Surface analysis

XPS and AES spectral analysis

Sample/Spectrometer Energy Level Diagram-
Insulating Sample
e-

Sample Spectrometer
Free Electron Energy
KE(1s)

spec
Vacuum Level, Ev
hv Ech
Fermi Level, Ef

BE(1s)
E1s
A relative build-up of electrons at the spectrometer
raises the Fermi level of the spectrometer relative to the
sample. A potential Ech will develop.
Binding Energy Referencing
BE = hv - KE - spec- Ech

Where: BE= Electron Binding Energy

KE= Electron Kinetic Energy
spec= Spectrometer Work Function
Ech= Surface Charge Energy

Ech can be determined by electrically calibrating the

instrument to a spectral feature.

C1s at 285.0 eV
Au4f7/2 at 84.0 eV
 XPS: Spectral Interpretation

 Orbital binding energies can be interpreted based on correlation tables, empirical

trends and theoretical analysis.

 Peaks appear in XPS spectra for distinguishable atomic and molecular orbitals.

 Auger peaks also appear in XPS spectra – they are easily distinguished by comparing
the XPS spectra from two sources (e.g. Mg and Al K lines).

 The Auger peaks remain unchanged w.r.t. kinetic energy, while the XPS peaks shift.
Interpretation of XPS spectra
Example 1 - the XPS spectrum of Pd metal
The diagram below shows a real XPS spectrum obtained from a Pd metal sample using Mg K radiation

XPS spectra are represented either with kinetic energy (Left) or with binding energy (right)
Interpretation of XPS spectra
• These peak assignments are as follows: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 4d10
The valence band (4d,5s) emission occurs at a binding energy of 0 ~ 8 eV (measured with respect to the Fermi
level).
• The emission from the 4p and 4s levels gives weak peaks at 54 eV and 88 eV respectively
• The most intense peak at 335 eV is due to emission from the 3d levels of the Pd atoms, whilst the 3p and 3s
levels give rise to the peaks at 534/561 eV and 673 eV respectively.
• The remaining peak is not an XPS peak at all ! it is an Auger peak arising from x-ray induced Auger emission.
The Concept of Chemical Shift
• Photoelectron core level peaks in elemental samples occur at the same binding, for
example, a gold surface.

• In compounds, where ionic or covalent bonding occurs, the peak position may shift.

• For example, Si in pure Si wafer, the binding energy of Si 2p is 99 eV, in contrast, Si in

SiO2, the binding energy of Si 2p is 102.3 eV

Therefore, XPS is also called ESCA (Electron Spectroscopy for Chemical Analysis). The
term ESCA was coined by Kai Siegbahn, Uppsala University, Sweden during his seminal
studies of this methodology. He was awarded the Nobel Prize in Chemistry for his efforts.
Chemical Shift-Molecular Orbital Calculations
• Charge Q is transferred from A to B, and a chemical bond is formed.

• The average valence electron radius in A+ shrinks and B- expands to maintain charge neutrality.

• To reflect this change, the binding energy of the orbitals must be changed.

• This results in a change in the overall binding energy structure of each atom and is known as
CHEMICAL SHIFT.
XPS peak -chemical shift
Atoms of a higher positive oxidation state exhibit a higher binding energy due to
the extra coulombic interaction between the photo-emitted electron and the ion
core. This ability to discriminate between different oxidation states and chemical
environments is one of the major strengths of the XPS technique
 XPS: Chemical Shifts

 Peaks appear in XPS spectra for

distinguishable atomic and molecular orbitals.

 Effects that cause chemical shifts in XPS

spectra:
– Oxidation states

– Covalent structure

– Neighbouring electron withdrawing groups

– Anything else that can affect ionization/orbital

energies
 XPS: Typical Spectra
 An XPS survey spectrum of stainless steel:

Spectrum image from http://www.mee-inc.com/esca.html

 XPS: Typical Spectra
 An expanded XPS spectrum of the C1s region of PET:

Spectrum image from http://www.mee-inc.com/esca.html

 XPS: Depth Profiling
 Option 1: Sputtering techniques
– Disadvantage – can damage the surface

– Advantage – wide range of depths can be sampled, e.g. 100 A0 normal

 Option 2: Angle-resolved XPS (AR-XPS) electron

– Reducing the photoelectron take-off angle (measured from the

sample surface) reduces the depth from which the XPS
grazing
information is obtained. XPS is more surface sensitive for
grazing take-off angles than for angles close to the surface
normal.
Sample
– The most important application of angle resolved XPS (AR-XPS)
is in the estimation of the thickness of thin films e.g.
contamination, implantation, sputtering-altered and
segregation layers.
For more on AR-XPS, see Briggs and Seah, Practical Surface Analysis, 2nd Ed., Vol. 1. “Auger and X-ray Photoelectron Spectroscopy,” Wiley, 1990, pp. 183-186, 244-250
 Depth Profiling with Angle-Resolved XPS
 AR-XPS data is often acquired by tilting the specimen
 Example: gallium arsenside with a thin oxide layer on its surface:

bulk
electron

Grazing angle surface

(X-ray takeoff angle) (grazing)

Sample

AR-XPS figure from C. R. Brundle, J. F. Watts and J. Wolstenholme, in Ewing’s Analytical Instrumentation Handbook 3 rd Ed., Dekker 2005.
 XPS: Applications
 A modern application of XPS – study the nature of PEG as a surface coating to prevent biofouling
in biosensors
– Biofouling: the tendency of proteins to adsorb to silicon-based surfaces

 XPS can be used, with AFM, to observe the coating of PEG onto silicon surfaces (PEG-silane
coupling) - Increased C 1s C-O signal indicates greater grafting density

S. Sharma, et al., “XPS and AFM analysis of antifouling PEG interfaces for microfabricated silicon biosensors”, Biosensors and Bioelectronics, 20 227–239 (2004).
 XPS: Quantitative Applications

 Quantitative XPS is not as widely used as the qualitative version of the technique.

 Variations in instrument parameters and set-up have traditionally caused problems with
reproducibility

 Using internal standards, XPS can achieve quantitative accuracies of 3-10% in most cases
 AES and XPS: Combined Systems
 Dual Auger/XPS systems are very common, also combined with a basic SEM
– Note - SAM = scanning Auger microprobe

 Auger is seen as complementary to XPS with generally better lateral resolution

 Both are extreme surface sensitive techniques:
– AES better elemental quantitative analysis

– XPS contains more chemical information

 Also, remember that Auger peaks are often seen in XPS spectra (and are hence useful
analytically) – they can be identified by changing source, so that the X-ray peaks
shift (the Auger peaks do not).
 AES: Surface Analysis
AES is very surface sensitive (10-50 Ǻ) and its reliance on an electron beam results in
excellent lateral resolution
• Electron beam does not have to be
monochromatic
Note: an X-ray beam can also be used for AES,
but is less desirable b/c it cannot currently be
focused as tightly (as is the case in XPS)

• Auger electrons typically have energies of

< 1000 eV, so they are only emitted from
surface layers.
AES spectrum

• Initial core hole can be generated by x-rays (Auger peaks in XPS) or

electrons (most common in AES)
• Spectrum contains Auger and inelastically scattered electrons but no
photoemission peaks.
• Auger (electron or x-ray excited) spectra contain closely-spaced groups of
multiple peaks!
 AES: Elemental Surface Analysis

 Very common application of AES - elemental surface analysis

 For true surface analysis, AES is better than SEM/X-ray emission

(electron microprobe) because it is much more surface sensitive

 AES can be easily made quantitative using standards.

Image from http://www.cem.msu.edu/~cem924sg/ (accessed 12-Nov-2004)

 AES: Chemical Shifts

 Chemical information (i.e. on bonding, oxidation

states) should be found in Auger spectra because
the electron energy levels are sensitive to the
chemical environment.

 In practice, it is not (usually) there because too

many electron energy levels are involved – it is
difficult to calculate and simulate Auger spectra.