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Diffraction

Absorption
Fluorescence
Reflectivity

AMS 2000-Rigaku representative


Analytical Division

Claudia Gavrilescu
Product Manager

Introducing Rigaku
Since its inception in Japan in 1951, Rigaku has been at
the forefront of analytical and industrial instrumentation
technology. In fact, Rigaku means physical science in
Japanese, the core of instrumentation.

Rigaku Facts:
Over 1100 employees worldwide
Consolidated worldwide sales US$350M
Presence in 57 countries
Explicitly focused on X-ray technologies
Our expertise allows us to provide
complete X-ray analysis solutions we
make everything from X-ray sources, to
optics and detectors.

Rigaku group
Tokyo, Japan Rigaku Group Headquarters
Rigaku Corporation
R&D, Application Research Lab. Sales & Service
Three factories in Japan:
Tokyo for XRD and TA, Osaka for XRF
and Yamanashi for XRD, XRF
manufacturing

Berlin, Germany
Rigaku European Headquarters
Sales & Service

Prague, Czech Republic


Rigaku Innovative Technologies Europe
Detector and Optics R&D
Manufacturing

Sevenoaks, Kent, England


Rigaku Europe
Sales and Service

Beijing, China
Major offices

R&D
Manufacturing
Sales & Service

Major distributors

Houston, TX, USA


Rigaku Americas Corporation
Sales & Service

R&D, Application Research


Lab.
Manufacturing

Auburn Hills, MI, USA


Rigaku Innovative Technologies Inc.
Advanced Optics R&D,

Application Research Lab.


Manufacturing
Sales & Service

San Diego, CA, USA

Tucson AZ, USA

Rigaku Automation Inc.

EIT

Crystallization & Sample


Prep Automation
Manufacturing
Sales & Service

CCD
R&D and manufacturing

MAKE A
CHOICE....

Product areas

XRD

XRF

Cryogenics

SAXS

Optics

Automation

Detectors

Stress
Analysis

Protein
Crystallography

Small
Molecule

X-ray
Generators

Semiconductor

Rigaku creates X-ray


instruments and components
for use in a diverse variety of
applications and fields,
presenting scientists with a
unique level of depth and
configurability.

G eneral presentation of R igak u com pany

R ange of R igak u products


X - R a y d iffra ction ( X R D )
Affordable general purpose diffraction:
MiniFlex II worlds smallest XRD system
MiniflexII

Advanced XRD instrumentation:


Ultima IV / TTRAX III multi-purpose /versatile XRD systems
D/MAX Rapid high sen./res. Microdiffraction

Specialty XRD instrumentation:

Ultima IV

SmartLab Series systems for thin film evaluation


Nanoviewer-SAXS small angle scattering
PSPC/MSF stress analyzer
XRD-DSC hybrid tool w/ scanning calorimetry

SmartLab

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X-Ray Fluorescence (XRF)
Sequential wavelength dispersive systems
Supermini

Supermini The world's first high-powered bench top wavelength dispersive XRF
ZSX Primus/ZSX Primus II flexible ultra-high-performance

Simultaneous wavelength dispersive systems


- Simultix 12 for extremely high throughput

- Simultix 14 Multi-channel-type wavelength dispersive system

Primus II

Single channel wavelength dispersive system


Mini-Z series Bench top WDXRF analyzers :
Mini-Z(Ni, Si ,S ,Zr )
Mini-Z

Simultix14

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Sm. Mol. Crystallography

Benchtop X-ray crystallography


- SCXmini

- the first benchtop X-ray crystallography system for automated three


dimensional (3D) chemical structure determination

- XtaLAB mini worlds smallest for routine structure analysis


SCXmini

CCD systems
- Saturn 724+ is the next generation of CCD camera
for small molecule crystallography

XtaLAB mini

- Mercury 2 affordable compact design, ideal compact CCD for small molecule
crystallography

X-ray generators

- ultraX 18 high-frequency 18 kW X-ray generator designed for flexibility, high


and low maintenance operation

stability

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Total Reflection X-ray Spectrometry (TXRF)
TXRF spectrometer for material, chemical, environment
- NANOHUNTER (Winner of the 2007 R&D 100 Award for technical innovation)
The system can measure the full range of samples, including bulk solids, liquids, powders,
and thin films.
Perform trace level elemental analysis
- Produce results without a wet lab
- Predict thin-film chemical properties

Nanohunter

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X-ray Absorption Spectroscopy (EXAFS & XANES)

X-ray absorption spectrometer (R-XAS) is a versatile in-house instrument capable of


performing XAS, XANES, and EXAFS measurements.

The X-ray absorption spectrum can be divided into near edge and extended fine
structure.

Features:
Both transmission and fluorescence measurements are possible.
Ca to U measurements capabilities for both opaque and transparent
samples with little sample preparations
Horizontal or vertical sample mounting.

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X-ray Absorption Spectroscopy (EXAFS & XANES)

Applications:
EXAFS (Extended X-ray absorption fine structure)
Coordination environment
Bond lengths
Local disorder
Valence state

XANES (X-ray absorption near-edge structure)


Fermi energy
Local coordination geometry

The interpretation of XANES spectra is substantially more complicated than EXAFS


spectra.

R ange of R igak u products


Semiconductor Metrology

Thin film characterization process tools

- MFM65 for metal film monitor - Integrates EDXRF & XRR in one tool (300 mm)
WaferX 300 for thickness & composition
WDXRF for high resolution & throughput (300 mm)

Contamination process tools


TXRF-V300

TXRF-V300 for in-process wafer contamination


Worlds first integrated VPD(vapor phase decomposition) & TXRF
(300 mm), 107 atoms/cm2 sensitivity

Specialty & R&D metrology tools


3272 very large sample XRF for sputtering targets
XRT-300 X-ray topographic imaging (300 mm)
ATX Series XRD tool for thin films

M ethods with A pplications in


M icro and N anotechnology
The common factor in nanotechnology is the dimension of the structures studied.
Nanotechnology research and development relies on accurate measurement of atomic
and molecular distances within structures ranging from semiconductor devices to nanopowders.

X-ray diffraction (XRD) and associated techniques are primary tools for the
nanotechnology researcher.
X-ray reflectometry (XRR) determines layer thickness, roughness, and density for
amorphous and/or crystalline materials.
High-resolution X-ray diffraction can measure layer thickness, roughness, chemical
composition, lattice spacing, relaxation and more (single crystal).

X-ray diffuse scattering is used to determine lateral and transversal correlations,


distortions, density, and porosity.

M ethods with A pplications in


M icro and N anotechnology
In-plane grazing incidence diffraction(GID) is employed to study lateral correlations of
thinnest organic and inorganic layers as well as depth profiling and Inhomogeneities in
materials.
Small angle X-ray scattering (SAXS) can determine the size, shape, distribution,
orientation, and correlation of nano-particles present in solids or solutions.
High-resolution triple-axis X-ray diffraction provides a nondestructive, quick,
and quantitative measure of the film quality and possible defect density.
Total Reflection X-ray Spectrometry (TXRF) and VPD-TXRF are tools for contamination
measurement, trace-level elemental analysis, provide evaluation of the physical nature of
the sample and provide chemical information as a function of analysis depth.
X-ray absorption spectroscopy(XAS) can measure the atomic valence and coordination
state of selected element by measuring its absorption spectrum. XAS/EXAFS/XANES
helps probe materials used in crystals, batteries, proteins, films, semiconductor surface
and more.

Si
Si (substrate)

Modern methods of analyzing the


structure of material science

Thin film analysis and


SAXS applications

TM

Phase ID & quantitative analysis


BB
ZnO, MgO, Al2O3 mixture sample

Al2O3 : 44%

ZnO : 20%

MgO : 36%
2 (deg.)

Focusing vs. Parallel Beam


XG

XG

DS

SS

RS

Detector
PSA

DS
Detector

Mirror
Sample

Sample
Cause of
Flat sample
systematic errors Axial divergence
Sample absorption
Sample displacement
Calibration
Internal (preferred)
Intensity
High
Good for
Indentification of trace
phases

Axial divergence
External
Medium
Identification of sample with
curvature/rough surface
Structure refinement
In-situ measurements

Sample preparation

12000

5000

10000

4000

Intensity ( CPS )

Intensity ( CPS )

PB

8000
6000
4000

3000
2000
1000

2000

0
30

40
50
2 ( deg. )

60

30

40
50
2 ( deg. )

60

Preferred orientation
PB
Packed

Loose
10000

8000

8000

009

6000
4000
2000
0

Intensity ( CPS )

Intensity ( CPS )

003 006

10000

6000
4000
2000
0

-2000

-2000

-4000

-4000
5

10 15 20 25 30 35 40 45 50
2 ( deg. )

10 15 20 25 30 35 40 45 50
2 ( deg. )

Thin film analysis


PB
Photocatalyst
film ( 200nm ) on glass
10000
--- : /2 scan
--- : 2 scan
--- : Anatase

Intensity ( a.u. )

8000
6000
4000
2000
0
10

20

30

22 (deg.)
( deg. )

40

50

60

Goniometer & optics

Cross Beam Optics


Rigaku patented technology
BB and PB geometries are simultaneously
mounted, aligned, and selectable.
X-ray source
Focusing beam is selected.

Parallel beam is selected.

Multilayer mirror
Sample
Bragg-Brentano focusing geometry (BB)

Sample
Parallel beam geometry (PB)

Optics
Bragg-Brentano focusing
Phase id, crystal structure, etc.
for powders
Parallel beam
Phase id, crystal structure, etc.
for thin films
Ge 2-bounce
Crystal structure, film thickness, etc.
for imperfect crystals
High resolution / triple-axis
Crystal structure, film thickness, etc.
for highly perfect crystals
In-plane geometry
Depth controlled phase id, etc.
for ultra thin films

Applications & optics


CBO + Automatic Alignment

Nano materials
SAXS with x-ray mirror

Thin films

Triple axis

Ge 4-bounce
Ge 2-bounce

Powder / bulk

Powder

C
B

Parallel beam with x-ray mirror

CBO w/o module exchanges

Bragg-Brentano focusing

USAXS
Challenge for Large Particle Size Determination
U-SAXS (Ultra SAXS)
Light Scattering
Small-Angle
XS
A
X-ray ScatteringS

XS Ultra Small-Angle
A
US
X-ray Scattering

10m

1m

100nm 10nm

1nm

0.1nm

SAXS analysis deals with the size of about 2nm~100nm.


(Various micelles, polymers, or colloids can be targeted.)

USAXS
Challenge for Large Particle Size Determination
U-SAXS (Ultra SAXS)

Bonse-Hart camera (USAXS)


in experimental hutch 1 (EH1)
ESRF

USAXS

Sealed-off and rotating anode


x-ray tube
Seald-off x-ray tube
2-3 kW
filament

Rotating anode tube


9-18 kW

target
rotating

filament
window

target

USAXS
Challenge for Large Particle Size Determination
U-SAXS (Ultra SAXS)

Slit3
X-ray source

Slit1

Sample

Z axis
Multilayer Ge(220) Height limit slit
mirror

Slit2

Ge(220)

Detector

Attenuator
*Custom-order geometry

USAXS
Small angle resolution
(cps)
3.0x10

2.5x108

Direct Beam Profile

SAXS
10 mm HLS

USAXS
2 mm HLS

2.0x108
1.5x108
q=0.0023 nm-1

1.0x108
5.0x107
0
-0.1

0.05

0
q(1/nm)

0.05

0.1

FWHM in USAXS was q=0.0023 nm-1 (2=0.0032 deg).


FWHM in 2slits SAXS was q=0.041 nm-1 (2=0.0578 deg).

USAXS
Colloidal silica USAXS

(cps)
106

The shape of the silica was


assumed to be spherical.

10

The average particle size


measured by USAXS agreed
with values obtained using the
light scattering method in both
samples.

103

The concentration of silica


was 5 wt % in both samples. The
scattering intensity became
stronger as particle size
increased.

USAXS Profile

200nm
750nm

104

102
101
100
0.02

sample

0.042

0.062
q(1/nm)

0.082

USAXS

Light scattering

average

average

200nm

193

198

750nm

728

747

In-Plane
XRD
Whats

in-plane XRD ?

Observation of planes perpendicular to the surface


Measurements of ultra-thin films
Application to pole figure measurement

In Plane

Diffracted X-ray

Diffraction angle 2BraggReflected

Incidence X-ray

Out of Plane

X-ray

In-Plane
XRD3-dimensional

structure analysis

PB/out
Pentacene 50nm

PB/in
Pentacene 50nm

50 x 10
Out-of-plane

90
In-plane

Intensity ( CPS )

Intensity ( CPS )

40
30
20

60

30

10
0

0
5

10 15 20 25 30 35 40 45 50 55 60
2 ( deg. )

10 15 20 25 30 35 40 45 50 55 60
2 ( deg. )

In-Plane
XRD

Probed depth control


extinction distance (nm)

1
1000

0.1

0.01

100

0.001
10
0.0001
0.0

0.2

0.4

0.6

0.8

1.0

incident angle (degree)

Sample:Al Wavelength:1.54056 CuK1

In-Plane
XRD

Example 1
CVD-Al layer for wiring

250

Intensity (cps)

Glancing Angle
0.2 degree
0.5 degree

Al(111)

200

150

Al+Cu

100

Al+Cu
Cu(111)
Cu(200)

50

Al-Cu alloy transition layer


was detected.
interface layer
Al
Al+Cu
300nm

Al(220)
Al(311)
Cu(220)
Al(222)

Cu
SiO2
Si (substrate)

0
30

40

50

60

70

80

2 / (degree)
+

+ In-Plane

Ta

In-Plane
XRD

Example 2

Evaluation of FePt magnetic thin film

Ag / FePt (15 nm) / Glass


(0 - 1 nm thick Ag top layer)
1 nm
15 nm

Ag cap
FePt
Glass sub.

+ In-Plane

In-Plane
XRD

Example 2

Evaluation of FePt magnetic thin film


Haro from glass
substrate is obvious.

Out-of-Plane diffraction profiles for samples with Ag top layer


5000

Ag 0 nm

Intensity [a.u.]

4500

Ag 0.25 nm

4000

Ag 0.5nm

3500

Ag 1.0nm

Only FePt(111) can


be observed from
thin film layer.

3000
2500
2000

There is no specific
observation from Ag
cap layer.

1500
1000
500
0
20

30

40

50

2th out [deg]

60

70

80

In-Plane
Example
3
XRD
Evaluation of FePt magnetic thin film
FePt expected as a high density magnetic recording
media

FePt (fct) 15nm


Glass sub.
fct (face centered
tetragonal)

FePt (fcc) 15nm


Glass sub.
fcc (face centered
cubic)

Intensity [arb. unit]

Ag cap 1nm

20

FePt (fcc
fct)

Ag(111)
FePt (fct)

with Ag cap
no Ag cap

30

(Appl. Phys. Lett. 83, 2196 (2003))

40

50

60

70

80

Diffraction angle 2 / [deg.]


(Appl. Phys. Lett. 83, 2196 (2003))
+

+ In-Plane

In-Plane
XRD

Motion of goniometer in pole


figure measurement by standard
sample horizontal goniometer

Motion axes are


axis(step) axis(scan)
Incident X-ray

rotation
axis

Diffraction X-ray

Sample

Sample is inclined so
sample is not kept
horizontally.

axis

Flapping motion of sample is easy to understand


because this is managed by one axis (chi axis).
There is loss of intensity in position of
=0degree InPlane measurement ,as
incident line focus X-ray and sample surface
makes perpendicular layout.

In-Plane
XRD

Pole figure measurement in sample horizontal in-plane


goniometer

At all time a ample is kept horizontally It is possible to measure from

In-plane to out-of-plane direction continuously

rotation
axis

Path of Incident
optics

Path of
detector

10mm

Incident X-ray
Beam width

1.0mm

Incident X-ray
Diffracted X-ray
2

Receiving slit
2.0mm 20mm or
Parallel Slit Analyzer

Detector

Parallel Slit
Analyzer

Evaluation of thin films


Organic film

Method?
?

Optics ?
?

Crystal structure

Dielectric film

Texture

Compound
semiconductor

Crystallinity

Magnetic film

Thickness

Single crystal
wafer

Particle / pore
size

Evaluation of thin films


Organic film
Dielectric film

Crystal structure
Texture

Compound
semiconductor

Crystallinity

Magnetic film

Thickness

Single crystal
wafer

Particle / pore
size

Selecting application
Select application

Sample alignment

SmartLab
5 simple parameters

Sample alignment

SmartLab
5 simple parameters
Manual setting
35 parameters

Maximum flexibility

Optical component sensors


Photo sensors

Ge(220)x2 + Soller slit

Marks

Setting up optics

SmartLab

Wrong parts are sensed and indicated!!

Measurement

Basic file and sample information

Automatic alignment
Source height
Incident beam
direction
Mirror angle
Divergence slit height
Sample height
2 zero point
Detector setting

THANK YOU FOR YOUR ATTENTION!