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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
XPS Background
XPS technique is based on Einsteins 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 1960s 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
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 on the surface.
The X-Ray source produces photons with certain energies: MgK photon with an energy of 1253.6 eV AlK photon with an energy of 1486.6 eV Normally, the sample will be radiated with photons of a single energy (MgK or AlK). This is known as a monoenergetic XRay beam.
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.
Valence eCore eAtom
B.E.
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+ These electrons are attracted to the proton with certain binding energy x
Energy Levels
Vacumm Level
Fermi Level BE
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.
XPS Instrument
University of Texas at El Paso, Physics Department Front view of the Phi 560 XPS/AES/SIMS UHV System
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.
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
XPS Instrument
X-Ray Source
Ion Source
SIMS Analyzer
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
A monoenergetic x-ray beam emits photoelectrons from the from the surface of the sample.
The X-Rays either of two energies:
The x-ray photons The penetration about a micrometer of the sample The XPS spectrum contains information only about the top 10 - 100 of the sample.
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.
Atoms layers
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.
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.
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.
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.
Auger Electron
Free e- released to analyze e-
e- of high energy that will occupy the vacancy of the core level
4
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.
Atom layers
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.
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.
Slit
0V
0V
+V +V Sample Holder
+V +V
0V
0V
Detector
Equation
KE=hv-BE-
KE
hv
BE
Equation
KE=hv-BE-
The equation will calculate the energy needed to get an e- out from the surface of the solid. Knowing KE, hv and the BE can be calculated.
KE versus BE
KE can be plotted depending on BE
# of electrons
Each peak represents the amount of e-s at a certain energy that is characteristic of some element.
BE increase from right to left
1000 eV
E E E
0 eV
The X-Ray will hit the e-s in the bulk (inner elayers) of the sample e- will collide with other efrom 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.
# of electrons
N = noise
N4 N3 N2 N1
Binding energy
Ntot= N1 + N2 + N3 + N4
XPS Spectrum
O 1s O Auger
XPS Spectrum
O because of Mg source C Al O 2s
Al
Sample and graphic provided by William Durrer, Ph.D. Department of Physics at the Univertsity of Texas at El Paso
Auger Spectrum
Sample and graphic provided by William Durrer, Ph.D. Department of Physics at the Univertsity of Texas at El Paso
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.
X-Rays
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.
XPS Technology
Consider as nondestructive
because it produces soft x-rays to induce photoelectron emission from the sample surface
Polymer surface Catalyst Corrosion Adhesion Semiconductors Dielectric materials Electronics packaging Magnetic media Thin film coatings
References
Dr.William Durrer for explanations on XPS technique, Department of Physics at UTEP. www.uksaf.com www.casaxps.com www.nwsl.net XPS instrument from the Physics Department.
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