
from the software of peak seperation, which has been improved. This holds equally well
Advances in XRay Analysis, Vol. 33 277

for X-rays and neutrons, however in neutron diffraction this progress is available today
routinely. The evaluation of such a measurement yields a set of pole figures.
We have studied,by neutron diffraction,complicated samples consisting of several

phases of even low symmetry, to obtain pole figures and to calculate orientation dis-
tributions (ODF's).
DATA AQUISITION
Neutron beams are large, in our case up to 100 x 50 mm ; neutrons are in general
little absorbed in the material and as a consequence large samples several cm in di-
ameter can be measured. Inhomogeneous samples or samples with coarse grains
ranging up to millimeters cause no difficulties; we can penetrate and therefore explore
the whole sample containing a sufficient number of grains with respect to statistics, we
can measure in transmission and therefore record and calculate complete pole figures.
Neutrons measure the "global" texture; in comparison,X-rays measure the "local" tex-
ture at the sample surface.
X-rays and neutron are complementary in many cases because of significant dif-
ferences in the scattering powers of the elements. In combination they are therefore
an excellent and powerful technique. This was demonstrated in a study on calcite 5,
CaC0 3, where some reflections like (00.6) are too weak in the X-ray diagram, however
very strong in the neutron diagram. For (11.0) and (20.2) the reverse is true.
In multiphase samples, like rocks or ores often containing low symmetry crystals,
but also in modern ceramic materials,the diffraction patterns contain a large number
of reflections which in general are highly overlapped. For a successful texture analysis
of such samples two requirements have to be fulfilled:
1. We must measure an extended portion of the diffraction diagram, e.g. we must

measure the whole peak or a group of peaks and not just stationary at the peak
maximum.
2. We must separate or deconvolute overlapping peaks.
600
I II
;; n~
~N
"0
N
~
~O
I
I I IOJ I I I
n
0
0
0
~
N
0
N
"0
I I
400 N
;; "
0
'"c I OJ
2 OJ OJ
~
OJ
n
0
n
z 0
.0
ON
200
15 20 25 30 35
2Theto
Fig. 1. Individual di,ffraction diagram with q> = 20 0 and X = 90 0 • The time spent was 3
minutes.
s:. 4
~
I I
'"00 '"
~
~
""0
N
I
Im m
0
N
f: i::N
3 m m
m I I m I ml
0
N
0
;'
0
~
0
0
N
N
<0
0
0
'""" i::""
I I
Ul
C
;:> 1m m I 0] 10]
,. ,.:::'
:; 0] Q] Im m I
(l)
2
·0
;'
'"00 ;' '" o~ 0 '"'" "" '"
0 "-
z ~ I
~O
~ NO]
""
0
~
I
N
I "" 0
0
,.
~
I I I I I;::: I~ ~ ~I ~I h
NO
ON :::' 0
N
N
N
I I
2Theto
Fig. 2. Sum-diagram generated by adding up 621 individual diagrams like that shown in
Fig. 2. Included is the result of the profile analysis. The indices refer to the two
phases, H = hematite, B = biotite.
In our laboratory we have developed a position sensitive detector for neutrons on

a solid state scintillator basis. It is called JULIOS 6, and is commercially available. The
detection medium is a 6Li containing glass plate coupled to a set of linearly arranged
24 photomultipliers. With a distance sample-to-PSD of 1500 mm JULIOS covers a 29-
range of 25°. Therefore the angle of the maximum blind area is 6.25°. We spend about
1 to 4 minutes at each sample position depending primarily on sample size and scat-
tering power of the atomic constituents. The individual diagram, as shown in Fig. 1 for
cp = 20°, X = 10° is of rather poor counting statistics.
PEAK SEPARATION BY PROFilE ANALYSIS
The crucial point in the data analysis of multiphase and/or low-symmetry materi-
als is the separation of overlapping peaks. This can be done by profile analysis and
pattern decomposition. I n the authors' laboratory powerfu I programs have been devel-
oped 7 analysing the data in 4 successive steps:
1. A sum-diagram is generated by adding up all the individual cp-x-diffraction patterns

(Fig. 2).
2. The background of the sum-diagram is determined by polygons, polynoms or

splines. This yields a reliable background-shape-function which is needed later in
step 4 for background adjustment of the individual diagrams.
3. 29-positions, halfwidths (FWHM) and the intensities of the sum-diagram reflections

are determined by rrofile fittin~ and deconvolution of overlapping peaks using the
programs PROFAN or FUlFIT. Profile fitting in PROFAN works interactively and
is especially useful in texture work. It is started by splitting the measured diagram
into several smaller sections. The profile analysis is then done in front of the screen
with the help of a cursor. The cursor is placed on expected peak positions, which
can be found either mathematically through the second derivative, or by calculating
theoretical powder diagrams using e.g. POWlS 9,10. In texture analysis we can as-
sume that the mineralogical or metallurgical composition of the sample in terms
of the phases is known, otherwise it can be determined from the sum-diagram. The
resulting 29-positions and FWHM values of all fitted reflections are then used as
input-parameters for the intensity analysis of the individual cp-X diffraction patterns.
Examples for a profile analysed section of the pattern pattern are given in Fig. 3.
I
n
I m
C'J
3 ,0
C'J
I m
"
0
~
o
C'J
C'J
m m
:r: m m
2
n n
n
I
C'J
o
N
24 26 28 30
2Theto
Fig. 3. Profile analysed peak cluster of a 29 range from 22.2° - 30S
4. Based on the known backgrou nd-shape-fu nction, the 29- positions and the FWHM
values the orientatioll-dependent intensities of the individual patterns are now de-
termined in an automated procedure by applying LSQ routines. In the given exam-
ple this took about 420 minutes for 636 individual diagrams using an IBM PC AT.
POLFIGURE MEASUREMENTS ON A HEMATITE ORE
This procedure has been applied for the texture analysis of a hematite ore using
the neutron texture diffractometer of Bonn University at the FRJ-2 in the KFA Julich.
This diffractometer is equipped with the PSD JULIOS. The wavelength used was
1.09 A. The detector covered a 29 region from 12.5° - 37.5°. Fig. 4 gives a sequence
of such diffraction diagrams of varying x-angles. The highly developed texture of the
sample can be seen easily by the appearance and disappearance of peaks. The sample
16000
14000
20 30
2 Thela
Fig. 4. Sequence of hematite diffraction diagrams of varying x-angles
(a) (b)
Hematite Hematite
hkl =003
(c) (d)
Hematite Biot ite
hkl= 113 hkl=003
,
-'
:..
--, . - '
" "
, /
Fig. 5. Representat ive pole figures calcu lated from the integrated intensit ies after pro-
file analysis of all individual diagrams. Maximum and minimum pole densities
are (a) 12.47 and 0.02 (b) 5.37 and 0.09 (c) 3.03 and 0.15 (d) 4.42 and 0.42.
investigated consisted of two phases - hematite and biotite, a mica with monoclinic
symmetry. The measurement yielded a total of 31 reflections (Fig . 2), of which 15 were
considered to have enough intensities for pole figure representations. Fig. 5 depicts
four out of the 15 pole figures. The biotite content is quite small, about 5 vol.%, therefore
the further discussion concentrates on hematite.
Fig. 5a reveals the c-axis distribution of hematite, which is highly concentrated

perpendicular to the sample. Texture can be depicted, for example, as sailboats on the
DDDD
FMAX = 13.53
FM1N = -0.53
CONTOUR LEVELS
Z.O,
4.0,
DDDD
6.0,
8.0,
lD.O,
lZ.0X RANDOM
LSDCSu
uuDD
D 'Pl'
90.0' 97.5' 105.0' 112.5'
I <1> _ _
120.0'
Fig. 6. Orientation distribution fu nction (OOF) of hematite, projection ({J1 + ({J2 = const.
ocean. In this case all sailboats are concentrated around one point with a ±30° devi-
ation in E-W-direction. If we are interested in the direction the boats are heading we
must study the a-axis [1010J distribution, or equivalent (crystallographic) directions,
like [1120J (in Fig.5 we omit the hexagonal index i = -(h + k) for brevity); 110 of Fig. 5b
are the prismatic planes; Fig. 5c with 113 the pyramidal plane distribution.
ODF-CACULATIONS
Pole figures are 2-dimensional representations of one crystallographic plane. A

3-dimensional representation of the orientaion distribution, 00, is obtained by Fourier
inversion of several, or many pole figures, as measured here. Several mathematical
procedures are applied today with some controversy between them. (For details see
for example Wenk et al. 11; there are also the angles in Euler space defined). We have
used the harmonic series expansion method up to terms Lmax= 23. The result is shown
in Fig. 6. Basicly we observe only one component along the c-axis. The OOF analysis
reveals, more clearly than the pole figures, that the distribution of the a-axis perpen-
dicular to the c-axis is random. This is revealed in Fig. 6 by almost equal densities at
the origin in all sections. This can be interpreted as an inverse fiber diagram.
ACKNOWLEDGEMENT
This work has been funded by the German Federal Minister for Research and Tech-
nology (BMFT) under the Contract Number 03-WI1BON.
REFERENCES
1. A. March, "Mathematische Theorie der Regelu ng nach der Korngestalt bei Affiner
Deformation.", Z. Krist., 81:285 (1932)
2. W.A. Dollase, "Correction of Intensities for Preferred Orientation in Powder

Diffractometry: Application of the March-Modell", J. Appl. Cryst, 19:267 (1986)
3. G. Will, M. Bellotto, W. Parrish and M. Hart, "Crystal Structures of Quarz and

Magnesium Germanate by Profile Analysis of Synchrotron-Radiation High-
Resolution Powder Data", J. Appl. Cryst, 21:182 (1988)
4. G. Will, W. Schafer and P. Merz, "Texture Analysis by Neutron Diffraction Using a

linear Position Sensitive Detector", Textures and Microstructures, 1989, in print
5. H.R. Wenk, H. Kern, W. Schafer and G. Will, "Comparison of Neutron and X-Ray
Diffraction in Texture Analysis of Deformed Carbonate Rocks," J.Struct.Geology,
6:687 (1984).
6. W. Schafer, E. Jansen, F. Elf and G. Will, "A Linear Position Sensitive Scintillation
Detector for Neutron Powder Diffractometry," J.AppI.Cryst., 17:159 (1984).
7. E. Jansen, W. Schafer and G. Will, 1986, Applications of Profile Analysis Methods in

Texture Measurements Using Position Sensitive Detectors, in "Experimental Tech-
niques of Texture Analysis," H.J. Bunge, ed. Oberursel DGM Informations-
gesellschaft Verlag.
8. E. Jansen, W. Schafer and G. Will, "Profile Fitting and the Two-Stage Method in
Neutron Powder Diffractometry for Structure and Texture Analysis," J.AppI.Cryst.,
21 :228 (1988).
9. G. Will, "paWLS: A Powder least Squares Program", J.Appl. Cryst., 12:483 (1979).
10. G. Will, E. Jansen and W. Schafer, "POWlS-80. A Program for Refinement of Powder
Diffraction Data," KFA-Report Jul-1867 (1987).
11. S. Matheis, H.R. Wenk and G.W. Vinel, "Some Basic Concepts of Texture Analysis
and Comparision of three Methods to Calculate Orientation Distributions from Pole
Figures", J.Appl. Cryst., 21:285 (1988).
PROBLEMS IN THE DERIVATION OF d -VALVES FROM
EXPERIMENTAL DIGITAL XRD PATTERNS
Ron Jenkins
JCPDS-ICDD
Swarthmore, PA
Monte Nichols

Livermore, CA
ABSTRACT
Most commercially available, automated powder diffractometers include

software packages for the determination of d-values from experimentally recorded
digitized patterns. While many of these patterns offer great flexibility to the user,
indications from a recent Round-Robin Study [1] are that many users are confused as to
the correct use of such parameters as choice of step size and counting time, the degree
of data smoothing, peak-hunting parameters, setting of background level, and the
consequences of background subtraction and Q2 stripping. This paper will reviews these
various factors and give some guidelines as to tile establishment of optimum conditions.
USE OF THE REDUCED DIFFRACTION PATTERN

At this stage of the development of the powder method for qualitative work, it is
common practice not to use the full diffractogram as recorded, but rather to work with
a reduced :pattern, in which profiles are expressed as single unique "d" (or 2e) values,
with intensIties expressed as a percentage of the strongest line in the pattern. Although
it is may be more useful in some cases to utilize the full diffractogram [2,3], until
recently, storage liInitations have inhibited the development of a pattern reference file
of fully-digitized patterns [4]. In the data processing to get a reduced pattern, it is
necessary to conSIder errors introduced both in the collection of the original (raw)
diffractogram, as well as in the production of the reduced pattern. Problems of this type
are especially critical in the case of automated powder diffractometers where the data
collection and treatment process are initiated by a series of pre-defined steps and
operator intervention is minimal once these processes are initiated.
In spite of the numerous sources of error in the measurement of 29 values and

subsequent conversion to d-spacings, the derived d's are generally of sufficient quality
to allow qualitative phase identification. As an example, Table 1 shows data from a

Table 1. Average 28 precision obtained with ZnO/CaC03 mixtures

ALL DATA SETS (OEG)
LINE AVERAGE SIGMA
Zl100 31.793 0.052
ZlO02 34.448 0.041
ZlllO 56.603 0.049
Zl103 62.867 0.046
Zl1l2 67.958 0.048
Zl213 116.269 0.043
C/012 23.072 0.050
C/104 29.428 0.051
C/1l3 39.433 0.051
C/202 43.169 0.053
C/1l6 48.519 0.046
C/3l4 83.759 0.040
AVERAGE 2-THETA PRECISION
ZNO 0.047
CAC03 0.049
recent round-robin test [1] in which participants were asked to measure samples of the
binary mixture CaC03/ZnO. Here the multi-person! multi-laboratory precision
(SIGMA) is about 0.048° . More often than not, the problem arises not so much from
the quality of the peak data as from the number of peaks found. Three questions should
be considered:
a) Were all of the "true" peaks identified?
b) Were additional (real) peaks found?
c) Were any false peaks found?
One major source of confusion is often the recognition of peaks by a given
automated system on a certain specimen, especially where data collected by manual and
automated methods are being compared (as is often the case in quahtative phase
identification!). The extreme sensitivity of, for example, the second-derivative
peak-hunting method may give significantly more lines than would be found manually.
Additionallx, the number of peaks found is very sensitive to the method of defining
what a sigmficant signal above background is. Many of these "peaks" may not be true
peaks at all but simply statistical variations in the background or on the shoulders of
real peaks. As an example, a recent round-robin [1] showed that for a well
characterized specimen of a-AI 20 3, the number of peaks reported by different users,
representing a range of instrument types, over the same 29 range varied from 25 to 53,
whereas the calculated number is 42.
TREATMENT OF SOURCE POLYCHROMATICITY

A major contributor of additional weak lines and artifacts in a diffractogram is
the polychromatic nature of the source. Probably in excess of 90% of all powder work
in the U.S.A. today is done with Cu Ka radiation. A copper tube emits a broad band of
continuous or white radiation, along with intense characteristic a and {3 lines. However,
the emitted spectrum may also contain contaminant lines from other elements from the
X-ray tube target or tube window. Notable among these contaminant elements is
tungsten, which comes from deposition on the tar~et anode surface of this element
from the tube filament. Radiation striking the speCImen or the specimen support may
be diffracted, scattered, or produce secondary fluorescence radiation. X-radiation
which eventually reaches the detector IS further modified by whatever
monochromatizatlOn process is employed. Although it is generally the intent to
consider just diffraction from the Cu Ka 1,2 doublet, in fact, the radiation actually being
R. JENKINS AND M. NICHOLS 287
- l~' J-
Compton
Seitter
COK«l
NIK«l
Cu K« 1
W L«
CuK« 2
CoK« 2
CoK{3
.J ~!e~lLro~~d
NI K« 2 CUK{3
NIK{31
7.0 7.5
I 8.0 8.5
____ ...J
9.0
level
(keY)
Figure 1. Band pass of the pyrolytic graphite monochromator, the Si(Li)

detector and the p-filter
diffracted and detected may be more than simply the Ka doublet. The eu Ka emission
is actually made up of six a lines, but for most practical purposes it can be considered
bichromatic [5]. Figure 1 shows the spectral distribution in the energy region around
copper K radiation. The Cu Ka and Kp doublets are shown along with other lines
which could fall within the acceptance range of the monochromatizationldetection
device. There are three methods that are commonly employed to render the radiation
monochromatic (in actual fact, bichromatic because the Kal/Ka2 doublet is generally
employed). These techniques are: a) use of a p filter; b) use of a diffracted-beam
monochromator, or c) use of a solid-state detector, typically Si(Li). The Si(Li) detector
is now being used as a replacement for the conventional scintillation detector in some
powder diffraction instruments. While the advantages of wavelength selectability and
high quantum counting efficiency are somewhat counteracted by large dead time
problems, it is clear that the Si(Li) detector has an important role to play, especially for
the detection/measurement of very weak peaks. However, of the three
monochromatization devices, the diffracted beam monochromator is the more
commonly employed in automated powder diffractometers.
Figure 1 also shows the relative band pass regions for the three
monochromatization systems discussed. Because intensity is at a premium in most
diffraction experiments, most diffracted-beam monochromators employ a pyrolytic
graphite crystal, which has high reflectivity but poor dispersion relative to a "perfect"
single crystal. The angular dispersion of the pyrolytic graphite crystal is less than 100
eV, but because its mosaic structure allows diffractIon over a wide angular range, it has
an effective band pass of around 500 to 1,000 eV, which, if correctly employed, is still
sufficient to remove the Kp radiation. The actual band-pass value for a given
monochromator will depend upon the widths and positions of limiting apertures which
are placed somewhere on the focusing circle of the monochromator. It should also be
appreciated that a slight mis-setting of the monochromator can displace its energy
acceptance window to either lower or higher energy. From the foregoing, it is clear that
even with correctly set-up monochromatizing devices, it is possible that undesirable
radiation can pass through the monochromator to the counting circuits. When the
monochromatizing device is incorrectly set, even more radiation may be passed.
12~---------------------------,
'"
~
C>
"<D" 0.6
'"
U
0.4
0.2
0.0 L....__________________________- - '

20 40 60 80 100 120 140 160
Angle (28 degrees)
Figure 2. Dispersion of the a lIa2 doublet as a function of 2e
/'
a)
Maximum -2.L ; 0
d(28)
b)
Average of points of Inflection
c)
Figure 3. Methods of defining the peak position

Most powder diffraction work is carried out using the Cu Ka.JaZ doublet, and
one of the greatest experimental inconveniences arising from this chOice IS the variable
angular dispersion of the diffractometer. The angular dispersion of a diffractometer
de/dA is e<I,ual to (n/2d CoSe). Because the angular dispersion of the diffractometer
increases With increasing 2e, the a doublet is unresolved at low 2e values, while at high
2e values it is completely separated. In the mid-an~ular ran~e the lines are only
partially resolved, leading to some distortion of the diffracted hne profile, as well as
giving difficulties in numerical techniques used to separate a 1 from a2. The absolute
value of the angular dispersion varies from about 100 eV at low 2e values to about 2eV
at high 2e values. Thus the Ka 1/Ka2 doublet typically starts to be resolved at about 50°
2e;Figure 2 shows the angular dispersion as a function of 2e and indicates where the
al/a2lines are resolved at the half-maximum J?osition for different values of the line
Width. When usin~ manual peak-finding techmques, it is common practice to use the
weighted geometnc average of the al/a2 wavelength as the experimental wavelength, at
least until a 2e value is reached where the a 1/a2 doublet is sufficiently resolved to allow
accurate measurement of the alline. Where automated methods are used, a2 stripping
is generally employed over the whole range of the measured pattern.
PROBLEMS IN DEFINING THE PEAK

As illustrated in Figure 3, there are various ways in which a "peak" can be
defined. These include: (a) use of dUde = zero; (b) taking the average of inflexion
points or (c) use of profile centroids. When the peak is reasonably symmetrical, each of
these methods will give essentially the same result. When the peak is asymmetric, due
to specimen or instrument effects, or due to partial a2 resolutIOn, the choice may vary
depending on the method. Because the width of a peak may also be dependent upon
the crystallite size or strain of the specimen, it is useful to have available a measure of
the peak widths, during data evaluation. There are a variety of factors which determine
the shape of a diffracted line profile and the more imJ?ortant of these factors include
the axial divergence of the X-ray beam, the crystalhte size and/or micro-strain of
specimen, the monochromatic nature of the source, and the degree of data smoothing
employed in the processing of the raw data. Because of these various influences, the
peak shape is typically variable and asymmetric. The data shown in Table 2 were taken
on the (020) line of Mo03 at 12.8° 2e and show that, even though the peak widths at
20%, 50% and 80% of peak maximum vary quite significantly over a range of different
instruments, the relative shapes of the profiles are remarkably consistent. Peak
distortion of this type can lead to problems III the estimation of peak maxima.
Table 2. Data taken on the (020) line of Mo03 showing consistency of peak
shapes
FRACTIONAL
AVERAGE WIDTH (3 RUNS) WIDTH RATIOED
AT FRACTION OF PEAK MAX TO WIDTH @ 50%
USER 20% 50% 80% 20% 80%

M 0.150 0.087 0.050 1. 73 0.58
Q 0.213 0.110 0.057 1. 94 0.52
T 0.228 0.111 0.063 2.06 0.57
R 0.207 0.113 0.060 1.82 0.53
P 0.237 0.120 0.067 1. 97 0.56
H 0.253 0.133 0.077 1. 90 0.58
K 0.270 0.143 0.083 1.88 0.58
L 0.275 0.145 0.055 1. 90 0.38
I 0.270 0.150 0.083 1.80 0.56
0 0.273 0.153 0.077 1. 78 0.50
D 0.327 0.153 0.080 2.13 0.52
E 0.340 0.173 0.087 1. 96 0.50
AVG 0.254 0.133 0.070 1. 91 0.53
MAX 0.340 0.173 0.087 2.13 0.58
MIN 0.150 0.087 0.050 1. 73 0.38
290 IV . ANALYSIS OF DIGITAL DIFFRACTION DATA INCLUDING RIETVELD
Non-linear background in an X-ray diffraction pattern can also cause difficulties

in picking out small peaks and defining a true intensity. Variation in the background is
mainly due to five factors: scatter from the sample holder (generally seen at low values
of 29 where too wide a divergence slit is chosen); fluorescence from the specimen
(controllable to a certain extent by the use of a diffracted-beam monochromator or by
pulse height selection); presence of significant amounts of amo~hous material in the
specimen; scatter from the specimen mount substrate (seen in 'thin" specimens, but
controllable by use of "low-background" holders), or air scatter (which has the greatest
effect at low 2e values).
PROBLEMS IN FINDING THE PEAK.
More than 90% of all new powder diffractometers now sold in the USA are
automated. Many excellent computer programs are provided with these instruments to
aid the diffractionist in the reduction of powder data. Unfortunately, there can be
pitfalls in the use of some of these programs, especially for the newcomer to the
diffraction field. A popular misconception is that automated diffractometers are easier
to use than manual systems. What in fact is true, is that automated powder
diffractometers can give many hours of unattended and reliable data collection and can
greatly assist in the tedious and routine tasks of data analysis provided one is careful to
apply the programs in the correct manner.
Because of the limitations associated with traditional rate-meter scanning, most

modern diffractometers employ a system of step scanning in place of rate-meter
scanning. Although the use of step scanning offers the diffractionist great flexibility,
special care must always be taken in setting up the step scan conditions, especially in
those cases where computer treatment of the raw data is anticipated. Typical processing
steps include data smoothing, background subtraction, a:2 stripping and peak hunting
[6]. Each of the steps must be considered in the light of all others. For example, too
large a step size followed by a high degree of smoothing will lead to marked
suppression of the peak intensity. Conversely, too small a step size and too little
smoothing may lead to peak shifts and/or spurious peaks. The Ideal step size is one
which gives between 5 and 15 individual data pomts above the full width at half
maximum of the 8eak. Experience with one particular diffractometer indicates that for
a peak width of .2°. Using a relatively short counting time, a step size of 0.04 ° was
most advantageous, followed by a 9-point smooth using 7 points for the parabolic fit to
the peak. Using a somewhat longer counting time, a step size of 0.02° was best, with a
19-point smooth. For well-crystallized materials, the peak width is typically (but not
always) about 0.1 - 0.3 29. As the peak width broadens due to the influence of
0
crystallite size and/or strain, one should increase the step width accordingly. The
situation is clearly different where profile fitting techniques are employed because, in
this case, much more of the profile data are being used.
Essentially two computer-based methods of peak hunting are in use at the
present time - profile fitting and a combination of smoothing, a:2 and background
stripping, and a derivative method of peak location. The latter of these options is by far
the most common, even though the success of derivative methods has a strong
dependence on random counting errors. To minimize such errors, a combination of raw
data smoothing and differentiation of data by the least squares technique may be
employed [7]. The second-derivative peak-location method is commonly employed
[8,9], and this technique yields information about both the peak width and peak
position. Typical steps which may be employed in the data treatment process [10]
mclude the collection of the digitized data, smoothing and background subtraction of
the data, a:2 stripping [11] and finally, use of a peak-location method. This peak
location is typically done using a second-derivative method in which the negative space
is fitted to a parabola and the minimum calculated. A 2e calibration may then be
applied, based either on an internal standard or an external calibration curve. Finally

the peak data are converted to a d-spacing and stored to an appropriate significance.
Although different data-handling systems may apply these steps in a slightly different
order, most software schemes include all of these steps.
Great care must be exercised in com{>aring data treated by one method with data
treated by another method. As an example, If an experimental data set has been derived
using a modern automated diffractometer with second derivative peak hunting and a2
stripping, the d-I list obtained will almost certainly differ from a data set similarly
obtamed using an older manual diffractometer employing a strip chart recorder. The
widths of the diffracted lines along with the efficiency of the peak location process will
both be major factor in the number of lines reported by the automated system. The use
of an a2 stripping program can modify both the number of lines reported as well as the
relative intensities of these lines. As an example, at low 2e values where the a l/a2 is
not resolved, application of an a2 stripping program will reduce the residual peak
height by about one third.
Peak-hunting methods based on profile fitting procedures are now becoming
popular. These methods are ideally suited for the analysis of closely overlap{>ed peaks
which can be extremely difficult to analyze using the more conventional techruques now
in common use. These techniques range all the way from total pattern fitting usin~ an
internal standard [12], to more conventional profile fitting methods that utIlize
instrumental parameters derived by very carefully collecting experimental data from a
series of well characterized standards [13,14]. One of these pro~rams, "SHADOW"
[15], can be utilized without the need to run standards, and is espeCIally useful when the
requirement is to separate and measure the individual peak positions without the need
to completely describe the profile of the peaks.
PROBLEMS IN THE CONVERSION OF 2e MAXIMA TO D-SPACINGS

The measured parameters in a diffraction experiment are the absolute line
intensities and the angles at which lines occur. In qualitative phase identification the
parameters used to characterize a phase are the equivalent inter-planar "d" spacings and
the relative intensities. An important point to consider is the effect of an error in 2e on
the d-spacing. The relationship between the two is of the form Ad/d = Ae. Cote, It will
be clear from the plot that a fixed error in 28 has a greater impact on d-spacing
accuracy at low angles than it does at high angles.
One important use of standards is for the checking of the alignment of a
diffractometer. Once an alignment has been established, it is necessary to check first
that the ali~nment is correct and at frequent intervals, to ensure that the integrity of the
alignment IS maintained. The first of these steps might be quite complex and takes
several hours to perform. The second of the steps needs to be based on a rapid, simple
procedure which can be completed in a few minutes. In both cases, however, it is
necessary that the tests be very reproducible without the introduction of day-to-day
errors, for instance, in sample mounting. To aid in this area, most equipment
manufacturers supply a mounted, permanent- alignment reference with the
diffractometer. The standard is typIcally a specimen of fine-grained a-quartz
(novaculite) cemented into a holder and surface ground to ensure that there is no
seecimen dIsplacement. Other materials which have been used for this purpose include
SIlicon, tungsten and gold. The type of instrument alignment standard described above
can also be used as an external alIgnment standard to establish a calibration curve for a
given instrument. By this means, all data can be corrected to the external standard.
One important point to note, however, is that use of the external standard will not
correct for the specimen displacement error or transparency. It is also not good practice
to use an external standard to compensate for poor alignment of the diffractometer.
USE OF FIGURES-OF-MERIT
The major problem which most diffractionists face in setting up a given

diffraction experiment, is whether or not their selection of the instrument and/or
software variables represent the optimum set of experimental conditions. To this end,
the use of a figure-of-merit may offer some assistance. The figure-of-merit will often
provide useful guidelines in the establishment of optimum conditions. Such
figures-of-merit based on counting-statistical limitations have long been used in, for
example, X-ray fluorescence spectrometry [16]. However, in X-ray fluorescence the
line-broadening parameters are determined purely by the fixed collimators and line
shapes are easily correlated with diffraction angle. In X-ray diffractometry the situation
is much more complicated, and conventional figures-of-merit based on peaks and
background are not directly applicable.
Although intensity is important in powder diffraction measurements, the ease of

interpretation of the resultant diffractogram is invariably dependent on the resolution
of the pattern. A pattern made up of broad lines superimposed on a high, variable
background is much more difficult to process than one in WhICh the lines are sharp and
well-resolved and the back~round is low and flat. In the setting up of instrumental
parameters for a given senes of experiments, there are many variables under the
control of the operator-source conditions, receiving slit width, scan speed, step
increment, etc. Jenkins and Schreiner have addressed this problem in their review of
data from an intensity round-robin test [1] and have suggested an instrument parameter
figure-of-merit for X-ray powder diffraction. This figure-of-merit (FOM) has the form:
FOM = M J[W/(M + 4B)]
Figure 4 illustrates the case of a simple peak in which the full width at half maximum is
given by W, the width at the base as 2W, the average background is B, and the
maximum peak intensity above background is given as M.
Figure 4. Definition of a peak for a figure-of-merit
The area under the peak is equal to MW and that under the background is 2BW.
It will be clear from this that as W increases (due to, for example, a specimen of small
crystallite-size), whereas MW does not change appreciably, 2BW increases
significantly. Application of the figure-of-merit to a wide range of data from different
diffractometer configurations and types has shown that the larger the value of FOM,
the statistically better are the net count data.
REFERENCES
1 Jenkins, R and Schreiner, W.N., Intensity round-robin report, Powder

Diffraction, ~ (1989) 74-100
2 Smith, D.K., Johnson, G.G.Jr. and Wims, A., Use of full diffraction
spectra, both experimental and calculated, in quantitative powder
diffraction analysis, Austr.J.Phys., 41 (1988) 311-321
3 Taylor, J.e. and Pecover, S.R, Quantitative analysis of phases in zeolite
bearing rocks from full X-ray diffraction patterns, Austr. J.Phys., 41
(1988) 323-335
4 Jenkins, Rand Holomany, M., PC-PDF - A search/display system
utilizing the CD-ROM and the complete Powder Diffraction File, Powder
Diffraction, J. (1987) 215-219
5 Jenkins,R, On the selection of the experimental wavelength in powder
diffraction measurements, Adv. X-ray Anal., 32 (1989) 551-556
6 Huang, T.C., Precision peak determination in X-ray powder diffraction,
AustJ.Phys., 41 (1988) 201-212
7 Savits~, A. amd Golay, MJ.E., Smoothing and differentiation of data by
simplifzed least squares procedures, Anal. Chern., 36 (1964) 1627
8 Mallory, C.L and Snyder, RL., The control and processing of data from
an automated powder diffractometer, Adv. X-ray Anal., 22 (1978) 121-131
9 Schreiner, W.N. and Jenkins, R., A second derivative algorithm for
identification of peaks in powder diffraction patterns, Adv. X-ray Anal.,
23 (1980) 287-293
10 Jenkins, R., Profile data aquisition for the JCPDS-ICDD database,
Austr.J.Phys. 41 (1988) 145-153
11 Rachinger, W.A., A correction for the a.l/a.2 doublet in the measurement of
widths of X-ray diffraction lines, lSci.Instrum., ~ (1948) 254-259
12 Huang, T.e., et al., Derivation of d-values from digitized X-ray and
synchrotron diffraction data, Adv. X-ray Anal., 3.3. (1989) in press
13 Parrish, W., Huang, T.C. and Ayers, G.L., Profile Fitting: A powerful
method of computer X-ray instrumentation and analysis, Am. Cryst.
Assoc. Monograph, 12 (1976) 55-73
14 Snyder, R.L. and Howard, S.A., An evaluation of some profile models
and the optimization procedures used in profile fitting, Adv. X-ray Anal.,
26 (1982) 73-80
15 "MICRO-SHADOW' A system [or X-ray powder diffraction analysis, by
Scott A. Howard, (1988). AvaIlable from Materials Data Inc., P.O.Box
791, Livermore, CA 94550
16 Jenkins, R. and de Vries, J.L., An Introduction to X-ray Spectrometry,
2nd. Ed., Springer-Verlag:New York, (1977) Sections 5.8 and 5.9
DERIVATION of d-VALUES FROM DIGITIZED X-RAY AND SYNCHROTRON DIFFRACTION DATA
T. C. Huang, W. Parrish, N. Masciocchi*, and P. W. Wang
IBM Research Division, Almaden Research Center, San Jose, CA 95120
* Permanent address: Istituto di Chimica Strutturistica Inorganica

Universita, Milano, Italy
ABSTRACT
A precise and practical method for the determination of d-values and lattice parameters
from digital diffraction data is described. Systematic errors are corrected mathematically
during a d-spacing (lattice-parameter least-squares refinement process making it unneces-
sary to use internal standards. X-ray and synchrotron diffraction data of an ICDD alumina
plate obtained with a wide variety of experimental conditions and analysis parameters were
used to study the precision in the derivation of d-values and the accuracy in the determi-
nation of lattice parameters. Results showed that the precision in determining d-values was
high with I~d/dlava ranging from 2x 10- 5 to 4x 10- 5. Using the results obtained from the high
precision XRD analysis as a reference standard, the accuracy in the lattice parameter de-
terminations from the synchrotron diffraction data reached the 1-2xlO-6 range. Lattice
parameters, with an accuracy in the high 10- 5 range, were also obtained using parameters
commonly used in a routine XRD analysis such as a wide RS (0.11°) for high intensity,
peaks only in the front reflection region, no Kcx 2 stripping, and a single 28 0 parameter for
systematic error corrections.
INTRODUCTION
The use of digitized data eliminates the time-constant errors associated with the analogue
strip-chart recordings and permits the data to be analyzed by computers. The data col-
lection method most frequently used is step-scanning with selectable fixed increment ~28
and constant counting time t per step, with the diffractometer under computer control.
There are a number of factors which limit the precision of the d's and the intensities. I As
in most experimental data there are two major types of errors: random and systematic. The
random errors can usually be reduced by improving the experimental conditions, e.g. using
longer counting times and reducing the background in the intensity measurements. The
systematic errors are generally inherent in the instrument geometry and require a knowledge
of their origin to properly handle them. In practice, most can be corrected in the least-
squares refinement and with standards.

The quality of the pattern is often limited by the quality of the specimen. Studies of the
effect of particle size statistics in polycrystalline specimens show that small particle sizes
(< lO,um) and/or specimen rotation are necessary to obtain reliable experimental data. 2 ,3 In
conventional X-ray tube focusing geometry each reflection is a KIX-doublet, and the ge-
ometrical aberrations such as specimen surface displacement, flat specimen, etc. vary with
28 causing systematic errors in the peak positions. 2 In parallel beam synchrotron radiation
powder diffractometry, the radiation is a single narrow wavelength which is selectable to
obtain high peak-to-background ratios, and the geometrical aberrations are absent, thus
eliminating most of the systematic errors. In addition, the resolution is high and the peak
shapes are virtually symmetrical. 3 - 5
The derivation of d-values from digitized data is one of the most basic data reduction
processes in diffraction analysis. The peak search (PS) method can 'be used for precision
peak determination of non-overlapped peaks, while the profile fitting (PF) method is needed
to resolve overlaps.6-8 The resolution, peak shape, and step size are important factors in
deriving d's from overlapping and tight clusters of reflections by both methods. A recent
JCPDS-ICDD round robin study on d-spacing accuracy reported large spreads of J128 or
J1d for analyses with no internal-standard corrections for systematic errors. 9
In this paper, an effective procedure of determining precise d-values from diffraction

data without the use of internal standards is described. Results of analyzing digitized X-ray
and synchrotron diffraction data of an ICDD alumina plate are reported. The effects of
experimental and analysis parameters on the results will also be discussed.
EXPERIMENTAL
Diffraction data obtained directly from the ICDD alumina plate with no specimen prepa-
ration and a wide range of experimental conditions were used in this study. As shown in
Table I, data were collected from a conventional Cu-target X-ray source at the IBM
Almaden Research Center and from synchrotron radiation at Stanford Synchrotron Radi-
ation Laboratory (SSRL). The resolution calculated from full width at half maxima
(FWHM) of the observed alumina diffraction profiles are plotted in Fig. 1. The top two
curves are obtained from XRD, and the bottom curve from SSRL synchrotron diffraction
data. Values of FWHM and the resolution of the XRD data vary depending on the aper-
ture of the receiving slit (RS) used. The larger the RS aperture, the larger the FWHM and
the lower the resolution. The synchrotron diffraction data obtained at SSRL have higher
resolution, and were obtained with an incident-beam SiC Ill) channel monochromator and
a set of long horizontal parallel slits to define the diffracted beam.
Table 1. Experimental Conditions for the Analysis of the ICDD Alumina Plate
Radiation ,.\ RS Resolution Step Size 28 Range
X-Rays Cu KIX 0.03 0 Medium 0.020 20 - 160 0

Cu KIX O.llo Low 0.020 20 - 160 0
Synchrotron 1.54A N.A. High 0.010 20 - 1400

1.54A N.A. High 0.020 20 - 70 0
T. C. HUANG ET AL. 297
0.2'
Fig. I.
2
I Plots of FWH\1 vs. 28.
~
u.
RS=O.ll' The increasing width at
the higher 28's is caused
• by wavelength dispersion.
0.1'
RS=0.03' 0
0
SSRL
O~~~--~~~~~~~~--~~~--~~~~
o 20 40 60 80 100 120 140 160 '20
DATA ANALYSIS
The procedure for deriving the d-values is given in Fig. 2. The analysis can be either done
directly from experimentally observed Cu-Kcx] 2 diffraction peaks or from the net Cu-Kcx]
peaks with the Kcx 2 components removed mathematically. The Kcx 2 overlap may have a
significant effect on observed peak positions. The smaller the peak 28, the larger the effect
of overlap. For example, an analysis of the alumina XRD pattern obtained with
RS = 0.03° shows that the 28 displacements between observed Kcx],2 and pure Kcx] peak
positions were 0.009°, 0.004°, and 0 for peaks at 25.6°, 52.6°, and 70.4°, respectively. The
effect of overlap is more severe for peaks recorded with a wider RS.
The diffraction peak positions are determined either by peak search based on derivative
methods or by profile fitting. Systematic errors are then corrected by simultaneous least-
Collection of Digital Data

(X-Ray or Synchrotron Radiation)
Stripping of the KlX2 Overlaps

(Not Required for Synchrotron Data)
L (Optional for XRD Data)
Determination of Peak Positions

(Peak Search or Profile Fitting)
Correction for Systematic Errors

(Least-Squares Refinement)
Calculation of d-Values &

Estimation of Precision (~d/d)
Fig. 2. Procedure for derivation of d-values.

squares refinement of the d-spacings and the lattice parameters. ID •II Mathematically, all
systematic errors including zero-angle calibration, specimen surface displacement, flat
specimen, specimen transparency, axial divergence, etc. which may affect the peak posi-
tions can be included in the refinement. It has been found that the largest errors are due
to zero-angle calibration and specimen surface displacement, and can be represented
mathematically by 28 0 and Clcos8, respectively. The solution of a least-squares refinement
is reached and the values of 28 0 , C I and the lattice parameters are obtained when the sum
of the squares of the differences between the observed 28s, corrected for the systematic er-
rors, and the calculated 28s derived from the lattice parameters reaches a minimum.
Values of the observed d-spacings corrected for systematic errors (dear) by the least-
squares refinement and the theoretical d-spacings calculated from the refined lattice pa-
rameters (deal) are then calculated using the Bragg law. (The value of wavelength used in
the analysis of XRD data was 1.540562A.) The overall precision of the analysis is esti-
mated from the value of I~d!dl, where ~d = dear-deal' averaged over all peaks.
RESULTS A:--iD DISCUSSION
Analysis of XRD Data
A typical XRD pattern of the ICDD alumina plate obtained with RS=0.03° is plotted in
Fig. 3. It should be noted that the intensities of the back reflection peaks which are plotted
in the the lower half of Fig. 3 have been expanded by a factor of 10.
The diffraction profiles of alumina reflections shown in Fig. 3 are relatively sharp, with
no significant line broadening, indicating that the material is well-crystallized. Diffraction
profiles obtained with RS = 0.11-" are slightly broader because of the wider RS. Typical
results of a least-squares refinement using PS data of the RS = 0.11 ° pattern are listed in
Table 2 for the front reflection region. Values of the 28 cor and dcor (corrected for systematic
errors), and deal calculated from the refined lattice parameters are given in columns 3, 4 and
100
~
Q)
.~
iii
E
0 0
c: 30 40 50 60 70 80 90
....> 10
'c;;
c:
....Q)
.5
o~~~~~~~~~~~~~~~~~~~~
90 100 110 120 130 140 150
Fig. 3. XRD pattern of the ICDD alumina plate.
Table 2. XRD Data of the ICDD Alumina Plate Obtained with RS = O.ll 0
h k Ifla t 20 care} dcarCA) dcalA) ddjd (l0-5):j:
0 2 45 25.578 3.47973 3.48007 -9.8

0 4 100 35.152 2.55084 2.55110 -10.2
0 21 37.776 2.37947 2.37942 +2.1
0 0 6 2 41.675 2.16542 2.16547 -2.3
3 66 43.355 2.08532 2.08542 -4.8
2 0 2 46.175 1.96431 1.96419 +6.1
0 2 4 34 52.549 1.74007 1.74003 +2.3
1 6 89 57.496 1.60155 1.60153 +1.2
2 1 1 59.739 1.54667 1.54662 +3.2
2 2 2 61.117 1.51506 1.51476 + 19.8
0 8 14 61.298 1.51101 1.51101 0.0
2 1 4 23 66.519 1.40451 1.40454 -2.1
3 0 0 27 68.212 1.37372 1.37376 -2.9
1 2 5 1 70.418 1.33599 1.33604 -3.7
2 0 8 2 74.297 1.27555 1.27555 0.0
1 0 10 29 76.869 1.23915 1.23916 -0.8
1 9 12 77.224 1.23434 1.23424 +7.8
2 7 80.419 1.19315 1.19319 -3.3
2 2 0 2 80.698 1.18973 1.18971 +1.7
3 0 6 83.215 1.16002 1.16002 0.0
2 2 3 3 84.356 1.14721 1.14721 0.0
1 3 1 <1 85.140 1.13862 1.13860 + 1.8
3 2 2 86.360 1.12566 1.12574 -7.1
1 2 8 3 86.501 1.12419 1.12420 -0.8
0 2 10 9 88.994 1.09903 1.09905 -1.8
t Normalized peak intensity

:j:M=dcor -dcal
5, respectively. The precision in determining deor of each reflection is listed in column 6.

The average and the maximum values of l.1d/dl are 3.8xlO- 5 and 19.8xlO-5, respectively.
Similarly, the average and maximum values of 1.1281, where .128 = 28eor-28eal' are 0.0025 0
and 0.013 respectively. To evaluate the accuracy, completeness, and reliability of the
0
,
measured d-values, the figures-of-merit I2 ,13 of the PS data were calculated using the PC
version of the 1\BS* AIDS program l4 : F 25 = 406 (0.0025,25) and M20 = 606 (1.1589, 20).
The XRD patterns obtained with RS=0.03° and O.llo were analyzed using a wide range
of analysis parameters. Results of four selected analyses are discussed below. The param-
eters used in these analyses and the results of determining d- values and lattice parameters
are summarized in Table 3. Both analyses #1 and #2 use the same RS = 0.03 pattern, 0
Kill peaks with KIl2 components removed, PS method for peak-position determination, and
28 a + Clcos8 for corrections of systematic errors. However, analysis #1 was refined using
Table 3. Summary of the XRD Results
Analysis # 2 3 4
28 Range 90-160° 20-160° 20-90° 20-90°

RSn 0.03 0.03 O.ll 0.11
Ka 2 Stripping Yes Yes No No
Peak Location PS PS PS PS+PF
Systematic 28 0 +C 1 cos 8 28 0 +C 1 cos 8 28 0 28 0
Errors
I dd/d lavg 2.2x 10- 5 2.6x 10- 5 3.9x 10- 5 3.9x 10- 5
a (A) 4.75845 (3) 4.75851 (3) 4.75883 (7) 4.75882 (6)
c (A) 12.99190 (12) 12.9920 I (9) 12.99281 (30) 12.99283 (26)
Ida/al l.3x 10- 5 8.0x 10- 5 7.8x 10- 5
Idc/cl 0.9x 10- 5 7.0x 10- 5 7.lx 10- 5
only the high-angle peaks between 90-160°, and analysis #2 using the entire pattern from
20-160°. The precision in the derivation of d-values as estimated from the average value
of Idd/dl were 2.2xlO- 5 and 2.6xlO- s, respectively. Results also show that the a- and c-
lattice parameters obtained from these two analyses are practically the same.
Parameters commonly used in a routine XRD analysis including Ka peaks with no Ka 2

stripping and a single 28 0 parameter for systematic error corrections, were also used to an-
alyze the front reflection region of the XRD pattern obtained with a large RS=O.llO. The
refined XRD Data of individual reflections obtained from this relatively high intensity but
lower resolution pattern are listed in Table 2.
As shown in Table 2, the maximum values of dd/d and d28 are 19.5xlO-s and -0.013°,
respectively, for the weak (122) reflection overlapped by the strong (OIS) reflection. The
overlaps of (122) and (0 IS) reflections can be resolved by PF. The results obtained from
the PS data of the non-overlapping peaks and the PF data of the overlaps of (122) and
(018) reduce the maximum values of Idd/dl and Id281 to 13xI0-5 and 0.009°, respectively.
The figures-of-merit also improve to F25 = 426 (0.0025, 25) and :\120 = 654 (1.15S9, 20).
Results obtained from the PS (analysis #3) and the PS+ PF data (analysis #4) are listed in
columns 4 and 5 of Table 3. Values of Idd/dl avg ' Ida/ai, and Idc!cl of both analyses are
slightly higher than those of analyses #1 and #2 probably because of lower precision for
peaks in the front reflection region.
Analysis of Synchrotron Diffraction Data
As noted in the Introduction, synchrotron peaks have the advantage of single symmetrical
narrow profiles, which is important in deriving the values of 28's and d's with high preci-
sion. If desired, the number of peaks and the d-range can be greatly expanded by using
100
'0
Q)
.!::!
"iii
E
oc:: O~~~~~~~~~~~~A-~~~~~~~~~~
20 30 40 50 60 70 80
~
.;;;
20
c::
~
c::
O~~~~~~~~~~ __~~~~~~~~~
80 90 100 110 120 130 140 °20
Fig. 4. SSRL synchrotron diffraction pattern of the ICDD alumina plate.

,{ = 1.54A, .128 = 0.01 0, and t = 1 second.
shorter wavelengths. Two runs were made at SSRL with ,{ = 1.54A, and the synchrotron
diffraction pattern of one of the runs is plotted in Fig. 4. During the data collection of this
pattern, there were some difficulties with the source stability. This made the high angle
section of the pattern unsuitable for a high precision an,alysis. The experimental data with
28>80° were therefore not used in the least-squares refinement calculation.
The parameters used in the synchrotron data analysis are listed in Table 4. Analysis #5
was from data recorded with 0.01°28 steps, 1 second per step, and analysis #6 was a fast
Table 4. Summary of the Synchrotron Diffraction Results
Analysis # 5 6 1*
Laboratory SSRL SSRL IB\1/ARC

28 Range 20-80° 20-70° 90-160°
Peak Location PS PS PS
Systematic 28 0 28 0 28 0 + C 1cos8
Errors
} (A) 1.535929 1.536079 1.540562

I .1d/d lavg 3.1x 10- 5 2.7x 10- 5 2.2x 10- 5
a (A) 4.75844 (6) 4.75846 (5) 4.75845 (3)
c (A) 12.99192 (19) 12.99187 (25) 12.99190 (12)
l.1a/al 2.lx 10- 6 2.lx 10-6
l.1cjcl 1.5x 10- 6 1.5x 10-6
* Reference XRD data from Table 3.

run recorded with 0.02° steps and 0.5 second per step. Both synchrotron diffraction pat-
terns have very high figures-of-merit with F Nand MN above 600 and 999.90, respectively.
It is worth noting that a preliminary analysis of a synchrotron diffraction pattern re-

cently obtained at the Daresbury Laboratory with ..{ = IA had exceptional high figures-of-
merit above the upper limit of 999.90 set in the ~BS*AIDS program. A modification of
the program was necessary to obtain the true values of figures-of-merit: F30 = 1381
(0.0007, 32) and M20 = 1333 (1.1578, 20).
To derive the values of d-spacings and lattice parameters, the actual wavelength used in
the synchrotron experiment must first be determined. Unlike the radiation obtained from
a conventional X-ray source for which wavelength tables of the characteristic spectral lines
are available, there are no lines in the synchrotron-radiation spectrum. Different methods
for experimentally determining the value of synchrotron wavelength have been used, e. g.
absorption edges and a silicon powder standard. 6
In this study, the wavelength was determined by making the sum of the lattice parame-
ters obtained from the calculation equal to that of the high precision XRD analysis # I; the
values are listed in Table 4. The precision in determining 28's and d's were good (i.e.,
1~2elavg:S:;0.00 16° and I~d! dl avg :S:;3.1 x 10- 5). Excellent agreement in lattice parameters were
also obtained. The discrepancies are negligible and well within the standard deviations es-
timated by the least-squares refinements (see numbers in the parentheses). Using the values
of analysis # I as a reference standard, the accuracy of the synchrotron lattice parameters
reaches the 1-2x 10-6 range (see values of I~a/al and I~c!cllisted at the bottom of Table 4).
It should be noted that the diffraction patterns collected using t~e same instrument at
SSRL but slightly different wavelengths and operating parameters both give practically the
same values of lattice parameters.
SUMMARY
It has been demonstrated that precise d-values and accurate lattice parameters can be ob-
tained from digitized diffraction data by proper corrections for systematic errors during the
d-spacing / lattice parameter least-squares refinement without using internal standards.
An analysis of the XRD and synchrotron data of the ICDD alumina plate showed that
results with l~didlavg;::::2.2xIO-5, l~a/al;::::2.lxlO-6, and l~c/cl;::::l.5xlO-6 were obtained.
ACK~OWLEDGEMENTS
We thank SSRL for providing the synchrotron radiation facilities for this study, R. Cernik
and M. Hart for the Daresbury pattern, R. Jenkins of JCPDS-ICDD and W. Y Schreiner
of the Philips laboratories for supplying the ICDD alumina plate, and R. G. Garvey of the
1\0rth Dakota State University for modifying the NBS*AIDS program.
REFERENCES
1 R. Jenkins, "Methods & Practices", lCPDS - ICDD, Swarthmore, PA 19081 (1989).
2 W. Parrish, "X-Ray Analysis Papers", Eindhoven, Centrex (1965).

3 W. Parrish and T. C. Huang, Adv. X-Ray Ana!. 26, 35 (1983).
4 W. Parrish, M. Hart, and T. C. Huang, J. App!. Cryst. 19,92 (1986).
5 W. Parrish and M. Hart, Adv. X-Ray Anal. 32,481 (1989).
6 T. C. Huang and W. Parrish Adv. X-Ray Anal. 27,45 (1984)
7 T. C. Huang, W. Parrish, and G. Lim, Adv. X-Ray Anal. 27,53 (1984).
8 T. C. Huang, Aust. J. Phys. 41,201 (1988).
9 W. Schreiner and T. Fawcett, Adv. X-Ray Anal. 28, 309 (1985).
10 W. Parrish and T. C. Huang, Proc. Symp. on Accuracy in Powder Diffraction, p. 95,

NBS, Washington D.C. (1979).
II W. Parrish, M. Hart, T. C. Huang, and M. Bellotto, Adv. X-Ray Anal. 30,373 (1987).
12 G. S. Smith and R. L. Snyder, J. Appl. Cryst. 12,60 (1979).
13 P. M. de Woff, J. Appl. Cryst. I, 108 (1968).
14 A. D. Mighell, C. R. Hubbard, and J. K. Stalick, NBS Technical Note 1141, National

Institute of Standards and Technology, Gaithersburg, MD 20899 (1987).
THE OPTIMIZATION OF STEP SIZE WHILE COLLECTING A DIGITIZED
DIFFRACTION PATTERN AT A CONSTANT TOTAL SCAN TIME
John R. Burleson
Materials Analysis Laboratory

AC Rochester Div., General Motors Corp.
Flint, MI 48556
INTRODUCTION
Given a limited amount of time for data collection, what parameters do

you select to generate the highest quality x-ray diffraction pattern from an
automated diffractometer? This paper addresses the major topic of diffrac-
tometer step size or its equivalent, chopper size, for instruments running
in the continuous scanning mode. In general, step size and chopper size
will be interchanged freely. A minor topic intertwined into the discussion
will be the receiver slit width.
The data presented was collected from an alumina substrate obtained

from the JCPDS. It was acquired on a Scintag PAD V diffractometer, pri-
marily in the continuous mode, with a copper target fine focus tube powered
at 45KV and 4lmA. The diffractometer is equipped with a germanium detector
and was set to a radius of 230 rnm. The graphics were displayed on a high
resolution Tektronix 4115 color CRT driven by the modified OEM's software
running on a Data General S-120 with multi-tasking. The maximum time al-
lowed for the total scan was set at forty minutes. This time is based on a
scan from 4 to 70 degrees two theta at 2 degrees per minute.
A NEGATIVE POINT OF DECREASED STEP SIZE - INCREASED COMPUTER USAGE
Processing time and disk storage penalties are paid as the step/chop
size is decreased. See Table I. The processing times listed are those
required to execute the background subtraction and peak finder routines and
TABLE I - MEMORY AND DATA PROCESSING PENALTIES WITH DECREASING STEP SIZE
STEP SIZE ( 20)

0.01 0.02 --0.03 0.04 0.05
FILE SETS/MEGABYTE ~ 70 98 123 140
(four files per scan)
DRAWING TIME (sec.) 292 143 97 72 57
PROCESSING TIME (m:s) 37:32 19: 52 13 :24 10:04 8:14

Edited by C.S. Barrett et a/.
w
o
m
TABLE II - BACKGROUND NOISE AND PEAK STATISTICS <:

l>
STEP POINTS PER PRESET AVERAGE ONE MIN. EXTRA AVERAGE POINTS WEAK PEAK AVERAGE cis AII>VE THREE Z
SIZE HALF DEG. TIME COUNTS STD. COUNTS I 0 • 10 COUNTS AVERAGED AVERAGE Cis SIGMA PLUS BACKGROUND l>
r
(SEC) ISTEP DEV. TO SEE PEAK ISEC PER 0.1 (0.1 DEG.) WEAK PEAK STRONG PEAK -<
DEGREE ~
en
.005 101 0.15 7 3 160 49 21 108 7 3750 0
-n
0
.0lD 51 0.3 15 4 115 49 11 110 24 3825 C)
:::j
l>
.030 17 0.9 45 7 66 50 4 108 38 3525 r
0
.040 13 1.2 53 57 44 3 105 39 3500 -n
-n
::IJ
.050 11 1.5 71 8 51 47 3 100 36 3100 l>
C")
-l
(5
.080 7 2.4 112 11 39 47 2 104 43 2975 Z
0
.125 5 3.75 175 13 33 47 2 88 30 2175 l>
-l
l>
Z
C")
r
C
0
Z
Gl
~
m
-l
<
m
r
0
J. R. BURLESON 307
to draw the pattern four times. As with most of the data presented here,
the weight of the positive or negative effects of an item will depend on the
capabilities of the individual system and the sample through-put of your
laboratory. Your situation may be more or less sensitive to computer memory
limitations or time spent to draw a particular pattern.
ANOTHER NEGATIVE POINT OF DECREASED STEP SIZE - POOR COUNTING STATISTICS
The detection of weak peaks is, to a great extent, the ability to dis-
tinguish the weak peak from the background noise. If the total scan time
is held constant and the step size is decreased, background noise is
increased. The noise is generated by the deteriorating counting statistics
caused by the dwindling counting time. A typical situation is displayed in
Table II. The effect is easily seen by examining the size of one standard
deviation (one sigma) and the total number of extra counts needed to produce
a peak 0.1 degrees wide and three sigma above the background. Note that the
average count rate in counts per second remains rather constant for all
seven data sets. Remembering the background data, examine the data from a
weak and a strong peak. The average intensity of both peaks generally in-
creases as step size is decreased. However, for the weak peak collected
with a small step size, the intensity above background is very low but in-
creases for moderate step sizes.
The data for Table II was developed from patterns collected during con-
tinuous scanning. For step scanning, the counting statistics deteriorate
when the scan is collected during the same fixed time. The reason is that
during step scanning, a larger portion of the time required to collect the
scan is spent doing bookkeeping, not counting. The total time required to
collect a single scan may be expressed as the summation of: (1) the time re-
quired to change the sample, setup and close the computer files, (2) the
time actually spent counting, (3) the time spent stepping the diffractometer
to the next location and (4) the time spent reading and clearing the counter
after each step. When a well designed diffractometer is used in the contin-
uous scanning mode, the third term is zero and the fourth term approaches
zero. The summation (T ts ) may also be expressed in terms of an initial
constant (Ci), the angular range scanned (A), the step size moved (S), the
preset or counting time at each step (Tp ), the speed at which the
diffractometer moves (R) and the delay time spent for bookkeeping before
and/or after each step (D).
Tts Tinitial + Tcounting + Tmoving + Tresetting

C'1 + AIR + A·D/s (For step scanning)
C'1 + 0 + A·D/s (For continuous.)
The equations can be rewritten to yield the step size required as a

function of the preset time or the preset time given the selected step
size. Equations may also be generated to calculate the efficiency of data
collection. Efficiency is defined as the ratio of the time spent counting
to the time required to collect all the data points.
To obtain an estimate of the delay time D and the stepping rate R for
various diffractometers, I asked several of my x-ray diffraction colleagues
around the country to make two scans on their automated units. The request
was for one eleven-degree scan with 0.1 degree steps and a preset time of
one second. The other was to be stepped at 0.01 degrees with a 0.1 second
preset time. With two sets of data, the two unknowns could be determined.
308 IV . ANALYSIS OF DIGITAL DIFFRACTION DATA INCLUDING RIETVELD
TABLE III - RESET TIME AND STEPPING SPEED
MODEL PRESET STEPPING RESET EFF STEP

TIME RATE TIME % SIZE
~ (DEG/MIN) (SEC) (DEG)
A 37 0.056 90 .035
B 1 19 1. 24 40 .075
B 0.1 19 1.24 7 .045
C 8 0.078 72 .040
D 1 32 0.24 76 .040
D 0.1 32 0.24 28 .0lD
E (Con- 1 1.8 0.000005 99.9+ 0.03

E tinuous) 0.01 1.8 0.000005 99.9+ 1/3200
Some of the instruments could not count for preset times less than one sec-
ond. For these instruments another scan with different parameters was sub-
stituted. The data from instruments of four different manufacturers is
shown in Table III. R ranges from 8 to 37 degrees per minute and D ranges
from 0.056 to 1.24 seconds per step. The efficiency of data collection av-
eraged 70% with a preset time of one second and declined to an average of
18% with a preset time of a tenth of a second. With the specified 40 minute
total scan time and Ci set at 3 1/2 minutes, the smallest possible step
size averaged around 0.04 degrees. On the other hand, for the two instru-
ments in our laboratory capable of continuous scanning, one commercial and
one home brewed, the counting efficiency is 99.9+%. This is based on our
designed and the OEM's specified delay times D in the range of 5 micro-
seconds. With these very short delay times, there is no practical lower
limit on the chopper size.
THE POSITIVE POINTS OF DECREASED STEP SIZE - MORE ACCURATE PEAK INFORMATION
Table IV displays three values for many combinations of slit width and
step size for the most intense peak of alpha alumina. As a measure of the
peak profile, the first entry for each combination is the full width of the
TABLE IV - PEAK WIDTH AS A FUNCTION OF CHOPPER AND SLIT SIZES

WITH MAXIMUM PEAK INTENSITY AND ITS LOCATION
Slit
Width Chopper Size
nun (degrees two theta)
(Degrees)
0.001 0.005 O.OlD 0.020 0.030 0.040 0.050 0.080 0.125
0.05 0.042 0.043 0.048 * 0.051 0.059 0.084 (FWHM) ~-- ---
(0.013) 783 787 713 * 681 618 472 (Maximum Intensity)
43.374 .375 .380 * .380 .360 .360 (Location of Maximum)
0.10 0.054 0.054 0.057 * 0.060 0.081 0.118

(0.025) 2090 2080 1932 * 1934 1614 1237
43.370 .370 .380 * .360 .360 .350
0.20 0.083 0.083 0.085 0.093 0.099 0.097 * 0.216 0.186

( 0.050) 5550 5550 5300 5231 5064 5023 * 3410 3420
43.355 .350 .360 .340 .360 .350 * .320 .375
0.30 0.115 0.117 0.132 0.151 * 0.209 0.181

(0.075) 8230 8128 7681 7709 * 5872 6087
43.345 .350 .330 .350 * .320 .375
J. R. BURLESON 309
TABLE V - RESOLUTION OF GRAPHIC DISPLAYS
GRAPHICS RESOLUTION AVAILABLE MAX STEP SIZE

DEVICE POINTS 4-70· SCAN
LOW RESOLUTION 480 408 0.160

COLOR CRT PIXELS
liED. RESOLUTION 640 544 0.120

COLOR CRT
HIGH RESOLUTION 1280 1088 0.060

COLOR CRT
ULTRA RESOLUTION 4096 3480 0.019

IIONO CRT
HIGH RESOLUTION 150 1200 A 0.054

COLOR COPIER DOTS/INCH 2075 B 0.032 (0.064)
COLOR PLOTTER 1020 (85) 8810 (733) A 0.090

DOT/INCH 14144 (1178) B 0.056
peak at half its maximum intensity (FWHM). The second line for each combin-
ation is the maximum intensity of the peak in counts per second. This is
followed by the location of this maximum count.
The smaller step sizes do improve the profile of the diffraction peak.
However, the noisy statistics of the low count rates are exaggerated by the
very short preset times of the very small step sizes. A point of minute
gain in either intensity, location or peak width occurs when the step or
chopper size is less than the angular width of the receiver slit. The ang-
ular widths of the receiver slits (at 230 mm) are included in this table.
Asterisks mark the approximate location of these slit widths. Diffraction
patterns from combinations to the left of the asterisks follow the same pro-
file as the one just right of them, only they are noisier. The profile of
the peak also gradually degrades with increasing step size, but even at
0.125, the peak is still very evident: Note that as the step size in-
creases, the probability of a data point falling close to a peak maxima
decreases. Therefore, peak maxima move around to the location of the near-
est data point. For stepping, the maximum intensity decreases due to the
position of the data point on the side of the peak. For continuous scan-
ning, the decrease is due to the larger contribution of lower intensity data
from the sides of the peak.
A NEUTRAL POINT OF DECREASED STEP SIZE - THE PROPOSED USE OF THE DATA
One must consider the end usage of the pattern before scanning
parameters are selected. The previous discussion has shown that when the
task is simply to check for the existence of major phases, large step sizes
are satisfactory. If, on the other hand, information about a peak profile
or the location of a peak is sought, smaller step sizes are Ln order.
A NEUTRAL POINT OF DECREASED STEP SIZE - GRAPHICS RESOLUTION
Another item to consider is the computer graphics display to be used to

view the pattern. Resolution information about six graphic devices is shown
in Table V. Assuming that about 85% of the field is actually available to
display data, the maximum number of data points that can be displayed is
listed. For hardcopy units, data for both A and B size paper is given. For
a typical 66 degree scan, the size of the step with a one to one ratio of
data points to display points is given. It is now apparent why scans with
CPS 2.63 2.06 1. 70 1. 45

1500.0~~--------------L---------------~-----------------L------,
THE EFFECT OF CHOPPER S:~"ON VIEWING' [ULL

PATTERN
13<;0.0 f-
~JL ~L ~h~ ~P_.~_~_0 '_'~L.-__ ~_~~_

1200.0
1050.0 _ '.__ ___ __
900.0
750.0
600.0
450.0
J
300.0
150.0 f-
0.010
44 54 64
Figure 1. Three half patterns with decreasing chopper size, originally
displayed on high-resolution color graphics equipment.
very large step sizes were included in the various tables. For many color
CRT's, that is all that can be displayed. If full scans to 70 degrees are
only to be displayed on a low or medium resolution CRT, step sizes less than
0.12 are a waste of resources and generate noise. One note on thin-line
hardcopy color devices, if the line is too thin, the human eye can't dif-
ferentiate the various colors. On AC's high-resolution color copier, with B
size paper, it is necessary to double the line width to allow the observer
to distinguish the different colors. Color plotters have a very high number
of addressable points, but the fine tip pens are twelve times wider than the
point addressed.
The fact that small step size has very little effect on the display of
even half of a full pattern is shown in Figure I. Very little difference is
detected between the three patterns collected with chopper sizes of 0.01,
0.03 and 0.05 degrees. Note that the three patterns have all been normal-
ized to 500 counts per second full scale.
A NEUTRAL POINT OF DECREASED STEP SIZE - BALANCING SLIT AND STEP SIZES.
Peak profiles are a function of both step size and optics. However,
not all combinations enhance the pattern and may actually reduce the quality
of the pattern. Also, changing a slit does have an effect on the alignment
of the instrument. If more precise data is needed, just going to finer
slits and longer counting times may not yield any better information. Try
changing just the antiscatter slit that is ahead of the detector slit.
While intensity is increased greatly with larger slits, the location of the
maximum intensity and the peak centroid shifts toward lower angles.
CONCLUS IONS
* For increased efficiency, if your instrument is designed to do con-

tinuous scanning, use it in that manner.
J.R.BURLESON 311
* Select the scanning parameters by considering the end use of the pat-
tern.
* Experiment with your instrument. Determine how the slits are related
to each other and how, in conjunction with changing the step size, they
affect:
Peak intensity,
Peak profile and
Peak position.
* For the radius of your instrument, calculate the angular width of

each receiving slit. Then match the step size to the receiver slit selected.
* For routine phase analysis, step sizes in the range of 0.03 to 0.04
degrees are fine if:
A good quality CRT is used for viewing the pattern and
The pattern is to be viewed in sections.
* For verification of major phases, step sizes in the range of 0.08 to

0.12 are adequate. However, be sure to install the wide receiver slits.
* For peak profile studies, select smaller step sizes. However,

stepping much smaller than the angular width of the receiver slit will:
Generate noise due to the shorter counting time and
Yield only very slight improvements.
XRD ACQUISITION PARAMETERS FOR DETECTION OF WEAK PEAKS
P. W. Seabaugh, D. B. Sullenger & C. R. Hudgens

EG&G Mound Applied Technologies
Miamisburg, Ohio
M. C. Nichols & D. R. Boehme

Livermore, California
INTRODUCTION
The use of high-intensity, 8Kw, x-ray sources (Rigaku rotating-anode

generator and wide - angle goniometer for this study) provides both
opportunities and challenges. With high -intensity x-ray sources,
detection limits can be lowered significantly while still offering count
times of practical duration. On the other hand, the availability of high
intensity x-ray sources puts greater demands on information extraction
procedures and on the mechanical preciseness of sample containment and
support. In particular we addressed the use of a cylindrical aluminum
sample cell with a 0.010" polycrystalline (cold rolled) beryllium window
electron-beam welded to an aluminum frame. See Figure 1. This cell
permitted analysis of various air-sensitive specimens. The sample was
pressed against the back of the beryllium window by a spring-loaded
backing plate.
The purpose of this study was to determine the important parameters

for the measurement of very weak peaks in reactive samples that needed to
be isolated from the atmosphere.
MODIFICATION OF SPECIMEN CELLS
Diffraction patterns obtained from empty specimen cells exhibited

relatively strong lines characteristic of Al, A1 20 3 , Be and BeO plus a
few other lines, possibly from Be-Al alloys. Removal of the strong Be
lines is not possible because they are produced from the Be window
itself. The extraneous lines were somewhat removed by careful centering
of the cell window in the beam, horizontal confinement of the beam with
slits, and vertical confinement of the beam with a Pb foil mask. These
measures helped to keep the image of the x-ray beam almost totally within
the weld ring of the window.
To further resolve the origin of the remaining extraneous lines, the

x-ray path from the incident slit to the cell window was checked by
painting a phosphor on a cell frame. After inserting it in the
Advances In X-Ray Ana/ysis, Vol. 33 313

51al""' ..
51..IFrb
Boo Window
Figure 1 - X-ray Diffraction

Specimen Cell
diffractometer and opening the incident beam shutter, it was found that
the beam, in fact , grazed the frame at lowe angles . The cell's Al
reference surface parallel to the face plate was found to be too far
forward on the diffracting circle. The x-rays were thereby occulted at
very low angles, producing an anomalously low background and also
generating interfering aluminum and aluminum oxide diffraction peaks, when
exposed to the high-intensity x-ray beam. This was corrected by machining
back the aluminum frame surrounding the Be window so as to make the
reference surface coplanar with the inside surface of the Be window, i.e . ,
the front surface of the contained specimen. Following such modification,
the cell was again checked with phosphor on the reference surface . With a
1/2 0 incident beam slit for diffraction angles from 10 0 to 25 0 , and
a 1 0 slit for diffraction angles of 25 0 and above (see next section),
the x-ray beam no longer struck the frame, and the aluminum/aluminum oxide
lines were no longer present in the diffraction pattern .
SLIT CONSIDERATIONS IN HIGH PRECISION DIFFRACTOMETRY
The allowable horizontal angular divergence is dependent on the

lowest two - theta angle to be measured, and is easily calculated. A minor
complication arises from the need for asymmetry of the horizontal
divergence -- divergence which maximizes irridation of the sample is not
the same on both sides of the center line of the vertical slit . The
necessary slit modifications were calculable, and easily effected.
P. W. SEABAUGH ET AL. 315
Vertical divergence, however, is defined by a stack of short soller

slits, which makes calculations of the vertical penumbra imprecise. It is
better, therefore, to actually measure vertical divergence by irradiating
a soft glass slide placed at the sample position for an hour or so, which
gives an image of the irradiating beam. By measuring this image and
comparing it to the size of the defining incident beam window. (which is
not physically a part of the defining slit), a mask can be defined which
will satisfactorily limit the beam in the vertical direction.
Thus, beam definition consists of a broad vertical slit (a large

aperture) which is constant for all two-theta regions, crossed with a
horizontal divergence slit of size appropriate to the lowest two-theta.
For this work, two horizontal divergence slits (1/2 and 1 degree) were
selected as a practical solution for maximizing the x-ray intensities over
the angular range of interest.
Alignment of the center of the diffractometer with the x-ray beam

was effected by the use of a gauge especially constructed for the purpose.
The gauge effectively places a very narrow slit precisely on the center of
the diffractometer, exactly parallel to the axis of rotation. With its
use it becomes a simple matter to locate the beam on center, and to adjust
the tilt of the diffractometer so that its own slit system is parallel to
the x-ray image on the target (which also maximizes intensity).
Rechecking this alignment is a matter of 2 - 3 minutes. By its periodic
use, the system has been found to be mechanically very stable.
There is some indication that the slits themselves, particularly

those of the incident -beam slit system, contribute artifacts to the
diffraction patterns, particularly those of high counting precision.
DISCUSSION
The quality of an analysis is affected by data collection and

analysis strategies. Control of the background level, sample factors,
total counts and alignment of the diffractometer are all important
elements in a data collection strategy. Availability and the selection of
a specific software package can also affect an analysis strategy.
For this study, control of the background, background assessment,

total counts and alignment of the diffractometer were the principal
controllable experimental parameters. As indicated in the previous
section, the background noise was controlled by machining back the cell
frame to eliminate scattering from the aluminum frame, controlling the
beam divergence so that the maximum sample area could be irradiated
without spilling the incident beam onto the supporting frame, changing the
divergence slit with 20 to keep the sample area irradiated while
containing the beam within the weld ring of the beryllium window, and
centering the cell window in the beam with a micrometer.
Figure 2 shows the importance of running a control line profile of

the empty sample cell before running a loaded cell. Without the
corresponding pairs of profiles, weak lines which become observable after
long exposures at high power could mistakenly be interpreted as sample
peaks. To avoid misinterpretation, it is important to run the empty cell
(background) profile for a time at least as long as that for the sample
profile. In Figures 3 and 4, the enhancement of the individual peak
shapes with increasing time is clearly evidenced. It is unlikely that the
1000
925
~
.~ 850
oS!
..5
775
700
21.5 22.0 22.5 23.0 23.5 24.0 24.5 25.0
2-Theta
Figure 2 -100 Second Count Time
peaks at 41.84 0 20 would be detected with the four second or 0.4

second step scan. The 100 second scan gives an intermediate result.
Sample attributes and containment requirements affect the quality of

the diffraction pattern. These include factors such as crystallinity,
quantity of sample, and the number of phases. Environmentally sensitive
and/or radioactive samples require special containment considerations and
4000
3125
~
.~ 2250
CI)
\
];
\"-~~
1375
\ 4 Second Scan
500
40.000 40.714 41.429 42.143 42.857 43.571 44.286 45.000
2-Theta
Figure 3 - Comparison of 400, 100 and 4 Second Scans

P. W. SEABAUGH ET AL. 317
2250.0
1812.5
~
'iii
1375.0
gs::::
.E
937.5
0.4 Second Scan
500.0
41.0 41.5 42.0 42.5 43.0 43.5 44.0 44.5
2-Theta
Figure 4 - Comparison of 100, 4 and 0.4 Second Scans
must be kept in a sample holder with functionality similar to that

described in the introduction. The effect of sample amount is also shown
in Figure 2, where sample 6x contained three times the quantity of sample
4c. This is reflected in the relative peak sizes at 24.79 0 20. For
very weak peaks, the quantity of sample can be critical both in terms of
detectability and resolution.
Deciphering the precise peak position and peak intensity can be a

difficult task, particularly for weak and unresolved peaks. Credibility
of interpretation and conclusions can be enhanced by analysis packages
that consider peak shape and background fit. The package used in this
work was SHADOW (1), which evolved from earlier work by Howard and Snyder
(2) and Howard (3). The basic idea in profile fitting is indicated in
Figure 5, wherein two individual synthetic profiles are used to fit the
unresolved experimental profile. As depicted, the two synthetic profiles
provide an excellent fit to both the unresolved peaks and the background
for the 20 region of interest. Decoupling the two profiles minimizes
the effect the major peak could have on the 20 and intensity values
for the shoulder peak. Using an offset 20 value or an inappropriate
intensity value determined from a standard peak-finding program could lead
to a misinterpretation. Similarly, without a credible background -
fitting capability, weak peaks could be missed -- or included when in fact
they did not exist.
SUMMARY
With the use of a high intensity x-ray source, the extraction of weak
peaks under adverse conditions is possible. Success, however, depends
both on control of experimental parameters and on the use of the more
evolved analytical tools which provide profile - fitting capabilities.
Among the experiment factors of prime interest are: control of the
background; precise and accurate assessment of the background through the
3000
2250
Fitted Data
~
.~ 1500
oS!
.E
Synthetic Profile 1
750
o
29.2 29.6 30.0 30.4 30.8 31.2 31.6 32.0
2-Theta
Figure 5 - Doublet in the 4c Sample
use of background profiles; consideration of the divergence slit as a

function of 20; the recognition that there is no way around counting
statistics (the need for extended counting times); the precise control
over the sample holder; and the precise centering of the diffractometer.
Profile fitting helps to m1n1m1ze the inadvertent use of an offset 20
value or an inappropriate intensity value, which could lead to
misinterpretation of the diffraction profile.
ACKNOWLEDGEMENT
This work was performed under the auspices of the U. S. Department of

Energy by EG&G Mound Applied Technologies and by Sandia National
Laboratories, under contract DE-AC04-88-DP43495 and DE-AC04-76-DP000789.
REFERENCES
1. S. A. Howard, SHADOW:. A ,System for X-Ray Diffraction Pattern

Analysis (1988), Adv. in X-Ray Anal., 32; 523-530 (198~
2. S. A. Howard, R. L. Snyder, An Evaluation of Some Profile Models and

the Optimization Procedures Used in Profile Filling, Adv. in X-ray
Anal., 26; 73-81 (1983).
3. S. A. Howard, Incorporating W*G Deconvolution in X-ray Rietveld

Structure Refinement, Ph.D. Thesis, New York State College of Ceramics
(1984).
X-RAY EXAMINATION OF FRACTURE SURFACES OF
SILICON NITRIDE CERAMICS
Zenjiro Yajima
Department of Mechanical Engineering, Kanazawa Institute of

Technology, 7-1 Oogigaoka, Nonoichi, Kanazawa 921, Japan
Yukio Hirose
Department of Material Science, Kanazawa University

1-1 Marunouchi, Kanazawa 920, Japan
and
Keisuke Tanaka
Department of Engineering Science, Kyoto University

Yoshida-hommachi, Sakyo-ku, Kyoto 606, Japan
INTRODUCTION
The residual stress left on the fracture surface is one of the

important parameters in X-ray fractography. It has been used to analyze
fracture mechanisms in fracture toughness and fatigue tests especially of
iron and steels. 1 - 4
In the present paper, X-ray fractography was applied to the brittle

fracture surface of a silicon nitride ceramics. The first part deals with
the determination of the stress constant for diffraction from Si3N4(411)
plane by Cr-Ka radiation. The second part describes the effect of the
notch-tip radius on the fracture toughness value. In the last part, the
plastic zone depth was determined from the residual stress destribution
beneath the fracture surface.
Material and Fracture Tests
The material used was sintered silicon nitride ceramics with additions
of Y203 and A1203 as bonding compounds. Young's modulus was 276 GPa.
The bending strength was 399 MPa. The three-point bending specimen was
used for the fracture tests. 5 The radius of the notch-tip was varried
between 0.10 and 0.50 mm. The notch was made with diamond blades and

320 V. X-RAY STRESS ANALYSIS
finished by chemical polishing. The specimen with a tip radius of

0.10 mm was used for pre-cracking. Pre-cracking was introduced by the
longitudinal compression method. 5
All the specimens were fractured under three-point bending. The onset
of crack extension was detected from the load-displacement record and
the acoustic emission method. 5 The fracture toughness value was expressed
in terms of the stress intensity factor which was calculated using the
initial notch length as the crack length for notched specimen. 3
X-Ray Observation
X-ray equipment used for the measurement of the residual stress was a
stress analyser ( Rigaku MSF). The diffraction profile of Si 3 N4 (411)
plane was obtained by Cr-Ka X-ray from the area of 2 mm in diameter.
The X-ray stress constant was first determined. Fig. 1 shows the loading
apparatus used for the measurement of the stress constant. The conditions
of X-ray observation are given in Table 1. The incident angles of X-rays
weneO°, 10°, 15°, 25°, 30°, 45°. The residual stress in the crack-growth
direction on the fracture surface was determined by the sin2~ method.
The distribution of the residual stress beneath the fracture surface was
obtained by irradiating X-rays on the new surface revealed by successive
chemical polishing. Fig. 2 shows the schematic illustration of the X-ray-
irradiated area on the fracture surface.
Strain gage specimen
Fig. 1. Loading device for Fig. 2. Schematic illustration of X-ray

calibration of X-ray irradiated area on the fracture
stress constant. surface (in mm).
Table 1. X-ray conditions for stress measurement.
Characteristic X-ray Cr-Ka

Diffraction plane Si,N. (411)
Filter V foil
Detector PSPC
Tube voltage 30 kV
Tube current 20 rnA
X-ray fixed time 100 sec
Z. YAJIMA ET AL. 321
Determination of X-Ray Stress Constant and Residual Stress
Fig. 3 shows 28 - sin2~ curves obtained for the specimen under

applied strain Ea at 0, 400, 800 and 1200xlO- 6 • The four curves can be
approximated by straight lines. The slope M of 28 - sin2~ diagrams was
determined by a least-square regression program. The relation between M
and Ea is shown in Fig. 4. The X-ray stress constant K was determined
from Fig. 4 by using the following equation:
(1)
125.4
Ea (xl0-6)
--------
---0-
- -fr-- 400
0
125.3
7-.'-----z
--0-- 800
- .. ~ 1200
01
T----.Q._~,~
-e _-1:.--_
QI
~ 125.2 .n.
CD ----~-- -
0
"~--
N
1251 "----
125.0
o 0.2 0.4 0.6
Fig. 3. 28 - sin2~ curves.
0.1
o
01
QI
'0 -0.1
~I~
CDN
N C
~iii
ttl -0.2
o
-0.3
-0.4 L -_ _-'--_ _- ' -_ _ ~ _ __'__ _ ~ _ ___'
o 400 800 1200

Applied strain Ea (Xl0-6)
d ( 28 )
Fig. 4. vs. Ea'
d sin2~
where EM is the mechanical Young's modulus ( 276 GPa). The obtained value
was K = -932 MPa/deg. By using K = -932 MPa/deg. the residual stress oR is
determined from the measurement of M through
(2)
Fracture Toughness Tests
Fig. 5 shows the record of load versus crack opening displacement for
p = 0.40 mm. The change in acoustic emission total count and total energy
with displacement are also shown in the figure. The relation was linear
up to the point of the fracture. The fracture toughness, Kp , of bluntly
notched specimens is plotted against the square root of the notch radius in
Fig. 6. As seen in the figure, the relation could be roughly approximated
by two straight lines. Kp was proportional to IP at large p values.
It approached a constant value Kp, i.e., the fracture toughness of the pre-
cracked specimen, as p became smaller.
X-Ray Observation of Fracture Surface
Fig. 7 shows the distribution of the residual stress near the fracture
surface. The residual stress measured on the fracture surface was
compression. As the depth increased, the compressive residual stress
slightly increased and then gradually diminished. At a certain depth, the
residual stress approached a constant value. The residual stress was cause,
by the local plastic deformation near the crack-tip.
o.5.----~--.--....._-.__-~2.0 1.0
p = 0.40mm
0.4
N
----.. 0.8
1.5
N
>
z 0.3 Z O.Sw
"" E C
1.0 ~
u
'0
"o
-'
05
02
L--~~--~~--~---~O o
10 20
Displacement u (fJm)
Fig. 5. Load versus load point displacement and

acoustic emission difference.
10
~0
Q.
~
8
Co.
:.::
;;
:.::
..
tf
6
Ci"
>
..
In
In
I:
.c / I'( p (mm)
4
'"
/
0 0
2"
/
()
.. I
/ 0.10
t> 0.15
•
I
I
~U 2 I
I 0.25
a I l::. 0.40
tt I 0 0.50
I
I
I
I
0
0 0.2 0.4 0.6 0.8
Square root of notch radius .fjf (Iffiiii)
Fig. 6. Relation between fracture toughness value

and square root of notch-tip radius.
50r------.-------r------,-------r-----~
0
Q.
~
~
In
In
~
iii -100 ""-
0
p(mm)
a
C
t> 0.15
"
.. •
u
iii -150 0.25
a:
0 0.50
-200
0 10 20 30 40 50
Depth from fracture surface y (fJm)
Fig. 7. Residual stress distribution near fracture surface.
Plastic Zone Size
The plastic zone size, Wy , can be defined as the depth where the
residual stress approaches zero. In Fig. 8, the depth was plotted against
the toughness divided by the bending strength aBo The value of Wy was
proportional to the square of Kp/aB' i.e.
(3)
where a 0.067. According to our previous studies 1 - S the a value was

0.048 for alumina ceramics and 0.12 ~ 0.15 for metallic materials.
Equation (3) was extremely important for determining the fracture toughness
of silicon nitride ceramics from the X-ray measurement of the residual
stress near the fracture surface.
In Table 2, the values of a obtained in a similar way for the fracture

toughness tests are summarized. The a value for this test is smaller than
that for the fracture toughness test of TiC-Cr3C2 ceramic composite. S
40
E
:1
20
3'"
..
~
0.
..
"0
c
0
10 ~ p(mm}
N
0 0
u
V;
() 010
a::" t) 015
5
•
t:.
o 25
o 40
0 050
02 0.5 10
Kpl crB ( Imffi" )
Fig. 8. Relation between plastic zone depth and stress

intensity factor divided by bending strength.
Table 2. Values of a[= Wy /(KP/cry)2] and yield stress in the plastic zone.
Bending Bending
strength strength
a in plastic zone
a H (MPa) a H • (MPa)
Si, N. 399 0.067 597
TiC-Cr,C 2 689 0_ 1 08 812
Al 2 O, 263 0.048 465
.Si3N4
.. TiC- Cr3CZ
a 1500 o
Q. • Alz03
~ o Ductile cast iron
"t) o Quenched-and-
.c:
0
tempered steel
t:. Normalized steel
N
1000
.~
111
0
a.
c:
111
111 ay'=- 5396 .15130'y
~ 500
iii
'0
Q;
>
o~--~----~----~----~--~
o 500 1000
Monotonic yield stress cry (MPa)
Fig. 9. Yield stress determined from plastic zone size.
Levy et al. 6 derived a = 0.15 on the basis of the elastic-plastic finite-

element method for elastic perfectly plastic material. The a value
different from 0.15 is now assumed to be caused by the difference of the
yield stress in the plastic zone from that in simple tension test.
The yield stress in the plastic zone Oy~ is evaluated from the following
equation:
Wy = 0.15 ( Kp/oy~ )2 a ( Kp/oy )2 (4)

~ 1,1
Oy = ( O. 15/ a) • Oy (5)
The calculated values of Oy~ are given in Table 2, where Oy is taken as

bending strength 0B.
From the previously published data of a measured for the fracture

surface of various steels l - 4 and ceramics 5 the value of oy~ was calculated
by using equation (5) and correlated to Oy in Fig. 9. The following linear
relation is obtained between Oy~ and Oy:
Oy~= -53.96 + 1.5130y (6)
The result of the present study agrees with this equation. From equations
(5) and (6), the a value is given as a function of Oy.
a = 0.15 [ Oy/( -53.96 + 1.5l30y ) ]2 (7)
In the analysis of failure accidents, the apparent stress intensity factor

can be determined from the measurement of the plastic zone by using a
obtained from equation (7).
326 v. X-RAY STRESS ANALYSIS
CONCLUSION
The main results obtained in the present study are summarized as

follows:
(1) The fracture toughness was proportional to the square root of the
notch-tip radius for the cases of notch-root radius larger than 0.10 mm.
For the cases of sharper notches and pre-cracks, the fracture toughness
was nearly constant.
(2) The residual stress in the immediate vicinity of the fracture

surface was compression. The compressive residual stress slightly increased
and then gradually diminished; at a certain depth, the residual stress
became almost constant.
(3) The plastic zone size wy was determined on the basis of the
distribution of the residual stress beneath the fracture surface.
The size was related to the fracture toughness value Kp and the bending
strength 0B through
(4) The published data on the a value determined for various kinds of
steel and ceramics are related to yield stress 0y by the following function:
a = 0.15 [ oy/( -53.96 + 1.5130y ) ]2
where 0y is taken as the bending strength 0B'
REFERENCES
1. Z. Yaj ima , Y. Hirose, and K. Tanaka,"X-Ray Fractography of Fatigue

Fracture of Low-Alloy Steel in Air and in 3.5% NaCl Solution,"
J. Soci. Mat. Sci. Jap., 35:725 (1986).
2. Z. Yajima, Y. Simazu, K. Ishikawa, Y. Hirose, and K. Tanaka,"X-Ray
Fractographic Study on Fracture Surface Made by Fatigue Crack
Propagation Tests of Ductile Cast Iron," J. Jap. Soc. Strength and
Fracture of Materials, 22.121 (1988).
3. Y. Hirose, Z. Yajima, and K. Tanaka,"X-Ray Fractographic Approach to
Fracture Toughness of AISI 4340 Steel," Advances in X-Ray Analysis,
28:289 (1985).
4. Y. Hirose, and K. Tanaka , "X-Ray Measurement of Residual Stress Near
Fatigue Fracture Surfaces of High Strength Steel,:
Advances in X-Ray Analysis, 29:265 (1986).
5. Z. Yajima, Y. Hirose, Y. Nanayama, and K.Tanaka,"X-Ray Fractographic
Study on Fracture Surface of Metal Ceramics Composite," Proc. of The
26th Symposium on X-Ray Studies on Mechanical Behavior of Materials,
The Society of Materials Science, Japan, 116 (1989).
6. N. Levy, P. V. Marcal, W. J. Ostengren, and J. R. Rice,"Small Scale
Yielding Near A Crack in Plane Strain: A Finite Element Analysis,"
Int. J. Frac., 7:143 (1971).
X-RAY RESIDUAL STRESS MEASUREMENT ON FRACTURE SURFACE OF STRESS
C0RROSION CRACKING
Masaaki Tsuda, Yukio Hirose
Department of Material Science, Kanazawa University

1-1 Marunouchi, Kanazawa 920, Japan
Zenjiro Yajima
Department of Mechanical Engineering, Kanazawa Institute of

Technology, 7-1 Oogigaoka, Nonoichi, Kanazawa 921, Japan
and
Keisuke Tanaka
Department of Engineering Science, Kyoto University

Yoshida-honmachi, Sakyo-ku, Kyoto 606, Japan
INTRODUCTION
X-ray fractography is a new method utilizing the X-ray diffraction

technique to observe the fracture surface for the analysis of the micro-
mechanisms and mechanics of fracture. The X-ray residual stress has been
confirmed to be a particularly useful parameter ~hen studying the fracture
surfaces of high strength steels. l The method has been applied to the
fracture surface of fracture toughness and fatigue specimens. 2 ,3
In the present paper, the distribution of the residual stress beneath the
fracture surface of a high strength steel (AISI 4340) made by stress-corrosion
cracking was measured with the X-ray diffraction technique. Stress-corrosion
cracking tests were conducted by using compact tension specimens in 3.5% NaCl
solution environment at various temperature between 277 and 343K. Based on
the results, the mechanisms of stress-corrosion cracking were discussed.
The material used for experiments is a high-strength low-alloy steel

AISI 4340. The chemical composition (wt%) of the material was as follows:
0.39C, 0.74Mn, 1.38Ni, 0.78Cr, 0.23Mo. Compact tension specimens were
machined, and the specimens with plate thickness B=5.5 mm and sharp V notch-
tip were used for crack growth experiments. The specimen dimensions were
reported in a previous paper.4 The specimens were first normaiized at 1153K
for 1 hour. After being austenized at 1123K for 1 hour, they were quenched
into oil and then tempered at 473K for 2 hours. The yield and tensile
strength were 1530 MPa and 1880 MPa, respectively. The prior austenite grain
size of the material was about 12~m.

Plenum Press, New York. 1990
Polyethylene ball
Environmental solution
J Water bath
P
Fig.1 Experimental apparatus.
The stress-corrosion cracking tests were conducted on a simply

constructed lever-arm tensile machine in which it was possible to keep the
stress constant or the stress-intensity factor K constant during testing,by
changing the load. The environment was a circulating 3.5% NaCl solution and
the temperature of the solution was at several temperatures between 277 and
343K. Figure 1 shows the experimental apparatus. Hot water was circulated
between water bath and chamber by magnet pump.
The distribution of residual stress in the stress-corrosion fracture

surface was measured by the X-ray diffraction technique. The standard sin 2 ¥
method was adopted to obtain the residual stress by using a parallel beam of
Cr-K~ X-rays as described in a previous paper. 4 • 6 The area irradiated by
X-rays was of 1 mm width and 4 mm length at the middle of the thickness of
fracture surfaces of the specimens as indicated in Fig.2. To obtain the
subsurface distribution of the residual stress, the X-ray stress measurement
was repeated after removing thin layers successively by electropolishing.
The conditions of X-ray observation are given in Table 1.
Table 2 summarizes the permeation test of hydrogen in the present

material. As the temperature increased, the diffusion coefficient got larger.
The solubility decreased with increasing temperature above 293K.
X-ray irradiated area

Table 1 X-ray diffraction conditions
Characteristic X-ray Cr-K a
Filter V
Tube vol tage 30 kV
Tube current 30 rnA
X-ray fixed time 90 sec

Fig.2 Schematic illustration of I rrad i a ted area 4xl mrn 2
X-ray irradiated area on
Detee tor PSPC
the Fracture Surface.
M. TSUDA ET AL. 329
Table 2 Hydrogen content and diffusion coefficient
Temperature Diffusion coefficient Solubility

T (K) D (,10- 7 cm 2/sec ) Co (p.p.m.)
277 1.05 < 0.001

293 4.44 0.44
313 9.32 014
323 17.8 0016
343 310 0003
EXPERIMENTAL RESULTS AND DISCUSSION
Figure 3 shows the relation between the crack growth rate and the stress
intensity factor. The value of KISCC is the value at which no crack growth
could be detected after 240 hr. The value of KSC is the value of K above
which the crack becomes unstable. The curves are divided into three regions:
Region I is near KISCC' Region ill is near KSC' and Region II lies between
these two. The crack growth curves can be characterized in terms of the
following four quantities: (1) KISCC' (2) KSC' (3) KII is in the middle of
Region II, (4) crack growth rate is (da/ dt) II corresponding to KII •
The change of the crack growth rate with temperature at several K values
is shown in Fig.4, together with the diffusivity change with temperature. At
each stress intensity factor, the crack growth rate decreases linearly with
the inverse of temperature. The diffusivity shows a similar change with
temperature.
101 in 15·/.NaCI solution
C
E
E
S
U 10°
u
a
!:
2
:5
~
0
~ 10- 1 (> 277 K
-'"
u
v 283 K
2 0 293 K
u
b. 313 K
0 323 K
~ 343 K
o 20 40 60
Stress Intet1sity factor K (MPav'iTi)
Fig.3 Relation between stress intensity factor

and crack growth rate.
u
c: a.
10 2
~
~
E 10° N
E
E u
E
~
-
-0
0
"0
~
0
~
a. C
a.-
~ 10-' 10' ~
.r; *.
a.
~ 0
0 0 K=124MPav'ffi u
0, c:
.><
6 K=186MPaVm ~
u Ul
~ 0 K =24 8MPav'ffi ::J
U
oMPav'ffi \ '-:
•
'V K=31 0
10- 2
• 0 lO v
28 30 32 34 36
1 IT (xlO- 3K-')
Fig.4 Relation between temperature and crack growth rate.
(
~--
50llm
(a) K = 24 . 8 MPaliD T = 277 K
50 101m
• 1-------1
•
(b) K = 24 .8 MPafm T = 313 K
Fig.S Macroscopic features of stress-corrosion crack profile.

M. TSUDA ET AL. 331
40
E
::l...
3"'
30
/
M
.r:
J;V.:==~
1/
u
20
~
CJ1
c "-ij/
.r:
u
c
0
<>
~
co 10 277 K
0 293 K
'"
0
313
323
K
K
o '* 343
L - J -_ _ _ _ _ _- L_ _ _ _ _ _- L_ _ _ _ _ _
K
~
10 20 30 40
Stress Intensity factor K (MPalm)
Fig.6 Relation between stress intensity ·factor

and micro-branching width.
Figure 5 presents examples of micrographs of crac~s. The main crack is

accompanied by abundant microbranches. The amount of micro-branching is
dependent on the test temperature. The width of branching is measured from
micrographs. Figure 6 shows the variation of the branching width with K value
for each temperature. The width takes the maximum value at above the middle
of Regionrr • The maximum branching width was observed at 323K and the
maximum value at 277K.
Figures 7 and 8 show the distribution of the residual stress beneath

fracture surfaces. The residual stresses measured on the fracture surface
313 K
300 0 K = 12.4 MPa,(ril

a
"- to. K = 18.6 M Pa,(ril
~
0 K = 24.8 M Pa,(ril
'V K= 310 MPa,(ril
~ 200
'"
"'"
100
"'"
0:: 0
o 10 20 30 40 50
Depth from fracture surface ( I'm
Fig.7 Residual stress distribution beneath fracture surface.

K =18.6 MParm
300 <> 277 K
o 293 K
6. 313 K
o 323 K
~ 200 tr 343 K
'"''""
o 10 20 30
Depth from fracture surface (I'm)
Fig.8 Residual stress distribution beneath fracture surface.
were all tensions. The residual stress in the vicinity of a fracture

surface depends on the test temperature. The residual stress increases
gradually and then decreases with increasing distance from the surface. The
peak tensile stress in the subsurface increases with increasing K value and
the test temperature.
The plastic zone size, wY' is defined as the distance at which the
residual stress approaches the initial value. Figure 9 shows the relation
between plastic zone size, wY' and the stress intensity factor K divided by
the yield strength, Oy. It is noted that the plastic zone size, wY' is
proportional to the square of K/oy. The relation between the plastic zone
size, wY' and the stress intensity factor K can be approximated by the
100
[7
1 /
E
:l.
50
2
Q
/~/
/il
>-
3 ~ 0
s=
20
Q
/J
Q.
'"
,1/
"0
'"
c
0
10
N
a 0 277 K
U1 5 / 0 293 K
c
Cl. 6. 313K
o
2
* 323 K
343 K
0.2 0.5 10
K/CJ,. (rmm)
Fig.9 Relation between plastic zone depth and stress intensity factor
divided by yield strength.
M. TSUDA ET AL. 333
150 10'
a 10 3 E
a.
a.
10 2 0
U
1.00
10'
c:
~
10° c:
0
Co u
050 10-' c:
III
Ol
0
10- 2 -0>-
I
10-3
o
280 300 320 340
Tempera t ure T (K)
Fig.l0 Relation between the ~-value, Co and test temperature.
following fracture mechanics equation: 7
where Oy is the yield strength. The I). value is dependent on the temperature.
The proportional constant I). in eqn (1) was calculated to be 0.15 by Levy
etal. 8 with a finite element method for elastic perfectly plastic material.
The experimental value obtained in the present study was smaller than 0.15 and
varied depending on the temperature. Two factors can be responsible for the
decrease of ~ from 0.15. The one is the weakening of the stress concentration
of a crack due to micro-branching, and the other is the hardening of the
material within the plastic zone. Figure 10 shows the change of ~ with test
temperature. The ~ value was minimum at 293K and maximum at 343K.
The change of solubility is also shown in Fig.l0. The ~ value is minimum

when Co is maximum. There is an inverse relation between Co and~. The
amount of micro-branching is also related to the ~ value. At 277 and 343K,
the width of micro-branching is small; the ~ value is large. A large amount
of branching may shield the crack tip, reducing the stress concentration and
giving a small value of ~.
CONCLUSION
The results obtained are summarized as follows:
(1) The residual stresses measured on the fracture surface were all
tensions. The residual stress in the vicinity of the fracture surface depends
on the test temperature. The residual stress increases gradually and then
decreases with increasing distance from the surface. The peak tensile stress
in the subsurface increases with increasing K value and the test temperature.
(2) The relation between the plastic zone size, WY' and the stress
intensity factor, K can be approximated by the following fracture mechanics
equation:
W Y = ~ ( K/ 0 y ) 2
where ay is the yield strength. The a value depends on the test temperature.
The a value took minimum at 297K and maximum at 343K.
(3) The change of a value was related to the micro-branching width and
solubility, CO. At 277 and 343K, the width of micro-branching is small, the
a value is large. There is an inverse relation between a and C •
REFERENCES
1. Y.Hirose, K.Tanaka, Z.Yajima and M.Tsuda," Macro-and Microbranching of

Stress Corrosion Cracks in High Strength SNCM8 Steel", J. Sosi. Mat. Sci.
Jap., 31, 510-514(1982).
2. Z.Yajima, M.Tsuda, Y.Hirose and K.Tanaka,"Residual Stresses near SCC
Fracture Surfaces of AISI 4340 Steel", Advances in X-Ray Analysis,
32, 451-458(1989).
3. Y.Hirose, Z.Yajima and K.Tanaka,"X-Ray Examination of Fatigue Fracture
Surfaces of Nodular Cast Iron", Mech. Behaviour of Materials-V,
551-558(1987) •
4. M.Tsuda, Y.Hirose, Z.Yajima and K.Tanaka,"X-Ray Fractography of Stress
Corrosion Cracking in AISI 4340 Steel under Controlled Electrode
Potential", Advances in X-Ray Analysis, 31, 269-276(1988).
5. M.Tsuda, Y.Hirose, Z.Yajima and K.Tanaka,"Residual Stress near SCC
Fracture Surface of AISI 4340 Steel under Controlled Electrode
Potential", J. Soci. Mat. Sci. Jap., 37, 599-605(1988).
6. M.Tsuda, Y.Hirose, Z.Yajima and K.Tanaka,"Load variation Effect on Crack
Growth of Stress Corrosion in High Strength Steel", To be published in
Residual Stresses in Science and Technology, ICRS-2, (1990).
7. Y.Hirose and K.Tanaka,"Nucleation and Growth of Stress Corrosion Cracks
in Notched Plates of High Strength Steels", ICM3, 409-420(1979).
8. N.Levy, P.V.Marcal, W.J.Ostengren and J.R.Rice,"Small Scale Yielding near
A Crack in Plane Strain: A Finite Element Analysis", Int. J. Frac., 7,
143-156(1971) •
TIME-RESOLVED X-RAY STRESS MEASUREMENT DURING CYCLIC LOADING
Shin'ichi Ohya and Shozaburo Ohta
Musashi Institute of Technology

1-28 Tamazutsumi, Setagaya, Tokyo 158, Japan
INTRODUCTION
X-ray stress analysis is widely used in the measurement of residual

stress or stress under static loading. If it is possible to measure actual
stress at any applied stress level during cyclic loading by using x-rays, it
will be of much help in investigating dynamical fatigue behavior such as
crack closure and change of residual stress distribution.
Measuring stress with x-rays during cyclic loading requires a certain

technique to collect diffraction patterns having a proper intensity for a
short period of time. The authors have measured actual stresses at any
applied stress during cyclic loading by using an x-ray stress analyzer that
lets a zero-dimensional detector scan continuously. It was then necessary,
however, to reduce scanning speed of the detector because of the low
intensity of the diffracted x-rays. As a result, such stress measurement
took a long time. This showed that an ordinary x-ray stress analyzer cannot
be put into practical use to investigate dynamical fatigue behavior.
H. E. Gobel had already suggested that a position-sensitive

proportional counter (PSPC) is available to measure the lattice change
during dynamic processes. l Compared with the zero-dimensional detector, the
PSPC has a higher x-ray sensitivity. It may provide stress measurements in
a short period of time during cyclic loading since scanning is not required
when the PSPC is used with the x-ray stress analyzer.
In this study, it is proposed to measure x-ray stress at any applied

stress level during cyclic loading by the time-resolved technique, using the
x-ray stress analyzer with the PSPC. The accuracy of stress obtained by
time-resolved stress measurement is discussed.
THE PRINCIPLE OF TIME-RESOLVED X-RAY STRESS MEASUREMENT
Figure 1 shows the principle for time-resolved measurement of a

diffraction pattern during cyclic loading. The two-dots-dash line in the
figure shows the stress level targeted for measurement. As a rule, if it is
intended to measure actual stress at a certain applied stress level during

o 256(0)
Encoder number n (Time)
Fig.l The principle for time-resolved measurement of

a diffraction pattern during cyclic loading.
cyclic loading, it will be necessary to measure an instantaneous diffraction

pattern at a chosen applied stress level. Actually, however, it is obviously
impossible to collect instantaneous diffracted x-rays. In addition, diffrac-
tion profiles get low in intensity.
It is proposed to obtain a diffraction profile with enough intensity

as follows:
The x-ray beam is constantly irradiating the specimen under cyclic

loading. At time ni shown in Fig. I, the sample gate of a multi-channel
pulse height analyzer (MCA) for the PSPC is opened to start sampling the
diffracted x-rays. When time ne is reached, the sampling is stopped. Data
on diffracted x-rays counted during the sampling time ns is stored in the
memories of the MCA . This process in each cycle of applied stress is
repeated for several cycles to reach a diffraction pattern intensity
sufficient to determine the peak position. By carrying out such diffraction
pattern measurements at several incident angles of the x-ray beam, the
stress may be calculated by sin2~ method .
Amp.
MIll tf- cllannttt

Analyzttr
Diffraction pattttrn
Start
or
CPU
(NEC PC-980IVX)
Fig.2 The block diagram of system for time-resolved stress measurement.

S. OHYA AND S. OHTA 337
INSTRUMENTATION
Figure 2 shows a block diagram of the system for time-resolved stress

measurement. Cyclic stress was applied to the thin steel specimen by using
a four-point bending device; bending displacements were applied to the
specimen by rotating the off-centered circular cam. A single turn of the
cam generated a sine-functional tension stress of a constant amplitude on
the surface of the specimen. The rotary shaft of the cam was connected with
an absolute type rotary encoder for use as an applied stress sensor. Output
signals from the encoder were used to start and stop the sampling of the
diffracted x-rays (ni and ne) as described in Fig. 1.
The x-ray stress analyzer used in the experiment was an iso-inclination

method-based goniometer, and the angle formed by incident Cr x-ray beam and
the normal line to the PSPC was set at 24 0 for steel. A chamber full of
helium gas was placed in front of the PSPC to reduce the absorption by air in
the diffracted x-ray path. The chamber window on the specimen side was
sealed with a Cr KS filter, (vanadium foil). With this chamber installed,
the counting rate of x-rays was improved more than twofold.
The MCA used could be computer controlled for the start and end of
sampling of the diffracted x-rays. The MCA and the rotary encoder were
connected to a personal computer (PC980lVX) to measure time-resolved
diffraction patterns. This computer also handled the x-ray incident angle
settings, LPA correction, determination of peak position and stress
calculation.
DETERMINATION OF OPERATING CONDITIONS
The stress state changes substantially during the fatigue process, so

it was desirable to minimize the number of sampling cycles of diffracted
x-rays required for the time-resolved stress measurement. The number of
sampling cycles necessary for stress measurement depended mainly on such
measuring conditions as number of x-ray incident angles, peak counts of
diffraction profiles and sampling time of diffracted x-rays per applied
stress cycle. Of these, the number of x-ray incident angles used in the
current experiment was four.
155.10
1
tp' = o'
t>
~ ~ ~.
~ 155.05
!!Ff:]]~~~
• ~_ ,1(.1,. t ~:
., ....
f . 'J.6-;-
0
.a
.iI:,
I 00
~
~ 0
!
OJ
~<.J 156.00
o •
1...
...Ci"
~ t.
0..
J '--
155.950 1024 2048 3072
Peak counts of diffraction profile (counts)
Fig.3 Relation between diffraction angle and

peak counts of diffraction profile.
As the peak counts in a diffraction pattern increased, statistical

fluctuation in the peak position of the pattern was reduced while the
sampling cycles necessary for one measurement obviously increased. We
discuss here what diffraction pattern peak counts were suitable for the
present measurement.
Figure 3 shows the peak positions in the diffraction patterns as

measured by changing the peak counts for the same specimen. When the peak
counts were more than about 500 counts, statistical fluctuation in peak
position was almost constant and below 0.05 0 • If the peak counts were
less than 500 counts, the scattering of peak position greatly increased as
peak counts decreased. Accordingly, the collection of diffraction patterns
for time-resolved stress measurement was carried out by using a fixed peak
count method of 512 counts for any x-ray incident angle, keeping irregular
peak positions and sampling cycles of diffracted x-rays in mind.
EXPERIMENT
Measurement of Actual Stress during Cyclic Loading
The specimen used in this experiment was a low carbon steel with high
tensile strength. The yield strength was 853 MPa while the tensile strength
was 902 MPa. The specimen was 18 mm in width, 120 mm in length, and 1 mm in
thickness. The specimen had little initial residual stress.
The specimen was subjected to cyclic stress at the frequency of 2 Hz,

and the actual stresses at various applied stress levels during cyclic
loading were measured by the time-resolved technique. The area irradiated
by x-rays was rectangular: 1.5 mm x 10 mm. For comparison with stress
measured by the time-resolved method, an ordinary x-ray stress measurement
under static loading with the cam rotation of the bending device stopped was
also carried out.
Table 1 shows examples of actual stresses measured and confidence

limits at an applied stress of 180 MPa. When the sampling time was 20 ms or
30 ms, the stress and 95% confidence limit were almost the same as those in
Table 1 The examples of stress 2Hz

measured and confidence limits o
at applied stress of 180MPa. 300 "..-II_
," '\0
Sampling Stress Sampling 4 ~
time (ms) (MPa) cycles /
" 0 \
~ 200 '.
,£"
.... \~
4 215 ± 42* 8603 V)
8 143 ± 28* 4258

,
/0 \\
20 174 ± 15* 1685
100 ,i 0 Bms ~
" • 20ms ~'\
30 183 ± 16* ll08

~/
01 ~
'" static
.. . .;-. A~Plied stress
0
r
-·t
o 64 128 192 255

Ordinary 180 ± 12* -- Encoder number np
Fig.4 Actual stresses at various
*: 95% confidence limit applied stress level.
S. OHYA AND S. OHT A 339
the ordinary measurement. When sampling time was less than 8 ms, the stress
value did not agree with that of the ordinary measurement and the confidence
limit was more than twice as large. In addition the sampling cycles
necessary for one stress measurement increased in inverse proportion to the
decreases of sampling time.
Figure 4 shows the results of actual stresses measured at various

applied stresses. The two-dots-dash line in the figure indicates applied
stress measured with a strain gauge stuck to the specimen. Triangle marks
show stresses measured by ordinary measurement under static loading.
The stresses measured at a sampling time of 20 ms are almost on the

applied stress curve provided by the strain gauge and agree with those
measured under static loading. The stresses measured at sampling time of 8
ms, however, do not agree with the curve. When the sampling time was 8 ms,
a lot of scattering of the diffraction angle at any incident angle of x-ray
beam was observed, resulting in poor linearity of sin2~ diagrams. This did
not mean that such stresses were generated during cyclic loading, but that
stresses measured did not agree with the applied stress curve because of
errors in stress measurement.
Ideally, it is desirable to mlnlmlze sampling time for the measuring

of instantaneous stress during cyclic loading because stresses obtained from
such time-resolved measurement are the average value over the sampling
time. But as sampling time decreases, the sampling cycles and scatter of
stresses measured increase as shown in Table 1 and Fig. 4.
It was made obvious experimentally that it is not desirable to

minimize sampling time too much in time-resolved stress measurement.
In the meantime, measuring with sampling time of 20 ms required

sampling cycles of about 1700 cycles for stress measurement. With the x-ray
stress analyzer and the PSPC system, the sampling cycles were reduced to
one-fifth of those required with an x-ray analyzer that scanned a
scintillation counter continuously, and the accuracy of stress measured was
improved by using PSPC system.
400 Maximum (260MPa)

(j--Q--
Minimum (80MPd)
200 IIL-_~II_ _ :&
ti
~
"" 0
<J)
<J)
.......
Q)
() 2Hz
V)
(J 8Hz
-200 o Static
• Residual Stress
Width of specimen •
-9 o 9
Distance from center (mm)
Fig.5 Stress distributions at maximum and minimum applied stress.
Stress Distribution during Cyclic Loading
We used the time-resolved stress measurement method to observe stress

distribution behavior during cyclic loading. The specimen used was the same
in shape as mentioned above, except that the specimen was water-quenched
from 923K to generate a residual stress distribution. The distribution of
initial residual stress along the specimen width is shown in Fig. 5 by the
solid points. The cyclic frequencies of applied stresses applied were 2 Hz
and 8 Hz.
Figure 5 shows the stress distributions at maximum applied stress (260

MPa) and minimum applied stress (80 MPa) during cyclic loading. The stress
distributions are the same in shape as the initial residual stresses. They
are just the algebraic sum of the residual stress distribution and each
applied stress. There is no difference in the distributions between cyclic
frequencies of 2 Hz and 8 Hz, and these distributions are the same as that
obtained under static loading. Accordingly, it was noted that the cyclic
frequency of the applied stress did not affect stress distribution under
cyclic loading.
CONCLUSION
It was proposed to use a time-resolved method to measure the actual

stress at any applied stress during cyclic loading by using an x-ray stress
analyzer with a PSPC. With this method the actual stress and stress
distribution during cyclic loading were also measured.
The results obtained are as follows:
1) The accuracy of stress measured by using the time-resolved

measurement is equal to that of ordinary measurement in which diffracted
x-rays are continuously collected, but if the sampling time per applied
stress cycle is made too short, the confidence limit of the stress measured
is increased.
2) It was experimentally confirmed that actual stress and stress

distribution during cyclic loading were the algebraic sum of the residual
stress distribution and the applied stress in the same manner as under
static loading.
REFERENCE
1. H. E. Gobel, Advances in X-Ray Analysis, 24, 187 (1981)

DETERMINATION OF ROLLING CONTACT
STRESS DISTRIBUTION BY X-RAY DIFFRACTION
David L. Milam
Material Science Research
The Timken Company
Canton, Ohio
ABSTRACT
An investigation was conducted of the potential for detection of the
contact stress distribution in tapered roller bearing components made of
carburized steel. Various raceway stress distributions were created by
control of the profile and alignment of the rolling surfaces. Determination'
of residual stress in the rolling direction and peak breadth were made
using a multiple tilt sin~ w technique. The measurements were made at the
surface and at depths below the surface. It was found that the distribution
of residual stress and peak breadth perpendicular to the rolling direction
in the layers below the surface of the inner race correlated highly with
the imposed contact stress distribution. The correlation was less in the
case of the outer race. The residual stress distribution measured on the
surface of the inner race was observed to be inversely proportional to the
contact stress distribution.
INTRODUCTION
Tapered roller bearings consist of four basic components. Shown in
Figure 1 are the cone (inner ring), the cup (outer ring), tapered rollers,
and the cage (roller retainer). Under normal operating conditions, the
cone, cup, and rollers carry the load while the cage separates and retains
the rollers on the cone. For best performance and life of tapered roller
bearings, the cup and cone should be aligned such that their axes are
coincident. The angular deviation from coincidence is the measure of
misalignment. The causes of misalignment include shaft deflection, housing
deformations, and inaccuracies in machining of the shaft or housing.
The contact stress at the surface of an aligned bearing is a maximum
at the middle of the contact width, Figure 2. Subsurface shear stresses are
created by the contact stress distribution at the surface. The maximum
shear stress is the unidirectional shear stress acting on a plane
inclined 45° to the rolling surface, -r45; -r45 is a maximum beneath the
center of contact. A second important shear stress is the orthogonal shear
stress acting simultaneously on planes parallel and perpendicular to the
surface, -rOo The maximum value of -r0 is located below the edge of contact.
The contacts and stress distributions analyzed deviate from the line
contact concept to various degrees, but the general concepts still hold.

~ Rollers
Fig. 1 - The components of a tapered roller bearing.
The subsurface shear stresses alter the microstructure of bearing

components. The development of dark etching areas and white bands in
ball bearings has been described by Swahn et al [1) and by Zwirlein and
Schlicht [2). The appearance of these microstructural features has been
attributed to decomposition of martensite resulting from repeated plastic
deformation. Bush et al [3) and Voskamp et al [4) found that the depth
below the surface to the microstructural alterations is equal to the depth
of the maximum orthogonal stress, .0. At least 10~ stress cycles are
required for development of these features. [3,5)
On the other hand, alterations in the state of residual stress have
been observed in through-hardened bearing steel in as few as ten cycles
under high contact stress. [3,5-6) The minimum contact stress required to
alter the residual stress state has been reported by Muro and Tsushima [5J
as 3,500 MFa and 3,200 MFa by voskamp et al. [4J The depth to peak residual
Po
to ot
- -LOmax +LO max -
Fig. 2 - Subsurface shear stress distribution resulting

from line contact stress distribution.
D. L. MILAM 343
Table 1
Nominal Composition of Bearing Components weight percent
C Mn Si Cr Ni Mo
0.20 1.00 0.25 0.60 0.30 0.13
Table 2
Crown Radii of The Two Groups
The roller bodies of both groups had a crown radius of 175 inches.
Crown
Radius, inches
Group A Cone 25
Group A CUp 47
Group C Cone 280
Group C CUp 100
stress corresponds to the depth of the maximum unidirectional shear stress,

T45. [3,5-7] Because the depth to maximum T45 is proportional to the
contact stress, an estimate of the contact stress can be made by
measurement of the depth to peak residual stress. [2,5]
In addition to a compressive residual stress being generated below the
surface of through-hardened material, it has been found that the half-
height full width, ~, of the (211) diffraction peak is reduced by the
shear stresses.[8] The depth to minimum peak breadth was found to be equal
to the depth of maximum residual stress.
Misalignment causes the contact stress distribution along the roller-
raceway contact to be altered. The maximum contact stress is shifted toward
one end, possibly resulting in stress concentrations at the edge of
contact. Because the contact stress distribution of a highly misaligned
bearing is radically different from that of an aligned bearing, the
distribution across the raceway or roller body of induced residual stress,
decomposition of retained austenite, and decrease in beta should also be
different. Consequently, it should be possible to detect by X-ray
diffraction the existence of misalignment or edge stress concentration in
used tapered roller bearings. This is the objective of the investigation
work summarized here.
PROCEDURE
Bearings made from a carburized low alloy steel were subjected to an
induced misalignment condition. The nominal composition of the material is
shown in Table 1. The outer diameter of the bearing is 65 mm; the bore is
35 mm. A 0.00333 radian misalignment condition was created within a bearing
fatigue test machine by making the end cup and center cup adaptors off-
square. A peak radial stress of 2,570 MFa (assuming line contact) was
imposed on the bearings for 6 x l07revolutions. The lubricant was automatic
transmission fluid maintained at an inlet temperature of 63°C.
There were two treatment groups of bearings in this test, groups A and
C, differing in raceway contour. Group C bearings had a flatter crown on
the cup and cone than did group A, see Table 2.
,,
O+T--------+---------+---------+-~r_~--~
-1000
,,
\
Cd
\
~-2000 \
I
ts
\
\
\ /
/
/
\
,
/
~ -3000 /
\
U .,. ./
A
-4000
-~+---------~------~---------+--------~
1 2 3 4 S
Large Small
End Position on Raceway End
Fig. 3 - Cone-roller contact stress distribution across
the raceways of Group A and Group C cones.
The resultant cone-roller contact stress profiles are shown in Figure

3. These contact stress distributions were calculated using a model that
includes the induced misalignment caused by the housing and that due to
deflection of the shaft. The smaller crown radius of group A accommodated
the misalignment and caused the maximum contact stress to be less in group
A bearings than in group C. Furthermore, the maximum contact stress occurs
nearer the center of the raceway in group A bearings.
The maximum cup-roller contact stress of both groups was less than
that of the cone-roller contact. There was no significant difference in
contact stress distributions across the raceway of the cups.
Residual stress was calculated from X-ray diffraction measurements of
residual strain. Incident chromium radiation was passed through a 2 mm
round collimator prior to diffraction by the martensite (211) planes. The
diffracted beam was detected using a position sensitive detector.
Interplanar spacing was measured at five wangles for the cones (-43°,
-30°, 0°, 30°, and 43°) and six wangles for the cups (0°, 18.4°, 26.6°,
33.2°, 39.2°, and 45.0°). The selection of wangles for the components
differ because of preferred orientation noticed during the characterization
of cups. It has been shown by Marion and Cohen [9] that a closer spacing
of the wangles will reduce the error.
Residual stress was calculated using the s!ope 9f the d versus sin2w
plot and a material stress constant of 5.387 x 101 kPa '. This constant was
determined in our laboratory to be applicable to quenched and tempered
carburized low alloy steel. A two-dimensional residual stress state was
assumed in the present investigation. In the case of the cones, where
positive and negative wangles were used, some W splitting was observed.
This is a result of the induced shear stresses during the rolling contact.
Half height full width (~) of the diffraction peak was measured
electronically at a psi angle of 0°
D. L. MILAM 345
0+---------+---------+---------+---------+
-200 --- ....;::::--=-- -:-~:.-- --:::-- - - - -

--~-:----:::.. . --.. --.. --::::::-..-~=:::.:.. . -.:.::::.;;.-..
. -
......... - .... ............
Depthinmm
.-----. 0.05
- - - 0.10
- - - 0.15
- - 0.20
---- 0.25
- - 0.30
--_.- Surface
-800
......._•.....•...._........ _--_.._--_._-_...._..•.__...._....._--_..._._..._.........
-1000 +---------+---------+---------+---------4-
1 2 3 4 5
Large Small
Fig. 4 - Residual stress measurements of untested cones.
Residual stress and ~ were determined at five positions across the

raceway of the cups and cones. stress was measured in the circumferential
direction. ~ was determined at Wequal to 0° at each of the five positions.
Both tested and untested bearings were characterized.
These measurements were made both on and below the surface. Removal of
material was accomplished by localized electropolishing. No stress relief
correction was made to the subsurface residual stress calculations because
6.7 +---------'---------~---------i---------_I_
6.6
6.5
Depth in mm
bO - _.. Surface
-8 6.4
.-----. 0.05
f
~
6.3
- - - 0.10
- - - 0.15
- - 0.20
~
---- 0.25
~ 6.2 - - 0.30
6.1
6.0
~. . . . . . . . . . . . . ~......
---_.........-........-....... a •••••
-_
..... .....
~............ . . . .
5.9 +---------I--------~---------+---------I-
1 2 3 4 5
Large Small
Fig. 5 - Peak breadth measurements of untested cones.
-BOO -h-----+----+-----+-""7---+ 0
-- __ ..... , Tested
,,,
--
/C
-900 -1000
os
~
~
----- Untested -
-2000 t'"
(I)
tl
~
U
-1100 -3000
-1200 +-----+-----+-----1------+ -4000

1 2 3 4 S
Large Small
Fig. 6 - Surface residual stress measurements
of tested Group A cones.
the adjustment has been found by us to be insignificant at the shallow

depths utilized in this investigation.
RESULTS
The averages of the residual stress measurements made on untested

cones are shown in Figure 4. The residual stress is most compressive at the
surface. This is a result of the grinding operation. The residual stress
state existing below the surface, in the range -140 to -340 MFa, is created
during heat treatment. Both at and below the surface the residual stress is
more compressive at the large end (position 1) than at the small end. This
is attributable to the difference in case/core thickness ratios at the two
ends. Finally, the residual stress existing near the surface (0.05 - 0.10
mm) is more compressive than the residual stress existing at deeper depths
(0.15 - 0.30 mm). The state of residual stress existing in the untested
cups was not significantly different from that of the untested cones.
The average peak breadths, ~, measured on the untested cones and cups
are shown in Figure 5. ~ is minimum at the surface, again the result of the
grinding operation. Below the surface, ~ tends to decrease with depth,
especially at the small end (position 5). There is no significant variation
of ~ across the raceway. This is an indication that the microstructure does
not vary across the raceway.
Observations of the tested bearings showed that the residual stress
distribution across the raceway surface in Group A and Group C cones was
altered by the applied contact stress. The residual stress became more
compressive at the small end than at the large end. This is the reverse of
the situation existing prior to test, see Figures 6 and 7. An inverse
correlation exists between the measured residual stress in the tested
surface and the contact stress distribution. The correlation is greater in
the case of Group C cones, wherein the contact stress was greater.
D.l. MILAM 347
-800 +-----+-----I-----+----r--__+_ 0
-1000
-900
-1100
-4000
-1200 +-----+----+-----1------+ -5000

1 2 3 4 S
Large Small
Fig. 7 - Surface residual stress measurements
of tested Group C cones.
The subsurface residual stress distributions of the cones were also

altered by the contact stress, Figures 8 and 9. The maximum subsurface
compressive residual stress in Group C exists closer to the large end than
is the case in Group A. The contact stress distribution is also shown in
the figures. A good correlation is evident between the shape of the
residual stress distributions and the contact stress distribution at the
surface.
The residual stress distributions determined both on and below the
raceway surfaces of the cups were not significantly different from that of
the untested condition. Only at the small end of the tested cups was there
observed a difference between the tested and untested conditions. The
subsurface residual stress at the small end was approximately 70 MFa more
compressive than that found existing in the untested cups.
The greatest effect of the two different contact stress distributions
on the magnitude of peak breadth was found to be at the raceway surface of
Group C cones, Figures 10 and 11. The peak breadth was observed to have
increased at every position except the large end. The distribution of ~
across the surface of group A cones was altered only at the small end.
In contrast to the large effect of contact stress on the distribution
of ~ at the surface of the group C cones, the subsurface distribution of ~
in group C cones was altered significantly only at the two ends. In group
A cones, the magnitude of subsurface ~ was reduced at positions two and
three for all depths measured. The shape of the subsurface distribution of
a in group A cones is similar to the shape of the contact stress
distribution. This is not the case for group C cones.
The peak breadths measured below the surface of the tested cups were
found to have increased approximately 0.15° at all positions.
-1000
-200
os os Depth in mm
~.,; ~ - 0.05
2000 • ..----- 0.10
'" -300
~
- ~ _ . - 0.15
fIl ~ --- 020
fIl _ _ 0:25
~
u _ ... _ 0.30
~ -3000 ~ --_.._.. Contact
~ u
-400
-4000
-500 +-----+----+-----+-----+
1 2 3 4 5
Large Small
Fig. 8 - Subsurface residual stress measurements
-1000
-200
Depthinmm
~.,;
~
~ - - 0.05
-2000 1i .------ 0.10
15'" 15 _.- 0.15
fIl -300 fIl - - - 0.20
~ t) - - 0.25
::I
:sa -3000 U~o ---- 0.30
............ Contact
'"
Q.)
I:x:
-400
-4000
-500 +-----+----+-----+-----+
1 2 3 4 5
Large Small
Fig. 9 - Subsurface residual stress measurements
D. L. MILAM 349
6.8+-----01-----1-------1-----+
6.7
6.6
" ...
~
....""',\;- DeptbinDUD
--_...... Surface
-- 0.05
---~:. .-----. 0.10
"" _.-
---
--
0.15
0.20
0.25
---- 0.30
6.1
6.0
5.9+-------11------+----+-----+
1 2 3 4 5
Large Small
Fig. 10 - Peak breadth measurements
6.9
6.8
6.7
bO 6.6 Depth in DUD

-8 ............ Surface
- - 0.05
~os 6.5 .-----. 0.10
~ - - - 0.15
CO 6.4 / ........................•.•... - - - 0.20
~ ,'" - - 0.25
~ 6.3
/" ---- 0.30
,/
6.2 -
...............•.•....•...... ...../
.........
~-~
~..--- ....~
6.1
6.0 -t------+------+-----+------+
1 2 3 4 5
Large Small
Fig. 11 - Peak breadth measurements
DISCUSSION
The residual stress distribution across the raceway of the cones, both
on and below the surface, was observed to have been altered by the contact
stress. In the case of the cups, however, there was no significant change
in the state of residual stress (neither on nor below the surface). This
difference in observed residual stress differences is caused by the
difference between the cone - roller and the cup - roller contact stress
distributions. The magnitude of cup - roller contact stress distribution
was less than that of the cone - roller contact.
A contact stress greater than the yield stress is necessary for
plastic deformation and creation of residual stress. It has been reported
that a minimum contact stress of 3,200 MFa is necessary for alteration of
the pre-existing state of residual macros tress in through-hardened bearing
steel.[4] Because the pre-existing residual stress state in carburized
bearing steel is significantly different than that existing in through-
hardened bearing steel, it may be that the minimum threshold contact stress
for alteration of residual stress is different, too.
In the case of the Group A cup - roller contact, the maximum contact
stress is calculated to be 2,800 MFa at position 3. Because there was no
significant alteration of residual stress in the cups of Group A, the
minimum contact stress required for alteration of residual stress is
therefore greater than 2,800 MFa.
It is not possible to estimate the minimum contact stress necessary
for alteration of residual stress from the correlation between residual
stress and contact stress observed in this investigation because the
spatial resolution on the raceway surface is insufficient. The diameter of
the incident beam was nearly equal to the distance between positions. The
diameter of the irradiated area is too large relative to the large slope of
the cone - roller contact stress distribution at position 3 (Figure 3).
There exists a direct correlation between the subsurface residual
stress distributions and the contact stress distributions in both groups of
cones (Figures 8 and 9). The compressive contact stress generated a more
compressive increment to the pre-existing compressive residual stresses
shown in Figure 4. It is believed that the correlation can be improved by
the use of a smaller irradiated area. A 0.5 x 3.0 mm source collimator has
been used in more recent investigations with the long axis aligned in the
circumferential direction of the raceway. The width of this collimator is
one quarter of the diameter of collimator used in the present
investigation. The 3.0 mm length of the slit permits a tolerable intensity
of diffracted beam, but tests with this collimator have not yet been
completed.
There exists an inverse correlation between the residual stress
distribution at the surface and the contact stress distribution (see
Figures 6 and 7). On the area of the raceway where the contact stress was
most compressive, the residual stress became less compressive. The residual
stress became more compressive in the area of the raceway surface where the
contact stress was least compressive. It is suggested that this relation
is a result of accommodation between tension and compression at the
surface.
The correlation between the contact stress distributions and the peak
breadth distributions is not consistent. In the case of Group A cones, the
correlation is good only below the surface. In the case of Group C cones,
the correlation is good only at the surface. This inconsistency is
intriguing and cannot be explained.
D. L. MILAM 351
The alteration of residual stress was relatively greater than the

change observed in peak breadth. Residual stress is calculated from a
measure of the average (211) martensite interplanar spacing. The cone-
roller contact stress was sufficient to cause yielding and, hence, alter
the average interplanar spacing. Peak breadth for this material is
dependent primarily on the size of the martensite laths. A lesser
contributor to peak breadth is the non-uniform microstrain existing in the
laths. plastic deformation can also affect peak breadth but is believed to
be insufficient in the bearing components of this investigation. (A small
unquantifiable amount of untempered martensite, derived from transformation
of retained austenite, was observed). The only mechanism by which peak
breadth could change (in this investigation) is for either the size of the
martensite laths to change or the distribution of microstrain in the laths
to change. The size of the laths could change only by decomposition of
martensite, but the number of stress cycles was insufficient for
decomposition to occur. Alteration of the distribution of microstrains in
the laths is not expected to occur. Thus, there is no operative factor in
this investigation for significant alteration of peak breadth.
The microstructures of the specimens were examined for alteration due
to the repeated plastic strain. No microstructural alterations were found
despite the pronounced alteration of residual stress. This is consistent
with the observation that the change in peak breath was insignificant. Muro
and Tsushima [5] determined that alteration of residual stress occurs very
early in the running of rolling contact fatigue specimens. They found that
alteration of the microstructure occurs after 107 cycles when subjected to a
constant amplitude contact stress of 6,000 MPa. The cones examined in this
investigation were cycled for 6 x 10' revolutions at a maximum contact
stress of 2,750 MPa assuming line contact. (The maximum contact stress
results at a position on the inner race as it rotates about the axis only
if there is a roller on that position when that position is in the line of
the radial force). It may be that microstructural alterations would have
occurred if the cones had been run for a greater number of cycles.
The results of this investigation show that measurement of the
distribution of residual stress by x-ray diffraction can aid in the
detection of stress concentrations on the raceways of tapered roller
bearings provided that the maximum contact stress is sufficient to alter
the pre-existing state of residual stress. Measurement of the distribution
of residual stress on the surface is sufficient. Peak breadth and
microstructural alterations are dependent upon both the magnitude of stress
and the number of stress cycles; therefore, changes in these factors are
not as useful as x-ray measurement of residual stress for detection of
contact stress concentration.
CONCLUSION
The distribution of contact stress across the raceway of a tapered

roller bearing component can be detected by measurement of the residual
stress distribution at the surface by X-ray diffraction provided that the
maximum contact stress is sufficient to alter the pre-existing state of
residual stress. This technique can be used to validate the contact stress
distribution prediction of a model, as was done in this investigation. It
is suggested that this technique could be used in a failure analysis.
ACKNcmLEDGEMENTS
The author wishes to thank M. R. Hoeprich for sharing his knowledge of

bearing mechanics during this work. The author also wishes to thank D. H.
Gang for making the X-ray diffraction measurements. Finally, the author
thanks The Timken Company for permission to present the results of this
work.
REFERENCES
1. H. Swahn, P. C. Becker, and O. Vingsboro: Metal. Trans, A, 7A
(1976) 1099-1110.
2. O. Zwirlein and H. Schlicht: Rolling Contact Fatigue Testing of
Bearing Steels, ASTM 771, J. J. C. Hoo, Ed., Amer. Soc. for
Testing and Materials, 1982, pp 358-379.
3. J. J. Bush, W. L. Grube, and G. A. Robinson: Trans. ASM 54 (1961)
390-412.
4. A. P. Voskamp, R. Osterlund, P. C. Becker, and O. Vingsboro:
Metals Technology 7 (1980) 14-21.
5. H. Muro and N. Tsushima: Wear 15 (1970) 309-330.
6. A. J. Gentile, E. F. Jordan, and A. D. Martin: Trans. AlME 223
(1965) 1085-1093.
7. H. Muro, N. Tsushima, and K. Nunome: Wear 25 (1973) 345-356,
8. H. Schlicht, E. Schreiber, and O. Zwirlein, Ball and Roller
Bearing Engineering, 1987-1, FAG, 14-22.
9. R. H. Marion and J. B. Cohen: Advances in X-Ray Analysis 18
(1975) 466-501.
RESIDUAL STRESS DISTRIBUTION OF CERAMIC-METAL JOINT
Masanori Kurita, Makoto Sato, Ikuo Ihara
Nagaoka University of Technology

Nagaoka, 940-21 Japan
Akira Saito
Hi tachi, Ltd.
Chiyoda-ku, Tokyo, 101 Japan
ABSTRACT
Ceramics are sometimes bonded to ductile metals in order to make up

for their brittle behavior for industrial use. The residual stress will be
induced in ceramics bonded to metals at high temeprature, and it has a
strong influence on the strength of ceramic-metal joints. A silicon nitride
plate was bonded to a carbon steel plate by brazing to a copper sheet
sandwiched between the two materials. The residual stress distribution of
the joint specimen was determined by x-ray diffraction using the Gaussian
curve method. The measured residual stress distribution almost agreed with
that calculated by the three-dimensional thermoelastoplastic stress analysis
using FEM, but differed remarkably from that calculated by the
two-dimensional stress analysis. This is because a stress concentration
occurs at the ceramic-metal interface and the stress distributes three-
dimensionally. The stress ax in the axial direction on the surface of the
specimen takes maximum values at the center and the edge of the interface.
INTRODUCTION
Although ceramics have strong resistance to heat, corrosion and

abrasion, etc., they have a major defect of being brittle. Recently, many
investigations have been carried out in order to correct this defect by
bonding ceramics to ductile metals. 1 - 3 The bonding is usually done at a
high temperature. The difference in the coefficients of thermal expansion
and mechanical properties of both materials will cause residual stress in
the joint in cooling to room temperature, and they have a strong influence
on the strength of the joint.
Some two-dimensional residual stress analyses using the finite

elements method (FEM) have been carried out for cylindrical specimens. 4 5
In general, however, the stress is considered to distribute three-
dimensionally at the ceramic-metal interface except for cylindrical
specimens having an axisymmetrical stress distribution or thin specimens of
plane stress state. Also, since some parameters that may influence the

residual stress are not well defined and cannot ~e taken into account in
calculating the stress. Therefore, it is greatly desired in engineering and
industry to measure the residual stresses in the joints in order to develop
techniques of bonding that do not introduce large residual stress.
Since the x-ray technique for stress measurement can nondestructively

measure the residual stress in a small surface area of polycrystalline
materials, it is considered to be the most appropriate method for measuring
the residual stress at the interface of ceramic-metal joints that have
nonuniform stress distribution. Also, measurements obtained by x-ray
diffraction fluctuate due to counting statistics. Therefore, it is
important to evaluate the measured value with its standard deviation which
represents the magnitude of variability caused by counting statistics.
Fortunately, this standard deviation can be calculated analytically from a
single set of measurements with the fixed-time methods such as the Gaussian
curve method. 6 - 8
The residual stress distribution was determined on the surface of two

brazed silicon nitride-carbon steel joint specimens havin~ different widths,
by x-ray diffraction using the Gaussian curve method. The confidence
intervals of the measured stress values were also calculated analytically in
order to evaluate the reproducibility of the measurements. The measured
stress values were compared with the result by three-dimensional thermo-
elastoplastic stress analysis using FEM.
TEST PROCEDURES
Specimens
A pressureless sintered B-silicon nitride (8 -Si3N4) was bonded to a

structural carbon steel JIS-type S45C (0.45% carbon). An oxygen-free copper
sheet was sandwiched between the silicon nitride and the steel in order to
reduce the residual stress generated in the bonding process due to the
difference in the coefficients of expansion of the 8 -Si3N4 and steel. The
silicon nitride was brazed to the copper at a temperature of 1100 K in
vacuum by using an active brazing alloy (Ag-Cu-Ti alloy).
As shown in Fig. 1, two kinds of specimens, specimens W30 and W10 of

widths of 30 and 10 mm, respectively, were prepared in order to investigate
the effect of specimen width on the residual stress distribution. The
surfaces of the specimens were ground after bonding and lapped by about 10
~m to remove the surface layers work hardened by grinding. However, the
Carbon steel
II
Irradiated area
18 3
0.2 0.2
18
Thickness 3
(mm)
Fig. 1. Specimen.
M. KURITA ET AL. (1) 355
Table 1. Conditions for x-ray stress measurement

of silicon nitride.
Characteristic x-rays Copper Ka
Diffraction plane (323)
Fi Iter Nickel foil
Divergence angle of slit, deg 0.5
Preset ti me, s 24
Step size, deg 0.05
Tube voltage, kV 40
Tube current, mA 25
residual stresses shown later in Figs. 3 and 6 were measured on ground

surfaces in order to compare with the result from the lapped surface.
Residual Stress Measurement by X-Ray Diffraction
The residual stress on the surface of the silicon nitride was measured
by x-ray diffraction with copper Ka radiation, which may have eliminated the
influence of the work hardened surface layer by grinding and lapping because
of the deep penetration of the CuKa radiation. The (323) plane of silicon
nitride, having a diffraction angle of 141.5 0 , was measured by using an
automated x-ray diffractometer developed in our laboratory. 9 The effective
penetration depth that diffracts 90% of the total diffracted x-rays is 55 to
80 ~m for the (323) plane of silicon nitride with copper Ka radiation. The
conditions of x-ray stress measurement are given in Table 1. Both residual
stresses, ax and 0y' in the directions of x and y shown in Fig. 1 were
measured. The x-ray irradiated area was 1 x 3 mm. To measure both stresses
in the same irradiated area, the stresses ax and a were measured by the
iso- and side-inclination methods, respectively. the residual stress of the
silicon nitride adjacent to the bonding interface was measured by delimiting
the x-rays so that the irradiated area adjoined the interface. In both
methods, peak positions were determined by the Gaussian curve method using
the fixed lji method (the lji angle is fixed in determining a peak position);
the stress was determined by the sin 2 lji method where lji angles between the
specimen and diffraction plane normals were chosen as 00 , 24 0 , 35 0 , and 45 0 .
To reduce the measurement time, the background subtraction was omitted in
determining a peak position because it does not affect the stress value in
the Gaussian curve method. 6 , 8 A peak position was determined from x-ray
counts at eight to twelve data points. In calculating the stress, the
stress constant -779 MPa/deg obtained in a previous paperlO was used.
The standard deviation a s which represents the magnitude of

variability in measured stress values ar1s1ng from counting statistics was
calculated from a single set of measurements by using the equation given in
the previous papers. 6 , 8 Measured stress values were shown together with
their 95% confidence intervals, + 1.96 as, in order to evaluate the
reproducibility of the measurements. Stress values measured repetitively by
using the same measuring conditions have been shown to fall within the
intervals. 7
THREE-DIMENSIONAL THERMOELASTOPLASTIC STRESS ANALYSIS BY FEM
Along with the measurement by x-ray diffraction, the residual stress

generated in the bonding process was calculated from three-dimensional
thermoelastoplastic stress analysis by the finite elements method (FEM).
Eight nodal three-dimensional elements were used in FEM. As shown in Fig.
2, the elements were divided finely at the interface of the joint because a
LD
~
zt
~~SbN=4~:::=jl~-;
:OffillllffilllllllR=-=\=1=1:f=1
Steel 1:15,. 02 Cu 20 ,I
Fig. 2. Eight nodal solid elements of Specimen W30 used in FEM.
stress concentration may occur there. The numbers of the elements and nodal
points are 357 and 576, respectively, for Specimen WlO, and 612 and 936 for
Specimen W30. The residual stress was calculated which was generated in
cooling the joints from 923 K, at which the brazing alloy begins to sustain
stress, to 293 K with a decrement of 25 K. In the calculation of the
stress, the silicon nitride was treated as a linear elastic body, and the
steel and copper were treated as elastoplastic bodies, the temperature
dependence of Young's modulus and yield strength being taken into account.
The two-dimensional thermoelastoplastic stress analysis by FEM was also
carried out in order to compare with the three-dimensional analysis.
TEST RESULTS AND DISCUSSIONS
In Figures 3, 4, 5, 8, and 9, shown later, the curves representing

residual stresses calculated by FEM are also shown together with the values
measured by x-rays. The results for Specimen W30 are shown in Figs. 3 to 7,
and those for Specimen WlO are shown in Figs. 8 to 11.
300r---~--~=-------~
Ground Si3N4
8: 200
2
(/)
(/)
<1>
L-
Ui
~ -100
'0
~ -200
a: Measured
3-D FEM
0
•
-300 ~2--D~F~EM~----~--~1
-15 -10 -5 0 5 10 15
Distance y • mm
Fig. 3. Residual stress distributions on the ground surface of

the silicon nitride along the ceramic-metal interface of
Specimen W30.
300
Lapped SiJN4I
~ 200
~
100 ~£~2
V
:J
Ul
Ul i ~~
~ 0
U;
~ -100
!(.- --!/J'~h'<!<
I !----
u
&-200 Measured
cr,
a
cry
1 •
13-0 FEM 1-----
-300
I
-15 -10 -5 0 5 10 15
Distance y, mm
Fig. 4. Residual stress distributions on the lapped surface of
Specimen W30.
Figure 3 shows the residual stress distribution on the ground surface

of the silicon nitride along the region adjacent to the ceramic-metal
interface. In Figs. 3, 4, and 8 showing the residual stress distribution at
the interface, the average of the calculated stress values at the distances
of 0.13, 0.34 and 0.66 mm from the interface are shown for comparison with
the measured value which is also an average in the irradiated area of 1 x 3
mm. As can be seen from Fig. 3, the stress ax has its extreme tensile
stress values at the center and the edge of the specimen.
On the other hand, all the stresses a y are compressive and are lower
at the center and at both ends. The measured stress values approximately
agree with the values calculated from the three-dimensional analysis by FEM.
However, the stress values calculated by using the two-dimensional analysis
by FEM, assuming a plane stress state, do not agree with the measured stress
values. This is because the stress distributes three-dimensionally at the
interface, as will be shown later, and a plane stress state cannot be
assumed even in the specimen of thickness of 3 mm. The stress concentration
appearing in the calculated stress ax at the interface on both sides of the
specimen does not appear in the measurements because the measured stress
value was an average for the irradiated area of 1 x 3 mm.
Figure 4 also shows the residual stress distribution in the silicon

nitride at the interface; the surface of the specimen was lapped by 10 ~m
after grinding. The stress distribution calculated by the three-dimensional
stress FEM analysis is also shown in Fig. 4. The result of Fig. 4 is
similar to that of Fig. 3, although the stress ax is slightly smaller. This
shows that the use of copper Ka radiation having deep penetration depth
permits measurement of the residual stress without suffering strong effects
from the work-hardened surface layer. The curvature and ~ split in the
sin2~ diagram due to steep stress gradients and shear stresses in the
surface layer of the specimen were not observed in the measurement of the
ground and lapped surfaces in Figs. 3 and 4. The compressive residual
stresses a y shown in Figs. 3 and 4 might be attributed to the contraction of
the metal in the y direction being larger than that of the silicon nitride
in the cooling process due to the larger coefficient of expansion of the
metal.
Figure 5 shows the contour lines of the stress at room temperature on

the surface of Specimen W30 which were calculated by the three-dimensional
FEM. As shown in Fig. 5(a), the stress ax has the maximum tensile values at
Steel CU Si3N4 Stress ax. MPa

Yt 20
15 -160-
-120
-80
0
E
E
10 -20
» -40-
<!J
u
e
<1l
Ul -20-
0 5
x
0 , ~
0 120 80 40
(a) Distribution of stress ax
Steel Cu Si3N4 Stress O'y. MPa
Yt
15 O~
40-
80 -
120
E 160-
E 200-
10 240-
» 0
<!J 280
u
e 300-
<1l
Ul
i:5 5 320-
x
0 0
~
I I I I I I I I I I I I I
0 5 10 15 20
Distance x. mm
(b) Distribution of stress a y
Fig. 5. Contour lines of the residual stresses on the surface of

Specilen W30.
the interface at the center, (y=o) , and edge of the specimen. At the
distance of about 10 mm in the y direction from the center, the sign/ of the
stress Ox changes and the stress 0y takes the maximum compressive value, as
shown in Fig. 5(a) and (b).
Figure 6 shows the residual stress distribution along the center line
C (x-axis) on the surface of Specimen W'30. The calculated residual stress
Ox on the surface of the silicon nitride reaches a maximum value at a short
distance from the interface, and decreases rapidly with increasing distance
from the interface. The stress 0y takes small compressive value and varies
gently along the x-axis. The residual stresses Ox and 0y calculated from
the three-dimensional FEM, shown by the two lines, approximately agree with
the measured values. However, some measured Ox values do not agree well
with the calculated stress values. This is considered to be attributed to
Ground Si3N4 Ground Si3N4

300 cr, cry
8!. Measured 0 I •
~ 200 Q 13-0 FEMI-- I -----
100 \QQQOQQ
III
III
~ 0 ~--"
iii !_U_!_!~"!!---·r --,
'iii
:l
-100
'U _f-- Steel
-200
~ Cu~ -Cu
-300 :-_~_~_--=--_~-"---:'__.l-_-'::-_-:'.
-20 -15 -10 -5 0 5 10 15 20
Distance x, mm
Hg.6. Residual stress distributions along the center line of
Specilen W30.
the effect of the work-hardened surface layer, the size of the irradiated
area in the measurement by x-rays, the uncertainty of the elastic constants
and yield stress at high temperature, and errors accumulated in each
temperature decrement in calculating the residual stress by FEM.
Figure 7 gives the contour lines of stress in the cross section

through the center line of Specimen W30. The stress, especially the stress
ox' changes rapidly with depth at the interface. Therefore, the actual
stress distribution of the joints cannot be obtained by the two-dimensional
stress analysis because stress concentration occurs at the interface and the
stress distributes three-dimensionally as shown in Fig. 7.
Next, the stress distributions of the lapped Specimen WlO having a

width of 10 mm are given in Fig. 8 to Fig. 11. Figs. 8 and 9 show the
residual stress distributions on the surfaces of the silicon nitride along
the interface and the center line C, respectively. The stresses Ox and 0y
of specimen WlO decrease more rapidly than those of Specimen W30 with
E
E
- zt Stress O-x. MPa
N
2l 0 .-49 120 80 4.0 20 10 0
~ ~t?t22\ I I
QI
u
c 11-1
'"
iii
(5 Steel Cu Si3N4
Stresso-y. MPa
.:.- -'-
E
E Steel Cu Si3N4
N
2 '~~60 I
1 l 360 - =~
-40 -20 -10 0
I
QI
u
c 1 1 12
'(5" o
iii
0
Z.OO -80 -60
'
I I I I I I I I I I I I I I
0 5 10 15 20
Distance x, mm
Fig. 8. Residual stress distributions on the lapped surface of

Specimen 110.
.
300
Lapped SbN4
cr. cr
200 Measured
3-D FEM
0
Ul Q
Ul
100 5)
...
<l1 Q Q
iii
-4 -2 0 2 4
Distance y , mm
Fig. 7. Contour I ines of the residual stresses in the cross
section through the center line of Spesimen W30.
300
Lapped Si3N4
~ 200
~ Measured 0 •
/
3=-DXEM - -
Ul 100
Ul
~
U; 0
"iii
.g -100
Ul
8: -200 Steel
Cu
-300
0 5 10 15 20
Distance x, mm
Fig. 9. Residual stress distributions along the center line of
Specimen WlO.
Steel Cu Si3Nt; Stress O'x. MPa

y
E 20
E
:>.
5C~1
-80
-40
<l1
u -20 0
C
rt! X
U;
i:5
o 0
40 20
-7

Cu Stress Oy. MPa
5
Si3Nt.
E
E
:>.
<l1
u
c
f 40-
80-
100
rt! X
U; 0 -;>-
i:5
I I I I I I I I I I I I I I I I I I I I
0 5 10 15 20
Distance x, mm
Fig. 10. Contour lines of the residual stresses on the surface of
$pecilen WlO.
E
E t Stress O'x. MPa
2l
Z
N
o -40\ 40 0
1-1
I /
(l)
~ 40~~
u
C
<U \
iii
o Steel Cu Si3N4
(a) Distribution of stress a x
E Stress O'y. MPa

E
N 2 Zt -120 -40 0
(l)
u
c
<U
iii
1[ "t,fli\
o 0
180 -80
II i
I I
l-r
0 Steel Cu Si3N4
I I I I I I I I I I I I I I I I
0 5 10 15 20
Distance x. mm
Fig. 11. Contour I ines of the residual stresses in the cross

section through the center line of Spesimen WID.
increasing distance from the interface. The measured values agree

approximately with the values calculated from the three-dimensional stress
analysis using FEM.
Figures 10 and 11 show the contour lines of the stress on the surface
and in the cross section through the center line C for Specimen WIO,
respectively. The stress values in Figs. 10 and 11 are slightly smaller than
those for Specimen W30 that has a larger width (as seen in Figs. 5 and 7),
and the stress concentrates in a narrower region near the interface, showing
the effect of specimen width on the residual stress distribution.
CONCLUSIONS
The residual stress distribution on the surface of a silicon nitride

block bonded to a carbon steel block with a copper sheet inserted between
them was determined by x-ray diffraction using the Gaussian curve method.
Two kinds of specimens, W30 and WIO, having widths of 30 and 10 mm,
respectively, were used in order to investigate the effect of a specimen
width on the residual stress generated in the bonding process. The measured
values were compared with the results calculated from the three-dimensional
thermoelastoplastic stress analysis by FEM. The main conclusions are as
follows:
(1) The residual stress distribution measured by x-ray diffraction
almost agreed with that calculated by the three-dimensional stress analysis
using FEM, but deviates remarkably from that calculated by the two-
dimensional stress analysis. This is because stress concentration occurs at
the ceramic-metal interface and the stress distributes three-dimensionally.
Therefore, the three-dimensional stress analysis is necessary for
calculating the residual stress around the interface except for specimens
having an axisymmetrical stress distribution or a plane-stress state.
(2) The stress Ox on the surface of the specimen reaches maximum
tensile values at the interface at the center and the edge of the specimen.
(3) The residual stresses of WIO, having a width of 10 mm, reach
smaller values than those of Specimen W30, having a width of 30 mm, and the
stress concentrates in a narrower region around the interface.
ACKNOWLEDGMENTS
This study was supported by research grants from the Ministry of

Education, Japan. The specimens were prepared by Dr. S. Tanaka, Toshiba
Co., and provided by the Committee for Testing and Evaluation of Joined New
Materials, Japanese Welding Society.
REFERENCES
1. S. Morozumi, M. Endo and M. Kikuchi, Journal of Materials Science,

20 (1985), pp. 3976-3982.
2. J. T. Klomp, "Fundamentals of Diffusing Bonding, ed. Y. Ishida,"
Elsevier (1987), pp. 3-24.
3. M. G. Nicholas, "Fundamentals of Diffusion Bonding, ed. Y. Ishida,"
Elsevier (1987), pp. 25-41.
4. B. T. J. Stoop and G. den Ouden, "Joining Ceramics, Glass and Metal,
ed. W. Kraft," Informationsgesellshaft-Verlag (1989), pp. 235-242.
5. K. J. Ferenc and K. Tomaszewski, "Joining Ceramics, Glass and Metal,
ed. W. Kraft," Informationsgesellshaft-Verlag (1989), pp. 317-324.
6. M. Kurita, Journal of Testing and Evaluation, Vol. 9 No.5 (1981),
pp. 285-291.
7. M. Kurita, Journal of Testing and Evaluation, Vol. II, No.2 (1983),
pp. 143-149.
8. M. Kurita, Advances in X-Ray Analysis, Vol. 32 (1989), pp. 375-386.
9. M. Kurita, K. Sakiyama, H. Sakai, T. Yada and M. Miyagawa,
Transactions of Japan Society of Mechanical Engineers, Vol. 54,
No. 500 (1988), pp. 854-860 [in Japanese].
10. M. Kurita, I. Ihara and N. Ono, Advances in X-Ray Analysis, Vol. 32
(1989), pp. 455-466.
DIFFRACTION PLANE DEPENDENCE OF X-RAY ELASTIC CONSTANTS OF ALUMINA
Masanori Kur ita, Ikuo Ihara

Nagaoka University of Technology
Nagaoka, 940-21 Japan
Akira Saito
Hi tach i. Ltd.
Chiyoda-ku, Tokyo, 101 Japan
ABSTRACT
The 95% confidence limits of the x-ray elastic and stress constants
of a -a I um i na were determi ned from seven kinds of diffract ion planes by
the Gaussian curve method in order to investigate the diffraction plane
dependence of the constants. No difference in the elastic constants larger
than their 95% confidence intervals was observed for most diffraction
planes. Also, the measured elastic constants for most planes were closer
to the values calculated from the Voigt model than those from the Reuss
model. Since the diffraction line of the (410) plane measured with cobalt Ka
radiation by using an automated x-ray stress analyzer locates at the highest
diffraction angle of 168.4·, the use of this plane will allow the most
accurate stress measurement. Also, the measured x-ray elastic constants
for the (410) plane almost agreed with both values calculated from the Voigt
and Reuss models. Therefore, the (410) plane is the most appropriate plane
for x-ray stress measurement of alumina.
INTRODUCTION
X-ray diffraction technique can be considerd to be the most appropriate
method for measuring residual stress in ceramics because it permits a
rapid and nondestructive measurement of residual stress in a small area
on the surface of polycrystalline materials. In this method, the stress
value is calculated selectively from strains of a particular diffraction
plane in the grains which are favorably oriented for the diffraction; we
must first choose a diffraction plane to be measured. Then, we need to
determine the x-ray stress constant experimentally in order to measure the
stress accurately.
This method is based originally on the theory of elasticity for mac-
roscopically elastically-isotropic polycrystalline materials1. 2. In genera!,
however, the elastic constants of a single crystal depend on the plane of
the lattice; that is, a single crystal is elastically anisotropic. Various

analyses taking into account the influence of elastic anisotropy of the
constituent grains in randomly-oriented polycrystalline materials have
also been carried out 3 - 8 • In the Voigt model, a polycrystalline material
is assumed to be deformed so that the strain in the constituent grains is
constant 3 - 7 • The Reuss model, on the other hand, assumes a constant stress
in the constituent grains. The Kroner model compromises the above two
models 8 • However, all the calculations using these models are based on the
assumption that polycrystalline materials are composed of entirely randomly-
oriented crystals. The experimental observations show that these poly-
crystalline materials behave as macroscopically elastically-isotropic bodies.
All the analyses give a linear relationship between sin2¢ and the peak
position of the diffraction line, but give the elastic constants different
from the values calculated from the analysis for isotropic materials.
Elastic constants determined by x-rays are called x-ray elastic constants.
According to the Reuss and Kroner models, the x-ray elastic constants
depend on the diffraction plane measured, while the Voigt model gives the
elastic constants independent of the diffraction piane 3 - 8 • Since actual
poiycrystalline materials may be deformed by a more complicated mechanism,
it is important to investigate experimentally the diffraction plane depen-
dence of the x-ray elastic constants.
It is important to evaluate the measured values by means of their
standard deviations or confidence intervals because every value measured
by x-ray diffraction fluctuates due to x-ray counting statistics. Fortunate-
ly, the standard deviations which represent the size of the variation due
to counting statistics can be calculated from a single set of measurements
as shown in the previous papers 9 - 13 •
Alumina is the most widely used ceramic. Residual stress measurement
of alumina is important because residual stress has a strong influence on
the strength of alumina. The confidence limits of the x-ray elastic and
stress constants were determined from seven kinds of diffraction planes of
alumina by using the Gaussian curve method in order to evaluate the re-
producibility of these constants and to investigate the diffraction plane
dependence of the elastic constants.
EXPERIMENTAL DETERMINATION OF X-RAY ELASTIC CONSTANTS
The analyses which take into account the anisotropy of all the grains
in a polycrystalline material give the same linear relationship between
the strain and sin2¢ as the analysis for elastically isotropic materials,
but give the different constants S1 and S2; that is, the strain e pro-
duced in the direction making angle ¢ with the specimen normal by an
appl ied stress 'Z' in the x direction is given by3-5
e= ~2('Z'+'Z'~)sin2¢+s1('Z'+'Z'~+'Z'~) (1)
where
SI and S2 = compliances
'Z'~ and 'Z'y = residual stresses in the x and y directions on the sur-
face of the specimen, respectively.
The analysis by the theory of elasticity for elastically isotropic materials
gives
S1=-II/E
S2 = 2(1+ II )/E (2)
where, E and 11 are Young's modulus and Poisson's ratio for isotropic
materials.
Transforming the strain e in Eq. (1) to the peak position p (in 28)
of the diffraction line by using the Bragg law, is given approximately by
p = -,8s2('l"+'l"~)sin2¢-2,8s1('l"+'l"~+'l"~)+280 (3)
where 8 0 is a Bragg angle for a stress free specimen, and ,8 is a constant
given by
,8 = 180tan8 0 (4)
7l
From Eq.(3), we get the slope M of the sin2¢ diagram, a plot of the peak
position p versus sin2¢ , as
M= a a,P2¢
sin
= -,8s2('l"+'l"~) = ('l"+'l"~)/K (5)
where, K is the stress constant given by

K - - _1_ (6)
- ,8 S2
For elastically isotropic materials, the stress constant K is obtained by
substituting Eqs.(2) and (4) into Eq.(6) as
7l E cot8 0
K=-180 2(1+11) (7)
From Eq.(5), we can get
B-
_---a-r
a M -_ -,8 S2 _ 1
- -K- (8)
Equation (8) shows that the compliance S2 and the stress constant K can be
determined experimentally from the slope B of the linear relationship
between the slope M of the sin2¢ diagram and the applied stress 'l".
Also, the intercept N of the sin 2 ¢ diagram can be obtained by sub-
stituting zero for sin2¢ in Eq.(3) as
*
N= -2,8S1('l"+'l"~+t"~) + 28 0 (9)
From Eq.(9), we can get
C= = -2,8S1 (10)
Equation (10) shows that the compliance S1 can be obtained experimentally

from the slope C of the linear relationship between Nand 'l". We can
determine experimentally the compliances S1 and S2, and the stress constant
K from Eqs.(8) and (10).
TEST PROCEDURES
Specimen
A specimen shown in Fig.l was prepared from a sintered a-alumina

(a-AI20a) of purity of 99%. The surface layer of the specimen was ground
by 630tlm, and lapped by 30tlm in order to remove the work hardened sur-
face layer by grinding. The Young's modulus E and Poisson's ratio 11 which
were mechanically measured with a strain gauge by using a four-points
bending device were 384.4 GPa and 0.241, respectively.
JS21 0
~_ _ _ ~
"'<:0--_ _--=::.:55'-_ _ _;;oIJ
(mm)
Fig.!. Specimen.
X-Ray Stress Measurement

A bending stress was applied to the specimen by using a four-points
bending device. The applied stress 't" was measured with a strain gauge
attached on the back side of the specimen. At the same time, the stress on
the upper side of the specimen was measured by x-rays. The peak position
of the diffraction line was determined by the Gaussian curve method 10. 13,
by using an automated x-ray diffractometer 14 and an x-ray stress analyz-
er 1S developed in our laboratory. The diffraction lines having diffrac-
tion angles less than and larger than 160' were measured with the x-ray
diffractometer and the stress analyzer, respectively, because the maximum
scanning angles of the x-ray detectors for the two systems are 160' and
170', respectively. Parallel-beam slits were used for both the systems.
Seven kinds of diffraction planes of alumina were measured with chromium,
cobalt and copper Ka radiations. Table 1 shows the conditions for deter-
mining the peak position. where hexagonal indices are used.
The background subtraction was omitted in determing the peak position
by the Gaussian curve method and x-ray counts were corrected only for LPA
(Lorentz- polarization and absorption) factors, because it has been proved
not to affect the stress value1~ 1~ 13.
Choice of Diffraction Plane in Measuring Stress
By differentiating the Bragg law, we can obtain 16
~(28) = -2tan8 (11)
e
where, ~(28) is the change in diffraction angle, e is the strain of the
lattice, and 8 is the Bragg angle. Equat ion (11) shows that the change in
diffraction angle per unit strain is proportional to tan8. Also, as shown
in a previous paper 12 , the standard deviation O"K of the stress constant
K, which represents the size of the variation due to counting statistics,
Table 1 Conditions for measuring stress constant and x-ray elastic constants.
Characteristic x-rays CrK a CoK a CuKa

Filter V foil Fe fo i I Hi foil
Diffraction plane (220) (1.2.10) (318) (229) (324) (410) (4.0.10)

Tube voltage. kV 40 40 40 40 30 30 40
Tube current, mA 25 25 25 25 9 9 25
Divergence angle of slit, deg 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Angular interval, deg 0.05 0.04 0.05 0.05 0.05 0.06 0.03
Preset time, s 16 5 10 10 6 10 10
Irradiated area, mm 2 2x7 2x7 2x7 2x7 5x7 5x7 2x7
25
c
...
'jij
20
-
Vi
'c
~ 15
lii
0.
<D 10
N
.£
4> 5 ( 1.2. 10.)
Cl
c:
ttl
.s: 0
u
100 120 140 160 180
Diffraction angle x. deg
Fig. 2. Dependence of sensitivity to

strain measurement on diffrac-
tion angle.
is given by
aK = K2t'i= a1
a P 12
;; 1 1
2 (12)
where, a1 are constants, and a p 1 and n are the standard deviations and
the number of the peak positions used in determining the stress constant
K. From EQs.(7) and (12), we obtain
aKK a: K a: cot8 (13)
Equations (11) and (13) show that it is important to choose a diffraction
line having an diffraction angle as high as possible in order to determine
the stress constant and strain precisely.
Figure 2 shows the sensitivity (the change in 28 per unit strain) of
the strain measurement as a function of diffraction angle 28 for the
seven kinds of diffraction planes measured in this study. The (410) plane is
approximately 4.6 times as sensitive as the (1.2.10) plane as shown in Fig.2.
TEST RESULTS
Figures 3 and 4 show the diffraction lines measured with CoKa radi-
ation b~ using the automated x-ray diffractometer and the x-ray stress
4000,----------------------,
AJ,03
III
0. Co Kex radiation
u 3000
>. S?
~
N
;;;
~ 2000 o 0
o ~ a;
c: ~ N
N
>.
?
x
1000
OL-_ _ ~ __ ~ __ _ L_ _~_ _ _L__~
100 110 120 130 140 150 160

Diffraction angle, deg
Fig. 3. Diffraction I ines measured with cobalt Ka radiation
by using an automated diffractometer.
Alumina (410) plane

CoKa: radiation
6x10 4
4000
III
CoKa. :; ;:! C
III N :l
a.
- -
.-'
u
M c;j
(3
8
3000 N' 4
-'"
iii
c 2000
<11
~
C
III
:l
0
u
0;
C N ~
e J: 2
'-
!:::
1000
x
I
-g
0
~0
u 0
150 160 170 166 167 168 169 170
Diffraction angle x, deg Diffraction angle x, de<]
Fig. 4. Diffraction lines measured with Fig. 5. Approximation of cobalt Kat
cobalt Ka radiation by using diffraction peak of (410) plane
an automated x-ray stress by a Gaussian function.
analyzer.
analyzer, respectively. Figure 5 shows a Ka1 peak of the (410) plane

which locates at the highest angle in the diffraction lines measured in
this study. Also in Fig.5, a Gaussian function fitted to the data points
above 80% of the maximum counts by using the least squares method is
shown. The Ka 2 peak does not appear because it locates over the range of
the scanning of ax-ray detector. The half-width method, used widelY in
Japan for determining the peak position, is not applicable because the
background needed in this method cannot be determined for this diffraction
peak. However, the use of the Gaussian curve method allows to determine the
Ka1 peak position as shown in Fig.5.
Although the x-ray elastic constants were determined for all the
diffraction planes shown in Table 1, only the results for the (410) and
(1.2.10) planes which have the maximum and the minimum diffraction angles,
168.8 Al20 3 ( 41 0 ) plane

CoKa radiation
Cl A1 2O:J ( 1. 2.10 ) plane Applied

~ 168.6 CoKa radiation stress't,
g' MPa
'0 127.4
a. 0
a: h Il ~g6
~s:n~
55
§ 168.4 c
:;::;
.~
106 ~ 95'/, confidence \204
95% confidence
'iii 127.2 interval 255
a. interval
156 0
a.
"'~" 168.2 I Maxmum
20~ "'ttl<11" I Maxmum
Q. 254 Q. x Minimum
I Minimum 127.0
0 0.2 0.4 0.6 0 0.2 0.4 0.6

sin21j1 sin 2 1j1
Fig. 6. Sin 2 ¢ diagram of (410) plane Fig. 7. Sin 2 ¢ diagram of (1.2.10)
for various applied stresses. plane for various applied
stresses.
g'
"0
0.2
°)
AI 20 3 ( 4 1 plane l 0.6 A12~ (1.2.10) plane
CoKa radiation 0.4 CoKa radiation
~ 0.0
E
~ -0.2
~
'5 -0.4
<7
c:
'iii
-0.6
'0 -0.8 '0 -0.4
CI> CI>
a. a.
0
iii -1.0 ~ -0.6 '-'-_L---'-_L---'-_L---I
0 50 100 150 200 250 300 o 50 100 150 200 250 300
Appl ied stress t. MPa Applied stress t, MPa
Fig. 8. Linear dependence of slope of Fig. 9. Linear dependence of slope of

sin 2 ¢ diagram on appl ied sin2¢ diagram on applied
stress for (410) plane. stress for (1.2.10) plane.
respectively, will be illustrated in Figs. 6 to 11. Figures 6 and 7 show

the sin2¢ diagrams of the (410) and (1.2.10) planes for various applied
stresses ~. In these figures, only the maximum and the minimum 95% confi-
dence intervals of the peak position were shown to avoid the complexity
of the illustrations. In Figs.6 and 7, the slope M of the sin2¢ diagram
increases with the increasing applied stress L The change of the slope
Mof the (410) plane shown in Fig.6 is much larger than that of the (1.2.10)
plane shown in Fig.7 for almost the same appl ied stress ~. This is be-
cause the (410) plane has larger diffraction angle and has higher sensi-
tivity to strain measurement,as shown in Fig.2.
Figures 8 and 9 show the linear relationships between the applied stress
~ and the slope M of the sin2¢ diagrams shown in Figs.6 and 7. The 95%
confidence intervals of the slope Mare taken as the diameters of the cir-
cles in Figs.8 and 9 because they are too small to be shown. From Figs.8
and 9 and Eq.(8), the compliance S2 and the stress constant K can be de-
termined experimentally.The change in Mwith ~ for the (410) plane shown in
Fig.8 is 4.2 times larger than that for the (1.2.10) plane shown in Fig.9,
01 01
CI> CI>
"0 AI 20 3 ( 41a)plane "0 A12~ ( 1. 2.10 ) plane
168.65 CoKa. radiation z· 127.45 CoKa radiation
Z
E E
~ 168.60 t!! 127.40
~ ~
'5
~
'5
168.55 03- 127.35
03- N
N
c: c:
'iii 'iii
168.50 '0 127.30
'0 195% confidence
a. I 95% confidence
interval
a. interval
CI>
~
168.45 ...CI>fl 127.25
.s
CI>
0 50 100 150 200 250 300 .s 0 50 100 150 200 250300
Applied stress t ,MPa Applied stress t, MPa
Fig. 10. Linear dependence of intercept Fig. 11. Linear dependence of intercept
of sin 2¢ diagram on appl ied of sin 2 ¢ diagram on appl ied
stress for (410) plane. stress for (1.2.10) plane.
Table 2. 95% confidence limits of x-ray elastic and stress constants.

Characteristic CrKa CoK)X CuKa
x-rays
Diffraction planes (220) (1.2.10) (318) (229) (324) (410) (4.0.10)
Diffraction
angle 2 e, (deg) 148.4 127.4 146.3 154.1 160.5 168.4 145.2
(lOTPa)-l
I
Compliances, s2/2
s,
28.34±2.85 32.54±4.05 30.05± 1.88 28.50±1.71 27.43±1.21 28.36±0.73
4.68±0.88 5.63±1.09 5.31 ±O.64 5.19±O.57 5.02±0.43 5.52±O.28
27.98± 1.93
5.47±0.65
Young's modulus ~, 423±39 372±46 404±24 429± 24 446 ± 18 438± 10 444 ±30
(GPa
Poisson's ratio v 0.20±O.03 0.21 ±O.03 0.22±O.02 0.22±0.02 0.22±0.02 0.24 ±0.01 0.243± 0.02
Stress constnt K, -872± 88 -1325± 165 -879± 55 -704±42 -548±24 -314±8 -977± 67
(MPa deg)
indicating much higher sensitivity to the strain measurement of the (410)

plane.
Figures 10 and 11 show the linearrelationships between the applied
stress 't' and the intercept N of the s in 2 ¢ diagrams shown in Figs. 6 and
7. The 95% confidence intervals of N were also calculated from the equa-
tion given in a previous paper 12 and are shown in Figs. 10 and 11. From
these figures and Eq.(10), the compliance S1 can be determined experimen-
ta II y.
Table 2 summarize the 95% confidence limits of the x-ray elastic
constants and the stress constant which were calculated from the equations
given in a previous paper12. The Young's modulus E and Poisson's ratio II in
Table 2 were calculated from the compliances S1 and S2 given by Eq.(2)
which is based on the theory of elasticity for isotropic materials. The
stress constant K for the (410) plane has the smallest value, showing the
highest sensitivity to strain measurement by x-rays. Table 2 shows that
no difference larger than the 95% confidence intervals is observed in the
measured elastic constants for most planes.
1--0-1 Measured value wi th 95 °/0

confidence interval
, 8 ----l:r- Calculated from Reuss model
~ .!!! _._.- Calculated from Voigt model
III ><
0...
'",
g
~
u
6 Voigt model
VI
<lJ 4
u
c ---(121)
(221)
.~
a. (321)
(311)
E (hOI)
u
0 2
0
0 2 4 6 8
Compliance SI, (10TPa)-1
Fig. 12. Diffraction plane dependence

of compl iance s,.
4 ~----------------------~
I----()--I ~:;~~~e Y~tl~;Va1Wi th 95 '/0
----fr- Calculated from Reuss model

I
_._-- Calculated from Voigt model
U
Voigt model
Reuss model
N
......
Jl 2
-(121)
<lJ (221)
U
c --(321)
.!:!1 (311)
(hOI)
~1
o
u
2 3 4
Compliance 52/2. (TPa)-1
Fig. 13. Diffraction plane dependence
of compliance s2/2.
Figures 12 and 13 give the graphical representation of the 95% confi-

dence limits of the compliances S1 and S2 in Table 2 by taking r. an
angle between the diffraction plane normal and the c axis of a trigonal
lattice of alumina, as a polar coordinate. The values calculated from the
Reuss and Voigt models by using the equations given by Tanaka et al. 17 are
also shown in these figures. The measured x-ray elastic constants for the
(1.2.10),(220) and (410) planes are close to both values calculated from the
Reuss and Voigt models. The measured values of the other planes are closer
to the values calculated from the Voigt model than to those from the Reuss
model, suggesting that polycrystalline alumina is more likely to be deformed
keeping strains of all the grains constant rather than keeping the stress
constant. According to the theoretical analyses, the average elastic con-
stants fall between the values calculated from the Voigt and Reuss models,
and in general. measured x-ray elastic constants are close to the mean of
the calculated values 3 - 6 • However, some experimental observations show
that the compliances S2 of steels increase with increasing carbon content
and exceed the theoretical values based on the Voigt and Reuss models 3 •
Figures 12 and 13 show that the compliances S1 and S2 calculated from
the Reuss model for (229), (4.0.10) and (318) planes,having an angle r
equal approximately to 45·, deviate remarkably from both values calculated
from the Voigt model and the measured values. On the other hand, for the
(410) plane having the angle r of 90·, the measured and calculated com-
pliances almost agree. These findings, together with the location at the
highest diffraction angle, suggest that the (410) plane is the most appro-
priate plane for x-ray stress measurement of alumina.
CONCLUSIONS
(1) The 95% confidence limits of the x-ray elastic and stress constants
were determined by the Gaussian curve method from seven kinds of diffraction
planes of alumina in order to investigate the diffraction plane dependence
of the x-ray elastic constants.
(2) No difference larger than the 95% confidence intervals was observed
in x-ray elastic constants for most diffraction planes.
(3) The measured x-ray elastic constants for the (1.2.10), (220) and
(410) planes were close to both values calculated from the Reuss and Voigt
models. The measured elastic constants of the other planes were closer to
the values calculated from the Voigt model than those from the Reuss model.
(4) The relati ve error O'K/K of the stress constant K is proport ional
to cot8. Therefore, it is important to choose a diffraction plane having
a diffraction angle 28 as high as possible in order to measure the stress
constant precisely.
(5) Since the diffraction line of the (410) plane measured with
cobalt Ka radiation by using an automated x-ray stress analyzer locates
at the highest angle of 168.4', the use of this plane would allow the most
precise measurement of the stress and stress constant. Also, the measured
x-raY elastic constants for this plane almost agreed with both values
calculated from the Reuss and Voigt models. Therefore, the (410) plane is
the most appropriate plane for the x-ray stress measurement of alumina.
(6) The peak position of the (410) plane can not be measured by the
half-width method because the diffraction line of this plane locates at so
high angle that its background needed in this method can not be determined.
However,the Gaussian curve method can determine the peak position because
it does not need the background subtraction.
The authors would like to thank NGK Spark Plug Co. ,Japan, for preparing
the specimen.
REFERENCES
1. Cllity,B.D., "Elements of X-Ray Diffraction", 2nd ed., Addison-lYesley

(1978), pp.447-477.
2. Hilley,M.E., "Residual Stress Measurement by X-Ray Diffraction - SAE
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3. Macherauch,E., Experimental Mechanics, 6 (1966),140.
4. Macherauch,E. and Wolfstieg,U., Materials Science and Engineering, 30
(1977), 1.
5. Hilley,M.E.,ibid.,pp.48,49.
6. Greenough,G.B., "Progress in Metal PhYsics, Vol.3, ed. Chalmers,B. ",
Pergamon Press (1952). pp.176-219.
7. Noyan, I.C. and Cohen,J.B., "Residual Stress Measurement by Diffraction
and Interpretation", Springer-Verlag (1987), pp.62-74.
8. Kroner,~., Zeitschrift fur Physik, 151 (1958), 504.
9. Kurita,M., Journal of Testing and Evaluation, 9-2 (1981), 133.
12. Kurita,M., Advances in X-Ray Analysis, 32 (1989), 377.
13. Kurita,M., Ihara,1. and Ono,N., Advances in X-Ray Analysis, 32(989),
459.
14. Kurita,M. et al., Transactions of Japan Society of Mechanical Engineers
(A), 54-500(1988),854 (in Japanese).
15. Kurita,M. et al., JSME International Journal, 30-260 (1987),248.
16. Cullity,B.D., ibid.,pp.350,351.
17. Tanaka,K. et al., Journal of the Society of Materials Science, Japan,
36-407 (1987),792 (in Japanese).
THE IMPORTANCE OF CONSISTENT lid SCANS IN DETERMINING SIZE AND STRAIN BY
POWDER DIFFRACTION PROFILE ANALYSIS
Y. Zhang,* J. M. Stewart,t C. R. Hubbard,+ and B. Morosin**
*Previous address: Department of Chemistry, University of

Maryland, College Park, MD. Current address: Ceramics
Division, National Institute of Standards and Technology,
Gaithersburg, MD; tDepartment of Chemistry, University of
Maryland, College Park, MD; +Oak Ridge National Laboratory,
Bldg. 4515, MS 6064, P.O. Box 2008, Oak Ridge, TN; and
**Sandia National Laboratory, Albuquerque, NM
ABSTRACT
This paper reports and discusses the results of a computer

modeling study on powder diffraction profile analysis for
crystallite size and strain of polycrystalline materials. The
results of this computer modeling show that if the spans of
diffraction profiles in reciprocal space (lid) are not carefully
chosen, an overestimation on size and an underestimation on
strain may result in analysis by both the Warren-Averbach and
the Hall-Williamson methods. A general way to eliminate such
errors based on profile fitting and regeneration is presented
and discussed in this paper.
INTRODUCTION
Powder diffraction profile analysis is a widely used method to

characterize polycrystalline phases. Methods such as the Warren-Averbach
(W-A) approach l and the traditional "plotting" methods 2 may be used to
determine crystallite size and microstrain for powdered materials. Some
systematic errors in profile analysis have recently been summarized. 3
Among these errors, overestimation of the background and truncation of the
diffraction peak tails are often closely related, and they can
significantly affect the profile analysis results. Overlapping tails of
neighboring reflections cause the background intensity to be
overestimated. A zero level is then assigned incorrectly to the line
profile at its extremities.
In practice, the use of profile fitting has become a powerful

technique to effectively correct for background and truncation
errors. 4 , 5,6 In profile fitting, a mathematical model is fit to the

Plenum Press. New York, 1990
374 VI. DETERMINATION OF CRYSTALLITE SIZE AND STRAIN
observed intensity versus diffraction angle data. The model typically

involves parameters to describe background intensity, peak position,
intensi ty, profile shape, and profile asymmetry. After fitting, the
profile parameters can be used to calculate a complete, smooth profile
with sufficient width so that truncation is eliminated and background
reached. The generated profiles may then be used in subsequent profile
analysis, much as experimental profiles are used. For the generation of a
diffraction profile, it is necessary to select an appropriate span in 28
space so that the profile will extend to background on each side of the
peak. It is the authors' experience that in many instances the selection
of the profile width can have a great impact on the results of subsequent
profile analysis for size and strain. In order to explore this
observation and to investigate how the profile spans affect size and
strain analysis, we have carried out computer modeling studies using
profile fitting and two methods of profile analysis. This computer
modeling was performed with a set of simulated diffraction data with
assumed symmetric Gaussian forms previously used to test our profile
analysis software. The use of computer modeling can effectively exclude
other errors existing in real diffraction data and provide the diffraction
profiles which contain broadening information due to "known" size and
strains.
The computer modeling study utilized both the Gaussian-Squared (G-S)

plotting method and the W-A analysis method to 1) determine the importance
of selecting the same scan range in reciprocal (lid) space for every line
and 2) confirm that serious errors will result in the subsequent
calculations of size and strain unless the scan range is sufficient so
that background is reached for every peak in a given analysis. This paper
briefly describes the computer modeling procedures, discusses the results,
and gives suggestions on how to appropriately determine spans for the
diffraction peaks.
THE SPAN OF POWDER DIFFRACTION LINES IN RECIPROCAL SPACE
In powder diffraction profile analysis the scan range or span of a

line in reciprocal space (lid space) is given by the variable a3' as named
by Warren and Averbach.l The parameter a3' was defined in the derivation
of the W-A method and its relationship is shown in the following equation:
2a 3 'o(Sin8 2 - Sin8 0 )
_1_ 11
a '(- - -) (1)
2 A 3 d2 do
where 82 and 80 are the positions of the high angle limit and the peak
maxima, respectively. From this equation, the "span" of a diffraction
profile in lid space depends upon its a3' value.
COMPUTER MODELING PROCEDURES
(1) Simulation of diffraction data set
In order to study the impact of variously chosen a3' values of each

diffraction line on the crystallite size and strain results, a set of
diffraction lines, each normalized to a peak height of 1.0, was generated
based on the Si structure (Fd3m, a=5.430825 A) and Cu-Kal radiation. The
indices of the eight lines included in the data set are indicated in
Figure 1. To simplify the data generation and subsequent back-
Y. ZHANG ET AL. 375
1.14 ...------,-----,---..,.----r---,
..
CONSTANT a ~ = 25 'A
1.02 _._._.--~,.-.-- ••• -
o
o
0
0.90
~
N
;:z
..... 0.78
~
III
0
0 0.66 0
~ 0
0.54 ~o 0 -;::-N' 0 ;::'0

~o C\I ~
C\I 0 ("/)C\I
~C\I
£: ~~ :!. ~:!.
0.42
0 0.04 0.08 0.12 0.16 0.20
(SINe/Ai
Fig. 1. Gaussian-squared plots. The simulated Gaussian diffraction
profiles were calculated on the basis of 100 size and 0.001 A
strain values. The instrumental free or pure profile was
obtained by the usual Fourier transform method.
calculation, all eight profiles in these two data files were generated
with a symmetric Gaussian type function:
jC4ln2) X 2
I(x) • exp[-4ln2·(--) 1 (2)
J'/T·fJ fJ
where fJ is the full width at half maximum (FWHM) of the diffraction line.
It is clear that the primary step of the data generation for a Gaussian
profile is to determine the FWHM of the peak. Once the FWHM is obtained,
the diffraction data may be easily calculated at any desired diffraction
angle. Note that no background function was used. Thus, the generated
profiles extend to zero intensity on each side. The reference or
instrument profiles, get), were generated assuming that the profiles are
free of size and strain broadening effects. Therefore, the simulated
profiles of this hypothetical Si powder should contain only the broadening
due to instrumental effects. Langford et al. 7 have shown that for such
profiles a simple quadratic relationship may be used to determine the
FWHM as a function of 28: fJ2 = u(28)2 + v(8) + w. In that paper, the
u, v, w values were given as 0.1538, -0.0941, and 0.0977, respectively.
In our reference-profile generation, the quadratic relationship and these
coefficient values were used to determine the FWHM values at various
diffraction angles of the eight instrumental lines.
The determination of the FWHM values for the broadened profiles is

more complicated because these profiles are broadened not only by the
instrumental effects, get), but also by intrinsic sample broadening
effects of small crystallite size and large strain. The intrinsic sample
broadening profile, f (t), is referred to as the pure profile hereafter.
According to the superposition theorem,8 a convolution of profiles f(t)
and get) is required to obtain the composite profile h(t). Therefore, for
an arbitrary profile, it is difficult to obtain the FWHM values for get)
and f(t), respectively, from the composite profile h(t), and vice versa.
For the Gaussian profiles, however, the square of FWHM of a composite
Gaussian profile is equal to the summat~on of the squares of the FWHMs of
the component profiles. 9 If the contribution of both size and strain is

assumed to be Gaussian, the following well-known relationship exists
between the FWHM of the pure profile f(t) and the size and strain values
of the sample (G-S relation):
(3)
where DG and EG are the crystallite size and strain values for the
powdered material. Thus, for a known size and strain value, the FWHM of
the diffraction line at any given diffraction angle 20 may be calculated.
This relationship is adequate for our computer modeling study but is not
universally applicable for many real materials.
In the generation of our broadened data, it was assumed that the size
of the Si crystallite size is 100 A and the strain is 0.001. The FWHMs of
the profiles f(t) at each of the different line positions were then
calculated using equation (3). For each of the convoluted broadened
profiles, h(t), the FWHM was obtained by the summation of the squares of
the FWHM values of the corresponding reference profile (using Langford's
parameters; see above), get), and the pure profile, f(t), at the same
diffraction angle.
For both the reference and broadened data, the Cu-Kal wavelength
1.5405981 A was used. The simulated diffraction data contain contri-
but ions due only to Ql radiation and were calculated at a step interval of
0.005° 20. As a result, the simulated profiles are free of background,
statistical noise, and contributions from noncharacteristic radiation.
(2) Profile fitting with various a3' values
The profile fitting was carried out with the recently developed
computer program, XRAYL.10 This computer program is particularly useful
as a preprocessor program in profile analysis as it can be fitted by
least-squares refinement of a variety of profile models to the input
data, and then a smoothed profile based on the refined model parameters
and a user-specified a3' value can be calculated.
Our two generated Si data files were fitted by XRAYL using both
Gaussian and Pearson VII profile models. In each pair of refinements, a
different a3' value was used. Two types of profile widths were used: (1)
a constant a3' was used for all the peaks; (2) a3' values were randomly
chosen for each of the peaks. In the profile -fi tting procedure, each
generated Gaussian profile was treated as "raw" data and fitted by XRAYL.
Since the "raw" data were ideally generated, perfect fits were obtained in
the profile fitting: most fitting errors are zero, and the worst is 0.001%
due to computational rounding error.
(3) Calculation of size and strain values
Each pair of the XRAYL calculated profiles were then used to compute
the size and strain by the W-A and the G-S "plotting" methods. The
calculations for the size and strain were carried out using the computer
program, CRYSIZ. ll As customary with the W-A analysis, individual
crystallographic directions for which higher orders were available were
examined (the [111] and [100] directions in our case). In addition,
following a procedure we have used in the past, the entire set of lines
was also examined as a single group. This is accomplished by employing
Y. ZHANG ET AL. 377
1/d2 rather than the conventional order of the index. This results in
average values of size and strain parameters (we refer to these values as
"Overall Average Values" hereafter). CRYSIZ determines a background
intensity correction from the reference profile and subtracts it from both
the reference and broadened profiles. Since the generated reference
profile always reached zero intensity, no error in background level was
introduced and no "hook" effects appeared, as are common with
overestimated background corrections.
The assumption that the diffraction lines are Gaussian does not
affect the generality of the subsequent profile analysis. This is because
the Til-A method does not assume any specific functional form for the
profiles being analyzed. The G-S plotting method employs exactly the same
relationship as that assumed in the original data generation, equation
(3) .
Similar profile analysis results were obtained regardless of whether

Gaussian or Pearson VII functions were used in the profile fitting
procedure. Therefore, only the calculated size and strain results on the
basis of the Gaussian fitted profiles are given and discussed below.
(1) Effect of variable a3' values
Figure 1 shows two G-S curves for size and strain separation for our
simulated diffraction data using 100 A and 0.001 for size and strain,
respectively. The black dots (upper line) are for the data set that were
refined by using a constant a3' of 25 A, for all the profiles; while open
squares (lower curve) are for the data set where a3' values were randomly
.chosen (20-50 A). The peak width measurement, ~, used in these two curves
was the second moment calculated from the profile f(t) after Stokes cor-
rection (back Fourier back-transformed profiles). The curves in Figure I
show that random a3' values result in a scattering of points on the G-S
line and the slope and intercept of the least-squares line through these
points do not correspond to the "known" size and strain values. On the
other hand, a small constant a3' value gives a straight line that is
consistent with the predication of profile analysis theory and the "known"
values.
Observations such as shown in Figure 1 indicate that in order to

obtain reliable size and strain values from plotting methods on the basis
of back Fourier transformed profiles, the a3' values of the diffraction
peaks should be small and constant for all lines. In practice, by the
very nature of the spread of profiles as a function of lid, one is led to
choose regions in 20 space which approximate a constant a3'. However, the
modeling shows that having different a3' values for each profile
introduces extra noise in the subsequent profile analysis. Such
inconsistent a3' values used during the Fourier transformation and then
the Stokes correction cause the integral breadths (FWHM, second moments)
to be placed on different scales. In fact, Figure I illustrates the
introduced errors. From this figure, when a3' is small (the 0 data), ~ is
estimated too large. When a3' is large, ~ is underestimated (this is
consistent with Figures 2 and 3 shown below). However, it should be
pointed out that for the traditional plotting techniques which utilize a
direct measurement of peak widths on the experimentally obtained data, no
consideration of a3' is necessary. Today, with the help of powerful
130
120
0«
ci
UJ
I- 110 GAUSSIAN-SQUARED
UJ PLOTTING METHOD
:::i:
<{
a: 100
~
UJ
N
iii 90
80~----~----~----~--~~--~
10.0 20.0 30.0 40.0 50.0 60.0

a£ VALUES. (.&. l
Fig. 2. Size versus a3'. Simulated Gaussian diffraction profiles

calculated on the basis of 100 A size and 0.001 strain values
plus a typical instrumental contribution are employed to back
calculated size values for particular a3' values. Open
squares: the results of the G-S method using second moment as
the measure of peak widths; Solid circles: the results of W-A
method in the (100) direction.
computers, the computational complex deconvolution process can be readily

performed. Therefore, even for the application of plotting methods, the
measurement of peak width is now often based on the pure profile f(t) so
that the fJ values will reflect only size and strain effects. In such
cases, a consistent a3' value for the diffraction peaks is recommended
based on our simulation results.
1.07
1.01
0.95
"0
~ 0.89
z
«a:: 0.83
I-
(f)
0.77
0.71
0.65
20.0 40.0 60.0
aj VALUES. (Al
Fig. 3. Strain versus a3'. Simulated Gaussian diffraction profiles
calculated on the basis of 100 A size and 0.001 strain values
plus a typical instrumental contribution are employed to back
calculate strain values for particular a3' values. Open
squares: the results of the G-S method using second moment as
the measure of peak widths; Solid circles: the results of W-A
method in the [100] direction.
Y. ZHANG ET AL. 379
We have also examined the effect of altering the values of a3' within
a data set on W-A results. When a constant a3' value of 25 A was used for
all three calculations (two individual directions and the overall
average), the Fourier size-coefficient and root-mean-squared strain curves
are smooth and well-behaved (not shown). In the case of random a3' values
(20- 50 A), however, both the Fourier size -coefficient curves and the
strain curves versus domain length were severely scattered and the
corresponding size and strain estimates were incorrect. This arises
principally from the use of inconsistent a3' values which affect the
Fourier transformation process and later the Stokes correction. These
results also suggest that size and strain values from W-A method are
reliable only when a3' is small and equal for both of the paired peaks for
a crystallographic direction.
(2) Effect of the magnitude of a3'
Figures 2 and 3 present results obtained by the usual W-A and G-S
methods and show the crystallite -size and strain results versus a3',
respectively, using our simulated diffraction profiles. Two curves are
shown in each figure. One curve is the result of the G-S plotting method
employing all eight lines, and the other curve is the W-A calculations in
the [100] direction. While the a3' values used for the data sets in size
and strain calculations varied from 20 to 50 A, the a3' used for all the
peaks within each data set was the same value. Therefore, the variation
of size and strain values are primarily due to the difference in a3'
values. From Equation 1 the width of the data collection region depends
inversely on the a3' value. The curves in Figures 2 and 3 show that the
use of different spans for data collection affects the crystallite- size
and strain results and this is particularly significant when a3' is
large. For example, using a3' values of 55 and 40 A, the calculated size
values using the G-S method are 127 and 106.5 A, respectively (similar
large differences are noted for the W-A method). However, as a3' becomes
smaller than a certain value, a further decrease of a3' (increase of span)
will not further alter the size and strain results (the flat parts of the
two curves). These results (together with other model calculations with
various size and strain values) suggest that for both the W-A and the G-S
plotting methods, consistent and reliable size and strain values will not
be achieved unless the a3' values of the diffraction lines are small.
Further, for our simulated diffraction data based on a 100 A size and
O. 001 strain, only when a3' values are smaller than 30 A will the G-S
calculation give back the original assumed size and strain values (the
effect of a3' values with respect to the degree of broadening will be
discussed below). In the present example, when the a3' values were not
appropriately chosen, an overestimation up to 27% in the size value and an
underestimation up to 33% in the strain value were observed. Moreover, it
should be pointed out that in Figures 2 and 3 that the back-calculated
size and strain results by the W-A method are smaller than the assumed
values. This is not surprising because the "raw" data were generated
using the G-S relationship and the physical significance of the size and
strain deduced from the W-A and G-S approaches is different. The W-A
method gives "volume-weighted" size and strain while the G-S plotting
method gives "area-weighted" size and strain. 12
(3) Selecting an appropriate a3' value
How small an a3' value is "proper" for a given sample depends upon
the degree of broadening. What is well known, and confirmed in this
study, is that the profiles must reach background on both sides or Fourier
series errors due to truncation will result in miscalculation of size and

strain. Further, if the a3' value for all reflections is not a constant,
additional noise will be introduced into the analysis. In fact, if one
examines Warren's derivation l carefully, it can be found that the quantity
a3' is treated as a constant for the paired lines. However, this fact was
not emphasized explicitly in the literature nor even in Warren's original
derivation. Unfortunately, it is difficult to select appropriate a3'
values as the data are being gathered. The diffractometer will be set to
cover 20 scans of each profile or of a collection of profiles. On many
instruments the user decides the scan range for each peak in 20 based on
separation of neighboring peaks, estimated background, etc. Hence,
special precautions are necessary to achieve constant a3' values. In
cases where lines are closely spaced or even overlap, the user-selected
value of a3' and how it is used may also be overlooked. By our example
and applications, we have emphasized the importance of choosing a3' values
correctly for the diffraction peaks to be used in profile analysis.
Moreover, selection of a too - large a3' leads to overestimated

background and truncation errors which may become significant. Larger a3'
values (or randomly selected a3') would typically be used in the case of
rich (many-lines) diffraction patterns or when severely overlapped peaks
are present. To correct for this problem, the basic treatments require
correction of the truncation effects for all measured profiles (or roughly
speaking, adding the missing profile tails). In such cases, how much of
the "tails" should be added for each peak can be determined by choosing an
appropriate value of a3'. In the present example, 100 A crystallite size
and 0.001 strain were used which we believe represent the usual extreme
values for typical powders submitted for profile analysis. Thus, to
warrant good results in subsequent profile analysis, it is the authors'
recommendation that a small and constant a3' value, 20 to 30 A, be used
for all the diffraction lines used in profile analysis.
ACKNOWLEDGMENTS
Computing support for this work was furnished by the University of

Maryland Computer Science Center. This work was partially supported by
the U.S. Department of Energy, under contract DE-AC04-76DP00789, the U.S.
Department of Commerce, under NBS Grant 70N-ANB- 7H07l0, the Office of
Standard Reference Materials, and the U.S. Department of Energy, Assistant
Secretary for Conservation and Renewable Energy, Office of Transportation
Systems, as part of the High Temperature Materials Laboratory Program,
under contract DE-AC05-840R2l400 with Martin Marietta Energy Systems, Inc.
REFERENCES
l. B. E. Warren, "X-ray Diffraction," London: Addison Wesley,

Chapter 13 (1969).
2. W. H. Hall, Proc. Phys. Soc. A62:74l (1949).
3. R. Delhez, Th. H. deKeijser, and E. J. Mittermeijer, in
Accuracy in Powder Diffraction, S. Block and C. R. Hubbard,
eds., NBS Special Publication 567, p. 213 (1980).
4. D. Taupin, J. Appl. Cryst. 6:266 (1973).
5. W. Parrish, T. C. Huang, and G. L. Ayers, Trans. Am.
Crystallo~r. Assoc. 12:65 (1976).
6. S. Enzo and W. Parrish, Advances in X-ray Analysis 27:37
(1984).
Y. ZHANG ET AL. 381
7. J. I. Langford, D. Louer, E. J. Sonneve1d, and J. W. Visser,

Powder Diffraction 1:3, p. 211 (1986).
8. R. C. Spencer, J. App1. Phys. 20:413 (1949).
9. H. P. K1ug and L. E. Alexander, "X-ray Diffraction Procedures
for Po1ycrysta11ine and Amorphous Materials," 2nd ed.,
Wi1ey-Interscience (1974).
10. J. M. Stewart, Y. Zhang, C. R. Hubbard, B. Morosin, and E. L.
Venturini, "XRAYL: A New Powder Diffraction Profile
Refinement Program," NIST-IR 88-3850 (1988).
11. J. M. Stewart, Y. Zhang, C. R. Hubbard, and B. Morosin,
"CRYSIZ: A New Powder Diffraction Profile Analysis Computer
Code," in preparation (1989).
12. B. Morosin and R. A. Graham, X-Ray Diffraction Line-broadening
Studies on Shock Modified Rutile and Alumina, Materials
Sci. and Eng. 66:73 (1984).
THE COMPARISON OF SEVERAL STANDARD MATERIALS AND TECHNIQUES FOR THE
WARREN-AVERBACH DETERMINATION OF MICROSTRUCTURE CHARACTERISTICS OF
CALCIUM HYDROXIDE SORBENT MATERIALS
Frank E. Briden
U.S. Environmental Protection Agency

Air and Energy Engineering Research Laboratory
Research Triangle Park, NC 27711
INTRODUCTION
The Air and Energy Engineering Research Laboratory (AEERL) has been investigating the injection
of dry calcium hydroxide into combustion streams for the removal of sulfur oxides. It has been known, for
some time, that the reactivity of Ca(OH)2 with sulfur oxides varies over a wide range for different batches of
calcium hydroxide. The reactivity is a critical factor in the economics of the process. Because of this it is
desirable to have a method to predict the reactivity of calcium hydroxide batches. The reactivity can be
affected by many factors including the origin of the calcium carbonate mineral from which the hydroxide is
produced, the production conditions, and the concentration of additives used for reactivity enhancement. It
has been theorized that all of the preceding contribute to such physical characteristics as surface area, particle
size, and porosity. The examination of these physical characteristics has provided the basis for
understanding the reaction processes but has not provided all the factors necessary to correlate intrinsic
sorbent characteristics with reactivity.
The application of microstructure factors derived from X-ray Diffraction Line Profile (XLP) for the
characterization and reactivity prediction of calcium-hydroxide sorbent materials was tirst reported by Briden
and Natschke (1). In that study, the XLP derived microstructure factors from several calcium-hydroxide
factors were found to be related to their reactivities. In the study, the microstructure factor mean column
length eCL) was seen to be inversely proportional to reactivity while the strain at the mean CL was seen to be
directly proportional to reactivity. When the method was applied to more widely varying batches, the
relation was not as consistent. The original data had been generated, using bulk sample holders and zincite
as the instrument line-broadening standard. At this point, it was decided to investigate the effects of the
choice of standards, the use of thick samples versus thin, and the simultaneous use of more than one
microstructure factor in reactivity prediction.
EXPERIMENTAL
The experimental data were taken on a Siemens D-500 diffractometer. The x-ray source was a
copper-target tube running 50 kV and 40 rnA. The tube had a fine focus with a beam size of 0.4 x 12 mm
and a take-off angle of 60 resulting in an effective beam width of 0.040 mm. The collimation was a 10
divergence slit, a 2.4 0 incident-beam Soller slit, a 10 scatter slit, and after the sample another 10 scatter slit, a
20 Soller slit, a 0.05 0 receiving slit, a 0.15 0 monochrometer slit, and a graphite monochrometer. A
scintillation detector was used.
The bulk sample holders were end loaded and about 2 mm deep. The thin sample holders were zero
background quartz plates. The thin-mount samples were slurried in amyl acetate and then the slurry was
Advances in X·Ray Ana/ysis, Vol. 33 383

spread over the plate and allowed to evaporate. The samples were not ground in order to preserve the, as
received, crystallite size and strain conditions. In general, the samples would pass a 44 /lm mesh sieve.
The data were processed on the system DEC 11/73, with an RSXIIM operating system using the
Siemens DIFFRAC 500, version 1.1 software. For the Warren-Averbach method (Z) used to separate
crystallite size and strain effects, it was necessary to use diffraction peaks of at least two orders of the same
reflection. For Ca(OH)z (JCPDS No. 4-733), the only pair of reflections readily available are the 101 and
ZOZ because of low intensities and interferences. The standards used to compensate for instrument line shape
effects were LaB6 (SRM 660), Si (SRM 640B), CaFZ (Spex TMI-IO, Lot 01841 P), a-AIZ03 (Norton 871),
and ZnO (Fisher Reagent, Lot 80186).
In order to use the Siemens computer program CRYSIZE to determine microstructure factors with
the Warren-Averbach method, it is first necessary to fit the diffraction peak with one of several functions
available in the program FIT. This process improves the Warren-Averbach analysis by the reduction of
random noise and the elimination of interference from foreign peaks. In all cases, the Pearson 7 or Split
Pearson 7 functions were used. Six microstructure factors from the CRYSIZE output were examined. The
first three were the mean CL (the mean distance across the crystallites in the 101 direction), the mode CL
(CL occurring with the greatest frequency in the 101 direction), and the maximum calculated CL (the highest
CL determined at the iteration limit of the CRYSIZE algorithm in the 101 direction). Also the root mean
square strains (RMSS) for the three respective CLs were examined. The six microstructure factors were
determined for six commercial Ca(OH)z sorbent products [Linwood, Marblehead, Kemidol, Snowflake,
Modified Marblehead, and Illinois State Geological Survey (ISGS) Mixture] plus a more crystalline, reagent
grade material from Alfa Chemical Company (Lot 8171481). The six microstructure factors and the full
width at half maximum (FWHM) for the 101 and ZOZ peaks for the products are listed in Table I. The
products are listed from left to right in order of increasing reactivity [weight of Ca(0H)2 converted to
CaS04 divided by the total weight of Ca(0H)2 used times 100]. The reactivities were obtained on the EPA
innovative furnace reactor with a flow rate sufficient to give a residence time of 0.75 s between 538 and
4Z7 °C with an SOZ concentration of 3,000 ppm (3). In general, it can be seen that the CL factors decrease
with increasing reactivity while the root mean square strains increase with increasing reactivity.
It had been anticipated that the microstructure factors would be very dependent on the mass
absorption coefficient of the standard materials. When the mean CLs for the different Ca(OH)2 products
were plotted versus the FWHM of the second order standard peaks, a fairly good progression of increasing
mean CL with increasing FWHM was observed (Figure 1). However, it was also observed that the CLs were
not falling in order of the standard mass absorption coefficients. It appears that the mass absorption
coefficient effects are outweighed by whatever other factors influenced the FWHM. The lowest mean CLs
were obtained with CaFZ. However, it is noted that, even though the absolute values are different, the
relative rankings for a given standard are the same except in the case of Kemidol and Snowflake which are
extremely close. Of course, these Ca(OH)z samples all had very broad peaks and the difference between
them and the standards was very large.
The RMSS values at the mean CLs were also plotted versus the FWHM of the second order
standard peaks (Figure Z). The data point for the Kemidol sample with AlZ03 standard is obviously in error.
In general the RMSS is seen to decrease with increasing FWHM of the second order standard peaks. The
CLs obtained with Si are much lower than predicted. This, quite likely, indicates that the Si has a relatively
high RMSS. Some of the strains are slightly higher for CaFZ while some are slightly higher for LaB6
indicating that, within experimental error, their strains are small but equivalent. As with the CLs, the
absolute strain values vary with the FWHM but the relative order for the samples is constant.
The previous work (1) on relating microstructure factors to reactivity was limited to the
consideration of one factor at a time. As more widely varying sorbent prodUCl~ have been investigated, it has
become quite obvious that fairly wide deviations from the regression may occur. Because of this, it was
attempted to perform the regression with more than one microstructure factor. Of course, the more factors
considered the better the agreement that may be obtained. However, because of the limited size of data sets
that become available for testing, it was considered that no more than two factors at a time should be used.
F. E. BRIDEN 385
l .. M. ·
25
E 1 1 1 I
oS
.£ 20 ........................... :......... ·t.. · .. ·· ...... ·.... ·· .. ··
Cl
c
......... .................. ~l.. .. .............. ..................~
Q)
~
15
· rl
c
· · · · · · · r=~ · · · ·· ·
E
::;)
(5
U 10
c
!.... !........... .
cu 1 I 1 1 1
Q)
:E 5 ·.... ·...... ·.......... ·.... !" ............ ·t.. ................. .................... 1" ......
CaF2 LaBS AJ203 Si ZnO
0
0.05 0.06 0.07 0.08 0.09 0.1 0.11 0.12
FWHM Second Order Sid Peak (Oeg)
Reagent -+- Linwood Marblehead --e- Kernldol

~ Snowflake ~ Mod. Mblhd - &- ISGS Mix
Figure 1. Mean CLs for Seven Ca(OH)2 Products Calculated With Five Standard Materials Versus the
FWHM of the Second Order Standard Peaks.
30
.... ~ ............... I:I .
J}~~'~'.
25
<f ...
UJ 20
x
c: 15
.~
U5 I
(/)
~
a:
10 .... 1
I ~
II I
5 I I I
CaF2 LaB6 AI203 Si ZnO
0
0 .05 0.06 0.07 0.08 0.09 0.1 0 .1 1 0.12
FWHM Second Order SId Peak (Oeg)
Reagent -+- Linwood Marblehead --e- Kernldol

~ Snowllake -0- Mod. Mblhd -- ISGS Mix
Figure 2. RMS Strain at the Mean CL for Seven Ca(OH)2 Products Calculated with Five Standard Materials
Versus the FWHM of the Second Order Standard Peaks.
TABLE 1. Ca(OH)2 MICROSTRUCTURE FACTORS FROM X-RAY DIFFRACTION LINE PROFILES

(WITH CaF2 STANDARD AND BULK MOUNT)
XLP Mod. ISGS

Factor Reagent Linwood Marblhd Kemidol Snowflake Marblhd Mix
% Reactivity 37.0 56.8 58.3 59.7 60.4 67.4 73.4

ModeCL (nm) 7.9 6.2 5.7 6.8 6.3 5.1 6.0
MeanCL (nm) 16.0 12 11.0 12.7 12.5 9.0 10.7
Max CL (nm) 64 36 44 48 48 36 32
RMSS Mode 0.00173 0.00263 0.00197 0.00216 0.00179 0.00225 0.00329
RMSS Mean 0.00138 0.00232 0.00180 0.00171 0.00165 0.00189 0.00266
RMSS Max 0.00091 0.00170 0.00127 0.00113 0.00119 0.00119 0.00174
101 XRDPeak 0.290 0.4523 0.433 0.387 0.3685 0.540 0.5125
FWHM(Deg)
202XRDPeak 0.4405 0.7288 0.0691 0.634 0.603 0.8405 0.825
FWHM(Deg)
Tables 2 through 4 show the linear correlation coefficients for the six factors regressed, one and two at a
time, over the seven products, for the standards CaF2, LaB6, and Al203. In these tables, the coefficients on
the diagonals are for the single factors alone. The balance of the coefficients are the result of regressions of
the factors taken two at a time. For all of these standards, the mean CL and the maximum CL are the best
single predictors of reactivity. Of the strain factors, the strain at the average CL is the best predictor. It is
not fully accurate to compare the magnitude of these strain coefficients to the size coefficients because it has
been seen that the functions relating strain to reactivity are not linear and these coefficients came from linear
regressions of size and strain. Preliminary calculations have shown that, when strain regression is treated as
a second degree polynomial, the coefficients will improve. It would be logical to assume that any scheme to
reliably predict reactivity should be based on both size and strain components. The mean CL and the strain
at the mean CL are consistently high for all three standards.
The original work had started with bulk sample holders. It was desired to compare the results from
the bulk sample holders with those from the thin mounts on zero background quartz plates. Table 5 presents
the mean CL factors determined for CaF2 and LaB6 standard with bulk and thin samples. The absolute
values for LaB6 for bulk and thin samples are, in general, larger than those for CaF2. The order for both thin
samples is almost identical and likewise the order for both bulk samples is almost identical. However, the
order for the bulk samples is quite different from the order for the thin samples. Table 6 gives the correlation
coefficients for the regression of the microstructure factors for CaF2 standard calculations for the thin
samples. It is seen here that the single factor correlations are significantly lower than those for the bulk
samples (Table 2). The mean CL correlation is only 0.61 for thin samples where it was 0.77 for the bulk
samples. Because of the low correlations for the single factors (those on the diagonals) it was surprising to
find that several of the regression pair correlations were significantly higher than those for the bulk samples.
Of particular interest is the pair of factors maximum CL and RMSS at maximum CL. The first had a single
factor correlation coefficient of 0.69 and the other 0.03 but when regressed together they had the highest
correlation of 0.93. A theory that this evidence could support is that the better resolved thin sample peak
allows the separation of the peak profile parameters which contribute to the two factors. In cases where the
separate correlations are low but the simultaneous regression for the pair is high, the two factors could be
synergistic so that the contribution of each factor depends directly or inversely on the contribution of the
other.
CONCLUSIONS
1. When different standards were compared for Ca(OH)2 analysis, the CLs varied in a similar manner
to the standard peak widths. The CaF2, LaB6, Si, and AI203 standards all gave quite comparable
results. The absolute values obtained varied a little but the relative order in the series was hardly
affected.
F. E. BRIDEN 387
TABLE 2. CORRELATION COEFFICIENTS FOR THE REGRESSION OF REACTIVITY OF Ca(OH)2

SORBENT ON MICROSTRUCTURE FACTORS FROM X-RAY DIFFRACTION LINE PROFILES (CaF2
STANDARD AND BULK MOUNT)
Factor ModeCL MeanCL MaxCL RMSS Mode RMSS Mean RMSSMax
ModeCL 0.65 0.85 0.80 0.82 0.78 0.73

MeanCL 0.77 0.85 0.85 0.84 0.82
MaxCL 0.79 0.79 0.81 0.84
RMSS Mode 0.46 0.51 0.46
RMSS Mean 0.50 0.57
RMSS Max 0.38

SORBENT ON MICROSTRUCTURE FACTORS FROM X-RAY DIFFRACTION LINE PROFILES (LaB6
STANDARD AND BULK MOUNT)
Factor ModeCL MeanCL MaxCL RMSS Mode RMSS Mean RMSS Max
ModeCL 0.70 0.85 0.81 0.75 0.81 0.77

MeanCL 0.79 0.84 0.80 0.84 0.83
MaxCL 0.79 0.89 0.80 0.83
RMSS Mode 0.51 0.58 0.51
RMSS Mean 0.58 0.70
RMSS Max 0.40

SORBENT ON MICROSTRUCTURE FACTORS FROM X-RAY DIFFRACTION LINE PROFILES
(A1203 STANDARD AND BULK MOUNT)
Factor ModeCL MeanCL MaxCL RMSS Mode RMSS Mean RMSSMax
ModeCL 0.64 0.86 0.79 0.74 0.83 0.73

MeanCL 0.77 0.82 0.81 0.86 0.82
MaxCL 0.78 0.79 0.78 0.82
RMSS Mode 0.35 0.52 0.39
RMSS Mean 0.52 0.53
RMSS Max 0.38
TABLE 5. COMPARISON OF CRYSTALLITE MEAN CLs (nm) IN THE 101 DIRECTION OBTAINED
WITH CaF2 AND LaB6 STANDARDS WITH BULK AND THIN FILM MOUNTS
Standard! Mod
Mount Reagent Linwd Marblhd Kemidol Snowflk Marblhd ISGS Mix
CaF2 Bulk 16.0 12.0 11.0 12.7 12.5 9.0 10.7

CaF2 Film 16.4 14.0 12.2 9.3 14.7 11.2 9.3
LaB6 Bulk 17.6 12.6 11.6 13.4 13.4 9.3 11.1
LaB6Film 17.6 14.3 12.6 9.0 15.2 11.4 9.5
TABLE 6. CORRELATION COEFFICIENTS FOR THE REGRESSION OF THE REACTIVITY OF

Ca(0H)2 SORBENT ON MICROSTRUCTURE FACTORS FROM X-RAY DIFFRACTION LINE
PROFILES (CaF2 STANDARD, FILM MOUNT)
RMSS RMSS RMSS

Factors ModeCL MeanCL MaxCL Mode Mean Max
ModeCL 0.10 0.89 0.89 0.01 0.89 0.19

MeanCL 0.61 0.90 0.63 0.69 0.74
MaxCL 0.69 0.81 0.69 0.93
RMSS Mode 0.01 0.25 0.11
RMSS Mean 0.23 0.24
RMSS Max 0.03
2. The present data indicate that crystallite size is inversely proportional to the first order of reactivity.
The root mean square strains appear to be directly proportional to reactivity with a second degree
function. When the microstructure factors are used to predict reacti vity of solids for gases, the
results are improved considerably by regressing two factors at a time. .
3. The use of thin samples gave a different order of mean CLs than those obtained for a series of bulk
samples. The single factor correlation coefficients were lower for thin samples than bulk samples.
However, when the thin sample results were regressed two at a time, higher correlations were
achieved for some pairs than for those obtained for bulk samples. It is hypothesized that the thin
samples gave better resolved peaks allowing the separation of factors which were synergistically
related.
The assistance of David Natschke and Shawn Karns of Acurex Corporation, in collection and
reduction of data, is deeply appreciated.
REFERENCES
1. Briden, F.E. and Natschke, D.F., The Characterization of a Solid Sorbent With Crystallite Size and
Strain Data From X-ray Diffraction Line Broadening, Advances in X-ray Analysis, 32,
437-441,Plenum Press, NY, (1989).
2. Warren, B.E., "X-ray Diffraction," Addison Wesley Co., (1969), Chapter 13.
3. Bruce, K.R., "Furnace Sorbent Reactivity Testing for Control of S02 Emissions From Illinois
Coals." Acurex Corporation, Durham, NC, Personal Communication, (1989).
THE USE OF 2-D DETECTOR UTILIZING LASER-STIMULATED LUMINESCENCE FOR
X-RAY DIFFRACTION STUDIES ON MECHANICAL BEHAVIOUR OF MATERIALS
Y. Yoshioka, T. Shinkai and S. Ohya
Musachi Institute of Technology

INTRODUCTION
The development of linear position-sensitive detectors (PSD) has

resulted in a large reduction of data acquisition times in the field of
x-ray stress analysis. However, we also require two-dimensional (2-D)
diffraction patterns for material evaluation. Especially, the microbeam
x-ray diffraction technique gives valuable information on the structure of
crystalline materials and this technique has been applied to fracture
analysis by x-rays.l Many kinds of 2-D PSD have been developed that have
insufficient spatial resolution. So x-ray film has still been used as a 2-D
detector, but it requires relatively long exposure times and then the
process after exposure is very troublesome.
A new type of integrating 2-D detector system was developed for

diagnostic radiography during the 1980's.2 This detector utilizes
photostimulated luminescence and has many good features such as high
sensitivity, high spatial resolution, wide dynamic range and repeatable
use. As these features are desirable for microbeam x-ray work, we examined
the applicability of this 2-D detector to diffraction experiments for
studies on the mechanical behaviour of materials.
PRINCIPLE OF DETECTOR3
The detector consists of a flexible 0.5 mm-thick plastic plate coated

with fine photostimulable phosphor crystals, BaFBr:Eu 2+, typically 150 ~m in
thickness, combined in an organic binder. This detector is called the
imaging plate (IP). A 2-D x-ray image is temporarily stored as a
distribution of F-centers in this phosphor screen. When the x-ray image
stored in the IP is then stimulated by a focused He-Ne laser beam, the
phosphor emits the fluorescence (A~390 nm) which is proportional to the
x-ray intensity. This phenomenon is called "photostimulated luminescence"
(PSL). The residual x-ray image in the IP can be erased simply by exposing
it to a large dose of visible light; the IP can be used repeatedly. Fig. 1
shows the principle of the imaging plate.

Plenum Press. New York. 1990
Imaging Plate
Photostimurable
phosphor crystals
Support
~!l)j E'p",",'
L_a_:~~_~~~",-_~_~~~~~ng ~
Read out
Erase
Fig. 1. Principles of the detector system.
The IP has the following properties which are suitable for obtaining
high-quality images with low x-ray doses:
1) The absorption coefficient in the energy range below 20 KeV is more

than 90%.
2) The spectrum of the PSL radiation that is used is in the range
where the quantum efficiency of the photomultiplier is high.
3) The spatial resolution is about 0.15 mm(FWHM) when the pixel size
for read-out is O.lxO.l mm 2 . It may be improved to a few tens of ~m by
reducing the size of the laser beam and the thickness of the phosphor screen.
4) The dynamic range for linear response extends for 5 orders of
magnitude and there is no counting-rate limitation.
5) The background noise of the IP is less than 1/300 in comparison
with the x-ray film; the background noise corresponds to the intrinsic
chemical fog on film.
6) The exposure time can be shortened to 1/20-1/60 of the time
required for an x-ray film exposure.
Therefore, the IP can be used in almost the same way as an x-ray film
except for the repeated use, and the properties except for the spatial
resolution are superior to those of x-ray film.
IMAGE READER AND PROCESSOR
As the back-reflection x-ray technique is required for bulk specimens,

we used a square IF, 128 mm by 128 mm with a 12 mm diameter hole at its center.
After being exposed by x-rays, the x-ray image stored in the IP is
read out by a scanning He-Ne laser beam (A=632.8nm) which releases the PSL
radiation (A~390nm). Fig. 2 shows the schematic layout of the reading
system adopted in this study. The IP is put on a drum and rotated. When
the collimated laser beam hits the IP, the PSL radiation collected by a
cylindrical mirror is guided to a photomultiplier tube (PMT). A PMT output
signal which is proportional to the x-ray intensity is stored logarithm-
Y. YOSHIOKA ET AL. 391
ically, amplified and converted into a digital signal (12bit/pixel) with an

A/D converter. As the signal is read by scanning in the axial direction of
the rotating drum, two-dimensional digital data from the IP are stored in a
computer memory and are finally stored on magnetic tape. The scanning speed
is about 14 ~s per pixel and the minimum pixel size is designed to be
O.lxO.l rom 2 .
In this study, the digital data in the magnetic tape are again sent to
a magneto-optical disk (594MB) connected to a personal computer and the
image processing, such as subtraction of background noise and binarization
etc., is performed with assistance of an image processor.
EVALUATION OF THE SENSITIVITY OF THE IMAGING PLATE
Although Amemiya et al had already evaluated the sensitivity of the

Ip3, it was evaluated for our purpose from the viewpoint of practical use.
The material of the specimens was annealed low carbon steel and a Philips
x-ray diffraction tube with a fine focus was used as an x-ray source.
Diffraction from aFe(2ll) crystal planes was observed by the Cr-Ka x-ray
beam passing through a l-mm diameter pin-hole. X-ray film was also used for
comparison with the IP.
Fig. 3a shows an example of a (211) diffraction pattern of a low

carbon steel specimen on x-ray film. The distance between the detector and
the specimen was 80 rom and the exposure time was 30 minutes. A diffraction
pattern from the same position of the specimen was then measured by the IP,
as shown in Fig. 3b. The exposure time was only 90 seconds but the same
spotty pattern is obtained with sufficient intensity. Such comparisons were
carried out on several kinds of steel specimens and similar results were
also obtained. That is, by using the IP in place of the x-ray film, the
exposure time can be reduced by 1/15-1/20.
APPLICATION TO MICROBEAM X-RAY STUDY
The microbeam x-ray diffraction technique is a powerful means for

evaluation of crystalline structure. However, it takes much exposure time
PMT
~-<J
-1LOgAMP~
h-c:=J
!
Imaging Plate
Fig. 2. Schematic layout of the image read-out system.

a) b)
Fig. 3. (211) diffraction patterns from a low carbon steel.

a) By the x-ray film. Exposure time: 30 min.
b) By the imaging plate. Exposure time: 90 s.
to obtain a diffraction pattern when an x-ray film is used. In addition, it

is difficult to measure x-ray parameters from a pattern on film without
subjectivity. But the development of the image processing system has
enabled objective observation. If the IP has sufficient spatial resolution
for microbeam x-ray studies, the subjectivity problem will not appear.
Next, we investigated the application of the IP to a microbeam x-ray study
of fatigue.
Experimental
The material used was a 0.16%C carbon steel which has a yield stress
of 267 MPa. ,A fatigue test of an ASTM compact tension-type specimen was
conducted under a maximum load of 700 Kgf and a stress ratio of 0.05.
A Cr-Ka x-ray beam collimated by a 200 wm-diameter pin-hole was set

normal to the fracture surface of a specimen after fatigue, at a constant
Fig. 4. Diffraction pattern from fracture surface by microbeam

x-rays. Camera length: 80 min. Exposure time: 10 min.
position relative to the notch root, and a Debye-Scherrer pattern from (211)
crystal planes was recorded in the IP. The distance between the IP and the
specimen was 80 mm and the diameter of radiated area on the specimen surface
was about 0.9 mm. Several patterns were obtained at stated intervals in the
crack propagating direction, and a thin layer of fracture surface was
electropolished away. This process was repeated for measuring the plastic
zone size beneath the fracture surface.
Results and Discussion
Measurement of Arc Length. Fig. 4 shows a diffraction pattern from a

position on the fracture surface where the maximum stress intensity factor,
Kmax, is 20 MPa;;. The exposure time was 10 minutes, which is one-twentieth
that required for x-ray film. A continuous Debye-Scherrer (DS) ring is
obtained in this stage. However, as shown in Fig. Sa, the DS ring separates
to several arcs at the depth of 20 ~m from the fracture surface. The number
of arcs in a DS ring gradually increases and the length of arc decreases
with the depth from the surface. Fig. 6a shows the pattern from a depth of
100 ~m. Finally, the DS ring coincides with that which is diffracted from
the non-fatigued specimen at a depth that is equivalent to the plastic zone
size at the tip of the crack. The average arc length is used as the
parameter indicating the plastic deformation and this length was measured
with the help of the image processor system. .
It is necessary to make the binary pattern from the original gray

pattern for measuring the arc lengths. The binarization was performed by
using several threshold levels. The gradation of density ranged from 255
(white) to 0 (black) on the image processing system used and the maximum
density of the diffraction pattern was about 200. Six levels from
thresholding were adopted that ranged from 150 to 125. Figs. sb, sc, 6b and
6c show the binary patterns from the gray pattern in Figs. Sa and 6a,
respectively. The threshold level in Fig. sb and in Fig. 6b is 150, and
that in Fig. sc and in Fig. 6c is 130.
A definite change is observed between Figs. sb and sc. The change

from a continuous ring to the separated arcs is insufficient at the
threshold level of 150 in Fig. sb, but the number of arcs increases at the
level of 130 and the width of arcs in the radial direction also decreased.
However, there is little if any difference between patterns in Figs. 6b and
6c, because the separation of the DS ring into small arcs is already
observed in the gray pattern in Fig. 6a. The total circumference of the DS
ring, number of arcs and average arc length were measured at each threshold
level, and these values are plotted against the threshold value as shown in
Fig. 7a (at the depth of 20 ~m), and Fig. 7b (at the depth of 100 ~m),
respectively. These figures also show the number of the arcs in a DS ring.
The number of arcs and the average arc length depend on the threshold value
near a continuous DS ring such as that shown in Fig. Sa. When the few arcs
seen in the original pattern in Fig. Sa were compared with those in the
binary pattern at each threshold level, the average arc length in the
pattern at threshold level of 135 is nearly equal to that in the original
one. Thus, the average arc length at this level was adopted as the measured
value. On the DS ring separated as shown in Fig. 7b, however, changes in
the number of arcs and the average arc length are small. The decrease of
total area of the DS ring by the change in thresholding is caused by the
decrease of diffraction line width in the radial direction.
Observation of Sub-Grains. If a crystal grain divides into many

polygonal sub-grains during a plastic deformation process, we can observe
/ ,
.'.
a) f
a)
) "
I
/
a .. _ _ ; _
'/
., " -" ...
.,
•
.N •
,..
b) b)
/
/ "
..,.
.,
- ...... ~ ~
"......... - --:. -
~
/ ' -. ~ ...
c) I
f \ c)
\
\
/
"
"
I
"
..... - . . - ...
Fig. 5 a) Diffraction pattern at 20 Fig. 6 a) Diffraction pattern at 100

~m in depth from fracture ~m in depth from fracture
surface. surface.
b) & c) Binary patterns of a). b) & c) Binary patterns of a).
b) Threshold level: 150 b) Threshold level: 150
c) Threshold level: 130 c) Threshold level: 130
SI5C. Pmax=700Kgt. R=0.05

Kmax=20MPa/m . 20l'm
•
o Arc length
• Total area
• .....
~
E:
SI5C. Pmax=700Kgt. R=0.05
15 • -150 '"
~
Kmax=20MPa/m. 100l'm
~
~
• <..>
"- 10 f--
o Arc length
• Total area
V)
• 2>
~
"
.....
0
0
;: 10 ~ ~
"
""
c:: • 0 0 100
~ o ~
<..> 0
"- f--
'" t\J
")
o
5 0 - 50
I
130
I
140
I
150 o '--'_-;-,3-!,-0:;::-...I--:-,47 0"'-...1--:-,5;"0::' o
Threshold level Threshold level
Fig. 7. Changes in number of arcs, average length of arc and total area
of diffraction ring due to threshold value for binarization.
a) at 20 ~m in depth from fracture surface.
b) at 100 ~m in depth from fracture surface.
arcs which contain many small spots in a DS rin! and can measure the
sub-grain size by counting the number of spots.
Fig. 8 shows an enlargement of part of a Debye-Scherrer ring by the

use of the imaging plate. This pattern was diffracted from a position at
the depth of 50 ~m from the fracture surface, at which Kmax is equal to 30
MPalffi. The DS ring is formed from many small spots, insufficient in
separation, which indicates the existence of polygonal sub-grains and the
minimum size of spot is larger than the 100 ~m of pixel. This fact suggests
that the IP spatial resolution is also usable for microbeam x-rays. If such
diffraction is obtained by microbeam x-rays with higher resolution, the
separation of each spot in an arc will be clearer and the number of spots in
Fig. 8. A partial enlargement of

diffraction pattern at 50
~m in depth from fracture
surface.
a DS ring will be countable with the help of the imaging processing system.
In order to measure the sub-grain size, two or more diffraction patterns
which were taken under different exposure times are necessary.4 When x-ray
film was used for this measurement, however, it was difficult to count the
number of spots in a pattern of low density because of the superposition of
background noise caused by the chemical fog. As the background noise of the
IP is lower than that of the x-ray film because of the wide dynamic range of
the IP, such difficulties with weak patterns are reduced.
CONCLUSION
The suitability of a new 2-D detector utilizing laser-simulated

luminescence (imaging plate) was examined for the x-ray study of the
mechanical behaviour of materials. We conclude that this detector is usable
in almost the same way as an x-ray film. Especially, this detector system
can be very useful in the field of microbeam x-ray diffraction because of
its high sensitivity and wide dynamic range.
ACKNOWLEDGEMENT
We would like to thank Dr. Y. Amemiya and Dr. A. Nadagawa of the

National Laboratory for High Energy Physics, Japan, for the use of the image
reader developed by them.
REFERENCES
1) Izumiyama, A., Y. Yoshioka and M. Terasawa, Adv. X-Ray Analysis, 22:221

(1977)
2) Sonoda, M., M. Takano, J. Miyahara and H. Kato, Radiology, 148:833 (1983)
3) Miyahara, J., K. Takahashi, Y. Amemiya, N. Kamiya and Y. Satow, Nuclear
Instruments and Methods in Phys. Res., A246:572 (1986)
4) Hirsch, P. B. and J. N. Keller, Acta Cryst. 5:162 (1952)
CORRECTION OF X-RAY DIFFRACTION PROFILES MEASURED BY PSPC SYSTEM
Shin'ichi Ohya and Yasuo Yoshioka
Musashi Institute of Technology
INTRODUCTION
When an x-ray diffraction profile is measured for stress analysis or

profile analysis by the use of a linear (straight line) position
sensitive proportional counter (PSPC) , a convex-type background line is
obtained because of the geometrical problem and the absorption of x-
rays. Such phenomenon is remarkable when a wide angular range is set on a
linear PSPC and it is, in particular, necessary to correct with a
straight background for accurate measurement of diffraction angle or
half-value breadth of the broadened diffraction profile.
In this study, the cause of such convex type background line was
analyzed and we proposed an experimental correction method to linearlize
the background line.
ANALYSIS
Fig.1 shows a basic layout of stress measurement by the PSPC system.

x-rays diffracted radially spread from the irradiated position on the
specimen and reach to the PSPC. If a zero-dimensional detector is used,
as the detector is scanned round uniformly in a circular arc with center
at the x-ray irradiated point on the specimen, the intensity of
background x-rays is theoretically constant on this arc.
On the other hand, a PSPC is normally placed so that the peak of a

diffraction profile approximately coincides in the middle point of the
effective length of the PSPC. The distance from the x-ray irradiated
point on the specimen to the PSPC is shortest at the middle point of the
PSPCj and if a is an angle between the normal of the PSPC and the
diffracted x-ray beam in Fig.1, the distance increases with increase of
absolute value of a. The x-ray intensity is inversely proportional to the
square of the distance and, moreover, it is absorbed by air in the path.
In addition, x-ray intensity is also decreased by the oblique incidence
to the PSPC. Therefore, the background intensity measured by the PSPC has
a convex-type distribution over all the effective length.

Fig.1 Schematic layout of incident

x-ray beam, specimen, PSPC
and diffracted x-rays.
Effect of X-Ray Path Length
Let I be the x-ray intensity on the specimen position; the

distribution of x-ray intensity at the PSPC position is calculated under
the following assumptions.
1) The x-ray intensity is exponentially absorbed by air in the path of
x-rays.
2) The x-ray intensity is inversely proportional to the square of the
distance in the path of x-rays.
In Fig.1, the x-ray intensity after being absorbed by air at the

position of PSPC with an angle of a, Ii(a), is expressed as
where ~ is the absorpsion coefficient of air,and R is the length of

normal of the PSPC (setting length).
Moreover, the intensity also decreases in proportion to the square

of RI. Thus, the total intensity at the PSPC is
I(a)=Io cos 2a/R2 exp[-~R/cosa] (2)
If Imax is the x-ray intensity at a=O°, the ratio of I(a)/Imax can

be derived from (2).
I(a)/Imax=cos 2a exp[-~R(1/cosa-1)]
For example, if R is 200 mm and a is 14°, the decrease on the intensity

of Cr-Ka x-rays can be calculated as about 8%.
Effect of Oblique Incidence of X-Rays to PSPC
When the x-ray beam is obliquely entering the PSPC, the counting
efficiency is outwardly decreased as the result of the spread of spatial
resolution. Such decrease has to be experimentally measured because the
decrease is dependent on the PSPC used. The PSPC used in our work had an
effective length of 100 mm and the setting length was 200 mm i ; an
angular range of 28° could be covered for measurements. The counting
efficiency was measured for the x-ray source of 50 ~m width, which was
vertically placed at a distance R=200 mm with angle of a from the PSPC.
S. OHYA AND Y. YOSHIOKA 399
..
.
1',
~ 1 0
•.....,
•
"-
..... Fig.2 Distribution of intensity
with oblique incidence of
/' \, x-ray beam to PSPC used in
/ -9 ~ this study. (50 wm width
- - X-ray Cr-Ka x-rays)
R=200mm
o~~~~~~--~~~~~
-10 0 10
Incident angle a (deg)
The result is shown in Fig.2. The ratio I'(a)/I'max was measured as the
counting efficiency; the decrease at a= 14° was 55-60%. The total
relative intensity ratio at angle a, I(a)/Imax, resulting from the x-ray
path length was then computed.
Distortion of Diffraction Profile
The effects analyzed in the previous section bring about distortion

of the diffraction profile measured by the PSPC system. So the profile
by the PSPC was simulated from a normal profile measured by the zero-
dimensional detector. A Gaussian distribution with the half value breadth
of 6° was assumed as the normal profile and the effects mentioned before
were superimposed on this profile. Fig.3 shows the simulation result. The
decrease at both ends in the background line is remarkable when these
effects are introduced to the normal profile. If the half-value breadth
is determined from both ends of this line, it is 6.67° which differs from
the initial value of 6°.
EXPERIMENTAL
Measurement of Correction Factor
If the ratio of background intensity, I(et)/Imax, is experimentally

known, the inverse of this ratio, Imax/I(a), becomes the correction
Fig.3 Simulated Diffraction pro-

files. The solid curve is
the diffraction profile ob-
tained by a zero-dimensional
detector. Value of half
value breadth is 6°. The
two-dots dash curve is the
profile for PSPC •
.,-,/'"" ''-...,-
---------~-
-16 -8 0 8 16
Angle from peak position a (deg)
(j
.,:.
Smoothed
.........
•J.
1
'iii
c:: r " pc 'T" .,
Peak counts=1024 .....Cb A fter correction

~
256 512 256 512

Channel number n Channel number n
Fig.4 Distribution of scattering Fig.5 Correction factor by the use

X-rays from non-crystal of smoothing method (upper),
glass plate. and an example of background
line corrected (lower).
factor and the diffraction intensity at angle of a can be corrected by

multiplying the experimental diffraction intensity by this factor. Hence,
this correction factor was computed for our case of diffraction by Cr-Ka
x-rays. The ~umber of channels of pulse height analyzer (PHA) for data
processing was 512 and the angle per one channel was 0.0702°. A glass
plate which is a non-crystaline material was placed at the specimen
position and its scattering x-rays, having no Bragg peaks, was measured.
Before the experiment by the PSPC, we verified a flat distribution of
scattering' x-rays over 'the angular range of 142-170° in 28 by a zero-
dimensional scintillation counter. Fig.4 shows an example of the
distribution of scattered x-rays at W=O°. The preset peak count number
was 1024. Although statistical fluctuation was observed, there were
intensity decreases, unsymmetrical, at both ends of the effective length.
The statistical fluctuation was smaller when the peak count number was
increased, but the intensity distribution along the effective length
remained substantially unchanged.
The correction factor for linearizing the background line was deter-
mined from such distribution. The value of Imax!I(a) at each channel was
smoothed by a polynomial curve fitting reported by Savitzky-Golay2. The
inverse of this value was taken as the correction factor at each channel.
The upper part in Fig.5 shows the distribution of Imax!I(a) after being
smoothed by the data at 21 points. The intensity at each channel was
multiplied by the correction factor on that channel. This correction
wasapplied to another distribution measured under the same condition. The
lower part in Fig.5 shows the result of the correction. The statistical
fluctuation is still observed but a straight-line distribution is seen
over the entire effective length.
Correction of Diffraction Profile
In Fig.6, the lower curve is an original diffraction profile from a

quenched and tempered high carbon steel specimen. Background lines are
observed on both sides of the diffraction profile. The upper curve is a
profile after being corrected; flat background lines are seen. There are
changes in half-value breadth and peak position due to using the
background equation. In Fig.6, points A and AI are respectively the
starting points on the left and right sides for determining the
background equation, and points Band BI are the end points. The number
of channels of the PHA between AB and AIBI is 21 each. The background
S. OHYA AND Y. YOSHIOKA 401
line is calculated as a linear equation from these 42 points by the

least-squares method and then both the half-value breadth (FWHM) and the
peak position are measured. Such processes were performed for various
width, W, between the starting point A and the ending point B'.
Fig.7 shows the change in both the half-value breadth (FWHM) and the
peak position of profile due to changes in the choice of the width,' W.
The peak position on the corrected profile differs in absolute value from
that on the original. However, the shift of the peak position by applying
the correction is slight. On the contrary, the half-value breadth of the
original profile is evidently increased with increase of the width,
W,but the FWHM dependence on W is smaller after the corrections are
applied. In the range below channel-width 310, since the background
equation is determined from the 42 data including the skirts of the
diffraction profile, the level of background line id increased; therefor
the FWHM decreases. This phenomenon is more noticable on the broadened
profiles than the narrow ones. The same measurement was carried out on a
diffraction profile which showed a FWHM of only 2.3 0 and low background.
However, differences of peak position and half-value breadth before and
after being corrected were insignificant.
Influence on the Stress Value
The correction of profiles is theoretically necessary at each W

which is the angle between the normal to the diffracting planes and the
specimen normal for the stress measurement by the PSPC system because the
shape of the background depends on the wangle. Hence such correction
factors were determined at each Wangle used in our stress measurement
and the stresses in the surface of the high carbon steel specimen
mentioned above were computed before and after correction. The stresses
High carbon steel (HV=600)
High carbon steel (HV=600)

~155.8
'Cb
.......
~
~ 155.7
:;:::
'iii 000 0 0 0 0 0 0 0
C>
<:1.155.6
~
Cb
Q 155.5
4.4
~
Cb 0
.....
00
~ 4.3
~
~
l.&..
4.2
..
4./ L-~_ _ _-'--~_ _ _- ' - - '
250 300 350

Channel number n Width ot channel W (ch)
Fig.6 Examples of diffraction Fig.7 Peak position and half-value

profiles before and after breadth plotted against width
correction. of channels for determining
background equation.
determined by the sin 2 w method are as follows:
Before correction 0=-1055±35MPa

After correction 0=-1057±41MPa
The result shows that the correction was not necessary for the stress
determination even with these broadened diffraction profiles.
CONCLUSION
The distortion of diffraction profiles caused by the geometrical

factor of the PSPC method is discussed and a method of correction of the
profiles, using smoothing, is propsed.
Results are summarized as follows:
1) A convex-type background line is obtained by the PSPC method because

of the difference of diffracted x-ray path lengths and oblique incidence
on the PSPC.
2) Such background line can be experimentally corrected to a straight
line by measuring the intensity of scattering x-rays from non-crystal
material such as plate glass. The correction factor was determined by
smoothing the intensities of the PHA channels.
3) It is necessary to correct the profile in order to obtain a shape
parameter of the diffraction profile such as the half-value breadth.
4) On the other hand, it is not found necessary to correct the profile
in the case of x-ray stress measurement.
REFERENCES
1. Y.Yoshioka et aI, X-Ray Stress Measurement by Use of Synchrotron

Radiation Source, J. JSMS, 35:755 (1986)(in Japanese)
2. A.Savitzky and M.J.E.Golay, Smoothing and Differentiation of Data by
Simplified Least Squares Procedures, Analytical Chemistry, 36:1627
( 1964)
STRAIN AND PARTICLE SIZE OF PALLADIUM METAL POWDERS
BY TIME-OF-FLIGHT NEUTRON DIFFRACTION
A. C. Lawson, J. W. Conant, C. L. Talcott,

M. A. David, J. Vaninetti, J. A. Goldstone,
A. Williams*, R. B. Roof and R. B. Von Dreele
Los Alamos National Laboratory

Los Alamos, NM 87545
R. L. Hitterman, J. W. Richardson, Jr.,

and J. Faber, Jr.
Argonne National Laboratory

Argonne, IL 60439
ABSTRACT
We have determined the strain and particle size for several samples of
palladium powder by time-of-flight nrutron powder diffraction on two
different diffractometers and by x-ray powder diffraction. The results are
compared and found to be in fair agreement. The time-of-flight method gives
good enough precision to reveal deficiencies in the simple models used for
strain and particle size line broadening.
INTRODUCTION
This work was undertaken to illuminate the hypothesis that metal

surfaces constitute a distinct chemical species differing appreciably from
the bulk material. This is true whether the surface is the interface
between the material and vacuum, or an intergranular interface. It is not
unrealistic to consider the surface as a separate phase with its own
structural and thermodynamic properties.
The surface of palladium metal particles tends to occlude hydrogen

atoms in a subsurface monolayer configuration with a stability
uncharacteristic of bulk palladium. Low Energy Electron Diffraction
experiments by Gdowski et a1.l and Inelastic Neutron Scattering experiments
by Nicol et a1.2 support this possibility.
The a-phase of palladium hydride exists for hydrogen/metal ratios

(H/M) between 0.001 and 0.05, and the precise value of H/M depends on
* deceased

Edited by C.S. Barrett el a/.
crystallite size. We have hypothesized that the occurrence of this phase

can be explained by the hydrogrn occupying only the subsurface layer. We
suggest that the surface layer be defined to include the ordinary particle
to surrounding surface interface, the intercrystallite interface as
described above plus the layers of atoms surrounding a low energy zone such
as a dislocation. Calculations show that complete occupation of these
surfaces result in H/Pd ratios similar to those found in a-PdH x .
Frequently it is required to determine the specific surface for a

sample of palladium metal powder. Particle size measurements are one way to
do this. Both x-ray and neutron powder diffraction techniques have been
used to determine the strain and particle size contributions to the line-
broadening of several well-characterized palladium powders. The results of
this work are given in this paper.
We have been using time-of-flight (TOF) neutron diffraction together

with the Rietveld profile refinement technique for determining strain and
particle size in palladium powder samples. This method differs from the
usual x-ray methods in several important respects. First, the neutron TOF
diffractometer has a resolution ~d/d that is essentially independent of d.
Second, the Rietveld method makes a simultaneous analysis of many
reflections. In the case of palladium, the d-space range of 0.4 ~ d ~ 3 A
includes 40 reflections. Third, neutrons have a large penetration for most
materials, so that a bulk analysis is possible.
The Rietveld method analyzes the entire diffraction pattern and makes
a simultaneous fit of crystallographic parameters (lattice constants, atomic
positions, etc.) and materials parameters (strain, extinction and particle
size). In the simplest model, one that we used for the present study, the
effect of strain and particle size is assumed to be a Gaussian broadening of
each diffraction peak. 3 This Gaussian broadening is convoluted with the
intrinsic peak shape (which is generally quite unsymmetric for a TOF neutron
source).
The Gaussian contributions from strain and particle size have

different functional dependencies on d-spacing, so that the two effects can
be readily separated. The strain contribution to the variance is 012d 2 , and
the particle size contribution is 022d4 where d is the crystallite diameter.
It is easy to determine the variances, 01 2 and °2 2 , by making a simultaneous
fit of many reflections over a large range of d-spacings. There is also a
contribution to the variance from the diffractometer, 0li2d2, that looks
exactly like sample strain. This term must be determined by calibration
using a strain-free sample, and it is used to correct the measured 012.
The dimensionless strain is given by(6)
where C is the so-called diffractometer constant that relates TOF in

microseconds (ps) to d-spacing. The conventional units for these quantities
are [C] = ps/A and [012] = ps2/A2. The particle size is given by(6)
P = C {(8 ln2) 02 2 } -1/2

1'1
and the units here are [022] = ps2/A4 and [P] A.
A. C. LAWSON ET AL. 405
Table 1. Instrument parameters for GPPD and HIPD

2 2 2
C (.~Js/A) o Ii (JJS /A. )
GPPD 10444 47 0.15

HIPD 5035 35 0.28
The sensitivity expected for strain and particle size measurements

made by TOF neutron powder diffraction depends on the instrument
characteristics C and 0li 2 . For our studies we used two diffractometers,
GPPD and HIPD. The General Purpose Powder Diffractometer4 (GPPD) is at the
Intense Pulsed Neutron Source (IPNS) at Argonne National Laboratory. The
High Intensity Powder Diffractometer (HIPD) is at the Manuel Lujan, Jr.,
Neutron Scattering Center (LANSCE)S at the Los Alamos National Laboratory.
With a 20 m flight path, GPPD has high resolution, and with only a 9 m
flight path, HIPD has somewhat less. The data were analyzed using the
Generalized Structure Analysis System (GSAS)6 of Larson and Von Dreele. The
instruments were characterized with data from the same sample of UBe13 and
the results are given in Table 1. The table also shows the calculated
quantity 0li/C, which is the effective strain contribution from the
diffractometer. This number is a measure of the resolution, as it is
difficult to resolve sample strains less than about half this value. As
expected, GPPD has about twice the resolution as HIPD.
Five samples were investigated in detail. "Alloy" is a PdO. gRhO . 1

solid solution with very large ('V200]J) particle size. "Metz" and "Fischer"
are two samples of palladium black. "A4S73" and "old MB" and "new MB" are
samples of palladium powder.
Figs. 1 and 2 show Rietveld refinements of "alloy" data for GPPD and
HIPD. In our Rietveld plots, the crosses represent the observations, the
line through the data is the Rietveld fit, and the lower curve is the
residual. The difference in resolution between the two diffractometers is
clearly evident. Figs. 3 and 4 show GPPD data for the "old MB" and "Metz"
palladium samples. The "Metz" sample shows considerable line broadening.
Results of the Rietveld refinements are shown in Table 2. We have also
included results from x-ray diffraction analysis when available .
.
:::.
Pd o.• Rho
GPPD
t ..... eo
iii
~ "0
>--
Z ~ ".0
:J
oo 8
0
w
20 5: 2.0
!:::!
N
::;
« __-,....._____---J]L
:l;
....__
,:
.;
t .o----'-.,----~, ~~----------~. .------
~ 00
2
,.
oz
11 10 2" 2'2
.t 1.' 20 21 22
D-SPACING (AI O·SPACING (AI
Figs. 1 and 2. Rietveld refinements of alloy data for GPPD and HIPD,
respectively.
Table 2. Strain and Particle Size for Palladium Samples

2 2 2 2 2 4
Run # sample 01 (}Js fA ) 02 (}Js fA ) S (%) peA)
G-3339 alloy 89 (1) .146( 1) 4000

H-560 alloy 78 (2) .307(3) 2100
G-3340 Fischer 342 (4) 14 (1) .387(2) 1190( 40)

H-667 Fischer 102 (2) .383(4) 2100
X-ray Fischer 2000
G-3338 new MB 408 (10) 36 (4) .428(5) 740 (40)

G-3342 old MB 463 (11) 36 (4) .460(5) 740 (40)
H-554 old MB 193 (6) 7 (2) .588(9) 800(100)
X-ray new MB .13 (6) 310 (80)
G-3343 A4573 390 (12) 12 (4) .418(6) 1280(200)

H-472 A4573 240 (6) .670(8) 2100
X-ray A4573 .2 ( 2) 490(230)
G-3341 Metz 2600(100) 1450(60) 1.14 (2) 116 (2)

X-ray Metz .52 (5) 140 (30)
Generally the results from the two neutron diffractometers and the
x-ray results are in good agreement. However, the discrepancies exceed the
reported experimental errors, and it is evident from the residual curves of
the Rietveld plots that the fits are not perfect. We tentatively attribute
these discrepancies to the approximate nature of the models used for strain
and particle size, which assume that there are single values (or at worst
Gaussian distributions) for particle size and strain. These models are of
course too simple for the real world, and some discrepancies are bound to
occur. The inclusion of Lorentzian as well as Gaussian line broadening
would make the model more realistic, but only with a severe penalty of
increased calculation time. Future development is likely to be in that
direction.
..
::L
1S
OLOMB
GPPO
.,
::s. O.l
ill
METZ Pd BLACK
GPPO
z~ " !Z u
:>
8 os 50 0.1
oW
~
_ ': .~''....... "-----',l.;l____
C
w
N
~ QO
' u........
J_
. ~ o.o
~
II:
~
a:
o ---. ~-'----"i---ii'_~- - - - -
oz
Z
05 ,0 \5 2.Q
O·SPACING (A)
Figs. 3 and 4. GPPD data for "old MB" and "Metz" Pd samples,
respectively.
A. C. LAWSON ET AL. 407
We tried a simple improvement, a "rocks and dust" model that

incorporated two phases. One phase consisted of very large strained
particles, and the other of unstrained small particles. We refined the
phase fractions in addition to values of strain and particle size. This
model led to slightly improved fits, but the results were not consistent
among the various experimental methods, and the model was rejected.
CONCLUSIONS
We have shown that the application of Rietveld refinement to time-of-

flight neutron diffraction data gives good results when applied to the
problem of determining strain and particle size in metal powders. Agreement
between results of different TOF diffractometers and with x-ray diffraction
results is satisfactory. The desirability of improving line-broadening
models is indicated. We are currently attempting to correlate the
stoichiometry of the a-phase of palladium hydride with the particle size as
determined by this method.
ACKNOWLEDGEMENT
This work was supported under the auspices of the United States
Department of Energy. The Manuel Lujan, Jr., Neutron Scattering Center is a
national user facility funded by the United States Department of Energy,
Office of Basic Energy Science. The Intense Pulsed Neutron Source is
operated as a National User Facility by the United States Department of
Energy Basic Energy. Sciences - Materials Sciences, under contract No.
W-31-109-ENG-38.
REFERENCES
1. G. E. Gdowski, T. E. Felter and R. H. Stulen, Effect of Surface

Temperature on the Sorption of Hydrogen by Pd(lll), Surf. Sci.,
l81:Ll47, 1987.
2. J. M. Nicol, T. J. Udovic, J. J. Rush and R. D. Kelley, Isotope

Dilution Neutron Spectroscopy: A Vibrational Probe of Hydrogen/
Deuterium Adsorbate Interactions on Palladium Black, Langmuir, 4:294,
1988.
3. R. B. Von Dreele, Neutron Powder Diffraction, in Reviews in

Mineralogy, Vol. 20, D. L. Bish and J. E. Post, eds., to be published.
4. J. D. Jorgensen, J. Faber, Jr., J. M. Carpenter, R. E. Crawford,

J. R. Haumann, R. L. Hitterman, R. Kleb, G. E. Ostrowski, F. J. Rotella
and T. G. Worlton, Electronically-Focused Time-of-Flight Powder
Diffractometers at the Intense Pulsed Neutron Source, J. Appl. Cryst.,
to be published.
5. R. N. Silver, The Los Alamos Neutron Scattering Center, Physica'

B137:359, 1986.
6. A. C. Larson and R. B. Von Dreele, Generalized Structural Analysis

System, Los Alamos Report LAUR 86-748., 1987.
NUMERICAL RESOLUTION ENHANCEMENT OF X-RAY DIFFRACTION PATTERNS
Katsumi Ohno, Hiroshi Harada, Toshihiro Yamagata

and Michio Yamazaki
National Research Institute for Metals

2-3-12 Nakameguro, Meguro-ku, Tokyo 153, Japan
ABSTRACT
A numerical resolution-enhancement method was developed for x-ray

diffraction data measured with a conventional x-ray diffractometer. This
method removes the instrumental broadening due to x-ray optics, including
the spectral distribution of the x-ray source such as the CuRu doublet. The
advantages of this method are to separate the cluster of peaks in x-ray
powder patterns into individual peaks without previous knowledge of the
number of peaks, and to remove CuKa2 reflection peaks automatically.
The instrumental window function, which was approximated by a modified

pseudo-Voigt function, was calculated from the measured diffraction pattern
of NBS Standard Reference Materials (640B) by a non-linear least squares
method. The simple diffraction patterns, including no CuKa2 peaks, were
obtained from the diffraction patterns measured with the conventional x-ray
diffractometer by using the window function mentioned above.
The application of the method of determination of the lattice misfit

between y and y' phases in Ni-base supera110ys was also described.
INTRODUCTION
The systematic errors in x-ray diffractometry can be much larger than

the random errors and there has been no real agreement as to how best to
handle them in various experimental methods. Diffractometers were beginning
to be widely used, and many felt the new instrument should provide a far
better method to increase the accuracy of the peak angles and intensities.
However, there are difficulties because the diffractometer profiles are
broadened, distorted asymmetrically and displaced from their correct
positions by amounts that depend on the shape of the incident spectral
lines, the angular separation of Ka1 2 doublet peaks, and the instrumental
and geometrical aberrations inherent'in the experimental method.
Careful studies showed a number of possible sources of error, ariSing

from the x-ray tube source and geometrical x-ray optics, which limited the
accuracy. " Mathematical analysis and careful experimental studies of the
aberrations provided a basis for developing better methods and for
correcting data.

Many of the problems arise in the spectrum of the x-ray tube. The
angular separation of the Kal 2 doublet and its variation with sin e is the
major source of diffractomete~ peaks' asymmetry and may cause errors in
peak-angle measurement.
Synchrotron-radiation parallel-beam diffractometry is one of the most

accurate methods to obtain x-ray powder data. However, the limited
availability of the SR-sources makes it unlikely they will be used for the
routine analytical applications required on a daily basis for material
characterization. The numerical resolution-enhanced method, which removes
the asymmetric instrumental broadening and CuKa2 peaks from the powder data
measured with the conventional x-ray-tube focusing diffractometer, was
developed for routine material characterization on a daily basis.
EXPERIMENTAL
INSTRUMENTS: A commercial vertical-scanning diffractometer (JEOL's

JDX-8020 was used). The diffractometer was equipped with a diffracted-beam
focusing graphite monochrometer and a step scanning mechanism controlled by
16-bit personal computer; the collected data were stored in MS-DOS formatted
files for processing including profile fitting and deconvolution. A
conventional sealed-off Cu tube was operated at 40 kV and 50 rnA.
The synchrotron-radiation parallel-beam x-ray diffractometer (PFPD)

installed on the beam line 3B at the Photon Factory in the National
Laboratory for High Energy Physics 3 was used also to measure the triplet
reflection of a quartz specimen.
A personal computer (NEC's PC-9800VX, having 1-80266 with 80287) was

used for calculations of the profile fitting and the Fourier-transform
deconvolution. A modified simplex method 6 was used for the calculation of
the smearing function from the raw data and Cooly-Tukey's fast Fourier-
transform algorism 7 and Harning's filter were used for the deconvolution.
SPECIMENS: A well-characterized silicon powder standard (NBS-640B)

was used to obtain the raw data for the calculation of the smearing
functions. Superalloy specimens were prepared by the previously reported
method. 3 Each specimen was packed into the cavity of a standard glass
specimen holder, then pressed, and the surface was flattened with a glass
slide. Specimen sizes and holder were the same in both diffractometers.
The step-scan technique was used at 0.008 deg. intervals in 2e and with a
fixed time of 5 sec. Divergence and receiving slits of 2 deg. were used.
Fourier-Transform Deconvolution Method
The basis of this method is that the measured peak profile shapes pee)
result from the convolution of the smearing function [W(e)*G(e)]
(instrumental window function) of the diffractometer and the pure intrinsic
diffraction of the specimen.
P(6) = W(e)*O(e)*s(e) + BG (1)
where wee) is the spectral distribution of x-ray such as the CuKa doublet
received at the detector
G(e) is the convolution of all aberrations arising from the
diffraction geometry and process, BG is the background, and *
represents the convolution operator
K. OHNO ET AL. 411
The deconvolution method consists of two major steps:
1) Evaluation of the W(e)*G(e) function by measuring a number of

profiles of standard specimens by using a set of instrumental parameters
identical to those that will be used in the later analysis. This step
determines the smearing functions which were the convolution of the
instrumental window function and the spectral distribution of the
diffractometer. The specimens used to measure the smearing function must be
carefully prepared and free of any line broadening (due to strain, small
crystalline size, etc.).
2) Determination of See) by deconvolution with the smearing function

[W(e)*G(e)] mentioned above: the peak shape reflected from only the specimen
itself can be calculated by deconvolution of pee) with [W(e)*G(e)] after
background subtraction, if the [W(e)*G(e)] is known.
Fourier transformation of Eq.(l) after background subtraction leads to:
pew)
sew) = (2)
W( w)xG( w)
Therefore, the intrinsic peak shape reflected from the specimen can easily
be calculated by the use of a fast Fourier-transform algorism. The first
step is to determine experimentally the convolution W(w)*G(w) by accurate
measurement of the line profiles in an angular range of interest. This
provides the smearing function, which is the convolution of the instrumental
window function as one function and the spectral distribution of the x-ray
source, at the reflection angle common to all powder patterns under a given
experimental condition.
A modified pseudo-Voigt function (mp-V) gave the best fitting for the
raw data shown as Fig. 1.
mp-V = x·G + (1-x)'L
s(L)2 ]-1 [
+ (l-x).I p ex p -4 In(2)
FWHM(L)2
with
s(L) = s(G) =
1+a(28 - 28p )/FWHM(G)
where x, I p ' a, and 2e~ are, respectively, the fractional factor relating
the ratio of the peak lntensities of G to L, the maximum peak intensity, the
asymmetrical factor (skewing factor) and the peak angle. FWHM(L) and FWHM(G)
refer to the Lorentzian and Gaussian components.
Determination of smearing functions: Ten reflections (Ill), (220),

(311), (400), (331), (422), (333), (440), (531) and (620) of the silicon
standard (NBS-640b) were measured as the raw data to calculate the smearing
functions. The smearing functions were calculated from the raw reflection
data by a method of non-linear least squares. All peak profiles measured
and the results of fitting profiles including two component profiles were
calculated using the non-linear least squares method. Some examples of them
are shown in Fig. 1, since all profiles were similar in the shape and
components, with the exception of peak position and skewing factors. The
optimized parameters of these functions were determined by minimizing the
sum of the squares of the differences between the unsmoothed experimental
points.
The experimental points and the calculated profiles together with

component profiles (dotted lines) are shown in the upper part of Fig. 1.
Twice-amplified residuals are shown in the lower part of this figure.
Fig. 1 shows that the models of the smearing functions were accurate enough
because no significant differences between the residuals and the level of
statistical fluctuations were observed. In the 28 ranges of interest, the
smearing function was calculated by linear interpolation.
Si (111) Si(400)
1.0
>-
....In
.j.J
~ 0. 5
.j.J \
<!
) j\~1.
H
0.0 F-~~-....L~~--4- +0 .05

0.00
1 - -- "- - - - - . , . . . . - - -t_ -0.05
28 29 69 70
2e(deg . ) 2e(deg . )
Si (333) Si(620)
1.0
& Si(511)
..,>-
....
~ 0. 5
..,
QJ
C
H
1""".....=----.k-----"--==-"'I-+0.05
r--_~~~~~F~...-+ 0.00
\---...,.---.---.----.---+-0.05
95 96 127 128 129
2e(deg . ) 2e(deg .)
Fig. 1 Typical reflections fitted with modified pseudo-Voigt function.

Open circles are experimental points without smoothing.
Solid lines are the sum of two calculated component profiles
(dotted line) and twice amplified residuals are shown in the
lower part.
K. OHNO ET AL. 413
!.:. 1. 0
..
: .
: .
0.5
1.0
>-
........
<II
; 0.5
.u
c
H
67 &8 69
Ze(deg . )
Fig. 2 Three overlapped quartz reflections.

Upper: Open circles are experimental points obtained from
conventional 8-28 scan focusing CuKa1 2 doublet,
where 27515 counts was normalized to dnity.
Under : Deconvoluted profiles with smearing functions obtained
from diffraction profiles of Si-Standard(NBS-640B).
Deconvolution: The triplet reflection peaks of quartz measured with

the conventional focusing diffractometer are shown in the upper part of
Fig. 2, and the peak profiles calculated from the measured reflection peaks
by convolution with the smearing function mentioned above are shown in the
lower part of Fig. 2. Each reflection was a CuKal 2 doublet and the fourth
peak was an overlap of the (203) reflection of Ka2'and (301) of Kal.
~
.....
o
N
1.0
~ ~ ""
o
M
N M
.... 0
>- -a-.
C\I
x: •
N C\I I
.....u
.
N
""
III
; 0.5 ~
....
c
H
0.0 ~ _ _ L--.3._ _ o!!----=~...30 __ ~
66.0 66 .5 67 .0 67 68 69
2e(dcg . ) 28 (deg . )
Fig. 3 Quartz triplet peaks measured with P~PD(Left) and with X-ray
tube focusing diffractometer(Right) together with profile-
fitting showing relative intensities of the CuKa doublet.
The experimental points illustrated in the upper part of Fig. 2 are

for the well-known cluster of the three overlapped quartz reflections. In
the lower part of Fig. 2, the solid line is obtained from the deconvolution
of the experimental points with the smearing function, shown by Eq.(l),
which was calculated from the experimental points of the silicon powder
standard by the profile-fitting method. Both profiles were normalized to
compare the profile shapes. The deconvoluted peaks shown in the lower part
of Fig. 2 were not reflection peaks of CuKa2 because the reflection peaks of
CuKa2 were automatically removed by the deconvolution process.
The diffraction pattern of the same specimen measured with profile-

fitting powder diffractometry (PFPD) is also shown in Fig. 3. Each
reflection in Fig. 3 is a single peak, though the second peak has a small
shoulder; hence the relative intensities can be easily determined. Ringing
structures were observed in the deconvoluted peak profiles; however, no
shoulder on the second peak was observed in the deconvoluted peak profiles.
These results suggest that better resolution will be obtained by improving
the model of the smearing function and its interpolation method. The
difference of relative peak height between the two methods was ascribed to
the difference of the x-ray optics in the diffractometers used.
The comparison of the deconvoluted pattern in Fig. 2 and the results

of profile fitting (dotted line) with the PROFIT8 in the plot at the right
in Fig. 3 shows that each reflection was a CuKal,2 doublet in the measured
reflection of CaKa2 and (301) of Kal.
There was no significant difference between the order of the relative

intensities of the deconvoluted peak profiles shown in Fig. 2, as well as
their FWHM, and of those peak profiles measured by the PFPD shown in Fig. 3.
The advantages of this method were that it required no preliminary knowledge
of the number of peaks in the clustered peaks, and it could easily determine
the correct peak positions and the relative intensities. In addition, the
FWHMs obtained with the deconvolution method were more reasonable than those
obtained with the profile fitting method as shown in Fig. 3.
The (331) reflection peaks of superalloys, which contain y' precipitate

(an ordered FCC phase based on Ni3Al in the y-matrix having disordered FCC
structure), were measured to determine the lattice misfit between y and y'
1 Ilm
Negative ..."'~----- Lattice misfit- - - -- -... Positive
Photo. 1 Typical microstructure of superalloys having lattice missfit

values from negative to positive.
K. OHNO ET AL. 415
1.0
1.0 0.5
-------j 0.0
137 138 139 140 141

28(deg.)
Fig 4 Measured (331) reflection peaks of NASAIR-l00,whose micro-

structure is showed in Photo. l(A),and its deconvo1uted peaks
phases. The determination of the lattice misfit is very important for a

computer-aided alloy design system, because the shape of Y' precipitate is
strongly dependent on the coherency strains due to the lattice misfits.
Photo 1 shows the dark-field electron image of the superalloys, where

yand y' were observed as dark and white, respectively. Alloys A) and D)
were selected as specimens for XRD measurement. The alloys having a
structure similar to a brick fence, presented as A) in Photo 1, showed
better creep rupture life than those having the structure similar to a
gravel fence, such as the pictures D) and C) shown in Photo 1. The measured
(331) reflection profile and its deconvoluted one used to determine the
lattice misfits are shown in Fig. 4. In Fig. 4 the dotted line and the
solid line were the measured and deconvoluted profiles, respectively.
The small ringing structures appearing in all deconvoluted peak

profiles are considered to result from inferior models of the smearing
function. For example, the ringing structure will disappear if the
residuals in the higher Z8-angle in Fig. 1 are significantly decreased. A
1.0
1.0 \ 0.5
'~"'>':'~.: 'r",.o! Mea sur e d
"v...
:>, " ~:' ' ':' ' :.\. .:......",.:"".:-~ .

,'"
+-'
~ 0,51---- ------10,0
+-'
r:
H
Deconvoluhd
0,0 I - - - - - - - - - - - - - - - - - j
137 138 139 140 141

28(deg.)
Fig 5 The measured (331) reflection peaks of TMS-19 whose micro-

structure is showed in Photo. l(D) and its deconvoluted peaks
small shoulder in the lower-angle side of the main peak in Fig. 5 was not a
ringing peak because the shoulder was also observed in the pattern measured
with the PFPD.3 The reflection peaks from the superlattice of the Y'
precipitate in the Y-matrix were not measured because these reflection peaks
were very weak.
CONCLUSION
Application of the newly developed "Numerical resolution-enhancement

method" to the diffraction patterns measured with the conventional x-ray
tube focusing diffractometer had the following advantages:
1) The diffraction patterns deconvoluted trom the measured patterns with

the smearing function did not include the reflection peaks of CuKa2
which were automatically removed in the deconvolution process.
2) Preliminary knowledge of the number of clustered peaks was not

required.
3) Most instrumental broadening was removed and the peak profiles

obtained were essentially symmetrical because the instrumental
broadening and CuKa2 peaks were removed.
4) Overlapped peaks obtained by this method were easily separated into

individual peaks by using a simple profile fitting.
ACKNOWLEDGMENTS
This work was performed as a part of "The advanced alloys with

controlled crystalline structures," in a project from "The basic technology
for future industries," sponsored by the Agency of Industrial Science and
Technology of MITI.
The authors would like to express their thanks to Professor M. Ando

and K. Ohsumi of the National Laboratory for High Energy Physics for their
helpful cooperation.
REFERENCES
1) H. P. Klug and L. E. Alexander, X-Ray Diffraction Procedure for

Polycrystalline and Amorphous Materials, John Wiley, New York (1974).
2) K. Ohno, H. Harada, T. Yamagata and M. Yamazaki, Trans. ISIJ, 28,:218,
(1988).
3. K. Ohno, H. Harada, T. Yamagata and M. Yamazaki, Adv. X-Ray Anal.,
32: 365-375, (1989).
4. G. Will, W. Parrish and T. C. Huang, IBM Research Report, RJ 3962
(44720) 7/22/83, Physics.
5. W. Parrish and M. Hart, Zeit. fur Kristallograph., 179, 161, (1987).
6. J. A. NeIder and R. Mead, Computer J., 7, 308, (1965).
7. J. W. Cooley and J. W. Tukey, Math. Comput., 19, 297, (1965).
8. H. Toraya, J. App1. Cryst., 19, 440, (1986).
STANDARD DATABASE FORMAT FOR THE DISSEMINATION AND STORAGE
OF DIFFRACTION DATA· TASK GROUP PROGRESS REPORT ON JCAMP·DX
G.P. Hamill
GTE Laboratories, Incorporated, Waltham, MA
R Jenkins
JCPDS-Internationai Centre for Diffraction Data, Swarthmore, PA
W.N. Schreiner
Philips Laboratories, Briarcliff Manor, NY
ABSTRACT
In planning for PDF-3, the International Centre for Diffraction Data's full pattern
database of raw diffraction data, it is evident that a standard format for storage and
exchange of diffraction data is necessary. An evaluation of the JCAMP-DX protocol
[1] by a task group" of the International Centre for Diffraction Data has resulted in a
set of format codes specific to X-ray diffraction. The proposed structure of the data is
divided into four parts: the minimal component set required by the JCAMP-DX
definition (name, data, owner, sample identification, data type, etc.), a minimum item
set required to define the X-ray diffraction data, an open selection of requested but
not required information on the sample, its preparation and the instrument, and
finally the data itself in one of several specified formats. All information stored in
JCAMP-DX format is in ASCII characters. Therefore, these data are printable, easily
read by the user and compatible with almost any computer or media storage device.
Codes defining the information are primarily in shortened, but readable, English.
The task group is completing the work on this project and will be presenting its
proposals to JCAMP.
USEFULNESS OF A DIGITIZED PATTERN DATABASE

Until recently, computer-readable storage limitations has inhibited the storing of full
diffraction patterns and the common practice has been to reduce the full experimental
* Task group members:

P.F. Dj,5more1, G.P. Hamill2, M. Holomany & R Jenkins3, W.N. Schreiner4, RL
SnyderJ, B.H. Toby6 (with support from JCPDS-International Centre for Diffraction
Data, Swarthmore, PA).
lUnivj'sity of Delaware, Newark, DE.; 2GTE Laboratories, Incorporated, W,f;ltham,
MA; JCPDS-International Centre for Diffraction Data, Swarthmore, PA; Philips
Laboratories, Briarcliff Manor, NY; j Alfred University, Alfred, NY; 6University of
Pennsylvania, Philadelphia, PA

418 VII. PHASE IDENTIFICATION, STRUCTURAL AND QUANTITATIVE ANALYSIS
29·1496
Ke.,A1 z(Si,A1)40 11(OH)z dA lal dA !at dA lal
10.1 35 2.242 12 1.536 4b
PotassIUm Aluminum Silicate Hydroxide mite·IM 5.0 30 2.216 10 1.496 40
4.43 100 2.151 12b 1.312 4b
4.33 30 2.<l93 8 1.341 6b
RH. CuK .. l. 1.5418 FIller Ni IMp 4.11 14 2.023 8 1.292 12
Cal"" lal. DilfraClometer ......... 3.66 40 1.989 12
Ref. Brindley, G .. !'eM State University, University Park, !'eDDSyl·
varna, USA .. JCPDS G,QIIJ·iII·Aid Report. (I9TI) 3.31 35 1.951 8
3.06 40 1.903 3
Sy., S.G. 2.931 16 1.820 3
• 5.2 b 8.98 c A C 2.615 12 1.688 10
II y Z
"Ref. 2.560
2.445
85
16
1.663
1.631
12
12
2.386 25 1.585 4b
D.
Specimen from Hungary. K possibly kaolinite. Mica
group. dioctabedral subgroup.
Fig.I. Example of an analog tracing on a PDF card
pattern to a set of d-spacings and relative intensities. Such a list is easy to archive and
to search. However, there are several disadvantages in the use of the reduced pattern.
The most important of these is that information such as profile shapes and presence
or absence of amorphous background peaks is ignored in the data reduction process
and, because only the reduced pattern is archived, this and other information is lost.
In an attempt to retain some of this information, the International Centre does
include a portion of analog patterns on the PDF card in certain cases, notably, clay
minerals. An example of such a card is given in Fig. 1.
Unfortunately, such information is difficult to store in the analog format, and these
data cards are expensive to produce because they must be generated by manual
methods. Although identification by search/match methods may not have been
significantly affected in the present database, information about the crystalline
quality, crystallite size, the analytical procedure for calculating d-I pairs, and phase
purity of the material is irretrievable. A second disadvantage which stems from the
use of the reduced pattern is that data reduction techniques change over a period of
time and there may be problems in comparing old d-I lists with those obtained by
state-of-the-art methods.
Problems such as those indicated above could be avoided if the full experimental
pattern were archived along with suitable reference patterns to characterize the
Instrumentation used. Such archiving would allow better data treatment methods to
be used in the future to obtain d-I data. Other benefits that would accrue through the
availability of the complete experimental pattern include the potential use of pattern
recognition techniques in qualitative analysis, and the use of full pattern fitting for
quantitative analYSIS [2,3]. With the recent advent of low cost, high storage capacity
systems, based on CD-ROM technology [4] now available on all levels of computers,
fully digitized diffraction patterns can be saved for future review and use.
THE NEED FOR A STANDARD X-RAY DIFFRACTION DATABASE

FORMAT
Before a database of full diffraction patterns can be assembled it is necessary to
establish an acceptable format for data storage. Such a format should be usable by a
G. P. HAMILL ET AL. 419
wide range of software programs running on many different types of computers.

While it is not difficult to set up a system for the storage of the actual intensity/angle
data, the appending of "sufficient" experimental details does present some problems.
Within the file formats discussed in this paper these "absolutely necessary" labels are
referred to as "top level" labels. An ideal format is one which is easy to apply with the
minimum of top level labels. Similarly, the ideal software program for writing the
data file is not one requiring the entering of vast quantities of repetitive (even though
useful) data. The ideal system is also one which will allow future retrieval of all
information within the data file and l?ermits easy extension as new parameters are
needed. The need for a suitable digitIZed pattern database system is urgent because
digitized diffraction patterns are now being submitted to the ICDD headquarters from
all over the world. A standard database format is needed to ensure that these data can
be archived in an easily retrievable form for future use.
Round robin tests [5] have indicated that the angular effects of sample and instrument-
dependent parameters are difficult to correct for on a purely theoretical basis. The
next best alternative is to "model" the intensity sensitivity of individual diffractometers
by use of an instrument intensity-calibration standard. Such effects as divergence slit
aperture, detector dead time, etc., can each introduce systematic errors into the
experimental intensities which are very instrument dependent. Efforts are now
underway to accumulate reference data on as many different diffractometers as
possible in order that the problem can be better quantified and recommendations
made where appropriate. We anticipate the need to store, alon~ with each (set of)
diffraction pattern, a similarly recorded diffraction pattern of the mtensity calibration
standard.
JCAMP-DX STANDARD FILE FORMAT

The problem of the archiving and retrieval of full spectral data is one which is
common to most fields of absorption spectroscopy. The problem has been addressed
by the Joint Committee on Atomic and Molecular Properties (JCAMP), which has
produced a generalized database format referred to as JCAMP-DX [1]. JCAMP-DX
IS a standard file-form format for the exchange of infra-red spectra and related
chemical and physical information between spectrometer data systems of different
manufacturer, main-frame time-sharin~ systems, general-purpose laboratory
computers, and personal computers. It IS compatible with all media: telephone,
magnetic and optical disk, magnetic tape, and even the printed page (via optical
reader). Table 1 lists the major design criteria for the JCAMP-DX format.
All data are stored as labeled fields of variable length using printable ASCII
characters. A JCAMP-DX compatible spectrum is a text file which can be viewed,
Table 1. Design criteria for JCAMP-DX
1. Ability to represent exactly digital output of dispersive, FT-IR, tunable-filter,

and laser spectrometers, including spectra, mterferograms, transformed
spectra, and peak tables.
2. Ability to represent descriptive information on sample identity, sample
preparation, instrument parameters, computational parameters, and
comments, as well as spectra data, as appropriate for applications.
3. Internal documentation, readable by humans.
4. Aceptability by a wide variety of computers, communication systems, and
storage media.
5. Expandability of each data field to whatever length is required. Ability to add
new data fields as the need arises.
6. Sufficiently precise specifications for design of software to produce
JCAMP-DX files whIch can be decoded by other systems designed
independently to the same specifications.
corrected, and annotated with a text editor. Until recently, the main focus has been on
infrared spectra, but JCAMP-DX can easily accommodate Raman, UV, NMR, mass
and other types of spectra, X-ray powder patterns, chromatograms, thermograms, and
other data which require the capability of representing contours as well as peak
positions and intensity. JCAMP-DX also provides for combining adequate
mformation about the sample and method of observation with its spectrum.
PROGRAMS FOR CREATING JCAMP-DX FORMAT DATA

The ICDD recently established a task group to make recommendations for the
creation and use of a standardized database format. While the recommendations of
the task group are yet to be finalized, the task group did come to the following
conclusions:
a) An absolute minimum of top-level labels should be used; just sufficient
to identify the sample, plot the data, convert peaks to d-values, and
conform to minimum JCAMP-DX standards.
b) Provision must be made for recording all data elements thought to be
relevant by anyone, today or in the future. These non t0la-Ievel elements
should be organized and packed in a hierarchical orm. A default
IITITLE- 51 (Ill) FOR JENKINS NO RECEIVING SALIT

IIJCAHP-DX- 4.23
IlDATA TYPE- XRAY DIFFRACTOGRAH
"ORIGIN- CHEM. ENG. DEPT., UNIV. OF DELAWARE, NEWARK, DEL.
flSOURCE REFERENCE- DATA01 A: XR07. OAT
fI SOPERATOR- P. F. DISMORE
flDATE- 88/05/30
flTIME- 07: 27: 54
"$TARGET- CU
U$XRAYKV- 45
U$XRAYMA- 2
U$LAKBDA- 1.5418
"$INT STI>- SI
"$DIV SLIT- VARIABLE
"$REC SLIT- 6MM
"$COUNT TIME- .5
"$LOWPHA- 6
"SUPPHA- 99
"DELTAX- .02
flMAXY- 76197
IlXUNITS- 2THETA
"YUNITS- COUNTS
"XFACTOR- • 001
IIYFACTOR- 1
"PIRSTX- 4
"LASTX- 50
,'NPOINTS- 2301
flFIRSTY- 18
flXYDATA- (X++ (Y ••• Y»
4000 18 21 18 23 21 14 27 21 17 10
4200 19 18 23 17 12 19 22 18 16 20
4400 17 7 13 15 11 18 10 17 11 22
4600 16 15 16 12 11 15 11 7 16 10
4800 15 11 13 19 15 13 11 10 10 12
5000 14 11 9 8 12 12 11 15 6 15
5200 15 13 18 18 9 8 9 19 10 11
5400 16 9 8 16 6 11 19 14 11 13
5600 12 14 18 15 12 14 16 11 18 14
5800 13 13 14 15 13 15 7 12 6 10
6000 18 12 15 18 12 18 11 14 15 13
6200 15 14 15 17 8 21 13 24 13 17
6400 22 10 18 17 23 19 20 18 16 12
6600 19 20 18 16 22 14 11 21 15 14
6800 8 20 15 10 13 11 16 14 19 12
7000 16 16 16 19 11 17 17 11 16 6
7200 13 24 15 11 12 11 14 23 21 13
7400 7 15 11 16 13 22 13 21 11 13
7600 16 11 11 24 11 11 14 14 10 14
7800 15 13 17 15 20 13 17 14 17 11
8000 18 13 17 17 16 14 12 16 11 16
8200 13 15 11 15 12 11 21 19 14 20
8400 9 14 11 14 14 16 12 24 16 12
8600 18 13 16 13 16 18 11 11 12 15
8800 19 15 10 10 13 10 15 14 11 11
9000 15 15 11 17 15 15 18 17 13 14
9200 8 19 9 17 17 14 11 14 7 12
9400 13 6 18 11 10 12 6 16 15 15
9600 9 11 9 16 21 14 20 19 19 14
9800 16 9 16 21 17 20 13 14 16 15
10000 9 17 13 17 17 12 13 12 15 13
Fig. 2. Straight Flow Data Base Format for the storage of X-ray diffraction data
G. P. HAMILL ET AL. 421
format should be provided and extensions allowed provided that they

are self-defining.
c) The format must allow for other top-level XRD labels, if deemed
necessary by a given laboratory. However, such top-level data elements
must not be repeated elsewhere in the file.
d) Only formats for powder diffraction data should be created at this time,
even though electron and neutron diffraction files might be similar.
e) Multi-variable data must be accommodated.
There are essentially two approaches which can be taken to satisfy at least most of the
requirements listed above. The simplest approach is to use a simple "straight flow
format" in which a series of questions are posed to define the experimental
parameters. A more comprehensIve approach is to use a fully hierarchical database
format in which experimental details are broken down into top-level and ancillary
information. In practice, a combination of the two will meet the needs defined above.
A second distinction is data that vary from run to run and data that do not. For
example, the specimen identification is an "absolutely required" piece of information
for each sample run and is, therefore, top-level informatIOn. On the other hand, the
particular X-ray tube type (sealed fine-focus, rotating-anode, etc.) is constant in a
given laboratory and, while this experimental detail is relevant, the operator should
not be forced to define this detail for every sample run.
Programs for creating JCAMP-DX formatted data sets have been written for several
computers utilizing various methods for interacting with ASCII data. FORTRAN and
BASIC have been utilized to create straight-flow data sets. The hierarchical format of
the data was produced using the Shareware program PC-Outline [6] designed to create
indented tabs of information. Each program should be able to retrieve the majority of
information from a "standard information" file and the corresponding data file created
by the diffractometer. The final data sets, in all cases, can easily be modified by any
text editor. Therefore, data from any type of computer, written by any type of
program, can be safely stored in ASCII format and submitted to International Centre
for Diffraction Data for inclusion in the PDF-3 database.
STRAIGHT FWW FORMAT

Fig. 2 gives an example of a simple straight flow format program. The ## at the start
of each line, preceded only by blanks indicates the start of a data label. The =
indicates the end of the data label. A $ sign indicates the first character of a user
defined label. As examples, The "Data T~e" is preceded by a ## but has no $
because it is a required JCAMP-DX label. 'Target' is preceded by a ## because it is
a label, but also starts with a $ because it is a user defined label - being specific to
X-ray diffraction. Thus the straight flow format is simply a series of JCAMP-DX
reqUIred labels: "TITLE"; "DATA TYPE"; "FIRSTX"; etc., and user. defined labels:
"TARGET"; "COUNT TIME"; etc. Each individual experimental count datum is
entered as a real number which can be scaled by the "YFACTOR". Data are entered
and displayed in ten columns across the page preceded in each case by an X axis
indicator. This semi-compressed format is one standard presently available.
HIERARCHICAL DATABASE FORMAT

Fi~. 3 gives an example of program code for a hierarchical database format. Although
imtially the format appears more complex and, therefore, harder to interpret than the
straight flow format, all related information is grouped together. Laboratory
information, source and diffractometer types, and standard runs documentation, for
example, would each have independent labels with hierarchical subheadings.
B. **X-RAY SOURCE=
1. Tube:
a) Type = (Sealed Beam, Rotating Anode, .•• )
b) Anode = (Cu, Co, Fe, W, ..• )
c) Manufacturer = (Philips, Rigaku, Siemens, ••. j
d) Model = (LFF, FF, BF, cylinder, Disk ..• j
e) Focus Used
1) Line:
a> width = 0.5 [mm]
b> Length = 13 [mm]
2) Spot :
a> Diameter = 0.5 [mm]
f) Serial Number = 40983
g) Power Rating = 1800 [w]
h) Take-off Angle = 6.2 [deg]
2. Generator
a) Type = (Half Wave, Full Wave, Constant Current, Regulated,
••• j
b) Manufacturer = (Philips, Rigaku, Siemens, ••. j
c) Model = XRG-2000
d) Serial Number = 120-00309
e) Settings
1) Voltage = 45 [kV]
2) Current = 35 [mAl
f) Stabilization
1) Voltage = 0.01 [%]
2) Current = 1.0 [%]
Fig. 3. Hierarchical Data Base Format for the storage of X-ray diffraction data (A
portion of the section defining the "X-ray Source")
CONCLUSIONS
The JCAMP-DX format seems well suited for the storage of digitized X-ray powder
patterns. While the straight flow format for data entry provides the simplest system to
utilize, the greater experimental detail definition offered by the hierarchical system
may make its use preferable. The need to store intensity calibration data along with
each experimental pattern (or at least a reference to a full instrument calibration data
file) seems essential.
REFERENCES
[1] McDonald, RS. and Wilks, P.A,Jr., JCAMP-DX: A Standard Form for
Exchange of Infrared Spectra in Computer Readable Form, Appl. Spectrosc., 42
(1988) 151-162.
[2] Smith, D.K., Johnson, J.J.,Jr. and Wims, A, Use of full diffraction spectra, both
experimental and calculated, in quantitative powder diffraction analysis,
AustrJ.Phys., 41 (1988) 311-321
[3] Taylor, J.C. and Pecover, S.R, Quantitative analysis of phases in zeolite bearing
rocks from full X-ray diffraction patterns, AustrJ.Phys., 41 (1988) 323-335
[4] Jenkins, R and Holomany, M., PC-PDF - A search/display program utilizing
the CD-ROM and the complete powder diffraction file, Powder Diffraction, 1.,
(1987) 215-219
[5] Jenkins R and Schreiner, W.N., Intensity Round Robin Report, Powder
Diffraction, 1.. (1989) 74-100
[6] PC-Outline - available through Softworks Development, 750 Stierlin Rd., Suite
142-A, Mtn. View, CA 94043
X-RAY ANALYSIS OF THE STRUCTURE OF WHOLLY AROMATIC
COPOLYAMIDES AND COPOLYESTER CARBONATES
A. -I. Schneider and J. Blackwell

Department of Macromolecular Science
Case Western ReselVe University
Cleveland, Ohio 44106-2699
ABSTRACT
This paper summarizes our work on the structures of two wholly aromatic
copolymers: the copolyamide prepared from terephthalic acid, phenylene diamine, and
3,4' -diaminodiphenyl ether (mole ratio 50/25/25) and the copolyester carbonate prepared
from p-hydroxy benzoic acid and hydroquinone, with the introduction of carbonate units
(mole ratio 60/20/20). X-ray fiber diagrams of both copolymers exhibit a number of
aperiodic meridional maxima that are similar to those reported for a series of wholly
aromatic copolyesters. The latter systems have been shown to consist of arrays of parallel
chains of completely random comonomer sequence: the aperiodic maxima arise due to
structural correlations along the extended random sequences. The structures studied in the
present paper are more complex due to the presence of kinked units, i.e. the 1,3 phenylenes
and ether linkages of the copolyamide, and the carbonate groups of the copolyester
carbonate. The results obtained show that the x-ray data can be explained by completely
random monomer sequences. However, the chains are significantly distorted in order to
produce more extended conformations than might be expected for isolated chains. These
distortions minimize the effects of the kinked units and lead to better chain packing.
INTRODUCTION
In recent years there has been extensive x-ray work on the structure of a group of
wholly aromatic copolyesters and similar copolymers, including copolyamides and
copolyester carbonates. These polymers are finding commercial applications as high
strength fibers and high performance moldings (eg. Vectra (Hoechst-Celanese), Xydar
(Amoco) and Technora (Teijin».
Analysis of these structures has focussed mainly on one of the simplest copolymers,
the copolyester prepared from p-hydroxybenzoic acid (HBA) and 2-hydroxy-6-naphthoic
acid (RNA). The homo polyesters are crystalline infusible materials, but copolymerization
lowers the melting point to below 300°C in the middle of the composition range. The melts
are nematic due to the inherently extended chain conformation, which occurs as a result· of
the 1,4 and 2,6 aromatic linkages. The x-ray patterns of melt spun fibers indicate a high
degree of orientation along the direction of draw, and also that three dimensional order
crystallinity is present. This order increases further upon thermal annealing, with the
development of polymorphic crystalline structures. A most interesting feature of the data is

that the scattering in the molecular axis direction, along the meridian of the fiber diagram.
consists of a series of aperiodic maxima, i.e. they are not orders of a single repeat. The d-
spacings also shift with the monomer ratio and could be used analytically to determine the
composition.( 1)
It has been shown in this (1-4) and other laboratories that the above aperiodic
diffraction arises from a structure consisting of parallel chains of random sequences of the
two monomers. The meridional intensity is calculated as the Fourier transform of the
autocorrelation function of the chains, which define the probability and spatial relationship
of the nearest neighbors in the copolymer sequences. This calculation is performed most
effectively by treating the copolymer chain as a one dimensional paracrystal with bimodal
coordination statistics.(5) The intensity is calculated from the first nearest-neighbor
probability function, Ql(z). Ifwe treat the monomers as points, the Fourier transform of
Q 1(z) can be written as the product of three matrices P, M and X:
where
exp 2m ZZB 0
I o PN I
P = PB 0
M = IMBBMBN
MNBMNN
X=
o exp 2m ZZN
Here Z is the coordinate in reciprocal space in the chain axis direction and the subscripts B
and N designate HBA and RNA respectively. The P matrix defines the monomer ratios for
HBA and HNA, PB and PN; the M matrix defines the probabilities of forming the four
possible monomer pairs, and the X matrix contains phase terms defined by the lengths of
the two monomers. The meridional intensity I(Z) is given by
I(Z) = 1 + ~ ~ 2PARe[TAB(Z)]
where TAB(Z) is an element of the matrix T(Z) defined as
M·X(Z)
T(Z) = 1- M.X(Z)
in which I is the unity matrix. When we use atomic models for the monomers, the equation
becomes
FAB(Z) is the Fourier transform of the cross correlation of monomer A with monomer B,
given by
FAB(Z)= L Lf A,JB,jexp[21riZ (ZBrZA,d]

i j
Here f is the atomic scattering factor of the atom with axial coordinates z, and the
subscripts A,i and B,j designate the ith atom of monomer A and the jth atom of monomer
B.
Excellent agreement was obtained between observed and calculated data for models
consisting of completely random sequences of monomers.( 1,5) Modification of the M
A.-I. SCHNEIDER AND J. BLACKWELL 425
a) ~L@-A~ot-©-i.~N-@-0-@jN~,
b) ~~-@-~~%oJ(J)
60 20 20
Fig. 1 Chemical structure of a) the copolyamide of terephthalic acid,
phenylene diamine and 3,4' -diaminodiphenyl ether and b) the
copolyester carbonate of p-hydroxy benzoic acid, hydroquinone
and carbonate units.
matrix allows us to consider non-random sequences. This results in shifts and splitting of
the peaks predicted for random sequences, and the agreement with the observed data is
soon lost, such that we can eliminate all but minimal deviation from randomness.(5) This
conclusion has recently been confirmed by NMR work on partially deuterated
copoly(HBMINA) which pointed to a random sequence distribution for the polymerized
50/50 composition.(6)
The above methods have also been applied successfully to other copolyesters
containing three or more monomers.(7 ,8) In the present paper we describe analyses of still
more complex structures: a copoly amide prepared from terephthalic acid (TPA),
phenylene diamine (PDA) and 3,4' -diamino-diphenyl ether (DPE), and a copolyester
carbonate prepared from HBA and hydroquinone (HQ) with the insertion of carbonate
units. The monomers for these systems are shown in Fig. 1. The key point here is that the
presence of the 1,3 phenylene and ether linkagesdnthe copolyamide and the carbonate units
in the copolyester carbonate lead to "kinks" in the chains, i.e. they are not so straight as in
the copoly (HBMINA) system, which must affect the conformation and packing of the
chain.
EXPERIMENTAL
Specimens of 50/25/25 copoly(TPNDPFJPDA) were supplied by Teijin Co. (Osaka,

Japan) in the form of solution spun fibers (Technora). Species of 60/20/20
copoly(HBAlHQ/CO) were prepared by Dr. Pielartzik of Bayer A.G., Leverkusen, W.
Germany. Fibers of the latter were drawn by hand from the melt. X-ray fiber diagrams
were recorded using a Searle toroidal focussing camera and Ni-filtered CuKa radiation.
The d-spacings were calibrated with CaF 2. Diffractometer data recorded along the
meridional direction for aligned mats of fibers, using a PN 3550/10 diffractometer in the
transmission mode.
Copoly (TPNPDNDPE)
Fig. 2 shows x-ray patterns for solution spun fibers of copoly (TPNDPFJPDA) with
a 50/25/25 mole ratio. The x-ray fiber diagram shows a high orientation and a perhaps
surprisingly high degree of crystallinity when one considers that this is a copolymer. Fig.
3 (curve d) shows the diffractometer data recorded along the fiber axis (meridional)
direction: five maxima are observed, and two more weak maxima are seen in the film data,
and their positions are indicated by arrows. The d-spacings are indicated above the peaks
and are seen to be nonperiodic.
Fig. 2 X-ray pattern for solution spun fibers of

copoly(TPAlDPFJPDA).
Models for the monomers were constructed based on standard bond lengths and
angles. The lengths of the monomers are defined between the nitrogens of the amide
group. Thus the length of the PDA unit is set at 5.64A. The phenyl-amide inclination of
the TPA unit was set at 30°, approximately that found in poly(phenylene
terephthalamide)(9), and depending on the actual combination of torsion angles selected,
the TPA length can vary from 6.75 to 7.26A. The most variable structure is the DPE unit,
where changes of the phenyl-ether torsion angles lead to a range of nitrogen-nitrogen
lengths from 7.39 to 10.02A.(10)
In initial calculations, using both point and atomic, all combinations of monomer
lengths were explored, and the best fit obtained was for the maximum length in each case,
corresponding to a fully extended chain.(10) It is significant that when the DPE unit is at
its maximum length, the zig due to the 1,3 phenylene is compensated by the zag of the ether
linkage, such that linear progression of the chain is maintained. Curve a in Fig. 3 shows
the calculated meridional intensity for an atomic model, where the good agreement between
the observed and calculated d-spacings can be seen. In addition there is a reasonable match
for the intensities.
Nevertheless, an obvious discrepancy between curves a and d in Fig. 3 is the width
of the peak at d ~ 2.1A, where the calculated peak is much sharper than that observed.
Note that both peaks are truncated, and the actual areas under the peaks are approximately
equal. The sharpness of the calculated peak at this position has been seen previously in
work on the copolyesters, and it has been shown that this arises from the assumed linearity
of the chains.( 1,5) Stereochemically acceptable models for the chains are highly extended,
but not fully linear, so that the advance per monomer is only approximately consistent for
each monomer type. Some idea of the non-linearity can be obtained by surveying a number
of models and measuring the axial advance for each monomer. Fig. 4 shows projection of
typical chains, together with the results of a survey based on 100 such chains of 15
monomers, where the distributions of lengths are presented as histograms.( 11) This data
can be incorporated into the calculations via the X matrix, and the results for an atomic
model are shown as curve b in Fig. 3.
It can be seen that the peak at d 5! 2.IA has been broadened by incorporation of the
length distributions presented in the histograms. However, we still have not reproduced
2.14
d)
3.32
.1
c)
o 10 20 30 40 50
29 (degrees)
Fig. 3 a) Calculated meridional intensity for idealized linear chains of

random sequence. The peaks at d=4.3A and 2.1SA have been
truncated. d-spacings are shown above the individual peaks.
b) Calculated meridional intensity for non-linear chains defined
by the histograms in Fig. 4.
c) Calculated meridional intensity for a model in which the
widths of the histograms in Fig. 4 are quadrupled and then
shifted.
d) 8128 diffractometer scan of x-ray intensity scattered by the
copolyamide fibers along the meridional direction. Peaks
marked with an asterisk are off-meridional intensity arced over
the meridian due to disorientation.
a)
b) :m. POA TPA
'0 100.
~
Q)
E 100.
..0
:l
Z OPE
00.
O.~rr~----~~~--~~~-+~~~~~
0.0 5.5 6.0 6.5 7.0 9.5 10.0
Length of residues (A)
Fig. 4 a) Projections of models of typical chains of 15 monomer units.
b) Histograms of axial advance for the three monomer types
derived from 100 chains of 15 monomers.
the width of the observed peaks: to do this a broader distribution of lengths is necessary,
and we have found that we can match the peak widths if the length distribution is
broadened by a factor of 4. This means that the chains are rather more non-linear than
might have been imagined based on the models in Fig. 4. In addition, the length
distribution implies non-linearity which can only be achieved if we have a less extended
conformation. This results in shifts of all calculated peaks to lower d-spacings, since their
positions depend on the average axial advances for each type of residue, which are now
reduced from the fully extended values.
The only way to have agreement between the observed and calculated data is for the
average axial advance for each monomer to be approximately equal to the fully extended
lengths used previously (to generate curve a) and to incorporate broadened histograms.
This results in the calculated intensity curve shown in Fig. 3, curve c, which is in excellent
agreement with the observed data. ( 11) This leads to the following conclusions: the chains
are highly extended but also significantly non-linear, such that some of the monomers are a
little stretched beyond the lengths expected based on acceptable models for isolated chains.
This distortion probably arises because of the need to pack random copolymer sequences:
the kinks on identical sequences are easily accommodated but when random sequences
pack there will need to be some "flattening" of the chains, otherwise there will be
unacceptable spaces in the structure. Perhaps the most likely distortions will be in the
torsional angles of the amide groups, but some distortion of the bond angles and non-
planarity of the phenyl rings can also be expected.
Fig. 5 X-ray pattern of melt spun fibers of copoly(HBNHQ/CO)

arranged a) perpendicular to the beam and b) tilted by 21 0 from the
perpendicular.
Copoly(HBMIQlCO)
The above analyses have been extended to consider copolyester carbonates prepared
from HBA and hydroquinone, with the introduction of carbonate linkages by the addition
of biphenyl carbonate in the reaction mixture. Five different monomer ratios have been
examined, but only our results on the 60/20/20 composition are presented here. Fig. 5
shows the x-ray pattern of melt spun fibers arranged a) perpendicular to the beam and b)
tilted by 21 0 from the perpendicular. Four non-periodic meridionals are observed, and
these can be seen on the meridional diffractometer scan presented as Fig. 6, curve c, where
the d-spacings are indicated above the peaks.
Fig. 7a shows four random sequence chains in stereochemically acceptable extended
conformations. The presence of the carbonate groups leads to kinks in the chain, which
cannot immediately be compensated for, as was the case for the copolyamide. Hence there
is significant non-linearity, and axial progression becomes difficult unless we constrain the
kinks to alternate, as has been done for the chain in Fig. 7a. It seems obvious that there
3.22
2.15
0.00 10.0 20.0 30.0 40.0 50.0

29 (degrees)
Fig. 6 a) Calculated meridional intensity for non-linear chains shown in

Fig.7a.
b) Calculated meridional intensity for chains with distorted
carbonate units.
c) el2e diffractometer scan of x-ray intensity scattered by the
copolyester carbonate fibers along the meridional direction.
Peaks marked with an asterisk are off-meridional intensity
arced over the meridian due to disorientation.
b)
Fig. 7 Projections of models of typical chains with a) planar carbonates

and b) distorted carbonates.
would be major problems in packing chains like this, when the kinks occur randomly along
the monomer sequences. Nevertheless, we proceeded to treat the data in the same way as
for the previous copolymer, deriving histograms of monomer lengths and calculating the
meridional intensity, which is presented as Fig. 6, curve a. The agreement obtained is
very poor, in terms of position, intensity and profile of the peaks. The first predicted peak
is at d = 6.IIA, deviating significantly from the observed peak at d = 6.4 7±O.1 oA. This
first peak is a measure of the average advance per phenylene ring, and it is clear that the
chain must be more extended than those shown in Fig. 7a. The most likely way of
extending the chains would be by distorting the torsion angles of the carbonate unit. In
constructing the models in Fig. 7a, we assumed that the carbonates, like the ester units, are
planar due to delocalization of the carbonyl oxygen lone pairs. Torsion distortion of the
carbonate involves much less energy than similar distortion of the ester, and it is possible to
adjust this group so that we have a "crank shaft" structure in an otherwise straight chain.
Examples of chains incorporating this type of distortion are shown in Fig. 7b, and the
calculated meridional intensity for a nematic array of chains is shown in Fig. 6, curve b. It
can be seen that excellent agreement is obtained. It is also clear that introduction of
distortions to linearize the chains will also relieve most of the problems inherent in packing
the undistorted chains. We can conclude therefore that the distortions necessary to achieve
good agreement between the observed and calculated x-ray data occur because of the
requirements for chain packing of random sequences. The energy necessary to distort the
carbonate groups will be more than compensated by the better packing of the molecules.
Although we have only distorted the carbonate groups in our model, it is reasonable to
expect the distortions to be spread over the rest of the molecules to involve the ester and
phenyl groups, just as we proposed for the copolyamide discussed earlier. It should also
be noted that studies of deviations for random sequence show that unacceptable deviations
occur between the observed and calculated data for all but minimal non-randomness. The
results presented here for copoly(HBMIQ/CO) will be discussed in more detail in a
forthcoming publication.( 12)
CONCLUSIONS
X-ray analyses of the structure of random wholly aromatic copolyesters have been
extended to consider a copolyamide and a copolyester carbonate which contain "kinked"
units. In both cases, the results favor random monomer sequences that are highly
extended, and show that the requirements of packing lead to distortion of the chains away
from conformations that might be considered optimal for the isolated molecules.
Assemblies of these chains are now being considered by computer molecular modeling
methods, and the results of these studies will be presented at a future date.
ACKNOWLEDGEMENTS
This work was supported via NSF Grant No. DMR86-14093.
REFERENCES
1. Gutierrez, G.A.; Chivers, R.A.; Blackwell, J.; Stamatoff, J.B.; Yoon, H. Polymer,
1983, 24, 937.
2. Blackwell, J.; Gutierrez, G.A.; Chivers, R.A. Macromolecules 1984, 17, 1219.
3. Mitchell, G.R.; Windle, A.H. Colloid Polym. Sci., 1985,263,230.
4. Blackwell, 1.; Biswas, A.; Bonart, R. Macromolecules, 1985, 18,2126.
5. Biswas, A.; Blackwell, J. Macromolecules, 1987,20,2997.
6. Muhlbach, A.; Johnson, R.D.; Lyerla, J.; Economy, J. Macromolecules 1988,21,
3117-3119.
7. Blackwell, J.; Gutierrez, G.A. Polymer 1982, 29, 671.
8. Blackwell, J.; Cheng, H.-M.; Biswas, A. Macromolecules 1988,21,39-45.
9. Northolt, M.G. Eur. Polym. J. 1974, 10, 799.
10. Blackwell, J.; Cageao, R.A.; Biswas, A. Macromolecules 1987,20,677.
11. Cageao, R.A.; Schneider, A.-I.; Biswas, A.; Blackwell, J., Macromolecules in
press.
12. Schneider, A.-I.; Blackwell, 1.; Pielartzig, H. in preparation.
POLYMORPHISM IN SYNDIOTACTIC POLYSTYRENE
B.G. Landes, M.T. Malanga,* and B.P. Thill*
Polymeric Materials Research Center

Dow Chemical Co., Midland, MI 48667
*Designed Thermoplastics Research
Dow Chemical Co., Midland, MI 48667
INTRODUCTION
Polystyrene has been commercially manufactured for over fifty years.

Today it enjoys widespread application in appliances, food containers,
packaging, toys and thermal insulation. Generally, the term polystyrene is
used as a generic descriptor for the atactic configuration of the polymer
chain. In this context the term configuration refers to structural
regularity with respect to the substituted carbon atom within the polymer
chain. In atactic polystyrene (PS) the phenyl groups are distributed
randomly along either side of the polymer backbone (Figure 1). Since there
is no significant degree of long range order along this chain the polymer
will not crystallize to any appreciable level.
Isotactic polystyrene (IPS) was synthesized in the early 1950's. In

the isotactic configuration the phenyl groups all lie on the same side of
the polymer backbone (Figure 1). IPS will crystallize above the glass
transition (Tg) to form a high melting (-240'C) material with good solvent
resistance and improved mechanical properties. Unfortunately, the
commercial significance of IPS has been greatly limited by its relatively
slow crystallization rate.
Syndiotactic polystyrene (SPS) has been synthesized only recently (1-

4). In the syndiotactic polymer the phenyl groups vary alternately from
side to side of the polymer backbone (Figure 1). Above Tg , SPS will
crystallize to form a high melting (-270'C) material. This polymer
possesses a high crystallization rate, good solvent resistance and other
physical properties which are of commercial interest. It has been observed
both in our lab and elsewhere (1,5-7) that SPS can crystallize into

ISOTACTIC
R R R R R
, "' \""' \""' \""'

-1C,!~C,!_",./,!_",./, ~C,
" \"
SYNDIOTACTIC
" " " "
ATACTIC
,
R "
"\
R
"\
-1C'!~/'!""/'!·~l'!""/C,
"\
R
"\
"
" \R \" \" \R

Figure 1. "
" Schematic " "
representation of
chain configurations in
polystyrene (R = phenyl group).
different crystalline forms. In any given sample the crystalline form whicl
develops depends strongly on polymerization, crystallization and processing
conditions. In addition, exposure of SPS to selected solvents can induce
changes in the crystalline structure (8,9). This behavior has also been
reported for IPS (10,11).
We have analyzed SPS samples after a variety of sample treatments.

This paper reviews the characterization of these materials by x-ray
diffraction and simultaneous differential scanning calorimetry/x-ray
diffraction (DSC/XRD). Preliminary data is presented on the crystalline
forms of SPS and the transformation of one form to another as a function of
temperature.
EXPERIMENTAL
Syndiotactic polystyrene (SPS) samples were obtained in the as-

polymerized form from aliphatic solvent slurry reactions. The levels of
syndiotacticity in each sample were determined by NMR. Molecular weight
distributions were determined by high temperature gel permeation
chromatography (GPC). Samples of atactic polystyrene with known molecular
weight distributions were used to calibrate the GPC measurements. Weight-
average molecular weight (~) and percent syndiotacticity for each of the
analyzed samples are listed in table 1.
B. G. LANDES ET AL. 435
Table 1. Weight-Average Molecular Weights, Percent

Syndiotacticities and weight-Fraction
Crystallinities, (W c )' for SPS Samples
SAMPLE Mw %SYNDIOTACTIC Wc
API 86,000 90 51
AP2 354,000 >95 63
MCI 354,000 >95 52
MC2 354,000 >95 70
QU 354,000 >95 <5
Structural data was obtained from several SPS samples, each possessing
a different thermal history. Two as-polymerized resins were characterized.
These resins were polymerized using different catalyst systems and are
labeled API and AP2. Structural data was also gathered on two melt-
crystallized materials. The first melt-crystallized sample (MCl) was
prepared in a DSC cell by holding -100 mg of AP2 at 3l0'C for 1.5 minutes,
then cooling at 5·C per minute to room temperature. Sample MC2 was prepared
by heating -100 mg of AP2 in the DSC cell to 3l0'C for 1.5 minutes. The
premelted sample was placed in a second DSC cell for 120 minutes at 263'C,
then cooled to 25'C at a rate of 0.5·C per minute. Finally, a quenched SPS
sample (QU) was produced by holding -100 mg of AP2 in a DSC cell for 1.5
minutes at 3l0·C. The premelted sample was removed from the DSC cell and
immediately submerged in liquid nitrogen, then held there for one minute.
High-resolution x-ray diffraction data was obtained on samples AP2, MCI

and QU. A Huber-Guinier x-ray camera (asymmetric arrangement, transmission/
subtraction mode) was used to acquire the data. Cu Kal radiation was
obtained from a copper x-ray tube operated at 40 kV and 20 rnA and equipped
with an incident-beam monochromator. CEA Reflex 15 single emulsion x-ray
film was used to collect the diffraction patterns. Exposure times of 70
hours were used. An internal standard of As 2 0 3 was used to calibrate the
observed diffraction peak positions for each SPS sample. Similar
experimental conditions were used during collection of high-resolution x-ray
data from sample MC2. However, for this sample a symmetric transmission
camera arrangement and Fe Kal radiation was employed. A K-E Johansson LS-18
microdensitometer was used (step size=20~) to digitize the diffraction data.
Both peak positions and intensities were determined using a Dow-developed
profile fitting routine based on the split Pearson VII algorithm (12).
The Dow-developed simultaneous DSC/XRD (13) was used to monitor the

effect of temperature on SPS crystalline structure. The instrument design
consists of an XRD system utilizing Guinier transmission/subtraction optics
and a position sensitive proportional counter (PSPC). A second component of
the system is a DSC with both computerized temperature control and data
acquisition. A schematic representation of this instrument is pictured in
Figure 2. The PSPC is held in a fixed position and collects simultaneously
Mass spectrometry
Real·Hm" monltorlng
&conlrol
Real·tlme monitoring
&cOnlnll
Atmospheric x-ray
control diffraction
To
compulel
H.
R..I-Ume monitoring & control
Figure 2. Schematic diagram of the

DSC/XRD/MS instrument.
20'-25' two-theta of diffracted radiation. Temperature control in the DSC

cell is within O.I'C from 25'C to GOO'C. Samples API and AP2 were
characterized using this technique. The Cu K~1 x-ray source was operated at
40 kV, 20 rnA and the data collection time (per XRD pattern) was 3 minutes.
The DSC cell was heated at a rate of I'C per minute from 80'C to 290'C.
Each x-ray pattern spanned a 3'C temperature range.
Both lattice type and unit cell dimensions were determined using DrCVOL
(14) and TREOR-4 (15) trial and error indexing algorithms. Program inputs
included observed d and intensity values from the SPS diffraction data.
Experimentally determined unit cell dimensions were refined using the
Appleman least squares method (IG).
Weight-fraction crystallinities (W c ) were determined for each sample via

differential scanning calorimetry (DSC). A DuPont 2100 Thermal Analysis
System equipped with a DuPont 912 Dual DSC Cell was used. The heating rate
was set at 20'C per minute and data points were collected at 0.8 second
intervals. A known weight of indium metal was used to calibrate both the
temperature and energy response of the DSC cell. Sample crystallinities
were calculated based on a value of 53.5 J/gm for the heat of fusion of a
theoretically 100% crystalline SPS sample (17).
POLYMERIZATION CONDITIONS
(CuK",1' Guinier Optics, PSPC)
\~~ CATALYST I
--........---..
~ CATALYST II
...... """.........-~
10 20 30
28 (DEGREES)
Figure 3. XRD patterns of as-polymerized SPS.

API (Catalyst 1); AP2 (Catalyst 2).
In this section we will first review the observed effects of poly-

merization, crystallization and processing conditions on the crystalline
morphology of SPS. A description of SPS crystalline structure is presented
at the end of this section.
CRYSTALLIZATION CONDITIONS
(FeK",1' Huber Gulnler, Film)
MELT CRYSTALLIZED
29 (mm)
Figure 4. Guinier diffraction patterns of SPS samples with

different crystallization conditions: Melt-crys-
tallized (Mel); As-polymerized (API); Quenched (QU).
As 2 0 3 d values are shown.
SYNDIOTACTIC PS
CDMP. MOL.D-+ AIR COOL.

tELa 1263 C. 120 MtN.
CI«JBER GUINIER SYI'tMETAIC)
>
I-
u;
Z
W
I-
~
29 (mm)
Figure 5. Guinier diffraction pattern of SPS sample crys-

tallized from the melt (MC2). As 2 0 3 d values
are shown.
X-ray diffraction patterns of the as-polymerized samples (AP1, AP2) are

shown in figure 3. These patterns were acquired on the DSC/XRD instrument
held at room temperature. It appears from these data that more than one
crystal form is stable for SPS at room temperature. A different crystal
structure may exist in sample AP1 because of its highly defective nature
(-10% defects) and/or its significantly lower~. Alternatively, the two
different catalyst systems which were used during polymerization of these
samples may dictate the type of crystal structure which is produced in SPS.
However, definition of the crystalline structures from these data is
impossible because of the diffuse nature of the scattering patterns.
Guinier diffraction patterns for the melt-crystallized (MC1), as-

polymerized (AP2) and quenched (QU) SPS samples are pictured in figure 4.
It is apparent from these data that structural differences do exist between
the melt crystallized and the as polymerized samples. The lack of discrete
scattering from the quenched sample indicates that this material possesses a
very low level of crystallinity (see table 1) and/or a very small
crystallite size. The scattering pattern for sample QU is very similar to
that of atactic polystyrene - which is predominantly amorphous.
The XRD pattern for sample MC2 is pictured in figure 5. The high
crystallization temperature and slow cooling rate of this sample produced a
material of large crystallite size and substantial crystallinity (table 1).
A unique feature of this set of structural data is the large number of
diffraction peaks which possess d values greater than 6 A. Based on this
data one would expect that a large unit cell (>1000 A3 ) would describe the
crystalline structure of sample MC2 . Unfortunately, no choice of unit cells
(up to 2500 A3 ) could account for more than 80% of the observed diffraction
SIMULTANEOUS DSCIXRD
>-
I-
in
z
W
I-
~ .l
10 20
28 (DEGREES)
Figure 6. XRD patterns of sample APl as a function

of temperature. (Alternate patterns are
plotted. )
peaks from this material. This suggested that more than one crystalline
form may be present in the sample.
The simultaneous DSC/XRD instrument was used to monitor any changes

which occur in the x-ray scattering pattern of SPS as a function of
temperature. A plot of the XRD patterns for sample APl as a function of
TEMPERATURE
(CuK"", Gulnler Optics, PSPC)
TEMP. ('C)
>-
I- 150' C
in
z
W
I- 200'C
~
250'C
Cooled
100' C
10 20 30
28 (DEGREES)
Figure 7. XRD patterns of sample APl as a function

of temperature. Note the transformation
observed upon heating is not reversible.
SIMULTANEOUS OSCIXRO
(CuK a1 • Gulnler Optics. PSPC)
TEMP. (·C)
10 20 30
29 (DEGREES)
Figure B. XRD patterns of sample AP2 as a function

of temperature. (Alternate patterns are
plotted. )
temperature is pictured in figure 6. It is apparent that the structure/

morphology which exists in this sample at 2S·C is not present at
temperatures above lBO·C. A structural transformation is observed in the
diffraction data over the temperature range of l60·C to lBO·C. Figure 7
more clearly illustrates the effect of temperature on the crystalline
structure of sample APi. Under the studied conditions the structural
transition which is observed during sample heating is not reversible (to any
appreciable degree) upon cooling. This result is consistent with the
experimental data of Kobayashi et al. (6) and the molecular modeling studies
of Doherty et al. (18). The modeling studies suggest that both an all-trans
(T 4 ) or a T2 G2 chain conformation are possible, with the all trans form
being predicted as most stable at higher temperatures.
The XRD pattern which is observed for sample APl above l80·C is similar
to that for the AP2 sample. A plot of the XRD patterns for sample AP2 as a
function of temperature is pictured in figure B. Note that the XRD pattern
which is observed for this sample at 2S·C persists until the material is
heated through its melting transition. No structural transformation is
observed for this sample under these experimental conditions.
Data from DSC/XRD experiments on several different SPS samples were used
to identify the major scattering peaks of the different crystalline phases.
This data assisted us in defining the contributions of each crystal form to
the observed scattering pattern of sample MC2 (figure 5). Two separate sets
of d values and relative intensities (one from each structure) were
identified and used independently as input to the Treor-4 and DICVOL
Table 2. Observed Interplanar Spacings For

Two Crystal Forms Of Syndiotactic
Polystyrene (in A)
FORM I FORM I I
14.44 3.80 12.86 3.97

8.44 3.59 9.91 3.93
7.54 3.01 7.54 3.89
7.20 6.43 3.78
6.51 5.63 3.63
4.99 5.19 3.54
4.40 4.95 3.46
4.33 4.54 3.34
4.14 4.30 3.27
4.00 4.07 3.02
4.01
indexing algorithms. The observed interplanar spacings for each of the

structures are listed in table 2.
An orthorhombic form of SPS was identified from the first set of

structural data. Unit cell dimensions calculated from this data are in
agreement with those reported by Tosaka (19). However, the uncertainty in
our cell parameters is greater due to the limited number of diffraction
peaks observed from this phase. A monoclinic crystal form of SPS was
identified from the second set of structural data. Unit cell parameters for
both structures are listed in table 3.
The orthorhombic form of SPS is observed to predominate in the as

polymerized sample API. This structure is consistent with the P form
observed by Tosaka (19) and the planar I form reported by Chatani et al.
(5). A low level of this form is also observed in the melt crystallized
(MC2) sample. However, crystallization from the melt produces predominantly
a monoclinic crystal form of SPS. This structure is consistent with the
Table 3. Unit Cell Dimensions For Two

Observed Crystal Forms Of SPS
ORTHORHOMBIC MONOCLINIC
a=8.8 A a=19.8 A
b=28.9 A b=12.9 A
c=s.1 A c=s.1 A
P=9s"
planar II phase proposed by Chatani (5) and the a phase observed by

Kobayashi et. al. (6). This phase is also observed in as polymerized (AP2)
material which is produced via a second type of catalyst system.
An orthorhombic-to-monoclinic structural transformation is observed in

the DSC/XRD characterization of sample AP1 (figure 6). The orthorhombic
form is not observed to be stable above -180·C. The monoclinic crystal form
is stable in all samples up to the melting temperature (270·C) for SPS. It
is interesting to note that a small level of the orthorhombic crystal form
is observed in the sample cooled very slowly from the melt (MC2). It is
possible that these crystallization conditions promote more efficient
rejection of "defective" chains (chains containing non-syndiotactic
segments) from the growing monoclinic phase. Many of these defective chains
may more easily organize into an ordered phase which accommodates a higher
concentration of defects. This may be why the orthorhombic structure
predominates in the as polymerized sample (AP1) which contains a higher
concentration of chain defects. Additional studies are being conducted to
more fully define the role of defects in SPS crystallization.
CONCLUSIONS
The structure and morphology of a new thermoplastic polymer,

syndiotactic polystyrene (SPS), have been studied using both wide-·angle
x-ray scattering and simultaneous differential scanning calorimetry/x-ray
diffraction. Two crystalline forms of the polymer have been observed and
identified. Form A has an orthorhombic unit cell. This structure has been
observed in both as-polymerized and solution.·crystallized materials and is
stable up to -180·C. A monoclinic structure (Form B) of SPS has also been
identified. This structure has been observed in both as-polymerized and
melt-crystallized samples. The monoclinic form is stable up to the melting
temperature (-270·C).
Simultaneous DSC/XRD was used to monitor the structural transformation

from the orthorhombic to the monoclinic crystal form. This transition is
centered around 180·C. Our data indicates that this transformation is not
reversible upon cooling from the melt.
REFERENCES
1. N. Ishihara, T. Seimiya, M. Kuramoto and M. Uoi, Macromolecules,

19:2464 (1986).
2. Eur. Patent Appl. 210615(1987), invs.:N. Ishihara, T. Seimiya, M.
Kuramoto, M. Uoi, Chem. Abstr., 106, 177084p (1987).
3. A. Grassi, C. Pellecchia, P. Longo and A. Zambelli, Gazz. Chim. Ital.,
19:2465 (1987).
4. C. Pellecchia, P. Longo, A. Grassi, P. Ammendola and A. Zambelli,
Makromol. Chem., Rapid Commun., 8:277 (1987).
5. Y. Chatani, Y Fujii, Y. Shimane and T. Ijitsu, Polym. Prepr., Japan,

37 :26-0-12 (1988).
6. M. Kobayashi, T. Nakaoki and M. Uoi, Polym. Prepr., Japan, 37:26-0-20
(1988) .
7. R. Nyquist, Appl. Spectroscopy, 43:440 (1989).
8. V. Vittoria, Makromol. Chern., Rapid Commun., 9:765 (1988).
9. A. Immirzi, F. de Candia, P. Iannelli and A. Zambelli, Makromol. Chern.,
Rapid Commun., 9:761 (1988).
10. P. Sundararajan and N. Tyrer, Macromolecules, 15:1004 (1982).
11. N. Tyrer, T. Bluhm and P. Sundararajan, Macromolecules, 17:2296 (1984).
12. J. Edmonds and A. Brown, Adv. in X-ray Anal., 23:361 (1980).
13. T. Fawcett et al., U.S. Patent, Patent Number 4,821,303 (1989).
14. D. Louer and M. Louer, J. Appl. Cryst., 5:271 (1972).
15. P. Werner, Z. Krist., 120:375 (1963).
16. D. Appleman, H. Evans and D. Handwerker, U.S. Geological Survey,
USGS-GD-73-003 (1973).
17. A. Pasztor, B. Landes and P. Karjala, Thermo. Acta, submitted for
publication (1989).
18. D. Doherty and A. Hopfinger, Macromolecules, 22:2472 (1988).
19. M. Tosaka, M. Tsuji, A. Kawaguchi and K. Katayama, Polym. Prepr.,
Japan, 37 :26-0-16 (1988).
PHASE DIAGRAM STUDIES ON NEOPENTYLGLYCOL AND
PENTAERYTHRITOL-THERMAL ENERGY STORAGE MATERIALS
Dhanesh Chandra, Renee A. Lynch and Wei Ding

University of Nevada, Reno
Reno, Nevada 89557
John J. Tomlinson
Oak Ridge National Laboratory
Oak Ridge, TN 37831
ABSTRACT
Pentaerythritol (PE) and neopentylglycol (NPG) are organic molecular

crystals which have hydrogen-bonded lattices with layered- and chain-type
structures, respectively. The PE undergoes solid-state phase transitions at
4l6K, from tetragonal to a cubic (y') structure and NPG also undergoes this
transition at 3l7K from a monoclinic to a cubic (y) structure. The phase
transitions in binary PE-NPG solid solutions show more than one solid-solid
transition in which the NPG-rich S transforms to y at a constant temperature
but the transition of the PE-rich a phase to y' passes through a two-phase
field at a temperature that varies as a function of composition. Structural
analyses by high-temperature x-ray diffractometry have revealed some new,
interesting transitions. A phase diagram has been constructed for 0-30 mol%
NPG in the PE-NPG system, using x-ray diffraction and differential scanning
calorimetry results, and work is in progress to complete this diagram. The
variation of lattice parameters as a function of temperature in the a, y
and y' phases for PE+20 mol% NPG are presented here, together with a
discussion of phase transitions for certain compositions.
INTRODUCTION
The phase transitions in polyalcohols such as PE and NPG are of

special importance because large amounts of latent heat of solid-solid
transformation can be stored in these so-called "plastic" crystals. l ,2
These solid-solid transitions are of first order and occur well below the
melting temperatures. The polyalcohols are characterized by their large
entropy of solid-solid transitions, in the order of 35 cal/mole.oC, and low
entropy of solid-liquid transition, of 1-2 cal/mole. o C.2 There are
relatively few organic compounds which have reversible energetic
transitions, and adjustment of their transition temperature is desirable for
certain applications. Systems with two or more components can be used to
adjust the solid-solid transition temperatures of these polyalcohols.
Advances in X.Ray Analysis. Vol. 33 445

Edited by C.S. Barrett et 01.
Benson et al. 2 first reported the thermophysical properties of polyalcohols

such as PE, NPG and pentaglycerine (PG) and their combinations using thermal
analyses. Chandra and Barrett 3 and Chandra et al. 4 reported adjustment of
transition temperatures and effects of dopants on the crystal structural
properties of these polyalcohols.
The structure of PE [CSH12041 has been determined by Lwellyn S and

Nitta 6 to be tetragonal (14). It is a layered structure with OH bonding of
the PE molecules in the a-b plane. The solid-solid phase transition occurs
at l88 0 c and the melting temperature is approximately 260 0 C. Chandra et al. 7
determined thermal expansions of PE in the low-temperature phase II and high
temperature phase I. "Phases II" and "Phase I", as named by Timmermann8 and
Aston 9 , will be designated as Cl or 8 and y or y' phases, respectively, in
this study to differentiate the high and low temperature phases in the
proposed phase diagram. The thermal expansions are highly anisotropic in
PE; the crystal expands more in the c-direction than in the a-direction.
Neopentylglycol [CSH12031 has a monoclinic, highly anisotropic

structure with a space group of P2l/n, a modified setting of P2l/c-C2h with
molecules bonded in bimolecular chains. 3 ,lO The solid-solid phase
transition occurs at approximately 40 0C in reagent-grade NPG. However,
temperatures up to 48 0 C have been observed for high-purity or recrystallized
materials. The melting temperature is approximately l2SoC.2 The phase
changes occurring in the PE-NPG system, up to 30 mol% NPG, have been charac-
terized by high temperature x-ray diffraction and differential scanning
calorimetry to evaluate the solubilities of NPG in PE as a function of
temperature and composition. These results are important for understanding
the structural changes associated with the thermal behavior of polyalcohol
solid solutions whose phase transitions are not clearly understood. The
phase diagram, structural analyses, lattice expansions and undercooling
problems are discussed in this paper.
EXPERIMENTAL
(A) Sample Preparation
Sample preparation for crystal structure determination and for

analyses is very important because of undercooling of high temperature
phases to room or lower temperatures in these NPG-PE binaries. The PE and
NPG mixtures were melted in capped Pyrex test tubes and the melt slowly
cooled to room temperature. To attain equilibrium phases in this binary
system the following procedures were used. The solidified samples were
ground and resealed in capped test tubes and stored in a freezer (~-2S0C)
for a minimum of 12 hours. These powders were compacted into a disk form of
approximately 3/4" in diameter, with the thickness varying from ~1/8" to
'03/16" so that undercooled phases were precipitated by application of
pressure which supplied the strain energy for the transformation, in a
manner described by Barrett. ll These disks were reground without warming
and placed back into the freezer. A portion of a representative sample was
used for powder-diffraction experiments and some of the sample was placed in
0.7mm diameter Charles Supper Company's quartz capillaries and sealed with
an epoxy, for high temperature (Guinier) diffractometry experiments. A few
milligrams of these powders were used also for differential scanning
calorimetry (DSC) experiments. Aldrich NPG (99%) and PE (99%) were used for
these experiments. In general, two to three sets of these samples were made
to check the reproducibility of results.
D. CHANDRA ET AL. 447
(B) Instrumentation
The structural properties of these materials, at elevated temperatures,

were evaluated by a Huber Guinier x-ray diffraction system with a high-
temperature film attachment. A germanium crystal monochromator was used to
obtain CuKal radiation. The cassette holder for the film was advanced via a
Research Inc. Microstar controller, model number 828D, which also controlled
the furnace temperature. A modified Huber furnace was used whose details
are discussed in reference 4. Nine to twelve symmetric patterns were
obtained on one single-sided emulsion film. Room-temperature structural
analyses were also made using a Norelco diffractometer interfaced with a
Microvax II DEC computer. The d-spacings and lattice parameters were
obtained using Siemens software. An automated Philips 3S20 diffractometer
also was used to obtain room temperature diffraction data for some of the
samples. The room temperature where this diffractometer was located was
adjustable at approximately l7 0 C to make low temperature runs.
Thermal analyses were performed by using a A Perkin Elmer differential

scanning calorimeter, DSC-4, for all the samples. The sample size for these
was generally of the order of S-lO mg.
RESULTS AND DISCUSSIONS
X-ray diffraction results for PE with 10%, 20% and 30 mol% NPC show
that there is little solubility of NPC in PE and there are two distinct
phases present in the system at 19 0 C; these are monoclinic (8) and
tetragonal (a) phases. The PE-rich a phase is more abundant in this two-
phase mixture than in the NPC-rich 8 phase. These estimations have been
made based on the peak heights from the x-ray diffraction patterns by
monitoring the intensity of the (011) reflection of the monoclinic phase and
(002) of the tetragonal phase. It was observed that the intensity of (011)
of the monoclinic phase increased as the concentration of NPC increased,
suggesting little solid solubility of NPC in PE at approximately l7°C in
these melted and crystallized PE-NPC powders. These results are quite
different from results with the PC [CSH12H3l - NPC [CSH12H2l system, where a
large solubility of NPC in PC12 was observed, even though the structure of
PC is the same as that of PE (space group 14).
To characterize the phase transitions, high temperature x-ray

diffraction powder patterns were obtained for PE specimens containing 10%,
20% and 30 mol% NPC at 12 different temperatures. The XRPD patterns
obtained from PE doped with 10 mol% NPC, between 17 and 3l'~, showed several
lines that were identified as reflections from a and 8 phases. The pattern
obtained at 4l o C showed that the highly anisotropic structure of 8 had
transformed; however, it was not evident that new reflections from the
transformed phase were present in the pattern. Evaluation of higher-
temperature patterns suggested the presence of two overlapped peaks of a new
phase, identified as an NPC-rich, isotropic, Y phase. A portion of the
symmetric x-ray diffraction pattern obtained from this sample is shown in
Figure 1. It should be noted that the lines for the Y phase are very weak
due to the small amount of y present and may be difficult to see in the
reproduction of the x-ray film. Thermal analyses performed on these samples
confirmed 8 + y phase transitions and a solid-solid transition temperature
of ~38oC was established. The a and y phases were stable in the temperature
range of ~38°C to 10SoC, and a single a phase was stable between 127 0 to
lSloC; at l73 0 C a and y' (PE-rich) phases were observed. Further increases
in temperature yielded two characteristic reflections of (Ill) and (200)
.j>.
300,r-------------------------------- HIGH TEMPERATURE GUINIER .j>.
290 co
X-RAY DIFFRACTION PATIERNS
280 LlOUID ry'(200)
270
-210·CT y'
250 ~ --G_ y'+ LlOUID -197·Ci...:...-
260 ~ - - 173 OC!J!..±. y'
240 --e....!-_ w
a.. ~
, UJ -151·Ct ex
--127OC :5
m ---- (fl. ..., __ 105°C
220 o _ 92°C '"0
:r:
210 l>
y'-- l>
0'>
(31-.......
a.. ••
.. •
-.....l
'.
790C
680C o.+y l>
en
200 l> l> 51°C m
Z .~ 440C
IT 190:""'" e e o
~ 1W e *" ..~ -- 41·C m
0. + Y' -
_ - 36"C
31"C Z
~ 170 o " .,""
""II o.+~ :j
- - 250C 'T1
1= 160 o
0. -- 17°C n
~ 150 o l>
-l
~ 140
~ 130
oz
o Gl a + ~ phases
I- 120 en
o a + yphases 1'(111)1
110 -l
o a phases :0
100 __ 205"C~' C
o V a + y' phases --195OC (")
90 cx+y l> y'phases ~ E:::::::::~y~'(:I~I~I):-~, EIi:!, ~.:L::===~~~u.1I --182OC 0.+1' -l
C
80 --170OC :0
70 (fl. " ,_ --l58OC 0. l>
g . .... --145OC r-
60 o (3
. .Y.J
(I'I) ...._ _1IIiIIJ --l33OC l>
50 --122OC z
a.. __ 970CI o.+y o
40 -- 6O"C o
30 Z '. C
e cf!. I I -- 400C
Gl o .11i. -- 27"Ct A
l>
20 o.+~ (\I z
-- 19OC~1' -l
10
I!(OI :::j
OQ__--~--.---~--~--~---J l>
o 10 %NPG 20 30 -l
<:
m
Figure 1. Phase diagram of PE-30 mol % NPG constructed by using X-ray diffraction and differential l>
scanning calorimetric analyses. Guinier X-ray powder diffraction patterns obtained from z
l>
PE-10 mol % and PE-20 mol % are presented to show the phase stability ranges. (These X-ray r-
-<
en
diffraction results are important to determine the phase transitions, in particular, where
the enthalpies of transitions are very low and the DSC data is difficult to interpret.) en
from the PE-rich Y' phase. These results show that as the PE+10 mol% NPC is
heated, first a low temperature Y is formed and then this Y phase transforms
to a phase which in turn transforms to a high temperature Y' phase.
X-ray diffraction analyses of PE doped with 20 mol% NPC showed the

same trends as those of the sample with 10 mol% NPC; Cuinier films for this
composition also are shown in Figure 1. The a and B phases are stable up to ~
38°C, a and yare stable between ~380C to ~1400C; but between l40 0 C and l70 0 C
only the a phase is stable; the y-phase lines are missing. The XRPD
patterns obtained at l82°C and 192°C reveal the presence of another y' FCC
phase with only two reflections. The reason for the absence of broadening
or other reflections is uncertain; it may be due to rotation/oscillation of
the c-o bond around the C-C bond of the NPC molecules. 4 The phase
transitions determined by x-ray diffraction analyses for this PE+20 mol% NPC
sample are summarized below:
+ + a+y' +
l70 0 C-188°C
Above 24S o C the phase changes are y' + y' + Liq + Liq, as evidenced by the
DSC analyses. The results obtained from x-ray diffraction and DSC analyses
are combined and yield the phase diagram for the 0-30 mol% NPC range that is
plotted in Figure 1.
The lattice parameters of a and Y phases for PE+20 mol% NPC with
increasing temperatures are plotted in Figure 2. The lattice parameters for
the a phase in the a+B region below ~380C show a slight growth in the
c-direction with very little increase in the a-direction. (The monoclinic B
phase is not plotted in this graph.) As the temperature is increased the
a + B phases transform to a+ yphases and an increase in the c-parameter of
the a phase is observed while the a-parameter does not increase signifi-
cantly. In the temperature range of 40-97°C there is a gradual nonlinear
increase in the c-parameter associated with the changes in composition in
equilibrium at different temperatures. The solubility of the NPC in PE
increases with the increases in temperature. The composition change (~c)
per °c increase varies depending on the temperature range because of the
shape of the solubility curve. Note the anisotropic behavior of the a phase
in which the c-parameter increases significantly as compared to the
a-parameter throughout the two phase region. In the PE-rich single y' phase
region, increases in lattice parameters are linear because the composition
remains unchanged. The lattice parameters of the high-temperature phase of
the pure NPC (y) and PE (y') are comparable to those of the PE-NPC binary,
just above B + y and a +y' transition temperatures.
The thermal expansion coefficients in the a single phase region of

PE+20 mol% NPC are aa = 1.971 x 10-S/oe and a c = l2.S67 x 10-S/oe between
l4S and l70 0 C. The NPC-rich y + a transformation occurs at approximately
l40 0 C; when the a phase transforms completely to y' a volume increase of
10.8% is observed. In a similar manner x-ray diffraction patterns for PE+30
mol% were obtained at various temperature and some of the results were used
for the phase diagram. Additional work is in progress for some critical
composition ranges so that the complete phase diagram may be constructed.
Differential scanning calorimetry was used in which B + y and a + y ,

transitions were observed and were consistent with our x-ray diffraction
results. The solid-solid phase transition for pure PE at l88°e is well
established2 and our DSC results show the a + y' transition occurs at 186 0 ,
l84°C and l79 0 C for PE with 10, 20 and 30 mol% NPC, respectively. The area
under the endotherms, of B + y transition, increased as the concentration of
9.1.,-----------------,
9.0
en
a::
w
I-
W
::iE
c:(
a::
c:(
,:
a. 8.9
w
()
~
c:(
...J
8.8
if
~: a+~
8.75 .Y a+y a y'
6.1 ,'\'..
:01": J Iii i, 'H
~
'
: : '" a+y'
a(a)
6.05 t---.--.,---..-,.---.--,--.-...,.--.---1
o 50 100 150 200 2~0
TEMPERATURE
Figure 2. Lattice parameter changes in the a,yand Y'phases with

the increase in temperature in the PE+20 mol% NPG. It
should be noted that in the a+y region the
compositional changes associated with the changes in
the temperature which are nonlinear and dictated by
the solvus line in the phase diagram. The phase
stability regions are also shown.
NPG increased, due to increases in the quantity of the S phase in the

mixture. The L'lH for the CJ.""Y transitions decreased as the amount of NPG
increased and for 0%, 10%, 20% and 30% NPG additions to PE, L'lH of 67.5, 52,
92, 41.98 and 34.75 cal/gm, respectively, were obtained.
There are undercooling problems associated with these polyalcohol

binaries and the degree of undercooling depends upon the composition and
cooling rates. For some compositions, transitions near room temperature
could only be observed if phase transitions were induced by supplying strain
energy that accelerates the transformation ll or by cooling the sample to
temperatures well below the transition temperature.
In a previous study, Chandra et a1 4 made lattice parameter measure-

ments at room temperature for PE with up to 40% NPG that implied that there
was complete solubility of NPG in PE in this composition range. Benson et
al. 2 performed DSC analyses on these PE-NPG samples and reported observing
only one solid-solid transition, ayain suggesting presence of only a single

phase. More recently, Font et al. 3 reported observing only one transition
for PE-30% NPG at 175 0 C. Based on our current results, however, we realize
that the low temperature transitions were not observed because there was
undercooling so serious that the y phase coexisted with the a phase even at
room temperature. Diffraction patterns did not reveal the presence of this
y phase because the Y(lll) peak was overlapped with a(lOl) peak and the Y
(200) overlapped with a(002) in the patterns acquired at room temperature.
In the high resolution Guinier photographs, for example the patterns for
PE+10 mol% NPG and 20 mol% NPG samples in Figure 1, the Y-phase peaks became
apparent but only at elevated temperatures. In general, the transitions
appear to be complex as the amount of NPG is increased in PE. Interpretation
of the DSC patterns is difficult without the supporting high resolution
x-ray data. The DSC samples were prepared by making sure that no under-
cooled phases were present, and were stored at temperatures well below the
transformation temperature.
In summary, a phase diagram of PE-NPG (up to 30 mol% NPG, Figure 1),

is proposed, based on the x-ray diffraction and DSC results: complete
solubility of NPG in PE in the Y' phase is found at elevated temperatures,
but the solubility is smaller at lower temperatures. This phase diagram
includes more than one solid-solid transition; the S -)- Y occurs at 'U38 o C and
the a -)- Y' solid-solid transition temperature varies as a function of
composition. An NPG-rich Y phase is observed to be stable together with
the a phase in the two-phase region above 'U38 o C. Further x-ray diffraction
and DSC studies are in progress for this system.
ACKNOWLEDGEMENT
The authors would like to acknowledge the support of the U.S.

Department of Energy (Oak Ridge National Laboratory) under contract number
19X-SC644V.
REFERENCES
1. E. Murrill and L. Breed, Annual Summary Report No.1 NASA Contract No.
NAS 8-21452 (1969).
2. D. K. Benson, J. D. Webb, R. W. Burrows, J. D. McFadden, and
C. Christianson, SERI Report, Task Nos. 1275.00 and 1464.00 WPA 304
Mar. 1985 (available through NTIS, SERI/TR 255-1828 Category 62e).
3. D. Chandra and C. S. Barrett, Effect of Interstitial Dopants on the
Thermophysical Properties of Solid State Phase Change Materials.
Draft of Final Report DOE Contr No. DE-AC03-84SF-12205, Jan. 30 (1986).
4. D. Chandra, C. S. Barrett, and D. K. Benson, Adjustment of Solid-Solid
Phase Transition Temperatures of Polyalcohols by the use of Dopants,
"Advances in X-Ray Analysis," Plenum Publishing, 29: 305-313 (1986).
5. F. J. Llewellyn, E. G. Cox, T. H. Goodwin, J. Chern. Soc. 1883, (1937).
6. I. Nitta and Z. Krist, 112,234 (1959); and I. Nitta and T. Watanabe,
Bull Chern. Soc. Japan, Vol. 13, 28 (1938).
7. D. Chandra, J. J. Fitzpatrick and G. Jorgenson, Adv. in X-Ray Analysis
Vol. 28: 353, Plenum Publishing, (1985).
8. Timmermann, Solid State Phase Transitions in Pentaerytritol and
related Polyhydric Compounds, J. Phys. Chern. Solids, Pergamon Press,
v:18, No.1 (1961).
9. J. G. Aston, "Physics and Chemistry of Organic Solid State," Vol. 1,
Chapter 9, Interscience Publishers Inc., New York, NY, (1963).
10. D. Chandra, Thermal Energy Storage in "Plastic Crystals" Final Report,

DOE Contract No. DE-AC03-8716873, Jan (1989).
11. c. S. Barrett and L. Meyer, Phase Diagram Studies on Ar-N2 Gas System,
J. Chern. Phys. Vol 93, 1965.
12. D. Chandra, C. S. Barrett and D. K. Benson, Advances in X-Ray Analysis
Vol. 32 (1989).
13. J. Font, J. Muntase11, J. Navarro, J. L. Tamarit, and L1overras,
Calorimetric Study of the Mixtures PE/NPG and PG/NPG, Solar Energy
Materials, Elsevier Publishers BV., 15: 289-310, (1987).
CRYSTAL CHEMISTRY AND PHASE EQUILIBRIA OF THE BaO-Rz 0 3 -CuO SYSTEMS
Winnie Wong-Ng, Boris Paretzkin and Edwin R. Fuller, Jr.
Ceramics Division
National Institute of Standards and Technology
Gaithersburg, Md 20899
ABSTRACT
Two important factors, the progressively decreasing size of the

lanthanides, which is known as the lanthanide contraction, as well as the
stability of different oxidation states of these elements influence the
prediction of compound formation in the Ba-R-Cu-O systems. A systematic
investigation of these lanthanide systems and comparison with the Y
system has revealed a correlation of the effect of the above factors, in
particular the size factor, on the trend of phase formation, solid
solution formation and phase compatibility diagrams of the Ba-R-Cu-O
systems. For example, it has been found that the smaller the size of R3+
or the greater the mismatch between Ba z + and R3+ in the solid solution
series Baz-zRl+zCu306+x' the smaller the extent of solid solution
formation. This differing extent of solid solution formation influences
the ternary phase relationships.
INTRODUCTION
Low critical current density, flux creep and poor mechanical

behavior are a few of the problems which hinder the development of
applications of the high Tc superconductor materials Ba Z YCu 30 6+x ' The
discovery of the fact that a variety of lanthanide (R) substituted
compounds of general formulas Baz RCu 30 6 +x also exhibit superconducting
transition temperatures of ~90Kl provided us alternative materials with
similar structures for investigating possible improved properties.
The electronic structure, stable valence state and the size of the
lanthanide elements play important roles in governing compound formation.
Among these factors, the progressive reduction in size of these elements,
as one goes across the lanthanide series, known as the lanthanide
contraction, allows one to study the trend of the chemical and physical
properties and phase formation of compounds. Since knowledge of crystal
chemistry and phase equilibria is essential for controlling processing
parameters and understanding material properties, a systematic study of
the phase relationships in the BaO-Rz 0 3 -CuO systems has been initiated at
the National Institute of Standards and Technology (NIST). Our goal was

to characterize the trends of phase formation, solid solution formation

and the trend of phase diagrams of the BaO-R20 3 -CuO systems as a function
of the size of R.
Detailed phase diagram studies for the BaO-Y2 0 3 -CuO and BaO-La2 0 3 -
CuO systems have been prepared by Roth et al. 2 and Kilbanow et a1 3 (Fig.
1a and 1b). A comparison of these two diagrams reveals substantial
differences. For example, along the binary BaO-R20 3 edge, the La system
has only one compound while the Y system has four. Although both the
R2 0 3 -CuO systems contain only one binary phase, they are of different
composition; namely, the La system forms a 2:1 binary phase La 2 Cu0 4 while
the Y system forms a 1:1 binary phase Y2 Cu 2 0 S ' Furthermore, a few more
ternary compounds and solid solution series are found in the La system as
compared to the Y one. Presumbably the size of the lanthanide R has an
important effect on the phase diagrams. We have investigated the CuO-rich
region of the phase diagrams of several selective lanthanide systems with
R = Nd, Sm, Eu, Gd and Er with the size of R mostly between La and Y in
order to determine if a trend exists among them. Several series of binary
and ternary oxide compounds as well as a variety of compositions in the
BaO-R20 3 -CuO systems have been studied in order to be able to find out
the phase relationships. This report summarizes our current findings4-11.
EXPERIMENTAL
Solid state reaction techniques were used for all sample preparations.
Similar heat treatment procedures were adopted for all series of
Ba2-zRl+zCu306+x materials. Most compositions were prepared from
stoichiometric mixtures of CuO, R20 3 and BaC0 3 . In the case of R = La,
La(OH)3 was used instead of La 2 0 3 . Before each firing and annealing, the
powder was pressed into pellets and placed on MgO single crystals. The
pellets were heat treated at both 850°C and 900°C for one day, then fired
in air at 950°C. Several regrindings and annealings took place until a
single phase material was confirmed by .the X-ray powder diffraction.
To study phase relationships in the vicinity of the superconductor solid-

solution, Ba2-zRl+zCu306+x, and the "green-phase" compound, BaR2 CuO S '
compositions near the CuO corner of selected BaO-R2 0 3 -CuO systems were
also prepared. Most final sinterings were performed at 950°C and air-
quenched. For compositions very close to the CuO corners, a temperature
BaO(BaC03) BaO(BaC03)
Figure 1. Phase compatibility diagram at 950°C in air, (a)Ba-Y-Cu-O,

after Roth et al. 1 and (b) Ba-La-Cu-O, after Kilbanow et al. 2. The
notations 121, 213, 242 etc. signify the BaO:~R203 :CuO ratios at interior
points in the diagrams.
W. WONG-NG ET AL. 455
Table 1. Summary of Phase Formation in the BaO-Rz 0 3 -CuO Systems
R3+ La Nd Sm Eu Gd Dy Ho Y Er Tm Yb Lu
RZ0 3 -CuO:
Rz Cu0 4 1Z T T T T T
°T °T °T °T °T °T °T
Rz CUz Os 1 4 , 1 S
°°°°°
BaO-Rz 0 3 :
BaRz 0 4 8 T T T T T T T T T
°°°
Ba 3R4 0 9
°° T T T
BazRz Os
°°° T
Ba 4Rz 0 7
°°° T
BaO-Rz 0 3 -CuO:
Baz RCU 30 6+x zo T T T T T T T T T T T T
BaRzCuO s
green phase 7
°
Baz +z x R4 - Zx Cuz - x 10 - Zx
°° T T T T T T T T T T
brown phase 7
zo
T T
°° ° ° ° °T °T °°°
Ba3+xR1-xCuZ-z06.4-z
°T ° ° °° ° ° °°
BaR4CuS013+x16,17,18
Ba3R3Cu6014+X 10 °T °T °T ° ° ° °°
Ba 1+x Rz -x Cuz 0 6 - x /z Zl
T
° °° °°
°°° °°°° °°°
of 920°C was used instead to avoid melting. Tie-line relations were

established by X-ray powder diffraction characterization.
TREND OF PHASE FORMATION
Selective series of phases of binary and ternary oxides have been

prepared for the investigation of phase formation as related to the size
and the stable valence state of R. Table 1 summarizes our current results
of phase formation of binary and ternary oxide phases in the BaO-Rz 0 3 -CuO
systems. Both literature data and data obtained from our own laboratories
are being used to construct this summary. Across the top of the table the
stable R3+ ions including yttrium are listed. The left column illustrates
the chemical formulas of the binary oxide phases in the BaO-Rz 0 3 and
RZ03-CuO systems and the ternary oxide phases in the BaO-Rz 0 3 -CuO
systems. Inside the table, the symbol 'T' is used to indicate the
occurrence of the compound with the respective R. '0' indicates the
absence of such a compound. Further work is still required to complete
this table. If a new phase is discovered, the table will be expanded.
It is not the intention of this paper to give a full description of

the phase formation of every series of compounds. For details, the
readers are referred to individual references as listed in the table. The
phase formation (including solid solution formation) of three series of
compounds in the BaO-Rz 0 3 -CuO systems are selected to be discussed
individually in the sections below. Crystal structures of some of these
phases will also be described.
Figure 2. Polyhedral environment of R0 7 and RZOll found in structures of

BaRzCuO s , R=Sm, Eu, Gd, Dy, Y, Ho, Er, Yb and Lu.
Details of the phase formation of the 1:2:1 phases have been

reported elsewhere 7 . In brief, under ambient conditions, the commonly
known "green phases" BaRzCuO s have been prepared for R=Sm, Eu, Gd, Dy, Y,
Er, Tm, Yb and Lu. However, these phases do not form with lanthanides of
larger size. Among the oxides with a stable R3 + valence state, there is a
size range within which the substitution of R is possible. For example,
the formation of green phases for R=La 3 + and Nd 3 + does not take place.
The materials formed are brown and are found to have a completely
different crystal structure from that of the "green phase". While all
green phases are orthorhombic with space group Pbnm(62), Z=4, the "brown
phases" tend to form solid solutions of Baz+zxR4-ZxCuZ-x010-Zx' with a
tetragonal space group of P4/mbm(127). The solid solution range is
O.15~~O.25 for the La and O.O~~O.1 for the Nd system. Note that the La
solid solution series does not include the stoichiometric compound with
x=O.
In the green phase structure, basically each yttrium ion is

surrounded by seven oxygen atoms, as shown in Figure 2. The framework can
be considered as built up from distorted monocapped trigonal prisms, R0 7 ,
a b
Figure 3. Polyhedral environment of (a) R0 10 and (b) ROB found in the
structures of Baz+zxR4-ZxCuZ-x010-Zx' R=La and Nd.
o-+.~~-()-I--Z =}
eCu fl)Nd 00
Nd.Cu 0. -Type
Figure 4. Crystal structures of RZCu0 4 , (a) R=La, (b) R=Pr, Nd, Sm, Eu
and Cd.
which share one triangular face forming RZOll blocks. There is an

apparent size limit, bounded by Sm, beyond which stability of the
distorted monocapped trigonal prism, R0 7 , is unattainable. The framework
of the La and Nd materials is principally built from edge- and face-
sharing R0 1C and ROe polyhedra as illustrated in Figures 3a and 3b. These
octahedra and decahedra provide large enough space to accommodate the
La 3+ and Nd 3+ ions.
While all the RZ 0 3 :CuO systems contain only one binary compound at
ambient atmosphere, there exist two distinctive compositions. Binary
compounds of 2:1 composition with general formula RZ Cu0 4 can be prepared
with the lighter and larger size of R, for example, with R=La, Pr, Nd,
Sm, Eu and Cd, whereas oxides in the second half of the lanthanide series
tend to form a 2(~Rz03):2CuO binary compound RzCuzOs. Not all Rz Cu0 4
phases are isostructural. For example, while La Z Cu0 4 is orthorhombic
with space group Cmca, and has the distorted Kz NiF 4 type structure as
shown in Figure 4, Pr Z Cu0 4 , Ndz Cu0 4 , SmZ Cu0 4 , EUZCu0 4 and Cdz Cu0 4 are
tetragonal with space group P4/rnrnrn. These tetragonal structures do not
resemble the Kz NiF 4 type but have a coplanar Cu-O layer similar to that
found in CaF z type structure 1Z . These features are illustrated in Figure
4. Doping the La ZCu0 4 structure with a small amount of a 2+ ion such as
and Srz+ changes the structure from orthorhombic to tetragonal and
results in a superconductor phase.
Solid solution formation of the compositions (Rz-zAz)CU04-x with

A=Ba has been studied with R=La 3 and with a solid solution range of
O~z~O.25 has been reported. This series gives rise to superconductor
materials of Tc around 30K13 . With R=Nd and A=Ba and Sr, solid solution
could not be prepared (with z~O.05), whereas with A=Ca, a range of
substitution of O<z~O.l was found. Results of X-ray diffraction patterns
of (Nd2_zCaz)Cu04_x are shown in Figure 5. The pattern of Ndz Cu0 4 is also
included for comparison. A small number of diffraction peaks that do not
belong to the Ndz Cu0 4 phase begin to show up at z~O.2.
(e) z=O.3
>--
....
~o
~
.
~*
....
TWO - THETA (DEGREES)
Figure 5. X-ray diffraction patterns of (Ndz_zCaz)Cu04-x
RzCuzOs compounds are greenish in color, isostructural with space

group Pna2 1 , and can be prepared with the second half of the lanthanides,
with R = Tb, Dy, Ho, Y, Er, Tm, Yb and Lu. Figure 6 shows the atom
distribution of the unit cell of HOZCuZOS14.1S. Unlike those of many
other oxo-cuprates, the Cuz + has been found to have four nearest oxygen
neighbors arranged in a distorted tetrahedron configuration. Figure 6
further shows that each two of these polyhedra share a common edge and
~ 0 0
b 0
A 0
0 0
0
•
/}.
0
0
• 0
.Hol OHoD .Cul /}.cu D OOI-V
0
Figure 6. Projection for HOzCuzOs along [001].

2000 . . , - - - - - - - - - - - - - - - , 485.0 , - - - - - - - - - O - T - b - - - - - - ,
§ 1950
E
C
475.0
¢ lly
o " Pr o
o o flo
~ 1900
o "'0
" Nd Y
x X 465.0 0 Er
ill ill
E 1850 E 0 Tm
:>
o
>
" Sm g 455.0 0 Yb
1800 - " Eu
" Gd 0 Lu
175 a
10.5
.,. .- -r- -r- -r- - r- -.- -.~'~I~~~-r-r ,~J
11.0 11.5 12.0 12.5
445.0 +----~-__.__-~--r___-..,--~
10.0 10.5 11.0 11.5
Ionic Radius x 100 nm Ionic Radius x 100 nm
Figure 7. Size dependence of the unit cell volume of (a) R2 Cu0 4 , R = Pr,
Nd, Sm, Eu and Gd and (b) R2 CU2 Os , R = Tb, Dy, Ho, Er, Tm, Yb and Lu.
are connected via corners in a wavelike chain along [010]. The Ho 3 + ions
are surrounded by octahedra which form I-dimensional infinite chains
connected via edges.
Figures 7(a) and (b) are plots of the cell volume V of R2 Cu0 4 and
R2 Cu2 0 S versus the ionic radii of Shannon. The monotonic decrease in
crystallographic volumes, as the ionic radii of the lanthanides decrease
across the series, follows the well-known lanthanide contraction. The Gd
compound which deviates from this linear dependence may be due to the
special stability associated with the half-filled Gd 3 + (4f7) f-subshell.
This oxygen-defect perovskite is characterized by a mixed valence of

Cu(II) and Cu(III) in spite of the presence of numerous oxygen vacancies.
Figure 8. Crystal structure of the compound BaLa4 CuS 0 13 . The full and
open circles represent Cu atoms belonging to the CuOs pyramids and the
Cu06 octahedra, respectively. La 3 + and Ba2 + ions are located in the
hexagonal and pervoskite tunnels, respectively. The z-axis points out of
the plane of the paper.
103
110
2~. •.
TWO - THETA (DEGREES)
Figure 9. X-ray diffraction patterns of Baz-zLal+zCu306+x' The appearance
of the BaLa4Cu5013+x is indicated by the arrows for z=0.8 and 0.9.
The La system appears to be the only one among the lanthanide systems
that forms this black metallic conductor. The BaLa4CuS013+x compound is
tetragonal with space group P4/m. The lattice parameters of a sample
which was prepared in air at 950°C were found to be a= 0.86602(5) nm and
c = 0.38629(3) nm 16 , which are closely related to that of the cubic
perovskite: a~ap j5, and c=a p=.38594 nm. ~ichel et al. 16 . 17 described the
framework [Cus 013 1 to be bunt up from corner- sharing CuO s pyramids and
Cu0 6 octahedra forming hexagonal tunnels and perovskite cages where the
La 3+ and Baz + ions are located in an ordered manner. Figure 818 shows
the structure of BaLa 4 Cu S0 13 in which each CuO octahedron shares four
corners with four pyramids, and the two remaining corners with two other
octahedra. Each pyramid is then connected to four other pyramids and one
octahedron. Oxygen vacancies,which are found to be between pairs of
CuO s , form l-dimensional channels along the z-axis. The lanthanum ions
are located in the hexagonal tunnels whereas the barium ions are located
in the perovskite tunnels.
TREND OF SOLID SOLUTION FORMATION
The superconductor phase Ba ZYCu30 6+x is shown to be a point

compound in Figure 1 whereas Figure 2 shows that the Baz-zLa1+zCu306+x
forms a solid solution with Ba substituting for La. In order to find out
whether Ba substitution for other lanthanides also form solid solutions,
Table 2. Solid Solution Extent of Baz-zRl+zCu30S+x and

Ionic Radius of R3+ (rBa z + = 0.147 nm)
R z Ionic Radius
(nm)
La :!S: 0.7 0.1216

Nd :!S: 0.7 0.1163
Sm :!S: 0.7 0.1132
Eu :!S: 0.5 0.1120
Gd :!S: 0.2 0.1107
about 70 compositions with general formulas Baz-zRl+zCu30S+x ,R Nd,

Sm, Eu, Gd, Dy, Er, and Lu were prepared for this study.
Solid solutions could be prepared for the larger sizes of R,

namely, for La, Pr, Nd, Sm, Eu and Gd. Beyond Gd, only the point
composition (z=O) was obtained. The solid solution range is different for
each of these series. Figure 9 shows the X-ray powder diffraction
patterns of the selected compositions of Baz-zLal+zCu30S+x, where z 0.5
to 0.9. The upper limit of the solid solution series is discernible by
the presence of X-ray diffraction peaks from a different phase. For
example, a small number of peaks corresponding to BaLa4CuS013+x start to
appear at z~0.8, as indicated by the 'arrows'. The tendency for solid
solution formation is very great in the La system, and the point compound
Baz LaCu 30 s +x does not form; the lower limit of the solid solution
composition range is approximately z>O.l. The Sm samples show a solid
solution range going down to z:!S:0.7. The Gd sample on the other hand shows
only a small range of z:!S:0.2. Solid solution ceases to exist at Dy, Er and
Y, or at least is less than z~O.l, and presumably with superconductors
with smaller radius than Er.
The size compatibility between the Baz + and R3+ is a predominant

factor governing the formation of this solid solution. Shannon's ionic
radii of lanthanides R3+, where R=La, Pr, Nd, Sm, Eu, Gd, Dy and Y, using
the coordination number of nine are listed in Table 2. As the mismatch
between R3+ and Baz + increases, the range of substitution decreases.
Table 2 summarizes the approximate upper limit of the solid solution
range of Baz-zRl+zCu30S+x'
Structural phase transformation from an orthorhombic to a

tetragonal structure as the value of z increases is another feature
observed in all the Baz-zRl+zCu30S+x series. Since the high-temperature
(950°C) phase is most likely the tetragonal structure [at least this is
the case for R = Sm and Gd with z = 04.S,9], this transformation can
depend on how the quenching is performed. Results discussed below only
pertain to samples that were prepared at 950°C in air and air-quenched by
pulling them from the furnance. The X-ray diffraction patterns of
Baz-zEul+zCu30S+x shown in Figure 10 illustrate the progressive changes
of peak shape and convergence of multiplets into singlets when going from
the orthorhombic to the tetragonal structure. For the La series, the z
value for the structural phase transformation is found to be between
z=O.l and 0.2. For the Nd, Sm and Eu series the corresponding z values
are approximately the same; all are found to be between z = 0.2 and 0.3.
As the samples in each Baz-zRl+zCu306+x series were prepared at intervals
in z of 0.1, we are not able to distinguish any differences at this stage.
..
II!
"green"
103
110
TWO - TtETA (DEGREES)

Figure 10. X-ray diffraction patterns of Baz-zEul+zCu306+x'
X-ray characterization and X-ray powder standard diffraction

patterns of the tetragonal Bal.sRl.SCu307+x' with R=La, Pr, Nd, Sm, and
Eu composition has been reported lo . These tetragonal phases have up to
25% substitution of R in the Ba sites and therefore the chemical formula
can be represented as (BaO.7SRo.zs)zRCu307+x' or simply referred to as
the Ba3R3Cu60l4+x (336) composition. The crystallographic relationship of
these five materials can be described as a=b=1/3c, indicating that as the
R3+ ions replace the Baz + ions to an extent of 25%, the unit cell content
can be considered as a stack of three pseudo-cubes. The crystal structure
of the La composition has been determined by Sunshine et al. l9 using a
neutron powder diffraction technique. This structure is similar to the
structure of the superconductor Ba ZYCu 30 6+x except it is tetragonal with
smaller unit cell volume, and with oxygen partially located at both the
a- and b- basal axes. The structures of the Pr, Nd, Sm and Eu analogs are
presumbably isostructural with the La compound because of the similarity
of the X-ray diffraction patterns.
TREND OF PHASE COMPATIBILITY DIAGRAMS
Figure 11 shows the ternary diagrams of the CuO-rich regions of the

BaO-Rz 0 3 -CuO systems, where R=La, Nd, Sm, Eu, Gd, Y and Er. They are
arranged in the order from the largest size La to the smallest one. The
appearance of these diagrams features several definite trends. The La
diagram is the most complicated one. The presence of four solid solution
series (Baz+zxR4-ZxCuZ-x010-Zx' Baz-zRl+zCu306+x' Bal+xRz-xCuZ06-x/2' and
BaO(BaCO)
BaO(8aC03)
BaO(BaC03)
t.tJ2C~ CuO Y2CU20S CuO

(b) (f)
BaO(BaC03) BaO(BaC03)
BaO(BaCO)
Figure 11. Subsolidus phase compatibility diagrams of BaO-R2 03 -CuO near

the CuO corner for (a) La, (b) Nd, (c) Sm, (d) Eu, (e) Gd, (f) Y and (g)
Er at 950·C in air.
R2-zBazCu04-X) as well as the compound BaR4Cu5013+x in the La system

further makes the tie-line connection very different form the rest of the
lanthanide series. The number of solid solution series changes into two
in the Nd system (Ba2+2xR4-2xCu2-x010-2x' Ba2-zRl+zCu306+x) and reduces
into one at the Sm diagram (Ba2-zRl+zCu306+x)' The extent of the Ba2 _
zRl+zCu306+x solid solution decreases as the mismatch between Ba2+ and
R3+ increases. This range of solid solution diminishes and ceases to
exist beyond R=Gd. After the Gd system, only stoichiometric point
compounds are found in the CuO-rich region.
Another characteristic of these diagrams is illustrated by the tie-

line connection between the binary compound along the R2 0 3 -CuO edge to
the (121) phase and the (213) series. As has been discussed previously,
the R2 Cu0 4 compound can only be prepared with the larger size of R,
namely, from La to Gd, while the R2 CU2 0 5 phase exists with the smaller
size of R. The tie-line connection between this binary composition
R2Cu04/R2Cu205 and the high Tc superconductor compositions appears to
reflect the different extent of the Ba2-zRl+zCu306+x solid solution.
When R's are relatively large and the extent of the solid solution line
is long, e.g., R = Nd and Sm, a compatibility line is found to connect
the R2 Cu0 4 and the tetragonal end member of the Ba2-xRl+xCu306+X phase.
In the systems with R=Eu and Gd, the tie-line connection switches to join
the CuO phase and the BaEu2 Cu0 5 /BaGd2 Cu0 5 phase, respectively. This
trend remains hereafter in the systems with smaller R's.
CONCLUSION
Trends of phase and solid solution formation as well as phase

compatibility relationships have been discussed in the CuO-rich region of
the BaO-~R203-CuO systems. The size of the lanthanides, R3+, was found to
have a profound effect on these trends. The larger the size of R3+, the
greater the number of ternary compounds and solid solution series formed.
In the series of Ba2-zRl+zCu306+x, solid solution formation was
identified to exist with the larger size rare-earth ions, namely, La, Pr,
Nd, Sm, Eu and Gd. The range of this solid solution formation decreases
with increasing difference between the size of Ba2 + and R3+. The trend of
tie-line connection is also found to be dependent on the size of R3+ .
It is hoped that the relationships among compositions, structures

and the size of R3+ discussed in this report will enhance the
understanding of the physical properties of high Tc superconductors and
improve the strategy both for processing these materials with improved
properties and for the search for new materials.
ACKNOWLEDGEMENT
This project is partially supported by the Electric Power Research

Institute. The valuable discussions with Drs. L.P. Cook and R.S. Roth and
the critical review of the manuscript by Drs. H.F. McMurdie, L.P. Cook,
and J. Carpenter are appreciated.
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MEASUREMENT OF THE PHASE COMPOSITION OF PARTIALLY STABILIZED
ZIRCONIA (PSZ) TEST PARTS BY X-RAY POWDER DIFFRACTION
R. A. Newman
Analytical Sciences
Michigan Applied Science & Technology Laboratories
The Dow Chemical Company
Midland, Michigan 48667
INTRODUCTION
Zirconia (Zr02) is one of a number of ceramic materials under

development both at Dow and other companies for high cost, low-volume
applications under severe corrosion/wear conditions. To improve the
physical properties of zirconia, much work has been done worldwide in
recent years developing partially stabilized zirconia, or PSZ. This is
zirconium oxide which has been "stabilized" in the tetragonal form,
typically by the addition of calcium or yttrium oxide 1 ,2. The term
"partially stabilized" is given to these materials because the proper
amount of oxide stabilizer will cause the zirconia to crystallize almost
entirely in the tetragonal form under the proper processing conditions.
However, the PSZ fabricated part is not completely stabilized, because it
will undergo a tetragonal to monoclinic (T --> M) phase transformation when
subjected to an applied stress. Fabricated ceramic parts containing
primarily the tetragonal form of zirconia exhibit substantially improved
physical properties in comparison to monoclinic Zr02' even though small
amounts of other crystalline forms of zirconia are often present in
fabricated PSZ parts. The stress-induced martensitic transformation 3 - 6
from the T --> M form is most likely responsible for this improvement in
physical properties, especially fracture toughness, although there are
other theories which disagree with this conclusion 2 ,7,8.
This martensitic transformation is believed to be a primary factor in

determining the fracture toughness of PSZ parts. X-ray diffraction should
be able to to determine the monoclinic phase concentration in the samples,
as a non-destructive monitor of the "quality" of the parts tested - those

Fracture Test Part

Dimens ions: 15mm L x 10mm W x 4mm 0
Bround Surface
Fracture Surface
Figure 1. Shape and dimensions of partially stabilized zirconia test

parts.
which undergo a large degree of T --> M transformation under an applied

stress would be considered high quality parts, and should exhibit good
toughness.
EXPERIMENTAL
Three samples of fractured PSZ test parts, labeled A, Band F, were

analyzed using x-ray powder diffraction to determine the phase composition
in areas which were subjected to differing external stresses. The areas to
be studied for each part were: [1] a smooth polished surface, [2] a rough,
ground surface, and [3] a fracture surface. The shape and dimensions of
the PSZ test parts and surfaces of interest are shown in figure 1. In
addition to the phase chemistry, a qualitative determination of the degree
of annealing (crystallite growth) was obtained. Each surface of interest
was analyzed on the Siemens 0-500 automated diffractometer. A Huber
incident beam monochromator was utilized to obtain Cobalt KQ1 incident
radiation, and a position sensitive detector was used for data collection.
Typical instrumental conditions and data-collection parameters are listed
in table 1. In some cases, due to wide variations in the analysis results,
selected part surfaces were re-analyzed to obtain better statistical data.
In the case of the fracture surface of the PSZ parts, where the area
to be analyzed was small, the incident x-ray beam was collimated to
eliminate diffraction from other regions of the part surface (see figure
R. A. NEWMAN 469
Table 1. Instrumental Parameters

for PSZ test-part data collection
Parameter Setting
Co Source 40 kV, 25mA
Huber Incident
Beam Monochromator KOIl Radiation
Incident Slits 0.3 degree
Receiving Slits N/A
Detector MBraun PSD t with

soller slits
Scan Speed* 1 degree/min.
Data Increment 0.02 degrees/point
tEosition ~ensitive ~etector.

*step counting is not possible with the PSD system.
1). The positions of the highest-intensity diffraction lines for cubic(e),

tetragonal, and monoclinic Zr02 are shown in figure 2, superimposed on the
diffraction patterns of the three different surfaces of part A. The raw
diffraction data were subjected to profile fitting using DISPLAY, an
interactive data analysis program developed at Dow. 9 This program utilizes
a split-pearson VII algorithm which allows the analyst to determine precise
peak positions, intensities, and FWHM (~ll ~idth at ~alf ~aximum height)
with full visual and numerical evaluation of the quality of the results. A
measure of the degree of martensitic phase transformation which has occurred
on the different part surfaces can be determined from a ratio of the
intergrated areas of the highest intensity diffraction lines for the M and
T,e phases. The degree of stress-induced annealing, or crystallite growth,
can be determined from the FWHM of the diffraction peaks analyzed. A
numerical value for the average crystallite size may be obtained by
correcting the FWHM data for instrumental effects with a crystallite size
standard. The profile analyses of the T phase were compromised by the
nearly perfect overlap of the C phase and T phase reflections.
Typical results of profile fitting analyses performed on the data are

listed in Table 2. The data from Table 2 are illustrated graphically in
figures 3 through 5. The intensity ratio data in figure 3 shows the rela-
tive degree of observed martensitic transformation from the T --> M phase
under different external stresses (polishing, grinding, fracturing) for the
three samples. For comparison purposes, this can be considered a measure
of the percent conversion from the T and C phases to the M phase for this
STABILIZED ZIRCONIA
295.3 Sample A ~~
p$.<f
,\"
246.15
196.92
,..
0 (j~<QI'
..
4<
1/1
C
147.69 #'.~~>f.
~I
::I
0
0 98.46 Polished Surface
Ground Surface
49.23
26 28 30 32 34 36 38 40 42 44
2-Theta (deg)
Figure 2. Typical diffraction patterns obtained from the different surfaces
of interest on test part A. Note the near coincidence of the
cubic and tetragonal phase 1 1 1 reflections.
Table 2. Profile Fit Analysis Results

for Stabilized Zirconia Samplest
Monoclinic Monoclinic Tetragonal Tetragonal Relative %
Sample FWHM, deg FWHM, deg Monoclinic
"An-- ~ ~
Polished Surface 0.5874 59 0.5034 805 7.33
0.8888 80 0.4047 1353 5.91
Ground Surface 0.6246 59 0.2526 578 10.21
0.5800 39 0.6540 697 5.60
Fracture Surface 0.4940 95 0.2433 745 1~.~~
"B"
Polished Surface 0.6858 107 0.4376 1170 9.15
0.9704 77 0.5320 805 9.57
Ground Surface 0.6006 69 0.2740 770 8.96
0.6054 46 0.2720 779 5.91
0.5338 43 0.3030 443 9.71
0.7190 539 0.3013 6810 7.91
Fracture Surface 0.5224 155 0.2592 1295 11.97
0.5038 142 0.2135 961 "~~?L
"F"
Polished Surface o.aOOO 53 0.5152 837 6.33
0.7952 96 0.5515 1150 8.35
0.8000 72 0.4360 796 9.05
0.8200 53 0.4660 851 6.23
Ground Surface 0.7400 25 0.3338 481 5.20
0.6624 50 0.1950 932 5.36
0.8842 84 0.3362 988 8.53
0.7166 33 0.2346 665 4.96
Fracture Surface 0.5172 77 0.1628 655 11.76
0.5683 141 0.3039 1092 12.91
0.4414 58 0.2729 551 10.53
tThe intensities and FWHM values for the Tetragonal phase are less
reliable due to overlap with the 1 1 1 reflection of the cubic phase.
R.A. NEWMAN 471
TRANSFORMATION TOUGHENING IN STABIUZED ZIRCONIA

16
D Sample A
c-
<> Sample B
14 c-
Sample F
() r-
'E c-
'is0 12
c r-
0 0
::E 10 r- <> <>
#. r- II
~
Br-
~
'i
c- D
<>
II: 6c- A
r-
4r-
i
I L I
Polished Ground Fracture
Surface Surface Surface
Fig. 3. Transformation toughening, or degree of tetragonal --> monoclinic

phase transformation in the PSZ test parts. Intensity ratios were
determined from profile fitting of the diffraction spectra.
set of analyses. However, the agreement between these relative concen-

tration values and the actual phase concentrations is dependent upon the
x-ray scattering efficiency of the M, C and T phases. In this case, the
interference of the C phase diffraction line is actually fortuitous, since
we are interested in the concentration of the M phase in the entire sample
matrix, which includes both the T and C phases. The near coincidence of
the highest intensity T and C diffraction lines enables us to obtain the
"matrix" intensity value easily.
The FWHM data in figure 4 shows the degree of annealing, or crys-

tallite growth caused by the external applied stress for the T phase. In
contrast to the previous argument, the close proximity of the C and T phase
STRESS ANNEAUNG OF ZIRCONIA - TETRAGONAL PHASE

1.0
o Sample A
0.9 c- <> Sample B
O.B r- " Sample F
~ 0.7 c-
'tI
0.6 r-
:i
J:
0.5 c- 8"
~ 8
0.4 r- A
'"Il.
III
- A
g
CD
0.3 A
~
0.2 - §
0.1 -
0.0 I I J
Fig. 4. Crystallite growth observed in the tetragonal phase of the PSZ

test parts.
STRESS ANNEALING OF ZIRCONIA - MONOCliNIC PHASE

1.4
- o Sample A
<> Sample B
1.2 -
- Sample F
CIl
II)
1.0 - <>
,
"tl - 0
:i 0.8 - &.
J:
- <>
~ - ~
•
0.6 0 A
.lO:
10 -
-
II)
A
D.. 0.4
-
0.2 -
-
0.0 I I I
Fig. 5. Crystallite growth observed in the monoclinic phase of the PSZ

test parts.
reflections compromises the FWHM value of the T phase to some extent. In

most of the sample spectra, the presence of the C phase is observable, but
the actual position and intensity of the C phase reflection are not clear
due to the high degree of overlap with the T phase peak (see figure 2). We
can still observe a trend in stress-induced annealing in the T phase, but
only qualitative results can be obtained from this data. The FWHM data for
the M phase are shown in figure 5. This data shows a trend similar to the
T phase, as we would expect. In both figures, results obtained from
repetitive measurements are shown for most samples.
There is a significant degree of variability in the FWHM values for

both the T and M phases, especially in the case of the ground surfaces.
Some of the surfaces were analyzed as many as six times, in an attempt to
obtain reproducible results. In some cases, the results were fairly con-
sistent, while in others, no reproducibility was obtained. There are
several interrelated factors which could contribute to the observed vari-
ability: (a) Instrument stability, (b)sample purity, (c) sample area limi-
tations, (d) surface morphology, (e) preferred orientation, and (f) retained
stress. Of these factors, the last four are clearly the most serious, and
all of these are the result of the processing history of the samples. Be-
cause of the small sample size and sample mounting restrictions, the
samples were analyzed in static position, i. e. they were not rotated
during data collection. The irradiated area of the sample was fairly
small, so it was unlikely that the same area and orientation (with respect
to the incident x-ray beam) would be obtained for data collection. Both of
these experimental restrictions would tend to enhance the effects of (d)
through (f). Evidence for preferred orientation can be seen in figure 2,
where the intensity ratio between the 0 0 2 peak and 2 0 0 peak of the T
phase varies from 2.7 (for the polished surface) to 0.62 (for the fracture
R. A. NEWMAN 473
surface). This can be compared to an intensity ratio of 0.72 from JCPDS

standard pattern #17-923 for tetragonal Zr02' as a qualitative indication
of the degree of preferred orientation on the surfaces analyzed. The
observed orientation is due to directionally preferred crystallite growth,
with the highest degree of orientation (-4X) observed from the polished
surface. This indicates that the preferred crystallite growth is occurring
during part fabrication, not as a result of stresses applied to the part
after fabrication. The reduction in T-phase orientation observed on the
ground and fractured surfaces may be a "gradient effect" which occurred
during part fabrication. It could also be due to randomization from
stress-induced 3-dimensional crystallite growth during grinding or
fracturing. It is not possible to determine which effect is occurring from
the x-ray diffraction data. Similar orientation effects were observed in
the diffraction spectra for samples Band F.
CONCLUSIONS
Even though several limiting factors were present, the analyses yield-
ed the expected trend in T --> M phase transformation for the polished
surface and the fracture surface. The low values and wide range (from 5 to
>10 %) for the M phase concentration obtained for the ground surface of the
samples (see fig. 3) are due to the combination of preferred orientation
and the non-uniform grinding technique. This was clearly evident by visual
inspection of the samples. The degree of martensitic transformation to the
M phase in the fracture zone as observed by X-ray diffraction (ca. 10 - 14%
by intensity ratio) was less than expected for a high quality fabricated
PSZ ceramic part. Overall, the analyses were compromised by the small
dimensions of the part surfaces, which restricted the sampling of the phase
composition by the incident x-ray beam. The presence of interferences
(primarily preferred orientation) further degraded the quality of the
results. Better phase composition sampling and analysis results could be
obtained if larger test parts were provided, with more uniform surface
treatment areas.
REFERENCES
1. T. Masaki, Mechanical Properties of Toughened Zr02-Y203 Ceramics,

J. Am. Ceram. Soc., 69:638-640 (1986).
2. A. Yakawa et al., The Development of High Strength Zr02 (HIPed-

PSZ), Sumitomo Electric Technical Review, No. 25:179-188 (1986).
3. R. C. Garvie et al., Nature (Lond.), 258:703 (1975).
4. D. L. Porter and A. H. Heuer, Mechanisms of Toughening Partially

Stabilized Zirconia (PSZ), J. Am. Ceram. Soc., 60:183-184 (1977).
5. R. McMeeking and A. G. Evans, J. Am. Ceram. Soc., 65:282 (1982).
6. F. F. Lange, Transformation Toughening, J. Mat. Sci., 17:240-246

(1982) .
7. N. Claussen and M. Ruhle, Design of Transformation Toughened

Ceramics, Adv. in Ceram., 3:137-163 (1981).
8. M. V. Swain and L. R. F. Rose, ICF6, Adv. in Fracture Res., 1:473

(1984) .
9. A. Brown and J. W. Edmonds, Adv. in X-ray Anal., 23:361-373 (1980).

X-RAY MASS ABSORPTION COEFFICIENTS: MEASUREMENTS AND USES IN THE
QUANTITATIVE DIFFRACTION ANALYSIS OF PYRITE IN COALS
David L. Wertz, Charles B. Smithhart, and Stacey L. Wertz
Department of Chemistry and Center for Coal Product Research l

University of Southern Mississippi
Hattiesburg, MS 39406-5043 USA
INTRODUCTION
The mass absorption coefficient (~) of a weakly absorbing solid

material may be measured by either the transmission or the reflection
method. 2 - 6 The latter typically employs a crystalline substrate and the
diffraction method, measuring the transmission of the diffraction
peak(s) of the substrate through the analyte. Compressing or compacting
a powdered sample is not required when the reflection method is used.
Utilization of the mass absorption coefficient (rather than the

linear absorption coefficient) of a solid sample of unknown composition
precludes the necessity for utilizing either the density or the
thickness (complicated by interstices) of such a sample in the
conversion of measured intensities to the "intensity at infinite
thickness". 7
Presented below isa brief discussion of a direct quantitative XRD

method which has been used for the determination of the mass absorption
coefficient of a weakly absorbing powdered sample and for the conversion
of the measured diffractogram intensity (1M) obtained for that sample to
its "absorption corrected" diffractogram (1 0 ) using the mass absorption
coefficient. To utilize the method requires knowledge only of the
sample's irradiated mass (m) and its irradiated surface area (T) as well
as Y, which is an experimental constant defined by the conditions of the
experiment and which includes T. Also necessary is careful measurement
of the diffracted intensities.
An outline of the experimental technique by which ~ may be

measured and then used to convert 1M to 1 0 by7 :
10 (20) = ~·m·1M(20)/(Y·[l-exp(-2·~·m/T·sin0)1) (1)
is provided below, along with several sets of results which confirm the
accuracy of the technique both in the evaluation of ~ (for several
compounds of reagent grade purity) and for the measurement of the pyrite
abundance in each of the eight Argonne Premium Coals. 8 Quantitative

analysis protocols for other crystalline minerals are currently being

developed.
Advantages offered by the method are (a) only one sample

preparation/handling is required, (b) analysis may be accomplished with
high accuracy, and (c) rapid scan times when the analysis is limited
only to the pyrite abundance in coals.
EXPERIMENTAL
Each analyte was finely powdered and then lightly packed into a
conventional x-ray diffraction sample-holder (aluminum) in such a way as
to produce a "flat" surface for the powdered sample. The aluminum
sample-holder used in these experiments had an inside diameter of 2.54
cm and was machined to provide a sample depth of 0.05 cm.
The x-ray diffractometer utilized a theta compensating slit.

Diffraction data were accumulated using a conventional long fine focus
x-ray tube (copper target), a crystal monochromator in the diffracted
beam, and a scintillation counter to measure the intensity of the Cu Ka
diffracted beam. Data were accumulated at increments of 0.020 by
counting for three seconds at each of the angular settings using an
OmniComputer, Inc. data controller-processor in concert with a
microcomputer over the angular range from 8.00 0 to 88.00 0, see Figure 1.
Diffraction peak integrations were accomplished by computer

methods.
The irradiated surface area, P(20), was determined at the

scattering angle corresponding to each of the three intense diffraction
peaks of aluminum by measuring the irradiated surface area of a sample
of silver bromide. These were related to a irradiated surface area
constant by T = P(20)/sin0.
Fig. 1. Schematic of the Diffraction Experiment using the Aluminum

Sample-Holder as the Crystal Substrate. A. Long, Fine Focus
X-ray Target (Cu). B. Theta Compensating Slit. C. Crystal
Substrate. D. Receiving Slit(s). E. LiF Crystal
Monochromator. F. Scintillation Counter.
D. L. WERTZ ET AL. 477
10r-----------------------------------------------------------,----,
311
III
200
I
I .,ii, I
i~~,,---~J~I
A" I
,I
,I
I!
iI
i ______________~~
'L~l_. I
~
: ! I 1~IIIIIIIIIIIIIIIIIITillllilllillll'lllill
20 30 40 50 60 -;0 60
TWO THETA
Fig. 2a. Diffraction Pattern of the Crystal Substrate, Aluminum.

2b. Scattering Pattern of Amorphous Silicon Dioxide (0.0944 g)
Coalesced with the Diffraction Pattern of the Crystal
Substrate.
MEASURING THE MASS ABSORPTION COEFFICIENT OF KNOWN PHASES
Shown in Figure 2 is the diffractogram of the crystalline aluminum

sample-holder and of a 0.0944 gram sample of amorphous silicon dioxide
(SPEX INDUSTRIES, cat. no. 1250) which had been deposited onto the
sample-holder. The decrease in the area under each large diffraction
peak of aluminum may be used to evaluate the irradiated sample surface
area by:
p(2e) (2)
where 0 is 1/2 of the Bragg diffraction angle, and Ap and AS are the
integrated areas of the diffraction peaks of aluminum in the absence of
and in the presence of m grams of the powdered analyte, respectively.
For each of the three large diffraction peaks of aluminum, Twas
determined from the Ap/AS ratio (see TABLE I). For all subsequent
evaluations the arithmetic value of T (which agreed quite well with the
value for T determined by the AgBr experiments described above) was
used.
For this sample of amorphous silicon dioxide, or for other samples
whose absorption is less than "critical", the mass absorption may be
calculated from the decrease of the peak area(s) of the crystal
substrate peaks by:
~ = (T·sin0/2·m)·ln(AS/Ap). (3)
Table I. MASS ABSORPTION COEFFICIENT MEASUREMENTS FOR AMORPHOUS

SILICON DIOXIDE a
SAMPLE MASS = 0.0944 g

ALUMINUM SUBSTRATE
COPPER X-RAYS
A. EVALUATION OF THE SAMPLE IRRADIATION CONSTANT
AL PEAK PEAK AREA P(20) T

RETAINED
(ApJAS) '100 (cm 2 ) (cm 2)
111 3.65 % 2.008 6.091

200 5.32 % 2.265 5.953
311 18.07 % 3.884 6.156
MEAN VALUE OF T: 6.067
RELATIVE MEAN DEVIATION: 1.24%
B. DETERMINATION OF THE MASS ABSORPTION COEFFICIENT; T = 6.067 CM2JG
AL PEAK Jl
(cm 2Jg)
111 35.06
200 35.87
311 34.69
MEAN VALUE: 35.21
RELATIVE MEAN DEVIATION: 1.26%
a The calculated value (from tabulated atomic mass absorption

coefficients)9 is 35.2 cm 2Jg.
The mass absorption coefficient calculated for the powdered silicon

dioxide using each of the three large diffraction peaks of the aluminum
substrate is also shown in Table I.
Although similar to the the mass absorption relationships presented

by Williams 2 and by Leroux et al. 3 , each of the experimental terms
necessary for the evaluation of the mass absorption coefficient
presented in eq. 3 may be directly and conveniently measured with high
accuracy.
With stronger absorbers, the transmission of the 111 and the 200
are diminished much more than is the transmission of the 311 peak of
aluminum. While this effect provides less information from which the
mass absorption coefficient of the absorber may be calculated, it also
causes less of the diffractogram of the absorber to be complicated by
the diffraction peaks of the crystal substrate.
THE 311 DIFFRACTION PEAK OF ALUMINUM AS THE INTENSITY REFERENCE
In subsequent experiments only the transmission of the 311

diffraction peak of aluminum has been measured. This substrate peak was
selected because none of the analytes measured have diffraction peaks
which overlap this peak and because its transmission factor through the
analyte is the highest (and thus the most accurately measured) of the
major aluminum peaks.
Table II. MASS ABSORPTION COEFFICIENTS MEASURED FOR A WEAKLY ABSORBING

POLY-CYCLIC CARBONACEOUS MATERIAL -- ANTHRACENE
ALUMINUM SUBSTRATE, 311 PLANES
COPFER X-RAYS
MASS In{AS/Ap} llZxp

(g) (em /g)
0.1429 0.3337 4.47

0.3382 4.53
0.3397 4.55
0.1855 0.4274 4.41

0.4139 4.27
0.4139 4.27
0.2278 0.5142 4.32

0.5118 4.30
0.5225 4.39
MEAN EXPERIMENTAL VALUE: 4.39
RELATIVE MEAN DEVIATION: 2.02i.
CALCULATED VALUE9 OF ll: 4.35
To test the validity of using only one diffraction peak of the

crystal substrate as the basis for determining the mass absorption
coefficient, the absorptivity of several finely powdered reagent grade
materials was measured and then compared to accepted values. These
data were accumulated by collecting diffraction data over the region
from 76.50 0 to 79.50 0 ; i.e., the angular region which includes the 311
diffraction peak of the aluminum substrate.
The mass absorption coefficients of several samples of anthracene

(C14H10), a phase which is similar in molecular composition to the
carbonaceous species found in coals, have been determined (Table II)
using our crystal substrate technique. The diffraction intensities for
the sampleholder/substrate with each of the three anthracene absorbers
and with no absorber are shown in Figure 3.
The mass absorption coefficients of several weakly absorbing

minerals and several organic species similar to those found in coals
have also been measured from determination of AS and Ap using the 311
peak of aluminum. The results are shown in Table III.
Comparison between the mass absorption coefficients measured by the
reflection XRD method using aluminum as the crystalline substrate and
calculated values (from tables) indicates satisfactory agreement. For
none of these phases does the relative deviation exceed 5%, with the
average relative deviation being 2.7%. When all of the anthracene data
are included, the average relative deviation is reduced considerably.
The mass absorption coefficient for each of the eight Argonne

Premium Coals, and for numerous other coals, was also determined by this
method.
DIFFRACTION STUDIES OF COALS
Coals have been examined for many years by XRD methods. 10-14 Coals
represent complex "real life" samples which contain a carbonaceous
2.6 - , - - - -
2.4
2.2
1.8
.r-. 1.6
u ~
W"U
c
'-0 1.4
~
~ ~
+'
".c
C
01-
°
"
1.2
U'-'
0.8
0.6
0.4
0.2
0
76.4 76.8 77.2 77.6 78 78.4 78.8 79.2 79.6
Two-Theta
Fig. 3a. The 311 Diffraction Peak of Aluminum with No Anthracene

Deposited onto the Al Sample-Holder.
3b. 0.1429 g of Anthracene Deposited onto Al Sample-Holder.
3c. 0.1855 g of Anthracene Deposited onto Al Sample-Holder.
3d. 0.2278 g of Anthracene Deposited onto Al Sample-Holder.
(amorphous) matrix into which are embedded varying abundances of

minerals. Their diffractograms contain broad maxima and minima which
describe the amorphous species 14 as well as the diffraction peaks
characteristic of many, if not all, of the crystalline species
contained.
The diffractogram of APe 301 (Illinois No.6) is shown in Figure 4,

where the 1.63 A peak characteristic of pyrite is highlighted.
Table III. MASS ABSORPTION COEFFICIENTS SEVERAL COMPOUNDS SIMILAR TO

THOSE FOUND IN COALS
A. MINERALS
Phase llexp Accepted Relative

Value Deviation
(cm 2 jg) (cm 2 jg) (i.)
a-quartz 35.8 35.2 1.707.

corundum 30.6 31.1 1.617.
magnesia 26.8 27.8 3.607.
kaolinite 30.0 29.8 0.67%
B. ORGANIC COMPOUNDS
urea 7.2 7.5 4.007.

sucrose 7.4 7.7 3.897.
anthracene 4.4 4.4 0.047.
10 20 30 40 50 60 70 80
2 Theta
Fig. 4. The x-ray diffractogram of a 0.2356 g sample of Argonne
Premium Coal 301, a high volatile bituminous coal (Illinois
No.6). The coal reportedly contains 2.47% pyritic sulfur
and 2.01% organic sulfur. The 1.63 A diffraction peak of
pyrite is darkened. An * indicates the 311 peak of AI.
/
35
("')
'0 30
~
"; 25 -
/
Q)
Ul
o
j 20
<=:
;:l
o
u 15
<>:
'"<>:
~
10
:.:
;;j
p., 0······0······· ··0
5
{ji
O~~-------------------------------
0.00 6.00
% Pyrite
Fig. 5. 1.63 A Pyrite Peak Area (Qpy) Measured from IM(26) and the
1.63 A Pyrite Peak Area (Qopy) Measured from from 10 (26) vs.
Pyrite Abundance Reported for the Argonne Premium Coals.
QXRD OF PYRITE IN THE ARGONNE PREMIUM COALS USING THE ABSORPTION

CORRECTED DIFFRACTOGRAMS CALCULATED FROM THE MASS ABSORPTION COEFFICIENT
Shown in Figure 5 is a presentation of the area under the 1.63 A

peak of pyrite, Qpy, in each 1M graphed against the pyrite abundance in
each coal (as reported by the Premium Coal Sample Program. B) It is
clear that the pyrite peak area measured in 1M cannot be used to
determine the pyrite abundance in these coals in any direct manner even
though the diffracted intensities have been accurately measured.
The measured intensity for each of the Argonne Premium Coals was
converted to the corresponding absorption corrected intensity by eq. 1,
and the latter were used in subsequent analysis for the pyrite (FeS2)
abundance in each coal. Also shown in Figure 5 is a graphical
representation of area under the 1.63 A pyrite peak in the absorption
corrected diffractogram, QOpy, plotted versus pyrite abundance for the
eight Argonne Premium Coals. The linearity of the relationship is
expressed by R2 > 0.997.
The pyrite peak area measured in each absorption corrected

diffractogram is related to the pyrite abundance (wpy) in each coal by:
(R2 = 0.99749) (4a)

or
QOpy bl'wPy, with intercept = O. (R2 = 0.99736) (4b)
Rearrangement presents the QXRD analysis for pyrite in its most

useful form, i. e.,
(5)
The slope and intercept values presented in equations 4a and 4b and

utilized in equation 5 are consistent with the experimental conditions
in this laboratory. As with any quantitative x-ray diffraction method
based on intensity measurements, periodic recalibration is necessary for
optimum analysis results.
The lower limit of detection for pyrite in the eight Argonne

Premium Coals may be extended to ca. 0.3% (0.16% pyritic sulfur) by
weight when the absorption corrected intensities are used; the LLD is
~. 0.5% when the measured diffractograms are used.
CONCLUSIONS
The accuracy of the quantitative analysis for pyrite obtained from

analysis of the absorption corrected x-ray diffractograms, calculated
from the absorption corrected intensitiy via use of the mass absorption
coefficient of the sample, is consistent with the high level of
experimental accuracy with which each of the experimental terms may be
measured. The presence of other crystalline materials, moisture,
volatile and poly-cyclic material(s), all in widely varying amounts,
does not affect the accuracy of this quantitative x-ray diffraction
method.
REFERENCES
1. Support from the U. S. Department of Energy (Grant No. DE-FG97-

83WM46655) via the Mississippi Department of Energy and
Transportation (Contract No. 88-130-074) is gratefully acknowledged.
2. P. P. Williams, 1958, Anal. Chern., 31:1842.
3. J. Leroux, H. B. C. Davey, and A. Paillard, 1973, Am. Ind. gyg.
Assoc. I., 34:409.
4. Lange, B. A. and Haartz, J. C., 1979, Anal. Chern., 51:520.
5. Frevel, L. K. and Roth, W. C., 1982, Anal. Chern., 54:677.
6. Davis, B. L. and Johnson, 1988, in "Adv. X-Ray Anal.", 30:333.
7. Klug, H. P. and Alexander, L. E., 1974, "X-ray Diffraction
Procedures for PolyCrystalline and Amorphous Materials," Wiley-
Interscience, N. Y., p. 360.
8. Samples of the Argonne Premium Coals were provided by Dr. Karl
Vorres, Program Manager, Premium Coal Sample Program, Argonne
National Laboratory.
9. The absorption coefficient for each of the reagent grade materials
was calculated from tabular values by ~calc = ax'~x; where a is the
weight fraction of element x in the compound and ~x is its mass
absorption coefficient. The elemental mass absorption coefficients
were taken from "International Tables of X-Ray Crystallography.
Vol. III." International Union of Crystallography. The Kynoch
Press. Birmingham, England, 1962, p. 162.
10. R. E. Franklin, 1950, Acta Crystallogr., 3:10.
11. J. T. Kwan and T. F. Chen, 1976, ~roc. Div. Fuel Div. (ACS), 21:
67.
12. B. L. Davis, 1986, Powder Diffr., 1:244.
13. G. J. McCarthy, 1986, Powder Diffr., 1:50.
14. D. L. Wertz, 1988, Powder Diffr., 3:153.
AN OVERVIEW OF THE USE OF XRD AS A TOOL IN THE TOTAL ANALYSIS OF
POWDERED HOUSEHOLD LAUNDRY DETERGENTS
Margaret M. King and Evelyn M. Sabino
PQ Corporation, Research & Development Center

280 Cedar Grove Road
Conshohocken, PA
INTRODUCTION
Manufacturers of household laundry products and laundry detergent

builders want to know the exact formularies used in prospective customers'
and competitive product lines. No convenient source exists for this
information because published formularies are numerous and differ widely.
(See Table 1.)
Additionally, labelling requirements on consumer products vary greatly

throughout the world. The United States of America, which currently has one
of the most stringent rules, only requires generic chemical content label-
ling in descending order of concentration; many countries require none at
all.
Classically, detergents are analyzed by taking aliquots from aqueous

dilutions of the "as received" material and titrating. (See Milwidsky.)
These determinations produce general information about the alkali content,
active bleach and surfactants present, but not the specific chemical identi-
fication which is desired. (See Table 2.)
Here we present a scheme of analysis in which X-ray diffraction plays an

integral role in the determination of total composition of household laundry
products.
TECHNIQUE
Many of the detergent builders used in the detergent industry are

crystalline and patterns exist in the International Center for Diffraction
Data (ICDD) Powder Diffraction File (PDF). Typical detergent builders are
listed along with their PDF numbers and common chemical name in Table 3.
Various waters of hydration are also used but have not been included.
However, the diffractionist must remember these are used and often have
markedly different patterns.
Advances in X-Ray Ana/ysis. Vol. 33 485

Edited by C.S. Barrett el a/.
Plenum Press. New York, 1990
TABLE 1
NON-PHOSPHATE DRY-BLENDED LAUNDRY POWDERS*

HIGH DENS ITY - ONE QUARTER CUP
Premium Quality Good Qua l i ty

%w %w
NEODOL™ 23-6_5 13 NEODOL 23-6_5 13
NEODOL 23-3 7 NEODOL 23-3 7
zeolite™ 4A 45 Sodium carbonate 73
Sodium carbonate 27 Sodium silicate 5
Sodium silicate 6 CMC 2
CMC 2 Fluorescent whitening agent as desired
Fluorescent whitening agent as desired
Properties: Properties:
Powder density, gm/cc 0.6-0.8 Powder density, gm/cc 0.6-0.8
DRY-BLENDED LAUNDRY POWDERS CONTAINING PHOSPHATE'~
HIGH DENSITY - ONE QUARTER CUP
Premium Qual:ty High Quality

%w %w
NEODOL™ 23-6.5 13 NEODOL 23-6.5 13
NEODOL 23-3 7 NEODOL 23-3 7
Sodium tripolyphosphate 73 Sodium tripolyphosphate 58.4
Sodium silicate 5 Sodium carbonate 14.6
Antiredeposition agent 2 Sodium silicate 5
Fluorescent whitening agent as desired Antiredeposition agent 2
Fluorescent whitening agent as desired
Properties: Properties:
Powder density, gm/cc 0.6-0.8 Powder density, gm/cc 0.6-0.8
*Reproduced from Neodol™ Formulary, Shell Chemical Company, Technical Brochure

#SC:312·87.
Until recently this information could not be put to practical use when
analyzing the detergent for total composition due to the complicated
matrix. Today, with an understanding of detergent formulary and good
subtraction software, the diffractionist can often rapidly distinguish the
various species of builders and bleaches. Table 4 details the analytical
scheme used in our laboratory to speciate the various builders that may be
present.
Figures 1 - 4 illustrate the complexity of the raw diffractogram and

list the formulary deduced from our analytical scheme for detergents A and
B. Detergent A is a non-phosphate detergent, while detergent B is a
phosphate containing formulation. In order to do these analyses the
diffractionist must have available chemical information and computer
software which allow the subtraction of known phases and the searching of
the PDF on the remainder pattern. For this reason the diffractionist is
often not the first person to receive the sample.
M. M. KING AND E. M. SABINO 487
TABLE 2
CONVENTIONAL ANALYTICAL METHODS
ALKALINE BUILDERS
(e.g. sodium carbonate, sodium silicate, etc.)
Acid/base titration --- NO SPECIATION

Precipitation techniques --- TEDIOUS & NO SPECIATION
ACTIVE DETERGENT MATTER

(e.g. anionic, nonionic surfactants, etc.)
Alcohol extraction --- NO SPECIATION

Methylene blue titration --- classifies but NO IDENTIFICATION
SEQUESTERING AGENTS
(e.g. EDTA, NTA, etc.)
Titration with heavy-metal salts --- NO SPECIATION
BLEACHING COMPOUNDS
(e.g. sodium perborate, -chlorinated TSP, etc.)
Oxidation/reduction titrations --- NO SPECIATION
TABLE 3
TYPICAL DETERGENT BUILDERS

PDF# COMMON NAME CHEMICAL FORMULA
10-179, 11-652 Sodium Tripolypbospbate
27-778 Sodium Orthophosphate
10-187 Sodium Pyrophosphate
16-1181 Sodium Citrate HOC(COONa)(CH2COONa)2'H20
34-1981 Sodium Nitrilotriacetate N(CH2COONa)2CHZCOOH
5-631, 36-387 Sodium Sulfate NaZS04
5-628 Sodium Chloride NaCI
15-700 Sodium Bicarbonate
1-1166 Sodium Carbonate
11-643, 29-1447 Trona Na3H(C03)2'H20

(Sesquicarbonate) Na2C03 NaHC03 . 2H20
7-81 Sodium Per borate NaB03' 4H20
31-1884 Chlorinated Triazine trione C3H303N2NaCI'2H20

(Chlorisocyanurate)
38-241
1-1173 Sodium Hydroxide NaOH
16-818 Sodium Metasilicate Na2Si03
27-783 Sodium Orthosilicate Na4Si04

TABLE 4
ANALYTICAL SCHEME
HOUSEHOLD LAUNDRY PRODUCTS
LOD ENERGY DISPERS!VE TOTAL ALCOHOL EXTRACTABLES

(WATIR CONT£NT) SPECTROSCOPY
QUANTITATIVE
PHOSPHATE OR ZEOlITE BASED PROOUCT
SURFACTANT
HIGH PRESSURE FILTRATION CLASSIFICATION
& IDENTIFICATION
BY ION EXCIWIGE RESIN '" FT-IR
INSOLUBLE MATERIAL
I
SOLUBLE MATERIAL
C02 BY
>= 27- ACTIVE & TOTAL iON SELEClM:
I
ALKALI TITRATION
E1£CTROOE \
SPECTROSCOPY
SPECIES
IDENTIFICATION ION BY XRD
TOTAL CHROMATOGRAPHY SODIUM
BY X-RAY OlFfRAC11ON BLEA I CARBONAT£.
Oxidation/Reduction P, P SPECIES,
I
ZEOLITE An
Titration (COMFlRI! BY XRO)
SODIUM
BlCARIIONAT£.
Si de
I (SPECIES BY XRO) NTA,
SODIUM
SESQUICARIIONATE
SPECIES BY XRD
yls SODIUM PERBORATE
B
CITRATE,
SODlUII ISOCYANURATE
CHLORiNATED TSP
S04 de CI
QUANTIFY BY XRD (SPECIES BY XRO)
DETERGENT A
X10 31
~,110
4.05
3.20 lIater 10%
2.4:5 Total Surfactant 16
1.88 Insoluable Material 30
1.2:5 Sodium Sul fate 19
0.88
0.4:5
0.20
8.05
10.0 20.0 30 •• 41 •• sa ••
:5.88
4.05 Sodium Perborate 8%
3.28 Sodium Carbonate 11
2.4:5 Sodium Si l i cate 2
1.88
Mi sce II aneous _5_
1.25
100%
8.80
8.4:5
0.20
8.9:5
58.8 68.8 78.8 88.8 90.8
Fi g. 1 Raw diffractogram of Detergent A, a non-phosphate product. The water insoluble material

was quantified by XRD as 100% zeol ite A.
L DETERGENT A
190.8
88.8
68.0
48.8
28.0
:5.0 10.0 1:5.0 29.0 2:5.8 39.0 3:5.8 40.8 4:5.8

85.0% I I I I I I :5- 631
190.0% I I I II I I I I I I I I I I I 1111 I II I l!- i
3:5.0% I I III I I 1111 I II III 1111 II II III 1111 7- 81
190.0
88.8
60.0
48.8
28.8
5.8 18.8 1:5.0 28.8 2:5.8 39.0 35.8 48.8 4:5.8

Fig. 2 The upper sti ck plot represents the raw diffractogram of Detergent A. The lower stick
plot is a simulated diffratogram comprised of sodium sulfate (PDF #5·631); sodium zeolite
A (PQ "in·house" standard 0·1) and sodium perborate (PDF #7·81).
DETERGENT B
X18 31
~.i10
4.85 lIater 5 %
3.20
Total Surfactant 18
2.4:5
Insoluable Materi al 7
1.89
1.25 Sodium Sul fate 32
0.se
0.4:5
0.20
0.0:5
10.0 29.0 30.0 40.0 :50.0
5.90
4.85 Sodium Tripol yphosophate 16
3.29 Sodium Pyrophosphate 11
2.4:5
Sodium Sil i cate 3
1.88
Miscellaneous _5_
1.2:5
0.se 100%
0.4:5
0.20
0.0:5
58.0 68.0 78.0 80.0 90.0

Fi g. 3 Raw diffractogram of Detergent B, a phosphate containing product. The water insoluble
material was quantified by XRD as 100% zeol ite A.
L
198.9
89.9
60.9
49.9
28.9
5.9 19.9 15.9 29.9 25.9 30.9 35.9 40.9 45.9

199.9% I I I I I II I 36- 397
7.9% I I I I II I I I I I I I I I I I I III I I I I 9- 1
29.9% I II I I I III I II III III I I I HI MII 11M II II I n 1111 .NI 10- 186
35.9"/' I I I I I I II I II I I III I 1111 II III I II 19- 187
198.9
89.9
60.0
40.8
28.8
5.9 19.8 15.9 28.9 25.9 30.8 35.9 48.8 45.9

Fi g. 4 The upper stick plot represents the raw diffractogram of Detergent B. The lower stick
plot is a simulated diffractogram comprised of sodium sulfate (PDF #36-397): sodium
zeolite A (PO "in-house" standard 0-1), sodium pyrophosphate (PDF #10-187) and sodium
tripolyphosphate (10-186)_
LS~lel Tri~hloroisoc~i~
198.9
89.0
60.8
48.8
28.8
18.8 28.9
I I
39.8
I
40.9
I, I I I I
5&.8 60.8
I I I II I I I I 31-1956
198.8
89.9
60.9
40.8
28.9
18.9 29.8 30.8 40.8 5&.8 68.0

Fig. 5 The upper stick plot represents the raw diffractogram for tricholoroisocyanuric acid
collected in our laboratory. The lower stick plot represents the information contained
on the ICDD card for chlorinated-S-triazine trione PDF #31-1956.
Both the diffractionist and the detergent chemist must be aware that
the "jargon" used in each others' field is different for the same
compound; for example, the PDF lists Trona while detergent literature
refers to this as sesquicarbonate. The PDF also refers to chlorinated
isocyanurates as chlorinated-S-triazine trione. (See Figure 5.)
Since all manufacturers have their own series of formulations, it would

be difficult to present a standardized method that could be used when
analyzing detergent products for total composition. A brief description of
the analytical approach and interpretation aids for each class of builders
and bleaching agents is addressed below.
Bleaching Agents. An extensive list of bleaching compounds used in the

detergent industry exists which includes chlorinated trisodium phosphate,
sodium perborate and sodium trichloroisocyanurate. Conventional wet-
chemical techniques can not easily speciate the bleaching agent without a
long and tedious process specific to the anion present. While the redox
titration is still useful for quantifying the active material,
identification of the compound is simplified by XRD.
Carbonates. Again, there is not an easy way to identify the carbonate

species by conventional techniques. However, there are many methods, such
as ion-specific electrodes, which can quantify the carbonate anion. We
have successfully used diffraction to identify all three carbonate
compounds in various detergent products -- sodium carbonate, sodium
bicarbonate and trona (sodium sesquicarbonate).
Water Insoluble Material. The water-insoluble material is easily

separated from an aqueous slurry by high pressure filtration. The
resulting filter cake can then be analyzed by XRD and the crystalline
phases identified. (See King et al.) The most commonly used material in
this class is sodium zeolite A. On rare occasions we have found this water
insoluble material to be sand or a kaolin type clay.
Phosphates. Phosphates, in aqueous solutions, are easily quantified

and speciated by ion chromatography. Typically we use this information to
aid the diffractionist in determining the hydration of these compounds
since this can not be determined by ion chromatography. If the product has
been sprayed-dried,a minor amount of the dehydrated form usually is present,
contributing to the complexity of the observed spectrum. This information
is necessary for material balance calculations.
Silicates. Silicon is easily quantified by atomic spectroscopy. While

not all silicate species are crystalline, XRD will identify those that
are. Again, for material balance calculations negative information is as
important as positive.
Other Builders. Sulfates and chlorides are easily quantified by ion

chromatography techniques and their presence is confirmed by diffraction.
CONCLUSION
XRD is a technique which in conjunction with other analytical

techniques aids in reproducing the formulary of a detergent manufactured
anywhere in the world. When the diffractionist and the detergent chemist
work closely, the complete detergent formulation can be obtained in about
the same time required to perform the traditional analysis which only
provides general information and can not reproduce the formulary.
REFERENCES
Breck, Donald W. "Zeolite Molecular Sieves", John Wiley & Sons, New York,
(1974) .
King, M. M., Sabino, E. M. & Bass, J. L. "High Pressure Filtration/

Separation and Analysis by X-Ray Powder Diffraction of Zeolite A in
Household Laundry Detergents", 23rd Middle Atlantic Regional Meeting,
American Chemical Society, Cherry Hill, NJ, (1989).
Klug, Harold P. & Alexander, Leroy E. "X-Ray Differaction Procedures for

Polycrystalline and Amorphous Materials", John Wiley & Sons, New York,
(1974) .
Margia, A. "Rapid Practical Analysis for the Determination of Anhydrous and

Hydrated Tripolyphosphate by Means of X-Ray Powder Diffraction", Analyst,
108:540 (1983).
Milwidsky, B. M., "Practical Detergent Analysis", MacNair-Dorland,

New York, (1970).
Morgenthaler, W. W. Builder Trends in North American Detergent Products in

"Proceedings of the Second World Confeence on Detergents", Baldwin, A. R.,
ed., American Oil Chemists' Society, (1987).
William, J. "Determination of Sulphur, Phosphorous, Magnesium, Silicon and

Aluminum in Washing Powders by X-Ray Fluorescence", Analyst, 111:175
(1986) .
THE DETERMINAnON OF QUARTZ IN PERLITE BY X-RAY DIFFRACfION
R. D. Hamilton and N. G. Peletis
Manville Technical Center

Box 5108
Denver, CO 80217-5108
ABSTRACf
IARC's designation of crystalline silica as a "probable carcinogen" triggered the

requirement to label products containing greater than 0.1 % crystalline silica. For perlite and
other materials which may contain crystalline silica in levels close to 0.1 % an accurate
determination is critical from both legal and marketing considerations.
Existing analytical techniques for the determination of crystalline silica at levels of less
than 1.0% were found to be inadequate to meet the new requirements. An improved
technique based on x-ray diffraction has been developed specifically to analyze perlite for
crystalline silica, which occurs largely in the form of quartz, at the 0.1 % level. The
technique employs long counting times and improved sample preparation and mounting to
increase both precision and accuracy, and to lower the detection limit to less than 0.1 %.
The technique was tested on a large number of samples from a variety of sources and
proven to give excellent results for all types of expanded perlites and perlite ores. The
procedures developed are applicable to a wide variety of materials in addition to perlite.
INTRODUCTION
The publication of IARC Monograph 42 which assigned a 2A or "probable carcinogen"
classification to crystalline silica triggered an immediate need to accurately determine the
weight percent of crystalline silica in any material at the 0.1 % level. A wide variety of
procedures exist for determining total silica at levels well below 0.1 %, however, a review of
the literature, indicated that procedures for determining only the crystalline portion of the total
silica were generally limited to levels of 1% or greater. As a result of the need for analysis
and the lack of an acceptable procedure, research was undertaken to determine if satisfactory
procedures could be developed to analyze products which contain 0.1 to 1% crystalline silica.
Among the products studied was perlite and it is the results of this work which is presented
in this report.
DISCUSSION
Perlite is a hydrated volcanic glass, generally of rhyolitic composition (Table 1).
Mineralogically it is 95% plus glass with minor amourtts of micas, feldspar, and crystalline
silica.

Plenum Press, New York. 1990
Table I. Analysis of Typical Perlite Ore from No Agua, NM (weight %)
72.1 TiOZ 0.06 4.6

13.S Cao 0.89 4.4
0.8 MgO 0.50 3.8
Specific gravity 2.2 - 2.4
Crystalline silica in perlite may occur in a number of polymorphic forms the most
common of which are quartz, cristobalite, and tridymite. Experience has shown that
cristobalite and tridymite are very rare in perlite hence the research was focused entirely on
quartz. Because perlite is very high in total silica, any determination must be based on a
technique sensitive only to the crystalline portion since the results cannot be checked by an
analysis for total silica. Techniques which can discriminate between crystalline and
amorphous silica include infrared spectroscopy, x-ray diffraction, polarized light
microscopy, differential solubility, and heavy mineral separations. Combinations and
variations of all these techniques had either been tried in the past or were tried in the course of
the current research. X-ray diffraction was found to be the most satisfactory for perlite
despite a number of limitations. Diffraction analysis is the most cost effective, reliable, and
precise method available. It is the least sensitive to operator skill and variations in the nature
of the perlite. The combination of density separation, optical microscopy, and x-ray
diffraction is the most sensitive but, is slow, expensive, dependent on technique, and yields
results of lower precision.
Perlite is a difficult matrix in which to determine quartz by XRD. On one hand the
linear absorption coefficient is within 5% of that of quartz hence matrix absorption effects can
be ignored. On the other hand, the glassy material which makes up 95% + of the bulk
produces a very high background signal. The high background leads to a very poor peak to
background ratio which greatly reduces the accuracy of the measurement and raises the
detection limit. The other crystalline phases which are usually present in the perlite especially
micas and feldspar cause interferences with the quartz peak because of peak overlap. The
poor peak to background ratio can be compensated for by accumulating a large number of
counts. The peak overlap from other minerals can only be treated on a case-by-case basis by
a complete diffraction analysis of the sample.
In addition to analyzing the perlite ore it is also necessary to analyze the expanded
product. The expanded perlite has lost most of its water and has a bulk density of about 0.1
grams/cc. Fortunately the glassy foam produced by expansion is very brittle and can be
easily ground to resemble the ore in terms of particle size and bulk density.
PROCEDURE
Sample Preparation
A uniformly fine particle size is essential for accurate XRD analysis. The ideal
procedure would be to grind the sample to be analyzed to 100% <20 ]lm particle size.
Perlite ore and especially expanded perlite is difficult to grind and sieve. The ore tends to
Table 2. Operating Conditions for Siemens D-SOO
Radiation: CuK()( 40 Kv 30 rna

Detector: scintillation counter with graphite monochromator
Divergence Slit: 1°; receiving slit: O.ISo
Scan: 26.0 - 27.5 29.0So 29/step,
count 40 sec/step
Sample rotation: on, (30 rpm)
R. D. HAMilTON AND N. G. PElETIS 495
cake while grinding and the expanded material clumps because of electrostatic charge. Under
the circumstances it is best to grind the sample as fine and unifonnly as possible and not
sieve it.
A satisfactory procedure is to grind 5 to 10 grams of either ore or expanded perlite in a

tungsten carbide ring puck mill for three minutes. Optical analysis of the resulting powder
shows that 99% of the particles are less than 40 ]..l m in diameter. Based on the precision of
the results this size seems to be adequate.
Preparation of Standards
No standards for quartz in perlite or perlite-like material are generally available hence it
is necessary to prepare calibration standards. Standards for expanded perlite were prepared
by spiking quartz free expanded perlite ground as described above with -325 mesh quartz in
levels of 0.5 to 5 weight percent. The spikes are mixed by hand in an agate mortar and x-
rayed several times to verify their homogeneity. Standards for 0.1 and 0.2 weight percent
were made by diluting the 2% standard with quartz-free perlite.
Two approaches were used in generating ore standards. Because of concerns about the
effects of crystal size and degree of crystallinity,ore standards were generated from mixing
quartz.free ore with an ore of known quartz content. Samples were ground and mixed as
described above. A second set of standards was prepared by spiking a quart~-free ore in the
same way the expanded perlite samples were prepared. All three sets of standards produced
identical calibration curves. Because of the finer and more homogeneous particle size, the
standards prepared with expanded perlite were adopted for general use.
XRD Analysis
All samples were analyzed using a Siemens D500 diffractometer with a SIEMAC
interface and Siemens-supplied software. The D500 was configured as shown in Table 2.
The samples were mounted in custom-made aluminum holders. The holders are
machined from 1/8" thick aluminum which is cut into square 1-31/32" on a side with a 1"
hole cut in the center. The upper face is lapped flat and care is taken not to round the edges
of the central hole. The special holders are used because their greater dimensional stability
and flatness compared to the normal plastic holder minimizes displacement errors and
produces better peak intensity precision.
The powder is back packed in the holder against a glass plate by hand. To assure
uniform packing, a brass piston which is .004" smaller than the sample hole is used to pack
the sample. The packed sample is backed by pressing in a cardboard disk which is secured
with masking tape. Because preferred orientation is not a problem but peak intensity is, the
samples should be packed as firmly as possible. Experience shows that with uniform
grinding, firm packing greatly improves the reproducibility of peak intensities.
All samples are manually loaded into the diffractometer rather than using the sample
changer. Manual loading insures more accurate sample positioning and improves the
precision of the results.
Each sample is scanned from 26.0° to 27.5° 29 with a step of .05° and a count time of
40 seconds per step. Integrated peak intensities corrected for background for the quartz
(101) peak at 26.65° 29 are extracted from the raw data using the program provided by
Siemens.
Calibration
Standard samples prepared as described were run to establish a calibration curve

relating integrated peak intensity to weight percent quartz. The resulting curve is linear from
Table 3. Calculated and Observed Precision of Peak Intensities (d counts) for Quartz-Perlite
Standards Based on 40 sec/O.05° 29
% Quartz
1.0 2.5 3.6 5.1

0.25 9 11 19
0.10 21 18 26
a) d c = (lOOJR-l){R(R+ l)/N} 1/2 where R =peak to background ratio and N =total peak
counts.
b) multiple runs on the same mounted sample.
c) sample repacked between runs.
oto 5% quartz. With proper background correction the curve will intersect the origin. Any
of the standards which consistently falloff the nominal curve should be reform ed.
RESULTS
The procedure developed has been tested on over 100 perlite samples. To evaluate the
sensitivity,samples were checked using a combination of heavy-mineral separation and optical
microscopy. This method has a very high sensitivity but a low precision. The checks
verified that quartz was consistently detected at the 0.1 % level as long as no peak overlap
from other phases occurred. Despite the persistent presence of trace amounts of mica and
feldspars in most perlite ores, peak overlap was not found to be a significant problem.
Originally two calibration curves were used, one for ore and one for expanded perlite.
Theoretically the two curves should be identical if the powder can be packed to the same
density in both cases. Based on observed intensities the grinding and packing techniques
used did produce samples with identical densities.
40s
8s
0.5s
2 .00 .75 27.00 2 .25 2 .50

3.424 3.330 3.300 3.270 3.241
-- d SPACING
Figure 1. Diffraction profiles of 0.25% quartz in perlite illustrating the increase in peak
definition with increased counting time per .05 0 29 step.
R. D. HAMILTON AND N. G. PELETIS 497
Precision
The precision of the analyses can be expected to decrease as the peak--plus-background

to background ratio approaches 1.0 with decreasing quartz content. The measured precision
of the analyses at the 0.1, 0.25, and 1.0% quartz level are presented in Table 3. The
measured values are based on both multiple runs on a sample and multiple runs of the same
sample with repacking after each run. A comparison of the measured precision with the
expected precision based on counting statistics shows that the sample preparation and
anal ytical technique are satisfactory at the 0.1 % quartz level.
The 40 sec/step counting time was selected as a compromise between precision and
analytical time. The desired detection limit and precision was obtained. Taking into account
the inhomogeneity of geologic materials it is difficult to justify any attempts to increase the
precision of the determination. With a 40 sec count time the statistical variation in the
background is small enough to permit the peak fmder to reliably locate the quartz peak at the
0.1 % level. Figure I illustrates the improvement in peak discrimination resulting from longer
counting times.
Accuracy
At this point the accuracy can only be inferred from the precision, the linearity of the
calibration curves and checks with synthetically prepared material and verification by a
combination of heavy mineral separation techniques. Only when well characterized material
is available for standards will a better assessment of the accuracy be possible.
CONCLUSIONS AND RECOMMENDAnONS
The procedure developed is capable of providing a satisfactory determination of quartz

in perlite if proper techniques are employed. The critical factors are:
grinding to 100% less than <50 )..lm

uniform packing in precision sample holders
long counting times to provide good counting statistics with the
high background present.
preparation of accurate standards.
The procedure works on both ore and expanded product and does not appear to be
sensitive to either the origin or nature of the ore or the variation in the expanding process.
Although the method was developed for a Siemens D500 diffraction system it should
be easily transferable to any system as long as the critical points outlined are followed. When
attempting to use the techniques with an older Philips system two problems were
encountered. First the holders with a rectangular sample cavity were impossible to pack
uniformly and second, without sample rotation the precision dropped considerably.
Whenever this method is employed care should be taken to document the precision and
accuracy for the particular system in use.
Longer counting times should improve the precision but at the expense of productivity.
Each sample now takes about 20 minutes to run. To reduce the statistical counting error by
50%, the run time would have to be increased to about two hours. This appears to be a
situation where a position sensitive detector would greatly improve the precision and the
detection limit.
THE CONCEPT OF PATHLENGTH DISTRIBUTIONS
APPLIED TO FUNDAMENTAL PARAMETER APPROACH
H. Ebel, C. Pohn, R. Svagera, M. Mantler,

M. Wernle and M.F. Ebel
Institut fur Angewandte und Technische Physik

Technische Universitat Wi en
A 1040 Vienna (Austria)
INTRODUCTION
The fundamental parameter approach i , 2 for quantitative

x-ray fluorescence analysis is an application of t~e
equations derived by Sherman 3 , and by Shiraiwa and Fujino .
Both derivations assume plane and smooth specimen surfaces
and defined entrance and take-off angles of x-rays. Our
investigation is dedicated to a more general description of
measured characteristic signals. Consequently we have to deal
with equations that allow us to account for the parameters
mentioned below.
6
A concept proposed by Gardner and Hawthorne uses the
principle of Monte Carlo calculation and enables a
recognition of an angular divergence of incident and detec~
ed x-rays. Our concept is based on path length distributions.
The distribution functions are found either by r.1onte Carlo
calculation or, as will be shown,by scanning of-the digitized
roughness profiles. Both versions describe measured
characteristic signals from an unknown specimen in a much
more general way, when compared to the equations given by
Sherman, and Shiraiwa and Fujino. Such an improvement
requires a higher sophistication of algorithms, an additional
determination of roughness profiles and a significant
increase in the time that is needed for computation.
Especially the latter argument could be used to reject such
developments.
For this purpose we change from standard facilities

(MS-DOS 286/287 or 386/387) to transputer systems. A
comparison gave in its present state a ratio of times of 60 :
30 1. The software for quantitative x-ray fluorescence
analysis in its general modification is written in OCCAM.

500 VIII. X-RAY SPECTROMETRY DATA ANALYSIS
CONSIDERATIONS ON THE GEOMETRY

Fig.1a depicts the geometry, as used in the usual
equations for primary excitation of characteristic
x-radiation. Due to defined angles a and 8 and a plane sur-
face, there exists just one value of y=x· cosa/cos8 of the
fluorescent radiation for a given path x of the incident
x-radiation in the specimen. Expressed as distributions one
obtains distributions of y according to B-functions, for
defined values of x.
a)
b)
c) flo.
d)
e)
Figure 1: Dependence of escape length y of fluorescent x-rays

for given penetration length x of the incident
x-radiation. a) plane surface b) rough surface
c) a-divergence d) 8-divergence e) path of
incident radiation covers values from x to x+~x.
H. EBEL ET AL. 501
In Figs .1a to ld the penetration length x is kept at a

constant value. As the smooth surface of Fig.la is replaced
by a rough one, one observes according to Fig .1b no
longer a defined escape path y, but a pathlength distribution
It is a probability density distribution and describes the
probability to obtain an escape length in the interval y to
yHy. The distribution depends on a number of parameters.
They are x (or the interval x to X+AX) , the roughness
profile, the values of the angles a and (3 and finally the
existence of an angular distribution of a and (3 ( ~(y) = f(x,
Ax, profile, a, (3, Aa, A(3) ):
p(y, y+Ay) = ~(Y)'Ay
Figs.lc to le illustrate these statements for the case

of a plane and smooth surface of the specimen. In practice
there exists always a superposition of the mentioned
influences on ~(y), and it is essential to realize an
evaluation procedure for the determination of ~(y) from
measured roughness profiles.
For this purpose attention should be drawn to Fig.lb. As

the pair of rays is shifted for a distance A parallel to its
original position and again a path x is chosen, then a new
value of y will be found. After having collected a
statistically significant number of y-values it becomes
possible to represent ~(y) by a histogram. Its statistical
significance depends on the number of "events" and for this
reason in the course of our evaluations we collected about
10000 y-values per histogram. This is performed on roughness
profiles that have been measured with a surface ahalyzer.The
analog output of this instrument has been connected via an
ADC to the computer. For a scan width of 15 mm and 10000
positions the value of the shift A is 1.5pm.These histograms
describe the frequency of events (y-values) in the interval y
to y+Ay. In order to transform it to the probability density
distribution it has just to be normalized to an area of 1.
A next step is, for instance, a variation of a. The
procedure is repeated with the new value of a+Aa. When adding
the new histogram to the original, a frequency distribution
of a total of 20000 events results, which describes now the
frequency of y-values for an actual roughness profile, the
given values of x and (3 and an angular range of incident
x-rays from a to a+Aa. As the histogram finally should
reflect the frequency of events for angular ranges of a and (3
from a-min to a-max and (3-min to (3-max, one has to define a
series of a- and (3-values and to add all histograms to the
resultant histogram. An inhomogeneous intensity distribution
of the incident beam and similarly a local variation of the
detector efficiency must be recognized also. Both influences
can be taken into account by a variation in the width of Aa
and A(3 over the angular ranges from a-min to a-max and (3-min
to (3-max respectively. In the present evaluations we added to
all of the histograms of ~ (y) a least squares fit of a
Lorentzian distribution for a description of ~(y) by its
"halfwidth".
THE IDEAL SURFACE
A first introduction to the following considerations on

a practical determination of escape-length distributions is
based on the geometries depicted in Figs .1c and 1d. The
result of a series of evaluations is given in Fig. 2. The
abscissa of the distribution functions is y in millimeters
and the ordinate ~(y). Parameters are penetration lengths x
in millimeters. Common to all distributions is the angular
range of incidence from 15 to 25 degrees and of take-off from
35 to 45 degrees. A homogeneous distribution of incident
x-rays and sensitivity of detection in take-off direction
within these angular ranges has been assumed. When increasing
the angular ranges, the distributions become broader,and vice
versa. An essential feature of the distributions is the
linear dependence of halfwidths and position of maxima versus
penetration length x. It allows one to predict from a single
evaluation the result of all the other evaluations.
8 8.
I
15 . 811· to 2S . 811·
35. 811· to
.a. 18811 .a.48118
..... I ....~: 8 .186

.a.1M8
.a . 1I38
.a . 828
.a . 818
.a.88II~~----~--------r-------'-------~--------'---
.a.8811 .a. 1811 .a .2811 .a . 3811 .a .4811 .a . 5811
,......u..UOft 1entrU! l_)
Figure 2: Escape-length distributions t(y) of ideal surfaces

for specified angular ranges and penetration
depths (~x=O). The halfwidth of the Lorentzian fit
has been obtained from distributions of twelve
different penetration lengths.
H. EBEL ET AL. 503
THE ROUGH SURFACE

An aluminium specimen has been used for the roughness
profile of Fig. 3. Bars indicate the scales in vertical and
horizontal directions. A maximum distance from top to bottom
of about 0.03 rnrn characterizes the profile together with the
length of the scan of 17 rnrn. The horizontal line is the
median. It is calculated from the total number of input data.
As mentioned, we evaluate the profiles in steps of ~=1.5~m,
with a number of input data of 10 per micrometer.
Consequently the median of Fig.3 represents the linear least
squares fit of 17000 data points. This first calculation is
performed in order to put the scan into a horizontal position
on the screen of the monitor and additionally it is
automatically the reference of the depth profile. Our
evaluation of the frequency distribution of depth values with
respect to the median has been fitted by a Lorentzian
distribution with halfwidth of 11~m. There are obviously two
characteristics of the profile. One of them is the frequency
of depth values in vertical direction which is quantified by
the assumption of a distribution function, its halfwidth and
the maximum depth of 20~m. The other one is the frequency
spectrum in horizontal direction. A rough estimation
delivers about 10 "oscillations" per millimeter of the scan
and from these two values follows a maximum slope of the
profile of approximately 1 degree. A detailed evaluation of
experimental results gave a maximum slope of 17 degrees.
Such an estimation helps to set the limits of the angles
a and B for multiple intersection of the profile. This means
an angular range of up to nearly 73 degrees gives no rise to
an increase of the probability of multiple intersections.
8 . 838 _
haUwldth :
8.811861 _
.8.838
Figure 3: Roughness profile of an aluminium specimen and

depth distribution.
8 . 8763
ion (ength [1'",,] I
8.1817 8.
incidence angle: 28.88-

escape angle: 48.88-
.e.8388 .e.8688 .e .8'388 +8.1Z88 .e. 1588

length of escape [ftN]
.e.816
.e.812
+8.888
.e.884
+8.888 ~------,-------~------.------,------~-------r-------
.e.888 +8.388 .e.688 .e.988 +1.288 +1.588 +1.888
penetration length [NN]
Figure 4: Escape-length distributions t(y) of a rough surface

and halfwidth of the profiles versus penetration
length x.
Further evaluations of the measured profile are done in

order to obtain the escape length distributions. In Fig. 2
the evaluation of an "ideal" surface has been performed with
a variety of x-values. It is done for our rough surface in
just the same way. The result is given in Fig.4. It should be
mentioned that the distributions are representative for
constant incidence and take-off and defined values of
penetration length. Consequently the distributions reflect
primarily the influence of the roughness profile on escape
lengths.
A comparison of the responses of halfwidth versus

penetration length shows a completely different behaviour. An
increase is followed by a constant portion. The increase is
observed within a range of penetration lengths of up to lOO~m
and is nearly linear. A halfwidth of the horizontal response
of about 20~m can be explained when considering the halfwidth
of the roughness profile. In a depth of e.g. lmm from the
H. EBEL ET AL. 505
median, the profile appears broadened by l/cosa, when obser-

ved under an angle of a and therefore a width of 20~m is the
result of a convolution of two broadened responses of
halfwidths 11/cos20 and 11/cos40. The sum is 26~m. In case of
Lorentzian distributions halfwidths have to be added, whereas
for Gaussian distributions the square root of the sum of
squared halfwidths has to be used. It is 18.5~m and closer to
the value of Fig.4. But in fact there is no reasonable
explanation to describe a roughness profile either by a
Gaussian or by a Lorentzian distribution and the assumption
of a Lorentzian distribution has been made, as mentioned
earlier, only to represent the distribution by its halfwidth.
Going back to Fig.4 and the range of penetration lengths
x of up to 100~m, a slope of the linear response of
approximately 0.020/0.100 = 0.2 is obtained. In Fig.2 the
slope of the linear response is O.l.Under the assumption that
the final distribution is obtained from a number of
convolutions the two ranges of Fig. 4 have to be discussed
separately. Range 1 extends from pathlength 0 to 100~m and
range 2 covers pathlengths greater than 100~m.
i. Range 1
A convolution of the distributions due to angular
divergence and due to surface roughness is for our specific
example dominated by the influence of surface roughness. This
follows from the comparison of slopes in Figs. 2 and 4. A
smooth surface delivers nearly no contribution to the
resultant halfwidth, whereas a rough surface dominates the
response of halfwidth versus penetration length.
ii.Range 2
With increasing depth the influence of angular divergence
on the resultant halfwidth becomes more and more
pronounced. These considerations on "small" or "great" depths
must be combined with an estimation of attenuation of x-rays
along a path of 20~m or 250~m respectiyely. The mass
absorption co~fficient may be assumed as 50cm /g and the den-
sity as 5g/cm . With 20~m, an attenuation of 0.61 and with
250~m, of 0.002 is found. That means that the contribution to
the resultant signal of fluorescent x-radiation from incident
primary radiation is, in case of great penetration lengths,
nearly negligible.
These experiences indicate that range 1 of the distribu-
tion functions is most important and has to be evaluated as
carefully as possible. It explains the great care we take in
the evaluation procedure especially for small values of the
penetration length.
PENETRATION LENGTH DISTRIBUTION

Starting with Fig.l, the formation of the resultant
escape-length distribution from the distributions due to
angular divergence and roughness has been discussed. For an
application in quantitative x-ray fluorescence analysis an
additional contribution has to be recognized. It follows from
the numerical integration. When the concept of pathlength

distributions was published by us , a description of the
problem by integrals was used. For numerical integration
it changes to summations as shown in the following equation.
nj = a. b. c j . Pc . -T. .Wj . PI . 41t

S -1 Q
. fl'
.l/o
I
n (E). 't"E,1 . [[' exp (- 't"E,c' Pc' x) .

Eedge,1 0
.((:~:'X$.(Y). exp(- 't"j,c' Pc.y) dY)dX] dE! =

s -1 .001, Pj._.
a.b. c j. pc._I- Q
f j.
SI 41t
·l ~ n(EJ 't"Ek,I'[ ~ exp(- 't"Ek,C 'Pc' xJ.

(~$I(yJ. exp(-'t"j,c.Pc.yJ.t.ym) .t. X1t.Ek\
The meaning of symbols is standard and therefore not
given in detail. The meaning of subscripts has to be
explained. From all of the subscripts there are three
specific for numerical integration. These are k, I and m: k
def ines the actual energy range of primary x- rays, I the
actual penetration length and its interval and similarly, m,
the escape length and its interval. In other words x with
subscript I defines the averaged penetration according to the
l-th loop of x-summation and Ax with subscript I the width of
the range of x-values. Mathematically speaking, a further
convolution of the profiles has to be performed. The geometry
is shown in Fig.ld and since the x-values are equidistributed
within the interval of penetration length, a rectangular
distribution is expected. The final distribution function is
a convolution of distributions according to Figs.2 and 4 with
a rectangle of width Ax of the l-th interval divided by
cos (a+!1) .
Fig.5 depicts the systematic development of the final

function t(y). Beginning from the pure roughness profile in
the first distribution,the angular divergence is added in the
second one and finally a variation of the penetration length
is added and the halfwidth increases from 6.8~m to 7.3~m to
8.3~m.
In practice at least ten distributions have to be

evaluated from a measured roughness profile, and in
comparison to the evaluation by means of the Sherman- or
Shiraiwa and Fujino equation, two additional integration
loops are needed.
Another important application of the concept of

path length distributions is given in quantitative x-ray
photoelectron spectroscopy. Since the escape length of
H. EBEL ET AL. 507
incidence angle: 28.88-

escape angle : 48 .88-
penet..aUon length: 8.8ze8 _
_ an length of escape: 8.8249 _
ha If .. idth : 8.8868 _
Incidence angle: 15.88- to ZS.88-

escape angle : 35.88- to 45.88-
penet..ation length: 8.8ze8 _
__n length of escape: 8.8258 _
haU .. idth : 8.8873 _
incidence angle: 15.88- to ZS.88-

escape angle : 35.88- to 45.88-
penetraUon length: 8.8188 _ to
8.8228 _
__ n length of escape: 8.8258 -
haU .. idth : 8.8883 _
Figure 5: Development of the escape-length distribution ~(y)

for the application in fundamental-parameter
approach by a systematic addition of variables.
electrons is much smaller than the mean free path of the

incident x-radiation we recognize only the influence of
roughness, take-off angle 8 and divergence of 8 on the
resultant ~(y). The influence of a neglection of ~(y) becomes
well pronounced in experiments performed under a series of
different take-off angles .
TRANSPUTER
The transputer family is a new generation of RISe

microprocessors. Its architecture has been optimized for high-
speed processing as well as parallel working systems. The
T800 is a member of the transputer family. This is a 32 bit
microprocessor with a 64 bit floating-point unit on-chip,
which provides high-performance arithmetic and floating-point
operations (10 Mips, 1.5 Mflops at a processor speed of 20
MHz). It has 4 kbytes on-chip RAM for high-speed processing,
a configurable memory interface and four serial standard
communication links (20 Mbits per second). The links allow
formation of networks with concurrent working transputers by
direct pOint-to-point connections with no external logic.
With one T800, our problem is running in a time of 12

minutes. As it is possible to split our algorithm into
concurrent working parts we use a network of four T800 and
thus obtain a processing time of 3 minutes. The comparison in
the INTRODUCTION is related to the latter processing time.
REFERENCES
1. J.W. Criss and L.S. Birks, Anal.Chem. 40, 1080 (1968)
2. J.V. Gilfrich and L.S. Birks, Anal.Chem. 40, 1077 (1968)
3. J. Sherman, Spectrochimica Acta 7, 283 (1955)
4. J. Sherman, Spectrochimica Acta 11, 466 (1959)
5. T. Shiraiwa and N. Fujino, Jap.J.Appl.Phys. 5, 886 (1966)
6. R.G. Gardner and A.R.Hawthorne, X-Ray Spectrometry 4, 138
(1975)
7. H. Ebel and Ch. Pohn, X-Ray Spectrometry 18, 101 (1989)
8. M.F. Ebel, G. Moser, H. Ebel, A. Jablonski and H.
Oppolzer, J.Electron Spectrosc.Relat.Phenomena 42, 61
(1987)
ACKNOWLEDGEMENT
The research program has been supported by "Fonds zur
Forderung der wissenschaftlichen Forschung in Osterreich".
Project P 7012-PHY
A VERSATILE FUNDAMENTAL ALPHAS PROGRAM FOR USE WITH EITHER TUBE OR
SECONDARY TARGET EXCITATION
L. Feng* and P. A. Pella

National Institute of Standards and Technology
Gaithersburg, MD 20899
B. J. Cross
Kevex Instruments
San Carlos, CA 94070-1308
INTRODUCTION
During this decade, several influence-coefficient algorithms have

been published which utilize fundamental parameter equations to correct
interelement effects in bulk samples. The Comprehensive Algorithm of
Lachance (COLA) is one such algorithm and is used in the program
NBSGSC(l). Another COLA-based computer program called FLY-FPM has been
developed in China by one of the authors (L. Feng). Using FLY-FPM as a
starting point, we developed a new COLA-based program as part of a
Cooperative Research Agreement with Kevex Instruments**. This program
was designed for use with x-ray spectrom~ters that employ both tube and
secondary targets for excitation. For direct tub.e excitation, the NIST
tube spectral distribution algorithm is used in this program (2). For
secondary target excitation, the radiation is usually treated as being
monochromatic, and fundamental parameter expressions are formulated with
this in mind. This assumption is not rigorously true, however,
especially when low atomic number secondary targets are used. For this
reason, we have extended the NIST tube spectral-distribution algorithm in
this new program to include scattering phenomena from the secondary
target. Some of the main features of this program will be discussed in
this paper with emphasis on the theoretical treatment of both coherent
and incoherent primary source x-ray scattering from secondary targets.
*Research Associate, Kevex Instruments; Permanent address: Institute of

Geochemistry, Academia Sinica, Guiyang, P.R. China.
**Certain commercial equipment, instruments, or materials are identified
in this report to specify adequately the experimental procedure. Such
identification does not imply recommendation or endorsement by the
National Institute of Standards and Technology, nor does it imply that
the materials or equipment identified are necessarily the best
available for the purpose.

SPECTRAL DISTRIBUTION FROM SECONDARY TARGETS
X-rays emanating from a secondary target normally include three

major components: (1) the characteristic lines of the secondary target,
(2) scattered tube continuum, and (3) the scattered characteristic lines
of the x-ray tube anode material. In energy-dispersive XRF analysis
employing secondary targets for excitation of the sample, the target
selected depends on the energies of the absorption edges of the analyte
elements. For efficient analyte excitation, the selected target should
have characteristic lines whose energies fall just on the high energy
side of the analyte absorption edges. Therefore, the first component is
normally the most important contribution to analyte excitation, and the
intensities of the target characteristic lines can be calculated from
conventional fundamental parameter equations. However, there are cases
where the second and third components can contribute in a significant
way. For example, when a rhodium target tube is used with a titanium
secondary target for light element analysis, both the energy and
intensity of the scattered rhodium L lines can, in principle, be
sufficient to produce significant analyte intensity. A more rigorous
description of the spectral distribution from secondary targets will
permit analysis over a broader atomic number range. For instance, use of
an aluminum target-rhodium tube combination should allow measurement of
all major components of geological samples. The scatter contributions in
the extended algorithm are obtained as follows.
Scattered Tube Continuum
Assume an incident primary x-ray beam of intensity Ip(A), arrlvlng

at a thin layer with thickness dm in a secondary target, at angle ~, at a
distance m from the surface. If we also assume a scattered beam Is(A)
exiting the target surface at angle w (see Figure 1), a differential
expression for the intensity of the scattered continuum can be written as
follows:
dI.(A) = [Ip(A)exp(-p(A)m/sin~)ucoh + Ip(A-~A)exp
(-p(A-~A)m/sin~)uincohlexp(-p(A)m/sinw)dm (1)
where A denotes the continuum wavelength, ~A is the change in wavelength

due to Compton scattering, ucoh and uincoh represent the differential
coherent and incoherent mass scattering cross sections, respectively, and
p denotes the mass absorption coefficient. Assuming A - ~A = A, and
substituting in equation 1, the following expression is obtained after
integration:
_i dm
m1
Fig. 1.
~ I s( A)
Geometry for Calculation of Scattering From Secondary Targets
L. FENG ET AL. 511
(2)
~(A)(l/sin~ + l/sinw)
Scattered Tube Characteristic Lines
In the same manner, we can obtain expressions for both coherently and
incoherently scattered tube characteristic line intensities as follows:
(3)
~(ACh)(l/sin~ + l/sinw)
where ACh is the wavelength of the characteristic line, and
(4)
According to theory (3-6), the relevant differential mass scattering

cross sections can be calculated from the expressions:
(5)
and
Na [ a2 (l-COSIJ)2]
uincoh = A(Z) r!/2(l+a(1-coslJ)]-2 1+cos 2 1J + S(X,Z) (6)
1+a(l-cos/J )
where
/J = Scattering Angle
X = Momentum TransferParameter = Sin(IJ/2)/A
Z = AtomicNumber of Secondary Target
A(Z) = Atomic Weight as a function of Z
re = Classical Electron Radius = e 2 /mc 2 = 2.81794 x 10- 13 cm
a = hv/mo c 2 = E(keV)/511.006
e =
= Electron Charge; m, mo Electron Mass, Electron Rest Mass
c = Velocity of Light
Na = Avogadro's Number
F(X,Z) = Atomic Form Factor (Coherent Scattering Factor)
S(X,Z) = Incoherent Scattering Function
The terms F(X,Z), and S(X,Z) are tabulated by Hubbell et al. (7). We
applied a fourth degree log-log fit to the tabulated data to provide a
convenient way to calculate these quantities. The fitting equations are
as follows:
(7)
Table 1. Analysis of Standard Brass Samples*
A B C
Sample Cu Zn Cu R.E.% Zn R.E.% Cu R.E.% Zn R.E.%
CDA360 61.68 34.85 62.18 +0.80 34.00 -2.44 61. 92 +0.40 34.47 -1.10
CDA464 60.22 39.00 60.52 +0.50 38.01 -2.50 60.22 0 38.67 -0.85
CDA482 58.55 40.10 59.01 +0.80 38.97 -2.80 58.66 +0.19 39.62 -1.20
CDA485 59.67 38.00 60.24 +0.96 37.12 -2.30 59.95 +0.47 37.71 -0.76
CDA675 58.46 39.70 58.98 +0.90 38.62 -2.70 58.68 +0.38 39.30 -1.01
Mean +0.79 -2.50 +0.29 -0.98
*Data taken using Kevex microfluorescence spectrometer with Mo tube direct excitation
(50 kV, 1 rnA, 100 p aperture); standard used: CDA 836 (Cu 84.13%, Zn 5.78%).
A - Certified Value
B - ZnKp is not considered for enhancement of CoRa.
C - ZnKP is considered for enhancement of CoRa.
R.E. - Relative Error
and
S(x,Z) =Exp(a' + b' ·logX + c' ·log2 X + d' ·log3 X + e' ·log4 X)Z (8)
where a thru e, and a' thru e' are fitting constants for a certain atomic
number region. Over a range of X from 0.005 to 5, and an atomic number
range from 13 to 83, the average agreement between the tabulated and
calculated values is within ±5% relative. We are currently testing this
extended algorithm in the computer program for bulk analysis of selected
samples and will report these results in a future publication.
OTHER FEATURES OF THE PROGRAM
Secondary Fluorescence Calculation
In other COLA-based programs, secondary fluorescence from only one

selected line from the enhancing element j on the analyte line is
considered. Although this is usually adequate when type standards are
used, larger errors may occur when only non-type or pure element
standards are available. We now have included in the program the
contribution of as many as ten major lines from each enhancing element.
Improvements in analytical results have been observed for a series of
brass standard samples in which only the KP line of zinc, for example,
enhances the copper Ka analyte line. The results, which are summarized
in Table 1, show a 2-fold improvement in accuracy.
Treatment of Sample Systems
The various sample systems such as elements, oxides, or fused disks

are treated differently in this program compared to other COLA-based
programs. To deal with diversified sample systems, this program first
reduces all sample systems to elemental systems, if not already in this
form. After the results are calculated, the program then converts the
elemental concentrations to those corresponding to any chemical form as
defined by the user. This approach requires that the oxygen content be
quantified by difference or calculated by stoichiometry for both oxide
and fused disk systems.
L. FENG ET AL. 513
Ouantitation by Difference
Usually, in COLA-based programs, the concentrations of non-analyzed

components must be known and accounted for. In some applications this is
not desirable. For example, in the steel industry, iron is the major
component of most steels and is usually determined by difference. To
allow anyone constituent, including an analyte, to be quantified by
difference, the following condition must be satisfied:
(9)
where Cd is the concentration of the element d to be quantified by

difference. The general COLA equation can, therefore, be rewritten in
the form
Ci = Ri [l + ~ oijCj + ~ ~ oljkCjCk + AiCdl (10)

j~i j~i k>j
j~d j~d ~i
~d
where
aid + ~ oljdCj + ~ oidkCk (11)

j~i k>j
j~d ~i
~d
Substitution of 1- ~ C for Cd in equation 10 gives the following:

i~d i
Ci = Rf (1 + ~ ofjCj + ~ ~ ofjkCjCk ) (12)

j~i j~i k>j
j~d j~d ~i
~d
where
oi j - aid
(13)
oijk - oldk - oljd

(14)
1 + Ai
and
(15)
Rf
It can be seen from equations 12-15 that the terms associated with the
eliminated constituent are incorporated in ofj' ofjk' and Rf·
CONCLUDING REMARKS
Several other modifications have also been made in the program to

allow more flexibility. We can now employ up to 'five different sets of
excitation conditions (e.g., x-ray tube/secondary target/filters/
geometry). In addition, the user can decide whether to exclude some of
the COLA coefficients (i.e., Q2' Q3' Qijk) in a particular analysis based
on sample class, and can select from a prechosen set of standards which
standard samples are to be used for a particular analyte in a sample.
The speed of computation of COLA alphas has also been significantly
increased (i.e., by about a factor of five) by means of more efficient
computer code design. A recent update of the NIST tube spectral
distribution includes tube M lines and the capability of calculating
other minor tube characteristic lines that could be important for light
element analysis. These details will be published elsewhere.
REFERENCES
1. G. Y. Tao, P. A. Pella, and R. M. Rousseau, NBSGSC - A FORTRAN

Program for Quantitative X-Ray Fluorescence Analysis, NBS
Technical Note 1213 (1985).
2. P. A. Pella, L. Feng, and J. A. Small, An Analytical Algorithm for
Calculation of Spectral Distributions of X-Ray Tubes for
Quantitative X-Ray Fluorescence Analysis, X-Ray Spectrometry
14: 125 (1985).
3. A. H. Compton and S. K. Allison, X-Rays in Theory and Experiment,
2nd ed., Van Nostrand, Princeton, N.J. (1935).
4. D. T. Cromer and J. T. Waber, Scattering Factors Computed from
Relativistic Dirac-Slater Wave Functions, Acta Cryst. 18:104
(1965) .
5. D. T. Cromer and J. B. Mann, Compton Scattering Factors for
Spherically Symmetric Free Atoms, J. Chern. Phys. 47:1892 (1967).
6. D. T. Cromer, Compton Scatter Factors for Aspherical Free Atoms,
J. Chem. Phys. 50:4857 (1969).
7. J. H. Hubbell, W. J. Veigele, E. A. Briggs, R. T. Brown, and D. T.
Cromer, Atomic Form Factors, Incoherent Scattering Functions and
Photon Scattering Cross Sections, J. Phys. Ref. Data 4:471 (1975).
ABSORPTION CORRECTIONS VIA BACKSCATTERED RADIATION IN POLYCHROMATIC
EXCITATION ENERGY-DISPERSIVE X-RAY FLUORESCENCE SPECTROMETRY
F. Araajo-, F. He, P. Van Espen and R. Van Grieken
Department of Chemistry, University of Antwerp

(UIA), B-2610 Antwerp - Wilrijk, Belgium
INTRODUCTION
The incoherently and coherently scattered X-ray intensities with the

corresponding scatter factors have been used previously'·2 to define in a
sample matrix the light elements (Z<12) constituents which can not be as-
sessed via their fluorescent radiation in conventional XRF. Recently, a
more complete sample definition has been achieved based on the backscat-
tered X-rays, by using two excitation modes3.~. However, all quantitative
EDXRF methods, based on the scattered radiation from the sample relied
hitherto uniquely on the use of monochromatic excitation radiation.
When direct tube radiation is used as the excitation source, quan-

titative analysis becomes much more complicated due to the polychromatic
nature of the incident beam. First of all, the application of the fun-
damental parameters method requires the estimation of the spectral dis-
tribution. Also, the absorption corrections necessary to accomplish a
quantitative analysis of intermediate or thick samples require the
knowledge of the spectral distribution of the X-ray beam impinging on the
sample. Finally, although the use of a filter with the same composition
as the tube anode highly absorbs the Bremsstrahlung continuum, there is
still a significant component of the continuum that is not absorbed by
the f i Iter mater ia I: as a consequence, it becomes much more d i ff icu I t to
obtain the net count rates of the scattered K-lines of the anode, as they
are superimposed on a large continuum.
The new method described in this paper can be utilized to analyse

samples of variable and unknown thickness and composition, avoiding a
complicated sample preparation and the use of large sets of similar stan-
dards. It proved that the use of backscattered intensities to charac-
terize a sample is feasible without being restricted to a monochromatic
excitation mode. The overall procedure has been tested by the analysis of
geological standard reference materials.
Present address - Department of Chemistry (LNETI)

Estrada Nacional nQ 10, 2685 Sacavem, Portugal.

QUANTITATIVE ANALYSIS - PRINCIPLES AND THEORY
An accurate definition of spectral intensity distributions from

X-ray tubes is required for the sensitivity calibration and in the
development of matrix corrections procedure discussed below. The model
chosen to obtain the spectral distribution was the algorithm developed by
Pella et al . ' 5 . based on a modification of the Kramers' law that can be
used for several targets and over a wide range of accelerating voltages.
The proposed algorithm to obtain quantitative results for a light

elements composition is based on the assumption that a sample is
constituted of a light matrix and a heavy fraction 6 . 7 .
The method uses a fundamental- parameter sensitivity calibration

based on a calculated spectral distribution of the X-ray tubes. This is
combined with a semi-empirical approach to determine the mass per unit
area of the sample being analysed. The procedure utilizes the experimen-
tal relation between intensity of the scattered radiation per unit mass
and the atomic number of the elements composing the sample. to calculate
the effective mass per unit area of the sample (pO)9.
In a first approach. the program calculates the total mass per unit
area riC i (mg'cm- 2 ) of the high-Z elements from the area of their charac-
teristic peaks in the spectrum. by applying the well known equation 1.
and considering that the absorption of the sample matrix is negligible
(t E ,=1) .
where: R, is the measured counting rate of the characteristic X-rays of

element i; loG is the product of the incident beam intensity and geometry
factor; t Ei is the absorption correction factor; Ci is the concentration
of element i; K, is a factor including different physical constants and
E(Ei) is the detection efficiency for the radiation with energy Ei from
element i.
Because within certain limits. the coherently and incoherently scat-

tered intensities are directly proportional to the mass of the sample.
the scattered intensities due to the contribution of the different high-Z
elements can easily be calculated. according to the following equations:
(2 )
Ri n c (3)
where: Reoh and Rine are the measured count rates of the coherently and
incoherently scattered radiation. teoh and tine are the absorption cor-
rection factors. (pO) is the sample mass per unit area (mg·cm- 2 ) and Seoh
and Sine the coherent and incoherent scattering factors (counts·s-'.
mA-'.mg-'.cm 2 ) . These are calculated as the weighted sum of the contribu-
tions for all the elements constituents of the sample:
a L.t Wt Zi
O El.1
Sine (5)
where Wi is the weight fraction of element i and ao . boo a, and b, are

obtained by least-square fitting of the scatter factors. determined ex-
perimentally. via equations (2) and (3). for samples of known thickness
and composition 9 .
F. ARAUJO ET AL. 517
The absorption correction factors are evaluated taking into account

a calculated incident energy radiation (polychromatic) dependent on the
excitation condition and filter used ' °.
The scatter contribution due to the low-Z elements is then obtained

by difference and their average atomic number and mass per unit area
determined (equations 6 and 7).
If the atomic number of the elements constituents of the sample are

within a narrow range (e.g. low-Z elements). the mean atomic number of
the sample can be calculated:
< Z >
bo
= [---- ------Rcoh 1 1/(a..1-b1)
(6)
ao Rinc:
Combining equations (6). (5) and (3). the sample mass per uni t area
is given by:
Rinc
pD (7)
IoGt i n c bo <Z>b1
The calculation procedure is iterative. and in each step. analyte

concentrations are calculated from fluorescence intensities and the mass
per unit area of the low-Z elements estimated via their scattered X-rays.
The sum is normalized to 100%. Absorption corrections are calculated for
the characteristic lines and scatter peaks. using the total sample mass
determined in the previous step. Mass absorption coefficients for the
light matrix are linearly interpolated assuming that it is composed of
the two elements adjacent to the average atomic number <Z> and taking
into account their weighted concentrations. The definitive effective
sample mass is obtained when between the last two iterations the relative
difference of the total sample mass is smaller than an initially defined
value.
The determination of the elements with 12<Z<15 is made subsequently

using the second excitation condition (with higher sensitivities for this
energy range). The mass of these elements is calculated via their
fluorescence intensities using calculated sensitivities for the applied
excitation condition. In this second part. a similar iterative procedure
is used. However. the elements with 12<Z<15 are now considered like
high-Z and the total scattered intensities are recalculated taking into
account their approximate concentrations and the concentrations of the
elements with Z>17 previously determined. The procedure is over when the
effective sample mass is convergent and the relative difference of the
calculated thickness is smaller than a previously established level.
Mass absorption coefficients are calculated using the values com-

piled by McMaster et al. ". A percentage for the total not-measured light
elements (Z>12) is evaluated by difference to 100%.
EXPERIMENTAL
The overall method was checked by analysing five targets of

different geological standard reference materials (Granodiorite GSJ-JG-1
and Granite CRPG-GA). available from the Geological Survey of Japan and
Centre de Recherches Petrographiques et Geochimiques (France).
Table 1 - Sample mass (mg cm- 2 ) of sample supports determined

o
by weighing and derived from the scattered X-rays
pDCweighing) pD(scatter)
Mylar O.lfBlf ± 0.009 0.lf75 ± 0.005

Mylar (2 foils) 0.96B ± 0.013 0.93lf
Nuc\epore 0.B67 ± 0.031 O.BBO ± 0.013
Nuclepore (2 foils) 1 .73lf ± O.Olflf 1.727
They were prepared for analysis as thin slurries of variable unknown

thickness, deposited on Mylar foils supported by a Teflon ring. Different
volumes of the suspended ground sediments were pipetted into the sample
holder and dried at BOoC, to obtain a variable sample thickness.
Analyses of the geological standards were carried out utilizing fil-

tered continuum radiation from the Rh X-ray tube of the Tracor Spec trace
5000 EDXRF (Tracor X-ray, Mountain View, CA.). To measure the high-energy
X-ray range (high-Z elements) the analytical conditions chosen were 35 kV
accelerating voltage, 0.35 rnA applied current and a 0.050 mm Rh
filter. For the low-Z elements the spectrum emitted by the X-ray tube at
10 kV was used without filtering, with a current intensity of 0.05 rnA.
Samples were irradiated for 2000 s to determine the elements of higher
atomic number, and 500 s for the low-Z elements.
The net peak areas of the characteristic lines were evaluated using
a non-linear least-square fitting procedure, implemented in the software
package AXIL-PC '2 . Scatter intensities were evaluated by a summation over
the channels within the range 18.80-19.80 keV for the incoherently scat-
tered Ka and 19.98-20.lfO keV for the coherently scattered Ka after sub-
tracting the background. This was calculated over the energy range of
15-21 keV by an algorithm that iteratively eliminates the channels
containing peak information '3 .
Experimental scatter factors were applied to determine the mass per

unit area of some different sample supports composed of light elements
(Mylar and Nuclepore). Differences between the values obtained via the
scattered radiation and by weighing with a microbalance are not
significant (Table 1).
The elemental composition of some geological standard reference

materials of unknown thickness was determined to check the overall proce-
dure. Sample thickness determination via the described method, after sub-
tracting the contribution of the sample support, showed that they were
within the range 1-10 mg cm- 2 • Average results of five determinations as
o
well as the recommended values, are given in Table 2.
The agreement between the calculated and the certified values of the
elemental concentrations of the standards are generally very satisfac-
tory, usually within one standard deviation. The only systematic
F. ARAUJO ET AL. 519
Table 2 - Analysis of geological standard materials
GSJ-JG-1 (granodiorite) CRPG-GA (granite)
Element Measured* Recommended Measured* Recommended
AJ(%) 5.5 ± 0.9 7.52 6.0 ± 0.6 7.67

Si (%) 27.8 ± If . 1 33.72 28.2 ± 3.6 32.62
K(%) 3.78 ± 0.lf3 3.29 3.55 ± 0.78 3.3lf
Ca(%) 1 .lf5 ± 0.09 1.56 1.58 ± 0.32 1.75
Ti (%) 0.15 ± 0.02 0.16 0.21 ± 0.01 0.23
V(ppm) - 2lf - 36
Cr{ppm) 69 ± 10 (50) 25 ± 7 ( 10)
Mn{ppm) lf98 ± lf7 %5 609 ± 20 697
Fe(%) 1.52 ± 0.12 1.55 1.89 ± 0.10 1.98
Ni(ppm) 7 ±3 10 - 7
Cu(ppm) 12 ± 2 (3.3) 2lf ± If 1lf
zn(ppm) lf5 ± 6 36 81 ± 10 75
Ga(ppm) 16 ± 3 (20) 12 ± 3 16
Rb(ppm) 190 ± 11 186 165 ± 8 175
Sr{ppm) 198 ± 1lf 18lf 328 ± 10 305
Y (ppm) 22 ± If <30 19 ± 3 ( 18)
Zr(ppm) 172 ± 8 160 1lf6 ± 30 1lfO
Pb(ppm) 30 ± If 2lf 33 ± 6 -
(*) average of 5 determinations.

(-) below the detection limites.
deviations observed were the lower values for the low-Z elements (AI and
Si), probably because for such low atomic numbers the fundamental
parameters are less accurate and more dependent on the instrumental
specifications. Also, there are large uncertainties in the evaluation of
the characteristic lines, due to the high Bremsstrahlung in this spectral
region obtained with a direct excitation.
Some difficulties in resolving the X-ray spectrum due to the

existence of strong spectral interferences of emitted X-ray lines (K. L
and escape peaks) cause the results for V/Cr to be less accurate.
CONCLUSIONS
A method for the analysis of light matrix samples with a wide

variety of unknown composition and intermediate thickness was developed,
applying the experimental relations between scatter factors and the
atomic number of elements, combined with a fundamental parameter sen-
sitivity calibration.
The total sample absorption due to both light (Z<12) and heavy ele-
ments is calculated by an iterative procedure that yields self absorption
corrections. It utilizes the coherent and incoherent X-ray scatter peaks
to calculate an average atomic number <Z>, representative of the bulk
light element sample composition.
The method described. using the backscattered radiation to charac-

terize the sample matrix and to determine the light elements. presents
obvious advantages. First of all. the sample preparation is simple. since

the effective sample thickness is not limited to a given thickness range.
Besides. the absorption corrections for a continuum energy excitation
enlarge the applicability of the method to the use of different and op-
timized excitation conditions. by applying different high voltages and
filters. Also. a second excitation condition enables the determination of
lower-Z elements. which are major components of e.g. environmental and
geological samples with elevated sensitivities. Finally. the use of fil-
tered continuum radiation excitation only requires a low power tube which
involves a lower cost than for a secondary excitation. and it is ap-
plicable to the majority of the equipment commercially available.
REFERENCES
1. K. K. Nielson. Progress in X-ray fluorescence correction methods

using scattered radiation. Adv. X-Ray Anal. 22:303 (1979).
2. P. M. Van Dyck and R. E. Van Grieken. Absorption corrections via
scattered radiation in energy-dispersive X-ray fluorescence
analysis for samples of variable thickness and composition.
Anal. Chern .. 52:1859 (1980).
3. K. K. Nielson and V. C. Rogers. Comparison of X-ray backscatter
parameters for complete sample matrix definition.
Adv. X-Ray Anal. .27 :449 (1984).
4. A. Rachetti and W. Wegscheider. A fundamental parameters approach
including scattered radiation for monoenergetically excited
samples in energy-dispersive X-ray fluorescence spectrometry.
Anal. Chim. Acta. 188: 37 (1986).
5. P. A. Pella. L. Feng and J. A. Small. An analytical algorithm for
calculations of spectral distributions of X-ray tubes for
quantitative X-ray fluorescence analysis. X-Ray Spectrom .. 14:120
(1985) .
6. K. K. Nielson and R. W. Sanders. Multielemental analysis of unweighed
biological and geological samples using backscatter and
fundamental parameters. Adv. X-Ray Anal. 26:385 (1983).
7. P. Van Dyck. Fundamentele studie van de Energiedispersieve X-Stralen-
Fluorescentie-Analyse. Ph. D. thesis. University of Antwerp (UIA).
Wilrijk. Belgium (1982).
8. F. He and P. Van Espen. Fundamental parameter sensitivity calibration
of Bremsstrahlung EDXRF. Submitted to X-Ray Spectrometry (1989).
9. M. F. Araujo. P. Van Espen and R. Van Grieken. Sample thickness
determination via scattered radiation in X-ray fluorescence
spectrometry with filtered continuum excitation. Submitted to
X-Ray Spectrometry (1989).
10. M. F. Araujo. F.He. P. Van Espen and R. Van Grieken. In preparation.
11. W. H. McMaster. N. K. Del Grande. J. H. Mallet and J. H. Hubbell.
Compilation of X-Ray Cross Sections. UCRL-10174. Lawrence
Radiation Laboratory. California University Livermore. CA ..
Sec. I I. Rev. 1 (1969).
12. P. Van Espen. K. Janssens and J. Nobels. AXIL-PC. Software for the
analysis of complex X-ray spectra. Chemometrics and Intelligent
Laboratory System. 1: 109 (1986).
13. E. Clayton. P. Duerden and D. Cohen. A discussion of PIXAN and
PIXANPC: the AAEC PIXE analysis computer package. Nucl. Instrum.
Methods B. 22:64 (1987).
INTENSITY AND DISTRIBUTION OF BACKGROUND X-RAYS IN WAVELENGTH
DISPERSIVE SPECTROMETRY III
Tomoya Arai and Takashi Shoji

Takatsuki, Osaka, Japan
I. INTRODUCTION
In the spectroscopic analysis of composite elements by x-
ray fluorescence (XRF) , it is the fundamental feature of this
method that the background x-ray intensity is lower than that
with electron excitation. However, the background x-rays of
this method, which consist of Thomson (Rayleigh) and Compton
scattered x-rays from the primary radiation, impair the
analytical performance at the ppm level. In order to
investigate the intensity of the background x-rays precisely,
the study was conducted in two parts. The first part compared
the measured and theoretically calculated x-ray intensities for
Rh Ka and Rh KB peaks from various materials. The second part
examined the determination of low concentrations of lead,
arsenic and selenium in steel samples. The variation in the
background x-ray intensities of the analyzed elements was found
to be caused by the variation of the major elements and a
correction equation for it is derived.
II. OUTLINE OF CALCULATION OF TOTAL ATOMIC SCATTERING FACTOR
The formula that was used for calculating intensities was
derived for the x-ray intensity based upon the estimation of
Thomson and Compton scattered x-rays of an atom in previous
papers.' The formula is the product of the intensity
distribution term of the primary radiation (I), the combined
term of scattering and absorption for an atom, and the
instrumental term, in which a main part of this term is the
reflection of the analyzing crystal (c). The scattering term
in the formula is calculated with respect to the individual x-
rays, which consist of scattering terms in the numerator and
absorption terms in the denominator. The product of I and C
is numerically a constant for each x-ray for simplification.
From the calculated results the characteristic items shown
in Fig. 1 can be derived as follows: In each case of Thomson

I Thomson scattering ------ coherent

o atomic scattering
depending on atomic number IZ)
][ Compton scattering ------ AA shift

o .6>'·0.0242 I I-cos 9) A
o low Z - high intensity
o high Z _ low Intensity
I Absorption effects
olow Z - high intensity
o high Z - low Intensity $CoHered
I
Fl Material condition
o Crystalline
o Amorphous
o Liquid
A: Absapllon onenuallon
Figure 1. outline of calculation of total atomic

scattering factor.
scattering intensity, the combination of the square of the

atomic scattering factor in the numerator and the absorption
coefficient in the denominator is strongly related to the
calculated intensity.
When estimating the total scattering of continuous x-rays,

the Compton x-rays in the measured background, which have a
longer wavelength (~A), also known as the Compton shift, should
be inserted between the Thomson and Compton scattered x-rays
of the continuous x-rays. The calculations show that the
intensity of the Compton x-rays increases with decreasing
atomic number (Z). This is because the relative Compton
scattering factor in the numerator increases while the
absorption coefficient in the denominator decreases.
When the incident radiation hits a single-crystal sample,

the appearance of Thomson x-rays depends on the establishment
of the Bragg geometry conditions along the x-ray optical path
(e.g. the incident radiation source, the crystal net plane of
the sample and the detecting direction) . Although the intensity
patterns of monochromatic x-rays diffracted from crystalline
and glassy samples of quartz powder are sharp Bragg reflections
and a halo pattern, respectively, little difference was found
between the background x-ray intensities from these quartz
specimens.
III. EXPERIMENTAL RESULTS

a) Thomson and Compton x-rays of Rh-Ka and Rh-KB radiations
When the qualitative analysis scan is examined, a high

background distribution can be found in the analysis of a
sample consisting of light elements as the main component
elements. A low-intensity distribution is shown when a heavy
T. ARAI AND T. SHOJI 523
8
3070 -Ci.-17.633
LiF(2C01 cleawJ. .~
Fine soller slit u
50KV SOmA Rh 1
I
J:
0: Pb-L seri
I
J:
aE
c
UF10167
>. 8
...
0
I
~,
X E7
~J:
... 0:
-:2-
, AI 5.105
J:
0:
Pb
3.569
10 20 30
Figure 2. Thomson and Compton X-rays of Rh-Ka and Rh-KB

radiations scattered from Pb, Al and Lif
element sample is analyzed. In order to investigate Thomson
and Compton scattered x-rays of Rh-Ka and Rh-KB precisely, a
high-resolution spectrometer equipped with Rh target x-ray tube
(Type OEG-75H) was used.
It consisted of a double fine soller slit collimator and a
LiF(200) analyzing crystal with a cleavage surface. In Fig.
Polycryslalline materials 4.0
Pb Au W
Rh-Kcc Rh-I«<
r-~
3.5
VI
Q.
u Rh-Kp, Rh-Kp.
oX
1.0 Rh-Kp, 2D
~
..
VI
C
C
-;, 0.5
~
I Compton .Conllton
X
O~~ ____ ~ ______ ~ ______ ~ _____ ~ ______ ~ ____ ~
15" 20· 15" . 2(1' 15· 2(1'

RIGAKU,3070 ,50KV 50mA Rh • LlF (200) cleavage, Fire soller
Figure 3. Thomson and compton X-rays of Rh-Ka and Rh-KB

radiation scattered from heavy elements.
Table 1. Calculated and measured intensities of Thomson

and Compton X-rays of Rh-Ka and Rh-KB radiations
Spec1l11en L1F Al S1 Fe Cu W Au Pb
Caluculated ThOG! 11.60 2.15 2.01 Lilli 1.162 2.00 - 1.82 x 10-'
intensity Ka COGIp 27.8 8.01 5.53 0.794 0.580 0.197 - 0.lA6
COGIp/Tholll 6.011 3.73 2.75 0.551 O.A99 0.099 - 0.080
dW/dO ThOCll 4.99 2.3A 2.12 1.62 1.3AO 2.16 - 1. 9li

KP COGIp 36.7 11.5 7.87 1. 12 0.827 0.282 - 0.209
COGIp/TholD 7.35 11.91 3.71 0.691 0.617 0.131 - 0.108
Measured peak ThOCll 7.95 11.23 3.79 2.63 2.11 3.69 3.68 3.A2
intensity Ka COGIp 15.6 3.65 2.9A 0.372 0.25A 0.116 0.065 0.075
(kcps) COGIp/ThOCll 1.96 0.863 0.776 O.llil 0.120 0.031 0.018 0.022
ThOCll 1.24 0.701 0.637 0.560 O.A97 0.779 0.765 0.725

KP COGIp 3.85 0.9A3 0.710 0.108 0.070 0.032 0.020 0.021
COGIp/Thoca 3.10 1.35 1.11 0.193 O.Hl 0.0111 0.026 0.029
2, the intensities from Pb, AI, and LiF powder samples are
shown. In the case of a LiF powder sample, both the Thomson
and Compton scattered x-ray intensities are higher than those
from Al and Pb metals and the Compton x-ray intensity is higher
than that of the Thomson.
with the Aluminum metal sample the intensities of the two
scattered x-rays are roughly equal. with the lead metal sample
only the Thomson x-ray intensity can be seen clearly; the
Compton x-ray intensity is too low.
In Fig. 3 Thomson and Compton x-rays of Rh-Ka and Rh-KB
radiation scattered from Pb, Au and W metal specimens are
shown. It is clearly seen that the Compton x-ray intensity is
very low. Table 1 shows the calculated and measured
intensities for some typical materials.
I
RhK«
IQ LIF
/
'"ua.
.x
51
PI> ·AI
MY·
. ·~r
~
iii
.,c: ~I• ••
F.
"'
RhKpl
5
/
CU
.,o
.x
0 L·C:I
a.
.,
/
:b:'-.t:
t;;.. .~"11
."
Ni 51
Fe
~
/
o
'"
::!
o.1 u.wl 0.)1 QI

Calculated intensity
Figure 4. Comparison between calculated and measured

intensity of Thomson scattered X-rays of Rh-Ka and Rh-KB
using polycrystalline materials
3070. LI F cleavage. fine soller. 50 KV

50 rnA Rh
.
LIF
~ 10~--------r-------~~~----~
a.
<.J
.x
PI>
/
0.0 I L,-,-:------=-=1::-,------.:-I~----~.
0.000 I 0.00 I 0.0 I 0.1
Calculated intensity
Figure 5. Comparison between calculated and measured
intensity of Compton scattered X-rays of Rh-Ka and Rh-KB
b) Comparison between the calculated and measured intensities

of Thomson and Compton scattered x-rays of Rh-Ka and Rh-KB,
Fig. 4 shows the relationship between measured peak and
calculated intensities regarding Thomson x-rays of Rh-Ka and
Rh-KB scattered from the polycrystalline materials. The
intensity from LiF powder is three times higher than that from
a copper metal specimen and it is a very important fact that
the intensity from a tungsten metal sample is higher than that
from a copper metal sample.
Fig. 5 shows the relationship between measured and
calculated intensities of Compton x-rays of Rh-Ka and Rh-KB
scattered from the polycrystalline materials. The intensity
from LiF powder is over 100 times that of a lead metal specimen
and this is quite different from the Thomson scattered
intensities.
c) Background X-ray intensity from binary alloys of iron base
A low concentration level of lead, arsenic and selenium in
iron alloys was measured in order to investigate the background
intensity change. When the qualitative analysis scan was
examined, using a sequential spectrometer (Rigaku Model 3070),
high background intensity was found in binary iron alloy
specimens of molybdenum and tungsten and low background
intensity was found from the iron-nickel alloy specimens (Fig.
6). Investigations of the absorption at 28° 29 for wavelengths
of approximately 0.974 A show that the mass absorption
3.0 W__________~-+---H--~03070
°50KV SOmA
035-15 Rh
h
~}fMO
III
Co
u
oX
2.0
~
..
III
c:
.s
,.,
e
I • Mo
X
1.0
QO~2~~~--~---L~~~----~--~40~0~----
29 UF(200)
Figure 6. Background X-ray intensity from binary alloys
of iron
coefficient is large (around 200), that of chromium, manganese,

iron and nickel is moderate (60~100), and that of molybdenum
and niobium is small (45~50). Therefore, we can expect that
the high background intensity from the molybdenum-iron specimen
occurs as a result of low absorption. In case of the tungsten-
iron specimen, high background intensity results from the large
value of the Thomson scattering factor, in spite of the high
absorption of tungsten.
Table 2 shows the comparison between the calculated values
of dW/dn and measured intensity of iron-based binary alloys.
The Compton x-rays have a longer wavelength of 0.03046A and a
29 difference of 0.89° from the Thomson x-ray wavelength. In
Table 2. Comparison between calculated and measured

intensities at 28° on binary iron alloys.
Calculated and mesured 1ntens1 ty
Element Mo W Cr Hn f"e(NBS1265) Co N1
Spec1men
!ItS 7.07 19.8 30.3 9.9 Pure 20.0 79.b
Caluculated ThOll 0.862 0.946 0.810 0.780 0.773 0.710 x 10- 1

1ntens1ty Comp 0.213 0.150 0.224 0.212 0.209 0.175
dW/dO Total 1.07U 1.096 1.034 0.992 0.982 0.885
Cal. 1ntens1 ty (kcps) 1.188 1.213 1.1Ub 1.097 1.086 0.979
Heas. 1ntens1ty (kcps) 1.261 1.220 1.112 1.08b 1.086 1.072 1.001
Rat10 Cal./Heas. 0.942 0.994 1.029 1.012 1.000 0.978

high background sample

\ \
H \ \/ Ilf'"'---------------
\
\\ "'I't,--------t-----:<"7"
\ \
\\ \ ,, gradient • .!£.
\
,, AI
.
\
\
~ ""
I
,
X
~ 29 Content
wtOfo • (01 2 + bI +c ) ( 1+ LdljWj ) - I:lljWj + I: mijWj
i matrix over~ background change
Figure 7. Definition of correction factors for
background intensity change
order to compare the calculated and measured values, the

intensity of pure iron (NBS 1265) was adopted as the intensity
standard value. Very close agreement can be found between the
calculated and measured values.
Fig. 7 shows the derivation of the correction equation for

the background x-ray intensity change. As the correction is
small, it is assumed that the correction is proportional to the
concentration of an influence element. The correction
coefficient, mj , is defined as the value for 1 weight percent
of an influence element.
In Table 3 the correction coefficients of calculated and

measured values are shown for the Rigaku Simul tix. For
example, when samples that contain 1 weight percent of nickel,
Table 3. Correction factors for intensity change of

background X-rays in steel specimens
Simullix 5OKV.5OmA. Rh
liF(200)
mj: bwt'Y.(i)/Wf%!j)
Measuring X rays Pb-Lpi As-Kpi Se- Koe
28.2'1· ~.43· 31.87"
Interfering elements
Ni + 0.cxx)!3/0.cxx> 19 a 0::033/0.0::032 ot:rot:Jl:T 1 0
Co + /0.0::0091 /0.00015 IClCXXX)6
Mn - 0DJ)15/ 0 0.0::031/0.0::013 0.0::0018/
Cr - 0.00016/000012 O.ax>:o /0.00032 0.CXXlO31/0.cxxxl37
Ti - 0.0X24/ 0 0.0::067/0.0023 OJ:OX)52/000042
Nb /0.0018 /0.0053 10.r0::J38
Mo - 0.0010/0.0018 0.0031 /0.0054 0.Q)026 / CCJ:X:S)
w - o.OC035/O.OOO4 0.CXXl82/0.069* 0.0::014/0DI6*
* overlapping cal./mea.
1264
Simultix 50KV 50mA Rh, 1164

LI F (200)
1.20
.2
'§ 1.15
1.10
~
iii 1161
c 1.08
.s 1.10
II
'1162 1161
1.06
~
'-
I .'155
X
1.05 1155
'1161
• ·,263
1.04
-
1261
1.Q2 1117.'11"
1263
, gradienl ~ 1,ItA
,, 1.00, I I • I ' I •
12" 0002 QOO4 0.006
I I
001 002 003
Pb wI OJ.
Figure 8, Relationship between X-ray intensity and
chemical content in low alloy steel
Table 4, ~b-LB1 intensity from low-alloy and stainless

steel speclmens
Simuilix 50KV 50mA Rh
Sample Chemical Inlensify Precision Background Note
No content rotio correction
wt'% wI"!. WI -I.
N8S 1261 0.a:c025 1.0117 0.00026 -O.a::0J9
2 43 .03C6 13 65
3 220 .0415 16 26
4 24 .2726 41 117
5 15 I.CXX:O II I
1161 3 .e>:e2 9 23
2 6 .0923 25 53
3 12 .1652 31 57
4 20 2470 20 II
5 (I) .0016 12 I
6 13 .0253 12 2
7 6 .0283 14 62
8 (3) !X)66 16 25
1155 .0471 13 30
1267 fJ!I57 20 288
1170 .6455 48 89
I 0.9913 13 27 H-Ni ,H-Cr
2 ,0235 15 151
845 ,0576 16 357 L-Ni, H-Cr
6 ,0435 10 233
7 .0218 14 50
8 .0735 9 251 L-Ni, M-Cr
9 .0452 13 31
50 0.9748 15 + 406 H-Ni, L-Cr
JSS 650-1 .03<4 15 193 L-Ni, H-Cr
I 0.9961 II 68 H-Ni, H-Cr
2 .0<l51 13 427
3 0.9939 18 23 H-Ni, H-Cr
4 0.9881 12 + 70 H-Ni, H-Cr
5 .0471 17 119 H-Ni,H-Cr
the background intensity is decreased and the 0.00019 weight

percent correction should be added to the measured weight of
lead.
Therefore, it has been clearly shown that for the trace
element analysis at the ppm level, the background change
correction must be applied for the purpose of improving the
analytical accuracy.
Fig. 8 shows the analysis of low concentrations of lead in
low allow steel samples. The length of the small arrows
indicates the value for the correction. In the case of the
higher lead concentration samples, the correction is not as
important; however, in the range of low concentration (10, 20
and 40 ppm) it is very important to apply the correction.
Table 4 shows the numerical values of the lead analysis for
low alloy and stainless steel samples ratioed to the intensity
of the NBS 1265 standard. The intensity ratio of high nickel
content samples is below 1.00. The NBS 850 and JSS 654 samples
should have a positive correction. In the case of low nickel
and high chromium content samples, NBS 845, 848 and JSS 650-1,
the intensity ratio is high and a negative correction should
be applied. The stainless steel sample JSS 652-1 has a
negative correction because of high molybdenum content.
IV. CONCLUSIONS
The basic concept for the intensity and distribution of
background x-rays has been clarified using Rh-Ka and Rh-KB x-
rays. The intensity ratio of Thomson versus Compton x-rays
which are scattered from analyzed samples is dependent upon the
atomic number and the absorption of x-rays. It was also proven
that the intensities and distributions can be predicted.
In practical application for trace element analysis in steel
samples, the intensity change of background x-rays has been
studied and a correction formula has been proposed.
V. REFERENCES
1. T. Arai, Adv. X-ray Anal., 31 (1988), pp. 507-514 and T.
Arai, Adv. X-ray Anal., ~ (1989), pp. 83-87
AN ARTIFICIAL INTELLIGENCE SYSTEM FOR XRF DATA
ON A PERSONAL COMPUTER
Erland P. Wittig and Carl E. Rechsteiner
Chevron Research Company

P.O. Box 1627
Richmond, CA 94802
SUMMARY
Automation of X-ray fluorescence equipment has proliferated during the last 10

years. However, the focus has been on data collection and data massage. Data
presentation has been limited to a few rudimentary formats. These formats
generally involve printing the results in some arbitrary fashion, followed by manual
transfer to the client.
This paper describes a system (using rudimentary artificial intelligence techniques)

that automates data presentation. It handles data from 14 different methods;
evaluates the data against the requirements of the method (i.e. mass balance,
detection and reporting limits, and matrix interferences). Further, a data report is
generated in a consistent format, including the reporting of significant figures.
Additionally, an exception report is printed when the measured results are outside
the applicable range of the method or violate quality assurance constraints. In such
cases, alternative methods are recommended in the exception report.
INIRODUCTION
The value of good results depends upon the accurate and timely transfer of this
information to a customer in a format that the customer can assimilate readily.
This is a problem with many analytical instruments, including XRF systems. For
example, currently available XRF systems incorporate a high degree of automation.
The automation has focussed on instrument control and mathem:atical manipulation
of raw data. Such systems will therefore produce good results for well designed
experimental methods. However, the tools that allow the chemist to convey results
effectively are sadly lacking.

The commonality of this problem across a wide range of analytical instruments led
us to develop a consistent, modular system that could be adapted easily to convey a
variety of information from different analytical chemistry instruments. This system
has been adopted for a wide range of analytical instruments within Chevron
Research Company. This paper discusses the first implementation of this system, to
XRF. Since then, the system has been applied successfully to mass spectrometry,
thermal analysis, ICP and M spectrometry, and small chemical analyzers (e.g.,
sulfur analyzers, CHN analyzers, ... ).
A number of factors drove the design of this system. These factors all relate to the
customer need for receiving accurate, readily interpretable information. These
factors are:
• Quality Control
• was this the appropriate test?
• are the results out of range (above or below method reporting
limit)?
• were there significant interferences?
• were there other boundary problems (e.g., mass balance,
concentration of an added element)?
• Transcription errors
• did the analyst transcribe the results correctly?
• did the customer transcribe the results correctly?
• Costs
• transcription costs.
• rework due to transcription or QC errors.
• cost of having "bad data" in customer data base.
• Commercial systems deficiencies
• limited implementation of "multi-tasking."
• limited, if any, control over reporting formats.
• limited capabilities for data archival and retrieval.
In addition, any system designed to correct these deficiencies should also make it
easy for the analyst to implement and audit the process.
EXPERIMENTAL
Several approaches were possible to improve data presentation. These included

developing data presentation tools on the computer of the analytical instrument, or
developing an off-line set of modular tools that could be adapted to the needs of
any specific analytical instrument. We chose the latter alternative using the
ubiquitous IBM PC (or compatible) microcomputer (PC) to connect with any
analytical instrument and providing data presentation mo~ules on it.
The PC forms the central hub for our in-lab computing. It is connected to both a
Philips PW-1400 XRF and a Philips PW-1404 XRF through their PDP-ll based data
systems. It is further connected to a variety of customer systems via an in-house
voice-over-data network. A switch box selects the appropriate connection.
E. P. WITTIG AND C. E. RECHSTEINER 533
Table 1
List of Commercial Software and uses in PC system
DOS - Operating system

IBM Fixed Disk Organizer Disk Organizer and Menu system
VTERM III - Terminal emulation/file transfer
Microsoft QuickBasic - Language for User-written program
Norton Editor - Data/Program editor
Norton Utilities - Logging! Cleanup of Hard Disk
Polyboost - Operating system enhancement
The system blends commercial software with our modular software. A menu
system which clearly states each task in a logical sequence assists the user. The
commercial programs and their uses are listed in Table 1.
SYSfEM
The system was designed by examining the steps that happen between sample
receipt and data reporting. The transformation of data into the final form for the
customer is a critical step. The key steps of this process are outlined in Figure 1.
The data transfer is handled readily with command files on the instrument's data
system that are initiated from the terminal emulation program. Data archival is
important for Good Laboratory Practices, environmental work, and patent positions.
In the archival, the data is preserved in the original format and can be retrieved
readily.
Data transfer from instrument

Assemble raw data
Transmit data
Archive data
Data receipt by PC
Print full set
Option -- Edit known errors
Manipulate data
Split/sort data file
Treat data by test-method requirements
Read data
Validate data
Create output file
Create/Print exception list
Transmit data from PC to customer
Cleanup PC files
Figure 1
Functional Flow Chart of Program
Table 2
Key method requirements
Valid JD
Valid Analyst
Method's QC is in control
All elements are within the appropriate concentration range
Interferences are not significant
Mass balance is in control
Intensities from added elements are in range (e.g., internal standard)
The data received by the PC needs to be checked for extraneous information.

Because developmental work also is done on the instruments, not all the data that
is transmitted is appropriate for release to additional parties. Such data is not
subjected to data manipulation. Additionally, if the instrument is found to be out
of control for a method, the data from that method can be deleted without further
analysis. When the initial cleanup is done, the data is ready to be manipulated.
The data manipulation is the heart of the program. Key information, listed in Table
2, is checked. The data is compared to a rule-based system for checking the data
validity. Checks include things such as the mass balance on catalysts, the presence
of known interferences that may cause significant matrix effects, and validating that
the concentrations of the elements are within the range that the method can
handle. For some samples, dilutions are required to bring the instrument
concentrations into the method's range. Dilution data can be entered and the
appropriate concentrations determined.
All of the information about the test method was programmed to form the decision-
making engine. If, after analysis, the test is inappropriate, the system suggests
alternative analytical tests.
The data manipulation program creates output files which contain the data in the
appropriate format. This data is transmitted readily to other computers with the
same terminal emulation program used to gather the data from the instruments.
RESULTS
The overall system design includes the internal validation of data, reformatting, and
transmitting data. The system was running within 3 weeks after detailed
specifications were written. The data manipUlation program currently runs methods
with 25 results per sample. The upper limit is controlled by the array size which is
set at 200.
Some of the lab's tests are quite simple -- only one result being determined. For
example, the determination of low levels of Pb in gasoline closely follows ASTM
03229. In our implementation, the statistics are good enough to go down to 0.005
g/gal and the upper limit is 0.50 g/gal. The instrument output is shown in Figure
2. The checks done on the method verify that the data is within the method's
upper and lower concentration limits. If the result is less than the lower limit, it is
E. P. WITTIG AND C. E. RECHSTEINER 535
MP 8 CP 8 40201 LO-PB IN GAS G-GAL 23-JUL-89 10:08

CONCENTRATIONS 6101290 1618 TR 56
PB
0.011
Figure 2
Instrument Output for Ph in Gasoline
reported <0.005 glgal. If the result is within the range, it is reported to the third
place beyond the decimal point. If the result is greater the upper limit, it is
reported >0.500 glgal and the test method for higher level lead samples is
suggested, in this case ASTM D2599 Method B. The customer's computer to which
the results are normally transmitted expects a special packed format. Figure 3
shows the format for a series of samples and identifies the various fields. Each
field is separated by an asterisk and the last field can accept a comment if
appropriate. If the result is too high an alternative test is recommended. All such
recommendations are printed in an exception log.
Another example is the lubricating oil method (1) in which a number of items are
checked or computed. In addition to checking the concentration for each element
as in Pb in gas method, the program computes the dilution factor (if used) and
checks several additional elements for possible interference. For example, calcium
sulfonate is a frequently used additive with no Zn or P. If the additive is diluted
into the appropriate concentration range, the Ca and S concentrations can readily
be recovered by multiplying the results by the dilution factor. For reporting P and
Zn, the appropriate result is the lower limit of the method multiplied by the
dilution factor. If, for example, the dilution is insufficient and the Ca level is too
high, the data system will report the Ca as the dilution factor times the upper limit
and suggest a larger dilution. It will also report the other elemental results as not
available. They are meaningless because the matrix corrections cannot be applied
accurately. Included in the method are checks for other elements found in some
formulations for lubricating oils but not handled in this method. If the upper limit
of the apparent concentration of these interferences exceed a predetermined level,
then the results for Ca, P, S, and Zn will be biased and should not be reported by
this method. The data system reports which element was interfering and prints an
exception report which includes a recommended alternative method.
6101290*1618*.011 *G/GAL*404
6101454*1618*.399*G/GAL*404
6101344*1618*<.OOS*G/GAL*404
Figure 3
Compressed format for a Single element analysis
The fields are separated by asterisks. The fields are Sample

!D, analyst, result, units, and instrument code.
As a class, catalyst samples have their own particulars. Most of the hydroprocessing
and catalytic cracking catalysts are prepared with a lithium borate fusion. A check
on the mass balance provides a sample preparation check and also a check for
interfering elements not analyzed for in the method. Additionally, the amount of
non-wetting agent retained in the sample influences the total mass absorption and
needs to be within certain limits so as not to affect adversely the quality of the
results. Both of these checks operate similarly to the interfering elements check in
the lubricating oil method. For example, the mass balance check for fluid cracking
catalysts is 98-102 percent and samples outside that range are flagged.
The data system has been used for about a year and a half for over 19,000 samples
and pays for itself about every two months. It is also the model for other similar
systems -- mass spectrometry, ICP, MS, UV, Leco S, and Carlo Erba CHN. In
addition, it is being added to the 6 thermal analysis instruments, 3 viscosity
instruments, sorption-desorption instruments, HPLC and ICP-MS. Currently about
40% of the division's samples (>4000 samples/month) are transformed and
reported electronically though these systems.
CONCLUSIONS
A data handling system for XRF is reported. The system checks the data internally,
reformats, and sends it on to the client. A low-cost PC runs the user-friendly
system. It reduces the time spent transcribing data, reduces the transcription
errors, improves reporting consistency, and reduces rework for results reported
incorrectly.
The system is easily transferred to other instruments and methods because of its
modular design of commercial software and structured data manipulation program.
REFERENCES
1. E. P. Wittig, 'Wavelength-Dispersive X-ray Fluorescence (WDXRF) Analysis of

Fresh Lubricating Oils," 1986 Annual Denver Conference on Applications of X-ray
Analysis.
SPC: WHAT IS IT AND WHY SHOULD YOU USE IT IN YOUR X·RA Y
ANALYTICAL LABORATORY?
P. B. DeGroot
Hoechst Celanese Corp.

P. O. Box 9077
Corpus Christi, TX 78469
ABSTRACT
Statistical Process Control (SPC) methods have become extremely popular in quality control and
process improvement in the manufacturing environment, first in Japan and more recently in the U.S. They
are gradually being introduced into the research and development setting as well, where they offer some
advantages over more traditional statistical approaches. The greatest advantage of the SPC approach is that it
ensures that the statistical description generated is valid, i.e., that the data on which it is based incorporate
only random error. This is verified both initially and on a continuing basis. This means that the results
provide valid predictions of future performance, not just a description of an historical set of replicate samples.
SPC statistical evaluations of analytical results and instrument performance require only simple calculations
and are .easily applied in a consistent, valid manner by statistically unsophisticated analysts. Besides the
numerical statistical analysis tools, the SPC approach provides other problem-solving techniques for
improvement of the entire analysis process. These aspects of the SPC approach will be described and
illustrated with examples from our x-ray fluorescence analysis laboratory.
INTRODUCTION
Statistical Process Control, or SPC (sometimes also called Statistical Quality Control, SQC), is a
methodology developed out of conventional statistical principles. Unlike conventional statistical methods
which primarily aim to describe the capabilities (accuracy and precision) of measurement, SPC has as its
objectives both the statistical description of the measurement and the improvement of the measurements
and the process that generates them.
SPC was pioneered by the American statistician Deming! in the 1950's, who found a receptive climate
for his ideas in Japan as they tried to rebuild their industrial capacity after the war. Ironically, primarily
because of competition from Japan, these ideas recently have been reintroduced into the United States. They
have been widely adopted in manufacturing with great success. Acceptance in the research and development
area has been much slower, in part, perhaps, because of the previous emphasis on manufacturing and the
name "Process Control", which has a decidedly engineering connotation.
I will try to show that SPC has some distinct advantages in the R&D setting as well, first by
discussing an area already familiar to analytical chemists; the statistical description of measurement
capabilities. Then I will briefly introduce the other (perhaps more powerful) aspect of the SPC philosophy;
the improvement of measurements and measurement processes.

Edited by C.S. Barrett et a/.
DISCUSSION
Statistical Descriptions of Measurements

Let me emphasize at the outset that SPC methods and procedures have been developed entirely from
well known, accepted, conventional (and conservative) statistical principles and theory. It is primarily the
SPC implementation of these statistical principles which conveys considerable benefit to the analytical
chemist.
The greatest advantage of SPC in evaluation of measurement capabilities is its emphasis on continuous
monitoring of measurement capability. This results in greatly increased predictive value of SPC results
compared to the sort of "one-shot" statistical analyses to which analytical measurements are often subjected.
Some significant secondary benefits are also incorporated into the SPC approach. Since SPC methods and
calculations were designed to be used on the factory floor by the workers themselves, they are easy to apply
in a consistent manner by mathematically and statistically unsophisticated analysts. They are generally also
robust in the statistical sense. That is, the successful application of SPC principles does not depend on the
measurements in question having an approximately normal or Gaussian distribution. Finally, there is a great
emphasis on graphical presentation of results, which are much easier to interpret than numerical results.
The basic tool for measurement evaluation in SPC is the control chart. This document is a continuous
record of the performance of an analytical (or other) process, along with notations of external events and
conditions which mayor may not affect this process. A typical control chart is initiated by running 20 or
more replicate analyses of one or more standards or reference materials. These initial measurements are then
converted by means of simplified formulae 2,3 into a mean and upper- and lower control limits., as shown in
Figure 1. The initial measurements are represented by open circles.
Thus far, the SPC approach is quite similar to what one might commonly see in the literature as a
statistical evaluation of a newly-developed analysis, except that often the conventional evaluation is based on
far fewer replicates, and the results are usually presented in numerical rather than graphical form. The mean,
upper and lower control limits (UCL and LCL) are entirely analogous to the mean and ±3·Sigma limits of
conventional statistics.
Here the similarity usually ends. The next step in the SPC approach is to determine whether the initial
standardization data are, in fact, statistically valid (or "In Control" in the parlance of SPC). That is, whether
1.04,-----------------------------,
Upper Control Limit
.•
0 0
•
1.02
.,
0
"#. 0
• 5>
.., 0 0
c- 0
- •., • •
0 0 0 0 0
'';::; 00 0 000
~
n OO
uu v v 00
•• • •
c 0 Q)0
Q) 0 000 0 Q)o
(.) Q)
c 0 0
0 00
••
0 0 0 0
u
0
•
0
0.98 0 0 0 0
Lower Control Limit
5 10 15 20 25 30 4 9 14 19 24 29
MAY JUNE
Figure 1. An example of a control chart for x-ray fluorescence analysis results. • - initial data used to
establish centerline and control limits, 0 - continuing monitoring of analytical process.
P. B. DeGROOT (1 ) 539
TABLE 1. SPC Out of Control Criteria·
1. Any point outside the Control Limits

2. Seven consecutive points above or below the Centerline
3. Six consecutive points steadily increasing or decreasing
*There are additional, more complicated tests for the Out of Control condition, but these
three simplest rules will detect nearly all real problems and exclude spurious ones.
it is probable that no systematic, non-random errors are incorporated in this crucial initial data. This is easy
to do in SPC, by means which we shall learn shortly. It is, of course, also possible to make this evaluation
by appropriate conventional statistical methods, but I have almost never seen it done in the analytical
literature, regardless of the fact that it is ~ absolutely necessary first step in establishing the predictive
value of the statistical analysis. Despite this, such incomplete conventional statistical analyses are almost
universally used to predict future measurement capability.
Although this initial determination of the "In Control" (no non-random errors) nature of the analytical
process is necessary, it is not sufficient. One must assure that the analysis stays In Control. This is often
not done at all in the usual statistical treatment of a chemical analysis. The initial statistics are assumed to
prevail forever. At best, precision and accuracy are checked at arbitrary intervals with a few replicate
analyses. In Spc, this assurance is obtained by continuing to plot periodic standard or reference analysis
results on the Control Chart. The filled circles in figure 1 illustrate the continuing monitoring of the
results. Inspection of these results and comparison to a few simple criteria (Table 1) readily determine
whether the process is still In Control.
A very important additional benefit of the Control Chart is the elimination of "Wild Goose Chases".
This is the needless expenditure of corrective effort on perceived problems, when they are in fact part of the
natural statistical fluctuation in the results. Without the perspective of the control chart in figure 2, for
example, the sharp drop in the Si x-ray fluorescence intensity of a reference material on the morning after our
XRF spectrometer was subject to a power failure might initiate a needless search for an instrument problem.
3.05~--------------------------------------------~
______ ~r~~~_~~':1~!~~_~~~~~ _________________________________ _

3
en
••• •••
•• ••
0.
U
:..: 2.95
i
.u;
•• • • ••
• • •
c:
Q)
.E
•
<tl 2.9
:..::
(j)
----------------------------------------------------------~------
.....
2.85
Lower Control Limit :::J
0
Q;
~
0
0-
2.8 -t--,---,--r--,----r--r--r--r---,--,---,--,---,----r--r--,--J
12 14 16 18 20 22 24 26 28 30 1 3 5 7 9 11 13
JANUARY FEBRUARY
1988
Figure 2. Control chart to monitor general performance of an x-ray fluorescence spectrometer. Si K-alpha
and other intensity measurements are made on a special reference material every morning.
This brings up the importance of the notation of external events on the Control Chart. For papers and
presentations, a neat computer-generated representation such as figure 1 or 2 may be appropriate. For really
useful day-to-day SPC analysis, a hand-written chart with voluminous notes on external conditions is far
preferable. This ensures that important observations won't be missed because it is not convenient to log on
to the computer and run the software (most of which doesn't have provision for extensive note-taking
anyway). It also promotes the active participation of the analyst in the maintenance and improvement of the
quality of the results. Quality becomes more than just something that the computer or the supervisor does
with mechanically generated numbers.
Why are these Control Chart marginalia important, anyway? They are the beginnings of the second,
more powerful, aspect of SPC, the potential for correcting problems and improving the process. Some
systematic SPC tools for doing this will be introduced briefly in the next section, but often improvements
can be made or problems solved simply by correlation of external observations with Out of Control
conditions on the Control Chart.
One other benefit often claimed for the SPC approach to monitoring process performance is the
elimination of needless instrument recalibration, which can actually increase the scatter in analytical results.
This is the subject of a separate paper4. It turns out in practice to be a relatively minor consideration.
Process Improvement Tools and Techniques

The SPC philosophy incorporates a number of procedures and techniques for systematically analyzing
analytical or other processes and correcting problems or improving the processes. Most of these will be
familiar in form, if not in name, to most analysts (remember these tools were developed for scientifically
unsophisticated users).
Process Flow Charts. An example of this formal analysis of the steps of a process or sub-process is shown
in figure 3 for a sample preparation process for XRF analysis. Preparation of a formal process flow chart on
even a simple operation that one has taken for granted for a long time can be a real revelation. It can be very
helpful in suggesting steps in the process where the two other procedures described below can be used to
pinpoint a problem more exactly. Typically, every step in the overall process can be further resolved into
process flow charts of finer steps, to whatever level of detail seems to be needed.
CauselEffect CFishbone) Diagrams. Figure 4 shows a portion of such a systematic listing of effects
pertaining to a potential problem or cause of error, and the postulated possible causes. It is also sometimes
STRRT
Return to
~""T""'''ISubmitter
Select Window
Material
FRIL
OK
Ready for
Analysis
Figure 3. An example of a process flow chart for acceptance and preparation of samples for XRF analysis.
P. B. DeGROOT (1) 541
IRREPRODUCIBLE
PRESSED POWDER
PLANCHETS
Figure 4. An example of a cause and effect diagram applied to an XRF sample preparation process.
called a Fault Tree. The actual cause is usually pinpointed by collecting appropriate data and displaying it on
a Pareto Chart.
Pareto Charts. This is nothing more than a simple bar chart or histogram of the frequency of occurrence of
events (usually problems) in a process. This tells you where to concentrate further efforts at improvement to
have the biggest impact.
Although these process improvement tools have been treated very briefly, they are probably more important
than the Control Chart, which primarily serves to assure consistent, acceptable performance. The biggest
pay-off in any competitive situation is not generally from maintaining the status quo, but from improving
upon it. There are also a number of different types of control charts which have not been dealt with here.
Some of them are more effective than others in dealing with certain kinds of data, or in detecting subtle
changes such as slow drift in the data. I recommend further investigation of these SPC tools (2,3).
CONCLUSIONS
Although the application of SPC techniques to analytical procedures requires somewhat more effort than is
usually expended on the assay of the capabilities of the measurement process, it is worth it. SPC methods
assure valid predictions of the method's accuracy and precision and provide tools for the correction of
problems and the improvement of the method.
REFERENCES
1. Deming, W. E., Ouality. Productivity and Competitive Position, M. I. T. Press, Cambridge, MA,
(1982)
2. Wheeler, D. J. and D. S. Chambers, Understanding Statistical Process Control. Statistical Process
Controls, Inc., Knoxville, IN, (1986)
3. AT&T Technologies, Statistical Ouality Control Handbook_ AT&T Technologies, Indianapolis, IN,
(1958)
4. DeGroot, P. B., "SPC Analysis of Optimal Strategies for Restandardization of X-ray Fluorescence
Analyses", Adv. in X-ray Anal. 33:543 (1990)
SPC ANALYSIS OF OPTIMAL STRATEGIES FOR REST ANDARDIZA TION OF
X-RA Y FLUORESCENCE ANALYSES
P. B. DeGroot
Hoechst Celanese Corp.

P. O. Box 9077
Corpus Christi, TX 78469
ABSTRACT
Quantitative XRF analyses almost always depend on measurements of x-ray emission intensities of
standards of known composition. The usual approach is a careful initial standardization with multiple
standards that are checked for accuracy, stability, homogeneity, and internal consistency. This is followed by
limited periodic restandardization or recalibration with one or two of the initial standards or a reference
sample. The frequency and protocol of these periodic restandardizations tend to be rather arbitrary; for
example adjustment on the basis of the average of a triplicate measurement of a standard at the beginning of
the work day. There are certainly a large number of other possible restandardization strategies. They range
all they way from no restandardization at all, through single or n replicate restandardization measurements
before analysis of each group of m unknowns, to cumulative or moving averages, again with variable
replicate size, frequency, and now averaging range. This paper examines the outcomes of some of these
restandardization strategies applied to synthesized, realistic XRF analysis data which incorporate both abrupt
and gradual changes in instrument response. SPC (Statistical Process Control) control charts are shown to
be a very useful tool for determining optimum restandardization strategies. Optimal strategies (least scatter
in calculated concentrations with fewest standards ) which emerged from this study included not
restandardizing at all except when indicated by an SPC chart of a reference standard intensity run concurrently
with each unknown, and a moving range of 3, with standards run every 5 unknowns, coupled with SPC
monitoring of the standards used for this restandardization.
INTRODUCTION
Chemical analyses are usually carried out by initially calibrating or standardizing the analytical
instrument or procedure against materials of known composition, then periodically restandardizing against
one or more of these standards. The recent emphasis on statistical quality-control methods has lead to this
consideration of the optimum procedures for restandardization. These procedures were tested by statistically
evaluating the results of simulated XRF analyses using computer-generated normally-distributed standard and
unknown intensities.
Several possible restandardization strategies are considered, the simplest being no restandardization at all.
More complicated strategies include restandardization with n replicate standards before every m unknowns
and moving averages of the last n standards run individually before every m unknowns with the values of n
and m according to Table 1. As recommended by many SPC advocates! restandardization only when a
reference sample shows the analytical process to be out of control is also examined, with the reference
sample being run before every m unknowns as also designated in Table 1.
Advances in X.Ray Analysis, Vol. 33 543

Table 1. Restandardlzation strategies Investigated.
No. Standards Averaged, n , Recalibration before every m unknowns

m ... 1 5 10
Single Standard 1
• • •
Average of n 3
• • •
Replicate Stds. 6
• • •
Average of Moving 3
• • •
Range of n Stds. 6
• • •
Restandardize on SPC 1
• • •
Out-of-Control, group 3
• •
of n ref. intensities
6 • •
Simulated XRF analysis data were genemted by a BASIC computer program. This data consisted of
normally-distributed standard and unknown intensity data with the following characteristics:
Standard Intensities: Mean 180 Std. Dev. 1.80

Unknown Intensities: Mean ISO Std. Dev. 1.50
Standard concentration: 1.20
Modified sets of standard and unknown intensities simulating non-random instrumental malfunctions or
unplanned changes in analytical conditions were then generated from these sets of standard and unknown
intensities by superimposing a step function of 2,4, or 6 times the standard deviation of the intensity in
question, or a linear drift beginning at zero for sample 1 and ending at 2 or 4 sigma at standard or unknown
100. Seveml sets of 20 unmodified standard intensities were also genemted and used for initial calibration of
the method and restandardization according to the SPC protocol discussed later.
The relationship between the standard and unknown intensities and concentrations was assumed to be
linear with a zero intercept: that is, the unknown concentration is unknown intensity divided by standard
intensity times standard concentration. The unknown concentration thus calculated should avemge 1.00 from
the synthesized data.
Effects of restandardlzation on the scatter In the results
It is instructive initially to examine the advantages and disadvantages of two fairly extreme cases: no
restandardization at all, and restandardization with a single standard before every unknown. The results of
calculations for the concentrations of 100 unknown measurements by each of these strategies are shown in
figure 1. Note that restandardization with a single standard before every unknown actually increases the
variability of the calculated concentrations. This increase in scatter due to needless restandardization is often
stressed in the SPC approach. This additional scatter can be reduced by restandardizing with replicate
standards, and by restandardizing less frequently, as shown in figure 2. Of course, restandardizing with
replicates greatly increases the amount of work that has to be done. On the other hand, restandardizing at less
frequent intervals reduces this work (at the risk of letting a few bad analyses slip by between
restandardizations). Another mechanism for reducing the number standards that must be run, while retaining
1.04
1.02
c
o
'.p
~
+"
C
Q)
()
c
o
u
0.98
~- ----- . --------------------------------8 ---------------. ----_.
•• •
0.96 --'-------,-----.----,--------,--------,
20 4060 80 100
Analysis Number
Figure 1. Comparison of scatter in calculated concentrations with no restandardization ( [] ) vs
restandardization before every unknown ( .). Control limits are calculated from initial twenty
points with no restandardization.
1.5 J
1.4 13.~~~~!'!g!!~g!?!l.~i~~. _~Y_~~Y. _I,J_~!<,~~~!,!_ .. __ .
Rest~ndardjzatio~ Every 5th 9nkn~~
E 1.3 Restandardization Every 10th Unknown
OJ
U5
Q) 1.2
>
'';=
<0
~ 1.1 \-.. '.
....... .
~------------~~ ... -- .. -- .. -.... --- . -.... ----- .. ------------ .. -- ...
I I I I I I I I I I I
o 2 4 6 8 10 12 14 16 18 20
Number of Replicate Standards
Figure 2. Relationship between replication of standards, frequency of restandardization, and the net scatter in
the calculated concentration.
the advantages of decreasing scatter by averaging multiple standards, is to use a moving average of the last n
standards. This does introduce some correlation of results over time, however.
No restandardization at all has the advantage of lowest scatter in the result of interest and certainly the
least work. However, this is true only if the analysis is well-behaved, and few analysts are willing to take
this on faith. This means some additional work to determine under what conditions no restandardization is
justified, and how to restandardize when it is not. The approach suggested by most SPC advocates is to run
one or more reference samples (either a standard of known concentration or simply a stable material of
unchanging intensity), and restandardize only when this intensity indicates that the analytical process is out
of control according to SPC criteria.
The problem, then, reduces to just how much benefit (accurate concentration results with minimum
scatter) can be obtained at the least cost (number of standards or reference materials that must be run) under
conditions in which non-random perturbations to the analysis may be occurring. Before attempting to
quantify this benefit/cost relationship, however, a coarse screening of the strategies to eliminate clearly
unacceptable ones seemed in order.
Initial screening of strategies
The initial evaluation of the various combinations of the strategies according to Table 1 with the non-
random perturbations introduced above revealed several strategies which had severe problems. These
unsuccessful strategies produced excessive numbers (defined as 4 or more) of calculated unknown
concentrations outside the 3-sigma limit of the original unperturbed data. An example of such a failure using
the replicate-standards strategy is given in figure 3. In this figure, as in all other similar figures in this
paper, the data are presented in the manner of an SPC control chart, but the control limits are those of the
original. unperturbed data. This shows clearly where and by how much the various strategies deviate from
this best-case situation.
The pure SPC restandardization strategy also produced similar successes and failures. Standard SPC
criteria were used to determine at which point the analysis was out of control. Restandardization. again with
20 standards as initially, was done at this point. In general, failure of this strategy was due to the out-of-
control decision coming too late unless a reference sample was run before every unknown.
With the SPC strategy, a drift rather than a step perturbation caused the most difficulty. In the other
strategies, the greatest difficulty was generally with the large step discontinuity.
Benefit/Cost ratio of restandardlzatlon strategies
To further evaluate the remaining strategies which dealt more or less successfully with the simulated
analytical problems, a benefit-to-cost ratio was defined. Benefit was defined as the reciprocal of the standard
deviation of the 100 calculated values of concentration averaged over the results for 2 and 4 sigma step and
drift perturbations. Cost was defined as the number of standards that must be run, including the initial 20,
per 100 unknowns.
...••
1.06
.
1.04
..... ...
c -------------ii ----------------,-------. ----. ----------------.
..
... .
0
',p 1.02
• •
.. .
~ ~
...,
+'
C
Q)
(,)
c ~.-~-- ~----=--.----~~~~
0
U
0.98
------- -~-~- -- -- -- -- ------ -- -- -- -- ---- -- -~- ---------------------_.
0.96
2040 60 80 100
Analysis Number
Figure 3. An example of an unsuccessful restandardization strategy: Triplicate standards run before every
tenth unknown, data incorporate 4 sigma step discontinuity.
Moving Range 3
Every 5th Unknown
Single Standard
Every 5th Unknown
Triplicate Standards
Every 5th Unknown
SPC Single Standard

Every Unknown
Moving Range 3
Every Unknown
Triplicate Standards
Every Unknown
o 50 100 150 200 250 300

Benefit/Cost Ratio
Figure 4. Benefit/cost ratio of some successful restandardization strategies.
Figure 4 shows a bar graph of the benefit/cost ratio of some of the more promising strategies. The
most cost-effective strategy appears to be the moving range of 3 standards with one standard run every 5
unknowns. This is followed closely by a single standard restandardization every 5 unknowns, which has the
same cost in number of standards which must be run, but has slightly more scatter to the calculated
concentrations. The least cost-effective group, at about half to one-third the benefit/cost ratio of the two best
strategies includes the only "pure" SPC strategy that did not fail one or more of the step or drift simulations.
This is the strategy in which a reference sample is run before every unknown. This generates the lowest
scatter in the concentration results, but has a high cost in reference measurements. Running replicate SPC
reference standards did not noticeably improve the performance of the strategy, and, of course, increased the
cost still further.
Combined strategies
While the moving range of 3, standard every 5 unknowns seems the most attractive, there is a danger in
using it if the rate of change of a step or drift in the data is even a little larger than the maximum of 4 sigma
investigated thus far. In fact, a step of six sigma produces very unacceptable results.
This suggested combining the SPC strategy with the moving average as an optimal strategy. The
moving range is very good at compensating for small drift or step functions which are very difficult to detect
by SPC methods unless reference materials are run very frequently. On the other hand, SPC charts readily
detect large fluctuations in the data which cause problems with the moving-range strategy. This was, in fact,
quite successful, as figure 5 shows. The net cost of the combined moving-range-SPC strategy is only
slightly greater than the moving-range strategy alone. The moving range-standards can also serve as the SPC
reference intensities, and additional standards need be run only when SPC restandardization is necessary.
Incorporating an SPC control chart into the strategy has an additional benefit over relying only on
periodic restandardization. The SPC approach tells you when something is going wrong with your analysis,
while periodic restandardization merely compensates for whatever is occurring. It is much better, in my
opinion, to strive to operate with the best analytical technique rather than relying on compensation after the
fact.
....>-
'iii
cQ)
192
•
• • •••••
•
.. -•••• . -.
188
....
.E 184
...:
Q)
180
a:
----------------------_.- --------------------------------.
U 176
a..
en 172
SPC
1.08
RECALl8RATION
c 1.06 ~
•
0
.." 1.04
....C~ ----------------------------iii --------------------------.
-"'I.rI.';;" ,,~wt-
1.02
Q)
0
C
0
U 0.98
------------------------------------.-----------------_.
0.96
o 20 40 60 80 100
Analysis Number
Figure 5. A strategy combining the moving range method with the SPC approach is successful in dealing
with data incorporating a 6 sigma step perturbation.
CONCLUSIONS
The optimal restandardization strategy depends to some extent on the requirements imposed on the
analysis. If there is some leeway between the precision and accuracy capabilities of the analysis and outside
constraints such as specifications or the onset of undesirable effects in a product, then either a single standard
run about every 5th unknown, or the moving average of 3, with a standard run about every 5th unknown
combined with an SPC chart of these standard intensities is optimal. This allows a few analyses outside the
3 sigma limit of the unperturbed analysis to slip through if a perturbation in the analysis such as a step
change or continual drift occurs. The number of unknowns before repeating a standard measurement can be
adjusted to allow for the worst-case number of "bad" analyses one is willing to tolerate in case of a step
change.
On the other hand, if specifications or other outside constraints are very close to the capabilities of the
analysis, then the extra work in running a pure SPC strategy with reference standards run before every
unknown, or at least very frequently, is recommended. This will yield the least scatter in the results, and the
greatest assurance of being within the external constraints. Further, the SPC approach can lead to insights
into the analytical process which may allow an improvement in the precision of the process which will give
more leeway between the process capabilities and the external constraints.
In either case, including the SPC approach is recommended because it can tell the analyst when
something is going wrong in the analysis, and can yield clues as to how to fix or improve it if the SPC data
is correlated with other observations of factors which can potentially affect the analytical process.
REFERENCE
1. Wheeler, D. J. and D. S. Chambers, .lln.dersranding Statistical Process Control. Statistical Process

Controls, Inc., Knoxville, TN, (1986)
ANALYTICAL ERRORS FROM ELECTRONIC INSTABILITY
IN THE COUNTING CHAIN OF A WAVELENGTH-DISPERSIVE XRF SPECTROMETER
T. K. Smith and M. N. Ingham
British Geological Survey

London WC1X 8NG
United Kingdom
INTRODUCTION
Sporadic displacements of substantial magnitude were observed during

routine analysis in the concentration intercepts for some trace elements,
together with a similar change in the sensitivity (slope) for magnesium
when determined using a synthetic multilayer. These effects were traced
to the electronic circuit providing correction for pulse amplitude shift
with intensity.
The first manifestation of the fault appeared in the weekly check on

high purity calibration standards of Grade I magnesium oxide, calcium
carbonate, aluminium oxide, silica, ferric oxide, etc. Normally showing
little variation with time from close-to-zero concentration, they began to
display a trend of outliers for some trace elements of a value of about 10
mg/kg. Typical patterns are shown in Figs 1 and 2 and were similar for
either concentration or intensity on the y-axis.
Initial investigation showed that it appeared to affect only antimony

and tin, both of which used the scintillation counter exclusively. This
detector and its pre-amplifier were changed, but without improvement.
Suspicion then fell on the detector's high voltage supply but its
stability was good, as were those of the lower and upper level reference
voltages. The scintillation and flow counter amplifier cards were
interchanged without benefit. Later there was an extension of the fault
to silver, niobium and uranium and the magnitude of the error increased in
some cases to approximately 15 mg/kg.
It was thought that the digital circuit which replaced the sin (theta)
potentiometer fitted to earlier models might have been malfunctioning, or
that it was imprecisely defined because its steps for conversion were too
large and the settings irreproducible. Because of the sine function the
situation had always been more critical at low two-theta (higher
energies).
When a chromium anode tube was fitted in place of tungsten and an

attempt made to calibrate for major elements in silicate and carbonate

18.~-------------------------------------------'
7.
4.
1.
-2.~----r---~--~---r--~----r---~--'----r--~
428 462 496 538 564 598 632 . 666 788
X-axis: s.q. no. V-axis: r.1. di ff. fl"Olll ..... in % (IIIteolit,1
Fig.1 .. Example of sporadic variation in intensity of a channel
2.S~~---------------------------------------------------------------------~
'.
..
.. t.. ; .. .. .. +.
·-·-·-·-·-.-.-·-.-;-~.r·-·-·-·.!~-;·-'~·:·-·-·-·-:~·-·r·-.-;-:-.;:-,-;.-~_._._._._._._._._._,_._ .•. _._.
. .... . +... .
I.25&-
.... ..
. .. ..~... . , ........ ...
. .. +. : .... " .. " ".-+" .. - ..
.. : ..
"t.. .. .. " ..
.. .... .. .... " .... +•
:+. . :... : :..

...+.. . . .. . . " .+.. .
•' .. +• . ; +•
.. " .... ., +.
-1.25- .. .+
'-;-'-~-'_'_'_'-=.'_'_'_'_'_'_'_'_'_'_'_'.Jt_
+. . . ..•.. __: ._._._._._._._._._._._._._.""._.
...~. __.....
.";:"!_._._:""¥._.••
#
-2.5&+w----,---~~--_r----~--~----_r----._---.----_r--~
o 32 64 96 128 160 192 224 288

X-axis: s.q. no. V-axis: r.l. di ff. frOlll ..... in % (Ioteolityl
Fig. 2. Further example of sporadic variation in intenstity of a channel
rocks it was found that there was also a sporadic error of about 10%
relative in magnesium when determined using a PX1 multilayer. A pulse
distribution (Fig. 3) shows silicon fluorescence from the multilayer at
about 75% of the maximum energy of the window encroaching on the analyte
peak position at approximately 50%. Adjustment of the upper level to 60
or 65% reduced this effect but the sporadic errors continued.
PULSE SHIFT CORRECTION

In an automatic XRF spectrometer the pulse amplitude must be
automatically adjusted to pass through the energy window of the single
channel amplifier, whilst low energy noise and radiation from higher
orders of diffraction are stopped. This may be achieved by varying the
T. K. SMITH AND M. N. INGHAM 551
e.le9TTTTT--------------------------------------~~--~
kCPS
Maximum" 78.9:: R.solution" 33.5:: Qcalc= 33.6 QnoNI= 45.8 [)e.tKtor: FL

Inwsrat.d kCPS= 8.343 with LWI..: 25:: UPL: 75:: Thl./1>t.p" 3.88
Fig. 3. Pulse distribution showing silicon fluorescence

from PXl multilayer
high tension supply voltage to the detector, by adjustment of the upper

and lower levels of the window or, as in this instrument (Philips PW1404),
by varying the pulse amplification. In all cases account must be taken of
diffracting crystal, order of diffraction and two-theta angle.
At high countrates the energies of X-ray pulses as seen in the

detection chain are depressed and inaccuracies in analysis may occur. In
recent instruments correction is made for this problem e.g. by applying an
appropriate voltage to an amplifier through which the signal passes. The
magnitude of the compensation is determined by comparison of the
countrates passed by two equal windows situated symmetrically about the
energy midpoint (38-50 & 50-62%) immediately before the start of
measurement of each channel. However, where the countrate is low the
correction circuit must be switched out since a measurement cannot be made
with adequate statistical confidence.
It was discovered that the countrate was different dependent on
whether the corrector was switched in or out and that switching took place
at different intensities depending on whether it was increasing (about
4.4kcps) or decreasing (about 3.8kcps).
The fault manifested itself differently towards each end of the

energy spectrum covered by this instrument: over two orders of magnitude
separate them. At higher energies, where the energy profile exhibits
greater kurtosis, the tails of the distribution of the analyte are well
within a commonly chosen electronic window of 25-75% and only relatively
high countrates would have an effect if uncorrected. Similarly, higher
order reflections would have a narrow profile and their low-energy tails
would be unlikely to encroach except at high countrate. The situation
here would be satisfactory except for two reasons: firstly, that
inadequate design or component tolerance led to the count rate being
different depending on whether the corrector was switched in or out, and
with a close-to-zero analyte concentration and/or a gently sloping
background it was possible for the peak and background to be measured, one
wi th the corrector in, and one out. This was the case for low - level
determinations of antimony and tin using their Ka lines_ In addition, the
fault moved from element to element as countrates changed with tube
emission and detector response_ Secondly, the precision of description of
goniometer angle was inadequate (insufficient bits were allowed for in the
random access memory of the microprocessor). This had the effect of
"quantising" these low angles into large steps in an energy range where
the values were critical in determining the amount of correction to be
applied.
At low energies the energy profile is broader in relation to the
energy width of the window such that the tails may be close to the upper
and lower levels and correction lead to a different proportion being
counted. In the case of magnesium determined with a PX1 synthetic
multilayer there is a further complication in that silicon fluorescence
from the PX1, excited largely by calcium present in samples, is situated
just to the high -energy side of the magnesium peak in the energy
distribution. This necessitates ~etting of the upper level to a lower
value than normal (perhaps 60-65%) and the upper level is then on a
steeply sloping part of the distribution with a high derivative of
intensity with respect to energy leading to statistical unsoundness and,
if the correction circuit is faulty, a further change in intensity on
switching. If the upper level is set to 75% there will be sporadic
partial capture of silicon radiation as the countrate changes.
SOLUTION OF PROBLEM
Three modificatjons have been made to the design. Firstly, the

amplification circuitry for the detectors now includes a potentiometer to
allow it to be fine tuned to comp0nsate for variations in component values
so that countrates are the same in the switching zone whether the
corrector is in or out_ Secondly, greater precision is provided for in
the description of the goniometer angle_ Thirdly, the microprocessor
software disconnects the pulse shift correction circuit at all energies
below 1.4 keV i.e. below aluminium Ka and its possible higher energy
background. Hence the corrector is active for pentaerythritol when the
count rate is adequate.
The electronic fault has therefore been removed although an
applications problem remains with statistical uncertainty where the upper
level is on the steeply sloping side of an analyte energy peak, e.g. in the
case of magnesium with PX1.
ACKNOWLEDGEMENTS
The authors would like to thank A S Robertson for assistance with the
experimental work. This paper is published with the permission of the
Director, British Geological Survey (NERC).
CORRECTIONS FOR THE EFFECT OF SCATTERING ON XRF INTENSITY
J. E. Fernandez*, V. G. Molinari and M. Sumini
Laboratorio di Ingegneria Nucleare di Montecuccolino

Universita di Bologna
Via dei Colli 16, 40136 Bologna, Italy
ABSTRACT
Corrections for scattering on XRF intensity have commonly used integral

approaches and isotropic approximations, which give a limited knowledge on
this subject. An exact theoretical expression for XRF enhancement due to
coherent and incoherent scattering is presented in this paper. It has been
obtained as a solution of the Boltzmann transport equation for photons.
This equation describes the diffusion of photons in an infinite homogeneous
target. Both the excitation and the emission beams have been assumed to be
well collimated. The solution accounts for the mixed scattering and
photoelectric interactions. Complete kernels including atomic form factors
have been used for both types of scattering. An appropriate kernel has been
written for the photoelectric interaction. The correction is computed for
several pure elements and is compared with isotropic approximations.
INTRODUCTION
Coherent and incoherent scattering processes are commonly ignored in

XRF experiments. Keith and Loomisl estimated them to be within 2-5% of the
measured intensities. These authors discussed at length the importance of
considering second-order corrections and computed the corrected intensities
making some approximations. Their main approximation concerned the choosing
of special smooth angular functions for the scattering cross-sections which
allowed them to establish the corrections by recourse to an integral-like
theory. Such kind of formalism seems to be insufficient to guarantee the
correct description of problems like this, where there is a strong feedback
from one kind of interaction to the other.
* Member of CONICET, Argentina. On leave of absence from the Faculty of

Mathematics, Astronomy and Physics of the University of Cordoba, Argentina.

554 VIII. X-RAY SPECTROMETRY OAT A ANALYSIS
Equilibrium radiative-transfer techniques have been mainly used to

study particle transport, including photon transport· 2 ,3 They have been
applied recently4,S to study the XRF emission of a solid thick sample. This
approach uses Boltzmann's transport equation to describe the diffusion of
photons in an infinite-thickness homogeneous specimen. An exact solution4
of such an equation which is valid for all kinds of interactions has
recently been reported. This solution is particularly simple for a source
composed of a collimated and monochromatic x-ray beam. The capability of
computing separately every interaction, like coherent and incoherent
scattering, makes it particularly adequate to describe cross interaction
effects.
In this work we write the exact expressions for the corrective terms of
the XRF intensity due to enhancement by scattered radiation. We also show
how these expressions may be easily evaluated in the particular geometrical
case of normal incidence.
THEORY
We shall consider a semi-infinite and homogeneous medium of density p

which attenuates the incident radiation with a mass-attenuation coefficient
~. The monochromatic radiation source is plane and it is placed just in the
interface between' the two semi spaces. We are only interested in the inter-
acting photons in the lower semi space corresponding to the positive sign
of the z-axis. The photons going into the upper side can only be absorbed
in that portion of the space domain and can never return to the sample.
In standard notation (using ~ = w), the following balance equation

z
for a source of 10 photons per second results:
1)
af(Z,~,A)
8z ~
f(Z,W,A) + J
dA' J~ ~ ~
dw' k(W,A,W',A') 'U(z) f(z,~, ,A') +
4n
I o(z) O(~-~ ) O(A-A ) (1 )
o 0 0
where 'U(z) is the unitary-step Heaviside function. A7sketc~ of the geome-

trical arrangement is shown in Fig. 1. The flux f(Z,W,A) dw dA gives the
number of photons with wavelengths between A and A+dA, and with directions
b etween ~ ~ ~. . . .
wand w+dw, whlch cross a unlt area per unlt tlme. The wavelength A
is used in place of the energy E because it is convenient to our purpose of
maintaining close compatibility with the integral approach, but the use of
E should be entirely equivalent. The kernel k(~'A'~',A') gives the probabi-
lity of photon scattering into ~ and A from~' and A', per unit path
through the medium and per unit d~ and dA. It contains the sum of the indi-
vidual kernels of each one of the allowed processes with independent proba-
bility of occurrence.
A well known approach to solve the transport equation consists in deter-

mining separately the flux of the primaries and the once, twice, etc., scatter-
ed photons. In this way a Neumann-type series in powers of the kernel k is
obtained. Setting the flux f as
the Eq. (1) can be transformed into a set of non-coupled equations. The sum
J. E. FERNANDEZ ET AL. 555
of these equations for n = 0, 1, ... is identical with eq. (1). The solu-
tion of this set of transport equations gives us both the source-dependent
zeroth-order flux
I
o
(2)
and a generic nth-order flux (for positive z)
co
{ (l+sgn
2
1)
exp -TilT
(zll)
exp(W) J~A'Jd~' k(~,A,~',A') f(n-l)('t,~"A')
41£
co co
+ (l-~gn 1) Jd't exp(- 'til) JdA'Jd~' k( w,/\,w
~ ~ ~, ,/\~') f(n-l) ('t+z,w~'~')}
,/\ (3)
o TilT 0
41£
depending on the (n-1)th-order flux.
Since the intensity is the number of photons passing through a surface

element per unit time, it will be represented by the partial current of the
flux through the surface at z = 0 in the given direction, therefore by the
positive-defined quantity
I (4)
"1 = cos1}
"1o=cos*o
z
Fig. 1: Irradiation arrangement of a homogeneous specimen of infinite
thickness under the excitation of a plane monochromatic X-ray
source, represented with the photon-transport equation (1).
Eq. (4) shows that a second-order intensity is related to a second-

order flux, which in turn may be deduced from Eqs. (2) and (3) for some
generic chain of interactions a and b,
00 00
I~) (~,A) = (l-~gn '1)) I~T exp(-~) I~A'Id~' kb(~'A'~' ,A') ~ x
4n:
{( l+S g n n')
'f
Til' IT
exp(- ~)
T'II'
dT'exp( ~) g
(0) -7
(T' w' A') +
2 0 a TJi'T
" TJi'T
2
n n')
+ (1 -Sg'f IOO
dT'exp(-
0 WI
T' II'
~) g ( 0) (T'+Z W'
a
-,
A') }
"
(5)
where
00
-7, A')
ga(0) ( z,w, = IdA"Id~" ka (~, ' A' , ~" , A") flO) (z,~" ,A")
o 4n:
(l+sgn '1)0)
(6)
2
To obtain Eq. (5), the total kernel has been split into the terms cor-
responding to every process of interest. A couple of them have been named
generically a and b. Eq. (6) is valid for positive z and depends directly
on the shape of the kernel for the interaction a. It includes all the in-
formation on the source.
Replacing (6) in (5) we get the second-order intensity for the thin-
beam model resulting from the chain of interactions (a,b)
(l-sgn '1)) (l+sgn '1)0 ) I 1
0
I~) (~,A) x
2 2 11)0 1 fl flo
+
11) 1 11)0 1
00
1
IdA' Id~' kb(~,A,~"A') k a (~',A',~,A)
0 0 TJi'T x
0 4n:
1
{
1
(l+sgn
2
1)' )
11 11'
+
(l-sgn
2
'1)' )
110 11'
} (7)
+ +
1'1)1 1'1)' 1 1'1)01 1'1)' 1
Eq. (7) is valid for every type of photon-atom interaction in
place of a and b. For the energy range we are considering in this work, the
possible interactions are the coherent and the incoherent scattering and
the photoelectric effect. The possible cross-interactions between them are
shown in Figure 2.
The single-process interaction kernels play a very important role in

the Eq. (7) because they give the probability by unit wavelength, by unit
solid angle, and by unit path of one independent process change of the phase-
space variables (~, ,A') to (~,A). Therefore they are directly related to
the differential cross section of such a process. In what follows we write
the interaction kernels for the processes considered in this work.
Photoelectric-effect kernel
The kernel for a single XRF characteristic line that is emitted as a

consequence of photoelectric absorption by a pure element of the incident
A'-wavelength photons is given by
1
[l-'I1(A'-A )] (8)
41l e
The isotropy~of the photoelectric effect is reflected by the kernel inde-

pendence of wand by the 41l factor in the denominator. QAi (A') is the XRF
emission probability (in cm- 1) of one line with wavelength A,. It is a
l
function of the incident wavelength A'. It is related to the photoelectric-

attenuation coefficient T (A') of the emitter element s, to the absorption-
s
edge jump J Ai , to the fluorescence yield wAi ' and to the line emission
probability fAi of A into its own spectral series, by the dependent proba-
bility relation
Q (A') = T (A')
A s
i
The line can only be emitted when A' is lower than the threshold wavelength
of the absorption edge (A ei ) of the series to which this line belongs.
A complete discrete spectrum of emission is given by a sum of terms

like the kernel, Eq.(8), everyone for a different line (having a different
emission probability) .
Coherent-scattering kernel
The coherent scattering is a process where the photons change momentum

but not energy, which is expressed by a wavelength-delta. This scattering
takes place with the more bound electrons of the atom,which behaves rigidly
during the hit. The atomic kernel (in cm- 1) is
~ Photoelectric
effect
Coherent
scattering
Incoherent
scattering
~ XRF intensity scat- Modification of the
Photo- Secondary tered from other symmetry of the XRF
electric
XRF intensity scatter centers line due to the lower
effect
towards the detector energy Compton emiss.
Coherent scatter-
Coherent
ing enhancement to
scattering
the XRF intensity
Second-order
Incoherent scat- scattering
Incoherent tering enhancement
scattering to the XRF inten-
sity
Fig. 2. Physical meaning of the chain of interactions (a,b) for the main
processes affecting soft X-rays. In this work we analyze the lower
two chains of the first column.
2)
2 -+ -+
-? -? (1 -+ -+ F (A' ,w·w' , Z)
kCOh(w,A,W',A') = ~ 8(A-A') + (w'w') (9)
Z
where ~ = pNZ~ /w and ~ = r 2 /2, with r the classical electron radius, N

e e a a
the Avogadro's number, Z the atomic number and W the atomic weight. The
kernel, Eq. (9), has a strong angular dependence given by the two last
multiplicative factors. The first one has a classical meaning and was
explained by Thompson. The last one is the atomic form factor which takes
into account the limited binding of the inner electrons. 6 ,7 Veigele 8 et al.
gave to this form factor the rather simple closed expression estimated with
the Thomas-Fermi model
F (u) 0.388 -3
---Z--- = exp(-1.49 u ) (1 + exp(-0.3)) + 3.27xl0
where
AC ( 1- ~.w'
-+ -+ ) 1/2
u = 2
A
This expression will be used in this work to simplify the computations.
Experimental data and refined theoretical computations for many electrons
are reported in a very profuse bibliography6.
A simplified expression may be obtained if the electrons are considered

fixed rigidly, i.e. having the mass of the atom. This gives the so-called
Thompson kernel
kTh «(;), A, (;), , A') = ~ 8 (A-A') (1 + (~'~') 2) (10)
which does not depend on the energy.
Incoherent scattering kernel
In the incoherent-scattering, energy as well as momentum is transferred.

This process takes place with the outer electrons of the atom. The kernel is
where
The ~KKN(A,A')factor denotes the Klein-Nishina differential cross

6
section ,7,g (in cm- 1 ); Ac is the Compton-wavelength. The direction-
wavelengt~ 1elta fixes the integration path in the phase-space along the
line 1 - w'w'+ (A'-A)/A = O. S is a form factor taking into account the
c
binding of the electrons in the atom. The atomic form factor for incoherent
scattering has been estimated by veigele 8 et al. with the Thomas-Fermi mo-
del
5(0\9) = 1 - exp(-4.88 0\90.856)
where
2
3
A slightly simplified expression of the kernel may be obtained if the elec-

tron is assumed free. This gives the crude Compton-effect kernel
k (c3,?,c3',?") 0' K (?,?')

.. .
W'w'+ ?'~c?) (12)
Compton KN
EXACT EXPRESSIONS FOR THE CHAIN INTERACTIONS
We are interested in the chains producing an enhancement to the pure

XRF emission from a thick sample. They are substantially two: either the
coherent or the incoherent scattering of the source-incident radiation may
be absorbed by photoelectric effect giving place to an additional XRF emis-
sion. In what follows we will analyze separately both types of scattering
enhancement because of their different wavelength-behavior.
Coherent scattering - photoelectric
The XRF intensity produced by enhancement of coherent scattering is

obtained replacing the kernels ka and kb by kCOh and kPh respectively in
Eq. (7).
<iQ?(?) [l-ti(? -?
(2 ) -7
(l-sgn 11) (l+sgn 110 ) I
0
(5 (?-?. )
1 i
o 0 e i »)
I co h -p h (w,?)
2 2 1110 I Il Ilo 4n
+
1111 1110 I
.. .. 2 2 ....
1 + (w' ·wo ) F (\,w' 'w o' Z)
Jdc3' x
4n I11' I Z
1
}
1
{ (l+sgn 11' )
2
Il Il'
+
(l-sgn 11' )
2
Ilo Il'
(13)
+ +
1111 111' I 1110 1 111' I
Incoherent scattering - photoelectric
The XRF intensity produced by enhancement of incoherent scattering is

obtained replacing the kernels k and kb by k. hand k h respectively in
Eq. (7). a ~nco p
(l-sgn 11) (1+sgn 110 ) I (5 (?-?. ) 0'

(2) -7 0 1
I.~nco h -ph (w,?) x
2 2 1110 1 Il Ilo 4n
+
1111 1110 I
x
1 1
->
a (1 - w"w 0+
->
\~CA') {
(1+sgn 1)' )
2
+
(l-sgn 1)' )
2
M M' Mo M' }
+ +
11) 1 11)' 1 11)0 1 11)' 1
(14 )
COMPUTATION OF THE CHAIN INTERACTIONS
In the p~rticular case of normal incidence of the source beam, we have

that 1)0 = 1, W"W o = 1)' and there is azimuthal symmetry. Then Eq. (13)
reduces to
0- QA (\) [1-'U(A -A )]
(l-sgn 1)) I a(A-A, ) o e,
0 1 i
1(2) (i3,A)
coh-ph
1) ~l 2 M 2
0
+ Mo
11) 1
+ (1)' ) 2 F2 (A ,1)', Z) 1 F2 (\,-1)' ,Z) 1
{ }
1 1
0
Jd1)' + (15)
1)' Z M Mo Z Mo
+ Mo +
11) 1 1)' 1)'
and Eq. (14) reduces to
(l-sgn 1)) I a (A-A,) (J'
-7
I,(2) h h (W,A) I 0 1
x
lnco -p 1) ~1
2 2
0
/-I
+ Mo
11) 1
KKN(i\',\) QA(A') [1-'U(i\'-i\e)]
i
[1 +
A - i\'
~
1--- + M'M
C 11) 1
A +2i\ K (A',A) Q~(A') [1-'U(i\'-A )]

o C KN 0 1\ e
J di\'
i
(16)
A +A
o C
The integrals in Eqs. (15) and (16) must be numerically evaluated, be-
cause the total cross sections are better known experimentally as a func-
tion of energy and the form factors are not easily integrable functions.
Since the factor (J' in these equations is not the scattering cross section
taking part of the total cross section, these expressions must be fully
evaluated in order to be compared with the secondary-XRF intensity.
EqS. (15) and (16) have been studied for some pure elements of low and
medium Z. A Romberg quadrature algorithm generalized to improper
integrals 10 has been used in the computations. The integrals have been
evaluated with a precision of four figures.
As follows from Eqs. (15) and (16), the cross-term intensities depend
on the incident radiation wavelength, the atomic number of the irradiated
element and the take-off direction. Because of the azimuthal symmetry, the
intensity is the same along all the directions in the cone of aperture-
cosine 1/' .
The first thing to point out for low energy x-rays is that the
coherent-scattering correction decisively has a greater importance than the
incoherent one. Beyond 100 KeV the incoherent cross-section grows and
overcomes the coherent 9ne, but since the photoelectric probability for
these energies falls rapidly, we cannot wait for an increase in the
importance of the XRF intensity due to incoherent enhancement.
The behavior of each type of second-order intensity as a function of

the energy is shown in Figs. 3 and 4, respectively, for three different pure
samples observed with the same take-off angle. The absorption-edge energy
of every element marks the start point of the XRF-emission in the corres-
pondent graph. The coherent intensities have a short rise giving peaks
which spread out and grow in height with increasing Z. Every incoherent
enhancement also shows a maximum. In these cases the peak widths are
greater and are of lower heights than the coherent ones.
The enhancements to the XRF-intensity by both types of scattering are

shown in Fig. 5 in units of the primary-XRF of the observed line. A peak
appears for coherent enhancement whose maximum gives the energy of maximum
interference (see Fig. 5 a). The incoherent enhancement relative to the
primary-XRF has a monotonic growth as shown in Fig. 5 b. The total
scattering enhancement in units of the primary XRF is shown for an energy
range from 0 to 500 KeV in Fig. 5 c. The peak below 100 KeV represents the
contribution of the coherent scattering. In practice, this is the real
contribution because the XRF intensity is detectable for that energy range.
The incoherent-enhancement-to-primary-XRF ratio for higher energies may
overcome the 5%, but the photoelectric probability at these energies is
negligible.
Fig. 6 shows polar graphs describing the geometrical behavior of both

intensities for a fixed energy. Both graphs show a slight anisotropy toward
higher take-off angles. However these plots give us little information if
they are not compared with the primary XRF emission of the K line whose
enhancement we are studying.
The relative polar plots of Figs. 7 give at once a measure of the

importance of the correction and a direct comparison with an isotropic
process. The coherent correction seems to be almost an order of magnitude
more important than the incoherent one, and may be estimated to within about
1%. According to Fig. 7 a, the coherent correction shows a marked
anisotropy which reaches its maximum in the backscatter direction. The
incoherent correction shows an almost isotropic behavior for that energy.
CONCLUSIONS
The corrective terms to the XRF intensity due to both coherent and
incoherent scattering have been deduced using the photon-transport theory.
Complete kernels including atomic form factors have been used to obtain the
,~
i \
c \
\"----.
~ i
c
I
~
1:.
o
u
o I (a)
I
~
J II
U
r..
"-
x I ,
ENERGY [KeUI
10 -5 ~
~
\
(?
C
~
u
JIF \
1
~ \
.j
c
~ 1
2 1 (b)
J \ '\
1:.
o
U E
\
\
I
~
J
1J
r..
"x ~~
r , ,
r\
ENERG'! [KeUI
\
\
\
\
\
\
~
~
(c)
J
1J
r..
"x
, J
ENEDGY [KeUI
Fig. 3. Intensity correction due to coherent scattering as a function of

the energy for the same take-off angle and for different elements:
(al Si , (bl Ni, (cl Zr. Both the width and the height grow with Z,
hence the second-order intensity increases for every incident ener-
gy greater than the threshold.
1 ~,
(
I \.\\
I
I (a)
\
\
\
\
c \
•
l
I \.\
'"'-"~"
~
.c
~I
8c
,I
~
J
1)
1-______....
L
C!
X
ENEQG'/ (KeUJ
"
c". I
I ""~'-
~
I
I '~
'-,
/
~
c
• I (b)
I I
l
~
.c
I
Q 2
u
C I
/
I
~
1)
L
C!
X 0
I(
f- , ,
/--------~ ~
///
/
I
I
I
c
•
l
I /
~ I
.c I
Q
U I
C I
I
/ (c)
I
!
Q I
ENEQGY (KeUl
Fig. 4. Like Fig. 3. but due to incoherent scattering. The smooth growth
starting at the absorption edge energy is due to the partial con-
tribution of the wavelength-integrals of Eq. (16), for increasing
energy.
1 .---.
/ ~,
/
"-
"-
(
(a)
~""- , ..... ....
~-'-,.
0
I I
/
/
t-
a
x
t /
\
t-
o 2
(b)
/
/
X
I
1:
o
U
c
1
//
/'
J ~
------/
I ,
./
ENEQG'/ [K.UJ
L
a
x
;
./
/1
(c)
I //
I
\
t-
o E
",
3"
"
C'
C E /
/
c
~ //
",; 2
//
u
"'
-
I
1
/./
o / i--
I!
I--
0
I
ENERG'/ [KeUJ
Fig. 5. Second-order intensities are plotted in units of the primarv-XRF

intensity that they correct. The zero-level to the left of the
absorption edge energy has no meaning. (a) The peak for the cohe-
rent contribution marks the energy zone where the enhancement is
greater. (b) The incoherent grows monotonically for the higher
energies where the photoelectric absorption probability is very
low. (c) The total scattering enhancement below 500 KeV. The cohe-
rent correction is stronger for soft X-rays.
JQ
-,
II
l--- ~~~j,J, f ~-- --~
~ //
//. "
j/ '-" 1
" I
L " \ rI
1 \
I a) \\ til
\1
\ JI
\I
1I! .1
i
r ~
~
1
~ (b)
\ \, !
/ ~\ /1
\ /
// II
\ I
'\
f'" //
/ !
'""- , '-,
I
r-...... V ',,- -------/

0
1."'·1 ........ . 'I"" ", .... " .... 1, .. ,.. ,.. .. .....
", . 1........ ,1 ....
-I -J -2 I -I
10-1
X!lf tIJQ to (oherenl se'llering (PO[!tQ) xor dug to incoherent ml!ering (POLAR)
1. S"~PL£' IHCIDDiCE:H(1;~tt., E:iO.a K~U I. SAMPLE. IHClDENCE:NDRIIAL, (:40.0 KeU
Fig. 6. This polar graphs show the geometrical behavior of both the cohe-
rent (a) and the incoherent (b) corrections for a fixed energy.
Given the azimuthal symmetry, the full geometrical behavior can be
obtained as a revolution solid about the incidence direction axis.
// - --I----
--
'-"- 10 -of
/' "
---- - -".--.
/
/ '\,
/' \\, ,./-- -~
~
..
I
"
I ",
/' ",
! \
\ , ;/,.
"
"
(a)
I / \
/
I ~
\. I
\ !
/ (b)
\,\\
'-, //
0
'-, ~/ -- - - ---i
-------- \0 -4
Coh-XRF tXRF (POLAQ) Inc"h-tPr,xp, (:lOLAC!
2P SiitlPLE. INCiOENCE=NOQtlAL, 1:='10.0 K.. V
20 SAMPLE. INCIO(NCE:NOQHAL. (:40.0 KeU
Fig. 7. Polar graphs for both the coherent (a) and the incoherent (b) cor-
rections measured in units of the primary-XRF. The graphs show the
importance of the corrections as functions of the take-off angle.
They measure the differences with an isotropic process (like the
photoelectric one) also. The coherent enhancement is anisotropic.
The incoherent is almost isotropic.
intensity enhancement formulas of Eqs. (13) and (14). For the particular
case of normal incidence we have obtained the simpler expressions given by
Eqs. (15) and (16). These have been evaluated for some pure samples of low
and medium atomic number as functions of the incident energy and the
take-off angle.
Coherent enhancement seems to be the more important correction for

energies below 100 KeV where XRF-emission is highly detectable. Its
importance amounts to about 1% of the primary-XRF, depending on the take-off
angle and the element. The incoherent correction becomes very important for
higher energies where the photoelectric probability of interaction is
negligible.
However, in the studied geometry, the coherent correction shows a

marked anisotropic behavior with a maximum in the backscatter direction.
The incoherent enhancement, on the contrary, is almost isotropic.
A future step to continue the study of these corrections should

include the analysis of their influence for composite materials.
Computation of the general expressions may also give valuable information
for geometries where higher anisotropic effects are foreseen.
ACKNOWLEDGEMENTS
One of us, J.E.F., would like to express his gratitude to the Argenti-
nean Scientific Research Council (Consejo Nacional de Investigaciones Cien-
tificas y Tecnicas de la Republica Argentina) which supports him with a
postdoctoral fellowship at the University of Bologna.
REFERENCES
1. H.D. Keith and T.C. Loomis, X-Ray Spectrom. 7:225 (1978).

2. U. Fano, L.V. Spencer and M.J. Berger, Penetration and Diffusion of
X-Rays, in: "Handbuch der Physik" vol XXXVIII/2, S. Flugge, ed., Sprin-
ger, Berlin (1960), and references therein.
3. G.C. Pomraning, "The equations of radiation hydrodynamics", Pergamon
Press, Oxford (1973).
4. J.E. Fernandez, V.G. Molinari and M. Sumini, Nucl. Instr. and Meth. in
Phys. Res. A (1989), to appear.
5. J.E. Fernandez, submitted.
6. J.H. Hubbell, W.J. Veigele, E.A. Briggs, R.T. Brown, D.T. Cromer and
R.J. Howerton, ~ Phys. Chern. Ref. Data 4:471 (1975).
7. J.H. Hubbell, W.H. McMaster, N. Kerr del Grande and J.H. Mallett, X-Ray
cross sections and attenuation coefficients, in: "International Tables
for X-Ray Crystallography" Vol 4, J.A. Ibers and W.C. Hamilton, ed.,
Kynoch Press, Birmingham (1974).
8. W.J. Veigele, P.T. Tracy and E.M. Henry, Am. ~ Phys. 34:1116 (1966).
9. R.D. Evans, The Compton Effect, in: "Handbuch der Physik" Vol XXXIV, S.
Flugge, ed., Springer, Berlin (1958).
10. W.H. Press, B.P. Flannery, S.A. Teukolsky and W.T. Vetterling, "Numeri-
cal Recipes. The Art of Scientific Computing", Cambridge University
Press, Cambridge (1986).
XRFPC: A PROGRAM AND DATA BASE FOR XRF COMPUTATIONS
J. E. Fernandez*

INTRODUCTION
XRF intensity computations, for polychromatic x-ray sources and

multicomponent samples, need a high number of low speed floating-point
operations, making them a hard bone for any computer. The evaluations of
the intensity expression require the computation of complex attenuation
coefficients. They involve also a spread quantity of atomic data for a high
number of elements. And the users need to insert additional information on
the experiment, like the excitation-detection geometry or the x-ray tube
spectrum, interactively. Personal computers are an optimum target for this
kind of application mainly due to the low cost of the computation time and
the possibility to display high - resolution graphics. Moreover the
increasing power of microprocessors makes it possible to attack hard
computations like this on a PC.
XRFPC is a program for XRF computations developed for the IBM PC

family of microcomputers. It handles any chosen multicomponent sample with
10 elements or less. It allows the use of either published x-ray tube
spectra or experimental ones, because it maintains them in separated data
bases. It has data bases for the atomic parameters and for the attenuation
coefficients, by element, which may be modified easily to include the last
update of your datum. XRFPC may show the table of currently used atomic
parameters, for each element, or it may calculate the total attenuation
coefficient for a complex sample, showing the results as a table, or as a
graph. It may calculate primary- and secondary-XRF single-line intensities,
for monochromatic or polychromatic excitation, tabulating separately the
intensity enhancement due to every single line emitted by the matrix. Total
intensity for polychromatic excitation may be tabulated or plotted, either
for a uniform-height spectrum, to evidence the XRF internal characteristics,
or for the chosen x-ray tube spectrum.


Edited bv C.S. Barrett et 0/.
PARAMETER'S DATA BASE
XRFPC uses five files to compose its internal data base. Four of them
are ASCII files which can be edited and modified easily with a text editor.
PARAM contains the atomic number, the chemical symbol, the atomic
weight, the density and the conversion constant from
barns/atom to cm 2/g.
MCMASTER contains the McMaster l et al. coefficients for the photo-
electric series K, Land M, and for coherent and incoherent
scattering.
EDGES contains the absorption-edge related information as spectral
symbol, absorption-edge energy, absorption-edge jump, and
fluorescence yield. 2 ,3,4
LINES contains data on every single emission line as the s~ectral
series to which it belongs, its spectroscopic symbol, its
energy, its line fraction. 6 ,7,8
These files are read in during the initialization.
The fifth one is the file with the spectra. Since each spectrum
contains a high number of data points the original ASCII file needs to be
preprocessed by a program that transforms it to floating-point internal
format. XRFPC reads in the transformed file interactively.
PROGRAM ORGANIZATION
XRFPC is fully interactive. At the initial stage it displays a

Lotus-like menu with the program options. Two of them are devoted to the
parameter's data bases. The computational sections are divided into mass-
absorption coefficients computations and XRF intensity computations. Every
option has access to the full data-entry interface, asking for the
excitation-detection geometry, the sample composition, the x-ray tube
spectrum, and the lines of interest over which the intensity should be
computed. There is a logic to save data input. The excitation spectrum may
be changed without changing the geometry or the sample. However if the
sample composition is changed, the lines previously chosen will be forgotten.
Data Base Query
The query of the data base is very simple. There is not a utility
built into the program to change the data. The only allowed operation is
the reading of the data base, the parameters by atomic number (see Fig. 1),
and the spectra by classification number. At the end of a spectrum reading,
a plot of the spectrum is shown on the screen (see Fig. 2).
Computation of Mass-Attenuation Coefficients
Mass-attenuation coefficients may be computed for any mUlticomponent

mixture of elements in the data base. A grid of energies like that of
McMaster l et al. is generated. Two energy points per absorption edge, one
on each side of the edge, are interpolated into the grid vector, giving the
complete grid. Photoelectric effect, coherent scattering, incoherent
scattering and total mass-absorption coefficients are computed with five
figures and are tabulated on the screen for every energy in the grid.
Stops at full screens are inserted to permit hard copy. At the end of the
grid, a log-log plot of the total mass-attenuation of the sample is shown
J. E. FERNANDEZ 569
~ Z 19 h 91. 2200 DDlSI'IY 6.5300 CIE 1S1.~ PIIOTOX '.

a 12.75300
EDGE _ JU/'f OMEGA ElKeVI ~ LINE rAACC~ 1 8.697i1
L.JII 3.9766 9.Ee'J5 2.2236 Z -8.7~31
1.7'JZG ZR LL 9.9367 3 (UE645
2.9399 ZRLU 9.9960 PHO'IU L
2.&123 ~La:1 9.8193 9 15.29(66
L II 1.4100 9.~,}'1 2.3G7e 1 -2.38793
2.1244 ZR L111 a.9534 t -8.0'.1123
LI 1.1600 9.003'3 Z.S32G :-::-PHO'IU t1
x 6.7500 8.7300 17.9900 9 13.45000
15.6999 ZR KI[2 9.2924 1 -2.5~91
15.7751 ZRXd a.SS95 COHERENT
17.6548 ZRK1\3 a.&l41 9 6.72275
17.6678 ZRXfl1 a.as59 ~ 8.323%
17.8156 ZRXfIS 9.fmI 2 -6.3591&
17 .9700 KfIZ 9.9175 3 8. 8181,}
• -: -fHCOHEREHT- ·
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1 1.15297
2 -6.20012
3 8.Eai95
atOMic nUMber Z (EliD=a, JI'IDEX=-ll ?
Fig. 1. A screen with the parameters for Zr as given by the data base query
utility. Parameters on the right are the McMaster coefficients.
,
.-~
! '; 1
\\
1
I 1
i
/ '\1 "1 I
i ,
\,
.~
I.~ I \
\
I
I
C .I
(J, \
\. I f\
\\ I!\
:I \
Jl
~ \ Ii
I' \,
a \ ,J
q
\
I
\ \
x Ii
\
--", Ii ,- ....
'\,
t
!
r ~
~-----"--.---,
....-.....
'-- I"--_~-
n! I
I I II I I Ii I I! I I I i I II I I
3 5
Kei th & Loomis CR 45 KU x-ray tubE spectrum
Fig. 2. A tube spectrum from the data base is plotted as a function of the
wavelength.
(see Fig. 3). After that, asking for single energies allows the user to
select his own energies of interest.
Computation of XRF Intensities
Primary- and secondary-XRF intensities may be computed for monochro-

matic and for polychromatic excitation. The incident and outgoing beams are
assumed well collimated, allowing the use of the thin-beam models. 9 ,lO,11
Secondary enhancement is computed for every line able to excite the
absorption edge of some of the interest lines. Primary-XRF intensity is
separately shown for each interest line together with the tabulation of
every single-secondary enhancement with'the corresponding line symbol. The
sum of the primaries and the sum of the secondaries are given. The total
sum is given at the end of the single-energy record.
As for the mass-absorption coefficients, if no spectrum has been

selected, computations are executed for the energies that the user inputs
under request. Selecting a polychromatic tube-spectrum forces the program
to display the above-mentioned records following the sequence of energies of
the spectrum. The information about the spectrum intensity is added to that
of the monochromatic records. At the end of the continuous spectrum, the
records for the characteristic lines of the tube are displayed. The screen
display of this mass of data is continuous, to avoid long stops. Hard copy
is accepted when the screen has been previously stopped. At the end of the
single-energy computations, a numerical quadrature is computed on the
continuous data to which the single-lines results are added. Pairs of
energies at both sides of the absorption edges of the excited sample are
inserted into the energy vector, and spectrum intensities are interpolated
10i~------------+-------------+--------------
103 I=------>,,--------+-------------+-------------~
2~--------~~~~------------_+--------------~
~ 10
C.
~
U
::l 10 I~------------~------~-------+--------------~
r::
I~~-------------r----------~~,-------------~
10 -II:---------+--------+---------'=--....:::::-----l
I 2 3
10 10 10
ENERGY [KeUl
Totdl mass-attenu.3tion coefficient
Fig. 3. The total-mass attenuation coefficient can be plotted for multicom-
ponent mixtures providing a valuable tool to analyze complex
absorption chains.
J. E. FERNANDEZ 571
10 -2 8 SAMPLE
7
r
/1 FE 0.500
HI 0.300
CR 0.200
II I
I
E
Ii 1= J
,/
I
I
J'
,"'
5 ,I II
I II
'ri
~
[
~ ,l
III
'["' II LIliES I)
I
E ,1 II FE Kotl Ii
L-
:: II II I
a
x
2
~ /
I
i I
I
I
1 ;:
§ I
! II I
nJF=
~/ II
~ I I II I i I' I I i I I I I
3
INTENSIT'r' V5 LAMBOn WNIFOQM SPECTRUm

PSI(ll = 45.00 PSI( 2) = '15.00 ALPHA = 0.00
/--, ,
II \ i\\
,
!•. '~
.l I! '\
\,
2r---~~----~r-+-------~---------+--------~
/
I
L-
I
I
a
x i
t !
~/
II
I II I II I I
INTENsm vs Lr1!1BOA (KEITH CR 45 f:U)

PSI(\) = 45.00 PS!(2) = 45.00 ALPHA = 0.00 INTEGRnL = 3.005EtOO
Fig. 4. The integrated emission spectrum gives the XRF-intensity when the
excitation is polychromatic. How may this spectrum be affected
by the shape of the x-ray tube continuous spectrum? How is this
spectrum modified by changes in the excitation-detection geometry,
or in the sample composition? Answering these questions is easy
with the graph interface built into the XRF-intensity computation
module. The plots show the same intensity emission spectrum
(a) without x-ray tube interference, and (b) modulated by the
x-ray tube intensity.
for them. Including these energies allows the integration of every

continuous piece to avoid errors introduced by the discontinuities of the
mass-absorption coefficients.
At the end of the polychromatic-intensity computation two plots are

shown on the screen (see Fig. 4). Both show the shape of the XRF-intensity
emission as a function of the energy. The first one assumes a unitary
spectrum, i.e. gives the XRF-emission shape, free of the spectrum-intensity
modulation. It is only influenced by the energy spread of the spectrum.
The second one gives the XRF-intensity modulated by the excitation
intensities.
CONCLUSIONS
A program has been presented to compute mass-absorption coefficients

and XRF-intensities for the thin-beam model and reflection geometry. The
graphics interface is suitable for interactive query. The parameters in the
data base may be modified easily with a text editor.
Future upgrades will include tertiary and higher-order XRF

enhancements and corrections by coherent and incoherent scattering. It is
planned to associate to every correction a flag which will enable setting on
or off each correction independently. Also dependence on the tilt of the
propagation plane 12 will be added to the computation routines.
ACKNOWLEDGEMENTS
I would like to express my gratitude to the Argentinean Scientific

Research Council (Consejo Nacional de Investigaciones Cientificas y Tecnicas
de la Republica Argentina) which supports me with a postdoctoral fellowship
at the Uni1ersity of Bologna.
REFERENCES
1. W. H. McMaster, N. Kerr del Grande, J. H. Mallett and J. Hubbell,

"Report UCRL 50174," Lawrence Radiation Laboratory, Livermore (1969)
Sec. 2, Rev. l.
2. W. Bambynek, B. Crasemann, R. W. Fink, H. U. Freund and M. Mark Rev.
Mod. Phys. 44:716 (1972).
3. M. O. Krause, J. Phys. Chern. Data 8:307 (1979).
4. A. Langemberg and J. Van Eck, J. Phys. B 12:1331 (1979).
5. J. A. Bearden, Rev. Mod. Phys. 39:78 (1969).
6. J. H. Scoffield, Phys. Rev. 179:9 (1969); A 9:104 (1974).
7. J. S. Hansen, H. U. Freund and R. W. Fink, Nuc1. Phys. A 142:213
(1977) .
8. Md.R. Khan and M. Karimi, X-Ray Spectrom. 9:32 (1980).
9. J. Sherman, J. Spectrochim. Acta 7:283 (1955).
10. T. Shiraiwa and N. Fujino, Japan. J. App1. Phys. 5:886 (1966).
11. J. E. Fernandez, submitted.
12. J. E. Fernandez and M. Rubio, submitted.
THEORETICAL ESTIMATION OF THE FOURTH-ORDER XRF INTENSITY
J. E. Fernandez* and V. G. Molinari

ABSTRACT
A theoretical expression for the fourth-order XRF-intensity has been

found using the transport theory. An exact solution of the Boltzmann
equation for the photon flux in a semi-infinite homogeneous medium has
been applied iteratively to find the intensity. XRF emission has been
isolated from the scattering processes by considering only the photo-
electric effect in the interaction kernel. The incident and emitted beams
have been assumed as well-collimated.
Fourth-order intensity computations for a mult1component material are

reported as an example. Results show that the fourth-order intensity
remains below a tenth of the tertiary and therefore may be neglected in
most cases.
INTRODUCTION
Equilibrium radiative transfer techniques have been largely used to

study particle transport, including photon transport. l ,2,3 They have
recently been applied4 to study the primary-, secondary-, and tertiary-XRF
emission of a solid thick sample. Such an approach uses the Boltzmann
transport equation to describe the diffusion of photons in an infinite-
thickness homogeneous specimen. An exact solution 3 of such equation that
is valid for all kinds of interactions has recently been reported. This
solution is particularly simple for a source composed of a collimated and
monochromatic x-ray beam. The capability of computing separately every
interaction order makes it particularly suitable for describing multiple-
interaction effects like high-order XRF fluorescence.
In this work we write the exact expression for the correction term of
the XRF-intensity of a single line due to the multiple enhancement of
three other lines in the sample. We also show how this expression may be
numerically evaluated.

Advances in X·Ray Analysis. Vol. 33 573

THEORY
We shall consider a semi-infinite and homogeneous medium of density p

which attenuates the incident radiation with a mass attenuation coefficient
M. The monochromatic radiation source is plane and it is placed just in the
interface between the two semi-spaces. We are only interested in the inte-
racting photons in the lower semi-space corresponding to the positive sign
of the z-axis. The photons going into the upper side can only be absorbed
in that portion of the space domain and can never return to the sample.
In standard notation (using ~ = w), the following balance equation

for a source of I photons per second iesults:
o
af(Z'~'A)
f(Z'~'A) JdA'Jd~' k(~'A'~"A')
. ~
~ az -M(A) + 'U(z) f(z,w' ,A') +

41l
I o(z) O(~-~ ) O(A-A ) (1 )

o 0 0
where 'U(z) is the unitary-step Heaviside function. A sketch of the geome-

trical arrangement is shown in Fig. 1 of Fernandez et al. S in this volume.
The flux f(Z'~'A) d~ dA gives the number of photons with wavelengths
between A and A+dA, and with directions between ~ and ~+d~, which cross a
unit area per unit time. Th~ wavelength A is used in place of the energy E
because is convenient for our purpose of maintaining close compatibility
with the inte~ral approach, but the use of E should be entirely equivalent.
The kernel k(W'A'~' ,A') gives the probability of photon scattering into ~
and A from~' and A', per unit path through the medium and per unit d~ and
dA. It contains the sum of the individual kernels of each one of the
allowed processes with independent probability of occurrence.
A well known approach to solve the transport equation consists in

determining separately the flux of the primaries and once, twice, etc.,
scattered photons. In this way a Neumann-type series in powers of the
kernel k is obtained. Setting the flux f as
f = f(O) + f(1) + f(2) + ...
the Eq. (1) can be transformed to a set of non-coupled equations. The sum
of these equations for n = 0, 1, ... is identical with eq. (1). The solu-
tion of this set of transport equations gives us both the source-dependent
zeroth-order flux
I
o
(1 + sgn ~ sgn z) (2)
and a generic nth-order flux (for positive z)
f(n) (z,~, A) = k x
00
{ (1+sgn
2 ~) exp (zM)
-~
Jdz1: exp (~
1:M) JdA'Jd~' k(~'A'~"A') f(n-l)(1:,~',A')
I~I 0 I~I
o 41l
+ (l-~gn ~) J~1: exp(- 1:M) J~A'Jd~' k( W,I\,W,I\

~ ~ ~, ~') ~, ~') }
f(n-l) (1:+z,W,1\ (3)
o TllT 0
41l
depending on the (n-1)th-order flux.
J. E. FERNANDEZ AND V. G. MOLINARI 575
Since the intensity is the number of photons passing through a surface

element per unit time, it will be represented by the partial current of the
flux through the surface at z = °
in the given direction, therefore by the
positive-defined quantity
I = 11)1 f(O,it,i\) (4)
Eq. (4) and (3) show that an(n)th-order intensity is related to an

(n-1)th-order flux, which in turn is obtained from the (n-2)th-order flux,
and so on. In this way Eqs. (2) and (3) are enough to compose any mUltiple
chain of interactions.
THE EXACT EXPRESSION FOR A CHAIN OF FOUR PHOTOELECTRIC INTERACTIONS
The kernel for a single XRF characteristic line which is emitted as a

consequence of photoelectric absorption by an element of the incident
i\'-wavelength photons is given by
[1-'I1(i\' -i\ )1 (5)

e
The isotropy~of the photoelectric effect is reflected by the kernel inde-

pendence on wand by the 4n factor in the denominator. Qi\i (i\') is the XRF
emission probability (in cm 2 ;g) of one line with wavelength i\,. It is a
l
function of the incident wavelength i\'. It is related to the photoelectric

attenuation coefficient T (i\') of the emitter element s, to the weight
s
fraction W of the element s in the sample, to the absorption-edge jump
Ji\i' to the fluorescence yield Wi\i' and to the line emission probability
fi\i of i\i into its own spectral series, by the dependent probability
relation
Q (i\') = W T (i\')
i\ s s
i
The line may only be emitted if i\' is lower than the threshold wavelength
of the absorption edge (Aei ) of the series to which this line belongs.
A complete discrete spectrum of emission is given by a sum of terms

like the kernel (5), everyone for a different line (having a different
emission probability). In what follows we will consider a composite kernel
having four lines able to interact among them. We denote the single-line
partial kernels with the subindexes i, j, k, and p. We assume that the
line wavelengths satisfy the following relation
i\ < i\ <i\<i\ <i\ < i\ < i\ < i\ < i\

o e p ek k e j e
p j i
which consent the multiple interaction.
Iterating Eq. (3) with the kernel k (it,i\,it',i\') on fro) (1,it,i\) , then
with k (it,i\,it',i\') on fIll (tit,i\), then w:th k (it,i\,it' ,i\') on f(2) (tit,i\) ,
k
(3) -7 -7 j .
and finally with k, (it,i\,it',i\') on f (r,w,i\), we obta~n the XRF-emission
l
of the line with wavelength i\ which is enhanced by the line i\" which is
J
enhanced by the line Ak , which is enhanced by the line A.

p
The resulting
expression converted to an intensity as indicated by Eq. (4) is
x
41£ 2 2 I1J1)O/ + 11 0 /1)/
QA (Ao) QA (A ) QA (\) QA (A,)

p k P j i J
O(A-A ) x
i
8
1 1 1
J ~J~J~x
a 1)' a 1)" a s
!:i(a,a ,a ,a' ,a")

a i
(a/ a) (a/ a o ) (a'+ a) (a'+ a o ) (a'+ ail (a"+ a) (a"+ a o) (a"+ ail (a"+ a')
(6)
where
a a a' a" a
a
1)' 1)" s
and the function !:i(a,a ,a ,a' ,a") is a non-reducible polynomial, positive

a i
definite, which does not admit any factorization in integer powers of its
variables. Factors have been searched with the symbolic algebra program
MACSYMA 6, without success. The full expression for the numerator !:i of the
multiple-integral integrand is given in the Appendix 1.
The angular projections denoted by 1) and 1) always appear in Eq. (6)

a
between modulus bars (except when there are explicit references to their
signs). Though they are measured about the positive-z axis, their
absolute values are as if they were measured about the negative-z axis. In
such case, the projections will coincide with the angular measurement mode
,. , 7
used by Sherman ln hlS classlcal work .
Though the transport equation (5) used in this work is one-dimen-

sional, it is clear that the full angular information has been kept in the
flux solutions, which has been transferred to the XRF intensity.
As is evident from Eq. (6), only the angular projections of the incident
and take-off directions on the z-axis explicitly appear there. This is due
to the azimuthal symmetry around z inherent to the model, which is preser-
ved by the isotropy of the photoelectric kernel. It makes indistinguishable
all the directions contained in the surface of a cone with constant aper-
ture.
COMPUTATION
The integrand in Eq. (6) is a definite positive function since the

integration variables are positive, as are the mass attenuation coeffi-
cients. To avoid copy errors, the function ~ was translated to a sequence

of FORTRAN-like statements using the same MACSYMA. Given the complexity of
this function, a simplest type of numerical integration was carried out.
Eq. (6) has been studied for some few mixtures with elements of low
and medium Z. A ten-point Gauss quadrature algorithm generalized to
multidimensional integrals B has been used in the computations.
As follows from its definition, the fourth-order intensity depends on

the incident radiation wavelength, on the sample composition, and on the
incident and the take-off directions. Fig. 1 shows comparative plots of
primary-, secondary-, tertiary-, and fourth-order XRF intensity for a
reduced group of emission lines as a function of the excitation energy and
for a given geometry. For these computations only the Kal lines of every
element in the multicomponent sample Zn(25 %)-Ni(25 %)-Fe(25 %)-CR(25 %)
have been considered. The interest line is the Cr Kal which can be
enhanced by the other lines. Computations over this and other multi-
component samples show that the fourth-order XRF intensity is always lower
than 10 % of the tertiary correction to the intensity of the same line. A
note of caution should be inserted here. The present computations are
related to the simple chain of enhancements
A -> Cr Ka: primary

a 1
A -> Fe Ka: -> Cr Ka: secondary
a 1 1
A -> Ni Ka: -> Fe Ka: -> Cr Ka: tertiary
a 1 1 1
A -> Zn Ka: -> Ni Ka: -> Fe Ka: -> Cr Ka: fourth-order
a 1 1 1 1
Other interactions among these lines have been ignored, such as the
following
A -> Ni Ka: -> Cr Ka: secondary

a 1 1
A -> Zn Ka: -> Cr Ka: secondary
a 1 1
A -> Zn Ka: -> Fe Ka: -> Cr Ka: tertiary
a 1 1 1
A -> Zn Ka: -> Ni Ka: -> Cr Ka: tertiary
a 1 1 1
Our main scope has been to compare the fourth-order with the lower orders,
without entering in details about the complexity of the emission for a
particular class of material. It is worth to be noted that in a real
mUlticomponent material, the possibilities of crossed interactions are
many, since the number of interacting lines is very high.
CONCLUSIONS
The corrective term to the XRF intensity due to the fourth-order
XRF-intensity has been deduced using photon transport theory. We have
obtained eq. (6) by using an isotropic scattering kernel to describe the
photoelectric interaction.
Eq. (6) has been evaluated for some mixtures of low and medium atomic
number as functions of the excitation energy for fixed incident and
takeoff angles. Only simple interaction chains have been studied. In
such cases the fourth-order term does not exceed 10 % of the tertiary
correction in the same chain.
-~
I
10 - ~
t- i
~
~
i\ I
i
I
Jo
~
.~
~
~
i
i,
J
I
I
3[
L~
[ I
IJ! i
C
~ \.\
II
E i
L
a
x
~
I-
!I
, I
I
I
I
I- \ I
t: \1
.:::
II (a) Ii
~
~
I
F 11
1
~ i"'.
-t1 -----------,--
C! I
U
I
I
I, I
~ i ',._-
f'-~. ''-,
I 1111 II I II I I I II I I i I I
Energy [1~eUl
CQ(O.25) mO.25) NIW.25) ZN(O.25) - INCIOENCE=,5.0 TMKE -orr=45. 0
10 -8 et.
~ ~-\
E 11 \ I
\
;,
II
E Ii'I
Jo 6
~
II
\\ , I
I!
.~
tJl
C "
il \
Gi
jl \ (b)
c \j
Ii ~'"
L
ii
a
x ~ i\
'I
'\'\,
\..,
I
~
11
2,;:
;:
IiII'I
Ii
I \,
\
,
~
!E~------tr--------r-------+----~~~----~
Qr~-------4------~~------+--------r------~
I Iii i 1 Iii I II I I I 1
Energy [I~eUl
CQ(O.25) mO.25) NHO.25) ZN(O, 25) - INCrDENCE=,5.0 TAKE -orr=45. 0

Fig. 1_ A graphical comparison of the different orders of enhancement for a
single chain of K~l lines. The sample is Zn(25 %)-Ni(25 %)-
Fe(25 %)-Cr(25 %) and the geometry is fixed. (a) All the orders are
plotted in the same graph to compare them. (b) The fourth order
is plotted separately.
A future step to continue the study of these corrections should include

the analysis of the global emission from composite materials. To this end
all the enhancement lines should be considered.
The transport-equation approach seems to be a useful tool for study-

ing x-ray interactions. It has also been applied in these proceedings to
study cross interactions effects, like those between photoelectric and
Compton and coherent scattering.
ACKNOWLEDGEMENTS
One of us, J.E.F., would like to express his gratitude to the Argenti-
nean Scientific Research Council (Consejo Nacional de Investigaciones Cien-
tificas y Tecnicas de la Republica Argentina) which supports him with a
postdoctoral fellowship at the University of Bologna.
REFERENCES
1. U. Fano, L.V. Spencer and M.J. Berger, Penetration and Diffusion of

X-Rays, in: "Handbuch der Physik" vol XXXVIII/2, S. Flugge, ed., Sprin-
ger, Berlin (1960), and references therein.
2. G.C. Pomraning, "The equations of radiation hydrodynamics", Pergamon
Press, Oxford (1973).
3. J.E. Fernandez, V.G. Molinari and M. Sumini, Nucl. Instr. and Meth. in
Phys. Res. A (1989), to appear.
4. J.E. Fernandez, submitted.
5. J.E. Fernandez, V.G. Molinari and M. Sumini, in this volume.
6. "The MACSYMA Reference Manual", (Version 14.2), Symbolics (1988).
7. J. Sherman, Spectrochim. Acta 7:283 (1955).
8. W.H. Press, B.P. Flannery, S.A. Teukolsky and W.T. Vetterling, "Numeri-
cal Recipes. The Art of Scientific Computing", Cambridge University
Press, Cambridge (1986).
APPENDIX 1
The complete expression for the positive definite polynomial §' in

the numerator of the multiple-integral integrand follows:
§'(a,aO,ai,a' ,a") = a" (a" «a' «8 ai + 4 ao + 4 a) a'
+ ai (8 ai + 10 aD + 10 a) + aD (4 aD + 6 a) + 2 a 2 )
+ ai «4 aD + 4 a) ai + aD (2 ao + 6 a) + 4 a 2 )
+ aD (2 a aD + 2 a 2 )) a" + a'
(a' «8 ai + 4 aD + 4 a) a' + ai (16 ai + 21 aD + 21 a)
+ aD (8 aD + 13 a) + 5 a 2) + ai
(ai (8 ai + 21 aD + 21 a) + aD (15 ao + 30 a) + 15 a 2 )
+ aD (aD (4 aD + 11 a) + 9 a 2 ) + 2 a 3 )
+ ai (ai «4 ao + 4 a) ai + ao (5 ao + 13 a) + 8 a 2 )
+ ao (ao (2 ao + 9 a) + 11 a 2 ) + 4 a 2 )
+ ao (ao (2 a ao + 4 a 2 ) + 2 a 3 »
+ a' (a' «ai (8 ai + 10 ao + 10 a) + ao (4 ao + 6 a)
+ 2 a 2 ) a' + ai (ai (8 ai + 20 ao + 20 a)
+ ao (15 ao + 28 a) + 13 a 2 ) + ao (ao (4 ao + 11 a) + 8 a 2 )
+ a3) + ai (ai «10 ao + 10 a) ai + ao (13 ao + 28 a)
+ 15 a 2 ) + ao (ao (5 ao + 21 a) + 21 a 2 ) + 5 a 3 )
+ ao (ao (5 a ao + 8 a 2 ) + 3 a 3 »
+ ai (ai «ao (2 ao + 6 a) + 4 a 2 ) ai
+ ao (ao (ao + 8 a) + 11 a 2 ) + 4 a 3 )
+ ao (ao (3 a ao + 8 a 2 ) + 5 a 3 » + ao 2 (2 a 2 ao + 2 a 3 »
+ a' (a' «ai «4 ao + 4 a) ai + ao (2 ao + 6 a) + 4 a 2 )
+ ao (2 a ao + 2 a 2 » a' + ai
(ai «4 ao + 4 a) ai + ao (6 ao + 12 a) + 6 a 2 )
+ ao (ao (2 ao + 9 a) + 9 a 2 ) + 2 a 3 )
+ ao (ao (2 a ao + 3 a 2 ) + a 3 »
+ ai (ai ( (ao (4 ao + 6 a) + 2 a 2 ) ai
+ ao (ao (2 ao + 9 a) + 9 a 2 ) + 2 a 3)
+ ao (ao (3 a ao + 6 a 2 ) + 3 a 3 » + ao 2 (a 2 ao + a 3 »
+ ai (ai (ao (2 a ao + 2 a 2 ) ai
+ ao (ao (a ao + 3 a 2 ) + 2 a 3 » + ao 2 (a 2 ao + a 3 » (A1)
where a, ao' a,1 , a' and an are defined in the main text.
TXRFSPECTROMETERFORTRACEELEMENTDETECTION
F. Hegediis and P. Winkler

Paul Scherrer Institute (pSI)
CH-5232 Villigen PSI, Switzerland
P. Wobrauschek and Christina Streli

Atominstitut der Oesterreichischen Universitaten
Schiittelstrasse 115, A-1020 Vienna, Austria
Introduction
A method to measure low level iodine concentrations by means of a Total Reflectance X-

Ray Spectrometer (TXRF) was presented at the 1986 and 1988 Denver X-Ray Conferences
(Ref. I and 2.). The optimum set-up of the spectrometer for this purpose was obtained by
using a Cu-anode tube. The collimated beam was two times totally reflected: first on the
mirror and then on the ;synsil sample substrate. By these means the undesired high energy
bremsstrahlung was almost eliminated. This operational mode is very convenient for iodine
measurement by L-lines. The detection limit of iodine was as low as 100 pg.
For simultaneous measurement of several elements (12<Z<83) it was necessary to change

the set-up of the spectrometer.
Set-up of the Spectrometer
A W-anode tube, operated with 55kV, was used as the primary source. Mainly the W-L rays
(8.4 - 9.9 keY) have induced K lines of elements with Z<28 and L lines of elements
with Z<65. The bremsstrahlung has induced K lines of elements with Z<58 and L lines
of elements with Z>65. By these means a wide range of elements (l2<Z<83) was
measurable.
Fig. 1 shows the set-up of the spectrometer. The finely collimated beam (0.05 mm) was
directed on the synsil sample substrate with an incident angle of 0.5 mrad.
w
ANODE
COLLIMATOR
CHAMBER
~
I
132 145 277 405 mm
FIG.!. Set-up of the TXRF Spectrometer.

582 IX. XRF INSTRUMENTATION
/+
to Co Zn
>-
Mn~
l- Ni
0.5
ca/+ ;:r-\
(J)
z / E. ~
w o Au
l-
Sc Gd 0
z S~ I~
>-
<t
a:
01
K
/
/
+ 0
I
Cs
0
Ba
Ce
Re Hg
I
><
0.05
X-R AYE N ERG Y [KeV]

FIG. 2. X-Ray Intensity vs. X-Ray Energy
Nomlali:z.1tion: Co X-Ka-Ray Intensity = 1
( + =Ka, 0 =La)
Calibration of the spectrometer
Several calibration solutions containing 7-8 elements with equal concentrations (1.0 or 10.0
ng/ul) were prepared. Each solution contained two internal standards: Co and Mo. The
measured K- and L-line intensities below 10.5 keY were normalized to the Co K- and above
10.5 keY to the Mo K-line intensities. Two internal standards, Co and Mo, were used
because it was observed that the relative intensity of the lower energy lines compared to the
higher energy lines can vary from one measurement to another. This effect could be due to
the variation of: the incidence angle, the roughness of the substrate and the thickness of the
sample. Fig. 2. and 3. show the measured K- and L-line intensities of 30 elements.
>-
f- Rb
Se
to 0
Sr
(J)
Z
W 0.5 In
f-
Z ~b
>- ~I
~
<I:
a:
I
ru
0.1
>(
I
x
Cs
,
10 20 30
X-R A Y ENE R G Y [ KeV ]
FIG. 3. X-Ka-Ray Intensity vs. X-Ray Energy

Normalization: Mo X-Ka-Ray Intensity = 1
F. HEGEDOS ET AL. 583
~ ~~~--~--~~---r--~~--~-----r----~~~
C
w
l-
S -5.0
o
1:
<I:
W
...J
OJ
<I: 2.0
0::
::J
Ul
<I:
W
1: to
1:
::J
1:
....
z 0.5 40
.... 20 60 80
I:
ATOMIC NUMBER
FIG. 4. Minimum Measurable Amount VS. Atomic Number
To define the minimum measurable amounts for this experiment two criteria are introduced.
The first is that the net Kil or La peak intensity is 20% of the total counts in the inverval of
the region of interest. The second criterion is that the number of counts is higher than 3000.
Fig. 4 shows the minimum measurable amount vs. atomic number. It is to see that with one
short measurement (typically 2-5 min.) a sample could be analysed for a wide range of
elements. However for certain elements, e.g. Z<20 or 2>80, the detection limit is high. To
lower the detection limit for these elements, the sample could be remeasured with another
spectrometer set-up.
The spectrometer was successfully used for trace element detection in various
environmental samples, e.g. aerosol and water.
References
1. Advances in X-Ray Analysis, Vol. 30. 85-88,1987
2. Advances in X-Ray Analysis, Vol. 32. 251-253, 1989

A COMPACT ON-LINE XRF ANALYZER FOR CHEMICAL
AND PETROCHEMICAL PROCESSES
D. J. Kalnicky
PGT/Outokumpu, Princeton, NJ
A. I. Ahonen*, M. J. Hietala, and K. J. Kauhanen

Outokumpu Oy, Espoo, Finland
INTRODUCTION
The need for process control has led to the development of

improved instrumentation for measuring chemical contents of
process streams. In many instances, on-line X-ray Fluorescence
(XRF) analysis represents a straightforward method to
accomplish these kinds of analyses. The sample preparation is
often easy compared to many other methods and the XRF analyzer
can be calibrated with process stream or artificial standards.
Results are obtained in a time frame suitable for closed-loop
control strategies. The Courier 10 is a new, compact on-line
XRF analyzer which has been developed for chemical and
petrochemical process applications such as sulfur and/or lead
in gasoline; calcium in polymers; and chrome, iron ,nickel in
metal treatment baths.
ANALYZER COMPONENTS
The on-line analyzer described in this paper is called the

Courier 10; it is based on radioisotope excitation of the
process sample and detection of characteristic x-rays with a
proportional counter. The predecessor of this analyzer is
described in Reference 1. The analyzer is comprised of two
parts: the measurement head and the electronics unit (Figure
1) •
The radioisotope source, proportional counter detector, HV unit

for the detector, and preamplifier are mounted on a block
within the measurement head. This block moves the detector
between two fixed positions; one the actual sample measuring
position, and the other a reference - sample/ radiation- safety
position. In the event of any malfunction or opening of the
sample cell, the detector and source immediately move to the
*Present address: Teknillinen Korkeakoulu,

Kylmalaboratorio, Espoo, Finland

Electronics Unit
o 0
o 0
Printer o 0
Measurement
Head
¢
II
..
User
Terminal
I
II
Figure 1: Main Components of the Courier 10.
safety position. This ensures that the user is protected from

radiation exposure and that the source is not in contact with
sample if the flow cell window should rupture. Other major
parts in the measurement head are the positioning mechanism,
the sample cell window leakage detector, and the sample cell
itself.
The electronics unit contains the microprocessor for data

reduction and system control, multichannel analyzer, serial I/O
interfaces, indicator- lamp display panels, 4-20 rnA current
outputs, and interface for communication with the measurement
head.
Spectrum-gain stability, source-decay corrections, and other

efficiency effects are controlled by measurement of the
reference sample in the safety position between actual process
sample measurements.
MEASUREMENT OPTIMIZATION
Measurement Head: X-ray measurements with the Courier 10 may

be optimized depending on the requirements of the application.
The radioisotope sources normally used are: Fe55, Cd10 9,
Arn241, and Cm244; these afford excitation over a wide range of
X-ray energies. The detector efficiency can be optimized for
specific elements by proper selection of proportional-counter
gas mixture and pressure. In some cases a source filter may
also be used to enhance excitation efficiency for specific
elements. These parameters are chosen according to which
elements are to be measured with good accuracy and which others
should be suppressed.
The main parameter selection is based on whether light or

heavy element X-rays are to be measured. Light element X-rays
are excited with FeSS, heavy elements with Cd109, Arn241, or
Cm244. The light element FeSS source is of annular
construction which facilitates very compact and efficient
measurement geometry. Heavy element sources are of button
construction; measurement geometry is different than that for
light elements.
D. J. KALNICKY ET AL. 587
Elements of lower atomic number than Argon generally need very

thin sample cell and detector windows to minimize absorption
losses. Compact measurement geometry is also required because
air is a significant absorber for these X-ray energies.
Furthermore, the actual X-ray measurement will take place in a
very thin layer immediately behind the sample cell window and
this sets tight limits for window contamination and wear
control. In practice, phosphorus(P) is the lightest element
that can be reliably measured for control purposes. In some
cases some information can be obtained down to aluminum but the
windows tend to be too thin and fragile for practical on-line
use and there are too many sources of instability. Elements
lighter than phosphorus need either laboratory type analyzers
or other analytical techniques.
On-line XRF analyzers need very little if any sample

preparation compared to many other techniques. Of prime
importance when dealing with liquid, slurry, or solid samples
is that the surface at the cell window represents the whole
sample stream. Also, sample cell window wear and contamination
must be checked and controlled according to the requirements of
the application.
The Courier 10 sample cell actually has two windows, the

primary one for separating the sample from the analyzer and the
second for safety purposes to allow the leakage detector to
trigger closing of the sample line and emptying the sample cell
before leakage to the interior of the measurement head occurs.
There are two different leakage detection principles in use:
1) light reflection between the two sample cell windows; if the
space between windows is filled with sample, an alarm is
triggered and 2) collection of leaking sample in a recess where
a dipstick type light detector triggers the alarm when the
sample material blocks the light path.
Electronics Unit: The electronics unit contains a 256 channel

multichannel analyzer, microprocessor and memory unit,
necessary communications interfaces, and, if needed, a D/A
converter to present results in analog form (4 - 20 rnA current
signal); 256 channels are sufficient to separate neighboring
X-ray lines within the resolution of the detector, typically
13-14% at 5.9 KeV. More important than the number of channels
is the stability of the multichannel analyzer and detector
after elemental measurement channel limits have been defined in
the X-ray spectrum.
The microprocessor software controls the tasks of the analyzer

and allows up to 4 sample streams to be measured according to
a user-defined sequence. Multichannel-analyzer operations and
data reduction to convert measured spectral intensities into
final concentrations for process control are handled by this
software. The programs also monitor analyzer status to check
for proper operation and to trigger alarms for fault
situations.
Communication to/from the analyzer is accomplished through

either an RS232 or RS422 serial I/O format. Any ASCII terminal
with a printer or display is sufficient to operate/setup the
analyzer and get reports in a fixed format. An interface to a

PC is used for more flexible reporting and data reduction.
A very useful feature for process control purposes is the

analog signal output in 4-20 rnA format which is controlled by
the built-in analyzer software. Up to 8 different calculated
assays may be defined by the user and displayed separately;
these can be selected from any analysis for any stream. The
output holds the last value until a new one is ready; in case
of a failure in the analyzer, the output drops to zero.
Both the measurement head and electronics unit can be made

explosion proof for dealing with hazardous materials.
APPLICATION EXAMPLES
Several application examples will be discussed below to
illustrate the excellent performance of the Courier 10 for a
variety of sample types.
Sulfur in Gasoline: Figure 2 shows a plot of estimated vs.

assay values for sulfur - in - gasoline measurements using an
explosion-proof Courier 10 analyzer. These were made for 300
seconds with a 20 mCi Fe55 source using a light-element flow
cell and proprietary cell window. Regression of sulfur
concentration vs. X-ray counts yielded excellent results. The
correlation coefficient (R) was 0.997 with standard error of
fit(S) of 23 ppm. The statistical analysis uncertainty (one-
sigma) was 15 to 18 ppm for the 98-900 ppm concentration range
indicating that about 2/3 of overall error was due to counting
Cal ib,ation Resu Its

1 1
ppm S
o 9
0.8
o 7
~n
'"'19
t? c: o 6
'"
.-t;~
wg 0.5 0
Of-
'-v
U
o 4 0
0.3
0.2
0
o 1
0
0
0 o 2 o 4 o6 o 8
CThousands)
Assay Value
Figure 2: Sulfur in Gasoline with Courier 10
Ca I i brat ion Resu Its

260
240 Mg/L Pb
220
200
180
160
...~
f 140
...
Ul
w 120
...0
u 100
80
60
40
20
0
0 40 80 120 160 200 240
Assay Value
Figure 3: Lead in Gasoline with Courier 10
statistics. The 3-sigma minimum detection limit (MDL) was 50

ppm; a 40 mCi Fe55 source would yield a 36 ppm MDL. These
excellent results demonstrate the Courier 10's capability for
control of critical sulfur levels in on-line gasoline blending
applications.
Lead in Gasoline: Figure 3 shows lead in gasoline measurements

using a Courier 10 equipped with a heavy element head. Data
were collected for 300 seconds with a 2 mCi Cdl09 source for
samples containing 0-208 mg/liter lead. Excellent calibration
results were obtained: R = 0.9999 and S = 1.6 mg/liter. A
measurement channel was defined for Pb+Br since gasolines
contain bromine as well as lead; this overlap correction was
not needed in the final model because the Pb/Br ratio was
constant for these samples. The MDL was 2.6 mg/liter and
statistical error 1.5 mg/liter; the latter accounting for
almost all the fitting error. This demonstrates the Courier
10's suitability for controlling lead content in lead free gas
blending operations.
Calcium in Ca-Stearate Treated Polyolefins: Figure 4 shows
calibration results for ppm levels of calcium in Ca-stearate
treated polymer pellets. These pellets were approximately 5mm
x 2mm x 3mm (length, width, height) and were measured for 600
seconds with a 20 mCi Fe55 light-element Courier 10. They were
poured into a slurry cell and measured 'as is' without any
preparation. Replicate measurements in which the first sample
was emptied and a fresh sample poured showed reproducibility
within counting statistics indicating that packing density
Calib,ation Results
160
150
ppm Ca
140
130
...al 120
~
...
Ul
w 110
0
..-
u
100
90
80
70
70 90 110 130 150
Assay Value
Figure 4: Calcium in Polymer Pellets with Courier 10
Ca lib, a t ion Res u Its
o 9 ~NI
0.8
o 7
o
...al 0.6
o
~
... 0.5
8l
o
..-
0
u
o 4
o 3
0 2
o 1
0
0 o 2 o 4 o 6 o 8
Assay Value
Figure 5: Ni in Metal Treatment Bath with Courier 10
effects were negligible. Regression results gave R = 0.9966

and S = 2 ppm for Ca from 87 - 139 ppm. The final model
included a background correction term dependent on source
backscatter (BS) which gave a factor-of-two improvement in the
standard error compared to a fit with no correction. The
statistical uncertainty of 1.3 ppm was the major source of
error, NOT instrument stability or sample packing effects.
This study showed the Courier 10's ability to analyze irregular
shaped materials with minimal sample preparation/handling.
Cr, Fe, Ni in Metal Treatment Baths: Figure 5 shows results

for the analysis of Ni in Sulfuric- and Nitric/HF-based metal
treatment baths; separate calibration models were not required.
This means that a single model for each element is sufficient
to control compositions in both bath types which simplifies
operations for analysis/process control. Calibration results
for Ni were: R =0.9949, S = 0.028 for a concentration range of
0-0.8% Ni in the presence of 0-8.0% Fe. The Ni model included
a correction term for Fe overlap interference; ratios to source
backscatter accounted for matrix absorption effects. Similar
results were also obtained for Cr(0-0.8%) and for Fe itself; no
interelement - correction terms were needed for the Fe model.
Several unknown samples containing 1-3.6% total metals were
analyzed; Courier 10 results were in good agreement with these
nominal total metals values.
SUMMARY
This paper has described a new compact, rugged, and reliable

on-line X-ray analyzer, the Courier 10, which has been
developed to meet the demands of chemical and petrochemical
process stream analyses. The unit is optimized for specific
applications by careful attention to details such as system
construction, sample handling, measurement geometry,
excitation/detection optimization, and explosion proofing. The
Courier 10 is capable of excellent on-line performance for many
applications such as process liquids, slurries, solids (eg.,
polymer pellets), powders, and others. Numerous laboratory
feasibility studies have demonstrated good results for a number
of applications. Several installations are now producing
actual process data and we expect to report good results from
these in the near future.
REFERENCE
1. M. Hietala and J. Viitanen, "A Radioisotope On-Stream
Analyzer for the Mining Industry", Advances in X-Ray
Analysis, Vol. ,21, Plenum, New York (1978).
XRF MACRO PROBE ANALYSIS OF GEOLOGIC MATERIALS
N.L. Gilfrich and D.E. Leyden

Department of Chemistry
Colorado State University
Fort Collins, Colorado
E.A. Erslev
Department of Earth Resources
Colorado State University
Fort Collins, Colorado
INTRODUCTION
An x-ray fluorescence macroprobe was built for
intermediate-scale compositional mapping to bridge the
gap in spatial resolution between bulk x-ray fluorescence
and electron beam methods. The macroprobe was optimized
for quantitative whole rock mapping on a millimeter scale
to evaluate changes in bulk composition of fine-grained
mineral aggregates.
Previous studies of changes in bulk composition have
been hindered by the limited volume of material excited
by electron beam methods. X-ray excitation was chosen
over electron beam excitation because of the order of
magnitude greater effective penetration of the x-rays,
the greater stability of x-ray tubes and the relative
absence of surface effects such as charging.
X-ray "milliprobes" have been used to analyze small
areas of geologic materials in the past (1,2,3,4). These
wavelength dispersive instruments were designed for
single spot analysis, not automated for the mapping of
large areas. Recent advances in x-ray microfluorescence
aim for resolutions close to that obtainable with an
electron beam (5,6). Our goal was to develop an instru-
ment which complements existing electron beam and micro-

Edited by C.S. Barrett e{ al.
L~ DEWAR
Figure 1. Diagram of the XRF macroprobe.
fluorescence methods by analyzing at an intermediate

scale.
This paper will describe the design and features of
the macroprobe and report the analytical precision and
accuracy obtained by standardization with slates of known
composition for fundamental parameters calculations.
Preliminary results demonstrate the use of macroprobe
analysis for documenting element flux and volume-loss in
cleaved rocks.
INSTRUMENT
The Colorado State University XRF macroprobe consists
of a vacuum-tight sample chamber, computer-driven x-y
translational stage, a micro focus x-ray tube and an
energy dispersive Si(Li) detector (Figure 1). The sample
chamber was designed allowing maximum stage movement
while mounting both the x-ray tube and the detector
window as close to the sample as possible. The 3/8 inch
thick stainless steel walls of the sample chamber have a
door on the front for sample introduction and a leaded
glass window to allow viewing of the sample with a
binocular microscope.
The x-ray tube is a Kevex (Scotts Valley, CAl 50
watt, Rh anode, water-cooled Kevex microfocus tube. The
electron beam diameter at the anode is 0.10 x 0.15 mm,
yielding a more concentrated x-ray beam than conventional
tubes. The tube was mounted on the chamber at 45 degrees
N. L. GILFRICH ET AL. 595
relative to the sample surface. The beam is collimated

using perforated molybdenum disks, generating an ellipt-
ical spot on the sample surface ranging from 0.7 x 1.0 mm
to 20 x 30 rnrn.
The Tracor Xray, Inc. (Mountain View, CA) detector is
a liquid nitrogen cooled, 30 rnrn2 , Si(Li) detector mounted
at 45 degrees relative to the sample surface. The snout
sits less than a millimeter above the sample. A Tracor
Spectrace 6100 Analyzer is used to process the detector
signals.
Tracor Xray software controls the translational
stage, data acquisition and fundamental parameters
routine used for analyses. The total motion of the stage
is 10 cm in both the x and y directions, with a minimum
increment of 80 micrometers. A block of analyses is set
up by selecting the starting and ending positions and x,
y increments. The instrument collects a spectrum at each
point, saves it and moves to the next point until it
reaches the end position.
PRECISION
The overall precision of the macroprobe was evaluated
and the contributions of collimator size and stage pos-
itioning were determined. Three sets of 10 replicate
measurements were performed on a single area of a slate
sample. The relative standard deviations (RSD) in
percent were calculated from the intensities for each of
nine elements (Table 1). The first set of measurements
was performed using the 0.7 x 1.0 mm beam spot size. The
RSD ranges from 0.26% to 5.45%.
Table 1. Relative standard deviations (RSD) for 10 replicate

measurements of slate sample CSU1.
RSQ(11'
0.7 x 1. 0 rom Sl20t 1.0 x 2.0 rom Sl20t
wt. % Count Count Count wt. %
Element of oxide Rate Rate Rate2 of oxide
Mg 3.18 5.26 3.14 2.81 3.02
Al 15.3 0.63 0.33 0.64 0.43
Si 57.0 0.26 0.21 0.17 0.25
S 0.72 1.44 1.04 0.60 1. 08
K 3.42 0.96 0.30 0.44 0.32
Ca 3.68 0.75 0.39 0.45 0.45
Ti 0.79 1.16 0.59 0.97 0.71
Mn 0.07 5.45 2.03 3.40 1.84
Fe 8.33 0.27 0.14 0.12 0.17
1. RSD(%) = (standard deviation/mean) x 100.
2. without repositioning between measurements.
The other two sets of measurements were acquired with

the 1.0 x 2.0 rom spot size both with and without repos-
itioning the sample between measurements. The RSD without
repositioning ranges from 0.12% to 2.81% while with
repositioning the range is 0.14% to 3.14%. The weight
percent data showed an RSD range of 0.17% to 3.02%.
The smaller spot size yields poorer precision as a
result of lower x-ray flux through the collimator. No
consistent difference was seen between the set of spectra
collected with the stage re-positioning between each
spectrum and the set of spectra collected without re-
positioning. Thus, errors due to stage positioning
appear to be minimal. For all three sets of measure-
ments, the elements yielding the poorest precision were
magnesium and manganese. The RSD for MgO is the highest
due to its low atomic number, x-ray absorption of the
detector window and the excitation conditions employed.
The RSD for MnO is high because the MnO concentration in
the sample is only 0.07 weight percent.
STANDARDIZATION
The fundamental parameters computations developed by
Criss and Birks (7) and implemented by the Tracor soft-
ware was used to quantify the analyses. Because the
fine-grained rocks to be analyzed show little similarity
to traditional standards (e.g., fluxed disks or pressed
pellets), homogeneous slates of known composition were
used as standards.
A fine-grained, optically homogeneous slate (CSU1)
was chosen as a standard to analyze other slates. Part
of this rock was sent to the u.S. Geological Survey
(USGS) and analyzed by WDXRF (8). Sulfur was determined
with a LECO sulfur analyzer. The other part of the rock
was mounted for analysis with the macroprobe. In order
to standardize for an analysis, several spots on this
slate were analyzed in the macroprobe. The peak intens-
ities for the elements from each spectrum were extracted
and averaged. These average intensities were combined
with the weight percent composition from the USGS for the
standardization.
ACCURACY
The macroprobe accuracy using the above standard-
ization procedure was evaluated by analyzing two other
slate samples also analyzed by the USGS (W91 and W92). A
group of spectra were collected from different points on
these samples and the weight percent composition of each
spot was determined. Table 2 compares the average macro-
Table 2. comparison of USGS and macroprobe (MACRO) analysis of

slate samples W91 and W92.
W91 W92
USGS MACRO OIFF' %OIFFz USGS MACRO OIFF' %OIFF Z
SiOz 60.5 61.5 1. 00 1.65 53.4 51.0 2.40 4.44

Al z0 3 12.1 12.1 0 0 14.7 12.9 1.80 12.2
Fe Z0 3" 8.33 8.40 0.07 0.84 8.76 7.22 1.54 17.6
MgO 4.80 5.56 0.76 15.8 3.10 2.84 0.26 8.29
CaO 2.44 2.84 0.40 16.4 5.98 5.89 0.09 1. 59
K~O 4.20 4.43 0.23 5.48 3.42 3.25 0.17 5.03
T~Oz 0.53 0.58 0.05 8.70 0.76 0.77 0.01 1.45
PzOs 0.10 N03 0.10 0.15 N03 0.15
MnO 0.39 0.40 0.01 1.30 0.11 0.10 0.01 8.18
S JilL 0.13 0.13 0.82 0.81 0.01 1. 34
TOTAL 93.4 95.9 2.75 91.2 84.8 6.44
1. OIFF = absolute value (USGS - MACRO).

2. %OIFF = (OIFFjUSGS) x 100.
3. NO = not detected.
probe compositions with the bulk rock compositions ob-

tained by the USGS.
Several factors must be considered when comparing
the macroprobe results to those obtained by the USGS.
First, the samples being analyzed in the two cases are
parts of the same rock but are not the same. Second, the
slates are heterogeneous and differing proportions and
compositions of individual mineral grains will contribute
to uncertainties in the matrix effects. Finally, the USGS
method utilizes a large number of standards and an emp-
irical matrix correction algorithm, while the macroprobe
analysis used a single standard and a fundamental para-
meters calculation.
Absolute and percent differences were calculated for
each component of W91 and W92 in Table 2. For W91, the
absolute differences range from zero to 0.76 weight
percent and the sum of these differences is 2.75 weight
percent. For W92, the absolute differences range from
0.01 to 2.40 weight percent and the total is 6.44 weight
percent. The percent differences for the two samples
range from 0.00 to 17.6 percent. The larger differences
for different elements in W91 and W92 suggests that they
are a result of sample preparation differences, inhomo-
geneity in both standard and unknown and the use of a
single standard for the macroprobe analyses. The fact
that the macroprobe results were slightly higher for W91
and lower for W92 suggests that small differences in
sample elevation may be responsible for some of the
variation. Recalculating the results so that the total
oxide composition equals 100 weight percent removes this
bias and reduces the total absolute arror to 2.59 weight
percent for W91 and 4.42 weight percent for W92.
~ SAMPLE CM- 3A
A
Figure 2. Slate sample CM-3A.
CLEAVED SLATE ANALYSIS

As part of an on-going study of element flux and
volume-loss in cleavage zones, a slate with excellent
spaced cleavage was selected for a reconnaissance study.
The sample (Figure 2) contains several bands of cleavage
separated by uncleaved areas. The deformation of the
layers shows a 37% shortening perpendicular to cleavage.
This estimate is consistent with adjacent folds of dolo-
mite siltstone which show 40% to 43% shortening perpen-
dicular to cleavage. Macroprobe analyses were used to
distinguish volume-loss shortening from cleavage-
parallel, constant volume shortening.
Data were acquired along a bedding-parallel tra-
verse from A to AI in Figure 2. The beam diameter in the
direction of the traverse was 0.7 rom and the spots were
spaced 0.56 rom apart. The data from 35 analyses were
converted to weight percent compositions using the method
described earlier.
Figure 3a,b shows the weight percent oxide plotted

versus weight percent Al 20 3 • The linear relationships
between the oxides suggest that compositional variability
is largely due to variation in Si0 2 • Figure 3c shows the
ratio of weight percent oxide to weight percent Al 20 3 for
each spot analyzed versus distance along the traverse.
The consistent Fe 20 3/Al 20 3 , K20/Al 20 3 and Ti02/Al 20 3 ratios
A Oxides Versus AI203 8 Oxides Versus AI203

11 80
10
9 ..". !.
70
60
o 00
o o~ 0
....
0 0 0
.: "
II 7 II 50
~ 6 ," , :Q
5 40
,. ,,
t:.t;l> t:.
5 ,
~ 4 t, ~,
"
~ 30
3
20
2
x
X
xxx xxt)( 10
1 o· } x x
0 "" 0 + .+
9 11 13 15 17 19 21 23 25 9 11 13 15 17 19 21 23 25
Wt%AI203 Wt%Al203
+ Fe203 6 K20 x TI02 v MnO o SI02 + cao
c Oxides/Al203 Versus Distance
D
Volume-Loss Versus Distance
70
0.8
0.6 60
g
0.4 50
C/l
0.2+-_ _ _ _ _ _ _ _ _ _ _ _---1 g40
i . . . . - . . . . . .- -. - -.-
w
~ ~.2
~ 30
~::
~ 20
.J -0.8 "f-
-1 lO
-1.2
0
-1.4
-1.6 +-.---.-_._r-+_,_~___.',.....,r_r__._r__r_,_~___,__1 ·10
o 2 6 8 10 12 14 16 18 20 0 2 8 10 12 14 16 18 20
Distance (mm) Distance (mm)
o Si02 I- cao 0 Fe203 6 K20 y Ti02 Avg Vol. Loss = 42%
Figure 3. Results of slate traverse. a,b. Weight

percent oxides versus weight percent Al 203 ;
c. Ratios of weight percent oxides to weight percent
Al 20 3 versus distance moved on the sample; d. Vol-
ume-loss versus distance moved on the sample.
indicate that these elements are concentrated together.

The low Si0 2/Al 20 3 ratios correspond to the most intensely
cleaved areas, and the highest Si02/Al20~ ratios cor-
respond to the uncleaved band seen in Flgure 2. This
suggests that Si02 was mobile relative to Al 20 3 , Fe20 3 , K20
and Ti02 which probably accumulated as insoluble residues
in the cleavage zones.
If the region of highest Si02/Al 20 3 ratio represents
the original bed composition, the volume-loss can be
calculated from the composition (9) for each point (Fig-
ure 3d). The average volume-loss calculated from the
macroprobe traverse is 42%, in excellent agreement with
the 37-43% shortening from geometric criteria. Thus, the
macroprobe analysis provides a method for distinguishing
volume-loss from distortional strain. This has major
implications to the genesis of rock cleavage, a funda-

mental unknown in the geosciences.
CONCLUSION
The XRF macroprobe has provided a good method for
volume-loss determination in slates. The technique shows
promise for further studies of millimeter-scale element
fractionation. Tests of macroprobe precision on a rela-
tively homogeneous slate yielded relative standard
deviations for different components ranging from 0.17% to
3.02%, with poorer precision obtained using a smaller
spot size. The accuracy obtained for the slates was
limited by the use of inhomogeneous standards and un-
knowns yielding total absolute errors after normalization
of 2.59 and 4.42 weight percent for two different
samples.
ACKNOWLEDGEMENTS
The authors would like to acknowledge the National
Science Foundation (Grant EAR-8720824) for funding the
construction of the macroprobe. We would also like to
extend appreciation to D. Ward for sample preparation, J.
Taggart of the USGS for the WDXRF analyses and A. Harding
from Tracor Xray, Inc. for his assistance with the pro-
ject.
REFERENCES
1. I. Adler, J.M. Axelrod, American Mineralogist, 41,
524, 1956.
2. I. Adler, J. Axelrod, J.J.R. Branco, Proceedings
Seventh Annual Conference of Industrial Applications of
X-ray Analysis, 167, 1958.
3. K.F.J. Heinrich, Advances in X-ray Analysis,s, 1,
1962.
4. H.J. Rose, Jr., R.P. Christian, J.R. Lindsay, R.R.
Larson, U.S. Geological Society Professional Paper 650-B,
128, 1969.
5. M.C. Nichols, D.R. Boehme, R.W. Ryon, D. Wherry, B.
Cross, G. Aden, Advances in X-ray Analysis, 30, 45, 1986.
6. D.A. Carpenter, M.A. Taylor, C.E. Holcombe, Advances
in X-ray Analysis, 32, 115, 1989.
7. J.W. Criss, L.S. Birks, Analytical Chemistry, 40,

1080, 1968.
8. J.E. Taggart, Jr., J.R. Lindsay, B.A. Scott, D.V.
vivit, A.J.Bantel, K.J. Stewart, U.S. Geological Survey
Bulletin 1770, E1, 1987.
9. E. Erslev, C. Mann, Proceedings of the Pennsylvania
Academy of Science, 58, 84, 1984.
QUALITATIVE XRF ANALYSIS WITH PATTERN RECOGNITION
Lo I Yin
Code 682, Laboratory for Astronomy and Solar Physics, NASA Goddard
Space Flight Center, Greenbelt, MD 20771
Stephen M. Seltzer
Center for Radiation Research, National Institute of Standards and

Technology, Gaithersburg, MD 20899
ABSTRACT
In many applications of energy-dispersive XRF analysis, quantitative

information concerning the chemical composition of the samples is not
required. Rather, one is interested in whether a given sample is similar to
some reference material or whether the chemical composition is changing from
one sample to the next. We have investigated the use of pattern-recognition
techniques in such applications. It will be demonstrated with experimental
data that the pattern-recognition approach is extremely simple and fast. It
uses only a single parameter, the normalized correlation coefficient, and
can be applied directly to raw data. The efficacy of the method is
illustrated with Si(Li) spectra of geological and pigment samples, and
proportional counter spectra of geological samples. The pattern-recognition
method should be ideally suited for field XRF applications, and the
algorithm can be easily implemented on a personal computer.
INTRODUCTION
It is well known that a person experienced with energy-dispersive X-ray

fluorescence (XRF) analysis can often arrive at a rough estimate of the
chemical composition of a sample simply by visual inspection of the spectra~
features. Such an ability can be valuable in numerous applications where
quantitative chemical composition of the sample is not of primary concern.
For example, in quality control, one is only interested in whether a given
sample has the same compositional distribution as that of a known standard.
Similarly, in sorting operations, one wishes to select, identify, and group
samples with similar compositions. In both of these examples detailed
knowledge of the quantitative chemical concentrations of the elements in the
samples is not needed. For such applications we propose the use of a
pattern-recognition technique which is'simple, efficient, and fast. The
pattern-recognition method essentially emulates visual inspection of the XRF

spectral features by the spectroscopist, but places the inspection on a more

quantitative basis so that it can be easily adapted for analysis by a
personal computer in near-real time.
Our interest in using the pattern-recognition approach for qualitative

XRF spectral analysis originated from our desire to design and implement an
automated XRF system on the Mars Rover Sample Return mission to select
Martian samples to be returned to Earth. Therefore, we will introduce the
method and test its validity and efficacy by way of a brief review of the
experimental data obtained from geological samples (Yin et al., 1989).
Later we will illustrate its usage in the presence of strong background by
analyzing some pigment spectra as well as spectra with poor resolution
obtained with a proportional counter.
THE PATTERN-RECOGNITION TECHNIQUE
It is easy to see the rationale for the pattern-recognition technique

if we examine some measured energy-dispersive XRF spectra. Figure I shows a
group of five spectra from standard geological samples under the same
experimental conditions. The samples are: AGV (andesite), BIR (basalt), W2
(diabase), G2 (granite), and RGM (rhyolite). The samples, in the form of
pressed powder pellets consisting of 50% cellulose and 50% sample, were
provided by Robert G. Johnson of the U.S. Geological Survey (USGS). The
spectrum was taken at the USGS in collaboration with R.G. Johnson using the
Kevex 8000/0700 energy-dispersive X-ray spectrometer with a vacuum chamber
and a carousel sample holder for such standardized pellet samples. The X-
ray tube with a rhodium anode was operated at 40 kV and an anode current of
10 ~A. A Si(Li) detector with a beryllium window was the energy-dispersive
detector. A standard nuclear-spectroscopy amplifier with a 12 ~s shaping
time constant and a 2048-channel multichannel analyzer were used to collect
the XRF pulse-height spectrum. The peak at about 2.7 keV is due to the Rh L
lines from the anode which are coherently scattered by the sample into the
detector. The spectra are displayed in logarithmic scale so that the
spectral shapes remain invariant with changes in absolute intensity, and
thus can be considered as specifically characteristic of the samples.
By inspection, it is immediately obvious that BIR and W2 have similar

features, implying similar chemical compositions; G2 and RGM are also
similar; but both pairs are different from each other and from sample AGV.
To put this kind of visual analysis on a more quantitative basis, we invoke
a technique used in pattern recognition. Each spectrum is assumed to be a
n-component column vector in a n-dimensional pattern space. For example, if
each spectrum has 2048 channels, then each is considered as a 2048-component
column vector. In pattern recognition, two vectors are considered similar
if the Euclidean distance between them in the n-dimensional pattern space is
small. In other words, if all the components of the two vectors are near
each other in a component-by-component comparison, the two vectors must be
similar. However, in the case of XRF, the spectral pattern is unaffected by
absolute intensities, as long as the excitation high voltage is held
constant. For instance, aside from statistical fluctuations, the spectral
pattern will remain invariant if we change the anode current or the data
accumulation time. In this case, the spectral pattern will be similar even
if the Euclidean distance is large. Hence, the pattern discriminant
function must be non-metric. Realizing that if each of the components of a
vector is decreased or increased by the same proportionality constant, the
new vector will be displaced from the old vector along the same direction
from the origin of the n-dimensional pattern space, it is easy to see that
L. I. YIN AND S. M. SELTZER 605
..,
O~r-~~~~~-r-r~~~~~~~
o
o
co
o
ID
o
2~
c
:J
or-
U 0
ID
o
n
o
~
o
..,
o
N
o
0.0 1.5 3.0 4.5 6.0 7.5

Energy, keV
Fig. 1. XRF spectra from standard samples in
vacuum: AGV-l (andesite), BIR-l
(basalt), W-2 (diabase), G-2
(granite), and RGM-l (rhyolite).
cosO, as defined below, is just such a discriminant function (Tou and

Gonzales, 1974):
(1)
Equation (1) is written in matrix notation. 0 is the angle between the

two n-dimensional vectors a and b, aT and b T are their transposes. The
numerator is the dot product of the two vectors, and the denominator is the
product of their magnitudes (aTa) and (bTb). Since the numerator is also
the correlation coefficient of a and b, and the denominator a normalization
factor, cosO is referred to as the normalized correlation coefficient (Nee).
The value of cosB will be close to 1 for two XRF spectra with similar
features, independent of intensities, because these two vectors will lie
along the same direction in pattern space with the angle between them close
to zero.
Before applying Eq.(l) to the actual spectra, there is one important

feature which must be addressed. In comparing similar spectra, frequently
one of the components is predominant over other features, such as the Fe or
the Si peak in the geological samples. In such cases, if all the components
of the vector were given equal weight, the vector will lie in the direction
of the most prominent component. Two such vectors tend to lie in the same
direction in pattern space, i.e. with Nee close to 1, even if their detailed
Table I. Normalized correlation coefficients (NCC's) derived from the XRF spectra of 14 standard
pellets of geological samples. All spectra were taken under identical conditions and with comparable
counting statistics. The pairwise correlation coefficients form a triangular matrix, and have been
multipled by 100 to convert them to percentages. Pairs of spectra with very similar patterns have
NCC's near 100%.
AGV BCR BHVO BIR ONC G1 G2 GSP PCC RGH ST1A STH W1 W2
AGV 100.00
BCR 95.79100.00
BHVO 92.35 95.97 100.00
BIR 89.15 91.04 98.24 100.00
ONC 91.06 92.45 98.17 99.76 100.00
G1 82.79 65.41 57.81 55.09 58.16100.00
G2 87.58 71.38 64.58 61.69 64.63 98.88 100.00
GSP 91.44 78.32 70.46 66.69 69.63 97.78 98.87 100.00
PCC 78.68 87.24 73.79 67.08 70.36 51.74 55.35 63.49100.00
RGM 82.42 64.51 56.44 53.67 56.93 98.65 99.26 97.04 50.98 100.00
ST1A 93.51 98.58 98.47 96.02 96.85 58.42 65.02 71.98 82.98 57.39 100.00
STH 93.54 88.49 76.62 71.55 75.18 87.11 88.75 93.19 85.27 85.72 82.34 100.00
W1 92.83 96.51 99.12 98.45 98.95 58.44 64.77 71.01 78.16 57.00 99.30 79.57 100.00
W2 93.48 94.99 99.10 99.27 99.63 61.31 67.84 73.07 73.35 60.29 98.18 78.59 99.51 100.00
structures are different. In visual analogy, two patterns with similar

prominent features tend to appear similar at first glance, until we examine
the fine features. To make the NCC effective in these cases, we adopted the
simple procedure of giving the prominent component an attenuation factor so
that it is cut down to approximately the same order of magnitude as the
other features. Of course the same attenuation factor must be applied to
all the spectra which are being compared.
We applied Eq.(l) to 14 XRF spectra from standard geological samples

with well-known chemical compositions. Only a crude background subtraction
was performed on the raw data, whereby the lowest count (a constant) in the
region of interest was subtracted from all the channels in the region. We
attenuated the Si peaks by a factor of 2, Fe by a factor of 4, and Rh by a
factor of 10 so as to eliminate the latter altogether. These factors were
chosen simply by visual inspection of all the spectra. The NCCs were then
evaluated for all possible pairs of spectra, resulting in a triangular
matrix as shown in Table I. For easy readability the NCCs were multiplied
by 100 to convert them into percentages. Using raw data, the computation of
the 105 pairwise comparisons of 14 spectra, where each spectrum is
represented by a 6l7-component vector, took only about 15 s on a 80286/287
based personal computer.
If two XRF spectra have a NCC of 99%, are their chemical compositions
really very similar? To answer this question, we took the published
chemical compositions of these samples, treated each set of chemical
concentrations as a vector in pattern space, and applied Eq.(l) to these
vectors. In this way, we obtained another set of NCCs based on chemical
concentrations. This set of "chemical" NCCs were arrived at by attenuating
the concentrations of A1203 by a factor of 4, and Si02 by a factor of 15 in
order to make them comparable in magnitude with the other components. The
results are shown in Table II. For easy inspection, we have also set those
NCCs below 97% to 0 to highlight the strongly correlated samples. It is
seen that, with only three exceptions, high NCCs in XRF spectra also reflect
high similarities in chemical concentrations. In fact, when all the
"chemical" NCCs are plotted against the "spectral" NCCs, they follow each
other very well as shown in Fig. 2.
Having verified the validity of the pattern-recognition technique with

standardized samples with well-known compositions, we also applied it to
Table IJ. C~rison of the NCC matrix derived from the XRF spectra with that derived from the
chemical c~sitions. for the same set of 14 standard sa~les. The matrices list only those NCC
values above 97% to select those sa~le pairs which have either highly similar spectral patterns or
highly similar chemical c~sitions. The two matrices produce very similar selections.
From the XRF Spectra
AGV BCR BHVO BIR ONC G1 G2 GSP PCC RGH ST1A STH 111 112
AGV 100.00
BCR 0.00 100.00
BHVO 0.00 0.00 100.00
BIR 0.00 0.00 98.24 100.00
ONC 0.00 0.00 98.17 99.76 100.00
G1 0.00 0.00 0.00 0.00 0.00 100.00
G2 0.00 0.00 0.00 0.00 0.00 98.88 100.00
GSP 0.00 0.00 0.00 0.00 0.00 97.78 98.87 100.00
PCC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00
RGH 0.00 0.00 0.00 0.00 0.00 98.65 99.26 97.04 0.00 100.00
ST1A 0.00 98.58 98.47 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00
STH 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00
111 0.00 0.00 99.12 98.45 98.95 0.00 0.00 0.00 0.00 0.00 99.30 0.00 100.00
112 0.00 0.00 99.10 99.27 99.63 0.00 0.00 0.00 0.00 0.00 98.18 0.00 99.51 100.00
From the Chemical C~sitions
AGV BCR BHVO BIR ONC G1 G2 GSP PCC RGH ST1A STH 111 112
AGV 100.00
BCR 0.00 100.00
BHVO 0.00 0.00 100.00
BIR 0.00 0.00 98.72 100.00
ONC 0.00 0.00 98.26 99.65 100.00
G1 0.00 0.00 0.00 0.00 0.00 100.00
G2 0.00 0.00 0.00 0.00 0.00 98.50 100.00
GSP 0.00 0.00 0.00 0.00 0.00 0.00 98.47 100.00
PCC 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00
RGH 0.00 0.00 0.00 0.00 0.00 99.38 98.92 0.00 0.00 100.00
ST1A 0.00 98.91 98.69 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00
STH 0.00 0.00 0.00 0.00 0.00 0.00 0.00 97.48 0.00 0.00 0.00 100.00
111 0.00 0.00 99.48 99.47 99.43 0.00 0.00 0.00 0.00 0.00 98.15 0.00 100.00
112 0.00 0.00 99.39 99.54 99.57 0.00 0.00 0.00 0.00 0.00 97.86 0.00 99.99 100.00
unprepared rock samples, with irregular surfaces. Because of the irregular

surfaces we took repeated spectra from the same sample at random
orientations. In almost all cases, the NCCs of the spectra from the same
sample were above 97%. The two exceptions were from two rocks where
portions of the surface had crusts of clearly different color. Where
chemical composition data were available, the chemical NCCs also mirrored
the pattern of the spectral NCCs.
As expected, the general pattern-recognition results are not very

sensitive to the choice of the precise value of the attenuation factor.
Furthermore it was found that when the peak count in Fe line was decreased
from 2xl04 to 200, the NCCs from the same sample still remain above 97%.
This means, even with poor statistics, these vectors did not diverge by more
than 14 0 in pattern space. The inter-sample NCCs also did not change by
more than a few percent over this large range of counting statistics.
SPECTRA WITH STRONG BACKGROUND (PIGMENT SAMPLES)
Because all the geological samples have relatively large concentrations

of Si and Fe, with some fine variations among the elements in between, they
have roughly similar spectral features as indicated by the lowest NCC being
around 50%. Next we applied the pattern-recognition technique to a set of
o
O;-__. -__. -__. -__, -__, -__, -__, -__. -__. -__. -__.-~~
)~
U')
OJ O~
o O~ 0
OJ
o o 0
0 0 0
U')
co o o
o o
lo...
""0
o 00
~co
a. o@
U'lU') o
Er-- o
o
lo...
o 00
.... 0
or--
o 8ft; 0
o 0 0 0
'B@
ZU')
to
o o
to
U')
U')
0
U')~
0 __<;)
~ __ ~ __ ~ __ ~ __ ~ __ ~ __4 -__4 -__ ~ __ ~ __ ~~
40 45 50 55 60 65 70 75 80 85 90 95 100
NCC from Compositions
Fig. 2. NCCs derived from XRF spectra of 14
standard geological samples versus
those derived from tabulated
chemical concentrations for the same
set of samples.
samples which poses a very different kind of problem. We obtained from R.A.
Livingston of the University of Maryland a set of pigment samples which
simulated those used by ancient Egyptians for their wall paintings. The
various pigments were painted as round spots of about 0.5 cm in diameter on
a large limestone block. For each pigment, painted spots were prepared
using pigment concentrations of 100%, 50%, 25%, 12.5% and 6.25%. The XRF
spectra were collected in air using a small portable low-power x-ray
generator with a tungsten anode operated at 45 kV and 25 pA, and a Si(Li)
detector. Because the size of the x-ray beam is larger than the painted
spots, each spectrum contains considerable contribution from the limestone
background. Furthermore, this background does not remain constant. As the
concentration of the pigment decreases the relative intensities of the
background features increase. Under these circumstances, we are interested
in whether the pattern-recognition technique could still sort and identify
the pigments, and if so, down to what concentration level.
Fig. 3 shows the spectra of some of the pigment samples. The bottom
spectrum is from the limestone background without any pigment. We see that
although the spectra contain many features, most of them are from the
background, i.e., Ca, Fe, W (L lines) and Sr. The W L lines originated from
the W anode which were coherently scattered by the sample into the detector.
The pigments represented in Fig. 3 are: malachite green (Cu carbonate),
cobalt blue (Co), ochre red (Fe), realgar orange (arsenic sulfide), and
cinnabar brown (HgS) , all at 100% concentration. The predominance of the
background features tend to make all of these spectra highly correlated.
Furthermore, in the case of cinnabar, there is strong overlap among the Hg
and W L lines. Faced with this complexity, we implemented a very simple
routine to subtract the background spectrum. We normalized the intensities
of the background spectrum against each pigment spectrum using the three
major peaks common to all spectra: Ca Ka (3.7 keV) , one of the W L lines at
8.4 keV, and Sr Ka (14.1 keV). The largest normalization factor among the
three was chosen to multiply the background spectrum which was then
subtracted from the sample spectrum. Negative counts due to over
subtraction were set to zero. The largest normalization factor was chosen
because residual background counts could be mistakenly interpreted as
spectral features by the pattern-recognition algorithm, especially when the
signal was low, whereas zeroes could not contribute to any artifacts.
After subtracting the background spectrum in this manner, Eq.(l) was

then applied to the residual spectra. The results are shown in Table III.
Now, because the residual pigment spectra are very different from each other
after subtracting the background spectrum, many NCCs are below 1%, in sharp
contrast to the geological samples. We applied a 90% threshold in the Nee
matrix to show that pattern recognition could indeed, with the exception of
ultramarine blue, sort out the pigments as well as recognizing the same
pigment down to 6.25% concentration. The pigment ultramarine blue is a
mineral consisting of mainly Na, AI, Si, Sand 0, whose X rays cannot be
detected due to air absorption. The strong overlap between Hg and W L lines
in the cinnabar spectra caused their mutual Nee values to be lower than the
other pigment groups even after subtracting the background spectrum. The
Nee value between cinnabar pigments of 100% and 6.25% concentrations came
out to be 88.7%, just below the 90% threshold.
"0
•
'0
,.,
'0
N
'0
0
'0
..
0
2C ~
"'10
0 0
u
....
0
.0
"0
•0
~
,.,
0
N
0
0.0 3.0 6.0 9.0 12.0 15.0 18.0

Energy, keV
Fig. 3. XRF spectra from five paint samples

on limestone. The bottom spectrum
is from unpainted limestone.
0)
.....
o
Table III. Normalized correlation coefficients (NCC's) derived from the XRF spectra of 6 paints, diluted to the indicated concen·
trations. The spectra were measured with the samples painted on a plaster surface. The Nee's were calculated after subtracting
from each spectrum the plaster·only background spectrum. In the matrix below, all Nee values below 90% were set equal to 0 to
to facilitate the recognition of highly correlated pairs.
ochre ultramarine blue cobal t blue malachite cinnabar realgar
100% 25% 6% 100% 25% 6% 100% 25% 6% 100% 25% 6% 100% 25% 6% 100% 25% 6%
100% 100.00
25% 98.46 100.00
6% 96.59 97.11 100.00
100% 0.00 0.00 0.00 100.00
25% 0.00 0.00 0.00 0.00 100.00
6% 0.00 0.00 0.00 0.00 0.00 100.00
100% 0.00 0.00 0.00 0.00 0.00 0.00 100.00
25% 0.00 0.00 0.00 0.00 0.00 0.00 99.94 100.00
6% 0.00 0.00 0.00 0.00 0.00 0.00 98.42 98.58 100.00
100% 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00
25% 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 99.91 100.00
6% 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 96.76 97.00 100.00
100% 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00 X
25% 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 93.70 100.00
6% 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 91.84 100.00 X
:0
"'T1
100% 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 100.00 Z
25% 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 99.94 100.00 en
6% 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 99.75 99.79 100.00 -!
:0
c:
:s:
m
Z
-!
~
-!
0
Z
PROPORTIONAL-COUNTER SPECTRA
To further test the pattern-recognition technique, we also obtained XRF

spectra of standard geological samples with a proportional counter.
Proportional counters are not frequently used as energy-dispersive XRF
analyzers because of their poor energy resolution. In addition, there is
the problem of the escape peak from the detector gas. Fig. 4 shows, for
some geological samples, proportional-counter spectra between 0 and 10 keV
measured in air, with the x-ray generator operated at 9 kV and 70 ~A. The
bottom spectrum is that of a pure Fe foil. In this spectrum one sees both
the Fe K x-ray peak at 6.4 keV and the Ar K-escape peak about 3 keV below,
at 3.4 keV. Because Fe is a prominent component in most geological samples,
these two peaks tend to dominate all the spectra. Unfortunately, the escape
peak of Fe also overlaps the Ca K x-ray peak at 3.7 keV. In addition,
unlike the previous spectra of geological samples which were obtained with
Si(Li) detector in vacuum, air absorption precluded the detection of
elements such as Mg, Al and Si whose K x rays are below 3 keV.
Nevertheless, it is interesting to find out how much the pattern-recognition
technique could accomplish under these extremely unfavorable circumstances.
First we applied the background subtraction program to subtract the

pure Fe spectrum from that of each geological sample, normalizing to the Fe
'"o~-r'-~-r'-~-r~~rT~~~-r~
.o
,...
o
.,
o
2c
::J
o
U
OJ
o
•o
,.,
o
N
o
0.0 2.0 4.0 6.0 8.0 10.0

Energy, keY
Fig. 4. Proportional-counter XRF spectra of
geological samples in air. The
bottom spectrum, from a pure Fe
foil, shows the Ar K-escape peak.
Table IV. C~rison of the NCC matrix derived from the proportional-counter
XRF spectra with that derived from the chemical compositions, for the same
set of 9 standard geological s8fl1)les.
From the Chemical Compositions, Threshold = 95.00

AGV BCR BIR DNC DTS G2 GSP OlO 112
AGV 100.00
BCR 95.21 100.00
BIR 0.00 0.00 100.00
DNC 0.00 0.00 99.94 100.00
DTS 0.00 0.00 0.00 0.00 100.00
G2 0.00 0.00 0.00 0.00 0.00 100.00
GSP 0.00 0.00 0.00 0.00 0.00 99.81 100.00
olO 95.25 0.00 0.00 0.00 0.00 95.11 0.00 100.00
112 0.00 96.27 99.81 99.79 0.00 0.00 0.00 0.00 100.00
From the XRF Spectra, Threshold = 97.00

AGV BCR BIR DNC DTS G2 GSP OlO 112
AGV 100.00
BCR 97.86 100.00
BIR 0.00 0.00 100.00
DNC 0.00 0.00 99.79 100.00
DTS 0.00 0.00 0.00 0.00 100.00
G2 0.00 0.00 0.00 0.00 0.00 100.00
GSP 0.00 0.00 0.00 0.00 0.00 99.61 100.00
olO 98.51 0.00 0.00 0.00 0.00 99.14 99.21 100.00
112 0.00 0.00 99.72 99.40 0.00 0.00 0.00 0.00 100.00
K x-ray peak. Although this procedure helped to subtract out the escape
peak of Fe from the Ca region, it also eliminated the Fe peak as a
distinguishing spectral feature. The NCC matrix, computed after spectrum
subtraction, is shown in Table IV based on a 97% threshold. For comparison,
we also show the "chemical" NCC matrix using a 95% threshold and based only
on those constituents which contributed to proportional-counter "spectral"
NCCs (i.e., K Ca, Ti, Cr, and Mn). It is seen that even under such
unfavorable e~perimental conditions the agreement between the two matrices
of NCCs is still quite acceptable.
CONCLUSIONS
We have demonstrated the validity and the effectiveness of the pattern-

recognition technique in a few selected XRF applications. The pattern-
recognition technique involves only one parameter, the normalized
correlation coefficient. It can be calculated in near-real time from raw
data. An interactive program including graphics is being developed for the
personal computer so that it could be made available to others who may be
interested in the general application of this technique in qualitative XRF
analysis. Finally, we wish to emphasize that because pattern recognition is
a generic method, its applications are obviously not limited to the analyses
of XRF spectra.
ACKNOWLEDGEMENTS
We gratefully acknowledge the support of this research through NASA

RTOP 682-157-03-50. We are indebted to Robert G. Johnson of the U.S.
Geological Survey for his collaboration in the geochemical portion of this
work and to Richard A. Livingston of the University of Maryland for
providing us with the pigment samples.
L.I. YIN AND S. M. SELTZER 613
REFERENCES
Tou, J. T., and Gonzales, R. C., 1974, "Pattern Recognition Principles",

Chapter 3, Addison-Wesley Publishing Co., Inc., Reading, MA.
Yin, L.I, Trombka, J.1., Seltzer, S.M., Johnson, R.G., and Philpotts, J.A.,
1989, Possible use of pattern recognition for the analysis of Mars-
rover X-ray fluorescence spectra, J. Geophys. Res., in press.
DESIGN OF HIGH PERFORMANCE SOFT X-RAY WINDOWS
Raymond T. Perkins, David D. Allred, Larry V. Knight
Department of Physics and Astronomy

and
Center for X-ray Imaging
Brigham Young University, Provo, Utah 84602
James M. Thorne
Department of Chemistry
and
Center for X-ray Imaging
Brigham Young University, Provo, Utah 84602
INTRODUCTION
X-ray windows are used in sources and detectors to separate the neighborhood
of the x-ray generation or detection from the use environment. While each use has
its own requirements, there are some principles that should be used in designing an
optimal x-ray window. Because x rays are absorbed to some extent by all materials,
minimizing absorption is one criterion in preparing windows. Also, for most uses
there is a pressure difference across the window so that ensuring pinhole-free structure
and sufficient mechanical strength to support the differential is another criterion for
window design. Traditionally, absorption is minimized by fabricating the window with
lower atomic number (low Z) elements such as Be, B or C. However, the wavelength
(energy) region of interest becomes a very important complicating factor.
Over the years many different materials have been used as windows for soft x-
rays. A primary use has been for proportional counters. More recently interest has
developed for Si(Li) detectors. The materials used to date for proportional counters
include: polypropylene, lexan, and formvar l - 4 . Materials used for Si(Li) detectors
have been Be, BN x , formvar, a-C:H (diamond-like carbon), and mylar 5 . The purpose
of this paper is to discuss the design of x-ray windows with particular emphasis on
windows for detectors in the soft x-ray region. This is because existing windows can
typically be made thin enough to have very good transmission for the harder x-rays.
MODELING AND METHODOLOGY OF STUDY

For this study, two primary criteria were chosen for window study: film transmis-
sion and material integrity. Evaluation of the first is amenable to computer simulation

and this is the approach taken in this study. The second is more subjective and will
be treated in a descriptive fashion. While materials can be ranked according to bulk
moduli and yield strengths, the integrity and mechanical properties of thin films are
very dependent on preparation techniques and microstructure.
The calculations were done using a computer code called UM which was designed
and written by us. It is written in FORTRAN 77 and was designed to do a wide variety
of calculations involving x-rays, thin films, and crystals. It accesses a data base of
atomic scattering factors. For the problem at hand these are used to calculate optical
constants.
The atomic scattering factors were obtained from Henke's tables and expanded at
BYU and Lawrence Livermore National Laboratory. Beer's law was used in optical
calculations. This is justifiable since the films are always much thicker than the
wavelength of soft x rays and hence interference effects are negligible. In addition,
the reflection of x rays from front and back suriaces of the windows at near normal
incidence was calculated to be much smaller than 10- 4 and thus could be neglected
over the whole range.
Calculations were made over the range lOA. to 70A. (170 eV to 1200 eV). X rays
of this range are too soft to be transmitted through the beryllium windows used in
typical Si(Li) detectors. This ranges includes the Ka radiation of all elements with
atomic numbers from Z = 5 to 11 (boron to sodium).
RESULTS
In Figure 1 and Figure 2 is shown the computed transmission of windows which

have typically been used for x-ray applications. Typical thicknesses were used in the
computations and are noted in the figure. The bottom curve is that of 8 J.lm (0.3
mil) beryllium (this is the thinnest rolled Be foil used for Si(Li) detectors). Such a
thickness allows only about 45% of the sodium Ka radiation to be transmitted and
a negligible fraction of x rays less energetic than that. (In practice the transmission
of sodium Ka radiation is much less than 45%. This is due in part to at least two
causes. First, the Be is typically overcoated with a polymer to plug the holes that are
usually found in such thin rolled Be. Second, since it is rolled, there will be a high
percentage of beryllium oxide. This oxygen causes undesirable absorption of soft x
rays.)
Another common window is 6 J.lm (i mil) polypropylene, metallized with alu-

minum ("" 20 nm thick). This is used in proportional counters and is the next most
transmissive material/thickness combination. Polypropylene windows 2 J.lm and 1
J.lm thick are also used. Curves for all three are shown in the figures.
It will be noted that the polypropylene is much more transmissive than is the
typical Be window for the soft x ray region, particularly on the low energy side of
the C absorption edge. One can see the effect of the carbon content by the rather
dramatic absorption edge; the nitrogen Ka radiation is highly attenuated. In this
respect, polypropylene resembles a carbon K-edge filter (allows carbon x rays to pass
but blocks more energetic, particularly nitrogen, x rays). This is an important design
point since any material which is predominantly a single element or a single element
with hydrogen will act as an edge filter. Polypropylene is not a single element but
acts as such for soft x rays since the hydrogen is transparent and can be ignored. The
transmission curve for 400 nm of diamond is shown in Figure 3. Like polypropylene
it acts as an edge filter, extinguishing nitrogen x rays. However, because of its higher
density and low hydrogen content, 0.4 J.lm of diamond is equivalent to about 1.9 J.lm
of polypropylene.
There is a variety of materials that incorporate various low-Z elements into their
structure. The transmission of 400 nm of formvar (polyvinyl formal), which has been
R. T. PERKINS ET AL. 617
1.0
0.9
I
0.7
0.6
0.5
~ 0.4
~ 0.3
0.2
,
,
0.1
,
0.0 '____'__...L.:..~"--__'_......:..:..:...w..._..L.-;:J.....L_ _l..._...L__'____'__...J
10 15 20 25 30 35 .0 45 50 55 60 65 70
WAVELENGTH ( ANGSTROMS )
Figure 1. Transmission for 1 Jlm (solid line), 2 Jlm (dotted) and 6 Jlm (dashed)
thick polypropylene. '
0.9
0.6
I:
~ 0.5
o~ 0.4
~ 0.3
0.2
0.1
0.0 '--__'__"""'""_""-----L_-'-_~---'_ __'__..L__'____'__....J
10 15 20 25 30 35 40 45 50 55 60 65 70
WAVELENGTH ( IN ANGSTROMS )
Figure 2. Transmission for 8 Jlm thick beryllium.
used in the past for proportional counter windows, is shown in Figure 3. Another
material which may be used for soft x-ray windows is a boron containing material
such as BN. Also shown in Figure 3 is the 'transmission for 400 nm of hexagonal BN.
Note that for equivalent thicknesses of 400 nm , BN windows, and especially formvar
windows, are much more transparent than diamond for F, 0, and N x rays. In this
case the BN falls below diamond for carbon x-ray transmission but is still useable at
this thickness.
The superiority of the compound materials comes about for two reasons. First,
formvar has a lower density than diamond, and second but more important than
1.0
0.9
.\
0.8
\
0.7 \
0.8
0.5 , ...
0.4 \
\
0.3
0.2 , ,,
0.1
0.0 ':---:':-~---:':--l...--':''''-'-''........L-~_l.--......L_...L..---l'-----.J
10 15 20 25 30 35 40 45 50 55 60 65 70
WAVELENGTH ( IN ANGSI'ROMS )
Figure 3. Transmission for 400 nm of formvar (solid line), diamond (dotted), and
BN (dashed).
.... :
0.0 l---'-_~_.L..---'-_-'-_..L---'_--'-_...L-_L----'-_-'
10 15 20 25 30 35 40 45 50 55 60 65 70
WAVELENGTH ( IN A.~GSI'ROMS )
Figure 4. Transmission for 400 nm of formvar (solid line), 138.8 nm of diamond

(dotted), and 213.3 nm of BN (dashed).
density, it is not a single element. It contains a mixture of carbon and oxygen. The
importance of this second point can be seen in Figure 4, which is the transmission
of the same three materials as in Figure 3 but for the same mass per unit area
instead of equal thickness. This suggests that the best window material from the
point of view of high transmission for a given mass thickness would be a mixture of
C, N, and O. Hydrogen would be used as required to tie up the dangling bonds. A
transmission curve for such a material is shown in Figure 5. This is in contrast with
10
09
08
z
0 0.7
Bl
Si
CIl 0.6
~ 0.5
~
z 0.4
0
~ 0.3
0.2
0.1
0.0 70
10 15 20 25 30 35 40
WAVElENGTH
t5)
A
50 55 60 65
Figure 5. Transmission for 400 nm of an idealized material.
1.0 .....
0.9
i
0.6
0.7
0.6
0.5
~ 0.4
~ 0.3
0.2
0.1
0.0
10 15 20 25 30 35 40 45 50 55 60 65 70
WAVElENGTH ( IN ANGSTROMS )
Figure 6. Transmission for 10 (solid line), 20 (solid line) and 40 nm of Al (dashed).
single element windows like diamond which are "colored" in that they transmit the
certain wavelengths better than others. Windows with 1:1:1 mixtures of the elements
will transmit roughly equivalently the wavelengths that correspond to each element.
Such windows would be approximately neutral density for elemental soft x rays and
can be termed "gray windows". Producing a "gray window" would be a noteworthy
achievement. Probably it will not be possible to produce such a window with a 1:1:1
mixture exactly, but in practice it may be possible to develop a compound with nearly
these ratios. It should be noted some of the families of materials which contain C, N,
and 0 are the polyimides, nylon and Kevlar.
Nonmetallic x-ray windows are normally metallized. In the case of proportional
counters to prevent charge build up. In the case of Si(Li) detectors this is to block the
transmission of infrared and visible light which would otherwise generate unwanted
noise. The metallic coating should be as thin as possible to to minimize x-ray absorp-
tion. The metal almost invariably chosen for this task is· aluminum. It shows about
the highest ratio of visible light extinction to soft x-ray extinction of any metal and
is self passivating in air. It is also a safer material to work than beryllium. We have
calculated the transmittance of light as a function of metal thickness using Airy's
formulae 6 and assuming normal incidence. The calculations show that Al is superior
to Be for blocking light. For example, at a wavelength of 578 nm a pair of 20 nm
Al layers have a combined transmittance of 0.504%. This is to be compared with a
transmittance of 43.04% for similar Be layers. Even though Be has a low mass absorp-
tion coefficient for x rays, the thickness required makes it inferior to Al for blocking
transmission of visible and UV light to Si(Li) detectors. We have not found a metal
superior to Al in this regard. The soft x-ray transmission of various thicknesses of
Al are shown in Figure 6. In the visible range 40 nm of aluminum extinguishes more
than 95% of the incident light. The overall transmission of the x rays is the product
of the film and the aluminum transmission.
The x-ray transmission is only one issue. The window must possess mechani-
cal properties commensurate with the task of maintaining a pressure differential of
approximately one atmosphere for long periods of time and/or under cycling condi-
tions. The properties which go into achieving this include film mechanical strength,
film perfection, and the support structure. It must have sufficient strength to survive
a pressure differential of over one atmosphere and sufficient rigidity not to flow. For
an aluminized polymer such as polypropylene, flow or stretching can cause cracking
of the aluminum thus compromising the window.
As has been discussed above, it is desirable for transmission purposes to make
a window as thin as possible. As a material is made thinner, there comes a point
at which it is not mechanically robust or reliable. This will depend upon the area
being spanned. The larger the area, the greater is the practical limiting thickness.
It was long ago realized that with some kind of support grid, effectively larger areas
could be covered with thin films. Recently our group at BYU developed a method
of making a very close-spaced grid for the support of thin films for the purpose of
soft x-ray windows for Si(Li) detectors. See Figure 7. A patent is pending for the
method and resulting structure. The method consists of micromachining a grid from
silicon. Typically the structure has ribs 25 11m wide separated by 100 11m, resulting
in a fractional free area of 80%. Windows with such a support structure have been
made using formvar, Si 3 N4 , a-C:H, and other materials.
Figure 7. Cut-away schematic of x-ray window showing micromachined support

structure and film.
50
20
'"
G1
"0
>-
0
10
'0
'"c:
"tJ
III
5
'"
::l
0
.t::
t-
85 80 80 70 80 50 40 30 20 10 5
Cumulative Percent Remaining
Figure 8. Pressure cycle results for 400 nm of aluminized formvar on 80% transmis-
sion grid.
With such a structure, film strength rarely is a serious issue. Calculations show
that as little as 1 nm of SbN4 , if the material were to possess bulk properties 111HI
were free of defects, when stretched over a 200 {tm opening could support a pressur.·
differential of one atmosphere. Such a thin film is not practical since thin films rarely
possess bulk properties and a single weak spot could render worthless an otherwise
acceptable window. Window integrity is thus usually more important than bulk yield
strength as a window selection criterion. It is well known that film perfection depends
on film formation. Such factors include care, cleanliness, and choice of formation
techniques.
Film structure must fulfill another role with Si(Li) detectors. It must hlock the
diffusion of gases into the region of the detector. this puts further constraints on
the microstructure of the window membrane and particularly discriminates against
polycrystalline materials such as diamond. For polymer windows for Si(Li) detectors
then, gas permeability is an additional reason for aluminization.
Windows made of 400 nm of formvar with 40 nm of Al have been pressure cycled.

The films were on a silicon support structure with a bar width of 25 {tm and a spacing
of 100 {tm. The active area was circular with a diameter of 6 mm. Typically these
have very low visible light transmission and have a He leak rate of less than 10- 10
std.atm.-cc/sec. The high pressure side was pressure cycled to 15 PSIG of argon.
A pressure sensor was on the other side of the window. The time to pressurize and
depressurize was 1 sec. Cycle times have been 2 sec. and 6 sec. There was no
discernable difference in results for the two cycle times. The results of this stress
test are summarized in Figure 8. The data have been fit to a lognormal curve (see
Appendix). These data indicate a T50 (median cycles to fail) of 5800 cycles. The
mean cycles to fail is approximately 5000.
CONCLUSION
Criteria for designing soft x-ray windows have been discussed. It was shown
that a thin material containing several elements, most notably 0, N, and C will
create a reasonably neutral window for the 10 A to 70 A region. Furthermore, it

was pointed out that materials such as diamond or polypropylene are essentially
edge filters. A structure which allows creation of very thin, high transmission, and
mechanically strong windows was disclosed. Pressure cycling data for such a window
were presented.
APPENDIX
The lognormal distribution is probably the most common wearout distribution

in nature. It is defined as follows:
The probability density is given by
where log = 10g10, T is the independent parameter; in our case it is the number
of cycles to failure, and T50 is the number of cycles for 50% of the samples to fail. It
is very difficult to obtain sufficient data to "divine" the probability density itself, but
it is easy to get the cumulative probability distribution.
The cumulative probability distribution is
F(T) = l x =T 1
-exp{--(
x=o J'Ei 2
1 log
a
x
T5°?}d(
log
a
x
T5o ),
where a is found from

a = 10gT50 - 10gT16
and where T16 is the number of cycles for 16% cumulative failures.
REFERENCES
1. B.L. Henke, et aI, Adv. X-Ray AnaL, ~, 277(1965)
2. B.L. Henke, et aI, Adv. X-Ray Anal., 18 ,76(1975)
3. G.D. Borley, et aI, "A Method of Producing Mounted Thin Windows for X-Ray
Spectrometer Flow Counters", X-Ray Spectrometry, Vol. 5, pp 13-15, 1976.
4. F. Williamson, et aI, "Thin Films for X-Ray Astronomy", Rev. Sci. Instrum.,
vol. 46, pp 50-52, 1975.
5. S. Priyokumar Singh, et aI, "Aluminized Mylar as Si(Li) Detector Window For

X-Ray Fluorescence Spectrometer", Nuclear Instruments and Methods
vol. 167, pp 223-225, 1979.
6. P. Yeh, Optical Waves in Layered Media, pp 90-97, Wiley, N.Y. (1988)

X-RAY CAPILLARY MICROBEAM SPECTROMETER
S. Larsson, P. Engstrom and A. Rindby

Chalmers University of Technology Physics Dept.
S-4l2 96 Goteborg, Sweden
B. Stocklassa
National Laboratory of Forensic Science
Linkoping, Sweden
ABSTRACT
By utilizing the total reflecting properties of x-rays inside glass

capillary tubes, intensive fine- or microbeams of x-rays can be attained.
By using a conventional x-ray tube in combination with capillary technique,
microbeams with a diameter of a few ~m and with an intensity sufficient for
trace elements, analyses have been achieved. By moving the sample, line-
and areas can can be performed and trace element information can be directly
superimposed on a micrograph from a built-in optical microscope.
The background of the capillary technique is reviewed and an EDXRF

microbeam spectrometer for trace elements is described. Examples of
applications for the microbeam spectrometer are given.
INTRODUCTION
In the last decade there has been a rapid development within the field
of SEM (Scanning Electron Microscopy) and microbeam PIXE (Protron Induced
X-Ray Emission). These techniques, which utilize the characteristic x-rays
from different elements, have enhanced the possibility to determine the
spatial distribution of elements in a sample on a microscale level. However,
in order to determine trace amounts of an element from the intensity of its
characteristic radiation, particle-induced x-ray emission methods might be
inadequate due to the severe background of x-rays generated by secondary
electron emission.
These problems can be avoided by using x-rays instead of electrons or

protrons. So far the problem has been to construct an x-ray microbeam with
sufficient intensity. With the use of synchrotron radiation and conventional
x-ray optics, high-intensity microbeams of x-rays have been attained and are
now in operation at several labs allover the world. l
In this paper we describe a "tabletop" x-ray microbeam spectrometer

for trace element analysis. The spectrometer is based on a conventional

x-ray tube and uses a capillary optical system for generating microbeams
down to a few microns.
CAPILLARY OPTICS
X-ray optics have been developed for over thirty years and much effort
has been devoted to constructing intense x-ray microbeams. The basic
difficulties in constructing an x-ray microbeam are related to the problem
of focusing a divergent x-ray beam into a focal point. As the attenuation
of x-rays is normally very strong, x-ray optics are normally based on mirror
optics. However, as the refractive indices of x-rays are very close to
unity the reflectivity for x-rays is normally extremely small and reasonable
reflectivity can only be achieved below the critical angle. As the critical
angle for x-rays typically is in the range of a few seconds of are, mirror
optics for x-rays will generally have a very large focal length and low
efficiency.
Owing to total reflection of x-rays, small glass capillaries with a

sufficient surface quality can be used as waveguides for x-rays in analogy
to the optical-fibre technique. With this technique microbeams of x-rays
can easily be obtained with relative high efficiency. Glass capillaries
have previously been used for constructing fine- bea,m collimators for micro
radiography2 and the total reflecting properties of glass capillaries have
been demonstrated by many authors. 3 - o In an earlier paper 7 one of us has
demonstrated the energy dependence of the intensity gained by guiding x-rays
in the x-ray tube anode with the energy-dependent gainfactor for
capillaries, a virtually monochromatic x-ray beam can be achieved from a
conventional x-ray tube. This technique has been utilized to generate a
200 ~m beam for trace element analysis. 8 By using conical-shaped
capillaries, beamsizes down to a few microns can easily be attained (see
Fig. 1). Conical capillaries also have much more sophisticated bandpass
properties for x-rays (as compared with a straight capillary) and seem to be
suitable for focusing radiation from an x-ray synchrotron source. 9 A more
comprehensive description of capillary optics has been given by Rindby et
al. IO
f.
R - -- -
---
Fig. 1. Micrograph of a capillary cross section with an
inner diameter of 19 ~m. (The grid size is 25 ~m)
S. LARSSON ET AL. 625
THE SPECTROMETER
The spectrometer consists basically of four different parts; the x-ray

tube, the capillary collimator, the optical microscope monitor and the semi-
conducting detector with the associated electronics (see Fig. 2).
Conventional Philips long-fine-focus diffraction x-ray tubes were used

as x-ray sources (with Cr and Mo anodes). The tubes were mounted on a
Philips PW 1011/02 high voltage power supply. The maximum power loading was
1080 W for the Cr tube and 1660 W for the Mo tube. The tube was positioned
vertically at the centre of the high-voltage power-supply table. In order
to facilitate the arrangement of the equipment around the x-ray tube, an
"optical table" was placed on top of the high voltage power supply table.
The "optical table" which consists of a 10 mm thick plate of stainless steel
with 400 screw-holes (M6) drilled in a regular pattern with a spacing of 50
mm (metric standard) allowed for a flexible and stable mounting of all kinds
of equipment on the table.
The capillary collimator consisted of a conical-shaped capillary of

boronsilicate glass with an inner diameter at the front end of 19 ~m. The
capillary was encapsulated into a stainless steel vessel filled with mercury
in order to prevent any x-rays from penetrating the vessel outside the
capillary. The mercury vessel was fitted into a standard five-axis gimbal
lensholder (Newport M-LP-05B) and put in close proximity to the point-focal
output of the x-ray tube shielding.
The detector used was a Si(Li) EDAX JSM-U3 with a 10 mm 2 active

surface and a 7.5 ~m thick beryllium window. The detector was connected via
an EDAX amp l83A to a MCA (Multi Channel Analyser) plug-in card in a
standard PC computer.
Fig. 2. The x-ray microbeam spectrometer set-up.

626 IX . XRF INSTRUMENTATION
Sulphur distribution Calcium distribution

5 400
4 300
'i
';:'3
::>
.r:.
%2
I
tU
0
200
rJ)
100
20 40 60 80 100 120 20 40 60 80 100 120

micrometer micrometer
Figs. 3 & 4. Sulphur and Calcium distribution across the hairstrand as
determined from the intensity of characteristic radiation .
Corrections for the attenuation of x-rays inside the sample
material has been taken into account.
The spectrometer is also equipped with a monitoring system consisting

of an optical microscope with a CCD camera. The camera was connected to a
frame grabber plug-in card in the PC computer. The microscope was mounted on
an X-Y mechanical table in order to adjust the optical axis of the
microscope in parallel with the x-ray microbeam. The microscope revolver
was also equipped with a room-temperature x - ray detector with associated
electronics for transmission analysis. The sample holder was mounted on an
X-y mechanical table at a plane perpendicular to the beam.
RESULTS
Hairstrand Crossection analysis
A single hairstrand was analyzed with the use of a 19 ~m microbeam of

Cr characteristic x-rays (see Fig. 6). The hairstrand was scanned cross-over
with a stepsize of 10 ~m. The intensity of characteristic radiation as well
as scattered primary radiation were recorded. As the concentration of
Hairstrand crossection
30
• a I •
20
•
g 10
Q)
E
•
0
.~ -1 0
E
-20
• • • •
-30
0 20 40 60 80 100 1 20
micrometer
Fig . 5. Hairstrand cross section as Fig. 6. Micrograph of the 19 ~m
determined from the intensity capillary end and a hair
of scattered primary radiation . strand (grid size 25 ~m) .
Corrections for the attenuation
of x-rays inside the sample
material have been taken in
account.
S. LARSSON ET AL. 627
Fig. 7. Micrograph of a leaf sample. The graph in the figure shows the
sample thickness profile as determined from the intensity of
scattered primary radiation. Scan increment is 20 11 m.
Note!- the inorganic particle incapsulated inside the leaf rib.
This particle contains high concentrations of Ca, Ti and Fe.
different elements are linearly dependent on the ratio of characteristic

radiation to scattered primary radiation, the distributions of elements
across the hairstrand were easily obtained (see Fig. 3 and 4). The
intensity of scattered primary radiation was used to reconstruct the cross-
sectional shape of the hairstrand (see Fig. 5) which then was used to
calculate the corrections for the attenuation of characteristic x-rays
inside the sample. When reconstructing the cross-section shape, a mirror
symmetric cross section was assumed. The result of the reconstruction was
in agreement with microscopique studies of the hairstrand.
Leaf-Scan Analysis
A birch leaf was scanned along the line indicated in Fig. 7 with the
use of a 19 11m microbeam Cr characteristic x-ray. The stepsize was 20 11m
and the intensity of characteristic radiation as well as scattered primary
Titanium Sulphur
Q) Q)
~
If)
~
If)
.ri
~
.e~
c: c:
o 0
~ ~
~o 'E
c:
~
c:
o 0
o 0
o 200 400 600 800 0 200 400 600 800
Distance (~m) Distance (~m)
Figs. 8 & 9. Concentration of Titanium and Sulphur as determined from the

intensity of the characteristic radiation along the scan line.
radiation were recorded. The ratio of characteristic radiation to scattered

primary radiation is presented in Figs. 8 & 9, representing the distribution
of different elements along the scan line. The variation of scattered
primary intensity is illustrated in Fig. 7, representing the thickness
profile along the scan line. Observe the inorganic particle in the
micrograph (Fig. 7) which is encapsulated inside the leaf-rib. Analysis
shows that such particles contain large concentrations of Ca, Ti and Fe.
These particles might be responsible for the increased concentrations of
titanium at the leaf-ribs (see Fig. 8).
CONCLUSIONS
It is clear that capillary optics offer a very simple and efficient

way to generate x-ray microbeams. In combination with a conventional x-ray
tube, Si(Li) detector, and an optical microscope, a complete instrument for
trace-element analysis on a microscopic level can be constructed. Compared
to other microprobe techniques, such as SEM or microbeam PIXE, x-ray
microbeam analysis offers a lot of advantages due to the simplicity of the
basic physical processes involved and the relatively small amount of energy
deposit in the sample. With a more adequate design of the x-ray source,
Si(Li) detector and capillary shape, a substantial increase of the
instrument efficiency can be attained.
REFERENCES
1. K. W. Jones and B. M. Gordon, Anal. Chern. 61:5 (1989) 341.

2. P. B. Hirch, X-Ray Diffraction of Polycrystalline Materials. (Chapman
and Hall, London 1960).
3. R. H. Pantell and P. S. Chung, Appl. Opt. 18 (1979) 897.
4. D. Mosher and J. Stephanakis, Appl. Phys. Lett. 29 (1976) 105.
5. W. T. Wetterling and R. V. Pound, Jour. Opt. Soc. Am. 66 (1976) 1048.
6. D. A. Carpenter, Microbeam Analysis 1988 MAS/EMSA Conference,
Milwaukee, WI, Aug 7-12, 1988.
7. A. Rindby, Nucl. Instrum. and Meth. A249 (1986) 536.
8. P. Engstrom, S. Larsson, A. Rindby and B. Stocklassa, Nucl. Instrum.
and Meth. B36 (1989) 222.
9. E. A. Stern, Z. Kalman, A. Lewis and K. Lieberman, Appl. Opt. 27 (1988)
5135.
10. A. Rindby, P. Engstrom, S. Larsson and B. Stocklassa, X-Ray Spectrom.
18, (1989) 109.
THE USE OF FIELD-PORTABLE X-RAY FLUORESCENCE
TECHNOLOGY IN THE HAZARDOUS WASTE INDUSTRY
G.A. Raab, C.A. Kuharic, W.H. Cole III,

R.E. Enwall and J.S. Duggan
Lockheed Engineering & Sciences Company
Las Vegas, NV
ABSTRACT
As the Environmental Protection Agency adds ever more sites to the National
Priorities List for Superfund clean-up, there is a tremendous need for a fast method of
screening for contaminants. In the case of inorganics, we can apply field-portable X-ray
fluorescence technology.
With commercially available field-portable X-ray fluorescence equipment using in-situ

measurements we can quickly screen a site (hundreds of measurements), input the data to a
portable computer, process it, and print a colored concentration isopleth map of the
contaminant of interest, all in realtime.
The in-situ measurement approach pioneered by Lockheed is the key to rapid

screening capability. Problems arising from particle size distribution, soil heterogeneity, and
bulk density are minimized by employing site-specific standards in the construction of our
calibration curves. Inherent in these site-specific standards are all the matrix problems which
occur in the routine samples.
The strength of field-portable X-ray fluorescence technology is the accuracy of

analysis above the quantitation limits. The difficulty in measuring low concentrations near the
detection limit is the weak point of field-portable units.
NOTICE: Although this research was funded in part by the U.S. EPA through
Contract 68-03-3249 to Lockheed Engineering & Sciences Company, it has not undergone
Agency review and does not necessarily reflect Agency policy.
INTRODUCTION
As the number of hazardous-waste sites continues to grow, the EPA has a growing
need for reliable analytical data In 1980 the EPA established the Contract Laboratory
Program, CLP, to specify standardized analytical methods and strict quality-assurance/quality-
control (QAlQC) protocol for the participating laboratories (U.S. EPA, 1986; U.S. EPA, 1989).
The QAlQC protocol includes intensive data and lab auditing by teams independent of the
labs. The resulting data is of known quality, and is ideally defensible in a court of law.
Under this system the cost of analyses is considerably higher with a much greater turnaround
time than for unregulated laboratory analyses.
Advances in X-Ray AnalYSIS, Vol. 33 629

630 X. XRF TECHNIQUES FOR HAZARDOUS WASTES AND OTHER APPLICATIONS
Lockheed Engineering and Sciences Company contracts to the EPA in Las Vegas,
Nevada to provide technological expertise in analytical chemistry, remote sensing and
logistical support. Under this mandate, we have been developing methodology for the use of
field-portable X-ray fluorescence in characterizing metal contamination in soils on hazardous-
waste sites (Raab, et ai, 1989; Raab, et ai, 1987). The goal of this work is to minimize both
time and expense, while providing data of known quality.
The traditional soil sampling and analysis pathway (Figure 1) is as follows: the sample
is taken, packaged, decontaminated, and sent by overnight courier to a CLP analytical lab for
chemical analysis. The results are then delivered to a data audit group for review. The
verified data are sent back to the EPA project manager, who meets with his contractors to
make the decisions on how to proceed. This process is lengthy and expensive with sample
turnaround of 21 to 45 days, at a cost of $200.00 to $4oo.00/sample for 24 analytes.
Field portable XRF (FPXRF) technology can be employed in site evaluation to save
time and money by meeting the following objectives:
o Develop an initial database from rapid on-site in-situ analysis, which requires no
intrusive sampling.
o Provide further analysis for questionable areas, after evaluation of the initial database.
o Yteld data of known quality from an established OAIQC program.
o Allow optimized selection of samples for laboratory analysis, after evaluation of the
enhanced database.
PACKING & SHIPPING
~, EPA
.O-z:_ ::o>I--.Y
JI II
EP A
CONTRACTons
ffi
OUI.~======v
Figure 1. Traditional Pathway for Sampling and Analysis
G. A. RAAB ET AL. 631
EQUIPMENT
The X-Met 880 is a field-portable, energy-dispersive X-ray fluorescence spectrometer

marketed by Columbia Scientific Industries Corporation, Austin, TX (Columbia Scientific
Industries, 1988). The unit is self-contained, battery powered, microprocessor based and
weighs 8.5 kg. The X-Met 880 is also hermetically sealed and can be decontaminated with
soap and water. The specially designed surface-analysis probe includes a radioisotope of
244-Curium, protected by an NRC-approved safety shutter, a Xe-gas proportional counter and
the associated electronics. While some sacrifice in sensitivity is entailed by using a gas
proportional counter instead of a SiLi detector, the analyses are sufficient for the data use
intended, and, in fact, compare favorably with values obtained using laboratory-grade
energy-dispersive X-ray fluorescence equipment(EDXRF), as shown in Table 1. Figure 2
illustrates a comparison of EDXRF and "wet' chemical concentrations for 4 analytes on two
different samples.
Table 1. A Cross Comparison of Routine Samples with Different XRF Methods

==============================================
Laboratory Grade EDXRF FPXRF
S
A Pellets Loose Loose
M soil in soil in
P cups cups
L
E All values in wt% Fe
#1 0.56 0.53 0.54

#2 0.73 0.68 0.75
#3 0.76 0.70 0.93
#4 0.71 0.60 0.67
#5 0.87 0.70 0.99
180
170
160
150
140
130
120
C>
"""-
C>
110
100
E
.; 90
II
0
80
::l
iii 70
> 60
SO
40
30
20
10
0
Cu Zn A. Ph
Elemenls
[22] lCP/AA [SS) EDXRF fiLZl 'CP/AA CS§j EDXRF
Figure 2. A Comparison of ICP, AA, and EDXRF Analyses

In-situ measurements are acquired by placing the probe directly on the soil, opening
the shutter, and taking a measurement of predetermined duration, usually 15 or 30 seconds.
The fluorescence intensity data is converted to concentrations by previously developed
calibration memories, or models. The electronic unit has 32 such calibration models. Each
model can be independently calibrated for as many as six elements. These can be used to
measure elements from silicon to uranium assuming the proper isotope source is available.
The routine data is recorded by hand as this unit has no memory for analyses.
PROCEDURE
The crux of FPXRF analysis is in the instrument calibration. Our instrument has no
fundamental parameters capability, so compensating for matrix effects must be done
empirically using calibration standards.
We have developed a two-step approach, summarized in Table 2. It involves the

generation of a set of site-specific standards, which are collected on a preliminary
reconnaissance trip, to construct the calibration curve.
Table 2. Instrument Calibration Standards
SITE TYPICAL (GENERIC)
APPROXIMATES MATRIX WITH RESPECT TO:
- Particle Size Distribution

- Bulk Density SCREENING IN SITU
- Heterogeneity
YIELDS RELATIVE CONCENTRATIONS ON

SPECIFIC SITE TO SELECT SAMPLE SUITE
~
SITE SPECIFIC
MATCHES MATRIX WITH RESPECT TO:
- Particle Size Distribution IN SITU ANALYSIS

- Bulk Density
- Heterogeneity
YIELDS QUANTITATIVE CAUBRATION CURVE
The instrument is first calibrated with a set of spiked soil samples, or site typical
standards. Numerous measurements are then taken over the site to obtain a wide range of
values typical of the site. This screening In-situ allows us to get a relative range of
concentrations for the analyte(s) of interest, from which we can better select samples to be
characterized and used as site-specific calibration standards. Physical samples are then
taken, dried, sieved through a 2mm mesh, homogenized and split. One split undergoes total
digestion in a Paar bomb (aqua/hydrofluoric regia/boric acids) and is run on AAS or ICP.
The total digest is used rather than the standard EPA extraction procedure, which is a nitric
acid/hydrogen peroxide leach, to avoid potential discrepancies between XRF totals and EPA
extraction results. Another split of the same soil is then measured on the XMET 880, and the
intensities are compared to the values obtained by the total digestion process. In this
manner a calibration curve using these site specific standards is constructed, and matrix
effects are minimized. Figure 3 illustrates a calibration curve used on a recent waste-site
analysis.
c
o
1.5
III
!::
c
1Il.Q
llCl.
c
O/fl
~i 1.0
III *
III
E *
II)
UJ 0.5
=
Correlation Coefficient: R 0.995
O.o~--------.--------.--------.--------,---------.----
0.0 0.4 0.7 1.1 1.5 1.9
Actual CLP Concentration
wt% Pb
Figure 3. Calibration Plot for Pb
Once the calibration curves for the analytes are generated from the site-specific
standards, the In-situ analysis can be performed.
In this step measurements are taken across the site on a grid pattern. The data is
recorded and transferred to a computer, and through the use of geostatistical software and a
plotter, concentration isopleth maps are constructed. These can be utilized to guide further
sampling or remediation efforts. For example, during the course of the remediation activity,
realtime maps can be produced on a daily basis to chart progress and delimit areas where
further work may be necessary.
The FPXRF program employs quality-control methods to ensure the calculation of

accuracy, precision, and detection limits. We analyze two quality-control check samples.
One of these is in the mid-calibration range, the other is a near-zero concentration. Prior to
beginning the in-situ measurements, after every tenth routine sample and at the end of a
sampling sequence these standards are measured in triplicate. The average value must be
within plus or minus 10% of the standard's actual value for the analyte of interest.
These consecutive measurements on the near-zero concentration sample are used to

generate detection limits. According to the American Chemical Society (ACS, 1983) the
instrument detection limit is three times the standard deviation of a series of nonconsecutive
blanks, or 3 sigma. The limit of quantitation is defined as 10 sigma. Table 3 gives some
numbers derived from the last few sites analyzed. A sample below the 3 sigma value is
recorded as a nondetect. Figure 4 gives a visual idea of the concept.
Table 3. FPXRF Detection Limits for Several Sites
Standard Pb Cu Cr
Deviation All values in mg/kg
1 sigma 25 50 15
3 sigma=ID 75 150 45
10 sigma=LOQ 250 500 150
Precision (est.) ± 5%, Accuracy (est.) ± 10%

r-
LIMIT OF
aUANTITA TION
10 a
- ,-
INSTRUMENT
DETECTION LIMIT
1 a
o
-
Sample
A
Sample
8
Sample
C
n
Sample
D
Figure 4. Visualization of Instrument Detection Limit
and the L1mH of Quantltatlon
At high concentrations, 10 sigma and above (Figure 4, Sample A), our measured
values show excellent correlation to laboratory values. Physical samples from this range are
not really necessary (ct. Table 1). The questionable measurements are those below 10 sigma
(Figure 4, Samples B, C, and D), and here corroboratory samples need to be taken and sent
to a laboratory.
Once the data are collected, processing begins. In general the data points are
assumed to be spatially autocorrelated, so that data analysis utilizing the theory of
regionalized variables, or geostatistics, can be employed to derive maps of element
distribution over the site. If this is not the case, then alternative interpolation methods are
used to contour the data.
AN EXAMPLE
The following three figures represent data from an hazardous waste site analyzed for
Pb. Figure 5 is a map of the site, showing the sampling locations and buildings on site.
Figure 6 is a spatial model of the Pb concentrations generated from the sample data. Using
this model, the software constructs a contour map of Pb concentrations, Figure 7.
Using the grid that was previously established, the 119 sample points were measured
in less than two days. At each sample point, field analysts made three measurements and
•
~ • • •••., •
~
• • • •
:::&r(~
•.....
• •••
•••• *~ -
....
~ •
~
:' - L,
•
•
• \
~
•
•
,--
•.,
., \
1
•
•
.,•
•
•
•
...•
•
., .,
D
., ., .,., .,
.,
• ., .,
., ., •
., ., .,., •
.,
• ., .,
•
., .,
••
., ~ ., ., f
0 ~ ,n
'-mi-'
ILKHC :ILL'LI
Figure 5. XRF Survey Points Hazardous Waste Site

'.soo
1 .000
3.500
~
~ 3.000
,.
.'"
w 2.500
u
w
2.000
'"
u
w
1.500
" 1.000
0.500
0.000
nnn
t.~~.
\tJ~o
Figure 6. Hazardous Waste Site Spatial PB Model - Kriging

Interpolation View From Southeast to Northwest
Figure 7. PB Contours - Concentration In Weight Percent

Contour Levels - 0.05,0.2,0.4,0.6,0.8,1.0,1.5,2.0,2.5,3.0,3.5,4.0
used an average value calculated in the data processing stage. The three measurements
help to compensate for variability in the soil, and increase sample representativeness.
CONCLUSIONS
Field portable XRF has been demonstrated to play a useful role in the hazardous
waste industry. It is economic of both time and money, as well as being a valuable tool to
aid in assessment planning. With the number of contaminated sites growing steadily, it offers
exciting potential for future applications for several reasons:
o We can effectively use in situ analyses to routinely analyze soils on hazardous waste
sites providing valuable information in realtime with defensible quality assurance
procedures.
o We can measure hundreds of locations in a short time without collecting physical

samples. Field personnel can examine realtime data and guide multistage sampling
and remediation.
o We can successfully measure high concentrations without corroboratory analyses,

thus reducing expenditures of time, effort and money.
REFERENCES
American Chemical Society on Environmental Quality (1983). Principles of Environmental

AnalYSis. Anal. Chem. 55: 2210-2218.
Columbia Scientific Industries Corporation (1988). X-MET 880 Portable XRF Analyzer
Operating Instructions.
Raab, G. A, D. Cardenas, and S. J. Simon, (1987). Evaluation of a Prototype Field Portable

X-Ray Fluorescence System for Hazardous Waste Screening. EPN600/4-87/021. U.S.
Environmental Protection Agency, Las Vegas, NV, 33 p.
Raab, G. A., M. L. Faber, and S. J. Simon, (1989). Development of a Field Portable X-Ray
Fluorescence System for On-Site Hazardous Waste Screening. !n: Proceeding of the
Thirteenth Annual British Columbia Mine Reclamation Symposium. Mining Association of
British Columbia, pp. 137-172.
U.S. EPA (1986). User's Guide to the Contract Laboratory Program. Office of Emergency
and Remedial Response, Washington, D.C., 20460.
U.S. EPA (1989). Contractor Laboratory Program Statement of Work for Inorganic Analyses,
SOW No. 788, Attachment A.
XRF TECHNIQUE AS A METHOD OF CHOICE FOR ON-SITE ANALYSIS
OF SOIL CONTAMINANTS AND WASTE MATERIAL
Stanislaw Piorek
Princeton Gamma-Tech
A Member of the Outokumpu Group
1200 State Road
Princeton, New Jersey 08540
ABSTRACT
Recent years were marked by a rapid increase of interest in the use of

x-ray fluorescence for on-site chemical characterization of contaminated
soils and waste materials.
The known advantages of the XRF technique, such as capability of simul-

taneous, multielement analysis, speed of measurement (10 to 100 seconds),
little or no sample preparation, wide concentration range, "portability,"
and ease of integration into environmental monitoring station(s), make it
specifically suited for this application.
Major difficulties still inhibiting wider use of the XRF for hazardous
waste screening stem from the lack of suitable calibration samples and
proper protocols, as well as from the low awareness of the industry about
the technique.
INTRODUCTION
The implementation of the Resource Conservation and Recovery Act (RCRA)

and the Comprehensive Environmental Response, Compensation and Liability Act
(Superfund) has greatly increased the need to measure the chemical character-
istics of wastes. The nature of the problem requires the measurements to be
rapid and inexpensive, yet with uncompromised accuracy and precision.
Moreover, most of the critical testing has to be done in the field rather
than in laboratory conditions if the program of environmental monitoring is
to be timely and cost effective. The magnitude of the problem is best
illustrated by the staggering number of 1217 hazardous waste sites included
in the national superfund priority list as the most dangerous ones. The
well known advantages of the mature and reliable x-ray fluorescence
technique make it a method of choice for this demanding field application.
The U.S. Environmental Protection Agency accepts Energy Dispersive

XRF as a Level II analytical method according to the guidelines for Data
Quality Objectives for Remedial Response Activities. l This means that XRF

can be used for screening and preliminary on-site evaluation of levels of

contaminants, with an accuracy up to ± 50% relative and precision up to ±
10% relative.
Field portable, battery powered, microprocessor controlled, radio-

isotope excited x-ray fluorescence analyzers are ideal tools for on-site
screening of hazardous waste.
PORTABLE X-RAY ANALYZER FOR HAZARDOUS WASTE SCREENING
A portable x-ray analyzer configured for on-site hazardous waste

analysis consists of a probe and an electronic unit. The probe contains an
x-ray source (or sources), a detector, and a means of reproducible
presentation of a sample for measurement. The electronic unit accepts the
signal from the probe, processes it, and displays the result. It also
contains power supplies and interfaces for communication with the operator
and peripheral devices.
A sealed radioisotope capsule emitting x-rays or low energy gamma rays

is the preferred source of primary radiation for portable instruments. Such
sources are compact, rugged, light weight, and drift free.
While the solid state detectors can completely resolve K x-rays from
neighboring elements, they mostly still require cooling for optimum
performance; this often contradicts the idea of portability. Gas filled
proportional detectors have been recognized traditionally as devices of
mediocre resolution (20% for the Fe K-alpha line). New developments in
proportional-counter technolog~ have yielded detectors with much better
energy resolution (10 to 12%). This, coupled with modern microprocessor
technology, has resulted in the commercial availability of a hand-portable
x-ray analyzer capable of simultaneous multielement analysis. 3
CALIBRATION
As a comparative analytical technique, x-ray fluorescence spectrometry

requires a number of well-characterized samples for calibration. Even so-
called standardless analysis needs at least one standard to verify its
theoretical predictions with practical reality. An analytical approach
based on the fundamental parameters method will not yield desired results if
the measured samples are not ground fine enough to reduce the influence of
particle-size induced errors on the algorithm convergence.
The other alternative is to rely on empirical calibration developed

with analyzed samples resembling measured unknowns as close as it is
practically possible. Two approaches can be distinguished in the empirical
calibration for hazardous waste analysis. One becomes known under the name
of "site-specific calibration," whereas the other is based on "synthetic
calibration samples."
The site-specific calibration requires a large pool of well

characterized samples collected on the site on which consecutive
measurements of unknown material will be made. Perhaps it is the best
empirical calibration in terms of matching the matrix in the unknown sample
with that of the standard. However, only well financed, large-scale
clean-up projects can provide the desired pool of samples covering all
elements of interest in varying concentrations. Creating the appropriate
s. PIOREK 641
set of site-specific samples is a very expensive and time-consuming process

the results of which are difficult to predict.
It is virtually impossible to get the set of site-specific samples for

the small hazardous-waste site. On the other hand, suitable materials have
not been available for calibration of x-ray analyzers for hazardous-waste
analysis. Finely ground geochemical and mineral quantities by NIST (NBS) or
CANMET, cannot be used for routine calibration of portable x-ray equipment.
These materials do not match the matrix of the unknown chemically or
physically, they do not contain the elements of interest in appropriate
concentration ranges, and their supply is limited. Therefore, calibration
samples have been developed specifically for portable x-ray analyzers set up
for hazardous-waste screening. 4
Synthetic calibration samples. Calibration samples were prepared from

a batch of clean soil collected from an area known to be free of pollutants.
About 20 kg of predominantly silicaeous soil was oven dried at 10SoC to
constant weight and then allowed to equilibrate to ambient humidity and
temperature. The dried soil was tumbled and agitated in order to break up
agglomerates and lumps; however, it was not ground. Next it was run through
a number 8 mesh sieve to yield about 12 kg of undersize fraction which was
then used as a starting material for calibration samples. Twenty aliquots
of 200 g each of the undersize material were weighed into clean plastic
containers and then spiked with appropriate amounts of the desired elements.
The elements chosen for spiking were copper, zinc, arsenic, lead, chromium,
and cadmium. After spiking, each 200 g aliquot was homogenized in its
container by tumbling. The dispersion of the spiking elements within each
200 g aliquot was estimated by taking for each analyte the ratio of the
standard deviation obtained on a series of ten subaliquots to the mean
intensity of the series. It was found that this ratio varied between the
spiking elements up to S.l% relative, which is entirely satisfactory for
calibration of a rapid screening method. In a similar manner, intrinsic
nonhomogeneity of the soil was estimated using the intensity of iron, which
was found to be 1.7% relative.
The preparation process described above imitates the widely accepted

procedure for sampling and analysis of contaminated soil. The procedure
calls for collecting about 100 to 200 g of soil, drying it at lOSoC,
removing foreign objects (twigs, pebbles, etc.), breaking up agglomerates
and lumps, sieving the material through an 8 mesh sieve, and collecting the
undersize fraction for consecutive analysis. As can be noticed, the
procedure does not involve grinding of the material, which would be the next
preparation step in an x-ray analysis of powdered material. However, the
introduction of grinding would defeat the whole idea of speed and
portability. Instead, an innovative approach is proposed to match physical
characteristics of the measured material and calibration standards by not
reducing particle size of the standards.
Table 1 lists final concentration values of the spiking elements in

each calibration standard.
MEASUREMENT OF CONTAMINANTS IN SOIL
Figure 1 shows an example of a typical calibration curve obtained with

the standards described above using a commercially available portable x-ray
fluorescence analyzer set up with a probe equipped with a gas-filled
proportional detector and a radioisotope source. The analyzer was a Model
Table 1. Ha"ardous Waste Calibration Standards

------------------------------------------------------------
Standard mg/kg of Element Added
Sample - _. - - _.. -- - - -- - - _. - - - - - _.- - - - - - - _.- - - - - - - - -- - - - - - - - -- - - -- - --
Cr Cu Zn As Cd Pb
-----------------------------------.--------------------------------
101 0 0 0 I) (I 4950
102 0 0 0 0 4950 0
103 0 0 0 4950 0 0
104 0 0 4950 0 I) 0
105 0 4950 0 0 0 0
106 49:30 0 0 0 0 0
107 9250 6480 3700 2780 1850 930
108 480 240 120 9640 6750 :3860
109 2940 1960 980 490 250 120
110 120 480 480 970 9690 2910
111 3710 9280 9280 6490 3710 1860
112 1890 940 6600 3770 28:30 6600
113 6740 3850 240 240 480 480
114 240 2900 1960 120 120 9680
115 980 120 2940 1960 490 250
116 0 0 0 0 0 0
117 0 2910 4850 0 0 0
118 0 4850 2913 0 (1 0
119 0 0 0 4850 (J 2910
120 0 0 0 2910 0 4850
------------------------------------_._------------- -------- _ _-- .. -
..
o
o
o i
I
i
~~~----,_---r----r_--,_--~----,_--_r----,_--~--_,-~
4 6 8 10 12
(Thousonds)
mg/kg Arsenic (ci,em.)
o
Calibration for Arsenic in Soil
S. PIOREK 643
Table 2. Typical Performance Data for Analysis of

Metallic Contaminants in Soil; (units are mg/kg).
Element: Cr Cu Zn As Pb (Lf3) Cd
Source: 6 mCi Cd-109 or 100 mCi Cm-244 6 mCi 100 mCi 30 mCi
Cd-109 Cm-244 Am-241
RMS
Error +/-100 +/-180 +/-150 +/-200 +/-180 +/-220 +/-130
Counting t/-60 +/-10 +/-10 +/-10 +/-20 +/-60 +/-10

Error +/-100 +/-90 +/-80 +/-80 +/-80 +/-130 +/-·40
Detection
Limit 200 100 100 120 100 200 50
NOTE: RMS Error is a measure of spread of data around calibration curve.

Detection Limit is equal to 3 std. dev. of counting statistics.
obtained on the "blank" sample.
Table 3. Results for Unknown Samples of Contaminated Soil (mg/kg)
Sample Copper Zinc Arsenic Lead
Number ref X--MET ref X-MET ref X-MET ref X-MET
5 6730 5701 6150 4750 2640 2592 1600 1824

20TS 9580 8108 7880 6067 2640 2240 1610 1 f,80
G 9970 8049 8180 6183 2820 2418 2090 1962
1L 5240 4302 5600 4123 2940 3018 1970 2513
3 6480 572.3 7630 6350 2170 2556 1630 242:3
3A 7600 6378 5850 4466 3240 2432 1930 1398
X-MET 880 manufactured by Outokumpu Electronics. Table 2 lists typical

performance data for the analysis of contaminants in soil.
Table 3 lists the results obtained for the unknown samples of

contaminated soil using the calibrated analyzer. The bias between the
measured and expected results is due to the fact that the unknown samples
were finely ground. This hypothesis has been verified in a separate
experiment. Nevertheless, the results are satisfactory in terms of
screening analysis which allows for an overall accuracy up to ± 50%
relative. 1
The analyzer can be used in the field to screen the contaminants

directly on the exposed soil surface with its special, dual source, surface
probe. Another feature of the analyzer very useful in the field is its
ability to store the measured data for future downloading to the computer
and processing. The data storage is accomplished by connecting the
analyzer, via its RS 232 port, with a pocket size, commercially available
programmable computer with an unlimited number of exchangeable memory chips.
After the data storage program is activated, it works in the background,
intercepting only those segments of the "dialogue" between the operator and
analyzer for which it was set up. Since the data are stored in a standard
ASCII format, they can be read directly by almost any data-processing or
report-generating software such as Lotus 123, Wordperfect, and the like.
Table 4. Results for Total Chlorine in Waste and Fuel Oil. mg/kg
Referee As Measured with X-MET in Three

Sample Analysis Aliquots of the Same Sample Remarks
1A 156 81 191 230

2A 500 455 424 400
3A 1140 1070 1046 1046 Calibration
4A 2123 2110 2113 2176 Samples
5A 5075 5081 5252 5080
6A 9994 9926 9935 9928
A1 717 771 788 704 Virgin

A2 1580 1667 1728 1732 Crankcase
A10 1071 1179 1250 1271 Oil
D1 1193 1012 1051 1103 Fuel Oil li2
E1 1101 1022 910 883 J!"uel Oil #6
F1 1321 1244 1283 1301

F2 1817 1718 1727 1677 Waste
F3 1226 1226 1250 1231 Crankcase
F4 2076 1877 1858 1860 Oil
F5 1476 1472 1411 1485
F6 1726 1603 1638 1674
--------------------------
-------------------------- -------------------------------------
-------------------------------------
Instrumental Precis on: +/-30 to +/-60 mg/kg
RMS ("Total" ) Error +/-55 mg/kg
Detection Limit: +/-100 mg/kg
ANALYSIS OF USED OIL FOR TOTAL CHLORINE
About 500 million gallons of used oil are burned each year in boilers
and industrial furnaces in the U.S.A. Used oil is often mixed with spent
chlorinated solvents; therefore, a real danger exists that boilers may emit
hazardous levels of solvents to ambient air, creating a cancer risk to
humans.
In 1985, EPA published the rules which ban sale of used oil for fuel
to nonindustrial users if the total halogen content of the oil exceeds 1000
mg/kg. Since it is not easy to determine a total halogen content, EPA has
agreed to interpret "total halogen" as total chlorine. As a consequence,
the affected community will have to determine total chlorine in used oils
and fuels.
Table 4 illustrates the results obtained for total chlorine in

different oils using a portable x-ray analyzer equipped with a light-element
probe and a 20 mCi Fe-55 radioactive source. 5 A 5 ml aliquot of each sample
was measured for 200 sec in a plastic cup with a 6 micron thick
polypropylene x-ray window.
As the results indicate, a portable x-ray analyzer can readily handle

varying matrix of waste and fuel oils, providing on-the-spot analysis for
total chlorine.
S. PIOREK 645
CONCLUSIONS
Small, portable, battery-operated x-ray analyzers become indispensable

tools for on-site field screening of hazardous waste and contaminated soil.
They are capable of detecting as low as 100 to 200 mg/kg of metallic
elements in an unprocessed sample of soil in a matter of 100 to 200 sec.
The combination of good sensitivity and portability makes the x-ray analyzer
an ideal tool for initial site assessment during which the areas of
increased contamination are usually delineated.
An operator equipped with a calibrated portable analyzer can scan the

area within hours or days leaving behind pinpointed sites of contamination
(so-called "hot spots") which might not get noticed otherwise. While the
other members of the clean-up operation step into action, the operator can
work on another site. Eventually, he can be called back as many times as
needed to verify the quality of the cleanup operation. This scenario is
much less expensive and much more effective when compared with the
traditional one where teams are waiting for weeks for the results of
analysis, often to learn that they have to collect some more samples and
wait longer.
REFERENCES
1. USEPA Data Quality Objectives for Remedial Response Activities

Development Process," EPA/540/G-7/003, 1987.
2. Jarvinen, M-L., Sipila, H. - "Effect of Pressure and Admixture of Neon

Penning Mixtures on Proportional Counter Resolution," Nucl. Instr.
Meth. 193 (1982), pp. 53-56.
3. Piorek, S., Rhodes, J. R. - "Application of a Microprocessor Based

Portable Analyzer to Rapid Nondestructive Alloy Identification,"
Advances in Instrumentation, Vol. 41, Part 3, pp. 1355-1368, ISA, 1986.
4. Piorek, S., Rhodes, J. R. - "A New Calibration Technique for X-Ray

Analyzers Used in Hazardous Waste Screening," Proceedings of the 5th
National Conference on Hazardous Wastes and Hazardous Materials, April
19-21, 1988, Las Vegas, pp. 428-433.
5. Gaskill, A., Estes, E.D., Hardison, D. L. - "Evaluation of Techniques

for Determining Chlorine in Used Oils," Res. Triangle Institute
Project #472U-3255-05, Contract Number 68-01-7075, August 1987.
APPLICATION OF FIELD MOBILE EDXRF ANALYSIS
TO CONTAMINATED SOIL CHARACTERIZATION
A.R. Harding
Tracor Xray, Inc.
345 E. Middlefield Rd.
Mountain View, CA 94043
J.P. Walsh
James P. Walsh and Assoc.
Boulder, CO 80306
INTRODUCTION
Effective assessment and remediation of hazardous waste sites
dictates that analytical methodologies be developed which
assist in the evaluation of site contamination and
simultaneously make efficient use of sampling time and
resources (1). Optimally, a technique would provide on-site
personnel with immediate and accurate information concerning
the identity and concentration of inorganic soil contaminants
(2) •
Inorganic pollutants can be readily determined in

contaminated soils with energy dispersive X-ray fluorescence
spectrometry (EDXRF) using a thermoelectrically cooled Si(Li)
detector (3). A field-mobile laboratory van or trailer can
accommodate the EDXRF system because the electrically cooled
detector, which provides high resolution EDXRF spectra, does
not require cryogenic cooling. Soil sample preparation for
EDXRF analysis is minimal, therefore, short turnaround times
are realized between sampling and reporting results.
This report will describe an EDXRF method developed to
determine four inorganic soil contaminants: lead, arsenic,
zinc, and cadmium at four sampling depths. Approximately two
hundred samples were analyzed with this method and the EDXRF
results of these samples will be presented as contour maps to
visually describe the analyte contamination plume. EDXRF
results will also be compared to results obtained for sample
splits submitted for AA/ICP analysis at an independent
laboratory. Accuracy and precision of the EDXRF method will
also be compared to the AA/ICP method using standard
reference materials and soil samples submitted in triplicate
to both laboratories.
Advances in X-Ray Analysis, Vol. 33. 647

648 X, XRF TECHNIQUES FOR HAZARDOUS WASTES AND OTHER APPLICATIONS
EXPERIMENTAL
The field mobile EDXRF spectrometer used in this work was a
Tracor Xray Spectrace 6000 (Tracor Xray, Inc., Mountain View,
CA). The EDXRF system consists of three modules: the
spectrometer, the control/pulse processing electronics, and
the data analysis computer. The compact size and weight (90
lbs.) of the modules permits installation of the system in a
laboratory trailer or van.
The bench-top spectrometer module, which can accommodate a
single soil sample, is powered by 110 V line or generator
feed. The excitation source used is a low-powered Rh-anode X-
ray tube (50 kV, 0.35 IDA (17 W) maximum output) positioned at
a 45° incident angle to the sample. Three primary radiation
filters permit optimum spectral acquisition conditions to be
computer selected.
The thermoelectrically cooled Si(Li) X-ray detector is
mounted at a'45° take-off angle in an inverted geometry with
respect to the sample. The 20 mm 2 Si(Li) crystal, which is
protected by a 0.5 mil Be window, is reduced to -90°C for
operation using a mUlti-stage thermoelectric (Peltier effect)
cooler. The 300 watts produced at the detector heat sink are
dissipated by forced ambient air. Thermoelectrically cooled
detectors provide typical resolutions of 185 eV (Mn Ka) •
A card-cage module is interfaced between the spectrometer and
an IBM PS/2 or PC/AT series computer. The microcomputer
serves as the contour mapping computer as well as the
spectral data acquisition/analysis module. The card-cage
components include the detector high voltage supply, the
pulse processing electronics, and the control circuit board
for the EDXRF spectrometer.
Sampling of the suspected waste site was performed using EPA
approved protocols in a Q500'x 3500' rectangular area. Forty
three (43) cores were collected and were partitioned into
four depth levels: surface to 2"; 2" to 6"; 6" to 12"; and
12" to 18", and designated levels 1 through 4, respectively.
At the site, samples were first homogenized and then split
into two fractions. One was submitted for EDXRF analysis and
the other sent to an independent lab for AA/ICP analysis.
The independent laboratory'used EPA SOW 846 methodology to
determine contaminant concentrations in the soil sample
split.
Sample preparation for the EDXRF analysis consisted of drying
the sample for 4 min. in a microwave oven followed by sieving
the dried sample to 2 mm. Sieving removes large foreign
objects such as pebbles and sticks. Drying the sample was
required due to the variable moisture content in the
submitted soils; some surface samples had the consistency of
mud. The sieved soil was then ground in a Spex shatterbox
grinder (Spex Ind., Edison, NJ) using tungsten carbide cups
for 2 min. The grinding cups were cleaned using soap and
tapwater. The cleaned cups were rinsed with
distilled/deionized water followed by isopropanol. The
A. R. HARDING AND J. P. WALSH 649
Table 1. Spectral acquisition conditions for

the EDXRF analysis of soils.
SPECTRAL REGION CONDITIONS ANALYTES
MID Z 35 kV, 0.35 mA, o .13mm Mn, Fe, Cu
Rh filter, 200 s lifetime Zn, Pb, As
HIGH Z 50 kV, 0.35 mA, 0.63mm Cd
Cu filter, 200 s lifetime
prepared soil sample was poured into a disposable 32 mm X-ray

sample cup and covered with a 6.3 Mm polypropylene film.
Approximately twenty five samples were prepared and analyzed
per day.
STANDARDIZATION METHOD
Two sets of excitation conditions were employed to determine
seven elements in the soil samples, four of which are of
specific environmental concern: Zn, As, Pb, and Cd. Table 1
lists the two sets of spectral acquisition conditions used
and which conditions were used to determine each analyte.
Figure 1 is a mid-Z spectrum of a soil sample that was found
,
e Z
r
I
I 'I~
I~ l ,/,,1
~.
:=: 11 17 14 1 ... KEV
Figure 1. Mid-Z spectrum of a soil sample containing 1100

ppm Pb, 729 ppm Zn, and 125 ppm As. Vertical full
scale is 2,000 counts.
Table 2. Lower limits of detection for the

analytes of interest.
Mn - 21 ppm Pb - 7 ppm
Fe - 19 ppm As - 12 ppm
Cu - 26 ppm Cd - 4 ppm
Zn - 19 ppm
to contain 125 ppm As, 1100 ppm Pb, and 729 ppm Zn. A
multiple linear least-squares peak fitting routine was used
for deconvolution of overlapped peaks.
The soil characterization method was standardized using four
standard reference materials (SRM): NBS 1648 (urban
particulate); NBS 2704 (river sediment); SO-l and SO-3, two
soil standards available from the Canada Centre for Mineral
and Energy Technology. Standards labeled NBS are available
from the National Institute for Standards and Technology
(NIST). These SRMs have certified concentrations of Fe, Mn,
Cu, Zn, Pb, and Cd.
A fundamental parameters (FP) method was employed as the data
treatment scheme and used the certified concentrations of Fe,
Mn, Cu, Zn, Pb, and Cd in the four standard materials. To
compute the instrumental sensitivity, the balance of the
standard was assumed to be comprised of SiOS to account for
the contribution of the matrix to the measured analyte X-ray
intensity. Arsenic sensitivity was determined using a
theoretical calculation based on the computed Zn sensitivity.
The selection of an FP method for standardization allows well-
characterized SRM's to be the basis of analyte sensitivities
and eliminates the need for site-specific soil standards.
The FP method permits accurate analyte concentrations to be
determined in samples with wide matrix variation without
restandardization. Theoretical analyte sensitivities can be
computed by the FP routine when a standard with a certified
analyte concentration is not available.
Table 2 lists the calculated (3jB) lower limits of detection
for the two sets of spectral acquisition conditions used.
For the analytes of specific environmental concern, the LLD's
are at the 10 ppm concentration level. Calculated LLD values
could be improved with longer spectrum-acquisition livetimes
and alternate excitation conditions.
Table 3. Correlation-plot data for the four analytes

of environmental interest.
CORRELATION
ANALYTE SLOPE INTERCEPT COEFFICIENT
Pb 1. 01±0. 03 10.0±13.8 0.96

As 1. 08±0. 05 0.98±3.54 0.92
Cd 1. 02±0. 03 3.09±2.19 0.94
Zn 1. 02±0. 02 63. 0±13. 6 0.98
1600 0 0
§
~ 1200
>-
CD
Ea. BOO
-5
CD
a..
400
1600
PB (ppm) BY EDXRF
Figure 2. Pb correlation plot for 138 samples.
Results for the determination of four analytes by EDXRF in

196 samples were compared to independent AA/ICP analysis
results in order to evaluate the level of agreement between
the two methods. Table 3 lists the correlation-plot data for
the analytes in terms of actual slope, intercept, errors, and
the correlation coefficient of the fit. Each analyte-
correlation plot included approximately 150 data points.
As shown in Table 3, slopes of the plots for Pb, Cd, Zn, and
As are within 8% of unity and all correlation coefficients
greater than 0.92. The calculated slope near 1.00 and
correlation coefficient greater than 0.90 indicates good
agreement between the two analytical techniques. Figure 2 is
a plot of 138 data points in the range of 0 to 1800 ppm Pb.
Figure 3 is a plot of 125 EDXRF and ICP analyzed samples for
cadmium and indicates good agreement between the results of
the two methods for this soil contaminant.
To evaluate the accuracy provided by the EDXRF method two

SRM's were submitted as unknowns for EDXRF analysis as well
as being submitted to the AA/ICP lab for analysis. Table 4
contains the results for two SRM's, SO-l and SO-2. SO-l was
used in the EDXRF standardization method and the EDXRF
350 0
0
280
a..
~
0
>- 210
CD
0
Ea. 0
-5 140 0
0
u
0
70
70 140 210 280 350

CD (ppm) BY EDXRF
Figure 3. Cd correlation plot for 125 samples.

Table 4. Results of the analysis of two SRM's by

AA/ICP and EDXRF methods. All values in ppm.
SAMPLE ANALYTE AA/ICP EDXRF CERTIFIED
50-1 Pb 41 14 21
Zn 129 147 146
50-2 Pb 19 17 21
Zn 55 123 124
results show good agreement with the certified

concentrations. The AA analysis for Pb in SO-1 is in error
by about 50%. EDXRF analysis of SO-2, which was not used in
the EDXRF method standardization, again provides results that
are in good agreement with certified values. The independent
AA/ICP analysis for zinc in SO-2 is biased low by a factor of
one-half.
Sample-to-sample precision for both the independent analysis
and EDXRF was evaluated by submitting three samples a total
of three times to each laboratory. Table 5 shows the
results for the two methods along with the calculated
standard deviation of the three replicate analyses. Note
that Cd in sample C was only reported by EDXRF to the nearest
1 ppm and three values of 9 ppm Cd were determined, hence the
zero standard deviation for the three replicates. EDXRF
sample-to-sample repeatability is within 10% in all but one
case (As in sample C) and is comparable to precision provided
by the AA/ICP methods.
The extent of contamination in the area is best illustrated
to on-site personnel with concentration contour plots of
EDXRF data for each element of interest. Figure 4 is a
contour plot of Cd concentration in the surface layer (0 to
2"). The method of estimating isopleths from individual
sample points is called kriging (4). The kriging and
plotting routine used here was Surfer (Golden Software,
Table 5. EDXRF and AA/ICP results for three soil

samples each analyzed in triplicate.
SAMPLE ELEMENT AA/ICP EDXRF
A As 45 ± 4 41 ± 3
Cd 20 ± 2 31 ± 3
Pb 286 ± 28 312 ± 12
Zn 185 ± 15 134 ± 10
B As 17 ± 3 14 ± 1
Cd 80 ± 6 58 ± 4
Pb 141 ± 15 158 ± 3
Zn 556 ± 39 529 ± 46
C As 17 ± 1 19 ± 4
Cd 10.0 ± 0.9 9 ± 0
Pb 117 ± 8 142 ± 14
Zn 173 ± 26 128 ± 3
7710.49 8878.86 10047.23 11215.60 7651.70 8839.67 10027.63 11215.60

10756.20 10756.20 10756.20 10756.20
9570.40 9570.40 9570.40
8384.60 8384.60 8384.60 8384.60
7198.80 7198.80 7198.80 7198.80
6012.99 6012.99 6012.99 6012.99
4827. I 9 4827.19 4827.19 4827.19
3641.39 3641.39 3641.39 3641.39
2455.59 2455.59 2455.59 2455.59
1269.79 1269.79 1269.79 1269.79

7710.49 8878.86 10047.23 11215.60 7651.70 8839.67 10027.63 11215.60
Figure 4. contour plot of Figure 5. Contour plot of

EDXRF results for Cd at EDXRF results for Cd at
depth level 1 (0-2 inches). depth level 3 (6-12
inches) .
Golden, CO) and was executed on the spectral data analysis

computer. Note that the highest Cd concentration level was
found at the 7200'(Y) x 8200'(X) quadrant of the site.
Cadmium is also the contaminant that exhibits the strongest
depth dependency. Figure 4 is the surface contour map for
Cd in 43 samples analyzed in the 0 to 2" layer. All soil
samples at this depth had EDXRF measurable Cd concentrations,
the largest reported at 767 ppm Cd. Elevated Cd soil
concentrations in the 7200'(Y) x 8200' (X) area correlates
with the position of elevated Pb and As concentrations. This
information indicates a similar source of contamination for
Pb, As, and Cd. Figure 5 is the contour map of Cd
concentration at level 3 (6 to 12") of forty three analyzed
samples at this depth. Thirty eight samples showed detectable
Cd concentration with the largest reported to be 131 ppm Cd.
Comparing Figures 4 and 5, the position of the maximum Cd
concentration is in the same quadrant. The trend of
decreasing Cd concentration with decreasing depth is
exhibited at each of the four sampling depths.
CONCLUSION
Field-mobile EDXRF analysis of soils suspected of being
contaminated provides information concerning the nature,
extent, and magnitude of the contamination. Due to the
minimal sample preparation necessary for EDXRF analysis,
sampling-to-result turnaround time is relatively short so the
most effective use of sampling resources is realized. The
plume of contamination is illustrated to on-site
assessment/remediation personnel in the form of concentration
contour plots. Accuracy and precision for the analytes of
interest using the EDXRF method was shown to be comparable
to results obtained with AA/ICP analysis. comparable results
for Cd, As, Pb, and Zn for the two methods validates the use
of EDXRF analysis for hazardous waste site investigations.
ACKNOWLEDGEMENTS
The authors would like to acknowledge L. Gilfrich and D.
Leland for assistance in the EDXRF analysis of the soil
samples, G. Bogart for data analysis work and K. Proctor for
assistance with graphics.
REFERENCES
(1) H. Vincent, Field screening Methods for Hazardous Waste
site Investigations Symposium Proceedings, 61, (1988).
(2) R. Perlis, M. Chapin, IILow Level XRF Screening Analysis
of Hazardous Waste Sites ll , Field Screening Methods for
Hazardous Waste site Investigations symposium
Proceedings, 81, (1988).
(3) N.W. Madden, G.H. Hanepen, B.C. Clark, IIA Low Power High
Resolution Thermoelectrically Cooled Si(Li)
Spectrometer II , IEEE Trans. Nuc. Sci., 33, (1), 303,
(1986) .
(4) Data Quality Objectives For Remedial Response Activities,
U.S. EPA, EPA 540/G-87,003, Appendix A, (1987).
SCREENING OF HAZARDOUS WASTE WITH AN ENERGY DISPERSIVE
X-RAY FLUORESCENCE SPECTROMETER
N.C. Jacobus
HNU X-RAY
1003 Larsen Drive, Oak Ridge, Tennessee 37830
INTRODUCTION
"HAZARDOUS WASTE SITE" - What picture do those words bring

to mind? Most people visualize a remote area behind a tall
chain-linked fence with signs prohibiting entrance and
warning of the dangers within. For these sites already
identified as hazardous waste sites, access is limited, and
all who enter must wear appropriate protective clothing when
working on the site. However, a yet to be identified
"hazardous waste site" may be as close by as the back lot of
a manufacturing facility in your town. Or, it may be a
vacant lot in your neighborhood or even your own property,
land on which children play and vegetable gardens grow.
Thus, those involved in locating hazardous contamination and
determining the extent of that contamination are not only
with the U.S. Environmental Protection Agency and its
contractors, but are also with state and local departments
of health as well. Commercially available portable and
transportable energy dispersive x-ray fluorescence (EDXRF)
spectrometers offer a solution for fast on-site field
screening of several of the priority pollutant metal
contaminants in soil. The U. S. Environmental Protection
Agency recommends that x-ray fluorescence analyzers be used
in remedial investigations and feasibility studies (RIfFS).'
with on-site XRF instrumentation, the investigation team can
locate contaminated areas and determine the extent of that
contamination while at the site,thereby minimizing the time
and the cost of wet chemical analyses through the Contract
Laboratory Program (CLP).
ANALYTICAL REQUIREMENT FOR METALS
In 1985 Furst et al. 2 described the analytical levels for

the analyses of metal contaminants. In 1987 Raab et al. 3
set the data quality requirements to those levels. For an

on-site field screening and preliminary evaluation, a
precision of ± 10%, an accuracy of ± 50%, and detection
limits of ~ 1000 ppm are required. The evaluation of the
exposure to both humans and animals requires the same
precision of ± 10%, an accuracy of ± 15% , and detection
limits of part per million. For litigation and regulatory
enforcement purposes, the requirements include precision of
± 5%, accuracy of ± 10%, and detection limits of parts per
billion. Energy dispersive x-ray fluorescence techniques can
meet the requirements for field screening and for evaluation
of exposure to humans and animals.
INSTRUMENTATION
The analyses of soil contaminated with lead at both

commercial and residential properties and arsenic
contaminated soil from chromium-copper arsenate at an
abandoned wood-preservative plant site are discussed. The
instrumentation used for the analyses was the battery-
powered HNU SEFA energy dispersive x-ray fluorescence (EDXRF)
spectrometer (Model 6124) equipped with 10 mCi Cd-lOg annular
radioisotope source and liquid nitrogen cooled Si(Li)
detector with resolution of ~ 170 eV at 5.9 keV. The
detector dewar has a holding time for liquid nitrogen of more
than 24 hours. Personal computers requiring battery or AC
power were used for quantitative analyses.
SAMPLE PREPARATION
All samples were analyzed as collected in 1.25-inch diameter
polyethylene cups with < 4 J,£m Mylar film windows. wet
samples were air dried. Selected samples were ground for
comparison. All samples were analyzed at 100 seconds live
time.
ANALYSES OF LEAD CONTAMINATION OF SOIL
Although multielement capability is available in this

instrumentation, the primary focus of this study was lead
contamination. Figure 1 is a plot of a spectrum for a
standard (15600 mg/kg Pb)4 used for semiquantitative analyses
and was one of the standards used for quantitative analyses
with interelement corrections. Semiquantitative results from
the spectrometer are obtained from the coefficients derived
from a single standard.
Figure 2 is a comparison of EDXRF semiquantitative results

and atomic absorption results for 33 analyses for lead
contamination in soil. The samples were not sieved or
ground. The values plotted are in the range of 180 - 15600
mg/kg, the average relative percent difference (RPD) between
N. C. JACOBUS 657
XRF ANALYSIS OF SOIL

10 mCi Cd-109 Source, Pb - 15600 mg/kg
400,-------------,,~------------------------------~
Cu Zn
Pb
300
Pb
....
III II
200~
Z
:J
o
U
I
Fe
4 6 8 10 12 14 16 18
keY
Figure 1. The x-ray energy spectrum for a soil

sample contaminated with lead, copper, and
zinc using a 10 mCi Cd-lOg radioisotope
source.
SEMIQUANTITATIVE ANALYSIS OF Pb IN SOIL

33 ANALYSES, LINEAR CORRELATION 0.9914
o 4000 8000 12,000 16,000

AA (mg/kg)
Figure 2. comparison of EDXRF semi-

quantitative analysis results and atomic
absorption results for 33 soil samples.
CONTAMINATED SOIL IN RESIDENTIAL AREA

XRF SEMI-QUANTITATIVE ANALYSIS FOR LEAD
j
a, 3000
S 3
...J w
~ 2000 c
iii
! t;
c 1000 w
~
...J ~
5 4 3 2
HOUSE SIDE 251eet
Figure 4. 3-D graphic representation of EDXRF

quantitative analyses of soil samples at a
residential location.
the listed values and the calculated semiquantitative values

was 7% (13 values, range 0% - 33%); 700 - 2000 mg/kg, RPD =
16% (10 values, range 3% - 63%); 180 - 700 mg/kg, RPD = 24%
(10 values, range 1% - 71%). Overall, the RPD was 15% (33
values, range 0% - 71%). Ninety-one percent of the samples
(30 values) were within field-£creening accuracy requirements
using the semiquantitative analysis method. Thus, by using
the semiquantitative analyses method without matrix
corrections, a good correlation can be obtained (0.9914 for
33 analyses).
Figure 3 is a 3-D graph map5 of the semiquantitative analysis
for lead contamination in a vacant lot in an old residential
neighborhood. The standard used for semiquantitative
analysis contained 2074 mg/kg lead. By sampling in a grid
pattern, it was possible to obtain more information for the
location than if random sampling were used. contamination
tends to be higher around the perimeter of the lot. It is
possible that this lot may have once had a house in the
center and that the soil had been contaminated by high lead
content paint. Samples taken at 3-3 to a depth of a foot
showed similar high concentrations of lead that was found in
the surface soil. Samples from other residential locations
in the same vicinity had lead concentrations up to 5000
mg/kg. Quantitative results6 for the same location were
based on eight standards in the range of 594 - 17700 mg/kg.
Corrections for enhancement and absorption effects were
applied. Although there was a decrease in the lead
contamination when interference corrections were used, the
pattern of the contamination remained the same. Figure 4 is
a 3-D graph of the quantitative results.
N. C. JACOBUS 659
CONTAMINATED SOIL IN RESIDENTIAL AREA

XRF QUANTITATIVE ANALYSIS FOR LEAD
i.... 3000
l
5 2000
1/1
!
c 1000
cW
....I
5 4 3 2
HOUSE SIDE
251eet

semiquantitative analyses of soil samples at
a residential location.
When 10 aliquots of a composite sample (1100 mg/kg Pb) from

this location were quantitatively analyzed, the coefficient
of variation was 17% for unground samples, 9% for ground
samples, and 8% for repeti ti ve analyses. These results
indicate that with minimum sample preparation (hand grinding
on site with a mortar and pestle) precision required for
field screening analyses can be met.
At another location, a manufacturing plant for ceramic tile,
the owner was required to have the lead-contaminated soil
removed until the lead levels were less than 500 mg/kg. Much
of the contaminated surface soil had already been removed.
On-site x-ray fluorescence field-screening analysis enabled
the clean-up contractor to analyze subsoil areas suspected
of still being contaminated with lead. Of the 13 data points
analyzed and depicted in the 3-D graph (Figure 5), six were
above the action limit. The on-site XRF analysis enabled
additional cleanup before final sampling was required for CLP
analyses.
ARSENIC ANALYSIS AT AN ABANDONED WOOD-PRESERVATIVE PLANT

Fast on-site analysis of arsenic in soil contaminated with
chromium-copper arsenate (CCA) at an abandoned wood-
preservative plant, enabled a remedial investigation team to
determine the extent of the surface-soil contamination and
the depth of that contamination at selected locations in a
few days. Initially, several samples were collected from the
site and were analyzed by AA spectroscopy. Figure 6 is a
spectrum typical of the contaminated-soil samples. A linear-
CONTAMINATED SOIL AT CERAMIC PLANT

XRF QUANTITATIVE ANALYSIS FOR LEAD
a.>t
....
-~--R
g) 3000
§.
g 2000
oJ
-Fil--lJ)
--UJ--
:!!:
~ 1000
w
oJ -~-~--g-/
SOUTH SIDE OF LOT
20 feel

quantitative analyses of soil samples at a
manufacturing plant.
SOIL CONTAMINATION
CHROMIUM-COPPER ARSENATE (CCA)
300
As
260
220
180
~
c:
"
0
0 140
100
Cu
60
20
3 5 7 9 11 13 15
keV
Figure 6. The ~-ray energy spectrum for a
soil sample contaminated with chromium-copper
arsenate at an abandoned wood preservative
plant using 10 mCi Cd-lOg radioisotope source.
N. C. JACOBUS 661
HAZARDOUS WASTE SITE

ABANDONED WOOD PRESERVATIVE SITE
""""-''-I'"""-f-+-+--+--+-+-+-+--IB
10 9 8 7 6 5 4 3 2
~
50 feel
Fiqure 7. 3-D graphic representation of EDXRF
quantitative analyses of arsenic in soil
samples at an abandoned wood-preservative
plant.
regression calibration with the site-specific standards was

used for quantification of arsenic. Three hundred and thirty
samples were analyzed on site. Each set of ten samples
analyzed included a reference sample (approximately 8000
mg/kg As), a set of duplicates, and a replicate analysis.
For arsenic contamination above 200 mg/kg, the RPD for
duplicates was 15% and for replicates was 5%. Analysis of
12 samples taken from the site indicate that the major source
of error in duplicate analysis is in obtaining a true
duplicate sample due to particle-size variations and sample
inhomogeneity. Ground samples with -200 mesh resulted in an
improvement in the RPD value. For arsenic concentration ~
200 mg/kg, the RPD was 2% for duplicates and 2% for
replicates. Semiquantitative analyses using the sample with
3179 mg/kg arsenic as a standard yielded RPD of 9% (range 3%
- 23%) between the AA results and the XRF results. Precision
was 1%.
On-site analysis permitted real-time analyses and prompt

determination of highly contaminated areas. Figure 7 is a
representation of the arsenic contamination at the site.
High concentrations had been expected at the far left of the
site in the process area. However, contamination at location
D5 was unexpected. On-site analysis enabled the
investigation team to decide upon the additional sampling
requirements immediately. with on-site EDXRF, it was
determined that the contamination was on the surface and
resulted from the cleaning of the RI/FS equipment.
SUBSURFACE SOIL SAMPLE - 00
5000
III
'"....
III
E
.!i
c
3000
GI
!!
<
1000
Depth in Feet
Figure 8. Depth profile for arsenic

contamination at one location at the abandoned
wood-preservative plant.
The remedial investigation team was able to have subsurface

soil samples taken at several locations at the abandoned
wood-preservative plant site. without on-site analysis
capabilities, there would have been several weeks delay
before analytical results were available to determine where
subsurface soil sampling was needed. Figure 8 is a depth
profile of the contamination measured with a 12-foot core
sample analyzed at every six inches. The concentration at
the surface was 909 mg/kg. At six inches the concentration
increased to 5702 mg/kg. The contamination dropped to low
levels increasing in concentration at a clay layer at the 5
to 7.5 depth. At this location cleanup soil removal below
7.5 feet was required. Cleanup activities at the abandoned
wood-preservative plant were activated with information
supplied by on-site EDXRF instrumentation without additional
information from CLP analyses.
CONCLUSION
with on-site XRF analysis instrumentation, the location and

extent of the metal contamination is available in real time.
The data quality is within the levels recommended for field
screening. Minimum sample preparation in the field will
yield results within the analytical accuracy requirements for
field screening. Grinding to a finer mesh size improves the
quality of the data for evaluation of exposure purposes.
N. C. JACOBUS 663
Qualitative, semiquantitative, and quantitative analysis data

obtained while on site enables the remedial investigation
team to maximize the information while on location in order
to minimize the number of samples requiring CLP analysis.
Typically, on-site EDXRF spectrometers can be justified by
cost savings on wet chemical analyses for one or two
contaminated sites and on the time saved for those
investigations.
REFERENCES
1 Data Quality objectives for Remedial Response
Activities, Example Scenario, united states Environmental
Protection Agency, EPA/540/G-87/004, March 1987, p. 4-7.
National Technical Information Service, PB88-131388.
2 Furst, G.A., V. Tillinghast, and T. Spittler, Screening
for Metals at Hazardous Waste sites: A Rapid Cost-Effective
Technique using X-Ray Fluorescence. Proceedings of the
National Conference on Management of Uncontrolled Hazardous
Waste sites. Hazardous Materials Controls Research
Institute, washington, D.C., p. 93-96, 1985.
3 Raab, G.A., D. Cardenas, S. J. Simon, and L.A. Eccles,
Evaluation of a Prototype Field-Portable X-Ray Fluorescence
System for Hazardous Waste Screening, Environmental
Monitoring Systems Laboratory, Las Vegas, NV, EPA/600/4-
87/021, National Technical Information Services, PB87-
227633, August 1987.
4 The standards and samples were provided by the
California Department of Health EETS. The wet chemical
analytical results were obtained by AA spectroscopy (HN0 3
digestion).
5 All the 3-D graphic plots were made with a "3-D
Graphics," enhanced graphics for Lotus users Copyright (c)
4-5-6 World Ltd/Ross Research 1987. Software Engineering by
Ross Research PS2 Version 1.02.
6 Quantitative results were obtained using an IBM AT
compatible personal computer, HNU's data acquisition software
based on Lotus 1-2-3/Lotus Measure, and HNU's ATAC regression
analysis software program. IBM AT is a trademark of
International Business Machines, Inc.
X-RAY FLUORESCENCE ANALYSIS OF TRACE METALS IN THE ANNUAL
GROWTH LAYERS OF FRESHWATER MUSSEL SHELLS*
William E. Maddox, Leon Duobinis-Gray,

David A. Owen, and James B. Sickel
Murray State University

Murray, Kentucky
INTRODUCTION
Freshwater mussels (Mollusca: Unionidae) are filter feeders that are

relatively immobile, widely distributed and are known to concentrate trace
metals in their shells (1,2,3). These characteristics make them good
candidates for monitoring metal pollution in lakes and rivers. Another
characteristic of mussels that make them particularly attractive as pollution
monitors is the fact the shell is deposited in distinctive, annual growth layers.
The concentrations of metals in these shell layers may provide a history of the
metals present in the environment where the mussel was collected.
The mussel shell actually consists of four different regions as illustrated in

the diagram of a shell cross section shown in Figure 1. Each of these four
regions has its own annual layers. The bulk of the shell is found in the
peripheral nacre with the thin prismatic and laminar layers enclosing it. The
periostracum is an outer protein membrane covering the inner three crystalline
CaC03 regions. In this work, mussel shells were separated into annual growth
layers by dividing each shell along the boundaries between the layers of the
peripheral nacre. The prismatic and Iqminar nacre regions are too thin to
permit easy divisions of these layers.
Mussels of three different species (Megalonaias gigantea, Amblema ~

and Quadrula guadrula) were collected from a site on Kentucky Lake in
Western Kentucky. Following a method used by Nelson (4), the shells were
separated into their annual growth layers and each layer was subsequently
analyzed by x-ray fluorescence (XRF) for concentrations of Mn, Fe and Sr.
*Work supported in part by a grant from the Center for Reservoir Research,
Murray State University, Murray, Kentucky.

2nd year
\
peripheral nacre
laminar nacre - - - '

Fig. 1: Cross section of a three and half year old mussel shell showing the four
major layers.
PROCEDURE
Each shell was thoroughly cleaned and separated into two separate valves.
Each valve was baked in a furnace at 3S0 oC for approximately 30 minutes.
This baking process destroyed the protein material holding together the layers
of CaC03 crystalline matter thus allowing the layers to be easily separated
using a sharp blade and a pair of tweezers. Baking the shells for shorter
periods of time or at lower temperature make it more difficult to separate layers
while over-cooking the shells caused them to crumble when handled.
Once the shells were separated into their annual growth layers, the material
was pulverized in a ball-mill grinder then pressed into a standard 1 1/4" pellet
suitable for XRF analysis. The XRF spectrometer and the method of analysis
have been described in a previous article (5).
RESULTS
The mussel shells were collected from a site at the 44.S-mile marker on
Kentucky Lake in Western Kentucky at a depth of approximately 7 meters. Ten
121111~---------------'
KENTUCKY LAKE SITE 113

MEGALONAIAS GIGANTEA
5. 9611
a.
c:
~ 7211
-to
(j
L
-to
& 4811
u
c:
U°
L 2411
lf1
71 73 75 77 79 81 83 85 87
Growth Yeor
Fig. 2: Layer concentrations of Sr in ten different Megalonajas gjganJ.e.a
shells.
W. E. MADDOX ET AL. 667
1280~---------------'

QQ, AP AND MG AVERAGES
5. 968
.9-
c
~ 728
....o
....L.
:fr 488
u
co
U AP
L. 240
lI'\ MG ------gg~~~.:-:.:===--~-----------=~~-;:~
71 73 75 77 79 61 63 65 67
Growth Yeor
Fig. 3: Layer averages of Sr concentrations in each of the three species.
shells of each species Megalonaias gigantea (MG), Ouadrula Quadrula (00)

and Amblema plicata (AP), were collected and separated into an average of
eight annual layers per shell. Each layer was analyzed for the concentrations
of Mn, Fe and Sr. Traces of Cr, Ni, and Zn were observed in some of the layers
but were not analyzed in this work.
Figure 2 shows the concentrations of Sr in theMG species plotted as a function

of the year which the layer was formed. Since the shells were collected in April
and May, 1989, the last layer is assigned the growth year of 1988. As can be
seen from the plot, there is very little variation in the Sr from layer to layer. The
data for the 00 and AP species for Sr concentrations follow a pattern similar to
that in Figure 2. Figure 3 shows the layer averages for the Sr concentrations in
each of the three species.
1~8;----------------'

5. 968
a.
c
~ 728
....o
....L.
:fr 488
u
c
o
u
OJ 248
u..
n n ~ n ~ ~ ~ ~ ~
Growth Yeor
Fig. 4: Layer concentrations of Fe in ten different Megalonajas ~
shells.
1280..-------------------,
-a 968
.9-
c.
~ 728
T-
o
L.
T-
&
u
488
c.
o
u
~ 240 00 /AP
MG ..... . -- --. -- '>"':"-.". :.::,::.,. . -~----t
71 73 75 77 79 61 63 65 67
Grollth Yeor
Fig. 5: Layer averages of Fe concentrations in each of the three species.
1280..--------------------.
a 968
.9-
c.
0 728
T-
o
L.
T-
c.
IV 488
u
C.
0
U
c. 240
~ ~_v-
71 73 75 77 79 61 83 65 67
Growth Yeor
Fig. 6: Layer concentrations of Mn in ten different Mega!onajas ~
shells.
1280 . . - - - - - - - - - - - - - - - - - - - ,
QUADRULA QUADRULA
a968
a.
c.
~ 728
T-
o
L
&
T-
488
u
o
c.
u
c. 248
~
71 73 75 77 79 61 63 65 67
Grollth Yeor
Fig. 7: Layer concentrations of Mn in 10 different QuaQ.w!a ~ shells.
W. E. MADDOX ET AL. 669
1288 . . . . - - - - - - - - - - - - - - - - - ,
-a
AMBLEMA PLICATA
968
a.
c
~ 728
t-
o
L.
t-
iu 488
c
o
u
c 248
:l:
71 73 75 77 79 61 63 65 67
Growth Yeor
Fig. 8: Layer concentrations of Mn in ten different Anl.b.lwna lllil:ala shells.
1288 , . . . - - - - - - - - - - - - - - - - - - .
a
a.
968
c
~ 728
t-
o
L.
t-
iu 488
c
o
u
c 248
:l:
MG --
71 73 75 77 79 61 63 65 67
Growth Yeor
Fig. 9: Layer averages of Mn concentration in each of the three species.
The concentration of Fe in the layers of the ten MG shells is plotted in Figure

4 with the layer averages of all three species shown in Figure 5. Again there is
little more than statistical variation in the Fe concentrations.
Figures 6, 7 and 8 show the layer concentrations of Mn in shells of all three

species. Unlike Fe and Sr, there is a wide range of concentration of Mn from
shell to shell and from layer to layer within a shell. Figure 9 shows the layer
averages for Mn in each of the three species. With the exception of one or two
of the very young shells, every shell showed a definite pattern for the Mn
concentration. Starting with the older layers and moving toward the younger
ones, the layers having an age of 14 down to 7 years had low concentrations of
Mn, typically less than 200 parts per million (ppm) by weight. From age 7 years
down to 1 year, the Mn concentrations steadily increased to a value 6 to 7
times that of the older layers. This pattern was evident in the oldest mussels
(up to 14 years) and in the youngest (down to 4 years) that were analyzed in
this work.
DISCUSSION
Clearly, the most interesting result of this work is the pattern of the
layer-to-Iayer concentrations of Mn in the shells. The higher Mn concentrations
in the more recently developed layers could indicate an increase in the Mn
concentration in the sediment of the lake where the mussel feeds, or it could be
a natural process that takes place in the shell development. Further studies
will have to be done on the relation between sediment concentrations and Mn
uptake by the mussel before definite conclusions can be drawn concerning this
Mn pattern. This work will continue with shells gathered from three additional
sites on Kentucky Lake. The Mn concentrations in the sediment of these sites
has been determined to be different from site to site (6) and an effort will be
made to correlate the shell concentrations with the sediment concentration.
ACKNOWLEDGEMENTS
The authors wish to thank Chris Blewett and Mike Keeling, undergraduate
students at Murray State University, for their many hours spent cooking,
separating and grinding the mussel shells used in this work.
REFERENCES
1. Sickel, James B. and Chandler, Carol C., "Commercial Mussel and

Asiatic Clam Fishery Evaluation", Report to Kentucky Department of
Fish and Wildlife Resources, Frankfort, Kentucky. Project No. 2-367-R.
77 pp, 1982.
2. Girardi, F. and Merlini, Margaret, "Studies on the Distribution of

Trace Elements in a Mollusk from a Freshwater Environment by
Activation Analysis", EURATOM: EUR 474.e., 25 pp, 1963.
3. Nelson, D.J., "High-Purity Calcium Carbonate in Freshwater Clam

Shell", Science, 152(3727), 1368-1370, 1966.
4. Nelson, D.J., "Deposition of Sr in Relation to Morphology of Clam

Shells", Verh. Internal. Verein. Limnol., 55: 898-902, 1964.
5. Maddox, W.E., "Application of a Polarized X-Ray Spectrometer for

Analysis of Ash from a Refuse-Fired Steam Generating Facility,"
Advances in X-Ray Analysis, Vol. 17, pp. 519-526, 1984.
6. Owen, David A. and York, Keith A., "A Study of the Forms, Concentrations,
and Interphase Dynamics of Iron and Manganese in Northern Kentucky
Lake Benthic Waters, Elutriates, Sediments, and Other Lacustrine-Based
Matrices", Report to Center for Reservoir Research, Murray State University,
Murray, Kentucky. 39 pp., 1988.
APPLICATION OF PIXE METHOD FOR ENVIRONMENTAL
PROTECTION IN POLAND
T. Zoltowski*, W. Ratynski**
M. Jaskola**, J. Parus*, L. Wawrzonek*
*Institute of Nuclear Chemistry and Technology

Warsaw, Poland
**Soltan Institute for Nuclear Studies
Swierk/Otwock, Poland
Specific problems of environmental protection in Central Europe and

dense industrialization in Poland that is powered by traditional power
plants and having developed heavy industry, have resulted in a need for a
special environmental protection policy. Reliable methods are needed to
analyze low concentrations of trace elements in pollutants existing in
atmospheres, precipitates, ground waters and soils. A knowledge of
trace-elements concentration can help in setting industrial limits for
emission, permanent control of emission perturbations and finally
epidemiological studies. During recent years, methods based on the x-ray
fluorescence phenomenon were being widely developed in Poland. 1 - 3 Now due
to the development of cyclotrons, proton-induced x-ray emission appears to
be very useful for pollutant control.
Sulfur is one of the major air pollutants in urban and industrial

areas and as such it may occur in several forms. When emitted to the
atmosphere from fossil-fuel combustion it is primarily in the form of
sot-.
gaseous S02 and during gas-to-particle conversion it may become oxidized to
As sulfates it can occur first as sulphuric acid, depending on the
environmental conditions, and later can be neutralized by ammonia to
ammonium bisulphate and finally ammonium sulphate. The concentration of
sulphur dioxide and nitric oxides in air over the territory of Poland is
excessive, (expected emission of S02 and NO x in Poland: 1990-(S02-4.9, NO x
-1.7); 1995-(S02-5.1, NO x -2.0); 2000-(S02-5.5, NO x -2.3) [min t./year]. Due
to the country regulations and international agreements until 1993 Poland
should limit emission of the mentioned pollutants about 30%.
To introduce the PIXE method for environmental protection in Poland,

intensive actions have to be initiated. Sol tan Institute of Nuclear Studies
in Swierk designed and constructed the C-30 cyclotron. The beam intensity
was 100 nA of peak proton current. The achieved parameters are satisfactory
for performing the PIXE method. However many authors have concluded that
the optimum proton energy range falls at about 3-4 MeV; therefore a small
C-3 cyclotron for 3 MeV protons is being constructed. The expected proton
current of several ~A will make it suitable for PIXE measurements in Poland

in the 1990's. The experience of Polish researchers with using the 2.8 MeV
Van de Graaff accelerator in Warsaw Center and the 5 MeV cyclotron in Cracow
Center during the last years will certainly be utilized. Actually, apart
from using the C-30 cyclotron for PIXE measurements, this machine will be
utilized for Proton Elastic-Scattering Analysis.
The chamber for beam preparation and holding a sample was constructed
in two versions. A first one has been used during PIXE experiments with the
Van de Graaff accelerator 4 , the second was designed according to Japanese
suggestions. Electronics consist of an ORTEC Si/Li detector located in the
backward direction of 135 0 to reduce bremsstrahlung background and an ORTEC
MCB 800A system with an IBM/PC computer for spectra evaluation.
Samples of air particulates are collected on membrane filters. For

this purpose we are starting in Poland the production of special filters
based on nuclear track membranes having pore diameters in the range of
0.2-2 ~m. Precipitate samples are prepared after evaporation; however
chemical methods for species preconcentration are being developed. For
spectra evaluation, the library least squares method, with the modification
by introducing the inner-outer iteration approach l , is applied.
The PIXE method will be devoted in the first place for quick
determination of sulphur species pollution in Poland territory. However the
concept to distinguish between PIXE spectra according to the sulphur
oxidation state could lead to a method for the determination of acidic forms
of H2S04 and the NH4HSO. The PIXE method will be used for the elemental
constituency measurement of coal waste products, due to an urgency to
utilize coal waste material which is in great quantity in Poland.
REFERENCES
1. J. Parus, T. Zoltowski, J. Kierzek, W. Ratynski, Adv. X-Ray Anal. 24,

395, 1981
2. J. Kajfosz, S. Szymczyk, G. Kornas, Nucl. Instr. Meth. in Phys. Res.
B3, 147, 1984
3. F. M. El-Ashry, G. Goclowski, L. Glowacka, M. Jaskola, J. Marczewski,
A. Wolkenberg, Nucl. Instr. Meth. in Phys. Res. B22, 450, 1987
4. B. Babinski, M. Goclowski, M. Jaskola, M. Kucharski, L. Zemlo,
Nucl. Instr. al Meth. 181, 523, 1981
MICROVOLUME ANALYSIS OF FLY ASH BY SYNCHROTRON RADIATION X-RAY
FLUORESCENCE (SRXRF) AND ELECTRON MICROPROBE X-RAY MICRO-
ANALYSIS (EPXMA)
Sz. Torok, Sz. Sandor, and H. Rausch
Central Research Institute for Physics, Budapest,

P.O.Box 49, H-1525 Hungary
INTRODUCTION
The assessment of the potential environmental and toxi-
cological effects of particulate material emitted to the at-
mosphere requires detailed physical and chemical characteri-
zation of the particles. One of the most widely studied types
of pollutant particles is coal fly ash as a byproduct of coal
combustion. These particles are inhomogeneous, highly varia-
ble, span a broad range of sizes and have diverse morphologies.
It has been shown that numerous toxic trace elements tend
to increase in bulk concentrations with decreasing particle
size (1).
The emission of black coal-fired power plants has been
discussed in several studies but the chemical formation of the
toxicological impact of brown coal or lignite-fired power
plants, typical for the geographical area of Middle-East Eu-
rope, is much less clear. In the mentioned previous studies
different analytical techniques were applied to bulk samples
and an average chemical composition was obtained for both the
larger particles and the smaller ones.
In a few studies, the morphology of individual fly-ash
particles was (2) also analysed with electron microprobe X-
ray analysis EPXMA (3). LAMMA technique also is commonly used
for such purposes but has some limitations with regard to
quantitative work because of the occasionally poor reprodu-
cibility of the laser power density and the heterogeneity of
the individual particles (4).
The aim of the present paper is to explore the feasibi-
lity of using EPXMA and SRXRF as highly sensitive and non-
destructive multielemental techniques to analyse trace and
especially toxic elements in individual particles combined
with the conventionally used bulk XRF techniques.

EXPERIMENTAL
SEM experiments were performed on a JEOL JSM 840 microscope

equipped with an EG&G ORTEC 5000 Energy Dispersive X-Ray
Spectrometer system. For the investigation, particles were
randomized on a polycarbonate membrane filter and coated
with about 50 nm carbon; the measurements were performed
at 25 kV and 35 kV high voltages and 0.3 to 1.0 nA electron
current.
The synchrotron radiation experiments were carried out in

Novosibirsk, using the VEPP-3 2 GeV accelerator equipped with
a 2T max. field Wiggler. The available XRF station was at a
distance of about 9 meters from the tangent point of the
storage ring. The synchrotron radiation produced passed through
a pyrolytic graphite monochromator with a mosaic spread of
about 1 %. A 5 mm thick ORTEC Si(Li) detector of 30 mm 2 was
aligned at 900 to the exciting beam. With this setup the ex-
citation energy could be tuned in the range of 10 to 40 keV.
Details of the station are described in ref.5. For individual
particle analysis a 100 ~m lead pinhole was placed close to
the sample in the exciting beam. The X-ray fluorescence radia-
tion was measured using a Reis-100 X-ray tube excitation at
50 keV and 30 nA (W anode). A pyrolytic graphite monochromator
was tuned to 35 keV.
An off-line spectrum deconvolution of all X-ray emission

spectra was applied by the AXIL program on an IBM PC/AT com-
patible computer (6).
For particle sizing an IMAGING system based on a Reichert-
Jung POLYVAR-t<1ET wide-field research microscope providing an
x-y field scanning by steps of 0.5 ~m, a TV23-l1/A type video
camera and an image processing unit were used. Particle sizing
can be performed within a diameter interval of 0.4 to 2000 ~m.
Simultaneously, microphotoqraphs of the particulates were also
made.
For imaging, samples were prepared by dispersion in
n-hexane and filtered on NUCLEPORE membrane filters with a
poresize of 0.4 ~m to produce a random distribution of the
particulates.
For bulk analysis the electrofilter-deposited fly-ash
samples were sieved into five size fractions, the smallest
being <60 ~m.
Individual particles and thin bulk samples were also pre-
pared by dispersing the fractions of fly ash in n-hexane-con-
taining adhesive substances and filtering on NUCLEPORE mem-
brane filters. For bulk analysis, samples were ground to avoid
particle-size effect.
For tube-excited XRF measurement pressed sample pellets

of 5 rnm diameter containing 15 to 20 mg substances were used.
Sz. TOROK ET AL. 675

Fly-ash samples were taken from the chimney top and from
electrofilters of four power stations in Hungary; Ajka (A),
Borsod (B), Pecs (p) and Gyongyosvisonta (G).
Size fractionation of the electrofilter fly ash was
carried out after sampling. In some cases the mass of the
samples taken from chimneys hardly exceeded 100-200 mg. For
X-ray emission analysis only 50 mg was left. Thus samples of
2-5 mg/cm 2 thickness were prepared. This low sample thickness
resulted in an ideal PIB ratio and relatively low double
Compton scatter peaks at higher energies as well as absorption
of the characteristic lines was low. In most cases an external
standard method was used for quantification. Sensitivity val-
ues were obtained from SRXRF spectra of NBS 1633 fly ash as
standard reference material.
It is well known that SRXRF is more sensitive than con-
ventional tube excited techniques. Especially toxic elements
of higher atomic number are difficult to measure by tube ex-
citation or PIXE (7).
In order to monitor all toxic elements fly-ash samples
had been measured at two monochromator energies. At 18 keV
Cr, Cu, Zn, As and Pb,whereas at 40 keV Mo, Sb and Ba were
analysed.
Results of fractional bulk analysis
It is remarkable that fly ash sampled at the top of the
chimney contained higher As, Pb and Sb concentrations in all
cases.
Several size fractions of fly ash were measured and en-
richment factors were calculated for some toxic elements
shown in Table 1. Enrichment factor is defined as elemental
concentration in the <60 vm size fraction/elemental con-
centration in bulk.
Table 1. Enrichment factors of some toxic

elements in the >60 vm size fraction
Sample
origin Cu Zn As Pb Sb
A not detected 2.5 3 1.5

B 1.5 1.2 1.7 2 1.4
G 3.5 3 2.1 1.6 2.5
P 2.1 2 2.2 1.8 2.2
8- fly ash
A - fly ash
Particle diameter [/Jm)
Fig. 1. Differential size distribution of two fly ash

samples taken from electrofilter
The enrichment factors for As, Pb and Mo are very similar in

spite of the different combustion technologies used at the in-
dividual stations. Considerable enrichment for Cu and Zn was
only observable in alkaline type fly ash from plant G burning
lignite at 1100 0 C.
Results also showed that the absolute As and Sb con-

centrations might depend, among others, on the remaining car-
bon content of the ash. Figure 1 shows the differential size
distributions of fly ash A and B. The presence of larger carbo-
nacious particles in type B is in good agreement with the higher
remaining carbon content and with morphological observations.
INDIVIDUAL PARTICLE ANALYSIS
Nowadays EPXMA is a widely used method for this purpose.

However it does not suit for the detection of low concentra-
tions (10-100 ppm). For elements Z>40 SRXRF is much more sen-
sitive. In EPXMA at 20 kV accelerating vQltage the excited
volume can be estimated as about 10 vm3 for a silicate par-
ticle with 2.6 g/cm 3 density.
With the available SRXRF station at VEPP-3, using 100 vm

diameter pinhole, the analysed volume is about 10 3 times
larger but this method still seems to be more suitable for the
determination of heavier elements in low concentration. Table 2
SZ. TOROK ET AL. 677
Table 2. Sensitivity (cps/ng) of EXPMA and SRXRF

for elements of fly-ash particles
EPXMA SRXRF
25 kV
15 keV 40 keV
AI-Fe 10 5 _10 4 10- 2-5 10- 3 -1

Zn-Y 10 2 -10 3 20-200 15-80
Zr-Ba not detectable not detectable 150-200
shows the sensitivity values for different elements in absolute

mass of the analyte.
;f proper focusing techniques are used, individual par-

ticles having diameters of 10-50 )lm could be analysed by SRXRF
for Cu, Zn, As, Sb, Ba or, with further filtering on the de-
tection side (8), Cd or Sn. Such measurements could offer a
unique tool for individual particle bulk analysis if the beam
position could be stabilized sufficiently.
CONCLUSION
SRXRF as analytical technique can be used efficiently to
measure toxic elements in small environmental samples of
different size fractions. Efficient focusing techniques should
be used for analysing individual particles of 10-100 )lm dia-
meter where lower concentrations could be determined than by
EPXMA for elements with Z>40.
ACKNOWLEDGEMENTS
This work was partially supported by IAEA Coordinated
Research Project No.4959/Rl/RB and by Hungarian National
Scientific Research Fundation under contract numbers 1030 and
1028.
REFERENCES
1. R.L. Davison, D.F. Natusch, J.R. Wallace. and J.R. Evans,
Environ.Sci.Technol. 8: 1107 (1974).
2. R.J. Lauf, L.A. Harris and S.S. Rawiston, Environ.Sci.
Technol. 16: 218 (1988).
3. Y. Mamane and T.G. Dzubay, Water, Air and Soil Pollu-
tion 37 :389 (1988).
4. E. Denoyer, D.F. Natusch, P. Surkyn and F. Adams,
Environ.Sci.Technol. 17:457 (1983).
5. V.B. Baryshev, G.N. Kulipanov, E.Z. Zaytsev, Ya.V.
Terekhow and V.J. Kalynzny, Nuc.Instr.Meth.
A251:279 (1987).
6. P. Van Espen, R. Nullens and F. Adams, Nucl.Instr.Meth.
142:243 (1977).
7. Sz. Torok, Z. Szokefa1vi-Nagy, Sz. Sandor, V.B.

Baryshev, K.V. Zo1otaryev and G.N. Ku1ipanov,
Nuc1.Instr.Meth. A, to be appear
8. V.B. Baryshev, G.N. Ku1ipanov and A. Skrinsky,
Nuc1. Instr. Meth. A246:739 (1986)
X-RAY FLUORESCENCE ANALYSIS OF ZEOLITES FOR THE DETERMINATION OF
SILICA:ALUMINA RATIO AND SODA:ALUMINA RATIO
P. A. Gokhale and M. R. Wuensche

Akzo Chemicals Inc.
Catalyst Division
Pasadena, Texas 77507
I NTRODUCTI ON
Zeolites-based fluid cracking catalysts are used in petroleum
refining. Zeolites are crystalline alumina silicates with a framework
based on extensive three-dimensional network of oxygen, and cations
which occupy nonframework positions. The distribution of silicon and
aluminum atoms within the framework determines many important properties
of zeolites, most notably catalytic, absorptive capacity, acidity,
stability, etc. For the zeolite scientist, information obtained from
the determination of silca:alumina ratio (SAR) and soda:alumina ratio
(NAR) during crystallization, dealumination and cationic exchange is
important for the optimization of preparative techniques and development
of new products.
Classical analytical wet techniques such as complexometric
titration, gravimetry and flame photometry are used for the
determinations. Recently application of atomic absorption spectrometry
(AAS) (1), and inductively coupled plasma-atomic emission spectrometry
(ICP-AES) (2), also have been reported. These techniques, though
accurate, are time consuming and therefore can't be applied when a
rapid analysis is required for a large number of zeolite samples.
Neutron diffraction, nuclear magnetic resonance (NMR) (3), infra-red
(IR) (4), Raman spectroscopy and X-ray diffraction (5), have been applied
for obtaining silica:alumina ratio within the framework, for elucidating
crystal structure and for locating cations and molecules within the
framework.
Whenever the primary objective is a determination of chemical
silica:alumina ratio and soda:alumina ratio, then the X-ray fluorescence
becomes the method of choice for the analysis because it is rapid,
simple to use, inexpensive and nondestructive. Multielements with
a wide variety of concentrations can be analyzed simultaneously with
high precision and accuracy. Application of borate fusion technique
for samples preparation eliminates grain-size influence and reduces
matrix effect, thus accurate analysis can be obtained for conventional
NaY zeolites as well as modern-day USY zeolites.

TABLE 1 STANDARDS
# 2 3 4 5 6 7 8 9 ID 11 12 13 14 15
%A1 203 24 23 20 30 28 18 21 19 22 17 31 19 16 21 13
%Si02 61 52 68 67 64 . 75 69 64 73 81 69 62 83 77 65
%Na 20 9 12 7 2 4 5 7 10 3 0 11 0.5 1 13
EXPERIMENTAL
Standards are prepared using precalcined high-purity alumina,
silica and sodium tetraborate. The sample in the slurry form is filtered
and washed with 01 water and then calcined at 300° for 15 minutes and
at BOO°C for 45 minutes. One gram of the calcined sample is fused
with 0.1 gram KI, 1.6 gram lithium rretaborate and 4.B gram lithium
tetraborate using Claisse-fluxer ® (6).
A Rigaku-3070® wavelength dispersive X-ray spectrometer with rhodium

target energized at 45 KV and 40 MA is utilized for the analysis.
For the analysis of alumina and silica, a pentaerythrital (PET) crystal
is used, whereas for the analysis of soda, a thalium acethalate (TAP)
crystal is utilized. For all the analytes Ka lines are selected
and pulses are collected for sixty seconds using a flow:proportional
detector. A background correction is applied.
A regression analysis of the data for the standards is carried
out and a set of correcting coefficients is generated for the
absorpt i on/enhancement effects and overl appi ng caused by the coexi sti ng
elements. An uncorrected concentration for the analyte is obtained
from equation 1, and the corrected concentration is calculated using
the Lachance and Trail model (7) (equation 2).
Ui = bli+c ..... . (1)
where Ui = uncorrected concentration of analyte

li = measured X-ray intensity of analyte
b,c = calibration curve constants
Wi = Ui[l + Ki + IAijFj] + IBijFj + IDijkFjFk + Ci...... (2)
j j j,k
where Wi = corrected concentration of analyte
Ui = uncorrected concentration of analyte
FjFK = concentration of coexisting element (j,K)
K,A,B,C,D = correction coefficient
The borate fusion technique for sample preparation results in
considerable dilution of the sample and because of the dilution, the
matrix effect is remarkably reduced. However, to achieve a higher
precision and accuracy for the analysis, corrections are applied for
the absorption/enhancement effects caused by the coexisting elements.
The plots of uncorrected concentration of analytes and corrected
concentration of the analytes show excellent linearity with minimum
P. A. GOKHALE AND M. R. WUENSCHE 681
REGRESSION ANALYSIS JOB
~ATRlX CORRECTIDN MODE

GROUP .• SODA
9 ···· .. ·EL'EHtNt :': ····S·j ............... ,... .
c
w
I-
u
W
0:
0:
a
u
:z
=>
N
o
... 7
.~
V')
l-
I
.....
<.!l
w
3:
ACCR .06664
5 7 8 9
WEIGHT %5;02 (CORRECTED)
Fig. 1. Matrix correction for the analysis of silica
REGRESSION ANALYSIS JOB
WEIGHT %Na 20 (CORRECTED)
Fig. 2. Matrix correction for the analysis of soda

REGRE SS ION ANAL YS I S JOB
A ~IX ~ORRECTION MODE

GROUP I SODA
ELEMENT I 'A f
o
...t
!
!
-";r .... ... .
ON
ACCR .01105
1£1· - -
2 3
WEIGH T S A1
Z03 (CORRECTED)
Fig. 3. Matrix correction for the analysis of alumina
scatter for the data points (Fig 1, Fig 2 and Fig 3). Better intensity
counts are desirable for the analysis of soda; it is possible to obtain
an accurate analysis even at a lower concentration of the analyte (Fig
2) .
An excellent comparative analysi sis obtained between the present XRF

method and chemical wet methods (Table 2). For the analysis of soda,
silica and alumina by wet methods, flame photometry, gravimetry and
complexometric titration were used respectively. For another study,
the data obtained from XRF analysis between two different laboratories
we re compa red.
The reference laboratory utilized a flux consisting of 65% lithium
tetraborate and 35% 1ithi urn metaborate with a small amount of 1ithi urn
iod~de. The fusion was carried out using Perl X2® fluxer equipped
with a 42 mm mold. A Phillips PW1480® wavelength dispersive X-ray
spectrometer provided with fundamental parameter software was utilized
for the analysis and excellent comparative data between the two
TABLE 2 A COMPARATIVE STUDY FOR THE DETERMINATION OF

SAlz03, SSi02 AND SNazO IN ZEOLITES
SilIIple Method SNazO SA1z03 SSi02 SAR NAR
No.
I chemical TIT 21.8 64.4 5.02 Q.99
XRF 12.9 22.0 64.4 5.0 0.96
2 chemical 12.1 19.0 68.9 6.2 1.05
XRF 12.1 18.8 69.1 6.2 1.06
3 chemical 4.0 24.4 71.0 4.94 0.27
XRF 4.1 24.4 71.5 4.98 0.28
4 chemical 4.2 24 . 2 70 .6 4.96 0.29
XRF 4.2 24.2 70.9 4.98 0.29
P. A. GOKHALE AND M. R. WUENSCHE 683
TABLE 3 A COMPARATIVE STUDY FOR THE DETERMINATION OF

SAlz03 SSi02 AND SNa20 IN ZEOLITES
Sample method fluxer SNazO SAlz03 1Si02 SAR NAR
No.
-1- XRF (empirical) Claisse '3.'i3 24.4 7T.'O '4:9 0.26
XRF (fundamental) Pearl ex 3.9 24.5 71.1 4.9 0.26
2 XRF (empirical) Claisse 1.5 18.6 79.0 7.2 0.13
XRF (fundamental) ,Pearlex 1.5 18.4 78.5 7.3 0.13
XRF (f ~lldamenta 1 ) Pea rl ex 1.5 15.1 82.2 9.2 0.16
XRF (fundamental) Pearlex 1.4 11.8 86.1 12.4 0.20
TABLE 4 DETERMINATION OF lAlz03. SSi02 AND lItazO IN ZEOLITES.

REPRODUCIBILITY OF ANALYSIS BETWEEN FUSED DISKS
DISK I lAlz03 SSi02 SNazO MASS SAR liAR
BALANCE
-1-- 22.'1 64.0 13.4 99.5 4.92 TJio
2 22.0 63.9 13.5 99.4 4.94 1.01
3 22.2 64.3 13.5 100.0 4.92 1.00
4 22.0 63.9 13.4 99.3 4.94 1.00
5 21. 9 64.0 13.3 99.3 4.97 1.00
6 22.2 64.5 13.6 100.3 4.94 1.01
7 22.0 64.0 13.4 99.4 4.94 1.01
x 22.06 64.1 13.4 99.6 4.94 1.00
ali) 0.10 0.21 0.09 0.36 0.02 0.045
v 0.48 0.33 0.67 0.36 0.32 0.45
1677 Y
1342
1006
II p
y
p
I
I P
Y
5
I
[I
y '(
I
670
II
I
y
III
y?
Y
5 S
334 P
YS
-1
Fig. 4. Crystalline impurity in Nay

Y = faujasite, S = gmelinite, P = phillipsite
laboratories were obtained for the determination of silica:alumina

molar ratio and soda:alumina molar ratio in zeolites (Table 3).
A precision study was done for the evaluation of sample preparation
and spectrometric performance for the analysis. For a NaY zeolite
sample, seven fused disks were obtained and analyzed. Excellent
reproducibility for the analysis was obtained between the fused disks
(Table 4).
The main advantage of the present XRF method is the abil ity for the
scientist to monitor chemical composition of zeolite crystals as the
crystallization progresses. This can further help in developing
innovative products and in the optimization of preparative techniques;
however, sometimes due to improper process control, either faujasite
(NaY) fails to crystallize completely or other zeolites such as gmelinite
and phill i psite also crysta 11 i ze along wi th NaY. In such cases XRF
values for SAR and NAR can lead to the wrong conclusions {Fig.4).
It is a good pra~tice to utilize other characterization techniques
such as X-ray diffraction and scanning electron microscopy to assure
the phase purity and then proceed to obtain SAR and NAR values by XRF
technique.
References:
1. M.E. Taro; 1987, Development of AAS and ICP method for the analysis
of Al, Na and Si in zeolites, Pittsburgh conference abstracts,
278.
2. M. E. Taro, V. Giampa and R. Collins; 1989, Dissolution of zeolites
for flame AA and ICP analysis, Spectroscopy, 4(2) PP. 18-22.
3. G. Engelhardt, B. Fahlke, M. E. Lippmma, Zeolites, 5, 49 (1985).
4. Flanigen, E. Khattani, H. Szymanski, Adv. Chern. Series, 1971, PP.
102-201.
5. D. W. Breck, Zeolite Molecular Sieves, Wiley, New York, 1974.
6. Claisse Fluxer, Instruction Manual.
7. Lachance G., Trail R., Canadian spectroscopy, March 1966, PP 43-48.
Lachance G., Trail R., Canadian spectroscopy, May 1966, PP 63-71.
ALUMINA CHARACTERIZATION BY XRF
Frank R. Feret
Alcan International Limited
Arvida Research and Development Centre
Jonquiere, Quebec, Canada G7$ 4K8
One of the most important properties that characterizes alumina is its

elemental composition. Although XRF has been appl ied to the analysis
of aluminas for the past three decades, special aluminas have always
presented a major challenge. Moreover, only recently did it become
possible to analyze for I ight elements such as Na. Two new sample pre-
paration techniques for elemental analysis of aluminas by XRF were
developed. One is based on briquetted powders, another involves fused
samples. Their advantages and I imitations wi I I be presented. In the
case of fusion one analytical program was appl ied to al I types of alu-
minas. The performance of each method wi I I be discussed.
INTRODUCTION
Alumina is produced in the Bayer process in which crushed bauxite is
digested with hot sodium hydroxide solution. One of the products is
aluminum trihydrate which is then calcined [1]. Depending on the
degree of calcination, metallurgical or ceramic grade aluminas are
produced. They differ with respect to the alpha alumina content,
grindabi I ity, particle shape and size, impurity content, etc. [2,3].
Appl ication of X- ray fluorescence for the analysis of alumina in the
Alcan system dates back to the sixties. However, the instrumental
technology existing at that time al lowed only the analysis of inter-
mediate atomic number elements beginning with Ca. With time the X-ray
methods for alumina characterization were upgraded and the I ight ele-
ments were included. In this paper two recently developed sample
preparation techniques for XRF elemental analysis wi I I be presented and
the analytical results discussed.
EXPERIMENTAL
Instrumental Conditions
AI I samples were analyzed on a sequential Phi I ips PW 1400 spectrometer

control led by a PDP 11/24 computer. The spectrometer was equipped with
a Sc tube [4] operated at 50 kV and 50 rnA. For Na a PX-1 crystal was
used, for Mg - TIAP, for Si - InSb, for S - Ge, and LiF was used for
Advances In X-Ray Ana/ysis, Vol. 33 685

the remaining elements. The counting time (peak + background) ranged

from 36 seconds for the group of elements Ca - Sn, up to 100 seconds
for Na and Mg. Background was measured on one side of the correspond-
ing peak for al I the elements concerned.
Briquetting Sample Preparation

In the method using briquetted powders, a 20.0 g sample and 5.0 g of
organic binder are ground together in a rotary mi I I for 1 minute. The
binder is composed of nine parts (by mass) styrene copolymer and one
part wax [5]. The components are avai lable in powder form consisting
of grains of 10 #m size and have to be wei I mixed prior to analysis.
The binder is not hygroscopic and has good self-binding properties.
The background arising from the pure binder pressed into a pel let is
very low for al I elements. The binder performs three major functions.
It serves as a lubricant reducing contamination and faci I itating
cleaning of the components of the rotary mi I I; it isolates very fine
from large grains and thus helps the grinding action; finally, it acts
as a binder in the briquetting operation.
This method provides very rei iable results for metallurgical grade
aluminas as shown for Na in Figure 1. Ceramic grade aluminas do not
give the same I inear response. It might be thought that longer grind-
ing and a separate cal ibration curve could be used. However, the grain
size is already small (in the range 1-10 #m) and further grinding is
not effective. The longer grinding time of abrasive material such as
ceramic alumina causes its inevitable contamination. At present, the
briquetting technique gives inacceptable results for the ceramic alu-
mina. To el iminate these inconveniences, get rid of the particle size
distribution effect and avoid shortage of cal ibration standards, new
attempts involving fusion sample preparation techniques were tried.
Fusion Sample Preparation

The optimized version of the fusion sample preparation technique
involves a relatively high sample to flux mass ratio. Using an
METALLURGICAL CERAMIC
ALUMINA ALUMINA
* +
1 . 5 . . - - - - -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _--,
lZ
<:}
~ 1.0 +
~
lZ
<:}
+
g 0.5
+
0.0 +
0.0 0.5 1.0 1.5 2.0
INTENSITY FUNCTION
Figure 1. Cal ibration graph for Na.

F.R.FERET 687
Table 1. Composition of Synthetic Standards (%)

ELEMENT STANDARD SAMPLE NUMBER
OXIDE
1 2 3 4 5 6 7 8 9
Na2
MgO
° 0
0
0
.003
0
.006
0
.012
0
.018
.25
0
.50
0
1.0
0
1.5
0
Si O2 0 0 0 0 0 .15 .30 .60 .90
P20S 0 .001 .002 .004 .006 0 0 0 0
S03 0 .0018 .0036 .0072 .011 .06 .12 .24 .36
CaD 0 .06 .12 .24 : .36 0 0 0 0
Ti O2 0 0 0 0 0 .003 .006 .012 .018
V2 0 S 0 .003 .006 .012 .018 0 0 0 0
,Cr 203 0 0 0 0 0 .0015 .003 .006 .009
iMnO 0 .0005 .001 .002 .003 .004 0 0 0
I
Fe2 03 0 0 0 0 0 .01 .02 .04 .06
NiO 0 .003 .006 .012 .018 0 0 0 0
CuD 0 0 0 0 0 .001 .002 .004 .006
InO 0 .003 .006 .012 .018 0 0 0 0
Ga 2 03 0 0 0 0 0 .003 .006 .012 .018
Mo0 2 0 .0013 .0025 .0038 .005 0 0 0 0
Sn02 0 0 0 0 0 .002 .004 .008 .012
PbO 0 .005 .010 .020 .030 0 0 0 0
automatic Claisse fluxer a four (4) g alumina sample is now fused with
nine (9) g of flux. The 4 g sample mass ensures a representative
sampl ing of trace elements. The flux is composed of 90~ Li 2B407 and
10~ LiF. Fluxes marketed by JMC, Aldrich, Spex, Laborlux ana Claisse
Corporation were tested with respect to their impurities content, and
the latter one was found to be the most adequate. The glass disk
diameter increase from 30 to 40 mm resulted in a 20-30~ intensity gain
for the elements concerned.
The cal ibration procedure was carried out using a set of synthetic
glass standards made of high purity element oxides and the flux. The
reagents used to prepare the synthetic standards were dried for a mini-
mum of one hour prior to weighing in order to obtain a known stoichio-
metry. To bui Id the set of synthetic standards, two "master" glass
discs were first cast. They were broken into sma I I pieces and ground
separately in a Shatterbox grinder. Smal I powdered portions of two
master discs (ranging in mass from 0 to 0.5 g), supplemented with high
purity alumina and flux were used to make nine synthetic standards.
Their composition in weight percent is given in Table 1.
Results
Tables 2-4 give important technical detai Is concerning alumina analysis

by X-ray fluorescence. In Table 2 selected cal ibration parameters are
presented for briquetting and fusion sample preparation techniques. No
estimated accuracy data is shown for some elements as they were not
certified in the avai lable alumina standards prepared as briquettes.
Table 2. Selected Calibration Parameters for Aluminas

Briquetting Fusion
Constituent Concentration Range Estimated Accuracy Estimated Accuracy
(%) 1 sigma (ppm) 1 sigma (ppm)
Na2
MgO
° 0.005-1.5
0 -0.012
210
-
100
8
S i 02 0.001-0.1 13 10
P2 0 S 0 -0.006 2 3
S03 0.01 -0.4 170 750
CaO 0.001-0.3 20 6
Ti 02 0 -0.02 7 6
V2 0 S 0 -0.02 5 5
Cr 2 03 0 -0.01 - 3
MnO 0 -0.001 3 3
Fe2 03 0.001-0.05 15 15
I NiO
I
0 -0.01 ,
- 4
! CuO 0 -0.01 - 4
0 -0.01 5 3
0 -0.025 7 4
0 -0.01 3
0 -0.03 6
Comparison of sensitivity (Kcts/sec.%) measured on a Phi I ips PW 1400

spectrometer for selected elements in NBS 699 alumina is made in
Table 3. In the fal I of 1987 we evaluated four different XRF spectro-
meters. One of the tests involved NBS 699 alumina prepared as a bri-
quette. Table 4 gives the LOD values calculated for ten elements. It
should be noted that the Phi I ips, Siemens and Rigaku instruments used
in the evaluation were sequential spectrometers. A goniometer was used
on the ARL 8680 simultaneous spectrometer, but this instrument has a
longer optical path (to accommodate fixed monochromators) than any
sequential spectrometer; this increases the radiation absorption.
Also, the sample holder mask on the ARL 8680 was 29 mm, whi Ie on the
others it was at least 34 mm.
Table 3. Comparison of Sensitivity (Kcts/sec %) for Selected Elements

in NBS 699 Alumina - Philips PW 1400 Spectrometer
CONSTITUENT CONCENTRATION SAMPLE AS BRIQUETTE SAMPLE AS GLASS DISK
(%)
Na 2 0 0.59 2.74 0.86
Si 02 0.014 5.21 6.43
CaO 0.036 232 206
°
V2 5
MnO
0.0005
0.0005
147
195
110
220
Fe2 03 0.013 122 115
ZnO 0.013 77 .4 57.4
Ga 2 03 0.010 87.6 177
F.R.FERET 689
Table 4. Detection Limits (2 sigma) in ppm for NBS 699 Alumina Pre-
pared as Briquette and Analyzed on Different Spectrometers
CONSTITUENT CONCENTRATIONi TIME PHILIPS SIEMENS RIGAKU ARL

(~) (sec) PW 1400 SRS 300 3071 8680
Na 2 0 0.59 80 38 15 13 26
Si 02 0.014 40 1 0.5 1.8* 6*
S03 0.012 40 0.5 0.2 0.2 -
CaD 0.036 40 0.3 2.2 2.8 3.5
Ti 02 0.0020 40 4 4.4 2.8 4
V2 0 S 0.0005 40 1 0.9 0.9 -
MnO 0.0005 40 0.3 0.3 1 0.7
Fe2 03 0.013 40 1.3 1.3 1.5 2
ZnO 0.013 40 1.5 0.7 0.7 1.6
Ga 2 03 0.010 40 1.6 0.8 0.7 1.3
* PET crystal was used instead of InSb.
Discussion
The fusion technique can be appl ied to al I types of aluminas since

grain size, shape, and hardness are no longer factors to be overcome.
In general, the fusion technique compared to briquetting offers: wider
cal ibration ranges, "absolute" cal ibration based on fewer synthetic
standards, analysis of several additional elements with the help of
synthetic standards, and better estimated accuracy for most elements
(except S, due to volati I ization). By contrast, the briquetting tech-
nique features very good performance for S, better sensitivity for Na,
and is more economical.
In the past the performance of the fusion method was I imited by in-
adequate instrumental sensitivity for Na due to matrix di lution.
Recent hardware improvements helped upgrade XRF analytical performance.
With the Phi I ips PW 1400 spectrometer, modified through the use of the
Sc anode tube and the multi layer PX-l crystal, the analysis of Na
became very rei iable. Yet better performance, in terms of lower limit
of detection and shorter analytical time, could be obtained using
spectrometers equipped with a Rh end window tube, as wei I as using
fluxes of higher purity than presently.
ACKNOWLEDGEMENT
The author would I ike to thank Dr. F.M. Kimmerle, Alcan's chief analy-
tical chemist, and Dr. G.F. Giasson for reviewing the manuscript and
fruitful discussions. He also wishes to thank Mrs. C. Gagnon, Mr. C.
Boulanger and Mr. J.M.N. Tropia for their assistance at the experimen-
tal stage.
REFERENCES
1. Wheat, T.A., Journal of the Canadian Ceramic Society, Vol. 40, p.
43, 1971.
2. Sleppy, W.C., Journal of Metals, p. 22, Nov. 1985.
3. Adamson, A.N., The Chemical Engineer, CE156, June 1970.
4. Feret, F., Canadian Journal of Spectroscopy, Vol. 31, No.1, 15,

1986.
5. Van Zyl, C., X-ray Spectrometry, Vol. 11, No.1, 29, 1982.
AUTHOR INDEX
Ahonen, A. I., 585 Fernandez, J. E., 553, 567, 573

Allred, D. D., 615 Ficalora, P., 177
Arai, T., 213, 225, 521 Fisher, G. R., 55
Araujo, F., 515 Fuller, Jr., E. R., 453
Avni, R., 129
Gaillard, F. , 247
Blackwell, J. , 423 Gilfrich, N. L. , 593
Boehme, D. R. , 313 Ginley, D. S. , 145
Bowen, D. K. , 13, 55 Gokha1e, P. A. , 679
Briden, F. E. , 383 Goldsmith, C. C. , 137, 177
Brouwer, P. N. , 237 Goldstone, J. A. , 403
Brown, R. A. , 197 Grill, A. , 129
Burleson, J. R. , 305 Gyani, A. K. , 247
Cernik, R. J., 101 Halliwell, M. A. G., 61

Chandra, D., 445 Hamill, G. P., 417
Charbonnier, M., 247 Hamilton, R. D., 493
Clark, S. M., 101 Harada, H., 409
Cohen, J. B., 25 Harding, A. R., 647
Cole, III, W. H., 629 Hart, L., 55
Conant, J. W., 403 He, F., 515
Cross, B. J., 509 Hegedus, F., 581
Hietala, M. J., 585
Dahms, M., 277 Hirose, Y., 319, 327
David, M. A., 403 Hitterman, R. L., 403
de Boer, D. K. G., 237 Huang, P. C., 67
DeGroot, P. B., 537, 543 Huang, T. C., 91, 295
Deyu, L., 269 Hubbard, C. R., 373
Ding, W., 445 Hudgens, C. R., 313
Duggan, J. S., 629
Duobinis-Gray, L., 665 Ihara, I., 353, 363
Iida, A., 205
Eatough, M. 0., 145 Ingham, M. N., 549
Ebe1, H., 499
Ebel, M. F., 499 Jacobus, N. C., 655
Engstrom, P., 623 Jansen, E., 261
Enwal1, R. E., 629 Jasko1a, M., 671
Erslev, E. A., 593 Jenkins, R., 285, 417
Jordan, B., 269
Faber, Jr., J., 403
Fatemi, M., 75, 83 Ka1nicky, D. J., 585
Fazey, P. G., 269 Kaplan, W., 121
Feng, G., 33 Kataoka, Y., 213, 225
Feng, L., 509 Kauhanen, K. J., 585
Feret, F. R., 685 Kimmel, G., 121, 129
691
692 AUTHOR INDEX
King, M. M., 485 Sabino, E. M., 485

Knight, L. V., 615 Saito, A., 353, 363
Kuharic, C. A., 629 Sakurai, K., 205
Kuramoto, M., 171 Sandor, Sz., 673
Kurita, M., 353, 363 Sasaki, T., 171
Sato, M., 353
Landes, B. G., 433 Schafer, W., 261, 277
Larsson, S., 623 Schneider, A.-I., 423
Lawson, A. C., 403 Schreiner, W. N., 417
Leyden, D. E., 593 Seabaugh, P. W., 313
Lo, C. F., 33 Seltzer, S. M., 603
Lynch, R. A., 445 Shanabrook, Jr., B. V., 75
Sheikh, G., 161
Maddox, W. E., 665 Shinkai, T., 389
Malanga, M. T., 433 Shoj i, T., 521
Mantler, M., 499 Sickel, J. B., 665
Masciocchi, N., 295 Smith, T. K., 549
Matsumoto, Y., 109 Smithhart, C. B., 475
Mayo, W. E., 33 Stewart, J. M., 373
McClusky, P., 247 Stock, S. R., 67
Merz, P., 277 Stocklassa, B., 623
Milam, D. L., 341 Streli, C., 581
Molinari, V. G., 553, 573 Sullenger, D. B., 313
Moore, F. E. 153 Sullivan, M. J., 177
Morosin, B., 145, 373 Sumini, M., 553
Summers, C. J., 67
Newman, R. A., 467 Svagera, R., 499
Nichols, M. C., 285, 313
Noyan, I. C., 137, 161 Takayama, T., 109
Talcott, C. L., 403
O'Connor, B. H. , 269 Tanaka, K., 319, 327
Ohno, K. , 409 Tanner, B. K., 1
Ohta, S. , 335 Thill, B. P., 433
Ohya, S. , 335, 389, 397 Thorne, J. M., 615
Owen, D. A. , 665 Toda, K., 197
Tomlinson, J. J., 445
Paretzkin, B., 453 Torabi, A., 67
Parrish, W., 295 Torok, Sz., 673
Parus, J., 671 Tsuda, M., 327
Pattison, P., 101
Peletis, N. G., 493 Urch, D. S., 247
Pella, P. A., 509
Perkins, R. T., 615 Van Espen, P., 515
Piorek, S., 639 Van Grieken, R., 515
Pohn, C., 499 Vaninetti, J., 403
Prokes, S., 75 Von Dreele, R. B., 403
Raab, G. A., 629 Walsh, J. P., 647

Ratynski, W., 671 Wang, K. L., 75
Rausch, H., 673 Wang, P. W., 295
Raveh, A., 129 Wawrzonek, L., 671
Raven, M. D., 269 Weissmann, S., 33
Rechsteiner, C. E., 531 Wernle, M., 499
Richardson, Jr., J. W., 403 Wertz, D. L., 475
Rindby, A., 623 Wertz, S. L., 475
Romand, M., 247 Will, G., 261, 277
Roof, R. B., 403 Williams, A., 403
AUTHOR INDEX 693
Willis, J. E. , 189 Yamagata, T. , 409

Wilson, R. L. , 197 Yamazaki, M., 409
Winkler, P. , 581 Yajima, Z. , 319, 327
Wittig, E. P. , 531 Yin, L. 1., 603
Wobrauschek, P. , 581 Yoshioka, Y., 171, 389, 397
Wong-Ng, W., 453
Wuensche, M. R. , 679 Zhang, Y., 373
Zoltowski, T. , 671
SUBJECT INDEX
Absorption corrections in polychro- BaO-R203-CuO crystal chemistry

matic XRF method, 515-520 structures, phase diagrams
Absorption spectra, Cr/Cr203 film, (cont'd)
208ff unit cell volume vs ionic radius,
Alpha-alumina: stress measurements 460
in, 363-372 XRPD patterns, 459, 462, 464
Alphas in XRF: COLA-based program, Borophosphosilicate glass: XRFA, 243
5l2ff
Alumina plate from ICDD: synchrotron Calcium in Ca-treated polymer
XRPD patterns, 295-303 pellets, XRFA for, 590
Aluminas, XRF of, 685-690 Ca(OH)2 for sulfur oxide removal: XRD
Aluminum as XRD reference intensity, tests, 383-388
478ff Capillary-microbeam x-ray spectro-
Amplifier design for WDXRF, 549-552 meter, 623-628
Annealing vs rocking-curves, 40ff conical-capillary advantages, 624
Arsenic in soil, XRFA of, 642 near monochromatization, 624
AS203 as XRD standard, 433-443 Catalysts, XRF analysis of, 536
Ceramic materials, XRD of
Background control in XRPD, 313, Zr02; stabilization,
3l6ff transformations, 467-474
Background estimation in XRPD Ceramics: alpha-A1203, stresses in,
analysis for cryst.-size . 363-372
and strain, 373-381 Ceramic-to-metal bonded joint:
CRYSIZ program, 377 residual stresses, 353-362
hook effect absent in model, 377 Chemical characterization, near-
XRAYL program for profile analysis surface layers, 205ff
376 Chemical state determined in films,
Background in WDXRF: intensities, 247-259
spectra, components, 521-529 Coal, quant. analysis of, 475-483
Background level in XRD patterns, 290 Coal-waste material, 671-672
effects of corrections, 397-402 CoCr, Co/Ge/Cr films on substrates:
for linear PSD, 397-402 XRFA, 237-245
measurement of correction factor, Compton and Thompson components of
398ff scattered x-rays, 521-529
on film, vs PSD, 395 Computer program (XRFPC) for multi-
perlite analysis, 494 element XRF, 567-572
BaO-R203-CuO crystal chemistry, Confidence limits: stress measure-
structures, phase diagrams, ments in alumina, 363-372
453-465 Contaminated soil: EDXRF analysis,
Ba-La-CuO and Ba-Y-CuO systems 655-663
compared, 454 Co on Si wafers: XRFA, 242ff
summary of phases with R3+ = La, Copolyamides and copolyester
Nd, Sm, Eu, Gd, Dy, Ho, Y, carbonates: structures of,
Er, Tm, Yb, Lu, 456 423-432
ternary phase diagrams near the kinks in chains: monomer-length
CuO corner, 464 models vs XRD patterns, 428ff
695
696 SUBJECT INDEX
Copolyamides and copolyester Differential scanning calorimetry

carbonates: structures of, combined with XRD in an
(cont'd) instrument, 434-436
model for fully-extended linear of polyalcohols, 445-452
chains XRD intensities, 425ff Diffractometer, double-crystal:
models for non-linear chains, XRD modified for surface-
peak widths, 427ff misalignment studies of
parallel chains with random/non- wafers, 83-90
random sequences, 424ff Diffractometer: optimization of
x-ray patterns interpreted, 428ff slits, steps, 305-310
Counting statistics; designing Diffractometry of thin layers, 1-11
scanning schemes, 305-310 asymmetric reflections, 7
Counting times: recording weak peaks, double-axis, 2
313-318 four-reflection, 4ff
Crack growth rates, 327-334 single-axis, 1
Critical angles for x-ray mirror triple-axis, 10
reflection, 110ff Dislocation arrangements, movements,
Crystal chemistry/phase equilibria in 33-53
BaO-R203-CuO systems, 453-465 Double-axis diffractometry
Crystallinities, structures, trans- epitaxial, 61-66
formations, in polystyrenes, of Si wafers, 55-60
433-443 superlattice, 67-74
Crystallinity values by Rietveld XRPD d's from 26's in XRPD, 285-293
272, 273 d-values from XRPD: methods,
Crystallite-size and strain: XRPD precision, 295-303
procedures and errors, EDXRF analysis
373-381 field-mobile unit's precision,
Crystallite size from FWHM in Zr02, accuracy, 655-663
470ff hazardous-waste sites, 655-663
Crystallite size/strain vs reactivity secondary target selection,
in Ca(OH)2, 383-388 509-514
bulk vs thin layer results, 386ff Electron-beam sources for XRF, 248
CaF2, LaB6, A1203 as standards, Electronic instability in WDXRF
386ff spectrometer, 549-552
correlation with FWHM, 384ff Electroplated Cr on Ni, 161-169
Cu-Au-Si02 thin-layer diffractometry, with cracks in the Cr, l64ff
109-120 interface integrity tests,
Cu films on Si wafers: residual l6lff, 168
stresses, 137-144 Poisson's ratio vs load, l64ff
Curium-244 in surface-analysis probe as a quality control tool, 168
629-637 strain tensor; stresses, 161-169
Electroplated layer on steel,
Data-base computation for XRF on PC stresses in, 171-175
microcomputers, 567-572 Energy-dispersive portable XRF
Data-handling system for many system, 629-637
analytical systems, 531-536 Energy-dispersive x-ray diffraction
Debye rings: arc lengths and numbers, (EDXRD)
with PSD, 389-396 at Daresbury synchrotron, 101-107
Detection limits, for Epitaxial growth on Si: XRD patterns,
contaminated soil analysis, 656 75-82
Detector: 2-D, using laser- Epitaxial-layer diffractometry, 1-11
stimulation, 389-396 asymmetric reflections, 7
Detector gated for time resolution determining structural parameters,
of cyclic stressing, 335-337 I, 7
Detergents, household-laundry, XRD embedded reflections, 9
analysis of grazing incidence, 8, 10
builders: formulas of, 487 lattice match/mismatch, I, 7, 10
conventional methods for, 487 mapping of scattering in recip.
XRD analysis scheme, 489 space, 10
SUBJECT INDEX 697
Epitaxial-layer diffractometry GaAs epitaxy, 64

(cont'd) Generalized Structure Analysis System
multiple-axis techniques, (GSAS), 405
1, 2, 5, 10 Geologic materials: macroprobe
structural data from 2nm thick precision, XRF, 593-600
layer, 10 Geological standard materials, 5l7ff
Epitaxial layers, modulated, XRD of, Gibbsite, Al(OH)3 XRPD patterns, 271
67-74 Glancing-angle EDXRD with synchrotron
Epitaxial layers: strain, structures critical angles: Cu, Au, 106
double-axis diffractometry of, depth probing, 106
64ff multilayers, 106
electron microscopy of, 62 patterns of Cu, Au on glass, 106
lattice tilts, 63 pressurized; under electrolytes;
rocking curves for Ge, GaAs, InP liquid crystals, 107
substrates, 63-65 Glancing-angle XRF for iodine
strain: relaxation measurement analysis, 581-583
with group IV, II-VI Granodiorite, granite, XRF analysis,
substrates, 61-66 519
Graphically displaying XRPD patterns,
Fatigue effects on Debye rings, 392 309
Fe203, Fe304, 93ff Grazing-incidence XRD
Fiber-texture patterns of a of thin films, 109-120
copolyamide, 426 topography, 17, 23
and a copolyester, 430 Grazing-incidence XRF, synchrotron
models of chains of monomers vs radiation, 205-211
XRD peak profiles, 423-432 absorption spectra, 208ff
Figure-of-merit, 292 reflectivity vs incident angle,
Film-to-substrate bond test: XRPD, 32 207ff
Finite-elements method (FEM) Guinier camera used at elevated
calculated stresses, 356ff temperatures, 446, 448ff
Fly-ash analysis (SRXRF) , 673-678
enrichment vs particle size, Hairstrand crossection microanalysis
675, 676 626
toxic elements, 675 Hazardous-waste site in soil, EDXRF
Fossil-fuel emission, PIXE analysis analysis of, 655-663
of, 671-672 required precision; detection
Fracture surface of ceramics: XRPD of limit, 656
319-326 semiquant. results vs atomic
Fracture toughness of ceramics, 323ff absorption, 658
Fundamental-alphas program and Hazardous waste: XRF analysis,
modifications, 509-514 629-637
Fundamental-parameters method portable-unit calibration, 632ff
computations (improved), 499-508 Hematite, Biotite pole figures, 281
expressions for primary and Hydrogen in Pd subsurface monolayer,
secondary excitation, 214ff 403
for basic studies of multi-layer
thin films, 213-223 InP epitaxy, 64
on multilayer films, 197-204 Integrated circuit film XRFA, 237-245
rough surface, 503 Iodine analysis by XRF with TXRF
thin films, 225-235 spectrometer, 581-583
FWHM vs crystallite size, with Iron alloys: WDXRF background
grazing-incidence x-rays, intensities, 521-529
109-120
FWHM vs 28, slits (synchrotron XRPD) , Joint Comm. on Atomic and Molecular
295-303 Properties (JCAMP)
creation of JCAMP-DX for XRPD
GaAs/A1GaAs superlattices, XRD of, data, 420-422
67-74 database JCAMP-DX 1, 419ff
698 SUBJECT INDEX
Kaolinite, QPA, fractional Multiple-line XRPD method for layer

crystallinity, 272 thickness (cont'd)
Kinematic theory, modified, for specimen tilt vs thickness
super1attices, 67-74 sensitivity, 122ff
Lathanide contraction in compound National Institute of Standards and

formation, 453-465 Technology (NIST)
Laundry detergents XRD analysis, systematic study of
485-492 superconducting materials,
Layer-thickness determined by XRPD, 453-465
121-127 Neopenty1g1yco1 (NPG) crystal
Lead and su1pher in gasoline, 588ff structures, 445, 446
Lead contamination: EDXRF analysis, Neutron diffraction
655-663 for textures in rocks, 277-283
Lower limits of detection by XRF Neutron-diffraction refinement
in soil, by mobile unit, 658 incommensurate magnetic structure
Lubricating oil, reporting XRFA of, determination, 267
535 in recent structure determinations
266
Macroprobe XRF analysis of rock, Na3P04, 268
593-600 Rietveld vs 2-step (POWLS) methods
Magnetic structures, incommensurate, 261-268
267 TbAs04, 267
Mass-absorption coeff. measurement, Neutron powder-diffraction at IPNS
use of, 475-483 and LANSCE, 405
for pyrite in coals, 475-483 diffractometers GPPD and HIPD,
in amorphous silicon dioxide, 476 405ff
in anthracine, 479, 480 Ni-base Alloy 600, rocking-curves,
in organic/inorganic compounds, 33-53
480 Ni, Fe, Cr in metal-treatment baths:
measurement method, 475-481 XRFA, 590
use for quant. analysis (QXRD) , Nitrided alloys of Ti-A1-V: XRPD,
481-483 129-135
Metallization: phases, reactions, Numerical Resolution Enhancement of
177-187 XRD patterns: profile
Metal pollution detected by XRFA, fitting, smearing, lattice
665-670 misfit, 409-416
Microbeam XRPD, 392ff
Microprocessor, RISC, T800 used for On-site analysis of soil (XRF) ,
XRF computation, 508 639-645
Microstrain/crysta11ite size Orientation-distribution function
in SmS and Sm-Gd-S films, 158 (ODF) for hematite, by
Minerals, qualitative XRFA of, neutron diffraction, 282
603-613 Oriented copo1yamides and copo1yester
Minimum detection limit (MOL) with carbonates, 423-432
TXRF spectrometer, 583 Oxygen in sputter-deposits: XRFA,
Monochromatization 242ff
by capillary microbeam, 624
for XRD, 287 Palladium hydride, 404
Multilayer film: thickness, Particle-size and strain analysis by
composition determined by XRD TOF and Rietveld, 404ff
plus XRF, 197-204 Particle-size induced errors in
Multilayer film XRFA, 237-245, Rietveld XRPD, 273
189-195 Pattern recognition for XRFA, 603-613
Mu1ti1ayers, W-C, 106 pattern-discriminant function
Multiple-line XRPD method for layer (Tou/Gonza1es), 605
thickness, 121-127 spectrum as n-component column
absolute vs relative intensities vector, 604
compared, 125
SUBJECT INDEX 699
Pb in gasoline, XRF reporting of, Profile analysis of phases, 94ff

534, 535 Profile fitting, XRPD
Peak breadth analysis, l48ff correcting for overlap of peak
Peak profiles, peak widths (XRPD) tails, 373-381
in roller bearings, 341-352 deconvolution, XRPD, 4l0ff
in thin films, Fe-oxides, 98 for zirconia, 470ff
with linear PSD, 397-402 program SHADOW, 317
(see also Profile fitting) program XRAYL for profile analysis
Peak visibility vs scan rates, 3l5ff 376
Penetration depth vs x-ray incidence, ringing structures; PROFIT, 414
92 Profile fitting, neutron-diffraction,
Pentaerythritol (PE) crystal 279, 280
structures, 445, 446 Profile fitting/peak-search XRPD data
Pentaerythritol-neopentylglycol analysis, 295-303
systems, 445-452 Profile-function analysis, pattern
differential scanning calorimetry decomposition, 26lff
results, 448, 449 Proton-induced x-ray emission (PIXE)
lattice parameters, 449, 450 analysis in Poland, 671-672
phase diagram, 448 Pyrite in coal, QXRD of, 475-483
XRPD data, 447ff
Perlite, ore and expanded, XRD Quantitative phase abundances (QPA)
analysis, 493-497 in mixtures of a A1203/Si02 and
Phase transformations ZnO/a Si02, 273
in Tl-supercond. films, 145-151 Quartz (alpha), QPA, fractional
Photon Factory at Nat'l Lab. for crystallinity, 272
High-Energy Physics, 410 Quartz in perlite, XRF at 0.1% level,
Pigments, qualitative XRFA of, 493-497
603-613 Quartz-triplet XRPD pattern, 413
Plastic zone near crack: XRD of,
323-326 Radioisotope excitation, 586ff
Plastic zone size seen by XRPD, 392 Radioisotope-excited XRF, 639-645
Poisson's ratio, effectively negative Refraction: XRPD peak shifts from,
in Sm-Y-S, 153 l12ff
Poland, development of PIXE in, Reporting results of analyses, system
671-672 for, 531-536
Pollution by metals in lakewater, Residual stresses/strains
XRFA, 665-670 by TOF with Rietveld, 404ff
Polya1cohols for energy storage, distribution (3-D) in ceramic-
445-452 metal joint, 353-362
Polystyrenes distribution near fracture
characterization, effects of surface, 325
temperature, 433-443 effect of background correction,
instrument for research on, 401, 402
434-436 effect on phase transformation in
isotactic/atactic/syndiotactic, Sm-Gd-S, Sm-Y-S, 153-158
434ff finite elements method (FEM)
orthorhombic and monoclinic stress calculations, 356ff
structures, 442 in corrorion-resistant layer on
Position-sensitive detector (PSD) steel, 171-175
background for linear PSD, 397-402 in Cr-electroplate on Ni, tensile
for texture analysis, 277-283 loaded, 161-169
non-linear, 267 in epitaxial layers, 61-66
photostimulated luminescence type, in GaAs/AlGaAs superlattices,
389-396 67-74
Position-sensitive proportional in roller bearings, 549-552
counter for stress analysis, in supercond. thin films, 145-151
335ff in surface of Si wafers, 55-60
Preparation of samples in thin films by bending vs XRD
for XRF probe of wastes, 632ff methods, 137-144
700 SUBJECT INDEX
Residual stresses/strains (cont'd) Rocking-curve widths,

in thin films: extrinsic, Ni-based Alloy 600 (cont'd)
intrinsic, 137 micro/macro strain-hardening, 37
in thin-film Sm-S alloys, 153-158 micros train distributions, 4lff
low incidence angle XRPD for thin recovery, 8ff
films, 153-158 stress-corrosion cracking, 45ff
particle-size and strain in Pd workhardening vs. microstructure,
samples, 406, 407 51
peak-profile simulations: Si Rocking curves
wafers, 58ff of GaAs/AlGaAs superlattices,
plastic zone near fracture 67-74
surface, 323ff of Si wafers vs depth, 55-60
recovery and mechanics of, 29ff (see also Epitaxial layers)
Si3N4 ceramics: fractures, 319-326 Rocks, errors in WDXRF of, and their
sin2 psi/Gaussian-curve method, removal, 549-552
355ff Roller bearings, stresses in, 351-352
strain-depth profiles in Si
wafers, 58ff Scattered XRF intensity calculations,
stress-intensity factor, 324 553-566
stress tensor in electroplate, Scattered x-rays, coherent/incoherent
162, 163 5l6ff
tapered roller bearings, 341-352 Scattering: coherent, incoherent in
Warren-Averbach and Hall- XRF, 509ff
Williamson procedures, COLA-based program for alphas;
errors, 373-381 modification of, 509, 5l2ff
when electroplate adhesion is Secondary excitation in XRF, 213-223
lost, 168 Seeman-Bohlin thin-film
with stress-corrosion cracking, diffractometry, 154
327-334 Si EDXRD patterns, 103
x-ray stress constant, 321 Si wafers: rocking-curves, 55-60
XRD of, with cyclic loading, Si wafers with (100) planes mis-
335-340 orientated with wafer
XRD topography of, 13-23 surface, 83-90
(see also Thin films' stresses/ SiGe/Si superlattices, 75-82
strains) mounting and geometric XRD
Restandardization in XRF analysis problems, 77ff
with SPC, 543-548 Silica, crystalline, XRD analysis,
Rh Ka. and Rh K S incident x-rays: 493-497
WDXRF backgrounds produced, standards for expanded perlite
52l-529 495, 496
Rietveld pattern-fitting quantitative Silicon nitride ceramics: residual
phase analysis (QPA) , 269-274 stresses, 319-326
Rietveld program vs 2-step program, Silicon nitride/copper/steel joint,
261-268 stresses in, 353-362
Rocking-curve and laser method for Si Sin 2 psi method vs bending for
wafer misalignment tests, stresses, 137-144
83-90 Sin 2 psi plots for electroplated
Rocking-curve widths, layer on steel, 171-175
Ni-based Alloy 600, 33-53 relation to Zn distribution, 174
by computer-aided rocking-curve Slate, XRF of, 593-600
analysis (CARCA), 33-53 oxide ratios to A1203, 598
dislocation arrangements, Soil, contaminants assessment by XRF,
36, 37, 40 655-663
dislocation obstacles in recovery contour plots, 662
52 Soils and waste materials, XRF of,
incremental microplasticity, 39 639-645
microcrack correlation, detection, Standardization cycles in XRF
53 analysis with SPC, 543-548
SUBJECT INDEX 701
Statistical Process Control (SPC) Synchrotron XRD topography, 13-23

advantages in analysis, 537-542 Synchrotron XRF analysis (SRXRF) of
restandardization in XRF analysis, fly ash, 673-678
543-548 compared with EPXMA and LAMMA,
Steel, XRPD after deformation/fatigue 673, 676, 677
389-396 Syndiotactic polystyrene, 433-443
Steel, Zn-Ni-alloy plated, Synsil substrate for XRF sample,
stresses in, 171-175 581-583
Step-size/counting-times, in XRD,
285, 290 Texture, determined by neutron-
Storage of XRPD data, plans for PDF-3 diffraction, 277, 283
417-422 Texture in Cr-electroplate, 163
Strain-hardening vs microstructure, Texture-weakened peaks in stress
37ff determination, 26ff
Stress applied cyclically, Textures, with Rietveld XRPA, 269-274
XRD measurement of, 335-340 Thermal expansion coefficients
Stress-corrosion cracking, 45ff Sm, Sm-Gd-S, fused quartz,
Stress-corrosion cracking: stresses, sapphire, CaF2, 155
327-334 effect of phase transition,
Stress-intensity factors, 327-334 153-158
Stress/strain measurement Thin films, characterized by
Gaussian-curve measurement method, synchrotron EDXRD, 101-107
366 Thin films, mu1ti1ayers; XRF
in alpha-alumina: confidence CoCr, Co/Ge/Cr, 237-245
limits, elastic constants, Cr/Cr203, 205-211
363-372 fundamental-parameter system,
Reuss, Voight and Kroner models of 225-235
strain, 364 LAMA-III program vs Dataflex 270
Structure of thermotropic software, 219ff
copolyesters and magnetic disk analyses: 4 layer,
copolyamides, 423-432 Ni, Co, Cr and thicknesses by
Structure refinement programs XRF, 231ff
POWLS-80, PROFAN, FULFIT, 261-268 magneto-optical disk analysis:
Sub-grains seen by XRD PSD, 395ff WDXRF vs EDXRF, 233ff
Sulphur emission in atmosphere, sources of analytical errors, 235
671-672 thickness and composition
Superalloys: phases, XRD peaks, calculation, 2l7ff
microstructure, 415ff Ti on Si: XRFA, 244
Superconductors (see also Epitaxial layers,
crystal structures of BaO-R203-CuO Thin films/thin layers)
systems, 453-465 Thin films/thin layers, XRPD
T1-Ca-Ba-Cu-O films, 145-151 GaAs/A1GaAs super1aticces, 67-74
Superlattice peaks, 75-82 metallization: adhesion,
Surface misorientation in Si wafers, fabrication, 177ff
83-90 methods for stress determination
Synchrotron at Novosibirsk, 2 GeV, compared, 137-144
674 multilayer analysis by XRD plus
Synchrotron, SRS Daresbury, EDXRD, XRF, 197-204
101-107 SiGe/Si XRD problems, 77ff
Synchrotron multi-layer Sin 2psi plotting for stresses, 27
diffractometry, 1-11 super1attice patterns, 75-82
Synchrotron radiation XRF, 205-211 Ti/Cu thin films on Si wafers,
Synchrotron radiation XRPD 177-187
data reduction, 295-303 Ti/TiCu on Si wafers, XRD: phases,
of Fe-oxide thin films, 97ff 177-187
Synchrotron-radiation XRD refinement backscattered energy spectrum
quartz structure, 263ff 180
Rietveld vs 2-step (POWLS) methods effects of heating, 181ff
261-268
702 SUBJECT INDEX
Thin films: XRF of Thin films: XRPD for stresses/strains

computed transmission through (cont'd)
grid-supported x-ray if trouble from weak peaks, 26
windows, 615-622 in Al-2%Cu evaporated film
magnetic recording/integrated (as in interconnects)
circuit films, 237-245 if passivated by quartz
Ni film on bulk sample of Sn, 194 sputtered layer, 29-32
secondary fluorescence effects, recovery of, 29
193 subjects needing more research
single-layer, intensity vs 26, 32
thickness, 189-192 test for the bond to substrate, 32
thin-layer XRF more intense than Ti-AI-V alloys, nitrided: XRPD of,
bulk, 193 129-135
two layer, multilayer, 192ff alpha', beta Ti, delta, epsilon
Thin films: XRF for chemical state phases, 129-135
analysis, 247-259 parameters vs concentration, 132ff
aluminum and A1203 spectra, 251ff ratios of phases, l34ff
aluminum-nitride film, 256ff Time-of-Flight (TOF) with Rietveld
low-E electron-excited x-rays, system, 404ff
247ff Time-resolved x-ray stress
silica glass with Band Padded, measurement, 335-340
258 Topography of thin layers, 13-23
zinc oxide film, 254ff contrast, resolution, 14, 16, 19
Thin films: XRPD of dislocations in epi1ayers, 19ff
Cr-e1ectroplate on Ni: x-ray double/triple-crystal methods,
stresses, 161-169 l8ff
samarium mono sulfide containing extinction distance, 17
rare earths, 153-158 with grazing incidence, 17, 23
stresses in Zn-Ni plating, 171-175 single-crystal methods, 14ff
superconducting TI-Ca-Ba-Cu-O Si-wafer preparation, 22ff
systems, 145-151 Total Reflectance X-Ray Spectrometer
peak-breadth analysis of, (TXRF)
148-151 used for low-level iodine XRF
texture, 148ff analysis, 581-583
testing for Si wafer misalignment, Toxic elements in fly ash, 673-678
83-90 Trace analysis with microbeam,
thickness by XRF (qualitative), 623-628
247-259 Trace-element detection by XRF,
XRD topography, 13-23 581-583
Thin films: XRPD by glancing- Transformation of phase
incidence, 91-100, 109-120 in PE-NPG system of polyalcoho1s
depth profile of phases, 94ff 445-452
Fe-oxides, 91-100 semiconductor/metallic in thin
FWHM vs crystallite size, films, 153-158
ll4ff, 119 stress-induced martensitic,
intensities vs incident angles, 467-474
17ff Zirconia, 467-474
magnetic-dead layer, 94, 96 Tricholoroisocyanuric acid, 491
peak shifts by refraction,
ll2ff, 119 Warren-Averbach and Ha1l-
peak widths, 98 Williamson procedures and
reflection from interface between errors, 373-381
layers, 114 Warren-Averbach method applied to
Thin films: XRPD for stresses/strains Ca(OH)2, 383-388
for triaxial stresses, tensors, CRYSIZE program, 384
27ff Wavelength-dispersive XRF (WDXRF):
for stresses in surface layers background spectra, 521-529
only, 28ff
SUBJECT INDEX 703
WDXRF spectrometer X-ray fluorescence analysis (XRFA)

electronic instability, (cont'd)
correction of, 549-552 with unprepared rock samples, 607
WDXRF vs EDXRF in multilayer analysis zeolites: Si02/A1203, and
233ff Na20/A1203 ratios, 679-684
zeolites, WDXRFA, 679-684
X-ray diffraction (XRD)/powder impurities, 683
diffraction (XRPD) (see also EDXRF)
automated diffractometry: cautions X-ray Powder Data File: plans for
285-293 PDF-3, 417-422
dispersion vs 29, stripping Ka2, X-ray refraction, 92
289 X-ray spectra, low-energy electron-
d's from 2Q's: common problems, excited, 247-259
285-293 X-ray spectrometer crystals, 250
figure-of-merit, 292 X-ray tube rotary-anode construction,
step-size, counting-time, 26
peak hunting, 290ff X-ray tube: rotating-anode for weak
slit choice for XRPD, 314 peaks, 313-318
X-ray diffractometer X-ray window design, 615-622
profile fitting; deconvolution, for detectors, 62lff
409-416 grids for support, 620ff
with synchrotron beam, 410 XRD analysis, quartz to 0.1% level,
X-ray fluorescence analysis (XRFA) 493-497
advantages of SPC, 537-542 XRF: back scattered, polychromatic
aluminas, 685-690 method, 515-520
Borate fusion for zeolite, XRF computer program (XRFPC),
680, 683, 684 for IBM PC,
calibration for contaminants, for multielements, 567-572
640ff data-base spectrum, 569
charts: Process Flow; intensity enhancement due to
Cause/Effect; Pareto, 537-542 single lines of matrix, 567ff
contaminated soil: mobile unit mass-absorption coeff's for single
used, 655-663 lines and total,
contaminated soil: portable unit 567, 568, 570
used, 629-636 pri.and sec. intensities, 567, 570
criteria for out-of-control SPC, XRF data-presentation system, for PC
539 microcomputer
detection limits, sensitivity, 689 commercial software employed, 533
energy-dispersive vs proportional data manipulation, tests, checks,
counters, 603, 611 531-536
field-portable analyzer, 640 XRF for hazardous waste
interactive program (proposed), mobile system, 655-663
613 portable system, 629-636
Mn in mussels vs year of growth, XRF on-stream analyser, 585-591
669ff XRF pathlength-distribution
mussels from Kentucky Lake, computations, 499-508
665-670 XRF scattered intensity
mussels indicate metal pollution, corrections, 553-566
665-670 basic theory, 553-557
normalized correlation coeff., 605 chain interactions; plots, 560
qualitative, with pattern coherent-scatt. kernel, 557, 559
recognition, 603-613 incoherent-scatt. kernel, 558, 559
site-specific, 639-645 photoelectric-effect kernel,
Sr, Fe in mussels, 666ff 557, 559
standard geological samples, XRF spectrometer, variable-angle, 244
604ff, 611 XRF theoretical fourth-order
thin films, 205-211 intensity, 573-580
with pigments, 608 Boltzmann's transport equation,
575
704 SUBJECT INDEX
XRF theoretical fourth-order XRPD patterns

intensity (cont'd) lines from holder, 313-318
multiple interactions, 573, 577 Ti-Al-V alloys, 129-135
spectrum of emission, 576-578 XRPD scanning: slit and step
XRF with microbeam, 623-628 optimization, 305-310
XRPD pattern indexing: algorithms XRPD synchrotron data reduction,
DrCVOL and TREOR, 436 295-303

Advances in X-Ray Analysis - Volume 33 - 1989

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ADVANCES IN

PLENUM PRESS • NEW YORK AND LONDON

v. iIIus. 24-28 cm. annual.

ISBN 978-1-4613-9998-8 ISBN 978-1-4613-9996-4 (eBook)

Proceedings of the Thirty-eighth Annual Conference on

© 1990 University of Denver

Plenum Press is a Division of Plenum Publishing Corporation

No part of this book may be reproduced, stored in a retrieval system, or transmitted

The 38th Annual Denver Conference on Applications of X-Ray Analysis

Brian Tanner, University of Durham, England, opened the session with a

The third talk, by Professor Jerome Cohen of Northwestern University,

The next talk was on the topic of thin film characterization by

The "Denver Conference," as it is generally known, is successful

This volume constitutes the proceedings of the 1989 Denver Conference

The conference plenary session was organized and chaired by C. C.

The invited papers on the program are listed below.

"High Resolution X-Ray Diffraction for the Characterization of Semiconducting

In addition to the Plenary Session, the following Special Sessions

o APPLICATION OF X-RAY METHODS TO THIN FILMS, chaired by C. C. Goldsmith,

WD-l X-RAY CHARACTERIZATION OF EPITAXIAL THIN FILMS I, D. K. Bowen,

The conference dinner attendance was 170. Prof. Sigmund Weissmann of

On behalf of the organizing committee, I would like to sincerely thank

My special thanks to the conference staff: Louise Carlson, John Getty,

"Scattering from Rigid-Rod Polymeric Fibers," W. Wade Adams, Wright-

"Rocking Curves and 'Rocking Curves' for the Analysis of Quaternary

"Integration Methods for Analyzing X-Ray Polymer and Powder Diffraction

"For his fundamental and wide-ranging work on the application of

In photo, left to right:

I. CHARACTERIZATION OF EPITAXIAL THIN FILMS

High Resolution X-Ray Diffraction for the Characterization

X-Ray Topography of Surface Layers and Epitaxial Films 13

Stresses in Thin Films 25

Deformation, Recovery and Stress Corrosion Cracking of Nickel-Base

X-Ray Characterisation of Residual Surface Strains after Polishing

Measurement of Relaxation in Strained Layer Semiconductor Structures 61

Characterization of Structural Inhomogeneities in GaAsjA1GaAs

X-Ray Diffraction Analysis of SiGejSi Superlattices 75

High Resolution Measurement of Surface Misorientation in

II. XRD CHARACTERIZATION OF POLYCRYSTALLINE THIN FILMS

Surface and Ultra-Thin Film Characterization by Grazing-Incidence

Study of Thin Films and Multilayers using Energy-Dispersive

Effects of Refraction and Reflection on Analysis of Thin Films

Enhanced Range of Measurable Thickness of Thin Crystalline Layers

X-Ray Diffraction of Plasma Nitrided Ti-6Al-4V . 129

A Comparative Study of Stress Determination Techniques in

X-Ray Line Broadening Analysis of TI-Superconducting Films . 145

Stress Analysis of Thin-Film SmS using a Seemann-Bohlin Diffractometer. 153

Residual Stresses and Differential Deformation of Electroplated

X-Ray Residual Stress Analysis of Zn-Ni Alloy Electroplating Layers . 171

XRD Characterization of Titanium/Copper Thin Films Heat Treated in

III. X-RAY SPECTROMETRIC CHARACTERIZATION OF THIN FILMS

Characterization of Thin Films Using XRF . 189

The Determination of Elemental Composition, Thickness and Crystalline

Near-Surface Chemical Characterization Using Grazing Incidence

Basic Studies of Multi-Layer Thin Film Analysis Using Fundamental

Application of Multi-Layer Thin Film Analysis by X-Ray Spectrometry

Fundamental Parameter-Based X-Ray Fluorescence Analysis of Thin

Non-Destructive Chemical-State Analysis of Thin Films and Surface

IV. ANALYSIS OF DIGITAL DIFFRACTION DATA INCLUDING RIETVELD

Structure Refinements in Chemistry and Physics. A Comparative

X-Ray Powder Diffraction QPA by Rietveld Pattern-Fitting - Scope

Application of Position Sensitive Detectors for Neutron Diffraction

Problems in the Derivation of d-Values from Experimental Digital