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Handbook of

X-ray Photoelectron

Spectroscopy

A Reference Book of Standard Spectra

for Identification and Interpretation of XPS Data

by

John F. Moulder

William F. Stickle

Peter E. Sobol

Kenneth D. Bomben

Edited by

Jill Chastain

Roger C. King, Jr.

Published by

ULVAC-PHI, Inc.

370 Enzo, Chigasaki 253-8522 Japan

Physical Electronics USA, Inc.

18725 Lake Drive East, Chanhassen,

Minnesota 55317, United States ofAmerica

Preface

X-ray Photoelectron Spectroscopy (XPS), also known as Electron Spectroscopy for Chemical Analysis (ESCA), is wide
ly used to investigate the chemical composition of surfaces. The use of XPS in analytical laboratories throughout the
Copyright 1992, 1995 world attests to the problem-solving capability of this technique. The ability to explore the first few atomic layers and
by assign chemical states to the detected atoms has shown XPS to be a powerful addition to any analytical laboratory.

A great deal of information has been published on the principles of the technique and the diverse range of applications
Physical Electronics, Inc. for which it is used. Volumes of XPS spectra exist in the scientific literature, and international committees are estab
lishing databases with reference spectra that will be made available to the general public. It is not the authors' intent to
All rights reserved. exclude these spectra or to ignore these databases. Rather the intent is to assemble a concise volume of standard spectra
to aid in the identification of XPS
No part of the contents of this book
The previous version of this handbook, published in 1978, contained data acquired with a cylindrical mirror analyzer
may be reproduced or transmitted (CMA). Since that time, our XPS hardware has evolved. We currently use a spherical capacitance analyzer (SCA) in
in any form or by any means conjunction with improved detector technology and the choice of either a high-perfonnance Al x-ray monochromator or
1e prior written permission of the publishers. an achromatic Mg/AI dual anode x-ray source. A 1992 version of this handbook was updated from the previous hand
book with data acquired using our current SCA, which has a transmission function different from that of a CMA, and
both monochromatic and achromatic x-ray sources. In addition, data are included from several elements not contained in
the 1978 version of the handbook. The current 1995 version of the handbook is a reprint of the 1992 version which
includes a few minor modifications. This handbook is meant to serve as a guide and reference work for the identifica
Printed in Japan tion, quantification, calibration and interpretation of XPS spectra for users of Physical Electronics XPS systems equipped
with SCAs and Omni FOCUS lenses. It is the authors' hope that this handbook will playa useful role in the practice of
XPS.

Physical Electronics, Inc.


October 1995
Handbook of X-ray Photoelectron Spectroscopy A. Introduction

A. Introduction
X-ray Photoelectron Spectroscopy (XPS) was developed in the electrons by energy. The spectrum is obtained as a plot of the
mid-1960s by Kai Siegbahn and his research group at the number of detected electrons per energy interval versus their
University of Uppsala, Sweden. The technique was first known kinetic energy. Each element has a unique spectrum. The
by the acronym ESC A (Electron Spectroscopy for Chemical spectrum from a mixture of elements is approximately the
Analysis). The advent of commercial manufacturing of surface sum of the peaks of the individual constituents. Because the
analysis equipment in the early 1970s enabled the placement mean free path of electrons in solids is very small, the
of equipment in laboratories throughout the world. In 1981, detected electrons originate from only the top few atomic
Siegbahn was awarded the Nobel Prize for Physics for his layers, making XPS a unique surface-sensitive technique for
work with XPS. chemical analysis. Quantitative data can be obtained from
peak heights or peak areas, and identification of chemical
This handbook is meant to furnish the user with much of the states often can be made from exact measurement of peak
information necessary to use XPS for diverse types of surface positions and separations, as well as from certain spectral fea
analysis. Information is provided on methods of sample tures.
preparation, data gathering, elemental identification, chemical
state identification, quantitative calculation and elemental dis Included in this handbook are survey spectra, strong line
tribution. spectra and x-ray excited Auger spectra for most of the ele
ments and some of their compounds, in addition to plots and
Surface analysis by XPS involves irradiating a solid in vacuo tables of energy shift data which aid in the identification of
with monoenergetic soft x-rays and analyzing the emitted chemical states.

<D PHYSICAL ELECTRONICS 9


B. Principles of the Technique Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy

B. Principles of the Technique 2p312


o, Fermi Level
Surface analysis by XPS is accomplished by irradiating a 6p
6s
sample with monoenergetic soft x-rays and analyzing the energy
5ds12
of the detected electrons. Mg Ka. (1253.6 eV), Al Ka. (1486.6
eV), or monochromatic Al Ka. (1486.7 eV) x-rays are usually
used. These photons have limited penetrating power in a solid 200 5P312

on the order of 1-10 micrometers. They interact with atoms in I- 5Pll2


the surface region, causing electrons to be emitted by the
photoelectric effect. The emitted electrons have measured I- 55
t--~~~-:::=:t

kinetic energies given by: ~ ~


105
~ ~
Binding Energy (eV)
KE hv - BE $5 (1)
Figure 2. High-resolution spectrum of single-crystal Si showin~
splitting of the 2p level.
where hv is the energy of the photon, BE is the binding energy
of the atomic orbital from which the electron originates, and $s :> 600f
is the spectrometer work function. ~ chemical potential and polarizability of compou
'"e."<> chemical shifts can be used to identify the chemical
The binding energy may be regarded as the energy difference ~1>0'" materials being analyzed.
between the initial and final states after the photoelectron has :a'" 4ds12

left the atom. Because there is a variety of possible final states iE


'" In addition to photoelectrons emitted in the p
of the ions from each type of atom, there is a corresponding process, Auger electrons may be emitted because 0
variety of kinetic energies of the emitted electrons. Moreover, of the excited ions remaining after photoemission.
there is a different probability or cross-section for each final electron emission occurs roughly 10- 14 seconds
state. Relative binding energies and ionization cross-sections for photoelectric event. The competing emission of a flu
an atom are shown schematically in Figure 1. The Fermi level l000f ray photon is a minor process in this energy rai'tge. II
corresponds to zero binding energy (by definition), and the 4P312 process (Figure 3), an outer electron falls into the iJ
depth beneath the Fermi level in the figure indicates the relative vacancy, and a second electron is simultaneously em
energy of the ion remaining after electron emission, or the bind jng off the excess energy. The Auger electron posse
ing energy of the electron. The line lengths indicate the relative energy equal to the difference between the energy 0
1200f
probabilities of the various ionization processes. The p, d and f ion and the doubly charged final ion, and is indepen
levels become split upon ionization, leading to vacancies in the I-- 4pII2
mode of the initial ionization. Thus, photoionizatio
PllZ, P312, d312 , d 512 , and f7/2. The spin-orbit splitting ratio is 1:2 leads to two emitted electrons - a photoelectron an,
for p levels, 2:3 for d levels and 3:4 for f levels. As an example, electron. The sum of the kinetic energies of thl
the spin-orbit splitting of the Si 2p is shown in Figure 2. 1400 ' emitted cannot exceed the energy of the ionizing pho!

Because each element has a unique set of binding energies, XPS Probabilities of electron interaction with matter far eJ
Figure 1. Relative binding energies and ionization cross-sections for U. The
can be used to identify and determine the concentration of the binding energy is proportional to the distance below the line indicating the
of the photons, so while the path length of the photo
elements in the surface. Variations in the elemental binding Fenni level. and the ionization cross-section is proportional to the length of order of micrometers, that of the electrons is of the OJ
energies (the chemical shifts) arise from differences in the the line. of angstroms. Thus, while ionization occurs to a dep

10
<D PHYSICAL ELECTRDNICS
<D PHYSICAL ELECTRDNICS
-
Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy B. Principles of the Technique

2p312
Si 2p
..................
... ... ... ......
~
L2,30r 2p

:hnique ____
em e
t 6p fiemli Level Ll or 2s
Or'~~-------------------------------------------------
adiating a
the energy
68

i:===- 5ds12

Photon e
Photoelectron

~a (1486.6 5d312 ~
~,.~.
lfe
/ / .... /,./""/"

in a solid
h atoms in
200F- 5P312

5Pl12 ----0
~. e Kor Is
ed by the
I- 5s
measured 105 95
4f712
Binding (eV)
Auger electron e
Figure 2. High-resolution spectrum of single-crystal Si showing the spin-orbit
l) splitting of the 2p level.
//
//
ling energy OmO-emue L2.30r 2p
ates, and :; chemical potential and polarizability of compounds. These
6001 I
~ chemical shifts can be used to identify the chemical state of the
'"e!'<> materials being analyzed. ... I1'... Llor2s
c ... "
r difference i:.J:.l

.S
Oil
4d512
~lectron has -g In addition to photoelectrons emitted in the photoelectric
a'\
final states process, Auger electrons may be emitted because of relaxation
Irresponding
. Moreover,
r each final
of the excited ions remaining after photoemission. This Auger
electron emission occurs roughly 10 14 seconds after the
photoelectric event. The competing emission of a fluorescent x
J
e---e Kor Is
-sections for ray photon is a minor process in this energy rai.'ge. In the Auger
Fermi level 10001 process (Figure 3), an outer electron falls into the 3. The XPS emission process (top) for a model atom. An incoming
1 - - - - - 4P3i2 photon causes the ejection of the photoelectron. The relaxation process (bot
In), and the vacancy, and a second electron is simultaneously emitted, carry a model atom resulting in the emission of a electron. The
; the relative ing off the excess energy. The Auger electron possesses kinetic simultaneous two-electron cou/ombic rearrangement results in a final state
or the energy equal to the difference between the energy of the initial with two electron vacancies.
~ the relative ion and the doubly charged final ion, and is independent of the
12001
le p, d and f mode of the initial ionization. Thus, photoionization normally
ancies in the 4p1f2 leads to two emitted electrons - a photoelectron and an Auger micrometers, only those electrons that originate within tens of
g ratio is 1:2 electron. The sum of the kinetic energies of the electrons angstroms below the solid surface can leave the surface without
, an example, emitted cannot exceed the energy of the ionizing photons. energy loss. These electrons which leave the surface without
Ire 2. 1400 L- energy loss produce the peaks in the spectra and are the most
Probabilities of electron interaction with matter far exceed those useful. The electrons that undergo inelastic loss processes before
nergies, XPS Figure 1. Relative binding energies and ionization cross-sectIOns for U. The of the photons, so while the path length of the photons is of the emerging form the background. Calculations of the inelastic
tration of the binding energy is proportional to the dL~tance below the line indicating the order of micrometers, that of the electrons is of the order of tens mean free paths of electrons in various materials are shown in
Fermi level, and the ionization cross-section is proportional to the length of of angstroms. Thus, while ionization occurs to a depth of a few
~ntal binding Figure 4.
the line.
ences in the

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11
C. Preparing and Mounting Samples Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron SpectroSl

45
The electrons leaving the sample are detected by an electron 3. Surface Etching
spectrometer according to their kinetic energy. The analyzer is 40
Ion sputter-etching or other erosion techn
usually operated as an energy window, referred to as the pass 35 the use of an oxygen plasma on organic
energy, accepting only those electrons having an energy within Section E.5.a.(3), p. 27), may be used to r
~ 30
the range of this window. To maintain a constant energy resolu "$ contaminants. This technique is particularl
Cu
tion, the pass energy is fixed. Incoming electrons are adjusted to ~ 25
Au removing adventitious hydrocarbons from
the pass energy before entering the energy analyzer. Scanning i when the native oxides, formed by expol
~ 2(}~
for different energies is accomplished by applying a variable ,;
mosphere, are not of interest.
electrostatic field before the analyzer. This retardation voltage
may be varied from zero up to and beyond the photon energy. Argon ion etching is commonly used to 0
Electrons are detected as discrete events, and the number of tion on composition as a function of the
electrons for a given detection time and energy is stored and to ion etching. Calibration of the sputteI
displayed. o 500 1000 1500 2000 2500
used to convert sputter time to information
Electron Energy (eV)
the specimen. Because sputtering may cal
the surface chemistry, identification of tI
Figure 4. Calculated inelastic electron mean/ree paths in various metals/rom
the method 0/ S. Tanuma, C.J. Powell and D.R. Penn, Surf. Interface Anal.
chemical states with depth may not reflect
17,911 (1991). position.

4. Abrasion
Abrasion of a surface can be done withe
c. Preparing and Mounting Samples contamination by using a laboratory wipe,
or a knife blade. This may cause local heat
tion with environmental gases may occur ((
In the majorIty of XPS applications, sample preparation and Removal of unwanted volatile materials is usually ac in air and formation of nitrides in nitrogel
mounting are not critical. Typically, the sample is mechanically complished by long-term pumping in a separate vacuum oxidation of more active materials, perfor
attached to the specimen mount, and analysis is begun with the system or by washing with a suitable solvent. Use fresh an inert atmosphere such as a glove box.
sample in the as-received condition. Additional sample prepara ly distilled solvent to avoid contamination by high boil material should then be transferred to
tion is discouraged in many cases because any preparation ing point impurities within the solvent. Choice of the vacuum (UHV) chamber in a sealed vess
might modify the surface composition. For those samples where solvent can be critical. Hexane or other light hydrocar the clean surface.
special preparation or mounting cannot be avoided, the follow bon solvents are probably least likely to alter the surface,
ing techniques are recommended. providing the solvent properties are satisfactory. Samples
S. Fracturing and Scraping
may also be washed efficiently in a Soxhlett extractor
With proper equipment, many materials ca
1. Removing Volatile Material using a suitable solvent.
or scraped within the test chamber undeI
Ordinarily, volatile material is removed from the sample
tions. While this obviates contamination b)
before analysis. [n exceptional cases, when the volatile 2. Removing Nonvolatile Organic Contaminants atmospheric gases, attention must be gi
layer is of interest, the sample may be cooled for When the nature of an organic contaminant is not of in
pected results which might occur. Fracturir
analysis. The cooling must be to a sufficiently low terest or when a contaminant obscures underlying
along the grain boundaries which may
temperature to guarantee that the volatile element is not material that is of interest, the contaminant may be
sentative of the bulk material. Scraping c
warmed to evaporation by any heat load that the analysis removed with appropriate organic solvents. As with
material with soft material when the sar
conditions may impart. volatile materials, the choice of solvent can be critical. phase.

12 (l) PHYSICAL ELECTRONICS


(l) PHYSICAL ELECTRONICS

Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy c. Preparing and Mounting Samples

an electron 3. Surface Etching 6. Grinding to Powder


analyzer is Ion sputter-etching or other erosion techniques, such as If spectra characteristic of bulk composition are desired,
as the pass the use of an oxygen plasma on organic materials (see samples may be ground to a powder in a mortar. Protec
nergy within Section E.5.a.(3), p. 27), may be used to remove surface tion of the fresh surfaces from the atmosphere is re
ergy resolu -:? contaminants. This technique is particularly useful when quired. When grinding samples, localized high tempera
"!ii I eu removing adventitious hydrocarbons from the sample or tures can be produced, so grinding should be done slow
e adjusted to ~ 25 !
~ when the native oxides, formed by exposure to the at ly to minimize heat-induced chemical changes at the
er. Scanning """ 20
g a variable :.l'"! mosphere, are not of interest. newly created surfaces. The mortar should be well
.~ 15 cleaned before reuse.
tion voltage ] Argon ion etching is commonly used to obtain informa
10ton energy. 10
tion on composition as a function of the exposure time 7. Mounting Powders for Analysis
number of
to ion etching. Calibration of the sputter rates can be There are a number of methods which can be used to
s stored and
0

2500
used to convert sputter time to information on depth into mount powders for analysis. Perhaps the most widely
500 1000 1500 2000

Electron Energy (eV) the specimen. Because sputtering may cause changes in used method is dusting the powder onto a polymer-based
the surface chemistry, identification of the changes in adhesive tape with a camel-hair brush. The powder must
Figure 4. Calculated inelastic electron mean free paths in various metals from chemical states with depth may not reflect the true com
the method of S. Tanuma, C.l Powell and D.R. Penn, Sutf. lnteiface Anal.
be dusted across the surface carefully and lightly,
position. no wiping strokes. Some researchers shun organic tape
17,911 (1991).
for UHV work, but others have successfully used certain
4. Abrasion types of tape in the 10- 10 Torr range.
Abrasion of a surface can be done without significant
contamination by using a laboratory wipe, a cork, a file Alternative methods for mounting powders include
nting Samples or a knife blade. This may cause local heating, and reac pressing the powder into indium or other soft foils, sup
tion with environmental gases may occur (e.g., oxidation porting the powder on a metallic mesh, pressing the
paration and Removal of unwanted volatile materials is usually ac in air and formation of nitrides in nitrogen). To prevent powder into pellets or simply depositing the powder by
mechanically complished by long-term pumping in a separate vacuum oxidation of more active materials, perform abrasion in gravity. With the foil method, the powder is pressed be
gun with the system or by washing with a suitable solvent. fresh an inert atmosphere such as a glove box. The abraded tween two pieces of pure foil. The pieces are then
pIe prepara ly distilled solvent to avoid contamination by high boil material should then be transferred to the ultra-high separated, and one of them is mounted for analysis. Suc
preparation ing point impurities within the solvent. Choice of the vacuum (UHV) chamber in a sealed vessel to preserve cess with this technique has been varied. Sometimes
amples where solvent can be critical. Hexane or other light hydrocar the clean surface. bare foil remains exposed and, if the sample is an in
, the follow- bon solvents are probably least likely to alter the surface, sulator, parts of the powder can charge differently. Dif
providing the solvent properties are satisfactory. Samples 5. Fracturing and Scraping ferential charging can also be a problem when a metallic
may also be washed efficiently in a Soxhlett extractor With proper equipment, many materials can be fractured mesh is used to support the powder. If a press is used to
using a suitable solvent. , or scraped within the test chamber under UHV condi form the powder into a pellet of workable dimensions, a
he sample tions. While this obviates contamination by reaction with press with hard and extremely clean working surfaces
e volatile 2. Removing Nonvolatile Organic Contaminants atmospheric gases, attention must be given to unex should be used. Gravity can effectively hold some
'ooled for When the nature of an organic contaminant is not of in pected results which might occur. Fracturing might occur materials in place, particularly if a shallow well or
ently low terest or when a contaminant obscures underlying along the grain boundaries which may not be repre depression is cut in the surface of the sample mount.
ent is not material that is of interest, the contaminant may be sentative of the bulk material. Scraping can cover hard Allowing a liquid suspension of the powder to dry on
.~e analysis removed with appropriate organic solvents. As with material with soft material when the sample is multi the specimen holder is an effective way of producing a
volatile materials, the choice of solvent can be criticaL phase.

(J) PHYSICAL ELECTRONICS


(J) PHYSICAL ELECTRONICS
13

D. Experimental Procedure Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spec1

unifonn layer. With these methods, care must be taken in the sample. A throttled roughing valve is especially ef Dualanode
pump-down to ensure that gas evolution does not disturb fective.

Energy analyzer
D. Experimental Procedure
1. Technique for Obtaining Spectra aperture. All of the spectra in this handbook were ob
All spectra in this handbook were obtained using a PHI tained using an 800 !lm diameter analysis area.
Model 5600 MultiTechnique system. A schematic
diagram of the apparatus (Figure 5)' illustrates the All of the spectra in this handbook were recorded and
relationship of major components, including the electron stored using the PHI ACCESSTM data system. The instru
energy analyzer, the x-ray source, and the ion gun used ment was calibrated daily, and the calibration was check
for sputter-etching. The Model 10-360 Electron Energy ed several times each day during data acquisition. The
Analyzer incorporated into the 5600 is an SCA, and the analyzer work function was determined assuming the
input lens to the analyzer is an Omni Focus III lens. The binding energy of the Au 4f7/2 peak to be 84.0 ev' All
excitation sources used were a Model 10-550 x-ray survey spectra scans were taken at a pass energy of 58.7 Vacuum chamber

source with a Model 10-410 monochromator and a eV. The narrow scans of strong lines were, in most
Model 04-548 dual-anode source which was used with a cases, just wide enough to encompass the peak(s) of in
magnesium anode. All of the spectra in the handbook terest and were obtained with a pass energy of 23.5 ev'
were taken with the x-ray source operating at 400 W (15 A lower pass energy may show more structure for some
kV - 27 rnA). The specimens were analyzed at an materials. The narrow spectra were necessary to ac
curately determine the energy, shape and spin-orbit split Figure 5, A schematic diagram of the PHI Model
electron take-off angle of 70, measured with respect to tern.
the surface plane. The monochromatic x-ray source is lo ting of the strong lines. On insulating samples, a high
cated perpendicular to the analyzer axis, and the stand resolution spectrum was taken of the adventitious
hydrocarbon on the surface of the sample to use as a without etching in order to avoid po
ard x-ray source is located at 54.7" relative to the
reference for charge correction. The generally accepted surface chemistry. Ne, Xe and Kr ~
analyzer axis.
binding energy for adventitious carbon is 284.8 eV. graphite and Ar in silicon via ion in
In the PHI Model 5600 MultiTechnique system, energy known concentrations prior to analysis.
distribution, energy resolution and analysis area are aU a The samples analyzed to obtain the spectra in this hand
function of the analyzer. For all of the spectra in this book are standard materials of known composition. 2. Instrument Calibration
handbook, the spectrometer was operated in a standard Metal foils and polycrystalline materials with large sur To ensure the accuracy of the data
mode. The Omni Focus III lens was used to scan the face areas were mechanically fastened to the specimen handbook, the instrument used to ob
spectrum while the SCA was operated at a constant pass mount. Powder samples were ground with a mortar and calibrated regularly throughout th
energy. This resulted in constant resolution (8E) across pestle to expose fresh surfaces and were dusted onto ad process. The best way to check cal
the entire energy spectrum. The size of the analysis area hesive tape. Most elemental standards were sputter method used here, is to record suital
was defined by the aperture selection of the Omni Focus etched immediately prior to analysis to remove surface known, conducting specimen. Typicall:
1II lens. Analyzer energy resolution (LlEIE) was deter contamination. Most compounds, however, were ground 2p and 3p lines are used. The lines s1
mined by the choice of pass energy and the selected or cleaved, and the freshly exposed surface was analyzed with a narrow sweep width in the ran~

14 (J) PHYSICAL ELECTRONICS (J) PHYSICAL ELECTRONICS


Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy D. Experimental Procedure

e taken in the sample. A throttled roughing valve is especially ef Dual-anode x-ray source
a pass energy of 23.5 eV or less (corresponding to the
ot disturb fective. pass energy normally used for high resolution scans)
should be used.

There is general agreement on accurate values of Cu, Au


Energy analyzer and Ag standard line energies. The values in Table 1 are
dure recommended for clean Au, Ag and Cu:

aperture. All of the spectra in this handbook were ob Table 1. Reference Binding Energies (eV)

ng a PHI tained using an 800 !lm diameter analysis area. AIKa. MgKa.
chematic X-ray monochromator eu 3p 75.14 75.13
rates the All of the spectra in this handbook were recorded and Au 4f7/2 83.98 84.00
electron stored using the PHI ACCESSTM data system. The instru 3d5/2 368.26 368.27
ment was calibrated daily, and the calibration was check eu L3MM 567.96 334.94
gun used
ed several times each day during data acquisition. The eu 2P3/2 932.67 932.66
n Energy Ag M4NN 1128.78 895.75
, and the analyzer work function was determined assuming the
lens. The binding energy of the Au 4f712 peak to be 84.0 eV. All from M. P. Seah Surf. Interface Anal. 14,488 (1989)
50 x-ray survey spectra scans were taken at a pass energy of 58.7 Vacuum chamber

r and a eV. The narrow scans of strong lines were, in most Because the 2P3/2 and 3p3/2 photoelectron peak energies
ed with a cases, just wide enough to encompass the peak(s) of in of Cu are widely separated in energy, measurement of
handbook terest and were obtained with a pass energy of 23.5 eV. these peak binding energies provides a quick and simple
00 W (15 A lower pass energy may show more structure for some means of checking the accuracy of the binding energy
ed at an materials. The narrow spectra were necessary to ac scale. Utilizing all of the above standard energies estab
curately determine the energy, shape and spin-orbit split Figure 5. A schematic diagram of the PHI Model 5600 MultiTechnique sys the linearity of the energy scale and its position,
espect to tem.
rce is 10 ting of the strong lines. On insulating samples, a high i.e., the location of the Fermi level.
he stand resolution spectrum was taken of the adventitious
e to the hydrocarbon on the surface of the sample to use as a without etching in order to avoid possible changes in 3. Programming Scans for an Unknown Sample
reference for charge correction. The generally accepted surface chemistry. Ne, Xe and Kr were implanted in For a typical XPS investigation where the surface com
binding energy for adventitious carbon is 284.8 eV. graphite and Ar in silicon via ion implantation to un position is unknown, a broad scan survey spectrum
, energy known concentrations prior to analysis. should be obtained first to identify the elements present.
are all a The samples analyzed to obtain the spectra in this hand Once the elemental composition has been determined,
a in this book are standard materials of known composition. 2. Instrument Calibration narrower detailed scans of selected peaks can be used
standard Metal foils and polycrystalline materials with large sur To ensure the accuracy of the data presented in this for a more comprehensive picture of the chemical com
scan the face areas were mechanically fastened to the specimen handbook, the instrument used to obtain the data was position. This is the procedure that has been followed in
stant pass mount. Powder samples were ground with a mortar and calibrated regularly throughout the data-gathering compiling data for this handbook, even though specimen
E) across pestle to expose fresh surfaces and were dusted onto ad process. The best way to check calibration, and the composition was known prior to analysis.
lysis area hesive tape. Most elemental standards were sputter method used here, is to record suitable lines from a
ni Focus etched immediately prior to analysis to remove surface known, conducting specimen. Typically, the Au 4f or Cu a. Survey Scans. Most elements have major
as deter contamination. Most compounds, however, were ground 2p and 3p lines are used. The lines should be recorded photoelectron peaks below 1100 e V, and a scan range
selected or cleaved, and the freshly exposed surface was analyzed with a narrow sweep width in the range of 5-10 eV, and from 1100-0 e V binding energy is usually sufficient to

<D PHYSICAL ELECTRONICS


<D PHYSICAL ELECTRONICS
15

E. Data Interpretation Handbook of X-ray Photoelectron Spectroscopy


Handbook of X-ray Photoelectron Spe<

identify all detectable elements. The spectra in this hand terest, yet with small enough step sizes to permit
which have not suffered an inelastic
book were recorded with a scan range of 1400-0 eV (AI determination of the exact peak position. Sufficient
ing from the sample. Electrons that h
excitation) or 1200-0 eV (Mg excitation) binding energy. scanning must be done within the time limits of
crease the level of the background :
In an unknown sample, if specific elements are suspected the analysis in order to obtain good counting statis
higher than the peak energy. The b
at low concentrations, their standard spectra should be tics.
tinuous because the energy loss pro
consulted before programming the survey scan. If the
(2) Peaks from any species thought to be radia and multiple. The background in th
strongest line occurs above 1100 eV binding energy, the
tion-sensitive or transient should be run first. spectra is larger than the ba(
scan range can be modified accordingly.
Otherwise, any convenient order may be chosen. monochromated Al Ka induced spec
An analyzer pass energy of 187 e V, in conjunction with citation by Bremsstrahlung radiati
the appropriate aperture, is recommended for survey (3) No clear guidelines can be given on the maxi monochromated light.
scans with the PHI Model 5600 MultiTechnique system. mum duration of data gathering on anyone
sample. It should be recognized, however, that The "noise" in the spectrum is not ins
These settings result in adequate resolution for elemental
chemical states have vastly varying degrees of but is the consequence of the co
identification and produce very high signal intensities,
radiation sensitivity and that for anyone set of ir electrons as counts randomly spaced i
minimizing data acquisition time and maximizing
radiation conditions, there exists for many samples ard deviation for counts collected in aI
elemental detectability.
a condition beyond which it is impractical to at to the square root of the counts so that
b. Detail Scans. For purposes of chemical state iden tempt gathering data. ard deviation is 100/(counts) 112. The si
tification, for quantitative analysis of minor components is then proportional to the square roc
and for peak deconvolution or other mathematical (4) With the PHI Model 5600 MultiTechnique sys time. The background level upon whi
manipulations of the data, detail scans must be obtained tem, an analyzer pass energy of 23 eV is normally perimposed is a characteristic of the
for precise peak location and for accurate registration of used for routine detail scans. Where higher energy citation source and the transmission ch
line shapes. There are some logical rules for this resolution is needed, lower pass energies can be instrument.
programming. utilized. For example, the sputter-cleaned Si 2p on
p. 56, taken at 23 eV pass energy, can be compared b. Types of Lines. Several types of I=
to the chemically etched Si 2p shown in Figure 2 in XPS spectra. Some are fundamenta
(1) Scans should be wide enough to encompass
(p. 11). and are always observed. Others are dl
the background on both sides of the region of in-
exact physical and chemical nature I
third type is the result of instrumenta
lowing describes the various spectral
likely to be encountered:

E. Data Interpretation (1) Photoelectron Lines. The


photoelectron lines are relatively s)
1. The Nature of the Spectrum responds to a binding energy of 0 eV with reference to are typically the narrowest lines 0
the Fermi level (Equation 1, p. 10). Therefore, a binding spectra. Photoelectron lines of pUl
a. General Features. The spectrum is displayed as a energy scale with 0 at that point and increasing to the however, exhibit considerable asyr
plot of the number of electrons versus electron binding left is customarily used. coupling with conduction electrons.
energy in a fixed, small energy interval. The position on a convolution of the natural lir
the kinetic energy scale equal to the photon excitation The spectra in this handbook are typical for the various lifetime of the "hole" resultir
energy minus the spectrometer work function cor- elements. The well-defined peaks are due to electrons photo ionization process), the width
line which created the photelectron I

16 (D PHYSICAL ELECTRONICS
cD PHYSICAL ELECTRONICS

Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy E. Data Interpretation

is hand terest, yet with small enough step sizes to permit which have not suffered an inelastic energy loss emerg strumental contribution to the observed line width.
o eV (AI determination of the exact peak position. Sufficient ing from the sample. Electrons that have lost energy in Less intense photoelectron lines at higher binding
g energy. scanning must be done within the time limits of crease the level of the background at binding energies energies are usually wider by 1-4 eV than the lines
,uspected the analysis in order to obtain good counting statis higher than the peak energy. The background is con at lower binding energies. All of the photoelectron
hould be tics. tinuous because the energy loss processes are random lines of insulating solids are of the order of 0.5 eV
n. If the and multiple. The background in the Mg Ka induced wider than photoelectron lines of conductors. The
ergy, the (2) Peaks from any species thought to be radia
spectra is larger than the background in the approximate binding energies of all photoelectron
tion-sensitive or transient should be run first.
monochromated Al Ka induced spectra because of ex lines detectable by Al or Mg radiation are
Otherwise, any convenient order may be chosen.
citation by Bremsstrahlung radiation of the non cataloged in Appendices G and H.
tion with monochromated light.
r survey (3) No clear guidelines can be given on the maxi
(2) Auger Lines. These are groups of lines in
e system. mum duration of data gathering on anyone
The "noise" in the spectrum is not instrumental in origin rather complex patterns. There are four main
lemental sample. It should be recognized, however, that
but is the consequence of the collection of single Auger series observable in XPS. They are
tensities, chemical states have vastly varying degrees of
electrons as counts randomly spaced in time. The stand KLL, LMM, MNN and NOO series, identified by
ximizing radiation sensitivity and that for anyone set of ir
ard deviation for count.;; collected in any channel is equal specifying the initial and final vacancies in the
radiation conditions, there exists for many samples
to the square root of the counts so that the percent stand Auger transition. The KLL series, for example, in
a condition beyond which it is impractical to at
ard deviation is 1OO/(counts) 112. The signal-to-noise ratio cludes those processes with an initial vacancy in
ate iden tempt gathering data.
is then proportional to the square root of the counting the K shell and final double vacancy in the L shell.
mponents time. The background level upon which the peak is su The symbol V (e.g., KVV) indicates that the final
hematical With the PHI Model 5600 MultiTechnique sys
tem, an analyzer pass energy of 23 eV is normally perimposed is a characteristic of the specimen, the ex vacancies are in valence levels. The KLL series
obtained citation source and the transmission characteristics of the has, theoretically, nine lines, and others have still
tration of used for routine detail scans. Where higher energy
instrument. more. Because Auger lines have kinetic energies
for this resolution is needed, lower pass energies can be
utilized. For example, the sputter-cleaned Si 2p on which are independent of the ionizing radiation,
b. Types of Lines. Several types of peaks are observed they appear on a binding energy plot to be in dif
p. 56, taken at 23 eV pass energy, can be compared
in XPS spectra. Some are fundamental to the technique ferent positions when ionizing photons of different
)mpass to the chemically etched Si 2p shown in Figure 2
and are always observed. Others are dependent upon the energies (i.e., different x-ray sources) are used.
of in- (p. 11).
exact physical and chemical nature of the sample. A Core-type Auger lines (with final vacancies deeper
third type is the result of instrumental effects. The fol than the valence levels) usually have at least one
lowing describes the various spectral features that are component of intensity similar to the most intense
likely to be encountered: photoelectron line. Positions of the more
prominent Auger components are cataloged along
(1) Photoelectron Lines. The most intense with the photoelectron peaks in Appendices G and
photoelectron lines are relatively symmetrical and H.
are typically the narrowest lines observed in the
responds to a binding energy of 0 eV with reference to
the Fermi level (Equation 1, p. 10). Therefore, a binding spectra. Photoelectron lines of pure metals can, (3) X-ray Satellites. The x-ray emission spectrum
however, exhibit considerable asymmetry due to from a nonmonochromatic source used for irradia
ayed as a energy scale with 0 at that point and increasing to the
coupling with conduction electrons. Peak width is tion exhibits not only the characteristic x-ray but
n binding left is customarily used.
a convolution of the natural line width (the also some minor x -ray components at higher
osition on
The spectra in this handbook are typical for the various lifetime of the "hole" resulting from the photon energies. For each photoelectron peak that
excitation
elements. The well-defined peaks are due to electrons photoionization process), the width of the x-ray results from the routinely used Mg and Al Ka x
lion cor
line which created the photelectron line and the in

<D PHYSICAL ELECTRONICS


<D PHYSICAL ELECTRONICS
17
E. Data Interpretation Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron SPf

ray photons, there is a family of minor peaks at generation of x-rays within the sample itself. This
lower binding energies, with intensity and spacing last possibility is rare because the probability of
characteristic of the x-ray anode materia1. The pat x-ray emission is low relative to Auger electron
tern of such satellites for Mg and Al is shown in emission. Nevertheless, such minor lines can be
Table 2. A resultant spectrum using Mg x-rays is puzzling. Table 3 indicates where such peaks are
shown in Figure 6. most likely to occur relati ve to the most intense
photoelectron lines. Because such ghost lines rare
ly appear with nonmonochromatic x-ray sources
Table 2. X-ray Satellite Energies and Intensities
and are not possible with monochromatic x-ray 1t ~ 1t*

al,2 a3 a4 as (X{, p sources, they should not be considered in line


Mg displacement, e V 0 8.4 10.1 17.6 20.6 48.7 identification until all other possibilities are ex 300
relative height 100 8.0 4.1 0.6 0.5 0.5 cluded. Binding Energy (eV)

Al displacement, eV 0 9.8 U.8 20.1 23.4 69.7 Figure 7. The 1t bond shake-up satellite for CIs
relative height 100 6.4 3.2 0.4 0.3 0.6 Table 3. Displacement of X-ray Ghost Lines (eV) about 6.7 e V higher than the main photopeak.

Contaminating Anode Material


(X1,2
Radiation Mg Al approach that of the main line.
o (Ka) 728.7 961.7 satellite of a principal photoeiectf(
Cu (La) 323.9 556.9 be observed, as shown in Figure 8.
<X;;
Mg (Ka) 233.0
Al (Ka) -233.0 of such lines is sometimes also apj
spectral contours (Figure 9). Thf
p and relative intensities of shake-u
x 50
(5) Shake-Up Lines. Not all photoelectric proces sometimes be useful in identifyin
0:3
(X4 ses are simple ones which lead to the formation of state of an element, as discussed ir
ions in the ground state, but there is a finite prob (p.24).
ability that the ion will be left in an excited state a
300 220
Binding Energy (eV) few electron volts above the ground state. In this (6) Multiplet Splitting. Emission
event, the kinetic energy of the emitted from a core level of an atom that
Figure 6. Mg x-ray satellites observed in the C Is spectrum of graphite. photoelectron is reduced, with the difference cor (unpaired electrons in valence leve
responding to the energy difference between the vacancy in two or more ways. The
ground state and the excited state. This results in new unpaired electron left after
(4) X-ray Ghost Lines. Occasionally, x-radiation
the formation of a satellite peak a few electron from an s-type orbital with
from an element other than the x-ray source anode
volts lower in kinetic energy (higher in binding electrons in the atom can creat
material impinges upon the sample, resulting in
energy) than the main peak. For example, the char several possible final state config
small peaks corresponding to the most intense
acteristic shake-up line for carbon in aromatic many energies. This results in a pt
spectral peaks but displaced by a characteristic
compounds, a shake-up process involving the ener which is split asymmetrically int
energy interval. These lines may result from Mg
gy of the n ~ n* transition, is shown in Figure 7. ponents similar to the one shown if
impurity in the Al anode or vice versa, eu from
the anode base structure, oxidation of the anode, or Multiplet splitting also occurs in t
In some cases, most often with paramagnetic com
generation of x-ray photons in the Al foil x-ray p levels, but the result is more corr
pounds, the intensity of the shake-up satellite may
window. On occasion, such lines can originate via In favorable cases, it results in ar

18 (I) PHYSICAL ELECTRONICS


(I) PHYSICAL ELECTRONICS

Handbook of X-ray Photoelectron Spectroscopy Ha.ndbook of X-ray Photoelectron Spectroscopy E. Data Interpretation

generation of x-rays within the sample itself. This


r peaks at
last possibility is rare because the probability of
d spacing 2P312
x-ray emission is low relative to Auger electron
al. The pat
emission. Nevertheless, such minor lines can be
is shown
puzzling. Table 3 indicates where such peaks are
g x-rays is
most likely to occur relative to the most intense eu
photoelectron lines. Because such ghost lines rare-
appear with nonmonochromatic x-ray sources
1t ~ 1t*
tensities and are not possible with monochromatic x-ray
sources, they should not be considered in line
Ct(; (3 300 280
48.7
identification until all other possibilities are ex Energy (eV)
20.6
0.5 0.5 cluded.
Figure 7. The 1t bond shake-up satellite for C 1s in polystyrene. The peak is
23.4 69.7 about 6.7 eV higher than the main photopeak.
0.3 0.6 Table 3. Displacement of X-ray Ghost Lines (eV)

Contaminating Anode Material


approach that of the main line. More than one
Radiation Mg Al
satellite of a principal photoelectron line can also
o (Ka) 728.7 961.7
be observed, as shown in Figure 8. The occurrence
Cu (La) 323.9 556.9
Mg (Ka) 233.0 of such lines is sometimes also apparent in Auger
Al (Ka) -233.0 spectral contours (Figure 9). The displacements
and relative intensities of shake-up satel1ites can
~ sometimes be useful in identifying the chemical
(5) Shake-Up Lines. Not all photoelectric proces
state of an element, as discussed in Section E.3.d.
ses are simple ones which lead to the formation of
(p.24).
ions in the ground state, but there is a finite prob
ability that the ion will be left in an excited state a (6) Multiplet Splitting. Emission of an electron
220 few electron volts above the ground state. In this 970 925
from a core level of an atom that itself has a spin
event, the kinetic energy of the emitted Binding Energy (eV)
(unpaired electrons in valence levels) can create a
'ectrum of graphite. photoelectron is reduced, with the difference cor vacancy in two or more ways. The coupling of the Figure 8. Examples of shake-up lines (s) of the copper 2p observed in cop
responding to the energy difference between the new unpaired electron left after photoemission pe r compounds.
ground state and the excited state. This results in from an s-type orbital with other unpaired
y, x-radiation the formation of a satellite peak a few electron electrons in the atom can create an ion with increase in the spin doublet separation, evidenced
source anode volts lower in kinetic energy (higher in binding several possible final state configurations and as in the separation of the 2pll2 and 2p3/2 lines in
, resulting in energy) than the main peak. For example, the char many energies. This results in a photoelectron line first-row transition metals, and in the generation of
most intense acteristic shake-up line for carbon in aromatic which is split asymmetrically into several com a less easily noticed asymmetry in the line shape
characteristic compounds, a shake-up process involving the ener ponents similar to the one shown in Figure 10. of the components. Often such effects on the p
suIt from Mg gy of the n ~ n* transition, is shown in Figure 7. doublet are obscured by shake-up lines.
rsa, Cu from Multiplet splitting also occurs in the ionization of
the anode, or In some cases, most often with paramagnetic tom p levels, but the result is more complex and subtle. (7) Energy Loss Lines. With some materials, there
Al foil x-ray pounds, the intensity of the shake-up satellite may In favorable cases, it results in an apparent slight is an enhanced probability for loss of a specific
originate via

(J) PHYSICAL ELECTRDNICS (J) PHYSICAL ELECTRDNICS 19


E. Data Interpretation Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray

(C2H302)2' 4H20

Ni

580
850 600
Binding Energy (eV)
Figure 11. Energy loss em
Figure 9. Examples of the effects of chemical states on Auger line shapes in
nickel compounds.
r

MnC03
amount ot energy due to interaction between the
photoelectron and other electrons in the surface
region of the sample (Figure 11). The energy loss
phenomenon produces a distinct and rather sharp 120 80
hump 20-25 e V above the binding energy of the Binding Energy (eV)
parent line. Under certain conditions of spectral
display, energy loss lines can cause confusion. Figure 10. Multiplet splitting of the Mn 3s.
Normal b b
Such phenomena in insulators are rarely sharper
than that shown in Figure 11 and are usually much interval between the primary peak and the loss
more muted. They are different in each solid peak is called the plasmon energy. The so-called
medium. bulk plasmons are the more prominent of these 190
lines. A second series, the surface plasmons, exists
With metals, the effect is often much more
at energy intervals determined approximately by
dramatic, as indicated by the loss lines for Figure 12. Suiface (05) and
dividing the bulk plasmon energy by the square
aluminum shown in Figure 12. Energy loss to the at nonnal and grazing take-,
root of two. The effect is not easily observed in
conduction electrons occurs in well-defined quanta
nonconductors, nor is it prominent in all conduc
characteristic of each metal. These plasmons arise spectrum betwee
tors. Plasmon lines are especially prominent in the
from group oscillations of the conduction binding energy.
Groups Ia and IIa metal spectra in this handbook.
electrons. The photoelectron line, or the Auger photoelectron eI
is successively mirrored at intervals of higher (8) Valence Lines and Bands. Lines of low inten and from solid Sl
binding energy with reduced intensity. The energy sity occur in the low binding energy region of the

20 <D PHYSICAL ELECTRDNICS <D PHYSICAL ELE.


terpretation Handbook of X-ray Photoelectron of X-ray Photoelectron Spectroscopy E. Data Interpretation

tween insulators and conductors are especially


o Is noted by the absence or presence of electrons from
conduction bands at the Fermi level. Valence
bands may also be used to distinguish between
materials where the core level XPS photoelectron
lines are quite similar in shape and position. Ap
pendix D contains valence band spectra of several
materials.

2. Line Identification
In general, interpretation of the XPS spectrum is most
readily accomplished first by identifying the lines that
520 are almost always present (specifically those of C and
Mn Binding Energy (eV) 0), then by identifying major lines and associated
600

Energy (eV)
weaker lines, and lastly by identifying the remaining
loss envelope from the 0 1s line in Alz0 3 (sapphire).
weak lines. Most modern, commercially available
iples of the effects of chemical states on Auger line shapes in spectrometers have peak identification algorithms within
'05.
their data reduction packages. Poor signal-to-noise of the
data or database limitations may require manual iden
Ai 2s tification of some peaks. The following step-by-step pro

t of energy due to interaction between the


lectron and other electrons in the surface
cedure simplifies the data interpretation task and mini

of the sample (Figure 11). The energy loss


mizes data ambiguities.
menon produces a distinct and rather sharp 120
20-25 eV above the binding energy of the Binding Energy (eV)
Step 1. The Cis, 0 Is, C (KLL) and 0 (KLL)
b
line. Under certain conditions of spectral lines are usually prominent in any spectrum. Iden
y, energy loss lines can cause confusion. Figure 10. Multiplet splitting of the Mn 3s. b tify these lines first along with all derived x-ray
b satellites and energy loss envelopes.
phenomena in insulators are rarely sharper
at shown in Figure 11 and are usually much interval between the primary peak and
Step 2. Identify other intense lines (Appendix J)

muted. They are different in each solid peak is called the plasmon energy. The present in the spectrum, then label any related
m. bulk plasmons are the more prominent
110 satellites and other less intense spectral lines as
lines. A second series, the surface plasmons, Energy (eV) sociated with those elements. The energy positions
metals, the effect is often much more
at energy intervals determined approxi of the less intense lines are noted in the line posi
tic, as indicated by the loss lines for dividing the bulk plasmon energy by the :lUl.fac~ (s) and bulk (b) plasmon lines associated with the Al 2s
urn shown in Figure 12. Energy loss to the tion table with the spectra. Keep in mind that some
root of two. The effect is not easily ob~",...1 grazmg take-off angles.
ction electrons occurs in well-defined quanta lines may be interfered with by more intense,
nonconductors, nor is it prominent in all overlapping lines from other elements. The most
~teristic of each metal. These plasmons arise between the Fermi level and 10-20 eV
tors. Plasmon lines are especially prominent serious interferences by the C and 0 lines, for ex
group oscillations of the conduction energy. These lines are produced by
Groups Ia and IIa metal spectra in this ample, are Ru 3d by C Is, V 2p and Sb 3d by 0
ns. The photoelectron line, or the Auger emission from molecular orbitals
s successively mirrored at intervals of higher 1s, I (MNN) and Cr (LMM) by 0 (KLL), and Ru
(8) Valence Lines and Bands. Lines of low solid state energy bands. Differences be
g energy with reduced intensity. The energy (MNN) by C (KLL).
sity occur in the low binding energy region

C]) PHYSICAL J::LJ::LII ELECTRONICS 21


E. Data Interpretation Handbook of X-ray Photoelectron Spectroscopy
Handbook of X-ray P

Step 3. Identify any remammg minor lines. In doing electrons and tends to make the peaks appear at higher
Some precautions s
this, assume they are the most intense lines of an un binding energies, whereas excessive charge compensa
is heterogeneous on
known element. If not, they should already have been tion can make the peaks shift to lower binding energies.
different materials
identified in the previous steps. Again, keep in mind The following are four methods which are usually valid
and interpretation 01
possible line interferences. Small lines that seem uniden for charge correction on insulating samples:
ingly. One cannot J
tifiable can be ghost lines. Use Table 3 (p. 18) to check like Au or graphite
for the more intense parent photoelectron lines. (1) Measurement of the position of the CIs line
and validly use the
from adventitious hydrocarbon nearly always
reet for static chargl
Step 4. Check the conclusions by noting the spin present on samples introduced from the laboratory
mized to a great ex
doublets for p, d and f lines. They should have the right environment or from the glove box. This line, on
energy electrons.
separation (cf. spin orbit splitting for individual elements unsputtered inert metals such as Au or Cu, appears
and Appendices G and H) and should be in the correct at 284.8 eV, so any shift from this value can be b. Photoelectron 1
intensity ratio. The ratio for p lines should be about 1:2, taken as a measure of the static charge. At this tions. An important
d lines 2:3 and f lines 3:4. P lines, especially 4p lines, time, it is not known whether a reproducible line obtain information 0
may be less than 1:2. position exists for C remaining on the surface after in binding energi,
ion beam etching. photoelectron lines.
3. Chemical State Identification made to calculate cl
The identification of chemical states primarily depends (2) The use of an internal standard, such as a
energies, the facton
on the accurate determination of line energies. To deter hydrocarbon moiety of a polymer sample. For the
state) are imperfectl~
mine line energies accurately, the voltage scale of the study of supported catalysts or similar materials,
experimental data fI
instrument must be precisely calibrated (cf. Section D.2., one can adopt a suitable value for a constituent of
accompanying the s1
p. 15), a line with a narrow sweep range must be the support and use that to interrelate binding ener
siderable data from tl
recorded with good statistics (of the order of several gies of different samples. One must be certain that
specifically for this
thousand counts-per-channel above background), and ac treatments of the various samples are not so dif
been carefully eval",
curate correction must be made for static charge if the ferent that the inherent binding energies of support
and static charge ref,
sample is an insulator. constituents are changed.
therefore, directly COl
a. Determining Static Charge on Insulators. During (3) The use of a normally insulating sample so
Because occasional
analysis, insulating samples tend to acquire a steady thin that it effectively does not insulate. This can
sometimes necessary
state charge of as much as several volts. This steady be assumed if the spectrum of the underlying con
intense one in the sp
state charge is a balance between electron loss from the ductor appears in good intensity and if line posi
line are within 0.2
surface by emission and electron gain by conduction or tions are not affected by changes in electron flux
primary line. Howe
by acquisition of slow or thermal electrons from the from the charge neutralizer.
occur in paramagnet
vacuum. The steady-state charge, usually positive, can splitting. Separations
be minimized with an adjacent neutralizer or flood gun. (4) For the study of insulating polymer films,
mined approximately
It is often advantageous to do this to reduce differential binding energies of the C functional groups may
pendices G and H.
charging and sharpen the spectral lines. also be determined by applying a small amount of
poly(dimethyl siloxane) solution (10-6 M) to the c. Auger Line Cll
A serious problem is exactly determining the extent sample surface and charge reference to the Si 2p Parameter. Core-typl
of charging. Any positive charging retards outgoing of the silicone (at about 102.1 eV). with double vacancie~
have at least one corr

22 (J) PHYSICAL ELECTRONICS


(J) PHYSICAL ELEC

Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy E. Data Interpretation

oing electrons and tends to make the peaks appear at higher Some precautions should be kept in mind. If the sample often nearly as intense as the strongest photoelectron
un binding energies, whereas excessive charge compensa is heterogeneous on even a micrometer scale, particles of line (cf. spectra for F, Na, As, In, Te and Pb). There are
een tion can make the peaks shift to lower binding energies. different materials can be charged to different extents, four core Auger groups that can be generated by Mg or
ind The following are four methods which are usually valid and interpretation of the spectrum is complicated accord Al x-rays: the KLL (Na, Mg); the LMM (Cu, Zn, Ga,
den for charge correction on insulating samples: ingly. One cannot physically mix a conducting standard Ge, As, Se); the MNN (Ag, Cd, In, Sn, Sb, Te, I, Xe, Cs,
eck like Au or graphite of micron dimensions with a powder Ba); and NOO (Th, U). The MNN lines in the rare
(1) Measurement of the position of the CIs line and validly use the Au or graphite line in order to cor earths, while accessible, are very broad because of multi
from adventitious hydrocarbon nearly always rect for static charge. Differential charging can be mini plet splitting and shake-up phenomena with most of the
spin
present on samples introduced from the laboratory mized to a great extent by using a flood source of low compounds. Valence-type Auger lines (final states with
right environment or from the glove box. This line, on
energy electrons. vacancies in valence levels) - such as those for 0 and
ents
unsputtered inert metals such as Au or Cu, appears F (KLL); Mn, Fe, Co and Ni (LMM); and Ru, Rh and
rrect at 284.8 eV, so any shift from this value can be
b. Photoelectron Line Chemical Shifts and Separa Pd (MNN) - can be intense and are, therefore, also
1:2, taken as a measure of the static charge. At this tions. An important advantage of XPS is its ability to useful. Chemical shifts occur with Auger lines as well as
ines, time, it is not known whether a reproducible obtain information on chemical states from the variations with photoelectron lines. The chemical shifts are dif
position exists for C remaining on the surface after in binding energies, or chemical shifts, of the ferent from those of the photoelectron lines, but they are
ion beam etching. photoelectron lines. While many attempts have been often more pronounced. This can be very useful for
made to calculate chemical shifts and absolute binding identifying chemical states, especially in combination
ends (2) The use of an internal standard, such as a energies, the factors involved (especially in the solid with photoelectron chemical shift data. If data for the
eter hydrocarbon moiety of a polymer sample. For the state) are imperfectly understood, and one must rely on various chemical states of an element are plotted with
f the study of supported catalysts or similar materials, experimental data from standard materials. The tables the binding energy of the photoelectron line on the
D.2., one can adopt a suitable value for a constituent of accompanying the spectra in this handbook record con abscissa and the kinetic energy of the Auger line on the
't be
the support and use that to interrelate binding ener siderable data from the literature as well as data obtained ordinate, a two-dimensional chemical state plot can be
veral of different samples. One must be certain that specifically for this handbook. All literature data have obtained. Such plots are in Appendix A for F, Na, AI, Si,
d ac treatments of the various samples are not so dif been carefully evaluated to the instrumental calibration S, Cu, Zn, As, Se, Ag, Cd, In, Sn and Te.
f the ferent that the inherent binding energies of support and static charge reference values given above and are,
constituents are changed. therefore, directly comparable. With chemical states displayed in two dimensions, the
Auger parameter method becomes more powerful as a
uring The use of a normally insulating sample so Because occasional line interferences do occur, it is tool for identifying the chemical components than using
ady thin that it effectively does not insulate. This can sometimes necessary to use a line other than the most photoelectron chemical shifts alone. In the format
eady be assumed if the spectrum of the underlying con intense one in the spectrum. Chemical shifts of a minor adopted for this handbook, the kinetic energy of the
the ductor appears in good intensity and if line posi line are within 0.2 eV of the chemical shift of the Auger line is plotted against the binding energy of the
on or tions are not affected by changes in electron flux primary line. However, exceptional separations can photoelectron line, with the latter plotted in the -x direc
the from the charge neutralizer. occur in paramagnetic materials because of multiplet tion (kinetic energy is still, implicitly, +x). The kinetic
, can splitting. Separations of photoelectron lines can be deter energy of the Auger electron, referred to the Fermi level,
gun. (4) For the study of insulating polymer films, mined approximately from the line position tables in Ap is easily calculated by subtracting from the photon ener
'ential binding energies of the C functional groups may pendices G and H. gy the position of the Auger line on the binding energy
also be determined by applying a small amount of scale.
6
poly(dimethyl siloxane) solution (10- M) to the c. Auger Line Chemical Shifts and the Auger
~xtent sample surface and charge reference to the Si 2p Parameter. Core-type Auger lines (transitions ending With this arrangement, each diagonal line represent.;;
going of the silicone (at about 102.1 eV). with double vacancies below the valence levels) usually values of equal sums of Auger kinetic energy and
have at least one component that is narrow and intense,

(J) PHYSICAL ELECTRONICS


(J) PHYSICAL ELECTRONICS
23
E. Data Interpretation Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron St:

photoelectron binding energy. The Auger parameter, a, Table 4. General Guide to Paramagnetic Species
useful to accurately record the~
is defined as, and make comparisons with mod
Multiplet splitting and shake-up lines are generally expected in the paramag
netic states below:
a = KEA - KEp BEp BEA (2) (3) Auger Line Shape. Valence
Atomic No. Paramagnetic States Diamagnetic States tions form final-state ions w
or as the difference in binding energy between the 22 Ti(II) Ti(UI) Ti(IV) molecular orbitals. The distributit
photoelectron and Auger lines. This difference can be 23 VeIl), V(I1I), V(IV) V(V)
lines is strongly affected, theref(
accurately determined because static charge corrections 24 Cr(II), Cr(lll), Cr(IV), Cr(V) Cr(VI)
25 Mn(Il), Mn(lII), Mn(IV), Mn(V) Mn(VIJ) of the molecular orbitals in the t
cancel. With all kinetic and binding energies referenced states. Although little has yet t
26 Fc(II), Fe(III) K4Fe(CN)6, Fe(CO)4Br2
to the Fermi level, and recalling that: 27 Co(ll), Co(III) CoB, CO(N02)3NH3)3, this subject, the spectroscopist sh
K3CO(CN)6, Co(NH3)6CI3 the possible utility of Auger line ~
KE = hv - BE (3) 28 Ni(ll) K2Ni(CN)4,
square planar complexes
then... 29 Cu(lI) Cu(I) 4. Quantitative Analysis
42 Mo(IV), Mo(V) Mo(VI), MOS2. K4Mo(CN)8 For many XPS investigations, It IS
44 Ru(III). Ru(IV). Ru(V) Ru(ll) mine the relative concentrations c
KEA + BEp = hv + a (4)
47 Ag(II) Ag(l) stituents. Methods have been devel(
58 Ce(II1) Ce(IV)
or the sum of the kinetic energy of the Auger line and 59-70 Pr, Nd, Sm, Eu. Gd. Tb, Dy. the XPS measurement utilizing pI
the binding energy of the photoelectric line equals the Ho, Er, Tm, Yb compounds height sensitivity factors. The mel
Auger parameter plus the photon energy. A plot showing 74 W(IV), W(V) W(VI), W02, WCI4, peak area sensitivity factors typical
Auger kinetic energy versus photoelectron binding ener WC, K4W(CN)8 curate and is discussed below. This:
75 Re(II), Re(III), Re(JV), Re(VII), Re03 tory for quantitative work. For tran
gy then becomes independent of the photon energy. Rc(V), Re(VI)
76 Os(nn, Os(JV), Os(V) Os (II), Os(VI), Os(VIII) with prominent shake-up lines, it is
In general, polarizable materials, especially conductive 77 Ir(IV) entire 2p region when measuring peal
materials, have a high Auger parameter, while insulating 92 U(IIl), U(IV) U(VI)
compounds have a lower Auger parameter. For a sample that is homogeneOl
volume, the number of photoelectro
d. Chemical Information from Satellite Lines and specific spectra peak is given by:
Peak Shapes (2) Multiplet Splitting. On occasion, the multiplet
(1) Shake-up Lines. These satellite lines have in splitting phenomenon can also be helpful in iden I = nfcreyAAT
tenSIties and separations from the parent tifying chemical states. The 3s lines in the first
photoelectron line that are unique to each chemical series of transition metals, for example, exhibit where n is the number of atoms of tl
state (Figure 8, p. 19). Some Auger lines also ex separations characteristic of each paramagnetic of the sample, f is the x-ray flux in
hibit radical changes with chemical state that chemical state. The 3s line, however, is weak and is the photoelectric cross-section for tl
reflect these processes (Figure 9, p. 20). With tran therefore is not often useful analytically. The 2p interest in cm2, e is an angular effici
sition elements and rare earths, the absence of doublet separation is also affected by multiplet instrumental arrangement based on
shake-up satellites is usually characteristic of the splitting, and the lines are more intense. The effect the photon path and detected electron.
elemental or diamagnetic states. Prominent shake becomes very evident with Co compounds where in the photoelectric process f(
up patterns typically occur with paramagnetic the separation varies up to 1 eY. When first-row photoelectrons of the normal photoell
states. Table 4 is a guide to some expected transition metal compounds are under study, it is the mean free path of the photoelectI
paramagnetic states. A is the area of the sample from wt

24 cD PHYSICAL ELECTRONICS
cD PHYSICAL ELECTRONICS

'<_ _ _ _ _ _ __
:;~--::~::;]r:"''''

Handbook of X-ray Photoelectron Spectroscopy E. Data Interpretation


Handbook of X-ray Photoelectron Spectroscopy

useful to accurately record these line separations are detected, and T is the detection efficiency for
Table 4. General Guide to Paramagnetic Species
eter, a, and make comparisons with model compounds. electrons emitted from the sample. From Equation 5:
Multiplet splitting and shake-up lines are generally expected in the paramag
netic states below:
(3) Auger Line Shape. Valence-type Auger transi n = I/fcr8yAAT (6)
2) tions form final-state ions with vacancies in
Diamagnetic States
The denominator in Equation 6 can be defined as the
Atomic No.
Paramagnetic States
molecular orbitals. The distribution of the group of
Ti(lV)

een the 22
Ti(II) Ti(III)
lines is strongly affected, therefore, by the nature atomic sensitivity factor, S. If we consider a strong line
VeIl), V(III), V(lV)
V(V)

can be 23
Cr(Vl)
of the molecular orbitals in the different chemical from each of two elements, then:
24
Cr(II), Cr(III), Cr(lV), Cr(V)

rrections Mn(Il), Mn(III), Mn(IV), Mn(V)


Mn(VII)
states. Although little has yet been tabulated on
25
K4Fe(CN)6, Fe(CO)4Bf2
n] I]/S]
ferenced 26
Fe(II), Fe (III)
this subject, the spectroscopist should bear in mind (7)
CoB, CO(N02)3NH 3)3,
n2 h/S2
27
Co(H), Co(III)

K3CO(CN)6, Co(NH3)6 C13

the possible utility of Auger line shapes.


K2Ni(CN)4,
This expression may be used for all homogeneous
28 Ni(H)

(3) square planar complexes


4. Quantitative Analysis samples if the ratio S]/S 2 is matrix-independent for all
Cu(I)
For many XPS investigations, It IS Important to deter
29 Cu(H)
materials. It is certainly true that such quantities as cr
Mo(VI), MOS2, K4Mo(CN)s

42 Mo(lV), Mo(V)
mine the relative concentrations of the various con
Ru(III), Ru(lV), Ru(V)
Ru(II)
and A vary somewhat from material to material (espe
44 Ag(l)
stituents. Methods have been developed for quantifying cially A), but the ratio of each of the two quantities cr]/cr2
(4) 47 Ag(II)

Ce(lV)
the XPS measurement utilizing peak area and peak
58 Ce(III)
and A]/A2 remains nearly constant. Thus, for any
Pr, Nd, Sm, Eu, Gd, Tb, Dy,
height sensitivity factors. The method which utilizes spectrometer, it is possible to develop a set of relative
, line and 59-70
Ho, Er, Tm, Yb compounds
peak area sensitivity factors typically is the more ac values of S for all of the elements. Multiple sets of
:quals the W(Vl), W02, WC14,

74 W(lV), W(V)

WC, K4W(CN)s

curate and is discussed below. This approach is satisfac values may be necessary for instruments with multiple
t showing
Re(VIl), Re03
tory for quantitative work. For transition metal spectra x-ray sources at different angles relative to the analyzer.
ling ener 75 Re(Il), Re(III), Re(IV),

with prominent shake-up lines, it is best to include the


~rgy. Re(V), Re(VD

Os(II), Os(VI), Os(VIII)


entire 2p region when measuring peak area.
76 Os(III), Os(lV), Os(V)
A general expression for determining the atom fraction
lr(III)

:onductive 77 lr(IV)

U(VI)

of any constituent in a sample, Cx, can be written as an


92 U(III), U(lV) For a sample that is homogeneous in the analysis extension of Equation 7:
insulating
volume, the number of photoelectrons per second in a
specific spectra peak is given by: nx IxlSx
Cx (8)
:"ines and (2) Multiplet Splitting. On occasion, the multiplet Lni LI/Si
1= nfcr8yAAT (5)
splitting phenomenon can also be helpful in iden
lave in- tifying chemical states. The 3s lines in the first Values of S based on peak area measurements are indi
where n is the number of atoms of the element per cm3 cated in Appendices E and F. The values of S in the
parent series of transition metals, for example, exhibit
of the sample, f is the x-ray flux in photons/cm2 -sec, cr appendices are based on empirical data (C.D. Wagner et
:hemical separations characteristic of each paramagnetic
is the photoelectric cross-section for the atomic orbital of
also ex chemical state. The 3~ line, however, is weak and al. Surf. Interface Anal. 3, 211 (1981)) which have been
interest in cm2 , 8 is an angular efficiency factor for the corrected for the transmISSIOn function of the
ate that therefore is not often useful analytically. The 2p
instrumental arrangement based on the angle between spectrometer. The values in the appendix are only valid
Tith tran doublet separation is also affected by multiplet
the photon path and detected electron, y is the efficiency for and should only be applied when the electron energy
;ence of splitting, and the lines are more intense. The effect
in the photoelectric process for formation of analyzer used has the transmission characteristics of the
c of the becomes very evident with Co compounds where
photoelectrons of the normal photoelectron energy, A is SCA supplied by Physical Electronics. An example
It shake the separation varies up to 1 eY. When first-row
the mean free path of the photoelectrons in the sample, of the application of Equation 8 to analysis of a
magnetic transition metal compounds are under study, it is
A is the area of the sample from which photoelectrons
expected

G) PHYSICAL ELECTRONICS G) PHYSICAL ELECTRONICS 25


E. Data Interpretation Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spech

b. Transition metals, especially of the first series, have The presence or absence of an en
widely varying and low values of y, whereas y for the or envelope indicates whether the t:
F Is other elements is rather uniform at about 0.8 eV. Thus, a are in the bulk or at the surface. Bee
value of S determined on one chemical state for a transi from surface atoms do not traverse t
Atomic Concentration
tion metal may not be valid for another chemical state. from the surface atoms are syrnn
Theoretical Experimental
This effect can be minimized by including shake-up level baselines on both sides, and tl
C 33 33 peaks in the area measurement. peak is absent. For a homogeneous
F 67 67
from all elements win have similar
c. When peak interferences occur, alternative lines must structures.
sometimes be used. The ratios of spin doublets (except
4p) are rather uniform, and the weaker of the pair can (2) Elements whose spectra exhibit
often be substituted. The spectra of the elements should lines widely spaced in kinetic ener!
be consulted, but caution must be exercised because the proximately located by noting the int
F spectra of the elements themselves can be different from the lines. In the energy range above
the spectra of their compounds. 100 eV, electrons moving through
lower kinetic energy are attenuated .
C Is
d. Occasionally, an x-ray satellite from an intense than those with higher kinetic energ
photoelectron line interferes with measurement of a surface species, the low kinetic enerl
F weak component. A mathematical approach can then be will be relatively stronger than the
used to subtract the x-ray satellite before the measure energy component, compared to tha
1100 o ment. the pure material. The data for horne
Binding Energy (eV) solids can be compared with intens
For quantitative work, check the spectrometer operation
served on unknowns to determine qu
Figure 13. Quantitative analysis (~f poly(tetrafluoroethylene). frequently to ensure that analyzer response is constant
distribution of the element in the sar
and optimum. A useful test is the recording of the three
elements include Na and Mg (1s ane
sample of known composition, poly(tetrafluoroethylene), widely spaced spectral lines from Cu. Measurement of
Ge and As (2p312 and 3d); and Cd, II
is shown in Figure 13. the peak height in counts-per-second should be made on
I, Cs and Ba (3P312 and 4d or 3ds/2 anI
20-volt-wide scans of the 2P3/2, LMM Auger and 3p
The use of atomic senSItiVIty factors in the manner lines. Maintenance of such records makes it easy to When the element is a bulk homo
described will normally furnish semiquantitative results notice if an instrument change occurs that would affect beneath a thin contaminating layer
(within 10-20%), except in the following situations: quantitative analysis. teristic intensity ratio is modified in
direction. Thus, for a pair of lines fre
a. The technique cannot be applied rigorously to 5. Determining Element Location species, the low kinetic energy linl
heterogeneous samples. It can be useful with
tenuated more than the high kinetic
heterogeneous samples in measuring the relative number a. Depth. There are four methods of obtaining informa
distorting the characteristic intensity
of atoms detected, but one must be conscious that the tion on the depth of an element in the sample. The first
serving such intensity ratios and COl
microscopic character of the heterogeneous system in two methods described below utilize the characteristics
with the pure bulk elements, it i~
fluences the quantitative results. Moreover, an overlying of the spectrum itself but provide limited information.
deduce whether the observed lin
contamination' layer has the effect of diminishing the in The third provides more detailed information but is at
predominantly surface-, subsurface
tensity of high binding energy peaks more than that of tended by certain problems. The fourth utilizes measure
geneously distributed material.
low binding energy peaks. ments at two or more electron escape angles.

26 <D PHYSICAL ELECTRONICS


<D PHYSICAL ELECTRONICS

Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy E. Data Interpretation

b. Transition metals, especially of the first series, have The presence or absence of an energy loss peak (3) Depth profiling can be accomplished using
widely varying and low values of y, whereas y for the or envelope indicates whether the emitting atoms controlled erosion of the surface by ion sputtering.
other elements is rather uniform at about 0.8 eY. Thus, a are in the bulk or at the surface. Because electrons Table 5 lists some data on sputter rates as a
value of S determined on one chemical state for a transi from surface atoms do not traverse the bulk, peaks general guide. One can use this technique on or
tion metal may not be valid for another chemical state. from the surface atoms are symmetrical above ganic materials, but few data are available for
This effect can be minimized by including shake-up level baselines on both sides, and the energy loss calibration. Chemical states are often changed by
tal
peaks in the area measurement. peak is absent. For a homogeneous sample, peaks the sputter technique, but useful information on
from all elements will have similar inelastic loss elemental distribution can still be obtained.
c. When peak interferences occur, alternative lines must structures.
sometimes be used. The ratios of spin doublets (except Table 5. Relative Sputter Rates at 4 k V.
4p) are rather uniform, and the weaker of the pair can (2) Elements whose spectra exhibit photoelectron
Target Sputter Rate
often be substituted. The spectra of the elements should lines widely spaced in kinetic energy can be ap
be consulted, but caution must be exercised because the proximately located by noting the intensity ratio of Ta20s 1.00
spectra of the elements themselves can be different from the lines. In the energy range above approximately Si 0.90
100 eV, electrons moving through a solid with Si02 0.85
the spectra of their compounds.
lower kinetic energy are attenuated more strongly Pt 2.20
Cr 1.40
d. Occasionally, an x-ray satellite from an intense than those with higher kinetic energy. Thus, for a Al 0.95
photoelectron line interferes with measurement of a surface species, the low kinetic energy component Au 4.lO
weak component. A mathematical approach can then be will be relatively stronger than the high kinetic
F
used to subtract the x-ray satellite before the measure energy component, compared to that observed in Another useful method of controlled erosion, espe
ment. the pure material. The data for homogeneous bulk cially of organic materials, is reaction with oxygen
o
solids can be compared with intensity ratios ob atoms from a plasma. This technique may also
For quantitative work, check the spectrometer operation served on unknowns to determine qualitatively the change the chemical states in the affected surface.
frequently to ensure that analyzer response is constant distribution of the element in the sample. Suitable Further, because the elements differ in their rates
and optimum. A useful test is the recording of the three elements include Na and Mg (Is and 2s); Zn, Ga, of reaction with oxygen atoms, the rate of removal
lene), widely spaced spectral lines from Cu. Measurement of Ge and As (2p3/2 and 3d); and Cd, In, Sn, Sb, Te, of surface materials will be sample dependent.
the peak height in counts-per-second should be made on I, Cs and Ba (3p312 and 4d or 3ds12 and 4d).
20-volt-wide scans of the 2P312, LMM Auger and 3p (4) In XPS studies, the sample-mounting angle is
anner lines. Maintenance of such records makes it easy to When the element is in a bulk homogeneous layer not usually critical, though it does have some ef
results notice if an instrument change occurs that would affect beneath a thin contaminating layer, the charac fect on the spectra. Very shallow electron take-off
quantitative analysis. teristic intensity ratio is modified in the opposite angles accentuate the spectrum of any component
direction. Thus, for a pair of lines from subsurface segregated on the surface, whereas a sample
sly to 5. Determining Element Location species, the low kinetic energy line will be at mounted at an angle normal to the analyzer axis
with tenuated more than the high kinetic energy line, minimizes the contribution from such a com
umber a. Depth. There are four methods of obtaining informa distorting the characteristic intensity ratio. By ob ponent. This effect can be used to estimate the
at the tion on the depth of an element in the sample. The first serving such intensity ratios and comparing them depth of layers on or in the surface. This effect is
em in two methods described below utilize the characteristics with the pure bulk elements, it is possible to not limited to flat surfaces, because angular de
erlying of the spectrum itself but provide limited information. deduce whether the observed lines are from pendence is even observed with powders, though
the in The third provides more detailed information but is at predominantly surface-, subsurface- or homo the effects are muted. The spectrometer used to
that of tended by certain problems. The fourth utilizes measure geneously distributed material. obtain the spectra presented in this handbook in
ments at two or more electron escape angles.

(I) PHYSICAL ELECTRONICS


(I) PHYSICAL ELECTRONICS
27

E. Data Interpretation Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectrosc,

tegrates the signal over only a narrow range of


take-off angles. Si 2p
F. How to Use this
It is possible to change the angle between the
plane of the sample surface and the angle of 1. Qualitative Analysis
entrance to the analyzer. At 90 with respect to the Elemental and chemical identification of
surface plane, the signal from the bulk is maxi stituents can be performed by combining tl
mized relative to that from the surface layer. At Grazing in the survey spectra with the binding en
small angles, the signal from the surface becomes Appendices G, Hand J.
greatly enhanced, relative to that from the bulk.
The location of an element can thus be deduced by a. Identify all major photoelectron peaks
noting how the magnitude of its spectral peaks line position tables in Appendix J.
changes with sample orientation in relation to
those from other clements. The analysis depth may b. Compare the elemental identificati(
be estimated by d = Asine, where d is the analysis elemental survey spectra to see that line
depth of the overlayer, A is the inelastic mean free relative intensities are consistent. Also not
path, and e is the take-off angle of the analyzed the Auger electron peaks.
110 96
electrons. Binding Energy (eV) c. Review Section E (pp. 16-28) to ac<
Physical Electronics SCAs permit angle-dependent Figure 14. An example of the enhanced surface sensitivity achieved by vary
structures such as energy loss lines, sh
studies by simply varying the angle of the sample ing the electron take-off angle. A thin oxide on silicon is enhanced at the low satellite lines, etc., not identified in the hal
surface with respect to the input lens of the take-off angle. or energy tables.
analyzer. The magnification of the lens determines
the half-angle acceptance of the analyzer. An ex d. Identify any remaining peaks assumin
c. Insulating Domains on a Conductor. The occur tense photoelectron or Auger lines using
ample of the information that can be gained rence of steady-state charging of an insulator during
through the use of this capability is shown in Fig orR.
analysis sometimes has useful consequences. Micro
ure 14. Data were obtained at normal (near 90) scopic insulating domains on a conductor reach their e. Chemical state identification can be de
and grazing (near 15) take-off angles from a own steady-state charge, while the conductor remains at high resolution spectra of the strongest
silicon sample with a thin silicon oxide overlayer. spectrometer potential. Thus, an element in the same and sharpest Auger lines.
The observed intensity ratio of oxidized to elemen chemical state in both phases will exhibit two peaks. If a
tal Si is much greater at the low take-off angle. change is made in the supply of low-energy electrons (1) Correct binding energies for static
which stabilize the charge (as from the neutralizer fila insulators. When applicable, charge n
b. Surface Distribution. Many XPS systems have the
ment) or if a bias is applied to the conductor, the binding energy scale to the CIs p
capability to obtain data from areas as small as 30 !lm in
spectral peaks from the insulating phase will move rela peak at 284.8 eY.
diameter using lens defined areas. Alternately, analysis
tive to those from the conducting phase. For such
areas of < 10 !lm can be achieved with a scanning (2) Determine the chemical state
heterogeneous systems, this can be an extremely useful
focused photo beam. These relatively high lateral resolu measured shifts in the photoelectron b
technique. It makes it possible to determine whether the
tions allow for the acquisition of XPS maps which show
elements that contribute to the overall spectrum are in
both elemental and chemical state information.
the conducting phase, the insulating phase or both.

28 (]) PHYSICAL ELECTRONICS


(]) PHYSICAL ELECTRONICS

-
Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy F. How to Use this Handbook

;: of
2p
F. How to Use this Handbook
the
1. Qualitative Analysis gies by comparing the binding energy to the charts
~ of
Elemental and chemical identification of sample con
with the standard spectra and with the tabulated
) the
stituents can be perlormed by combining the information
data in Appendix B.
laxi
" At in the survey spectra with the binding energy tables of

Appendices G, Hand J.
(3) As suggested above, much about the chemical
)mes
state can be learned from the magnitude and posi
)ulk.
a. Identify all major photoelectron peaks by using the
tion of shake-up lines as well as from the energy
d by
line position tables in Appendix J.
and shape of valence Auger lines,
,eaks
n to
b. Compare the elemental identifications with the
For the elements F, Na, AI, Si, S, Cu, Zn, As,
may elemental survey spectra to see that line positions and
Se, Ag, Cd, In, Sn and Te, the Auger parameter
lysis relative intensities are consistent. Also note the positions
tables in Appendix A may prove useful. The Auger
free of the Auger electron peaks.
line positions may be converted to kinetic energy
yzed by subtracting from the photon energy (AI =
110
Binding Energy (eV) c. Review Section E (pp. 16-28) to account for fine
1486.6 eV, Mg = 1253.6 eV). Note the location of
structures such as energy loss lines, shake-up peaks,
the points for Auger kinetic energy and
ldent Figure 14. An example of the enhanced suiface sensitivity achieved by vary
ing the electron take-off angle. A thin oxide on silicon is enhanced at the low satellite lines, etc., not identified in the handbook spectra
photoelectron binding energy on the respective
mple
take-off angle. or energy tables.
elemental plot. Proximity of the experimental
, the
points to those of recorded chemical states should
nines d. Identify any remaining peaks assuming they are in
be considered probable identification. Note that
1 ex c. Insulating Domains on a Conductor. The occur tense photoelectron or Auger lines using Appendices G
experimental error is much greater along the Auger
lined rence of steady-state charging of an insulator during or H.
parameter grid than normal to the grid lines.
Fig- analysis sometimes has useful consequences, Micro
90) scopic insulating domains on a conductor reach their e. Chemical state identification can be determined from

)m a own steady-state charge, while the conductor remains at high resolution spectra of the strongest photoelectron
2. Quantification
layer. spectrometer potential, Thus, an element in the same and sharpest Auger lines,
The atomic sensitivity factors presented in Appendices E
men- chemical state in both phases will exhibit two peaks. If a
... change is made in the supply of low-energy electrons Correct binding energies for static charging of
and F are applicable to the Physical Electronics Model
SCA and the Omni Focus TIl lens. A
which stabilize the charge (as from the neutralizer fila insulators. When applicable, charge reference the expression to determine the atomic concentration of any
lave the ment) or if a bias is applied to the conductor, the binding energy scale to the CIs photoelectron element is given by Equation 8 (p. 25). However, the
,0 !lm in peak at 284.8 eY.
spectral peaks from the insulating phase will move rela accuracy is limited by the assumptions made in Section
analysis tive to those from the conducting phase. For such EA. (p. 25).
icanning heterogeneous systems, this can be an extremely useful (2) Determine the chemical state from the
1 resolu technique. It makes it possible to determine whether the measured shifts in the photoelectron binding ener
ch show elements that contribute to the overall spectrum are in
the conducting phase, the insulating phase or both.

<D PHYSICAL ELECTRONICS


<D PHYSICAL ELECTRONICS
29

Standard Spectra of the Elements

This section of the handbook contains survey spectra 81 elements, high resolution spectra of the most useful photoelectron lines, a chart of binding
energies for each of the obse rved photoelectron and major Auger electron peaks, and a photoelectron chemical state binding energy chart for each
the elements. Used in combination with the appendices, the survey spectra aid in elemental identification, while the high-resolution spectra and binding
energy data aid in the identification of chemical states.

Survey Spectra
The survey data include all of the lines which are nonnally usefuL For elements are only designated by the elemental symbol, and x-ray
most elements, the survey data were acquired with both a satellites and energy loss lines are not noted. For many elements, the
monochromatic AI x-ray source and a nonmonochromatic Mg x-ray Auger peaks are presented in expanded fonn.
source. When survey spectra for two compounds are presented, the
monochromatic source is used for both. The photon source for each The ordinate is left undesignated, but the general contours and inten
survey is noted on the survey. The photoelectron and Auger lines for sity ratios of the spectra are typical of measurements made using a
the element of interest are identified. Lines which occur due to other Physical Electronics Model 10-360 SCA with an Omni Focus lens.

High-Resolution Spectra
The high-resolution spectra of the most useful photoelectron peaks are The spectra of the inert gas atoms implanted in graphite or silicon
presented. Unless otherwise noted, the high-resolution data were ac deserve special mention. The high-resolution data often show an
using the same photon source as the survey on the same page. asymmetric peak shape or a second resolvable peak when a single
The binding energy of the main line is noted and when appropriate, the symmetric peak is expected. The intensity of the second, high binding
spin orbit separation (~) is given. The lines from insulators were energy peak is dependent on the implantation energy and is
charge-corrected to adventitious hydrocarbon at 284.8 e V. diminished at lower energies. The spectra are of inert gas atoms im
planted at 4 kV.

Photoelectron and Auger Electron Line Position Tables

The photoelectron and Auger line position tables ref1ect the energies reduced species, the measured values may differ by a few electron volts.
of the elemental peaks observed in this handbook. For oxidized or

Chemical State Binding Energy Tables


The binding energy tables have been constructed to ref1ect the general Abbreviations in the chemical state database are as follows: acac =
changes in binding energy with change in oxidation state or chemical acetyl acetonate; metallocene metal (CjHjh; Bu butyl; Et = ethyl;
environment. A more extensive listing with specific binding energy Me = methyl; Ph =phenyl; OAc = acetate.
values for more than 1500 compounds is presented in Appendix B.

tJ) PHYSICAL ELECTRONICS


33

Carbon C Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectrosco


Atomic Number 6

Is

C as graphite

Monochromated Al Ka
C as graphite

MgKa

1250 1200

Binding Energy (eV)

KVV

------\
1400 1200 1000 800 600 400 200 o 1200 1000 8(
Binding Energy (e V)

Line Positions (eV) 1s Binding Energy (eV)


Is 284.5 eV 280 282 284 286 288
Carbide
Photoelectron Lines Carbon
C with N
Is C with S
285 C with 0
Alcohols
Ethers
Ketones! Aldehydes
Auger Lines Carboxyls
Carbonates

KVV C with Cl
1223 (Al) C with F
990 (Mg) CHF
CFz
CF3
295 285 275
Energy (eV)

40 tJ) PHYSICAL ELECTRONICS tJ) PHYSICAL ELECTRONICS


Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy Carbon C
Atomic Number 6

Is

C as graphite Is
MgKa KVV

1200
Binding (eV) 1020 970
Binding Energy (eV)

800 600 400 200 o 1200 1000 800 600 400 200 o
Binding Energy (eV) Binding Energy (eV)

Line Positions (eV) 1s Binding Energy (e V)


Compound Type 280 282 284 286 288 290 292 294 Is
Carbide
Photoelectron Lines

Is

Carbon
C with N
C with S
l.j. .
285
C with 0

~.,.
Alcohols
Ethers
Ketones! Aldehydes
Auger Lines Carboxy Is
Carbonates

-.
KVV
C with CI
1223 (AI)
C with F
ClIF
990
CFz
CF3
275 295 285 275
Binding Energy (eV)

G) PHYSICAL ELECTRONICS G) PHYSICAL ELECTRONICS 41


Handbook of X-ray Photoelectron S]
Oxygen o Handbook of X-ray Photoelectron Spectroscopy
Atomic Number 8

o in A1203 (sapphire) Is
Monochromated Al Ka
o in Ah03 (sapphir
MgKa

1030 990 950


Binding Energy (eV)

KLL Al
Al

Ar

1400 1200 1000 800 600 400 200 o 1200 1000

Binding Energy (eV)

Line Positions (eV) Is Binding Energ.


Is = 531.0 eV 528 529 530
Metal Oxides
Photoelectron Lines Fe203
Si02
Is 2s
Hydroxides
531 23
Phosphates
Nitrates
Auger Lines
Sulfates
KLJLJ KLIL23 KL23L23 Carbonates
1013 999 978 (AI) Chlorates
780 766 745 (Mg)
Ah03
Silicones
545 535 525
Binding Energy (eV)

44 (l) PHYSICAL ELECTRONICS (l) PHYSICAL ELECTRONICS


Handbook of X ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy
Oxygen o
Atomic Number 8

Is Is
o in Ah03 (sapphire)
KLL
MgKa

KLL
790 720
Binding Energy (eV)

950
gy (eV)

Al Al Al
Al
Ar
Ar

800 600 200 o 1200 1000 800 600 400 200 a


Binding Energy (eV) Binding Energy (eV)

Line Positions (e V) 1s Binding Energy (eV)


532 533 534
Is 531.0 eV

Photoeleetron Lines
Si02
Is 2s
Hydroxides
531 23
Phosphates
Nitrates
Auger Lines
Sulfates
KLILI KL\L23 KL23L23 Carbonates
1OI3 999 978 (AI) Chi orate s
780 766 745 (Mg) Ab03

525
Silieones
545 535
Binding Energy (eV)
525

<D PHYSICAL ELECTRDNICS


<D PHYSICAL ELECTRDNICS
45
Magnesium Mg Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photo(
Atomic Number 12

Is
Monochromated Al Ka
KLL KLL
MgKa

390 340 290


(eV)

2s
2p

1400 1200 1000 800 600 400 200 o 1200 1


Binding Energy (eV)

Line Positions (eV) 2p Bindi


2p = 49.8 eV 2p Comoound Type 48

Photoelectron Lines
Mg
Is 2s 2p Mg2Cu
1303 89 50
Mg3Bh
MgF2
Mg(OHh
Auger Lines
MgAb04
KL1Ll KLIL23 KL23 L23
381 347 301 (AI)
148 114 68 (Mg)
60 50 40
Binding Energy (eV)

52 tl) PHYSICAL ELECTRONICS (I) PHYSICAL ELECTR


Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy
\
Silicon Si

KLL KLL MgKa


KLL

Plasmon from 2p

~JI
340 290
Binding Energy (eV) 85 70 55
Binding Energy (eV)

Ar

Ar

2s
2p

800 600 400 200 o 1200 1000 800 600 400 200 o
Binding Energy (eV) Binding Energy (eV)

Line Positions (e V) 2p Binding Energy (eV)


48 49 50 51
2p = 49.8 eV 2p

Photoelectron Lines

Is
1303
I
is
89
2p
50
Mg
Mg2CU
Mg3B h
MgF2
- -
40
Auger Lines

KLILI
381
148
KLIL23
347
114
KL23L23
301
68
(AI)
(Mg)
Mg(OH)2
MgAh04

-
60 50 40
Binding Energy (eV)

G) PHYSICAL ELECTRONICS G) PHYSICAL ELECTRONICS 53


Handbook of X-ray Photoelectron Spectroscopy HandboOk of X-ray Photoelectron Spectroscopy
Magnesium Mg

Atomic Number 12

2s

KLL KLL MgKa


KLL

Plasmon from 2p
KLL

2p

340 290

Binding Energy (eV)


85 70 55

Binding Energy (eV)

Ar

2s
2p

800 600 400 200 o


1200 1000 800 600 400 200 o

Binding Energy (eV)


Binding Energy (eV)

Line Positions (eV)


- 4g
2p Binding Energy (eV)
49 50 51 2p = 49.8 eV
2p

Photoelectron Lines

I
Mg 1 1 .1
1 I

-
Is 2s 2p Mg2CU

1303 g9 50
Mg3Bh
MgF2
Mg(OH)2

Auger Lines

KL1LI KL1L23 KL23L23


I MgAb04
1
381 347 301 (AI)

40
148 114 68 (Mg)

- 60 50
Energy (eV)
40

G) PHYSICAL ELECTRONICS G) PHYSICAL ELECTRONICS 53


Aluminum Al Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy
Atomic Number 13

LMM
2s MgKa
Monochromated Ai Ka

2p

~-, :.~
........
4\
illAr

.~

1400 1200 1000 800 600 400 200 0 1200 1000 800
Binding Energy (eV) Bi1

Line Positions (e V) 2p Binding Energy (eV)


2p
2p = 72.9 eV 72 73 74 75 76
Al
Photoelectron Lines
AlAs
2s AIGaAs
118 73
Halides
Auger Lines Alb

L23 M IM23
1419
1186
(AI)
(Mg)
Oxides
Ah03, sapphire
Ah03, alpha

Ah03, gamma
. --.---'- '-- - ..
AIOOH, boehmite
85 75
65
Binding Energy (eV)

54 cD PHYSICAL ELECTRDNICS cD PHYSICAL ELECTRDNICS


Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy
Aluminum Al
Atomic Number 13

LMM
2s Mg Ka

2p

2s
2p

800 600 400 200 o 1200 1000 800 600 400 200 o
Binding Energy (eV) Binding Energy (eV)

Line Positions (e V) 2p Binding Energy (eV)


/ Al in AI203 (sapphire)
72 73 ,/ 74 75 76 77

-
Monochromated Al Ka
Photoelectron Lines
Al
AlAs
AIGaAs
2p = 74.4 eV

I
2s 2p
118 73 I LiAIH4
Halides
Auger Lines AIF3


I-
Oxides
L23M1M23 Ah03, sapphire
1419 (AI)
Aha), alpha
1186 (Mg)
Ah03, gamma
65 I AIOOH, boehmite
85 75 65
Binding Energy (eV)

(J) PHYSICAL ELECTRONICS (J) PHYSICAL ELECTRONICS 55


Scandium Sc Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy
Atomic Number 21

2P3/2
LMM
Monochromated AI Ku
LMM MgKu

2P1l2

1170 1100
Binding Energy (eV)
LMM

3p
3s
Ar

940 Binding Ell(

1400 1200 1000 800 600 400 200 o 1200 1000 800
Binding Energy (eV)

Line Positions (eV) 2P312 Binding Energy (e V)


2P3/2 = 398.6 eV 2P3/2
A = 4.87 eV Compound Type 398 399 400 401 4C

Photoelectron Lines

..,
Sc
2s 2P1l2 2P3/2 3s 3p ScN
499 404 399 51 29 SC203

C1Sc(C5H5)2
Auger Lines Sc(C5H5)(CgHg)

LM23M23 L3M23M45 (lp)


1149 1118 (AI)
916 885 (Mg)

410 400 390


Binding Energy (eV)

70 (D PHYSICAL ELECTRONICS (D PHYSICAL ELECTRONICS


Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy Scandium Sc
Atomic Number 21

2P3/2 2P312
LMM
LMM MgKa
2P1l2
2PlI2

1100
Binding Energy (eV)

3p 3p
3s 3s
Ar

940 Binding Energy (eV) 870

800 600 200 o 1200 1000 800 600 400 200 o


Binding Energy (eV) Binding Energy (eV)

Line Positions (eV) 2P312 Binding Energy (eV) Sc in SC203


2P312
398 399 400 401 402 Monochromatcd Al Ka

Photoelectron 2P3/2 401.8 eV


Se A=4.4eV
2s 2Pll2 2P3/2 3s 3p SeN
499 404 399 51 29 SC203
ClSc(CsHsh
Auger Lines Se(C5Hs)(CsHg)

LM23 M 23 L3M 23M45


1149 1118
916 885 (Mg)
J
390 410 400 390
Binding Energy (eV)

(J) PHYSICAL ELECTRONICS <D PHYSICAL ELECTRONICS 71


Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy
Titanium Ti
Atomic Number 22

2P312
Monochromated AI Ka
MgKa

LMM

2plI2

1080 1065 1050


Binding Energy (eV)
2&
LMM

3p

3s
Ar Ar

1400 1200 1000 800 600 400 200 o 1200 1000 800
Binding Energy (eV)

I~I Line Positions (eV) 2P3/2 Binding Energy (eV)


2P3/2 = 454.1 eV 2P3n 455 456 457 458
A = 6.17 eV

Photoelectron Lines

2&
561
2plI2
460
2P3/2
454
3s
59
3p
33
TiB2
TiN
TiC14

TiO
Ti02
Auger Lines BaTi03 (cubic,
CaTi03
1
LM23M23 L3M 23M45 ( P) PbTi03
1098 1068 (Al)
SrTi03
865 835 (Mg)
Metallocene
470 460 450
Binding Energy (eV)

72 <D PHYSICAL ELECTRONICS <D PHYSICAL ELECTRONICS


Handbook of X-ray Photoelectron Spectroscopy Handbook of X-ray Photoelectron Spectroscopy Titanium Ti
Atomic Number 22

2P312
2P3/2
MgKa

LMM LMM

2pll2

1050 2s
y (eV)
2s

3p 3p
3s 3s
Ar Ar
Ar Ar

800 600 400 200 o 1200 1000 800 600 400 200 o
Binding Energy (eV) Binding Energy (e V)

Line Positions (e V) 2P312 Binding Energy (eV)


Ti in Ti02
453 454 455 456 457 458 459 460 Monochromated AI Ka

Photoelectron Lines
I
TiB2
TiN 2P312 = 458.8 eV
A = 5.54 eV
2s
561
2p 1/2
460
2P3/2
454
3s
59
3p
33
TiCl4
TiO
Ti02

Auger Lines BaTi03 (cubic, tetra.
CaTi03
LM23M23 L3 M23M45 PbTi03
1098 lO68 (AI) SrTi03
865 835 (Mg)
Metallocene
450 470 460 450
Binding Energy (eV)

<D PHYSICAL ELECTRONICS <D PHYSICAL ELECTRONICS 73


Handbook of X-ray Photoelectron ~nll...t .......,....~-:.: I1andbook of X-ray Photoelectron
Strontium Sr
Atomic Number 38

3d
Monochromated Al Ka
MgKa
3pl/2
3P312

3s

1400 1200 1000 800 600 400 200 o 1200 1000


Binding Energy (e V)

Line Positions (eV)


3dsf2 Binding E
3dsf2 = 134.3 eV
3dSf2 133 1~
Ll = 1.79 eV

3d312 Photoelectron Lines


Sr
SrO
3s
360
3Plf2
281
3P312
270
3d3f2
136
3dsf2
134
4s
39
4p
21
SrF2
SrC03
SrS04 -
150 140 130
Sr(N03h
SrMo04
SrRh204 -
Binding Energy (eV)

104 G) PHYSICAL ELECTRONICS G) PHYSICAL ELECTRON/l


Handbook of X-ray Photoelectron Spectrosenn Handbook of X-ray Photoelectron Spectroscopy Strontium Sr
Atomic Number 38

3d
3d
MgKa 3p1I2 3P312
3p1l2 II 3p312

38

3s

4p
4p

48 4s

800 600 400 200 o 1200 1000 800 600 400 200 o
Binding Energy (eV) Binding Energy (eV)

Line Positions (eV) 3d512 Binding Energy (e V)


133 134 135 136 3ds12 = 134.3 eV

- -
~ = 1.79 eV

Sr
Photoelectron Lines
SrO
3s
360
3p1I2
281
3P312
270
3d312
136
3ds12
134
4s
39
4p

21

SrF2
SrC03
SrS04 - -
130
Sr(N03h
SrMo04
SrRh204
- ISO 140 130
Binding Energy (eV)

(I) PHYSICAL ELECTRONICS (I) PHYSICAL ELECTRONICS 105


Yttrium Y Handbook of X-ray Photoelectron Spectroscnnl Handbook of X-ray Photoelectron Sp~
Atomic Number 39

3ds12
Monochrornated Al Ka
MNV MgKa
3d312
3P312

3P1l2

1375 1360 1345


(eV) 1140

3s
MNN

Ar
4p

4s

1400 1200 1000 800 600 400 200 o 1200 1000


Binding Energy (eV)

Line Positions (eV) 3d s12 Binding Ener!


156.0 eV 'onmrmnri Type 155
3ds12

-
2.05 eV
Photoelectron Lines
y

3s 3pll2 3P3/2 3d312 3ds12 4s Y203


394 311 299 158 156 45 24

Auger Lines

M4SN23 V
1356 (AI)
1123 (Mg)

170 160 150


Energy (eV)

106 <D PHYSICAL ELECTRONICS <D PHYSICAL ELECTRONICS


Handbook of X-ray Photoelectron Spectrosenl Handbook of X-ray Photoelectron Spectroscopy Yttrium Y
Atomic Number 39

3ds12
MNV 3ds12
MgKa
3d312 3d3/2

3P3/2

3p1l2

1360 1345 3s
Binding Energy (eV)
1140 1125
1110
Binding Energy (eV)

38

Ar
4p

48

800 600 200 o 1200 1000 800 600 400 200 o


Binding Energy (eV) Binding Energy (eV)

Line Positions (eV) 3ds12 Binding Energy (eV)

Compound Type 155 156 157

= 156.0 eV
2.05 eV
Photoelectron Lines
y
3s 3P1l2 3P3/2 3ds12 4s 4p Y203
394 311 299 158 156 45 24

Auger Lines

M45 N 23 V
1356 (AI)
1123 (Mg)

150 170 160 150


Binding Energy (eV)

cD PHYSICAL ELECTRDNICS cD PHYSICAL ELECTRDNICS 107


Handbook of X-ray Photoelectron Spectroscm lIandbook of X-ray Photoelectron Spectroscopy
Barium Ba
Atomic Number 56

3ds/2
Monochromated Al Ka MNN
MgKa
3d312
3d312

930 860
MNN Energy (eV)
3P3/2

4d

4p

5p
5s

1400 1200 1000 800 600 400 200 o 1200


1000 800
Binding Energy (eV)

Line Positions (eV) 3d512 Binding Energy (eV)


3ds12 = 780.6 eV 3ds12
778 779 780
~ = 15.33 eV
3d312 Photoelectron Lines
Ba
3s 3Pll2 3P312 3d312 3ds12 BaS
1292 1138 1064 796 781 BaO

4s 5s 5p Ba(N03h
4Pll2 4P3/2 4d3/2 4ds12
254 193 179 93 90 31 15 BaC03
BaS04
Auger Lines
BaCr04

820 795
Binding Energy (cV)

770
MsN4S N45
900
667
M4 N45 N45
886
653
(AI)
(Mg)

BaM004
BaRh204
-
138 <D PHYSICAL ELECTRONICS <D PHYSICAL ELECTRONICS
Handbook of X-ray Photoelectron ~pectroscon" Handbook of X-ray Photoelectron Spectroscopy Barium Ba
Atomic Number 56

3dS!2
MNN 3dS!2
MgKa MNN
3d3!2 3d3!2

930 860
-l Binding Energy (eV) 700 630
Binding Energy (eV)

MNN

4d

4d
4p

5PI 5s 5p
5s

800 600 400 200 o 1200 1000 800 600 400 200 o
Binding Energy (eV) Binding Energy (e V)

Line Positions (e V) 3dS!2 Binding Energy (e V)


778 779 780 781
3dS!2 = 780.6 eV 3dS!2
~ = 15.33 eV
Photoelectron Lines

3s
1292

4s
3P1I2
1138

4P1l2
3P3!2
1064

4P3!2
1
3d3/2
796

4d3!2
3ds!2
781

4ds!2 5s 5p
I Ba
BaS
BaO
Ba(N03h
-
254 193 179 93 90 31 15 BaC03
Auger Lines BaS04
BaCr04

-
MsN4S N 4S M4 N 4S N 4S BaMOO4
900 886 (AI) BaRh204
770 667 653 (Mg) 820 795 770
Binding Energy (eV)

(f) PHYSICAL ELECTRONICS (f) PHYSICAL ELECTRONICS 139


Handbook of X-ray Photoelectron Spectro.~mI lIandbook of X-ray Photoelectron Spectrosc(
Lanthanum La
Atomic Number 57

3ds/2
Monochromated Al Ku
MgKu
3d312
3d312

MNN

4d

MNN 4p
4s
5p
5s

1400 1200 1000 800 600 400 200 o 1200 1000


Binding Energy (eV)

3ds12 = 835.8 eV Line Positions (e V) 3ds/2 Binding Energy (eV:


d = 16.78 eV 3ds/2 833 834 835 836

Photoelectron Lines

I
La
3p1l2 3P3/2 3d3!2 3ds/2 LaH2
1208 1128 853 836
La203
4s 4p1l2 4P312 4d312 4ds12 5s 5p
275 213 197 106 103 34 17
Auger Lines

MsN4S N4S M4N4SN4S


867 854 (AI)
870 845 820 634 621 (Mg)
Binding Energy (eV)

140 (J) PHYSICAL ELECTRONICS (J) PHYSICAL ELECTRONICS


Handbook of X-ray Photoelectron ~pectroSl'nd Handbook of X-ray Photoelectron Spectroscopy Lanthanum La
Atomic Number 57

3d512
3d512
1312
MgKu
3d312

MNN
il
il
Iii.;
'I

Ilii
lli
4d I
;'i
!,I
4d ,I
1
MNN 4p
4p
4s 4s

5p

5s J

800 600 400 200 o 1200 1000 800 600 400 200 o
Binding Energy (eV) Binding Energy (e V)

Line Positions (e V) 3d512 Binding Energy (eV) 3d512 = 835.8 eV


Type 833 834 835 836 837 838 839 ~ = 16.78 eV 3d512

Photoelectron Lines 3d312


La
3pll2 3P312 3d312 3d512
LaH2
1208 1128 853 836

La203
4s 4pll2 4P312 4d312 4d512 5s
5p
275 213 197 106 103 34
17
Auger Lines

-
M5 N45 N45 M4 N45 N45

867 854 (AI)

820 634 621 (Mg)


I 870 845 820
I

l
"

Binding Energy (eV)

IIII1
II
1 "1",1

il,!I:
Iii
<D PHYSICAL ELECTRONICS <D PHYSICAL ELECTRONICS
1

141 I I
Handbook of X-ray Photoelectron SpectroSl'n11 IIandbook of X-ray Photoelectron Spectroscopy
Dysprosium Dy
Atomic Number 66

3d3/2

Monochromated Al Ku
MgKu

3ds12

MNN

4f

5s 5p
-_.
1400 1200 1000 800 600 400 200 o 1200 1000 800
Binding Energy (eV)

Line Positions (e V) Binding Energy (eV)


4d = 152.4 eV Compound 152 156 160 164 168
Photoelectron Lines

4d 3d3/2 3ds12 Dy
1333 1296
DY20 3
4s 4pll2 4P312 4d 5s 5p 4f
417 337 297 152 48 23 8
3ds12 Binding Energy (eV)
Auger Lines Type 1287 1289 1291 1293 129

M4S N 45 N 45 M4SN45V
526 368 (AI) Dy
DY203
200 170 140
Binding Energy (eV)

156 (I) PHYSICAL ELECTRONICS (I) PHYSICAL ELECTRONICS


Handbook of X-ray Photoelectron ~Dectrn!IIN J{andbook of X-ray Photoelectron Spectroscopy Dysprosium Dy
Atomic Number 66

4d
4p3/2

MgKa

MNN

4f

5p

4f

800 600 400 200 o


Binding Energy (eV)
1200 1000 800 600 400 200 o
Binding Energy (eV)

-----------------

Line Positions (eV) 4d Binding Energy (eV)


Photoelectron Lines Compound Type 152 156 160 164 168 = 152.4 eV
4d 3d3/2 3ds/2
1333 1296 Dy [II
45
DY203 I
4P1l2 4P3/2 4d 5s 5p 4f
417 337 297 152 48 23 8
3ds12 Binding Energy (eV)
Auger Lines
Compound Type 1287 1289 1291 1293 1295
M4Sf'

140
526 368 Dy
DY203
.,. 200 170
Binding Energy (eV)
140

Cl) PHYSICAL ELECTRDNICS Cl) PHYSICAL ELECTRDNICS 157


Appendix A. Auger Parameters Handbook of X-ray Photoelectro

The following tables plot the binding energy of the most intense photoelectron line versus the kinetic energy of the most intense Auger transition. The Auger
parameter plots are useful for further separation of the chemical states.

1344
662 1342
Fluorine Sodium

Compound F Is FKLL
Binding Energy (eVJ Kinetic Energy (eV) Compound Na Is
660 1340 Binding Energy (cV)
AgF 682.7 659.3
PbF2 683.6 658.5 Na2Se03 1070.8
BaF2 683.7 656.2 Na2C204 1070.8
K3 FeF6 684.0 656.0 1070.9
NaF 684.5 655.0 N aAs02 1070.9
CdF2 684.5 656.0 658 i------+'-----t--~t 1338 NaF 1071.0
CUF2 684.5 657.0 Na2 Cr04 1071.0
CUF2 684.5 656.2 Na3P04 1071.1
I
CUF2 684.5 656.2 II NaH2P02 1071.1
684.5 658.0
~
LaF3 Na2Sn03' 3H20 1071.1
ZnF2 684.6 655.6 NaOAc 1071.1
PrF3 684.6 657.2 656 1336 NaF 1071.2
SmF3 684.6 657.0 Na2S04 1071.2
K2 ZrF6 684.6 655.1 .S:!
NaOOCCH2SH 1071.2
CaF2 684.8 655.4 ~ 1071.3
::2 Na2S0 3
NdF3
ThF4
K2 TiF 6
684.8
684.9
684.9
657.0
657.0
655.7 654
/ /
Na
Na
1071.4
1071.4
NaBr 1071.4
S rF2 685.0 656.3 NaN03 1071.4
NiF2 685.0 655.5 Na2Cr04 1071.4
LiF 685.1 654.7 /
NaCI 1071.5
InF3 685.2 656.4 Na2C03 1071.5
K2TaF7 685.2 655.0 Na2HP04 1071.5
YF3 685.3 655.8 652
Na2S203 1071.6
Na2TiF6 685.3 655.1 NaN02 1071.6
NaSnF3 685.3 655.3 Na2 Cr20 7 1071.6
HfF4 685.4 655.3 NaI 1071.7
K2 NbF7 685.4 655.2 NaBr 1071.7
Na3AIF6 685.5 654.1 1071.7
II Na2C03
MgF2 685.8 654.4 NaOAc 1071.7
CsF 685.9 653.8 690 689 688 687 686 685 684 683 682 681 680
Na 1071.8
Binding Energy (eV)
Na2 GeF6 685.9 654.0 NaCI 1071.8
Na2SiF6 686.0 653.0 NaCl 1072.5
KSbF6 686.6 656.6 Na20 1072.5
NaBF4 687.0 652.8 Mol Sieve Y 1072.6
NiOOCCF3 688.4 652.9 NaBF4 1072.7
p-(CF2=CF2) 689.0 652.4

198 t1) PHYSICAL ELECTRONICS t1) PHYSICAL ELECTRON


dix A. Auger Parameters Handbook of X-ray Photoelectron Spectroscopy Appendix A. Auger Parameters

ense photoelectron line versus the kinetic energy of the most intense Auger transition. The Auger
at states.

1344
662 1000
1342
I
Sodium Flu rides I
11

Compound Na Is NaKLL 998 2088


660 Binding Energy (eV) Kinetic Energy (eV)
1340
Na2Se03 1070.8 991.0
~~
Na2 C20 4 1070.8 990.5
Na2Mo04 1070.9 991.0 996 2086
NaAs02 1070.9 990.7
658 1071.0 998.6
1338 NaF ."
Na2Cr04 1071.0 991.2 - [;l
Na3P04 1071.1
1071.1
990.1
989.8
--'/.,./ f~e als
..
~
&
NaH2P02 994 2084 +
NazSn03' 3H20 1071.1 990.3 ~
>. 1071.1 989.9
;> 0
NaOAc ~
~
!:.i 656 I ---7- 1336 1071.2 998.6 >.
1:)
1:1
r::: NaF
[.IJ

. Na2S04 1071.2 989.8 ff


r:::
[.IJ
OJ
.5 NaOOCCH2SH 1071.2 990.4 .Sl 992 2082
~ NaZS03 1071.3 990.4 1)
r:::
Na 1071.4 994.3 g
I~~/ ~ rI~
654 Na 1071.4 994.5 ~ Ionic Compo nds.
,....--,.....-. I ; i
NaBr 1071.4 990.6
NaN03 1071.4 989.6 990 ..1. 2080
1071.4 991.2
990.1
NaCl
NazC03
1071.5
1071.5 989.8
I
II

652 IL~I---Y __I NazHP04 1071.5 989.7 I
Na2S203
NaNOz
1071.6
1071.6
990.1
989.8
988
!
-
I
NaZCr207 1071.6 990.6
~~f
Nal 1071.7 991.2
NaBr 1071.7 990.6
Na2C03 1071.7 989.8 986 ,. jmll_1 I I I , I I f j jmll_1 mj j
690 689 688 687 686 685 684 683 682 681 680 NaOAc 1071.7 989.9
1074 1073 1072 1071 1070
Binding Energy (eV) Na 1071.8 994.3 Energy (eV)
NaCl 1071.8 990.1
NaCl 1072.5 990.0
Na20 1072.5 989.8
Mol Sieve Y 1072.6 987.8
NaBF4 1072.7 987.1

(J) PHYSICAL ELECTRONICS (J) PHYSICAL ELECTRONICS 199


Appendix A. Auger Parameters Handbook of X-ray Photoelectron Snp,..tr.....,~~_,.j Handbook of X-ray Ph<

Aluminum
1395
,---, IT . . -,- 1 !//.. . /1 ~
Sil
1394 . ~/~t- J:::=1
r ...
__ -' ~/;:.:c .Mt ~/
tal k/ . Compound
Bind
Compound Al2p AIKLL
~~.'7~/
Binding Energy (eV) Kinetic Energy (eV) 1 v/- y" :
I
~
V Si
1393
Al 72.8
1393.3
~/ ~,
......./ j / //
MoSiz
AlAs 73.6
1391.2
....../ / . I,....-../ - ! i---'/ PdSi
V' '. /,,/.
AIz03, gamma 73.7
1387.8
- . . . . . . L:~1 ......171 ,/ Mol Sieve A

~ ~ /.-~.
A1z03, alpha 73.9
1388.2
1392 Hydroxysodalite
74.0
1387.8
- VV Si3 N4
AIz03. gamma
Al(OH)}, gibbsite 74.0
1387.4
V/V""" V ......./
Mol Sieve X
Alz03, sapphire 74.2
1387.8
1391 ~ I ~ /~ ArJem r'e
j____ .-
/
f~V ......7 Natrolite
Mica, muscovite
-'./ . . . . . . . //.,V ,. . . . . .
AIOOH, boehmite 74.2
1387.6

Wollastonii, Ca3Si309
~~ ' k / k::'~
AI(OHh, bayerite 74.2
1387.7
.,'
p-Methylsil. (linear)
Ah03, gamma 74.3
1387.8
;;...
'V/ j/
AIN 74.4
1389.0

i:.ll
g 1390 ~t
....... ~_~v~ 1//. 1462 LiAISjz06, spodumene

~/" ~/ l.....-/'.~
~ NaAISi30s, albite
AlzSiOs, sillimanite 74.6
1386.9

.
V~
()
.~ i A1SiOs, sillimanite
!=:
. /" k<!- i-I

~i---- / ~V
p-Phenylsil. (resin)
y'- v-
::2 1389 1461
Vc- Mol Sieve Y
Pyrophyllite

1388
~/............-"""""'-/ OJ ide~ 2~-= ~.. ~/< / / p-Methylsil. (resin)
, ' / - 1 . VI I k/ //
Kaolinite
.}--'-~/
I
...........-/ Talc, Mg3Si401O(OH)z

1387 ~
,.....---/ ,/~ -",,,- ~~ ... (-- ....
SiOz, alpha cristobal
H Zeolon
I
~-...........-
V SiOz, gel
//" SiOz,Vycor
,~
I SiOz
1386 ~ - - - -. . .
I -I .... _ ...
!
SiOz, quartz

1385 nj II I I
L.L I
I
I I
I I I
I"
I iLL
'" I I
-1-1
I '+r T ' ,I IL
I I L
I I iLL
I I I +H I
75 74 73 72
Binding Energy (eV)

200 <D PHYSICAL ELECTRONICS <D PHYSICAL ELf


Appendix K. Periodic Table

Atomic number 19 1.0 1 pm sensitivity factor for designated photoelectron transition


Element symbol 1 F
1 Most intense photoelectron transition 15 685 Binding energy, most intense photoelectron transition 2

H Most intense Auger transition KLL 647 Kinetic energy, most intense Auger transition He
3 0.025 4 0.074 5 0.159 6 0.296 7 0.477 8 0.711 9 1.0 10 1.340

Li Be B C N 0 F Ne
IS 66 Is 112 ls 187 ls 286 ls 402 lS 631 ls 685 ls 863
KLL 43 KLL 103 KLL 177 KLL 264 KLL 380 KLL 509 KLl 666 KLL 818
11 1.685 12 0.252 13 0.193 14 0.283 15 0.412 16 0.570 170.770 18 1.011

Na Mg AI Si P S CI Ar
ls 1072 2p 60 2p 73 2p 99 2p 130 2p 164 2p 198 2p 242
KLL 994 KlL 1186 LMM 68 LMM 93 LMM 120 LMM 151 LMM 183 LMM 216
19 1.30 20 1.634 21 1.678 22 1.798 23 1.912 242.201 25 2.42 262.686 273.255 28 3.653 29 4.798 30 3.364 31 3.341 32 3.100 33 0.570 340.722 35 0.895 36 1.096

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
2p 294 2p 347 2p 399 2p 454 2p 512 2p 674 2p 638 2p 707 2p 778 2p 853 2p 933 2P3/21 022 2P3/21117 2p3/21217 3d 42 3d 56 3d 69 3d 87
LMM 248 lMM 290 LMM 338 LMM419 LMM473 LMM 528 LMM 687 LMM 703 LMM 774 LMM 846 LMM 919 LMM 992 LMM1068 LMM1145 LMM1226 LMMl306 MNV 101
37 1.316 38 1.578 39 1.867 40 2.216 41 2.517 42 2.867 43 3.266 44 3.696 45 4.179 464.643 475.198 483.444 49 3.777 504.095 51 4.473 524.925 53 5.337 54 5.702

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
3d 111 3d 134 3d 166 3d 179 3d 202 3d 228 3d 253 3d 280 3d 307 3d 336 3d 368 3dsI2406 3dsi7 444 3dsI2486 3dsI2628 3ds/2673 3dSi2619 3dsI2670
MMN102 MNV 131 MNV 160 MNV 168 MNV 188 MNN 246 MNN 276 MNN 302 MNN 328 MNN 358 MNN 384 MNN 411 MNN 438 MNN465 MNN 492 MNN 616 MNN 645
55 6.032 566.361 577.708 72 2.221 732.589 74 2.959 75 3.327 76 3.747 774.217 784.674 79 5.240 80 5.797 81 6.447 82 6.968 83 7.632 84 85 86

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn
3d5l2 726 3dSi2781 3d 836 41 14 41 22 41 31 41 40 41 51 41 61 41 71 41 84 41 101 41 118 41 137 41 157
MNN 569 MNN 601 MNN 633 NNN 181 NNN 181 NNN 180 NNN 178 NNN 176 NNN 163 NNN 170 NNN 163 NOO 81 NOO 88 NOO 96 NOO 104

87 88 89

Fr Ra Ac 587.399 59 6.356 604.697 61 3.764 62 2.907 632.210 642.207 652.201 662.198 67 2.189 68 2.164 69 2.172 702.169 71 2.156

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
3d 884 3d 932 3d 981 3d 1034 3ds/21Ml 4d 128 4d 140 4d 146 4d 152 4d 160 4d 167 4d 175 4d 182 41 7
MNN 654 MNN 690 MNN 729 MNN 773 MNN 805 MNN 860 MNN 885 MNN1076 MVV1119 MVV1173 MVV1214
90 7.498 91 928.476 93 94 95 96 97 98 99 100 101 102 103

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
417/2 333 4/712 337
NOV 68 NOV 75

*The values are for area measurements of the designated transitions and are only valid when the electron energy analyzer used has the transmission
characteristics of the spherical capacitor type analyzer equipped with an Omni Focus III lens supplied by Physical Electronics and with x-rays at 90 relative to the
analyzer. When a spin-orbit splitting is not designated, the value is for a measurement including both spin-orbit components.

(I) PHYSICAL ELECTRONICS 261

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