1. X-Ray Photoelectron Spectroscopy (XPS)
David Echevarría Torres
University of Texas at El Paso
College of Science
Chemistry Department

2. Outline XPS Background XPS Instrument How Does XPS Technology Work?
Auger Electron
Cylindrical Mirror Analyzer (CMA)
Equation
KE versus BE
Spectrum Background
Identification of XPS Peaks
X-rays vs. e- Beam
XPS Technology

3. XPS Background
XPS technique is based on Einstein’s idea about the photoelectric effect, developed around 1905
The concept of photons was used to describe the ejection of electrons from a surface when photons were impinged upon it
During the mid 1960’s Dr. Siegbahn and his research group developed the XPS technique.
In 1981, Dr. Siegbahn was awarded the Nobel Prize in Physics for the development of the XPS technique

4. X-Rays
Irradiate the sample surface, hitting the core electrons (e-) of the atoms.
The X-Rays penetrate the sample to a depth on the order of a micrometer.
Useful e- signal is obtained only from a depth of around 10 to 100 Å on the surface.
The X-Ray source produces photons with certain energies:
MgK photon with an energy of eV
AlK photon with an energy of eV
Normally, the sample will be radiated with photons of a single energy (MgK or AlK). This is known as a monoenergetic X-Ray beam.

5. Why the Core Electrons?
An electron near the Fermi level is far from the nucleus, moving in different directions all over the place, and will not carry information about any single atom.
Fermi level is the highest energy level occupied by an electron in a neutral solid at absolute 0 temperature.
Electron binding energy (BE) is calculated with respect to the Fermi level.
The core e-s are local close to the nucleus and have binding energies characteristic of their particular element.
The core e-s have a higher probability of matching the energies of AlK and MgK.
Core e-
Valence e-
Atom

6. Binding Energy (BE)
The Binding Energy (BE) is characteristic of the core electrons for each element. The BE is determined by the attraction of the electrons to the nucleus. If an electron with energy x is pulled away from the nucleus, the attraction between the electron and the nucleus decreases and the BE decreases. Eventually, there will be a point when the electron will be free of the nucleus.
This is the point with 0 energy of attraction between the electron and the nucleus. At this point the electron is free from the atom. x p+
B.E.
These electrons are attracted to the proton with certain binding energy x

7. Energy Levels Vacumm Level Fermi Level Lowest state of energy BE
Ø, which is the work function
At absolute 0 Kelvin the electrons fill from the lowest energy states up. When the electrons occupy up to this level the neutral solid is in its “ground state.”

8. XPS Instrument
XPS is also known as ESCA (Electron Spectroscopy for Chemical Analysis).
The technique is widely used because it is very simple to use and the data is easily analyzed.
XPS works by irradiating atoms of a surface of any solid material with X-Ray photons, causing the ejection of electrons.
University of Texas at El Paso, Physics Department
Front view of the Phi 560 XPS/AES/SIMS UHV System

9. University of Texas at El Paso, Physics Department
XPS Instrument
The XPS is controlled by using a computer system.
The computer system will control the X-Ray type and prepare the instrument for analysis.
University of Texas at El Paso, Physics Department
Front view of the Phi 560 XPS/AES/SIMS UHV System and the computer system that controls the XPS.

10. XPS Instrument
The instrument uses different pump systems to reach the goal of an Ultra High Vacuum (UHV) environment.
The Ultra High Vacuum environment will prevent contamination of the surface and aid an accurate analysis of the sample.
University of Texas at El Paso, Physics Department
Side view of the Phi 560 XPS/AES/SIMS UHV System

11. XPS Instrument X-Ray Source Ion Source SIMS Analyzer
Sample introduction
Chamber

12. Sample Introduction Chamber
The sample will be introduced through a chamber that is in contact with the outside environment
It will be closed and pumped to low vacuum.
After the first chamber is at low vacuum the sample will be introduced into the second chamber in which a UHV environment exists.
First Chamber
Second Chamber UHV

13. Diagram of the Side View of XPS System
X-Ray source
Ion source
Axial Electron Gun
Detector
CMA
sample
SIMS Analyzer
Sample introduction Chamber
Sample Holder
Ion Pump
Roughing Pump
Slits

14. How Does XPS Technology Work?
A monoenergetic x-ray beam emits photoelectrons from the from the surface of the sample.
The X-Rays either of two energies:
Al Ka (1486.6eV)
Mg Ka ( eV)
The x-ray photons The penetration about a micrometer of the sample
The XPS spectrum contains information only about the top Ǻ of the sample.
Ultrahigh vacuum environment to eliminate excessive surface contamination.
Cylindrical Mirror Analyzer (CMA) measures the KE of emitted e-s.
The spectrum plotted by the computer from the analyzer signal.
The binding energies can be determined from the peak positions and the elements present in the sample identified.

15. Why Does XPS Need UHV? Contamination of surface
XPS is a surface sensitive technique.
Contaminates will produce an XPS signal and lead to incorrect analysis of the surface of composition.
The pressure of the vacuum system is < 10-9 Torr
Removing contamination
To remove the contamination the sample surface is bombarded with argon ions (Ar+ = 3KeV).
heat and oxygen can be used to remove hydrocarbons
The XPS technique could cause damage to the surface, but it is negligible.

16. The Atom and the X-Ray X-Ray Free electron Valence electrons proton
neutron
electron
electron vacancy
Core electrons
The core electrons respond very well to the X-Ray energy

17. X-Rays on the Surface Atoms layers e- top layer e- lower layer
with collisions
but no collisions
X-Rays
Outer surface
Inner surface

18. X-Rays on the Surface
The X-Rays will penetrate to the core e- of the atoms in the sample.
Some e-s are going to be released without any problem giving the Kinetic Energies (KE) characteristic of their elements.
Other e-s will come from inner layers and collide with other e-s of upper layers
These e- will be lower in lower energy.
They will contribute to the noise signal of the spectrum.

19. X-Rays and the Electrons
Electron without collision
X-Ray
Electron with collision
The noise signal comes from the electrons that collide with other electrons of different layers. The collisions cause a decrease in energy of the electron and it no longer will contribute to the characteristic energy of the element.

20. What e-s can the Cylindrical Mirror Analyzer Detect?
The CMA not only can detect electrons from the irradiation of X-Rays, it can also detect electrons from irradiation by the e- gun.
The e- gun it is located inside the CMA while the X-Ray source is located on top of the instrument.
The only electrons normally used in a spectrum from irradiation by the e- gun are known as Auger e-s. Auger electrons are also produced by X-ray irradiation.

21. X-Rays and Auger Electrons
When the core electron leaves a vacancy an electron of higher energy will move down to occupy the vacancy while releasing energy by:
photons
Auger electrons
Each Auger electron carries a characteristic energy that can be measured.

22. Two Ways to Produce Auger Electrons
The X-Ray source can irradiate and remove the e- from the core level causing the e- to leave the atom
A higher level e- will occupy the vacancy.
The energy released is given to a third higher level e-.
This is the Auger electron that leaves the atom.
The axial e- gun can irradiate and remove the core e- by collision. Once the core vacancy is created, the Auger electron process occurs the same way.

23. Auger Electron 2 3 4 1 Free e- e- released to analyze e- Vacancy
e- of high energy that will occupy the vacancy of the core level
Free e- 3
e- released to analyze 4 1
e- gun
e- Vacancy
1, 2, 3 and 4 are the order of steps in which the e-s will move in the atom when hit by the e- gun.

24. Auger Electron Spectroscopy (AES)
e- released from
the top layer
Outer surface
Inner surface
Electron beam
from the e- gun
Atom layers

25. Cylindrical Mirror Analyzer (CMA)
The electrons ejected will pass through a device called a CMA.
The CMA has two concentric metal cylinders at different voltages.
One of the metal cylinders will have a positive voltage and the other will have a 0 voltage. This will create an electric field between the two cylinders.
The voltages on the CMA for XPS and Auger e-s are different.

26. Cylindrical Mirror Analyzer (CMA)
When the e-s pass through the metal cylinders, they will collide with one of the cylinders or they will just pass through.
If the e-’s velocity is too high it will collide with the outer cylinder
If is going too slow then will collide with the inner cylinder.
Only the e- with the right velocity will go through the cylinders to reach the detector.
With a change in cylinder voltage the acceptable kinetic energy will change and then you can count how many e-s have that KE to reach the detector.

27. Cylindrical Mirror Analyzer (CMA)
0 V +V
X-Rays
Source
Sample
Holder
Electron Pathway through the CMA
Slit
Detector

28. Equation
KE=hv-BE-Ø
KE Kinetic Energy (measure in the XPS spectrometer)
hv photon energy from the X-Ray source (controlled)
Ø spectrometer work function. It is a few eV, it gets more complicated because the materials in the instrument will affect it. Found by calibration.
BE is the unknown variable

29. Equation
KE=hv-BE-Ø
The equation will calculate the energy needed to get an e- out from the surface of the solid.
Knowing KE, hv and Ø the BE can be calculated.

30. KE versus BE KE can be plotted depending on BE
Each peak represents the amount of e-s at a certain energy that is characteristic of some element.
Binding energy
# of electrons
(eV)
BE increase from right to left
1000 eV
0 eV E
KE increase from left to right

31. Interpreting XPS Spectrum: Background
The X-Ray will hit the e-s in the bulk (inner e- layers) of the sample
e- will collide with other e- from top layers, decreasing its energy to contribute to the noise, at lower kinetic energy than the peak .
The background noise increases with BE because the SUM of all noise is taken from the beginning of the analysis.
Binding energy
# of electrons N1 N2 N3 N4
Ntot= N1 + N2 + N3 + N4
N = noise

32. XPS Spectrum The XPS peaks are sharp.
In a XPS graph it is possible to see Auger electron peaks.
The Auger peaks are usually wider peaks in a XPS spectrum.
Aluminum foil is used as an example on the next slide.

33. XPS Spectrum O 1s O Auger O because of Mg source C O 2s Al Al
Sample and graphic provided by William Durrer, Ph.D.
Department of Physics at the Univertsity of Texas at El Paso

34. Auger Spectrum Characteristic of Auger graphs
The graph goes up as KE increases.
Sample and graphic provided by William Durrer, Ph.D.
Department of Physics at the Univertsity of Texas at El Paso

35. Identification of XPS Peaks
The plot has characteristic peaks for each element found in the surface of the sample.
There are tables with the KE and BE already assigned to each element.
After the spectrum is plotted you can look for the designated value of the peak energy from the graph and find the element present on the surface.

36. X-rays vs. e- Beam X-Rays Electron Beam
Hit all sample area simultaneously permitting data acquisition that will give an idea of the average composition of the whole surface.
Electron Beam
It can be focused on a particular area of the sample to determine the composition of selected areas of the sample surface.

37. XPS Technology Consider as non-destructive
because it produces soft x-rays to induce photoelectron emission from the sample surface
Provide information about surface layers or thin film structures
Applications in the industry:
Polymer surface
Catalyst
Corrosion
Adhesion
Semiconductors
Dielectric materials
Electronics packaging
Magnetic media
Thin film coatings

38. References
Dr.William Durrer for explanations on XPS technique, Department of Physics at UTEP.
XPS instrument from the Physics Department.

39. Acknowledgements Elizabeth Gardner, Ph.D.
from the Department of Chemistry at the University of Texas at El Paso
William Durrer, Ph.D.
from the Department of Physics at the University of Texas at El Paso
Roberto De La Torre Roche
Lynn Marie Santiago