X-RAY PHOTOELECTRON SPECTROSCOPY (XPS)

• XPS is the most widely used surface analysis technique because of its relative simplicity in
use and data interpretation and also known as Electron Spectroscopy for Chemical Analysis
(ESCA).
• It is based on the photoelectric effect and was developed by Siegbahn from the University of
Uppsala, Sweden in the mid- 1960 in Sweden (Awarded Nobel Prize in Physics 1981)
• Other related techniques are Auger electron spectroscopy (AES) and Ultra violet
photoelectron spectroscopy (UPS).
• It extracts information from top 1 to 10 nm of material.
• XPS detects elements with Z >3 and cannot used to detect H or He as these are too small.
• It can analyze all types of compound including inorganic, alloys, polymers, glasses,
wood, plants, bones, oils, etc.
• XPS instruments typically consist of a monochromatic x-ray source, a photoelectron detector, and an
electron energy analyzer.

Emission processes of characteristic

electrons
• Principle
• XPS spectral lines are identified by the shell from which the electron is ejected such as1s, 2s, 2p, etc.).
• The kinetic energy of ejected photoelectron is

• K.E.=hn- (EB+ j)
• where j is the work function of the sample and EB is the B.E of the electron.
• Instrumentation
• It requires UHV of the order of 10-9-10-11 torr to maintain sample surface clean and
minimize scattering of the photoelectrons.

• Other Parts:
 X-ray source
 Electron energy analyzer
 Ar ion gas
 Neutralizer
 Electronic control system
 A high intensity x-ray beam with a narrow line width is used for the measurements.
Commonly used x-ray sources are Mg Kα (1253.6 eV) and Al Kα (1486.6 eV).
Diameter of the x-ray beam lies in the range of μm to mm.
X-ray penetration depth is ~ 1 μm
• A typical XPS spectrum is a plot of intensity versus binding energy. Photoelectrons are ejected from
different electronic shells and subshells. Each binding energy peak is marked as an element
symbol plus a shell symbol from where the photoelectron was emitted. For example Al 2p, O 1s. . .
XPS peaks are shown in the following figure.
• Chemical shifts can be determined using XPS.
• This is owing to the fact that binding energy doesn’t only depend on the shell of the electron.
• It also depends on the environment, that is, the bonds that the atom in question partake in.
• Therefore, a primary carbon would have a slightly different binding energy than a carboxyl carbon, for
example.

• XPS spectra. Graph showing the binding energies of electrons from different orbitals (F1s, O1s, Si2p,
etc.) and their intensities which tell the atomic composition of the sample based on the amounts of each
electron from different orbitals present.
• Each atom has a unique XPS spectra.

• XPS can determine elemental composition, stoichiometry, electrical/chemical states and

examine surface contamination.

• XPS is an elemental analysis technique that is unique in providing chemical state

information of the detected elements, such as distinguishing between sulfate and sulfide
forms of the element sulfur.
• When an electron with kinetic energy E moves through a solid matrix M, it has a probability of
traveling a certain distance before losing all or part of its energy due to an inelastic collision.

• The average distance traveled before such a collision is known as the inelastic mean free path
λM(E).

• Since the energy ranges used in XPS analysis are typically 50–1200 eV, the values of λ are
very small, corresponding to only a few monolayers.

• Photoelectrons must originate from atomic layers very close to surface to be detected.

• Therefore, the XPS technique is very surface-specific.

How to interpret generated data
• Peaks from the XPS spectra give relative number of electrons with a specific binding
energy.
• The shorter the peak, the less electrons represented.
• For example, if a peak, A, is half the height of another peak B, that means there were half as
many electrons detected with the binding energy at A compared to the number of electrons
detected with the binding energy at B.
• Therefore, the peak intensities give information about the percent composition of a
material.
• As seen in the figure above, the O1s has the largest peak, and it shows that the atomic
composition of oxygen is the greatest.
• NB: The strongest, sharpest, and most symmetric peak is the main XPS peak
• The greater the binding energy, the greater the attraction of that electron to the nucleus. i.e.
peaks from electrons in 1s will have a greater energy than peaks representing electrons
from 2s.
• Electrons in 2s will have greater energy than those in 2p.
• Some instruments have peak identification features, but otherwise, the identification of
peaks/lines on the spectra can be completed by looking at standards of different materials.
Moulder (1992) shows examples of these standards to help interpret the spectra.
• Moulder, John F. et al. Handbook of X-ray photoelectron spectroscopy: a reference book of standard spectra
for identification and interpretation of XPS data.
• Peak position: element and valence
• Peak intensity: content (depends on sensitivity)
• XPS is semi-quantitative; The intensity of the photoelectrons (I, peak area) scales linearly
with the content of the element (n). S – sensitivity factor (empirical value, may need calibration)
• n=I/S =
•  
• NB:

• Peaks of one element can differ in the intensity and S. Selecting peaks with high
intensity and large S improves sensitivity.
• Sensitivity of one element can vary due to its presence in different compounds, e.g.,
mixtures.
Why semi-quantitative?

• Peak area also depends on the mean free path of photoelectrons, cleanness of sample surface, valence,
X-ray intensity, and spectrometer condition. Therefore, XPS can give relative contents but not absolute
values.
• EDS (energy dispersive spectroscopy) & XPS both are techniques for elemental analysis.

Differences between EDS and XPS:

1) XPS uses X-ray, detects electrons; EDS uses electrons, detects X-ray;

2) EDS can only detect composition and content, not valence; detection limit is high (>2
atom%);
3) EDS is usually coupled with electron microscopy;XPS is typicallyused
independently.
• Example:
• A) An XPS electron was found to have a kinetic energy of 1055.3 eV when ejected with an AlKα source
(λ=0.83393nm) and measured in a spectrometer with a work function of 25.1 eV. The electron is
believed to be a N1s electron in NaNO3. NB: 1J= 6.242 x1018 eV. Work out the binding Energy for the
electron.
• Solution: Eb=hν-Ek-ϕ; ν== = 2.382 x10-16 J. Convert J to eV by multiplying with 6.24x1018= 1,486.7 eV.
• Eb=hν-Ek-ϕ= 1,486.7eV- 1,055. eV-25.1 eV=406eV

• b) What would be the kinetic E of the electron if a Mg Kα (λ= 0.989 nm) source were used?
• Hint: Ek=hν-Eb-ϕ;
• Answer: 822.2 eV