Electron Spectroscopy:

Auger Electron Spectroscopy

by Didik Setiyo W.

Introduction
Electron spect. Is a powerful method for Identification of all elements with exception of H and He Determination of elemental oxidation state and type of species bonded to it Learn the electron structure of molecules Most important: determination of surface chemistry of a solid (metal, alloy, semiconductor, heterogeneous catalyst)

Applications
Electron Spectroscopy has been successfully applied to Gas Solid Because of poor Solution penetrating power of Liquid electrons, these method
provide information that is restricted largely to a surface layer that is a few particles thick (20 to 50 )

Principles
Name
X-Ray photoelectron spect. (XPS or ESCA) Ultraviolet Photoelectron Spect. (UPS or PES) Auger Spectroscopy (AES) And others (INS, EIP, PIS)

Method of producing electrons from the analyte

Exposure to monochromatic X-rays Exposure to monochromatic, vacuum-ultraviolet radiation Bombardment with electrons or exposure to X-ray

Principles (..continued )
Ek = h - Eb
UV,h

Ek = h - Ev

Ev Ev Ev
X-rays,h

Eb Eb Eb

XPS or ESCA

UPS

Principles
(.continued )
Ek = Eb - 2Eb
Ev Ev Ev

hf = Eb Eb

eA
Eb Eb Eb

AES (low atomic number)

Vacant orbital

XFS (high A.N.)

The Auger Process

Comparing with other spect. methods

In the electron spectroscopy:
Kinetic energy of emitted electron is recorded Spectrum is a plot of number of electron emitted (power of electron beam) as a function of energy (frequency or wavelength) of electron emitted

AUGER SPECTROSCOPY
by Pierre V. Auger in the 1920s

Auger electron spectroscopy, AES, is a surface analytical technique that utilizes the Auger effect to measure the elemental composition of surfaces The method includes two-step process

Process involves formation of electronically exited ion, A+ * by exposing the analyte to a beam of X-ray or high energy electron Relaxation process The Auger effect is a process where an atom that has been ionized with the emission of a core level electron undergoes a transition in which a second electron, the Auger electron, is emitted.

Formation of Exited Ion with X-rays: A + h A+* + e with electron: A + e-i A+* + e-i + ewhere

e-i is an incident light e-i is an incident light after interacting ewith A electron ejected from one of the inner orbital of A

Relaxation Process
Relaxation process

A+*
or,

A++ + e-A
Auger electron

A+ *

A+ + hf
A fluorescent photon

Corresponding method: X-Ray Fluorescence Spectroscopy

Corresponding method
In line with releasing auger electron, this is a radiation less process Energy given up in relaxation results in the ejection of an electron, e-A with kinetic energy of Ek Ek do not depend on photon energy or electron to form vacant orbital formerly at Eb Ek is the difference between energy released in relaxation process and the energy required to remove a second electron from its orbits (Eb)

Corresponding method
Auger emission are described in term of the type of orbital transitions involved in the production of electron. e.g. KLL, LMM, etc. KLL Auger transition involves an initial
removal of a K electron followed by transition of an L electron to the K orbital with simultaneous ejection of a second L electron with spesific Ek
LMM MNN

Auger transitions
Nomenclature:
Transition label: KLILII
initial vacancy final vacancies The three symbols in the transition label correspond to the three energy levels involved in the transition.

Transition type vs Atomic number

Transition type vs Atomic number

Spectra
Consist of a few characteristics peaks lying in the region of 20 to 1000 eV Ordinate: derivative of a counting rate as a function of the kinetic energy of the electron, d N(E)/d(E)

The derivative:
To enhance small peak To repress the effect of the scattered electron background radiation

Spectra
High secondary electron background

The derivative

Spectra: a typical spectra of 70 % Cu 30 % Ni alloy

(McGuire, 1978)

Ni Cl O C 400 600 1200

Ni
Ni Cu

200

Auger electron energy (eV)

Instrumentation

Electron Spectrometers are made up of components whose functions are completely analogous to those encountered in optical spectroscopic instr. Integral unit from

which discreteSource energy electron Sample holder/container from the sample are directed An analyzer (like a monochromator) through a slit to Detector the electron Signal processor and readout analyzer

Instrumentation (.continued)
Source Electron gun:
Similar in construction to electron source in CRT Produce a beam of 1 to 10 keV Produce a beam of 5 to 10 um (Auger microprobe) that are employed for scanning solid surface in order to detect and determine the elemental composition of inhomogeneities

Instrumentation (.continued)
Sample Compartment Samples are mounted in a fixed position as close to electron source and the entrance slit of the spectrometer as possible
In vacuum (for better)
to avoid attenuation of the electron beam to avoid contamination by substance such as oxygen

Instrumentation (.continued)
Analyzer
Two basic type of analyzer are encountered: 1. Retarding field instrument 2. Dispersion type

Electron from the sample pass through to silidrical grids to an outer collector (also silindrical) Grid: metallic screen (provide 70 % transmission)
An increasing potential difference is applied across the grid to retard electron flowing from resource to the collector

Retarding field instrument ( ..cont.)

At high enough potential diff. electron of energy e2 will be retarded and the collector signal will decrease The collector signal q is amplified, differentiated and displayed on a recorder as the grid potential is scanned.
grid
source e1 e2

E0

E0/E

collector

Dispersion type
In this type of instrument the electron beam is deflected by an electrostatic or magnetic field in such a way that the electron travel in a curved path
The curvature is dependent upon the kinetic energy and the magnitude of the field By varying the field electrons of various kinetic energies can be focused on the detector The media is maintained vacuum

Detector
Mostly, the system are based upon solid-state, channel electron multipliers tube which is doped with lead or vanadium When a potential of several kilovolts is applied across these material, a pulse of 106 to 108 electron is produce for each incident electron The pulse then counted

Readout
CRT Recorder Alphanumeric display unit

Applicability

Qualitative and quantitative information about elemental composition of matter (solid surfaces)complementary system with
X-ray photoelectron spectroscopy

Useful structural information Particular strength:

Its sensitivity for atoms of low atomic number Its minimal matrix effect High spatial resolution Today to provide the kind of structural and oxidation state

Applicability (...cont.)
Qualitative Analysis Typically, Auger spectrum is obtained by bombarding a small area of surface with a beam of electron Advantage: that with low energy Auger electron (20 to 1000 eV) are able to penetrate only a few atomic layer (3 to 20 that is more grater depth below the surface), the spectrum is more likely in reflecting the true surface composition of solid than is an ESCA spectrum

Applicability (...cont.)
Depth profiling surface Depth profiling involves the determination of the elemental composition of a surface as it is being etched away by a beam of argon ions.
Etching rate is related to time, depth profile of elemental composition is obtained Above are of vital information in corrosion chem., catalyst, properties of semiconductor junction

A depth profile obtained on a specimen of Si which was coated in Au and then Ag and then Au again (provided after combining AES with etching ion beam)

Line Scanning Used to characterize surface composition as a function of distance along a straight line of 100 um or more

Problems
1. Describe the mechanism of the production of an a. MNN Auger electron ! b. LMM Auger electron ! 2. Explain the phenomenon of Auger electron ejection ! Differentiate those with generation of a fluorescent photon ! 3. What are the numerous information obtained by applying the method to solid surface? Explain ! 4. With the method, how can we come to conclusion of qualitative information of solid surface? Explain with typical data !

The Process A beam of energetic electrons, 3 to 25 keV, is used

to eject a core level electron from surface atoms To release energy, those atoms may emit Auger electrons from their induced excited state. The energy of the Auger electron, specific to the atom from which it originated, is measured and the quantity of Auger electrons is proportional to the .. concentration of the atoms on the surface Auger electron spectroscopy can measure two dimensional maps of elements on a surface and elemental depth profiles when accompanied by ion sputtering.

Ask the audience to continue the class

Auger transitions
Nomenclature:
Transition label: KLILII
initial vacancy final vacancies The three symbols in the transition label correspond to the three energy levels involved in the transition.
Back

A typical instrument of AES

(by Perkin-Elmer type PHI-651]

Back

Auger spectra
The Auger electrons have discreet energies, depending on the: chemical element transition oxidation state of the atom
Plotting the differential of the raw spectrum, dN(E)/dE, makes peaks more clear

Back

Raw Auger electron energy spectrum. Auger peaks are weak on strong background.
d[E x N(E)]/dE provides most clear structures. Commonly used to present Auger spectra

didie_chem@gmail.com
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