X-Ray Photoelectron

Spectroscopy (XPS)-2
Louis Scudiero

http://www.wsu.edu/~scudiero; 5-2669

Electron Spectroscopy for Chemical

Analysis (ESCA)
 hν
electron
e
The 3 –step model:
1.Optical excitation
2.Transport of electron to the e

surface (diffusion energy loss) Solid Vacuum

3.Escape into the vacuum
2
Diffusion energy
loss
3
1
Escape
Excitation

σ total
Photoemission intensity for a normal incidence I (θ ) ∝
4

At photon energy of 1254 eV (MgKα x-ray line), σΗ = 0.0002 and σC = 1.05

The intensity ratio is IH (90)/ IC (90) = 1.9 x10-4
(Based of the Scofield’s calculations of the cross-sections carried out relativistically
using the single potential Hartree-Slater atomic model)
 Lindau’s calculations of the cross-section for isolated atoms (using the one-
electron central-field frozen-core model and first –order perturbation theory)

σ total
I (θ ) ∝
4
0.0001

0.00001 For a photon energy of 1000 eV, σΗ = 0.00005

and σC = 0.07
The intensity ratio is IH (90)/ IC (90) = 7.1 x10-3
Survey spectrum

Loss peaks
 Six features seen in a typical XPS spectrum

1. Sharp peaks due to photoelectrons created within the first few atomic
layers (elastically scattered).

2. Multiplet splitting (occurs when unfilled shells contain unpaired

electrons).

3. A broad structure due to electrons from deeper in the solid which are
ineslastically scattered (reduced KE) forms the background.

4. Satellites (shake-off and shake-up) are due to a sudden change in

Coulombic potential as the photoejected electron passes through the
valence band.
5. Plasmons which are created by collective excitations of the valence band
• Extrinsic Plasmon: excited as the energetic PE propagates
through the solid after the photoelectric process.

• Intrinsic Plasmon: screening response of the solid to the sudden

creation of the core hole in one of its atom

The two kinds of Plasmon are indistinguishable.

6. Auger peaks produced by x-rays (transitions from L to K shell: O KLL or

C KLL). Photoelectron Auger electron
 Sharp Peak (core level)
F 1s peak

O 1s peak
 Doublet and satellites peaks for Ni and Cr 2p
3
x 10

45

40 Ni 2p Cr 2p
35
CPS

30

Sat Sat
25

20

885 880 875 870 865 860 855 850

Binding Energy (eV)

Washington State University--Pullman, WA

Multiplet splitting occurs when there are unfilled shells containing unpaired
electrons. For instance, transition metals with unfilled p and d orbitals and rare
earths with unfilled f orbitals all show multiplet splitting.
Vacancy created by photoionization (unpaired electron left behind (after ionization))
couples with a unpaired electron in the originally incompletely filled shell and
generates splitting of the orbital (p, d or f orbitals).
Example: Fe2O3 has 5 unpaired electrons in the 3d shell as shown below.
Following photoionization in the 3s shell, there are 2 possible final states.
Schematic of Multiplet Splitting following photoionization in Fe 3+ and XPS spectrum
Satellites arise when a core electron is removed by a photoionization. There
is a sudden change in the effective charge due to the loss of shielding
electrons. (This perturbation induces a transition in which an electron from a
bonding orbital can be transferred to an anti-bonding orbital simultaneously
with core ionization).

Two types of satellite are detected.

Shake-up: The outgoing electron interacts with a valence electron and

excites it (shakes it up) to a higher energy level. As a consequence the
energy core electron is reduced and a satellite structure appears a few eV
below (KE scale) the core level position.

Shake-off: The valence electron is ejected from the ion completely (to the
continuum). Appears as a broadening of the core level peak or contribute
to the inelastic background.
Shake-up satellites: distinct peaks a few eV below the main line.
Shake-off satellites: broad feature at lower energy w.r.t. to main line.

Ψnlm (r , θ ,ψ ) = Ylm (θ ,ψ ) Rn (r )
 Plasmons
This feature is specific to clean surfaces. 3
XPS Sp Si 2s

The photoelectron excites collective

x 10

35
Si 2s
oscillations in the conduction band (free-
electron gas), so called Plasmons. (discrete 30

energy loss). 25

The plasmon (bulk) energy is 20

CPS
4πne2

hω = h ( ) 1/ 2

plasmon
15

plasmon
p
m 10

n: e density, e: charge of e,
m: mass of e electron. 5

195 190 185 180 175 170 165 160 155 150 145
Binding Energy (eV)

Surface plasmon: bulk plasmon / 1.414. Washington State University--Pullman, WA

For Al, Mg, Na etc… the energies are 15.3 eV, 10.6 eV and 5.7 eV, respectively.
 Auger features
Auger electron emission occurs also when x-rays impinge a sample. Auger
electron is initiated by the creation of an ion with an inner shell vacancy.
Auger electrons are emitted 4
survey

x 10
in the relaxation of the excited
80

Cu 2p Peaks
ion. An electron from a higher 70

lying energy level fills the inner 60

shell vacancy with the simultaneous 50

emission of an Auger electron. 40

CPS

30

It is a three-electron process. Cu
2s
Cu Auger Peaks
20
Cu
O Cu 3p
3 Distinct Auger Peaks are 10
1s 3s

seen in the data for Copper 1200 1000 800 600 400 200 0
Binding Energy (eV)
Washington State University--Pullman, WA
Chemical shift arises in the initial state from the displacement of the electronic
charge from the atom towards its ligands, reducing the electrostatic potential at the
atom. There is a final state shift due to the polarization of the ligand by the core on
the central atom.
Core electron BE in molecular systems exhibits chemical shifts which are simply
related to various quantitative measures of covalency. Greater the electronegativity
of the ligands, the greater the BE of the core electron of the ligated atom.

Basic concept: The core electrons feel an alteration in Valence charge

R
the chemical environment when a change in the Q

potential (charge distribution) of the valence shell

occurs.
For example: let’s assume that the core electrons are
inside a hollow spherical charged shell. Each core
electron then sees a potential V. A change in Q by ΔQ
gives a change in V. 1 ΔQ
Core

ΔV =
electrons
where ΔV is the chemical shift 4πε 0 R
 Oxidized surfaces
3
x 10

12

Cr 2p ---data

10

Oxide peak
Oxide peak

8
CPS

Elemental Cr
Elemental Cr

590 580 570

Binding Energy (eV)

Oxidized and clean Cr 2p spectra (left). Oxidized and clean Cu 2p spectra (right).
The oxide layer resulted in extra peaks (shoulder at higher BE—left of the main
line). Satellites are also seen on the Cu 2p spectra.
 Angular Distributions
(C.S. Fadley, J.E.S. and R.P. (1974) 5 p 725-754)

The mean free paths (IMFP) are in the range of 5 -100Å falling within 5 –40 Å for
inorganic materials. To enhance the surface signal we can vary the photon energy—
closer to the attenuation length minimum or decrease the angle of electron emission
relative to a solid surface.

For example: Au 4f IMFP is about 22Å (d) at angle of 90° using AlKα. The depth (d)
probed by XPS becomes about 4-5 Å at angle of 10°.
Chemical Bonding
The curve fitting of the main
hydrocarbon line (CxHy) reveals
chemical shifts corresponding to
• Ether and alcohol groups (C-O at 1.55
eV higher BE),
• Carbonyl groups (C=O at 2.8 eV
higher),
• Ester and acid functional at 4.2 eV
• Carbonate groups at 5.2 eV higher
BE.
Finally, the π- π* satellite at 291.5 eV
appears at the extreme left.
 Spin-orbit and lines intensity
Multiplet splitting occurs when the system has unpaired electrons in the Valence
levels.
Example: Mn 2+ 1s2 2s2 2p6 3s2 3p6 3d5 4s2 (3d5 all unpaired and with // spins)

Also the total electronic angular momentum (j) is a combination of the orbital angular
(l) and spin (s) momenta. The j-j coupling is equal to |L ± S| where L and S are the
total orbital angular and spin momenta, respectively.

For angular quantum number l ≠ 0 the line is a doublet. (p1/2, p3/2).

Splitting: Final states are given by: j + = l + s and j - = l – s

Examples: For p orbitals the doublet will be p 1/2 and p 3/2 because l = 1 and s = ± 1/2
therefore j - = 1/2 and j + =3/2.

For d orbitals, the doublet will be dx1 and d x2 because l = and s = ± 1/2
therefore j - = x1 and j + = x2 .
Intensity ratio is given by (2j - +1) / (2j + +1)
For p orbitals the ratio is given by 2 x 1/2 +1 = 2 (p1/2 ) and 2 x 3/2 +1 = 4
(p3/2). Therefore the ratios for p orbitals doublet is 1/2, for d orbitals
doublet is 4/6 = 2/3

Cr 2p spectrum Au 4f spectrum

Ratio = 1/2 Ratio = ??

 Static Charging
XPS: It arises as a consequence of the build-up of a positive charge at the
surface of non-conducting specimens. The rate of photo-electron loss is
greater than that of their replacement from within the specimen.
It produces a retarding field at the surface that will e-
hν
shift the peaks (reduce the KE of the ejected electrons). ++++

-----
Suggestions:
1) Use of the adventitious Carbon line to correct any shift (most materials
exhibit a C 1s line).

2) Deposition of a very thin layer of gold (as use in SEM).

3) Use of a “flood gun” low energy electrons (0-5 eV).

 Static Charging (cont.)
Auger: Sample charging is a function of the total electron yield, f (Σ). Σ is
the sum of secondary electron and backscattering coefficient.
Σ > 1 samples charge positively. Auger (and XPS) peaks shift to lower KE
(higher BE).

Σ < 1 samples charge negatively. Auger (and XPS) peaks shift to higher KE
(lower BE).

Case 1, the emitted electrons have a reduced KE by a few tens of eV

Identification remains possible

Case 2, the KE of the emitted electrons increases due to the repulsive forces
between the charged surface and emitted electrons.
Analysis is often impossible.
 Linewidths (Γ)
The irreducible width Γ in XPS is due to the lifetime of the core hole state

2h
Γ= (Ag 3d core level τ = 10-14 -10-15 s)
τ
The resulting line shape is Lorenzian. A core level has a number of decay
channels that contribute to the width of the line.
Measurement of the lifetime width of a core hole state is complicated by the
existence of:
1. Resolution of the instrument: dual anode long tail due to the lifetime
width of the K-shell hole.
2. Phonon broadening (excitation of the lattice vibrations)
3. Inhomogeneous broadening (superposition of lines with different
chemical shifts).
 Peak Deconvolution (curve fitting)

Photoelectron lines have a Lorenzian shape corresponding to the lifetime of the core
hole that is created. Gaussian or Gaussian Lorentzian shape GL(30) curves are often
used for curve fitting purposes.
Deconvolution of the XPS Mo samples reveals the existence of several Mo species
(Mo0, Mo4+, Mo6+ but others could also be detected: Mo3+ and Mo5+).
 Peak Widths and Intensities
Peak widths: it is a convolution of the natural width of the core level, the width of
the x-ray line and the analyzer resolution:

ΔE = ( ΔE + ΔE + ΔE )
2 2 2 1/ 2

n p a

Intensities: Only the ratio of area of lines has some meaning (relative concentration).

[ A] = σ bζ bλbηb I a
[B ] σ aζ a λaηa I b

σ: cross-section; ζ: fraction of PE events (w/o intrinsic plasmon excitation); λ:

mean free path; η: KE dependent spectrometer transmission and I : area of the line
 Quantitative Analysis
1. Use of standards:
Ix is the amplitude of the element X in your sample,
Ix,std is the amplitude of the element X in pure material

The concentration of X in your sample is THEN given by Cx = Ix / Ix,std

PROBLEM with this approach is that you need a large No of Standards.

2. Modify Method:
It introduces the relative sensitivity factor, Sx based upon one pure element
standard (usually Ag, silver standard). So, if we want to calculate Sx :
sensitivity for element X from a compound XaYb we could do it by using:
( A + B) I x
Sx =
A I Ag ( pure )
 Quantitative Analysis (cont.)
( A + B) I x
Sx =
A I Ag ( pure )

Where Ix is the amplitude of the known compound, (A+B)/A is the 1 /

fraction of X atoms and Ix / IAg the ratio of peak to peak amplitudes.
THEN from an unknown sample: Cx = Ix / IAg . Sx = concentration

OR to make it self consistent Cx = (Ix/ Sx ) /∑a (Ia / Sa)

where Ix and Ia are measured and Sx and Sa are obtained from standards
as mentioned above
 XPSPeak41 (free software)

Deconvolution of Si 2p spectrum