Topic: XPS

Introduction:
• The technique of XPS is also known as Electron spectroscopy for chemical
Analysis(ESCA).
• X-ray photoelectron spectroscopy is the type of electron spectroscopy.
• It is an analytical technique to study the electronic structure and its dynamics in
atoms and molecules.
• XPS was invented by Kai Siegbahn in 1954, received Nobel Prize in 1981.
• In XPS, primary beam is X-ray photons which are irradiated on sample surface, the
secondary beam (electron)obtained is then analysed.
• The secondary beam is made up of electrons. The spectrum of XPS consist of plot of
number of electrons or power of electrons as a function of energy i.e. kinetic energy
or binding energy.
 Principle of XPS:

• Due to the bombardment of X-Ray photon on the sample surface the inner shell (i.e. K and L electron)are
ejected which are further analyzed by the analyzer.
• Let us consider Eb, Eb’ and Eb” are binding energy of lower energy levels of inner core orbitals. While Ev,
Ev’ and Ev” are the energies of the valance shell electrons.
• The monochromatic X-Rays photon (hw) when incident on the sample surface, the inner shell electron
abstract the energy from this X-ray photon and get ejected in terms of electron. Kinetic energy of the
ejected electron is recorded by spectrometer and it is given by

Ek=hw- Eb-@
 Where, Ek=kinetic energy of the ejected electron
hw=energy associated with the incident photon
Eb=binding energy ejected electron
@=work function of the instrument

Instrumentation:

• Its consist of
• source ,
• sample holder
• Analyser
• detector
• Signal processor and read out
 Source:

• The simplest X-ray photon source for XPS is X-ray tube equipped with magnesium or aluminium
metal target. Monochromator crystal can also provide X-Ray beam having bandwidth of 0.3ev.

• Provide much smaller spots on a surface to be examined

Sample holder:

• Sample holder is located in between the source and the entrance slit of the
spectrometer.
• Crystal disperser selects the photon of known energy from the source and incident
on the sample.
• The area inside the sample holder should be evacuated with 10^-5 torr pressure to
avoid contamination of the sample surface.
• The gaseous sample are introduced into sample compartment through a slit, to
provide a pressure of 10^-12 torr. If pressure is higher then attenuation of electron
beam may take place. If pressure is lower, weaker signals may be obtained.
Analyser:

• It is hemispherical in shape with very high electrostatic field is applied on

analyser.
• Pressure maintained inside the analyser is 10^-5 torr.
• When electron enters into the hemispherical analyser it travels in curved path
and radius of curvature depends upon magnitude of field and kinetic energy of
the electron.
Detector:

• The electron channel multiplier tube or transducer are required for XPS.
When single electron pass through the electron multiplier tube it gets
converted into number of electron or pluses of electron(10^6 to 10^8
electrons)
Signal processor and read out:

• The function of signal processor is to amplify the signal and read out
device converts signal into spectrum.
Application of XPS/ESCA

• Identification of active sites.

• Determination of surface contamination on semiconductors.
• Study of oxide layers on metal
• Analysis of dust on the sample
• Determination of oxidation state.
• All the elements of the periodic table can be determined or identified except
hydrogen and helium as they do not emit inner core electron.
Advantages of XPS:

• It is surface sensitive technique.

• Wide range of solid surface sample can be identified.
• Relatively non-destructive.
Disadvantages of XPS:

• It is very expensive.
• Slow and poor resolution power.
• Required high vacuum.