ABC’s of

Electrochemistry:
X-Ray Photoelectron
Spectroscopy (XPS)
Madhivanan Muthuvel
Center for Electrochemical Engineering Research (CEER)
Chemical and Biomolecular Engineering
Ohio University

Athens, Ohio
November 17, 2011
 Outline

• What is XPS?
• Background
• Principle
• Instrumentation
• Analysis of XPS Data
• Applications
• Facility at Ohio University
• Summary

Center for Electrochemical Engineering Research, Ohio University 2

 What is XPS?

• X-ray photoelectron spectroscopy (XPS) is also

known as ‘Electron Spectroscopy for Chemical
Analysis’ (ESCA)
• XPS is a surface analytical technique
• Widely used to determine the chemical information
in addition to elemental information of the samples
• Related techniques are Auger electron
spectroscopy (AES) and Ultra-violet photoelectron
spectroscopy (UPS)

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 Background

• In 1887, Heinrich Hertz observed the photoelectric effect

• In 1905, Albert Einstein explained the photoelectric effect with a simple

mathematical description, which lead to Nobel Prize in Physics

Ek = h - Eb
Ek and Eb is the kinetic energy and binding energy of the photoelectron,
respectively, and hν is the energy of the incident beam

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 Background

• Prof. Kai Siegbahn from the University of

Uppsala, Sweden, utilized the photoelectric
effect to develop an analytical technique
• During the mid-1960’s, Prof. Kai Siegbahn
and his co-workers developed the analytical
technique known as X-ray photoelectron
spectroscopy (XPS)
• He coined the term Electron spectroscopy
for chemical analysis (ESCA)
• In 1981, Prof. Kai Siegbahn was awarded
the Nobel Prize in Physics for the
development of the XPS technique

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 Principle
Conducting Sample

Ek = h  Eb  sample

Φsample is the work

function of the sample

Work function is the

energy difference
between Fermi level
and Vacuum level

University of Illinois at Urbana-Champaign [groups.mrl.illinois.edu/nuzzo/0-ppt/XPS Class 99.pps]

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 Principle
Analysis of sample with the XPS instrument
e-

Sample Spectrometer
Free Electron Energy
Ek (1s) Ek (1s)
Vacuum Level, Ev
sample spec
hv
Fermi Level, Ef

Eb (1s)
E1s

Ek = h  Eb  spec
University of Illinois at Urbana-Champaign [groups.mrl.illinois.edu/nuzzo/0-ppt/XPS Class 99.pps]

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 Instrumentation
Photo of a XPS Instrument

Kratos Axis Ultra model in Surface Science Western Laboratory

at The University of Western Ontario
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 Instrumentation
Schematic for a XPS instrument
Computer
System
Hemispherical Energy Analyzer

Outer Sphere Magnetic Shield

Inner Sphere Analyzer Control

Electron Multi-Channel Plate

Lenses for Energy
Optics Electron Multiplier
Adjustment
(Retardation) Resistive Anode
X-ray Encoder
Source Position Computer
Lenses for Analysis Position Address
Area Definition Converter
Position Sensitive
Detector (PSD)
Sample
5 4 .7
University of Illinois at Urbana-Champaign [groups.mrl.illinois.edu/nuzzo/0-ppt/XPS Class 99.pps]

Center for Electrochemical Engineering Research, Ohio University 9

 Instrumentation
Ultra high vacuum (UHV) chamber

• Typical pressure: 10-9 – 10-11 torr

• Reason to have UHV condition
– Maintain sample surface integrity
– Minimize scattering of the photoelectrons
– Maximize mean free path of the photoelectrons
– Helpful to use tungsten filament or other
electron source in the X-ray source cathode

Center for Electrochemical Engineering Research, Ohio University 10

 Instrumentation
Ultra high vacuum (UHV) chamber

XPS instrument with facility to perform electrochemical experiments

C. J. Corcoran, H. Tavassol, M. A. Rigsby, P. S. Bagus, and A. Wieckowski, Journal of Power Sources 195 (2010) 7856-7879.

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 Instrumentation
X-ray source
• Energy of the x-ray beam
depends on the anode material
in the x-ray source
• High intensity x-ray beam with a
narrow line width gives best
spectroscopic result
• Commonly Mg Kα (1253.6 eV)
and Al Kα (1486.6 eV) are used
• Dual-anode x-ray source
(Al/Mg, Mg/Zr, and Al/Zr) are
also used
• X-ray beam lines from
synchrotron facility can be used
for XPS analysis
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 Instrumentation
X-ray source

• Diameter of X-ray beam ranges

from 5 mm to 1-5 µm
• X-ray penetration depth ~ 1 µm
• Sampling depth depends on
wavelength of the x-ray beam
and sample material
• For Al Kα, sampling depth is
generally 10 nm and 10 atomic
layers for heavier elements

D. R. Vij, Handbook of Applied Solid State Spectroscopy, Springer, New York, 2006.

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 Instrumentation
Electron energy analyzer

Cylindrical mirror analyzer (CMA)

Electron Pathway through the CMA

X-Rays
Source

Slit

0V 0V

+V +V
+V +V
Sample
Holder
0V 0V

Concentric Detector

hemispherical
analyzer (CHA) Used in XPS and AES instruments

University of Western Ontario [mmrc.caltech.edu/SS_XPS/XPS_PPT/XPS_Slides.pdf]

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 Instrumentation
Samples for the XPS analysis
• Sample size depends on the instrument
• Evans Analytical Group (EAG) can handle samples up to 8” in
diameter and thickness till 1”
• Generally, sample’s lateral size cannot exceed 1” and
thickness within 0.5”
• Any solid sample (conducting and non-conducting) can be
analyzed
• Sample has to be compatible in the ultra high vacuum (10-9
torr) condition
• Sample preparation
– Degrease before loading in the holder
– Use conductive tape for attachment
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 Analysis of XPS Data
Example of XP spectrum

XPS Spectra, CasaXPS www.casaxps.com/help_manual/manual_updates/xps_spectra.pdf

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 Analysis of XPS Data
Identify Auger peaks in XP spectrum

Cu XP spectra illustrating the shift in auger peak positions with the change from Mg
to Al anodes in the X-ray source

D. R. Vij, Handbook of Applied Solid State Spectroscopy, Springer, New York, 2006.

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 Analysis of XPS Data
Peak quantification in XP spectrum

XPS Spectra, CasaXPS www.casaxps.com/help_manual/manual_updates/xps_spectra.pdf

Center for Electrochemical Engineering Research, Ohio University 18

 Chemical Effects in XPS

Chemical shift:
change in binding energy of a core electron of an element
due to a change in the chemical bonding of that element

increase in
Withdrawal of valence electron charge
Binding energy

decrease in
Addition of valence electron charge
Binding energy

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 Chemical Effects in XPS

Charges are withdrawn from Ti to

form Ti4+, which results in higher
Binding energy for the Ti 2p orbitals

Chemical shift information very

powerful tool for functional group,
chemical environment, and
oxidation state
University of Western Ontario [mmrc.caltech.edu/SS_XPS/XPS_PPT/XPS_Slides.pdf]

Center for Electrochemical Engineering Research, Ohio University 20

 Chemical Effects in XPS
Chemical shift for Gold (Au) 4f7/2 peak

University of Western Ontario [mmrc.caltech.edu/SS_XPS/XPS_PPT/XPS_Slides.pdf]

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 Chemical Effects in XPS
Curve fitting for Carbon 1s peak

C 1s region XP spectrum for polymethylmethacrylate (PMMA)

D. R. Vij, Handbook of Applied Solid State Spectroscopy, Springer, New York, 2006.

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 Depth Profile
Examples of XPS spectrum
Ar+ sputtering of the sample results in layer-by-layer
removal of the sample using Ion gun

XP spectrum of the sample surface was collected after

each step of Ar+ sputtering
XPS Spectra, CasaXPS www.casaxps.com/help_manual/manual_updates/xps_spectra.pdf

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 Depth Profile
Multi layer SiO / TiO2 sample

The set of O 1s spectra measured during a depth profiling experiment

XPS Spectra, CasaXPS www.casaxps.com/help_manual/manual_updates/xps_spectra.pdf

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 Depth Profile
Architectural Glass Coating sample

Atomic concentration for the elements found in the Architectural Glass

Coating sample from depth profiling experiment
University of Western Ontario [mmrc.caltech.edu/SS_XPS/XPS_PPT/XPS_Slides.pdf]

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 Strengths of X-ray Photoelectron Spectroscopy

• Surface sensitive technique (top 10 nm)

• Chemical state identification on surfaces
• Identification of all elements except for H and He
• Quantitative analysis, including chemical state
differences
• Applicable for a wide variety of materials, including non
conducting samples (paper, plastics, and glass)
• Depth profiling with matrix-level concentrations
• Oxide thickness measurements

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Limitations for X-ray Photoelectron Spectroscopy

• Detection limits typically ~ 0.1% atomic

• Smallest analytical area ~ 10 µm diameter
• Limited organic information (short-range bonding only)
• Samples must be ultra high vacuum compatible
• Samples that decompose under X-ray irradiation
cannot be studied

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 Applications

• Analyzing the composition of powders and debris

• Determining contaminant sources
• Examining polymer functionality before and after processing
• Bonding and adhesion issues
• Obtaining depth profiles of thin film stacks (both conducting and
non-conducting) for matrix level constituents
• Identifying stains and discolorations
• Characterizing cleaning processes
• Assessing the differences in oxide thickness between samples

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 Applications
Industries using XPS technique

• Aerospace • Pharmaceutical
• Automotive • Photonics
• Biomedical / • Polymer
Biotechnology
• Semiconductor
• Data Storage
• Solar Photovoltaics
• Defense
• Telecommunications
• Displays
• Electronics
• Lighting

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 Applications
Analysis of Pigment from Mummy Artwork
Pb3O4
Egyptian Mummy
2nd Century AD
World Heritage Museum
University of Illinois

PbO2

C
O
150 145 140 135 130
Binding Energy (eV)

P Pb
b
N XPS analysis showed
Ca that the pigment used
Na
Cl Pb
on the mummy
wrapping was Pb3O4
rather than Fe2O3
500 400 300 200 100 0
Binding Energy (eV)
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 Applications
Analysis of Carbon Fiber – Polymer Composite material

-C-C-

N(E)/E
-C-O

Woven carbon fiber -C=O

composite
-300 -295 -290 -285 -280
Binding energy (eV)

XPS analysis identifies the functional groups present on composite surface.

Chemical nature of fiber-polymer interface will influence its properties.

University of Illinois at Urbana-Champaign [groups.mrl.illinois.edu/nuzzo/0-ppt/XPS Class 99.pps]

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 Applications
Analysis of Nanoparticle catalysts used in DMFC
Nanoparticles were less than 4 nm in size.

(a) Pt/Ni (1:1), (b) Pt/Ni (3:1), (c) Pt/Ru/Ni (5:4:1),

and (d) Pt/Ru (1:1).

The dotted line is the Pt 4f7/2 peak position for

pure Pt. The peaks were shifted from 0.17 eV for
(c) Pt/Ru/Ni (5:4:1) to 0.35 eV for (a) Pt/Ni (1:1)
and 0.36 eV for (b) Pt/Ni (3:1).

Metallic Ni content in catalyst (a) is 11.8%,

catalyst (b) is 33.7%, and catalyst (c) is 14.4%.

These shifts were interpreted to result from

modification of the Pt electronic structure
by electron transfer from Ni to Pt.

C. J. Corcoran, H. Tavassol, M. A. Rigsby, P. S. Bagus, and A. Wieckowski, Journal of Power Sources 195 (2010) 7856-7879.

Center for Electrochemical Engineering Research, Ohio University 32

 Facility at Ohio University
Instrument and Location

XPS instrument is located in the

W. M. Keck Thin Film Analysis Facility

John E. Edwards Accelerator Laboratory

(across Clippinger building)
4.5 MV Tandem Accelerator

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 Facility at Ohio University
Contact Personnel
At John E. Edwards Accelerator Laboratory

Prof. David C. Ingram

Accelerator Lab Chairman
ingram@ohio.edu

At Center for Electrochemical Engineering Research (CEER)

Madhivanan Muthuvel Ph.D.

muthuvel@ohio.edu

John Goettge
goettge@ohio.edu
Center for Electrochemical Engineering Research, Ohio University 34
 Facility at Ohio University
XPS analysis of Pt/Ir catalyst developed at CEER
Dr. Madhi' samples. April 27th 2007
XPS Results: No sputtering
Pt Sample C only Sample PtIr1 sample PtIr2 sample PtIr3 sample PtIr4 sample PtIr5 sample
April 27th 2007 April 27th 2007 April 27th 2007 April 27th 2007 April 27th 2007 April 27th 2007 April 27th 2007
Mass Mass Mass Mass Mass Mass Mass
Component Conc % Conc % Conc % Conc % Conc % Conc % Conc %
Iridium(Ir) 0 0 24.76 14.64 12.83 15.61 31.20
Platinum (Pt) 94.44 0 70.04 76.95 80.59 75.57 64.60
Carbon ( C ) 5.56 100 5.21 8.40 6.58 8.83 4.20
Total 100.00 100.00 100.01 99.99 100.00 100.01 100.00

Binding energies for Pt and Ir Pt-Ir sample

element (NIST database)
Platinum (Pt) Iridium (Ir)
4d5/2 314.61 eV 296.31 eV
4f7/2 71.12 eV 60.84 eV

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 Summary

• X-ray photoelectron spectroscopy (XPS) is a surface

analytical technique

• This technique is used to identify elemental and chemical

information on the surface (~ 10 nm) of the sample

• The strengths of the XPS technique is extensively used by

various industries for there research and development

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 References

Power point presentations

• X-ray Photoelectron Spectroscopy (XPS), Center for Microanalysis of Materials,
University of Illinois at Urbana-Champaign [groups.mrl.illinois.edu/nuzzo/0-
ppt/XPS Class 99.pps]
• X-ray Photoelectron Spectroscopy, R. Smart et. al., Surface Science Western,
University of Western Ontario
[mmrc.caltech.edu/SS_XPS/XPS_PPT/XPS_Slides.pdf]
• X-ray Photoelectron Spectroscopy, D. Torres, University of Texas at El Paso
[nanohub.org/resources/2011/download/x-ray photoelectron spectroscopy
(xps).ppt]

Journal
• C. J. Corcoran, H. Tavassol, M. A. Rigsby, P. S. Bagus, and A. Wieckowski,
Journal of Power Sources 195 (2010) 7856-7879.

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 References

Web sites
• XPS Spectra, CasaXPS
www.casaxps.com/help_manual/manual_updates/xps_spectra.pdf
• X-ray Photoelectron Spectroscopy (XPS), Evans Analytical Group (EAG)
www.eaglabs.com/techniques/analytical_techniques/xps_esca.php
• John E. Edwards Accelerator Laboratory, Ohio University
edwards1.phy.ohiou.edu/~oual/

Books
• D. R. Vij, Handbook of Applied Solid State Spectroscopy, Springer, New York,
2006.
• F. A. Settle, Handbook of Instrumental Techniques for Analytical Chemistry,
Prentice-Hall, New Jersey, 1997.

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 Further Reading

Web site
• X-ray Photoelectron Spectroscopy (XPS) Reference Pages
xpsfitting.blogspot.com

Books
• A. T. Hubbard, The Handbook of Surface Imaging and Visualization, CRC Press,
Boca Raton, Florida, 1995.
• T. L. Barr, Modern ESCA: The principles and practice of X-ray Photoelectron
Spectroscopy, CRC Press, Boca Raton, Florida, 1994.
• J. Chastain, Handbook of X-ray Photoelectron Spectroscopy: A Reference Book
of Standard Spectra for Identification and Interpretation of XPS data, Perkin
Elmer Corporation, 1992.

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Thank You

Questions?
Contact:
Madhivanan Muthuvel at
muthuvel@ohio.edu