X-ray Photoelectron Spectroscopy XPS, ESCA

Photon inn electron out

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X-ray Photoelectron Spectroscopy

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XPS and AES are surface sensitive techniques

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Surface Sensitivity

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Surface sensitivity

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Photo emission process is often envisaged as three steps

Absorption and ionisation - (initial state effect) Response from atom and creation of photoelectron -(final state effect) Transport of electron to surface and escape - (extrinsic loss)
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XPS ESCA

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Introduction X-ray Photoelectron Spectroscopy (XPS)

X-ray photoelectron spectroscopy works by irradiating a sample material with mono energetic soft x-rays causing electrons to be ejected. Identification of the elements in the sample can be made directly from the kinetic energies of these ejected photoelectrons. The relative concentrations of elements can be determined from the photoelectron intensities.
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XPS - ESCA
Surface sensitive analysis technique based on photoelectric effect. Depth of analysis ~4-40 nm. All elements except Hydrogen. Wide range of materials: Polymers, Ceramics, metals . (vacuum compatible) Applications: corrosion, catalysis, thin films, surface coatings, segregation Gives information on chemical composition and chemical state.
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History
1887 Heinrich Hertz /1888 Wilhelm Hallwaches
illuminating metal surfaces resulted in electronic emission

1900 Max Planck -black body radiation 1905 Einstein - light is quantized

E=h 1950 Kai Siegbahn 1981 : Nobel Prize

studied photoejection of electrons with x-rays

1950: Instrumentation 1960: Chemical Applications

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Absorbing X-rays emitting Photoelectrons

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A closer look

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Relaxation - Auger

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XPS Peaks

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Basic equations:
The relationship governing the interaction of a photon with a core level is:
KE= h - BE KE = kinetic energy of ejected photoelectron h = characteristic energy of X-ray photon BE = binding energy of the atomic orbital from which the electron originates. = spectrometer work function

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XPS example: Gold

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Electronic structure and spectroscopy

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Binding energies?

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Spin-Orbit Coupling
Cu 2p 2p3/2

2p1/2

Orbital=p l=1 s=+/-1/2 ls=1/2,3/2

19.8 : 2 925

Peak Area 965

955 945 935 Binding Energy (eV)

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XPS spectra of Palladium

BE= h - KE
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WHAT IS THIS?
Survey scan : Most elements have major photoelectron peaks below 1100 eV, so a range from 1100 - 0 eV is usually sufficient. Al anode Mg anode ?

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Energy resolution ~1 eV

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Chemical shift binding energies in C 1s peak

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Chemical shift
Functional Group hydrocarbon amine alcohol, ether Cl bound to C F bound to C carbonyl C-H, C-C C-N C-O-H, C-O-C C-Cl C-F C=O Binding Energy (eV) 285.0 286.0 286.5 286.5 287.8 288.0

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Chemical shift

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Inelastic Background

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Plasmon loss

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Instrumentation
Surface analysis by XPS requires irradiating a solid in an Ultra-high Vacuum (UHV) chamber with monoenergetic soft X-rays and analysing the energies of the emitted electrons.

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XPS instrument at UIO?

Kratos Axis Ultra new in 2007

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Instrument
1. 2. 3. 4. 5. Chambers Vacuum and Pumps Sources Monochromator Analysers

Specimen handling Planning experiments

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Dual anode X-ray source

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Alternative X-ray sources

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Monochromator
N=2dsin For Al K =8.3
_

1010 planes in quartz: d= 4.25

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Monochromated X-rays

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Flooded or focused X-ray beam

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CHA with standard input lens

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Pass Energy and Resolution

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Pass Energy

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Ion Etching

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Survey scan : Most elements have major photoelectron peaks below 1100 eV, so a range from 1100 - 0 eV is usually sufficient. Al anode Mg anode ?

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Detail Scans
For purposes of chemical state identification, for quantitative analysis of minor components and peak deconvolution or other mathematical manipulation of data.

Scan should be wide enough to encompass the background on both sides of the region of interest - yet with small enough step size - within a reasonable time. Radiation-sensitive peaks should be run first. Sufficient Signal / noise . Pass Energy ? E same for all scans !

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Oxidation of Titanium
Oxidation of Ti: Titanium has a big shift. Ti-metal (Tio) to TiO2 (Ti4+). Ti 2p-scan of Ti-metal and TiO2 Binding energies: metal:Ti 2p3/2=451.4 Ti 2p1/2=457.57 oxide:Ti 2p3/2=458.8 Ti 2p1/2=464.34 1.Not the same shift for the two spin doublets. 2. Metals have more asymmetric peaks than insulators/oxides. 3. Weak peak at 450.7eV - ghost (X-ray with higher energy = K)
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Density of state DOS

DOS Ti-metal

Degree of asymmetry proportional to DOS at EF

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Depth information from XPS

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Depth information from Ag-anode

Greater analysis depth The Al 2p spectra shown (Figure 3) were acquired with (a) Al and (b) Ag sources. Spectrum (b) is a clear illustration of the greater analysis depth of the Ag source as the element : oxide ratio is greater than that acquired with the Al source. An oxide thickness of 1.8nm indicated here was confirmed by independent angle resolved measurements.

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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 calibrating the instrument to a spectral feature. C1s at 285.0 eV Au4f7/2 at 84.0 eV
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Binding Energy Referencing

When analysing insulating samples more care is required because of sample charging and the uncertainty in the location of the Fermi Level within the band gap. The term Binding energy is often used without specifying the reference level.

Take care when evaluating spectra !

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Charge neutralization for insulating samples

Low-energy electrons from a cold cathode flood gun alleviates positive charging
Low-energy source of positive ions alleviates the surrounding negative charge
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Auger parameter
The Auger parameter is defined as:
A.P. = K.E(Auger) - K.E.(photoelectron) + Photon Excitation Energy = K.E.(Auger) + B.E.(photoemission)

Where K.E.(Auger) and B.E.(photoemission) are normally measured for the most intense photoemission and sharpest Auger lines available.
Its advantage as a probe of charges in screening energy is that (unlike photoemission or Auger line measurements taken separately) it is independent of energy referencing problems whilst still being measurable to a high precision. Hence small shifts in its value can be measured and interpreted.

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http://www.uksaf.org/data/table.html

Specimen preparation and handling

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Analysis of Multi-Layer Paint Cross Section

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Analysis of Materials for Solar Energy Collection by XPS Depth ProfilingThe amorphous-SiC/SnO2 Interface
Photo-voltaic Collector The profile indicates a reduction of the SnO2 occurred at the interface during deposition. Such a reduction would effect the collectors efficiency.

SnO2

Sn
Solar Energy

Conductive Oxide- SnO2 p-type a-SiC a-Si 500 496 492 488 484 480

Depth Binding Energy, eV Data courtesy A. Nurrudin and J. Abelson, University of Illinois

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Probing Glass Coatings

Windows are coated with complex Multi-layer thin films to meet demands: 1) Energy conservation 2) Appearance 3) Durability
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XPS 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)

Pb Pb

N Ca Na Cl

Pb

500
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400

300

200

100

XPS analysis showed that the pigment used on the mummy wrapping was Pb3O4 rather than Fe2O3

Binding Energy (eV)

Databases

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