Absorption Techniques in X-Ray Spectros

Absorption Techniques in X-ray Spectrometry
Jun Kawai
in
Encyclopedia of Analytical Chemistry
R.A. Meyers (Ed.)
pp. 13288–13315
 John Wiley & Sons Ltd, Chichester, 2000
ABSORPTION TECHNIQUES IN X-RAY SPECTROMETRY 1
Absorption Techniques in of analyte. X-ray absorption spectrometry is a technique

for analyzing the chemical environment of an element in
X-ray Spectrometry an unknown material. This method is closely related to
photoelectron spectroscopy, Auger electron spectroscopy,
and X-ray fluorescence spectroscopy.
Jun Kawai Chemical information in the chemical shift and line
Kyoto University, Kyoto, Japan shape of XANES (X-ray absorption near-edge structure)
spectra is described. The history and theory of EXAFS
(extended X-ray absorption fine structure) are discussed
1 Introduction 1 in relation to other experimental techniques. Data analysis
methods, databases, software packages, instrumentation,
2 Acronyms and a Brief History 3 and synchrotron radiation facilities for X-ray absorption
3 X-ray Absorption Near-edge Structure 5 analysis are overviewed. Alternative methods such as
3.1 Chemical Shift and Line Shape 5 electron energy loss spectroscopy (EELS), self-absorption
3.2 Calculation Method for X-ray effect, extended X-ray emission fine structure (EXEFS), X-
Absorption Near-edge Structure ray Raman scattering, diffraction anomalous fine structure
Spectra 8 (DAFS), b-environment fine structure (BEFS), and inverse
4 Theory of Extended X-ray Absorption photoemission spectroscopy (IPES) are also described.
Fine Structure 8
4.1 Single Scattering Theory 8
4.2 Relation to Other Techniques
(X-ray Photoelectron Diffraction, 1 INTRODUCTION
Low-energy Electron Diffraction,
X-ray Fluorescence Holography) 10 X-rays are absorbed in matter and the energy of
5 Data Analysis and Software Packages the X-rays is converted into the kinetic energy of
for X-ray Absorption Fine Structure 10 photoelectrons, Auger electrons, secondary electrons,
6 Instrumentation 13 or fluorescent X-rays. The incident X-ray energy finally
6.1 Laboratory Extended X-ray Absorp- becomes the thermal energy of the absorber.
tion Fine Structure 13 The amount of energy absorbed by a matter is usually
6.2 Synchrotron Radiation Extended estimated by a transmission method, but can also be
X-ray Absorption Fine Structure 13 estimated by measuring these secondary phenomena,
6.3 Secondary Yield Techniques and such as photoelectrons, Auger electrons, secondary
Applications 15 electrons, fluorescent X-rays, thermal radiation, and drain
electric currents. The X-ray intensity of wavelength l
7 Sources and Databases 21
before (I0 ) and after (I) the transmission of a thin film of
8 Alternative Methods 21 thickness d is expressed by I.l/ D I0 .l/ exp[ µi .l/ri d],
8.1 Electron Energy Loss Spectroscopy 21 where µi .l/ and ri are the mass absorption coefficient
8.2 Self-absorption 22 and mass density, respectively, of the ith element in the
8.3 Extended X-ray Emission Fine thin film and their dimensions are [cm2 g 1 ] and [g cm 3 ],
Structure 22 respectively..1 – 7/ The mass absorption coefficient µ of
8.4 X-ray Raman Scattering 22 a specimen which contains n kinds of elements is
8.5 Diffraction Anomalous Fine expressed by µ D µ1 .l/W1 C µ2 .l/W2 C Ð Ð Ð C µn .l/Wn ,
Structure 23 where W1 , W2 , . . . , Wn are the weight fractions of element
8.6 b-Environment Fine Structure 23 1, 2, . . . , n in the specimen. The wavelength dependence
8.7 Inverse Photoemission Spectroscopy 23 of the absorption coefficient µ.l/ is clarified when log µ.l/
9 Conclusion 23 is plotted against log l as shown in Figure 1; µ.l/ values
Abbreviations and Acronyms 23 are taken from Henke et al..8/ in this plot. Henke et al..8/
Related Articles 24 tabulated µ.l/ from Z D 1 to 92 at energy from 50 eV to
30 keV.
References 24
The plot of the mass absorption coefficients of matter
against the incident X-ray energy or wavelength is called
an X-ray absorption spectrum (XAS), where we find some
X-ray absorbance depends on the wavelength of the X-rays, jumps at particular X-ray energy, corresponding to K, LI ,
atomic number, chemical environment, and concentration LII , LIII , . . . electron shell binding energies as shown in
Encyclopedia of Analytical Chemistry

R.A. Meyers (Ed.) Copyright  John Wiley & Sons Ltd
2 X-RAY SPECTROMETRY
106 Table 1 Relation between the hole

state and the electron configuration
105 Hole state Electron configuration

Zn Fe V
K [1s]
L1 [2s]
104 L2 [2p1/2 ]
µ (cm2 g–1)
L3 [2p3/2 ]
M1 [3s]
103 L edge M2 [3p1/2 ]
M3 [3p3/2 ]
M4 [3d3/2 ]
102 M5 [3d5/2 ]
Zn Fe V
101 K edge state has a total angular momentum 12 , and the subscript 12
is usually omitted. The multiplicity of the state, which is
crudely proportional to the spectral intensity, is 2j C 1.
100
0.1 1.0 10.0 The jump is called the absorption edge, and the
Wavelength (nm) wavelength is highly correlated with the atomic number
similarly to Moseley’s law.1/ in X-ray emission spectra.
Figure 1 Mass absorption coefficients of V, Fe, and Zn plotted Moseley’s law in emission spectra is expressed as
against wavelength. Both axes are on a logarithmic scale. Equation (1):
1
L edge p D K.Z s/ .1/
l
Absorbance
where l is the X-ray wavelength, Z is the atomic number,

and K and s are constants for a spectral series. The
L1 absorption coefficient is crudely proportional to Z4 l3
except for the edge jumps. The energy at which the jump is
L2 observed is called the threshold energy, but the definition
L3
of the threshold is not exact, because it corresponds to the
transition from a core orbital to the lowest unoccupied
K edge
orbital. The ionization limit is a few or a few tens of
0 electron-volts higher than the edge energy.
1.4 1.2 1.0 0.8 0.6 0.4 0.2 The mass per unit area is given by rd, where r is
Wavelength (Å) the mass density. The linear absorption coefficient µl is
defined by µl D µr, and its dimension is [cm 1 ]. The X-
Figure 2 Platinum powder XAS. (Reproduced by permission ray attenuation length 1/µl is the length at which the
from Udagawa..9/ ) X-ray intensity becomes 1/e after traveling in matter. The
attenuation length of Cu Ka1 X-rays (8047.8 eV) is 79 µm
Figure 2..9/ K, LI , LII , and LIII denote electron deficiency in aluminum, 4.2 µm in iron, 24 µm in copper, and 3.9 µm in
states from 1s, 2s, 2p1/2 , and 2p3/2 orbitals, respectively. lead. The attenuation length of Al Ka X-rays (1486.7 eV)
Arabic numerals 1, 2, 3, . . . have more recently been used is 9.2 µm in aluminum and 0.4 µm in iron. The intensity of
in the subscript rather than Roman numerals I, II, III, . . . X-rays emitted by a copper target X-ray tube is, however,
The electron configuration of one electron deficiency attenuated by only half after transmission through 2-mm-
from the 2p orbital is expressed as 1s2 2s2 2p5 3s2 3p6 for an thick aluminum, but depends on the applied power
Ar atom. This state has two energy levels corresponding to on the X-ray tube, because the X-rays emitted from
j D 12 and 32 states, where j is the eigenvalue of vector sum an X-ray tube are not monochromatic. Thus it should
s C l, where s and l are called spin and angular momentum be noted that the X-ray shielding thickness for safety
vectors, respectively, and the vector j is called the total cannot be determined only from the monochromatic X-
angular momentum. These two states are written as 2p1/21 ray attenuation length.
and 2p3/21 , or [2p1/2 ] and [2p3/2 ]. The linear absorption coefficient can otherwise be
The relation between the electron deficient state and expressed as µ1 D 4pb/l, where l is the X-ray wavelength
the electron configuration is listed in Table 1. The s 1 hole and b the imaginary part of the complex refractive index
(n D 1 d ib)..7/ The atomic form factor, f D f1 C if2 , various methods described below, and to analyze the
which is used in the analysis of X-ray diffraction, is related obtained spectral line shapes to obtain information on the
to the refractive index (Equations 2 and 3): element, oxidation state, concentration, atomic distance,
coordination number, surface geometry, and reaction on
Nr0 l2 f1 solid surfaces, catalysts, or electrodes.
dD .2/
2p
Nr0 l2 f2
bD .3/
2p 2 ACRONYMS AND A BRIEF HISTORY
where N is the number of atoms in unit volume and
r0 D e2 /.mc2 / D 2.818 ð 10 13 cm is the classical electron The mass absorption coefficient plotted against the X-
radius (e the electron charge, m the mass, and c the speed ray energy is called the XAS. The X-ray absorption
of light). The real part f1 is the Fourier transform of spectra of condensed matter near the threshold energy
the electron density distribution in an atom. The relation have fine structures as shown in Figure 2. Fine struc-
between the absorption coefficient and atomic form factor tures are sometimes observable at energies less than
is used in DAFS described below. the threshold energy, and are called the pre-edge struc-
The mass absorption coefficient is the sum of two ture (Figure 3)..22/ These fine structures are called the
effects: photoelectric absorption and scattering of X- XANES, usually pronounced as ‘‘zaenz’’. The absorp-
rays. The photoelectric absorption is the ionization of an tion fine structure will extend up to 1000 eV above the
inner-shell electron. Therefore, the absorption coefficient threshold energy, and thus it is called the EXAFS,.23 – 26/
due to the photoelectric part can be calculated by the pronounced ‘‘eksafs’’. XANES is restricted from the
photoionization cross-section..8/ The scattering part is threshold to ca. 50 eV above (this energy approximately
due to the Rayleigh (coherent) and Compton (inelastic) corresponds to kR D 2p, where k is the ejected photo-
scattering of X-rays, but X-ray absorption spectra are electron momentum and R the nearest-neighbor atomic
often taken as if they represent only the photoelectric
absorption effect, although the experimental spectra
contain both effects.
The mass absorption coefficients or physically equiva-
lent parameters.8,9 – 13/ and the absorption edge energy or MnO
wavelength.14,15/ can be found in the literature. The value
of the absorption edge energy is close to the electron bind-
X-ray absorption intensity
ing energy, which is used in electron spectroscopy, ESCA

(electron spectroscopy for chemical analysis) or XPS (X-
ray photoelectron (photoemission) spectroscopy)..16,17/
The absorption edge jump is not exactly the same as
the electron binding energy, because the absorption edge
energy corresponds to the excitation of core electrons
into the lowest unoccupied molecular orbital (LUMO) KMnO4
in the molecular orbital picture, or Rydberg state in the
atomic orbital picture. The Rydberg state and contin-
uum state threshold are clearly seen in rare gas X-ray
absorption spectra but are not clear for condensed mat-
ter. The difference between the vacuum level and Fermi
energy, which defines the highest energy of electrons in
a conduction band, is called the work function, . This
is another source of the difference between the elec-
tron binding energy observed in XPS and the absorption
0 10 20 30 40 50
edge. The photoionization cross-sections.18,19/ and the
electron binding energies.20,21/ can be found in the liter- Energy (eV)
ature. The relation between the electron photoionization
cross-section (barns) and mass absorption coefficient is Figure 3 Mn K edge XANES spectra of MnO (octahedral, Oh ,
symmetry) and KMnO4 (tetrahedral, Td , symmetry). Pre-edge
simple when the angular dependence is averaged..11/ peak is found in the KMnO4 spectrum. Chemical shift of the
Absorption techniques in X-ray spectrometry are edge is found; the edge of KMnO4 is higher than that of MnO.
used to measure the X-ray absorption spectra using (Reproduced by permission from Pandya et al..22/ )
Photoelectron wave Scattered electron wave
k > k crt
EXAFS
k crt = 2π /R
XANES
k < k crt
Shape resonance
Figure 5 Schematic illustration of electron wave propagating

and scattering in a solid. (Reproduced by permission from
Udagawa..9/ )
and thus XANES was called the Kossel structure. The

Kossel theory was called short-range order (SRO) the-
ory, because the electronic structures of unoccupied levels
are mostly determined by orbital hybridization between
the center atom and the nearest-neighbor atoms. On
the other hand, Kronig.34/ explained that fine structure
was the result of the diffraction of photoelectrons as a
R
matter wave when moving in a conduction band of a
X-ray Electron solid. The electron matter wave travels in a solid when
absorbing scattering
atom atom
the wavelength of an electron le does not satisfy the
Bragg condition, 2d sin q D nle . When the Bragg condi-
Figure 4 Illustration of electron standing wave between the tion is satisfied, then the electrons are scattered and leave
X-ray absorption atom and its neighboring atom. (Reproduced the solid. His theory explained EXAFS and thus EXAFS
by permission from Udagawa.9/ and Ishii..26/ ) was called the Kronig structure. His theory was called
the long-range order (LRO) theory because the band
distance as shown in Figure 4.9,26/ ). The momentum of the structure is determined by the long-range periodic bound-
photoelectron is k D [2m.E E0 /]1/2 /h̄, where E is the ary conditions. Hayasi.35/ considered that the electron
photoelectron kinetic energy, E0 the threshold energy, m waves that satisfied the Bragg condition form a standing
the electron mass, and h̄ Planck’s constant. The photo- wave in a solid, and thus the electron transition from an
electron matter wave in a condensed system propagates inner orbital to a standing wave state yields a maximum
as a spherical wave and forms a standing wave as shown of X-ray absorption. Shiraiwa et al..36/ and Kozlenkov.37/
in Figure 5..9/ Recently, XANES has come to be called improved the SRO theory to explain the EXAFS, but
near-edge X-ray absorption fine structure (NEXAFS),.27/ their method needed to solve a Schrödinger equation to
pronounced ‘‘neksafs’’. All the fine structures including obtain the EXAFS. Sayers et al..38/ proposed a Fourier
NEXAFS and EXAFS are grouped into the term X-ray transform method to obtain local structural information
absorption fine structure (XAFS), pronounced ‘‘zafs’’. on condensed systems. Owing to their Fourier analysis,
The history of the development of the understand- we do not need to solve the Schrödinger equation directly
ing and application of XAFS has an interesting fea- to obtain the local structure of matter. EXAFS had at that
ture, as stated by Lytle et al.,.28/ Shiraiwa,.29/ Stern,.30/ time great potential to be developed as a powerful method
and Lytle..31/ Barkla (after Stern.30/ ) or de Broglie of analyzing the local structure of matter. The inelastic
(after Lytle.31/ ) firstly found the X-ray absorption edge. mean free path (IMFP) of a photoelectron is usually
Although XANES was found for both solids and gases, 2 nm. When the photoelectron is scattered inelastically,
EXAFS was found only for condensed matter such as the coherence is forgotten. The coherent length, i.e. the
molecules, solids and liquids. EXAFS was first reported length within which the electron matter waves emitted
by Fricke in 1920.32/ and was theoretically interpreted from a single source can interfere with each other, is
by Kossel..33/ He explained that the fine structure was an important length to apply in the EXAFS method to
due to the excitation of inner-shell electrons to an analyze a condensed system. When the IMFP is included
unoccupied level. This theory was valid for XANES, in the LRO theory, it is equivalent to the SRO theory.
EXAFS XANES S6+
Valence 2–
band O
εp S2O32– S S O
1s O
Unoccupied p S2–
state density
Total electron yield (arbitrary units)

ε 0
Energy S4+
Figure 6 Schematic illustration of X-ray absorption and pho-

toelectron excitation from the 1s to the unoccupied p state.
2–
The XAFS represents the unoccupied electron density S
SO32– OOO
of states for atoms, molecules, solids, or liquids. One of
the inner shell electrons, say a 1s electron, is excited into a
discrete or continuum unoccupied state by the incident X-
ray photon. The transition probability from the 1s to the
unoccupied state equals the X-ray absorption intensity
(only the photoelectric part is considered here), and S6+
thus the plot of the intensity against the incident X-ray
energy is the XAS of a specimen. XANES is chiefly due
to the transition from the inner shell to the unoccupied O 2–
discrete level (Figure 6), and EXAFS is to the unoccupied SO42– S
continuum level. OOO
3 X-RAY ABSORPTION NEAR-EDGE

STRUCTURE
3.1 Chemical Shift and Line Shape 2460 2470 2480 2490 2500 2510
The XANES spectra show both the line shape modifi- Energy (eV)
cation and chemical shift.39/ of the absorption edge or
peak. Figure 7.40/ shows typical examples for the S K Figure 7 Sulfur K edge absorption spectra of Na2 SO4 , Na2 SO3 ,
and Na2 S2 O3 . (Reproduced by permission from Sekiyama
edge for Na2 SO4 , Na2 SO3 , and Na2 S2 O3 . The sharp and et al..40/ )
prominent absorption peak shown in Figure 7.40/ is called
the ‘‘white line’’. This is because in the early days of X-ray
experiments a white line developed on the X-ray film was if the atom is negatively charged then the core level is
observed. The white line for insulators is usually sharper shifted to a shallower binding energy, and if an atom is
than that for metals, because it corresponds to a 1s ! pŁ positively charged then it is shifted to a deeper energy.
electron transition, where the asterisk denotes an unoccu- The source of the core level shift is the same as that of an
pied antibonding orbital. The pŁ state is usually a sharply ESCA chemical shift.
localized state. The metal has a broad conduction band, In Figure 9.42/ is shown another example of a chemical
and thus the absorption spectra show an edge jump but shift of the absorption edge for Al compounds: Al metal,
not a white line. AlN, and four- and six-fold coordinated oxides. The
The white line energy plotted against the oxidation Al O distance of four-fold coordinated aluminum oxide
number of sulfur is shown in Figure 8..41/ The source of (0.17 nm) is shorter than that of six-fold coordinated
the chemical shift is both the unoccupied level shift and oxide (0.19 nm), because the oxygen ions interfere with
core level shift. The range of the unoccupied level shift each other and cannot be close to the Al atom for six-fold
ranges from the Fermi level (D0 eV) to the band gap coordinated oxide. Thus the orbital hybridization of four-
energy (Da few electron-volts). The core level shift is due fold coordinated oxide is stronger than that of six-fold
to the screening of core electrons by valence electrons; coordinated oxide, and consequently the six-fold form is
2485 well of neighboring atomic potentials, is called the shape

resonance (Figure 4).
While the 1s ! pŁ transition is a sharp white line, the
peak energy (eV)
X-ray absorption
2480
1s ! sŁ transition usually results in a broad and weak
2–
S hump at higher energy,.44/ which is called the shape
OOO
2475
resonance. The term shape resonance is used in the field
S
2– of atomic spectra. The excited state or ionized state is
OOO bound in a potential wall, because of the centrifugal
2470 force potential of a high angular momentum orbital such
2–
O as an f orbital, or surrounding potential such as F in
S S O SF6 . However, as shown schematically in Figure 4, such a
O
2465 surrounding potential does not have sufficient height to
–2 0 2 4 6
enclose the electron, but a weak resonance is observable.
Nominal oxidation number This is the origin of the term shape resonance.
Figure 8 Relation between X-ray absorption peak and nominal The pre-edge structure shown in Figure 3 above is
sulfur oxidation number. (Reproduced by permission from observed for the K edge of transition metal compounds
Kawai et al..41/ ) whose local symmetry around the X-ray absorbing atom
is Td (tetrahedral). On the other hand, it is not observable
for locally Oh (octahedral) symmetry solids. This pre-edge
3 AIO6 in is sometimes said to be an electric quadrupole transition
Normalized absorbance
kyanite
from 1s to 3d, whereas ordinary optical absorption is the
AIO4 in electric dipole transition (1s ! 2p or 2p ! 3s, 3d). The
sodalite
2 quadrupole transition probability is, however, very weak,
as shown in Table 2, where the probability is calculated by
AIN4 in AIN
the Dirac – Fock method..45/ The origin of such a strong
absorption as shown in Figure 3 is due to the electric
1 AI metal dipole transition. The unoccupied p orbitals strongly
hybridize with the d band for tetrahedral symmetry
compounds based on the group theory as shown in
Table 3,.46/ where both p and d orbitals belong to the
0
t2 orbital. Thus the electric dipole transition is strongly
–10 0 10 20 30 40 observed at the energy of an empty d band. On the other
Energy – E0 (eV)
Figure 9 Al K edge XANES spectra of Al metal, AlN, sodalite, Table 2 Calculated transition
and kyanite. AlXn denotes the first shell coordination of probability for Cu
Al in each material. (Reproduced from J. Wong et al., ‘New
Opportunities in XAFS Investigation in the 1 – 2 keV Region’, K – L1 0.00000038
Solid State Commun., 92, 559 – 562,  1994, with permission K – L2 0.19
from Elsevier Science.) K – L3 0.37
K – M1 0.000000072
K – M2 0.022
ionic and the four-fold form is covalent. The effective K – M3 0.043
positive charge of six-fold coordinated Al3C is larger than K – M4 0.000025
K – M5 0.000036
that of four-fold coordinated oxide. The chemical shift
of six-fold coordinated oxide is larger than that of four-
fold coordinated oxide. The shift is strongly correlated
to Pauling’s electronegativity.43/ of the neighboring atom, Table 3 Part of the character table of Td
because the electronegativity determines the effective
Td p d
charge of the ion.
The unoccupied discrete level is composed of Rydberg a1 x2 C y2 C z2
states in the atomic picture, pŁ and sŁ orbitals in a2
the molecular-orbital picture (the asterisk denotes an e (2z2 x2 y2 , x2 y2 )
t1
antibonding molecular orbital), or conduction bands in t2 (x, y, z) (xy, xz, yz)
crystals. The sŁ transition, which is formed in a potential
Table 4 Part of the character table of Oh The chemical shifts of reference samples are measured
and plotted against the electronegativity, and then the
Oh p d neighboring atom type is estimated for an unknown
a1g x2 C y2 C z2 material from the chemical shift of the absorption edge.
a2g After the discovery of high-temperature superconduc-
eg (2z2 x2 y2 , x2 y2 ) tors,.49/ the understanding of the electron correlation
t1g effect of transition metal compounds.50/ and rare earth
t2g (xy, xz, yz)
a1u compounds has been greatly improved by the study of
a2u XPS. Consequently, the understanding of the correla-
eu tion effect, i.e. how the hole left in the final state of
t1u photoionization interacts with d holes in transition metal
t2u (x, y, z) compounds, has developed substantially. Many reports
have been published concerning the electron correla-
tion effect on the XANES line shape of complicated
C D
materials..51/
Mixed-valence rare earth compounds are clearly
E observed by the measurement of XANES, as shown in
Figure 11,.52/ but the intensity ratio sometimes does not
Absorption (arbitrary units)
directly represent the mixed-valence components because

of a dynamic electron transfer, i.e. correlation effect, due
to the core hole screening..53/ The peak decomposition
of XANES spectra into Eu2C and Eu3C , as shown in
[Co(NH3)6]l3 Figure 11, yields a rough estimate of the mixed-valence
B
A state. However, the core hole created by the X-ray
absorption rearranges the valence electrons and thus
[Co(NH3)6]Br3 the peak intensity does not always represent the exact
[Co(NH3)6]Cl3
1.5 273 K
1.0
7700 7750
Energy (eV)
0.5
Figure 10 Co K edge spectra of [Co(NH3 )6 ]X3 (X D Cl,
Br, and I). The vertical bars show calculated spectra for
[Co(NH3 )6 ]3C . Peak A is due to the electric quadrupole 0.0
transition but still mixed with the p orbital owing to the
skewing of the molecular structure from exact octahedral
symmetry. (Reproduced by permission from Sano..47/  1988 1.5 19 K
The American Chemical Society.)
1.0
hand, p and d orbitals never mix with each other for Oh
symmetry, as shown in Table 4,.46/ where the p orbital 0.5
belongs to t2u and d belongs to eg and t2g . Therefore, the
p transition emerges at a different energy from the empty 0.0
d band for octahedral symmetry compounds. The true
6.94 6.96 6.98 7.00
electric quadrupole transition is very weak, as shown in
Figure 10..47/ However, even in this case, the observable Energy (keV)
strength is due to the hybridization of the p character
into the empty d band. The intensity and energy shift of Figure 11 XANES spectra of EuNi2 Si0.5 Ge1.5 at 19 and 273 K.
The dashed-dotted and the dashed spectra indicate the Eu2C
the pre-edge peak are good indices for fingerprinting the and Eu3C final state components, respectively. (Reproduced
chemical environment in the compounds, especially for by permission from Wortmann et al..52/  1991 The American
biological samples..48/ Physical Society.)
portion of the Eu2C and Eu3C states before the X-ray is

absorbed.
Intensity
3.2 Calculation Method for X-ray Absorption
Near-edge Structure Spectra
The electronic states of photoelectrons whose kinetic
E
energy is from a few electron-volts to a few tens of
electron-volts are treated as conduction electrons in a T
conduction band. Thus a multiple scattering (MS) method
or Green’s function method, which has been used to 640 650
calculate the electronic structure of conduction electrons Energy (eV)
near the Fermi energy in metals, is applicable to calculate
the XANES of materials. The line shape of a XANES Figure 12 Mn L2,3 XAS (E) of MnF2 compared with atomic
spectrum represents the partial and local electron density 3d5 multiplet calculation including the crystal field splitting (T).
of states of the X-ray absorbing atom..54/ Hence any (Reproduced by permission from de Groot et al..60/  1990 The
American Physical Society.)
kinds of electronic structure calculations other than the
MS theory, such as the LCAO-MO (molecular orbital
derived from a linear combination of atomic orbitals) Hartree – Fock – Slater (HFS) method, and recently it has
method or the APW (augmented plane wave) method, are been developed as a local density approximation (LDA)
also applicable to interpret the near-edge fine structure. theory. The calculation method for XANES spectra is
One of the most popular methods for calculating XANES a modified MS-Xa method..58/ In another way, the MS
spectra is the MS theory. method is the expansion of the wave function of positive
In the MS theory, a sphere of radius ri centered at the ith energy by an infinite sum of the spherically outgoing and
atom is considered, and the solid is divided by spheres. A incoming scattering waves. The electrons excited into the
spherically symmetric atomic potential V.r/ is put inside continuum level have a wave function of a standing wave
each sphere and the potential equals zero or constant formed by the infinite number of incoming and outgo-
outside the spheres. This is called the muffin-tin (MT) ing spherically traveling waves. That is to say, a wave
potential. The wave function in the solid is expressed as whose intensity is V.r0 /y.r0 / coming from every point r0
the overlap of spherical Bessel functions (radial part of in space is synthesized and forms a wave y.r/ at point
the wave function) multiplied by the spherical harmonic r. This method produces a wave function similar to the
functions (angular part of the wave function). APW method, which is an appropriate method to cal-
The wave function y.r/ of a photoionized electron is culate a metallic band structure, but APW requires a
scattered by an atomic potential V.r/ near the ionized greater number of basis functions than the MS method.
atom, and finally it becomes itself after being scattered The wave function at point r is the sum of all the scattered
many times (Equation 4) waves multiplied by the phase factor. The LCAO-MO
Z method is another choice for calculating the electronic
1 exp.ikjr r0 j/ structures of solid or molecules, and is thus applicable to
y.r/ D V.r0 /y.r0 / dr0 .4/
4p jr r0 j the calculation of XANES spectra..59/
An atomic calculation yields a satisfactory agreement
where k2 D e is the kinetic energy of a photoelec- between experiment and theory, as shown in Figure 12,.60/
tron and k is real for e > 0 (photoionized electron), after the inclusion of the perturbation of crystal field
exp.ikjr r0 j//.jr r0 j/ represents a spherically expand- splittings. Bragg reflection of electrons in a crystal
ing wave, and V.r/ is the MT potential. This method reproduces a rough XANES spectrum..61/
is called the MS method, Green’s function method, or
Korringa – Kohn – Rostker (KKR) method..55/ The KKR
method is only exact for solids that have translational
symmetry, or periodic boundary conditions. Small clus- 4 THEORY OF EXTENDED X-RAY
ters, molecules, amorphous or surface adsorbates have a ABSORPTION FINE STRUCTURE
lower symmetry, and it is difficult to apply directly the
KKR method. Thus the cluster calculation method was 4.1 Single Scattering Theory
proposed by Johnson.56/ and was called the multiple scat- Whereas MS of photoelectrons in a solid is a good
tering Xa (MS-Xa) method, because Slater’s Xa exchange approximation to treat XANES, because the electron
potential.57/ is used in place of the Hartree – Fock (HF) kinetic energy of the EXAFS region is very high, single
exchange integral. The Xa method is also called the scattering is a good approximation to EXAFS except for
special cases. The wave function fk .r/ of a photoelectron 1.0

scattered by a single atom is asymptotically expressed by
f (θNi)(arbitrary units)
Equation (5): 50 eV 50 eV
f .#/
fk .r/ ! exp.ikz/ C exp.ikr/ .5/
r
100 100
where f .#/ is the scattering amplitude and # is the 140
200
scattering angle (# D 0° for forward scattering and 140 285
# D 180° for backscattering). The scattering amplitude 200
285
505 505
of an electron of velocity v scattered by an atom of atomic
number Z is expressed by the first Born approximation 1320 1320
(Equation 6): 0
0° 45° 90° 135° 180°
e2
1 Forward Back
f .#/ D [Z A.#/] 2
.6/ Scattering angle (θNi)
2mv2 sin .#/2/
where e and m are the charge and the mass of an electron, Figure 13 Calculated plane-wave scattering factor amplitude
respectively, and A.#/ is the atomic structure factor for jf j of nickel as a function of both the scattering angle qNi
and the photoelectron kinetic energy. (Reproduced from
X-rays, given by Equation (7): M. Sagurton et al., ‘Derivation of Surface Structures from
Z 1 Fourier Transforms of Photoelectron Diffraction Data’, Phys.
sin kr
A.#/ D 4p r.r/r2 dr .7/ Rev. B, 30, 7332 – 7335,  1984, with permission from Elsevier
0 kr Science.)
where k D .4pmv/h/ sin.#/2/ is the change in electron
momentum before and after the scattering and r.r/ is the The EXAFS oscillation amplitude is larger when the
charge distribution in an atom. The forward scattering atomic number of neighboring elements is higher. For
amplitude crudely depends on the atomic number in a example, the Si K edge EXAFS oscillation amplitude
way such that (Equation 8) of Si is stronger than that of SiO2 , because the atomic
Z number of Si is higher than that of O. The white line
1 1 1
f .0° / D 4pr.r/r4 dr D Zhr2 i .8/ of SiO2 is sharper and stronger than that of Si. Hence
3 0 3 the EXAFS oscillation and the white line intensity do
in atomic units, because (Equation 9).62/ not directly indicate the concentration of the atom in the
Z 1 analyte. However, the edge jump is a good measure of
concentration, and the measurement of edge jump could
ZD 4pr2 r.r/ dr .9/
0 determine the concentration without a working curve, as
shown in Table 5..65/
where h i denotes an average. The calculated scattering The effect of thermal vibration on the line shape
amplitude is shown in Figure 13..63/ of X-ray absorption spectra is shown schematically in
The EXAFS is expressed by Equation (10):.64/ Figure 14..44/ This is the line in the XANES region.
X Nj Similarily, the EXAFS oscillation becomes unclear owing
c.k/ D jf .k, p/j exp. 2s2j k2 / sin[2kRj C fj .k/]
2 j to thermal vibration. As the atomic number becomes
j
kR j
p .10/
where k D 2m.hn E0 //h̄ is the photoelectron wave Table 5 Results of copper – zinc
solution to test the trace element
vector, Nj is the number of nearest neighbors, jf .k, p/j
analysis
is the backscattering amplitude, and Rj is the distance
from the center atom. The exponential term contains Zn (µg mg 1 Edge jump
the Debye – Waller-like vibrational effect and dumping. Cu solution)
The dumping due to the finite coherent length of
0.092 0.0059
the photoelectron, exp[ 2Rj /l.k/], is multiplied for 0.049 0.0035
a more exact expression. The Debye – Waller factor 0.020 0.0021
contains both effects of thermal vibration and geometric 0.000 0.0010
randomness. The oscillating part of the EXAFS equation,
Reproduced by permission from
sin 2kR/.kR/2 , if plotted as a function of kR, is the Nomura..65/  1992 The American
EXAFS oscillation. Chemical Society.
Asymmetric lineshape
and it probes the local structure within the IMFP.
Thus 1 – 2 nm regularity, usually up to the next-nearest
neighbors, in the structure is sufficient for the EXAFS
oscillation to emerge.
Intensity (arbitrary units)
4.2 Relation to Other Techniques (X-ray Photoelectron

Diffraction, Low-energy Electron Diffraction, X-ray
Fluorescence Holography)
X-ray photoelectron diffraction (XPD).62/ is used to study

the local structure of surfaces. The photoelectron intensity
as a function of detected polar and azimuthal angles is
measured in this technique. The photoelectron intensity
is anisotropic in its detection angle. This effect is due to
photoelectron diffraction, but roughly speaking it is due
to the photoelectron’s forward scattering by the nearest-
neighbor atoms around the photoelectron-emitting atom.
Photon energy (arbitrary units) XPD uses forward scattering of photoelectrons; EXAFS
uses backscattering of photoelectrons.
Figure 14 Asymmetric line shape of X-ray absorption spectra Recently XPD has been treated as photoelectron
caused by the vibration of a diatomic molecule. (Reproduced by
permission from D.A. Outka, J. Stöhr, ‘Curve Fitting Analysis
holography (PEH)..67/ The intensity distribution of the
of Near-edge Core Excitation Spectra of Free, Adsorbed and photoelectrons of a single crystal is measured and Fourier
Polymeric Molecules’, J. Chem. Phys., 88, 3539 – 3554 (1988).  transformed, and then a local atomic structure of the
1998 American Institute of Physics.) single crystal near the photoelectron-emitting atom can be
constructed. The phase shift of electron waves scattered
higher, the core hole lifetime becomes shorter. A by a neighboring atom makes the analysis of the Fourier
shorter lifetime of the inner shell level indicates that transform for PEH complicated. The angular distribution
the energy of the inner shell becomes vague because of the X-ray fluorescence intensity is measured and the
of Heisenberg’s uncertainty principle. Consequently, the Fourier transform of the angular distribution reconstructs
EXAFS oscillation of the K spectrum for higher atomic the crystal image. This is called X-ray fluorescence
number elements is not clear compared with that of the holography (XFH)..67/ XFH is free from the phase shift
L edge spectrum of the same element. problem, but this method is bulk sensitive, whereas XPD
The IMFP of photoelectrons is a function of kinetic and PEH are surface sensitive.
energy for a particular material, as shown in Figure 15..66/ Low-energy electron diffraction (LEED).68/ is a surface
It is 1 – 2 nm for the usual EXAFS experiments. Hence the crystallography experimental method where electrons
photoelectron is only coherent within a few nanometers, of a few hundred electron-volts impinge on a single
crystal and a diffracted electron pattern is observed.
The penetration depth of these energy electrons is a
5
few nanometers, hence this method is surface sensitive.
Electron diffraction requires a periodic structure of at
Mean free path (nm)
4
least 10 nm on the surface, hence the LEED method
cannot probe the structure clusters of a few nanometers
3 on a surface.
5 DATA ANALYSIS AND SOFTWARE

1 PACKAGES FOR X-RAY ABSORPTION
FINE STRUCTURE
0
1 10 100 1000 10 000
Electron energy (eV) The measured (Figure 16a) X-ray absorption spectral
energy is converted into photoelectron momentum. The
Figure 15 Calculated IMFP of photoelectrons in gold. (Repro- smooth background µ0 .E/, which means an isolated atom
duced by permission from Kuzmin..66/ ) absorption coefficient, is subtracted from the observed
,,,,,,,,
,,,,,,,
0.8
,,
,,
FY E
,,,,,,,,,
,,,,,,,,,
0.7 TEY
,
0.6
,
0.5 R1
,
,
,
,
,,
0.4
Calc. EXAFS intensity

0.3
4.0 E C
0.2 1.3 Å
3.0 O
0.1
0.0 2.0
1800 1900 2000 2100 2200 2300 2400 2500
1.0
(a) Photon energy (eV)
0.0
2.5
FY
TEY 500 600 700 800 900 1000
(a) Photon energy (eV)

k 2 χ( k )
,,,,,,,,
,,,,,,,
0.0
,,,,,,,,,,,,
,,
,,,,,,,,,
, ,
,
,
,
,
,
–2.5 R2
4 6 8 10 12
Calc. EXAFS intensity
–1
(b) Wavenumber, k (Å ) 2.0
3.5 1.5
FY
3.0 TEY
1.0
O Cu
2.5 2.0 Å
0.5
F (R )
2.0
1.5 0.0
1.0 500 600 700 800 900 1000
0.5 (b) Photon energy (eV)

0.0 Figure 17 Schematic illustration of diatomic molecule (full
0 1 2 3 4 5 6 and open circles) adsorbed on a four-fold coordinated site
(c) Distance, R (Å) of metal substrate (hatched circles). When the incident X-ray
beam electric vector is parallel to the diatomic molecular axis,
Figure 16 (a) Si K edge EXAFS spectra of an Si(001) wafer the absorption spectrum of the molecule is obtained (a strong
measured using the X-ray fluorescence yield (XFY) method white line due to an insulating compound is observed). When
and total electron yield (TEY) method. (b) Oscillation function the incident X-ray beam electric vector is perpendicular to
of (a). (c) Fourier transforms of (b). (Reproduced by permission the molecular axis, information on the metallic bond between
from Y. Kitajima, ‘Fluorescence Yield X-ray Absorption Fine the adsorbed atom and the substrate metal is obtained.
Structure Measurements in the Soft X-ray Region’, Rev. Sci. (Reproduced by permission from J. Stöhr, ‘Geometry and Bond
Instrum., 66, 1413 – 1415 (1995).  1995 American Institute of Lengths of Chemisorbed Atoms and Molecules: NEXAFS and
Physics.) SEXAFS’, Z. Phys. B: Condens. Matter, 61, 439 – 445 (1985). 
1985 Springer-Verlag.)
value µ.E/ and normalized according to Equation (11):

This is the EXAFS oscillation. If we want to enlarge the
µ.E/ µ0 .E/ oscillation for a larger k region, we sometimes plot k3 c.k/
c.k/ D .11/
µ0 .E/ or k2 c.k/ in place of c.k/ as shown in Figure 16(b)..69/
Then this is Fourier transformed as shown in Figure 16(c),

and a radial distribution function is obtained. To
Total electron yield

obtain the coordination geometry, measurement of the
(arbitrary units)
polarization-dependent EXAFS oscillation is important,
as shown in Figure 17(a) and (b)..70/ An example of S K
edge spectra of CS2 on a Cu(111) surface is shown in
Figure 18..71/
A spline function or higher order polynomial deter-
mines the smooth background. Theoretically, the smooth
background has a shape of tan 1 q at the threshold,
because the discrete absorption line shape is a Lorentzian
function and its sum in a Rydberg series becomes tan 1 q 1840 1860 1880 1900 1920 1940 1960 1980 2000
as shown in Figure 18.
Photon energy (eV)
An incident X-ray beam forms a standing wave in
a large-sized single crystal. In this case, additional fine Figure 19 TEY spectrum of partially oxidized Si(111) wafer.
structure, the 1985-eV structure in Figure 19,.72/ for Additional structure at 1985 eV is due to the incident X-ray
example, depending on the incident angle of X-rays, Bragg diffraction (standing wave). (Reproduced from T. Ohta
is observable. The standing wave profile is sensitive to et al., ‘A Possible Use of the Soft X-ray Standing Wave Method
for Surface and Interface Structure Analysis’, Nucl. Instrum.
the location of impurity atoms in a crystal, i.e. which site Methods Phys. Res. A, 246, 760 – 762,  1986, with permission
in the lattice. The use of standing waves is one of the from Elsevier Science.)
π∗ surface analysis methods, but sometimes interferes with

CS2 /Cu(111)
obtaining c.k/, as shown in Figure 19.
θ = 55°
Total electron yield
92 K 30 L
Another effect interfering with the observation of c.k/
Exp.
σ∗ Calc. is the multiple ionization effect. The effect of an additional
one or two electrons ionized from outer shell(s) is not
negligibly small..73/ The double ionization probability is
sometimes more than 30% of single K shell ionization.
This is a source of error in EXAFS analysis.
92 K 0.02 L θ = 15° EXAFS Fourier analysis is sometimes not easy when
additional peaks such as multiple ionization, standing
wave structure, and impurity peaks originating from the
analyte, X-ray source, or X-ray optics emerge.
Data analysis methods have been developed and
θ = 55° several standard computer programs are now available.
Fluorescence yield
Table 6 XAFS analysis computer programs
ATOMS FUSE
θ = 90° AUTOBK G4XANES
AUTOFIT GNXAS
BAN LASE
CDXAS MacXAFS
CERIUS2 MURATA
EDA REDUCE
EX.TR.As REX
2460 2470 2480 2490 2500 2510 EXAFIT REX2
EXAFS and FITEX SEDEM
Photon energy (eV) EXAFS (for Mac) TT-MULTIPLETS
EXAFSPAK UWXAFS
Figure 18 Experimentally obtained S K-edge XANES spectra EXBACK WinXAS
(dots) of a CS2 multilayer (30 L) at an X-ray incident angle EXBROOK XAFS
of 55° , and submonolayer (0.02 L) at 15° , 55° , and 90° . EXCALIB XAID
(Reproduced from S. Yagi et al., ‘Structural and Electronic EXCURVE98 XANADU
Properties of Molecularly Adsorbed CS2 on Cu(III) Studied by FEFF XDAP
X-ray Absorption and Photoelectron Spectroscopies’, Surf. Sci., FEFFIT XFIT
311, 172 – 180,  1994, with permission from Elsevier Science.)
FEFF is the most popular program that is used by EXAFS
dete ensitive
users. The EXAFS analysis program is not difficult to X-ray source
ctor
code, and a laboratory that studies EXAFS may have
ion-s
its own program, but not always published. Some of the Sample
Posit
programs listed in Table 6 can be down-loaded from Web
sites.
ator
rom
och
Mon
6 INSTRUMENTATION
6.1 Laboratory Extended X-ray Absorption Fine

Structure
Figure 21 Example of EXAFS spectrometer using a posi-
To measure the X-ray absorption spectra, a strong X-ray tion-sensitive proportional counter. (Reproduced by permission
source of continuous energy is required, such as white from Maeda et al..75/ )
radiation from an X-ray tube or synchrotron radiation
(SR). A metallic wheel is rotated in vacuum and a
Mono-
high electric potential is applied between the wheel ber chromator
m
and a filament. Thermal electrons are emitted from the cha
tion
filament and bombard the wheel target. Water flows iza
Ion I0
inside the wheel to cool it against heating by the electron
bombardment. To eliminate the heating, the wheel is I
rotated. Therefore, this type of rotating anode X-ray tube X-r
ay
tube
produces one order of magnitude stronger X-rays than the
ordinary sealed X-ray tubes. The electron deceleration at Sample
the metal target converts the electron kinetic energy into
Figure 22 Laboratory EXAFS using a q – 2q goniometer.
X-ray energy. The X-rays thus produced are continuum (Reproduced by permission from K. Sakurai, ‘High-intensity
X-rays in addition to characteristic X-rays and the X-ray Line Focal Spot for Laboratory Extended X-ray Absorp-
maximum energy is the acceleration electric potential tion Fine-structure Experiments’, Rev. Sci. Instrum., 64, 267 – 268
applied. The X-rays from the X-ray tube are then (1993).  1993 American Institute of Physics.)
monochromated by a crystal monochromator using the
Bragg diffraction condition. Then the monochromatic 6.2 Synchrotron Radiation Extended X-ray Absorption
X-rays are incident on the specimen as shown in Fine Structure
Figure 20..74/ Sometimes, to compensate for the weak
source intensity, a position-sensitive proportional counter Recently, SR has frequently been used as an X-ray source.
is used as shown in Figure 21..75/ However, the very simple Synchrotron is the name of an electron (or positron)
experimental set-up shown in Figure 22.76/ is sometimes accelerator made of an ultrahigh vacuum (UHV) ring
used. and electrons rotating inside the ring. High voltage is
applied to the rotating electrons using variable-frequency
Bent crystal radio waves and the frequency is synchronized with the
X-ray source electron rotation during the acceleration of the electrons
Fluorescent
X-ray detector in the ring. When the electron speed reaches close to the
speed of light, a very sharp X-ray beam is emitted in a
tangential direction because of the relativistic effect. This
I0 X-ray beam is called the SR. Usually SR from a storage
ring is used. A ring in which electrons (or positrons) are
rotated at a certain constant speed is called the storage
ring. Usually electrons accelerated to a sufficient speed by
Sample
a synchrotron or a linear accelerator are injected into the
I storage ring, and the tangential radiation when a magnet
Rowland circle
bends the electron beam is used as an X-ray source..77/ The
SR thus produced from a bending magnet is continuous
Figure 20 Example of EXAFS spectrometer using a rotating over a wide range (more than 1000 eV) of X-ray energy
anode X-ray tube. (Reproduced by permission from Rigaku..74/ ) and a few orders of magnitude stronger than the rotating
27-pole wiggler
,,,,,,,,,,,,,,,,,
,,,,,,,,,,,,
,,,,,,,,,,,,
,,,,,,,,,,,,
,,,,,,,,,,,,
,,,,,,,,,,,,,,,,,,,
,,,,,,,,,,,,,,,,,,,,,,,,,
e+
,,,,,,,,,,,,,,,,, , , ,
2.5-GeV storage ring
Directly Sagittally bent
,,,,,,,,,,,,,,,,
water-cooled second crystal
,,,,,,,,,,,,,,
,,,,,,,,,,,,,,
,,,,,,,,,,,,,,
,,,,,,,,,,,,,,
,,,,,,,,,,,,,,
,,,,,,,,,,,,,,,,,,,,
first crystal
,,,,,,,
,
Vertical
focusing mirror i0
monitor
Slits
,,,
φ
,,,,,
,,,,,
,,
ω
Sample α
7-element Si(Li)
detector
Figure 23 Schematic view of X-ray wiggler beam line. (Reproduced by permission from Oyanagi et al..78/ )
anode X-ray tube. The smaller emittance indicates the use in X-ray absorption experiments than those from an
electron orbit stored in a storage ring being sharpened, undulator. An example of the experimental set-up of a
but practically it indicates a smaller X-ray beam size wiggler is shown in Figure 23..78/
and higher photon density. The emittance is measured in SR facilities are classified into first-, second-, and third-
meter Ð radians (m Ð rad). The emittance is a measure of generation sources. The first-generation synchrotrons
beam quality. The smaller the emittance, the more the were particle accelerators, and spectroscopists parasiti-
beam becomes parallel. The SR is monochromated by a cally used the SR. Such SR was unstable. The second-
single crystal. generation synchrotrons use a storage ring to obtain SR
Continuous X-rays from a bending magnet are most but the emittance is still not small enough, i.e. 10 7 mrad.
convenient for X-ray absorption spectroscopic experi- The emittance of the third-generation synchrotrons have
ments. The rotating axis of monochromator crystals is emittance as small as 10 9 m Ð rad. Such a small-emittance
parallel to the electric vector of the SR X-rays to make storage ring requires a large-radius electron orbit because
good use of the X-rays. To obtain stronger X-rays, SR a large number of magnets are required to keep the elec-
from an undulator or wiggler beam line is used. The tron beam cross-section small. The fourth generation of
undulator and wiggler are insertion devices in the storage synchrotron has not yet been constructed and not defined,
ring, and made of many strong permanent magnets. The but may be a free electron laser facility using an electron
electron beam in the storage ring is undulating when accelerator. The third-generation SR facilities are tabu-
it goes through an undulator, and a coherent quasi- lated in Table 7, and the second-generation SR facilities
monochromatic X-ray beam is produced. It consists of can be reached via the links of the Web pages listed.
many harmonics and each harmonic has a narrow (say The first crystal in the monochromator used in an SR
100 eV) bandwidth. By changing the magnet gap width, beam line experiences a high heat load, and the lattice
the peak energy of the X-rays from the undulator is constant is slightly different from the second crystal.
controlled; the wider the gap, the lower is the energy. The crystal optics should be cooled by flowing water.
Thus, to scan the energy over 1000 eV continuously using To adjust the difference in the lattice constant between
an undulator, both the undulator gap and monochroma- the first and the second crystals, usually one of the two
tor crystal rotation should be controlled simultaneously. crystals is independently finely moved by a piezoelectric
This is a difficult task but now routinely done in some
SR undulator beam lines. An undulator can produce a Table 7 Third-generation SR facilities and Web
few orders of magnitude stronger X-rays than a bending sites
magnet beam line. If the X-rays produced by undulat-
ing by magnets are not coherently interfered, such an ALS http://www-als.lbl.gov/als/
insertion device is called a wiggler. X-rays from a wiggler APS http://epics.aps.anl.gov/welcome.html
ESRF http://www.esrf.fr/
are not strong compared with those from an undulator SPring-8 http://www.spring8.or.jp/
but are continuous in energy, and thus much easier to
mechanism. The adjustment of the two crystals should Sample

always be monitored for the measurement of EXAFS for I0 I
the 1000-eV range. The monitoring of the adjustment is X-ray
done by measuring the incident X-ray intensity, which is (a)
maximized at every energy point scanned.
El
de ectro
tec n e
6.3 Secondary Yield Techniques and Applications tor
The intensity of the monochromated X-rays is moni- X-ray

(b)
tored by an ionization chamber. X-rays pass through
the ionization chamber (I0 ) and are then incident on a A
specimen, and the transmitted X-ray intensity is mea- e
sured by another ionization chamber. The XAS is Grid
the plot of log.I/I0 / against the X-ray energy. The X-ray
absorption spectra are usually measured by this trans- (c)
mission method as shown in Figure 24(a)..79/ When the
X-rays are absorbed strongly by the sample, the sec- A
ondary responses such as photoelectron intensity, sample X-ray
electric current intensity, secondary electron intensity (d)
(electrons whose kinetic energy < 50 eV is mostly the
secondary electrons), Auger electron intensity, and X-ray Flu
X-r ores
fluorescence intensity become strong. Therefore, equiv- X-ray ay cen
t
alent spectra to the absorption spectra are measurable detector
by these secondary phenomena such as photoelectron X-ray
intensity, secondary electron intensity, Auger electron (e)
intensity (Figure 24b), sample drain current (Figure 24c
Figure 24 Various methods of measuring X-ray absorption
and d), X-ray fluorescence intensity (Figure 24e), ion spectra. (a) Transmission method; (b) partial electron yield
intensity due to photostimulated desorption, and other method; (c, d) TEY method; and (e) XFY method. (Repro-
secondary techniques. duced from J. Kawai et al., ‘Depth Selective X-ray Absorption
The photoelectron intensity for a single crystal has Fine Structure Spectroscopy’, Spectrochim. Acta Part B, 49,
739 – 743,  1994, with permission from Elsevier Science.)
an anisotropy with respect to the observed direction
because of the photoelectron diffraction. The angular
average of the photoelectron intensity measured as emitted from the sample. The electrons produced in a
the change in incident X-ray energy is the XAS. This solid are scattered in the solid as shown in Figure 26,.81/
method is called the photoelectron yield method. If and only electrons produced near the surface contribute to
Auger electrons are detected, this is the Auger electron the electric drain current. When we detect ions desorbed
yield method. The intensity of Auger electrons from from the surface due to X-ray absorption, the ion intensity
a single crystal also has an angular anisotropy. The represents the surface top layer.
detection angle is therefore important for interpreting These methods of detecting electrons (or electric
the observed data for these electron yield methods. current) or ions are surface sensitive and therefore are
Many kinds of electrons are detected, such as secondary called surface extended X-ray absorption fine structure
electrons, core photoelectrons, valence photoelectrons, (SEXAFS). If the sample current is measured in an
and Auger electrons, as shown in Figure 25(a – c)..80/ air or helium atmosphere, then the ejected electrons are
The different kinetic energy electrons correspond to the converted into O2 or other ions and a positive or negative
different probing depths. Thus the electron yield spectra current is observable depending on the sample electric
are a mixture of various depth spectra as well as a mixture potential with respect to the ground. This method is called
of various processes of electron production. The relation the conversion electron yield (CEY) method.
between the X-ray absorption process and the electron The XFY method is not surface sensitive, because
emission process is neither direct nor clear. the fluorescent X-rays originate from as deep a location
The electric drain current is of the order of 10 9 A as the X-ray attenuation length. However, if XFY is
when using a bending magnet SR beam line. The electric combined with the grazing-incidence X-ray technique
drain current is a measure of X-ray absorption, and this (Figure 27),.82/ where the total reflection X-ray technique
method is called the TEY method. This is because the is combined with the TEY and CEY methods, it becomes
drain current represents the sum of all the electrons more surface sensitive than normal-incidence TEY or
EF EV
Binding energy (eV) O Kinetic energy (eV)
hν 1 Photoemission
A B VB
(a)
hν 2
,,,,, ,,,, ,, ,,,,,

,,,, ,,,,,, ,, ,,,,,
,, ,, ,,,, ,, ,,,,
,,,,, , ,,,,,, Auger
,
,
,
,
,
,
,
,
,
,
,
(b)
,
,
hν 3
,
,
,
,
B
,
A
,
,
,
Auger
VB
,
,
,
,
,
Yield window settings

,
Secondary
Elastic Auger
,,,
,
,
Partial Auger
,,
,
,
Total
,
,
(c) ES EP EA
Figure 25 Schematic photoelectron spectra for (a) the excitation energy below the excitation threshold of core level A, (b) just
above the absorption threshold but below the photoionization threshold, and (c) far above the threshold. The contributions to the
photoelectron intensity from different level photoelectrons and Auger electrons are indicated. At the bottom the window settings
for various electron yield X-ray absorption techniques are shown. (Reproduced by permission from Stöhr et al..80/  1984 The
CEY. The X-rays are totally reflected on the surface detected using the XFY method; the detection limit is
and the evanescent X-ray wave penetrates only a few <1012 atoms cm 2 .
nanometers from the surface. X-ray reflectivity is also a The X-rays emitted from a deep location in a specimen
measure of XAFS. suffer from the self-absorption effect and the spectral
The grazing exit angle method is also possible, as shown shape is different from that of an absorption-free
in Figure 28,.83/ because of the reciprocal theorem of spectrum..84/ The XFY method combined with the grazing
optical beams. The XFY method has atomic selectivity incidence method does not suffer heavily from the self-
because an X-ray detector usually has energy resolution, absorption effect compared with the normal-incidence
hence the signal-to-noise ratio is better than in the method.
TEY method, and minor elements adsorbed on the Some materials emit luminescence in the visible
surface can be detected by the XFY method. X- wavelength range when irradiated with X-rays. This
ray absorption spectra of very dilute analytes can be optical luminescence signal intensity corresponds to the
hν hν Proportional
counter
e−
Vacuum
,,,
,,
,,
,,
,,
,,
Adsorbate
θE
,
atoms
A
Electron
escape E
TEY
depth hν
L ~ 50 Å Substrate
atoms A
B
Sample
Photon e−
mean free Figure 28 Schematic experimental set-up of grazing exit angle
path
experiment for XFY and TEY. (Reproduced by permission
1/µ> 1000 Å
from Kitajima..83/ )
Heat is produced while the sample is irradiated by an

Figure 26 Photoabsorption and electron production in a solid
consisting of substrate atoms B and an adsorbed layer A. Only
optical beam and it diffuses during the beam chopping.
electrons originating within a depth L from the surface will The chopping frequency usually ranges from a few to
contribute to the TEY signal. (Reproduced from J. Stöhr et al., a few hundred hertz. The sound wave is detected by a
‘Surface Crystallography by Means of Electron and Ion Yield microphone or a piezoelectric device. When the chopping
SEXAFS’, Surf. Sci., 117, 503 – 524,  1982, with permission frequency is low, the heat diffuses into deeper location in
from Elsevier Science.)
the sample compared with when it is high. Thus the
probing depth is variable by changing the chopping
amount of X-rays absorbed by the specimen. Various frequency. All the incident photon energy is finally
processes of optical luminescence de-excitation are shown converted into thermal energy through nonradiative
in Figure 29..85/ Optical luminescence is usually strong transition processes in the solid. The PA process in the
for rare earth compounds, but some crystals which visible wavelength range is used for the very sensitive
have defects in their crystal structure emit stronger absorption spectrometry of thick bulk samples, which are
luminescence, although a perfect single crystal of the not transparent to an optical beam. This method has been
same material does not emit optical luminescence. applied to the measurement of the X-ray absorption,.86/
The photoacoustic (PA) effect produces sound on where the incident X-ray beam should be chopped to
irradiating a sample surface by a chopped photon beam. produce acoustic waves in the sample. This method is a
This effect was discovered by Alexander Graham Bell. thermal yield method.
Bias
voltage
Sample chamber
Image
Be Be intensifier
Si(111) mono.
window window Ionization
Slit chamber
Cu mesh
Ionization
SR chamber
Sample
Current
XY
amp.
slit
Current
amp. Beam
stop
Current V/F conv.
amp.
V/F conv.
Figure 27 Schematic experimental set-up for TEY and CEY at grazing angles. (Reproduced by permission from Zheng and
Gohshi..82/ )
,,,,,,,,,,
, ,
,,,,,,,,,,,
the photoconductive spectra; electrical conductivity is
, induced by the incident X-rays. Spectra thus measured
,,,,,,, , are sometimes the inverse of the transmission spectra and
sometimes similar to the transmission spectra, depending
,,,,,,,, on the concentration..88/ Electrode surface reaction
,,,,,, ,
processes can be measured using X-ray absorption in
combination with the total reflection X-ray technique.
X-ray submicrometer beams are now available in major
,,,,,
,,,,,
,,,,
,,,,, ,,,,,,,,,,,,,,,,
SR facilities, and using these beam lines micro- or
,
,
,
,,,,,,,,,,,,, ,,,,,,
,
nanobeam techniques are now applicable, as shown in

,,,,, ,
,
Figure 31,.89/ where the XFY is measured by a solid-state

,
,
,,,,
,,,
,,,
µ , detector (SSD). The energy resolution of an SSD is of the
,,,
,,,
3
,,, η2 η1 η3
order of 100 eV, while the energy shift of an absorption
,,
X-rays
edge is a few electron-volts. If the incident X-ray energy is
between the edge energies of two chemical states (say FeO
2s and Fe2 O3 ), then only one kind of chemical state (FeO)
can emit the X-ray fluorescence. Using this technique,
chemical state mapping is possible.
X-rays
X-rays
Using a bent crystal monochromator as shown in
Figure 32,.90/ multiple-energy X-rays can be focused
µ2 on a sample and the transmitted X-rays are detected
µ1 by a position-sensitive detector, which is made of a
photodiode array (PDA). Using such a kind of energy-
dispersive optics, one spectrum can be measured within
1s a few milliseconds..91/ This method is called quick X-ray
absorption fine structure (Q-XAFS).
Figure 29 Schematic diagram of X-ray absorption and optical Circularly polarized X-rays can be produced by
luminescence processes. Three different excitation processes, linearly polarized X-rays transmitted through a diamond
from the 1s orbital to a continuum state (absorption coeffi- single crystal at a special angle depending on its
cient µ1 ) and to a bound state (µ2 ), and from the 2s orbital
to a continuum state (µ3 ), give rise to a single luminescence wavelength, which is called the phase retarder, as shown in
with luminescence yields h1 , h2 , and h3 , respectively. X-ray flu- Figure 33..92/ The vertical and horizontal components, the
orescence, KLL Auger, electron multiscattering, nonradiative ratio of which is called helicity, of the X-ray electric vector
decay, and radiative decay processes are schematically shown. can be controlled by the small rotation and tilting of the
(Reproduced by permission from Emura et al..85/  1993 The diamond crystal. Absorption spectra of a magnetic sample
are measurable. This is X-ray magnetic circular dichroism
(XMCD) X-ray absorption. The magnetic S and N poles
applying the magnetic field to the sample are inverted
Leads
, ,,,,,,,,,,,,,,,,,,,, Quartz tube

,,, ,,,, ,,,,,, ,,,, , Microscope
,, , , , Ni
,,,,,,,,,,,,
,, ,
with CCD
,, ,,,
,, , ,,,,,
hν L w
electrodes
,, ,,,
,,,,,,
,
,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,
Sample
,
TV monitor Ionization y stage

Mylar Pinhole
,, , ,,l , , ,, , ,,
window chamber
SR
Leads
Figure 30 Schematic illustration of a liquid cell. (Reproduced Focusing mirror

Si(111)
by permission from T.K. Sham, R.A. Holroyd, ‘Photoconduc- monochromator
x
tivity Measurements of X-ray Absorption of Liquids: Fe K-edge
Spectrum of Ferrocene in 2,2,4-Trimethylpentane’, J. Chem. Si(Li) SSD
Phys., 80, 1026 – 1029 (1983).  1983 American Institute of Data
Electronics
processor
Physics.)
Figure 31 Schematic illustration of an X-ray fluorescence
Liquid samples are inserted into a cell shown in microprobe at the Photon Factory. (Reproduced from Nakai
Figure 30,.87/ and an electrode is used to measure et al.,.89/ courtesy of Marcel Dekker, Inc.)
Monochromator Magnetic field Energy
SR
Fermi energy
Sample
L3
L2
Position-sensitive
detector Figure 34 One-electron model used to explain the X-ray
absorption dichroism process and intensities. The d band is split
into spin-up and spin-down bands. The absorption of circularly
Figure 32 Energy-dispersive system at a synchrotron facility. polarized X-ray photons by the spin – orbit split 2p shell creates
(Reproduced by permission from Derbyshire et al..90/ )
a spin-polarized core hole. (Reproduced by permission from
Duda et al..93/  1994 The American Physical Society.)
or the circularly rotating direction of the X-ray electric
field is inverted and the difference in the absorbance absorption spectra, as shown in Figure 35..98/ This method
is measured. The former is usually used to measure can measure spin-selective X-ray absorption spectra
the dichroism. Magnetic thin multilayers have recently without applying a magnetic field to the sample. This
become important for information mass storage devices, method is useful for characterizing mixed-valence protein
and these materials are characterized with microbeam compounds.
XMCD X-rays. The difference in the absorption coeffi- The phase transition due to the temperature change is
cients for the left and right circularly polarized X-rays observable, as shown in Figure 36..99/ The phase transition
is illustrated schematically in Figure 34..93/ The details of is a small change in bond distance and bond angle,
MCD are described in several books..94 – 97/ and consequently the electronic structure of the sample
High-resolution X-ray fluorescence spectra of transition changes. Thus both XANES and EXAFS region spectra
metal compounds show multiplet splitting due to the change their line shapes.
exchange interaction between the unoccupied 3d level The surface of water, where a liquid monolayer is
and the core X-ray hole. Thus the XFY absorption present, could be analyzed by grazing incidence X-ray
spectrum of each multiplet line provides spin-selective reflection XAFS..100/ When the monolayer absorbs metal
Electromagnet
Si(111) double-crystal Diamond Ionization
monochromator phase retarder chamber (I 0) Ionization
chamber (I )
X-ray from
undulator
Piezo translator Sample
To current amplifier To current amplifier

From piezo driver
Figure 33 Experimental set-up for XMCD measurements with the helicity-modulation technique. (Reproduced by permission
from Suzuki et al..92/ )
line in the absorption spectra is a measure of the oxidation

state of an element in the particle.
The surface catalyst process could be elucidated by the
In
ci
de
3d 3d analysis of EXAFS spectra. The incident X-ray polariza-

n
tX
7
P tion dependence is an important parameter for the deter-
-ra
3p 3p
ys
mination of the geometry of a reactant and the surface..102/

K β 1,3 X-rays
X-ray detectors in the XFY method have been
developed for X-ray absorption experiments, such as
1s 1s a 19-element Ge detector array; a schematic illustration
of a seven-element detector is shown in Figure 23; a 100-
Photoionization X-ray fluorescence
of 1s electron by element detector array can be used for more efficient
X-ray absorption detection of X-rays.
Transition metals are usually a target of XAFS analysis,
Figure 35 Schematic illustration of absorption and emission the energy range of which is from 5 to 20 keV. The
(Kb1,3 lines) of X-rays due to 1s down-electron photoionization beamline for X-rays of this energy range uses Be and
of Mn2C ion; 1s up-electron photoionization produces the Kb0
X-ray emission spectral line. (Reproduced by permission from polymer films as windows to separate the vacuum system
Grush et al..98/ ) from the atmosphere. Both lower and higher energy
XAFS experiments require different techniques.
Soft X-ray XAFS experiments, ranging from 0.1 to
σ*
5 keV, require UHV techniques. This is because any
windows between the SR storage ring and the sample
π* heavily absorb X-rays, hence a windowless beamline is
Normalized intensity
d
required. Consequently, the sample chamber is made
RT of UHV components and must be baked out up to
200 ° C. The contaminants in X-ray windows and other
X-ray optics are carbon and oxygen, which are in the
soft X-ray region (250 – 600 eV). Hence a windowless
system is appropriate for the analysis of these elements.
The shortcoming of the soft X-ray region experiment
120 °C is the UHV system, because samples requiring X-ray
absorption analysis could not always be inserted into
the UHV system because they would emit gas into the
530 535 clean system. A vacuum of 10 2 Pa is sufficient to avoid
the absorption of X-rays in the X-ray path. The XAFS
Photon energy (eV)
spectra of this soft X-ray region are surface sensitive and
Figure 36 O 1s absorption spectra of VO2 measured at room the profile changes of the spectra due to chemical state
temperature and at 120 ° C. (Reproduced by permission from are very large. The spectra measured can be used for the
Abbate et al..99/  1991 The American Physical Society.) same purpose (chemical state analysis) as XPS or ESCA.
The detection limit of XAFS is usually lower than that of
ions from the water solution, the concentration of the ESCA, hence XAFS has an advantage over ESCA if SR
metal ion on the surface is slightly higher than that in the is available.
water. The coordination structure around the metal ion XAFS experiments higher than 20 keV require differ-
is analyzed by the EXAFS method. ent experimental techniques. The number of application
When a powder is measured by the XFY and TEY examples is not large, mainly because high-energy X-ray
methods on a substrate, then the depth-selective chemical sources are limited without using third-generation SR
state analysis of a fine particle can be performed. Fly ash facilities. In place of measuring this energy range K-edge
is a powder of micrometer-sized particles, which are a XAFS, the L-edge XAFS, the energy of which usually
source of acid rain when they are dispersed in the air. The falls in the range 5 – 20 keV, is measured. The L XAFS
particles are put on an aluminum foil and irradiated spectra are composed of L1 , L2 and L3 edge jumps, which
by monochromated X-rays, and XANES spectra are interfere with each other. To avoid this, the K edge is
measured by TEY and XFY methods..101/ The TEY useful for the analysis. The lifetime of the K hole state
method is sensitive to the surface chemical state of the of high-energy K-edge XAFS of higher atomic number
powder particle, and XFY is sensitive to deep parts of the elements is, however, shorter than the long-wavelength
particle (micrometers). The chemical shift of the white region. Because of the Heisenberg uncertainty principle,
the line widths of the absorption spectral components Table 8 List of international XAFS conferences and
are as large as 100 eV. Both the EXAFS oscillation and proceedings
XANES lose fine structure owing to this lifetime broad-
Conf. no. Date Location Ref.
ening. High-energy XAFS has recently been measured
with the development of third-generation SR facilities, 1st March 1981 Daresbury 103
because the numerical analysis overcomes the short life- 2nd September 1982 Frascati 104
time effect. 3rd July 1984 Stanford 105
4th July 1986 Fontevraud 106
5th August 1988 Seattle 107
6th August 1990 York 108
7 SOURCES AND DATABASES 7th August 1992 Kobe 109
8th August 1994 Berlin 110
Academic societies and E-mail lists discuss the standard- 9th August 1996 Grenoble 111
10th August 1998 Chicago 112
ization of X-ray absorption spectrometry. As XAFS is 11th August 2000 Ako –
used in many areas of research, standardization has been
required. To achieve standardization, the International
XAFS Society (IXS) was established in the 1990s. The Table 9 Source of information (journals)
purpose of the IXS is stated as follows:
Advances in X-ray Analysis
The International XAFS Society represents all those Analytical Chemistry, Fundamental Review, even years.113 – 120/
working on the fine structure associated with inner-shell Journal of X-ray Science and Technology
excitation (near-edge and extended) by various probes Journal of Electron Spectroscopy and Related Phenomena
(e.g. X-rays and electrons), and related techniques for Journal of Synchrotron Radiation
which the data are interpreted on the same physical basis. Physical Review B
The purpose of the IXS is to oversee activities which Surface Science
benefit the community as a whole, to establish operational Synchrotron Radiation News
committees, to provide for education in the field, to X-ray Spectrometry
disseminate relevant information, to work with other
related regional, national and professional organizations
in promoting and developing XAS and related disciplines,
and inner-shell processes and on vacuum ultraviolet
and to act as representative for the community to other
professional organizations. physics are sources of X-ray absorption spectroscopy
and spectrometry.
This society has a close relation to the International Union

of Crystallography (IUCr). The WWW home page of the 8 ALTERNATIVE METHODS
IXS is at Illinois Institute of Technology, http://ixs.iit.edu/,
where a large number of XAFS databases are presented. 8.1 Electron Energy Loss Spectroscopy
This WWW page links to other related WWW home
pages. National society and working groups are active An electron beam, with an energy from a few hun-
in many countries. All the information concerning these dred electron-volts to a few hundred kiloelectron-volts,
activities is obtainable at the international conferences on impinges on a sample and loses its kinetic energy. When
XAFS. The first XAFS international conference was held the sample is a bulk material, reflected electron energy is
at Daresbury, UK, in 1981, and subsequent conferences measured. Usually the loss of transmitted electron energy
are listed in Table 8. is measured for thin-film samples less than a few microm-
Many kinds of activity reports published by SR facilities eters or a few tens of nanometers thick. This is called
are useful sources of experimental methods and standard EELS..132/ EELS is usually combined with transmission
spectra. Journal sources are listed in Table 9. Fundamen- electron microscopy (TEM). The electron energy loss
tal reviews in Analytical Chemistry published in even structure is similar to the XAFS. The EXAFS region in
years relate to X-ray absorption spectrometry..113 – 120/ EELS is called the extended electron energy loss fine
In a book by Meisel et al.,.121/ references are classified structure (EXELFS). Forward-scattered (0° ) electron
by atomic number and spectral series. Recently several energy loss spectra, formed when electrons are trans-
books which treat newer X-ray techniques.122 – 126/ and mitted in a thin film, are approximately equivalent to the
concerning X-ray absorption.127,128/ have been published. optical spectra; the selection rule is the electric dipole.
The Materials Research Society has held symposia on Energy loss spectra of electrons scattered at a large angle
applications of SR in materials science..129 – 131/ are not treated by the electric dipole transition, and
The Denver X-ray analysis conference and interna- sometimes include optically forbidden transitions. The
tional conferences on electron spectroscopy, on X-ray transmission method used in TEM has a very high spatial
resolution, hence chemical state imaging by the chemi- 2500

cal shift of the absorption edge is possible..133,134/ High
Intensity (counts per 4 s)

energy resolution and high spatial resolution are not
2000
always achieved by a single instrument. The EELS spec-
tra are sensitive for low atomic number elements such as
boron and carbon. It is not easy to measure the XAFS 1500
spectra of these long wavelengths using an SR facility. A
1000
8.2 Self-absorption
Although the characteristic X-ray wavelength of an
element is usually separated from the absorption edge 500
B
wavelength of the same element for hard X-rays, they
are very close to each other for the soft X-ray region. 0
These close lines are, for example, transition metal La,b 1200 1180 1160 1140 1120 1100
X-ray emission lines and L2,3 absorption edges. The La
Energy (eV)
and Lb X-ray emission lines emitted in a deep location
in a solid are absorbed during the travel in the solid. Figure 37 (A) Low-energy satellites (the radiative Auger
Hence the X-ray emission spectra have dips due to the satellites) of the Ka X-ray fluorescence spectrum of MgO
X-ray absorption spectra. The profiles of the La,b X-ray compared with (B) XANES measured at an SR facility.
emission lines of transition metals excited by different (Reproduced by permission from Kawai and Takahashi..136/ )
electron energies (3 and 16 keV) change because of the
self-absorption effect..135/ If the electron energy is high
(16 keV), then the penetration depth of the electron
is deeper. Hence the X-ray emission spectrum suffers Rayleigh
heavily from the self-absorption effect. In contrast, if the
electron energy is low (3 keV), then the penetration depth θ = 60°
is shallow, and the X-ray emission spectrum is free from
the self-absorption effect. The comparison of these two
Intensity
spectra yields an X-ray absorption. Similarly, one set of

X-ray emission spectra is obtainable by tilting the sample Raman
to the X-ray detector or to the incident electron beam, ×10
when the electron energy is fixed.
Compton
8.3 Extended X-ray Emission Fine Structure
The radiative Auger effect (RAE) is always associated 0 500
with the X-ray characteristic lines and this effect is an 8265 7765
energy loss structure in characteristic X-ray emission, as
shown in Figure 37..136/ The second electron shaken up Energy (eV)
into an unoccupied orbital has similar information to the
XAFS. This is called EXEFS..137/ This method is used to Figure 38 Rayleigh, Compton, and Raman scattering spectra
of 8265-eV incident X-rays by graphite observed at q D 60° .
measure low atomic number elements such as Na, Mg, Al,
(Reproduced by permission from Tohji and Udagawa..138/ 
and Si, because the RAE satellite intensity is strong for 1987 The American Physical Society.)
these elements. If wavelength-dispersive electron probe
microanalysis (EPMA) is available, XAFS spectra of 1 µm
diameter area are measurable using this method. by conduction band electrons. X-ray Raman scattering is
a method for measuring soft X-ray absorption spectra
(say of carbon) with a hard X-ray spectrometer (a few
8.4 X-ray Raman Scattering
kiloelectron-volts). Hard X-rays can be measured in
X-ray Raman scattering is the effect of energy loss air; soft X-ray absorption spectroscopy, which usually
on X-ray scattering. Raman scattering is a similar requires UHV, is possible in air by this method. Hard X-
physical process to Compton scattering. The difference rays (8265 eV) impinge on a carbon-containing sample,
is that Raman scattering involves scattering by core and the X-rays lose energy by the carbon K edge due to the
electrons whereas Compton scattering involves scattering Raman scattering (ca. 300 eV), as shown in Figure 38..138/
The X-ray that should be detected is at ca. 8 keV, which also powerful for analyzing mixed chemical states in
still falls in the hard X-ray region. The XAFS study of industrial, environmental, and biological analytes. The
catalysts during reaction with gases is possible using the development of SR facilities will make it possible to
Raman effect. measure nanometer-sized samples in less than a few
milliseconds.
8.5 Diffraction Anomalous Fine Structure
DAFS was proposed by Stragier et al..139/ XAFS usually ABBREVIATIONS AND ACRONYMS
measures the wavelength dependence of f2 , the imaginary
part of the atomic structure factor; DAFS measures f1 . APW Augmented Plane Wave
The wavelength dependence of f1 and f2 has a close BEFS b-Environment Fine Structure
relation through the Kramers – Kronig transformation. BIS Bremsstrahlung Isochromat
In the DAFS experiment, the intensity of a diffraction Spectroscopy
peak of a specimen is measured by the change in the CEY Conversion Electron Yield
incident X-ray energy. The sample and detector angles DAFS Diffraction Anomalous Fine Structure
(q 2q) are measured by the change in the incident EELS Electron Energy Loss Spectroscopy
X-ray energy, or powder X-ray diffraction patterns are EPMA Electron Probe Microanalysis
measured by the change in incident X-ray energy. This ESCA Electron Spectroscopy for
method can measure site-selective XAFS of the same Chemical Analysis
element, because the diffraction peak corresponds to a
EXAFS Extended X-ray Absorption Fine
different site in the crystal. If the diffraction peaks which
Structure
originate from the surface and bulk phases are separated,
EXBIFS Extended X-ray Bremsstrahlung
space-selective EXAFS-like spectra are obtainable by
Isochromat Fine Structure
this method.
EXEFS Extended X-ray Emission Fine
Structure
8.6 b-Environment Fine Structure EXELFS Extended Electron Energy Loss
The b-electron emission process in a nuclear conversion Fine Structure
process suffers interference by the crystal structure for HF Hartree – Fock
the same reason as EXAFS. This method is called HFS Hartree – Fock – Slater
BEFS..140/ IMFP Inelastic Mean Free Path
IPES Inverse Photoemission Spectroscopy
8.7 Inverse Photoemission Spectroscopy IUCr International Union of
Crystallography
IPES is an alternative method to measure the unoc- IXS International XAFS Society
cupied electronic structure by irradiating electrons and KKR Korringa – Kohn – Rostker
detecting photons..141/ This method is otherwise called LCAO-MO Linear Combination of Atomic
bremsstrahlung isochromat spectroscopy (BIS). The Orbitals-Molecular Orbital
extended structure like EXAFS is also observable in BIS LDA Local Density Approximation
and this is called the extended X-ray bremsstrahlung LEED Low-energy Electron Diffraction
isochromat fine structure (EXBIFS)..142/ The BIS is LRO Long-range Order
usually combined with an ESCA instrument, and thus LUMO Lowest Unoccupied Molecular Orbital
occupied and unoccupied electronic structures (similar to MS Multiple Scattering
XANES) are measurable..143/ MS-Xa Multiple Scattering Xa
MT Muffin-tin
NEXAFS Near-edge X-ray Absorption Fine
9 CONCLUSION Structure
PA Photoacoustic
X-ray absorption spectroscopy is chiefly used in the area PDA Photodiode Array
of electronic structure study and structural analysis for PEH Photoelectron Holography
the study of new materials, surfaces, and catalysts. The Q-XAFS Quick X-ray Absorption Fine Structure
spectra measured are surface sensitive or bulk sensitive RAE Radiative Auger Effect
depending on the detection method. Chemical shift and SEXAFS Surface Extended X-ray Absorption
profile changes are observable. Thus the spectral analysis Fine Structure
is useful for materials characterization. This method is SR Synchrotron Radiation
SRO Short-range Order 4. A.E. Sandström, ‘Experimental Methods of X-ray Spec-

SSD Solid-state Detector troscopy: Ordinary Wavelengths’, in Handbuch der
TEM Transmission Electron Microscopy Physik, Vol. 30, Röntgenstrahlen, ed. S. Flügge, Springer,
TEY Total Electron Yield Berlin, 78 – 245, 1957.
UHV Ultrahigh Vacuum 5. R.W. James, The Optical Principles of the Diffraction of
XAFS X-ray Absorption Fine Structure X-rays, Ox Bow Press, Woodbridge, 1982.
XANES X-ray Absorption Near-edge Structure 6. B.K. Agarwal, X-ray Spectroscopy, 2nd edition, Springer,
XAS X-ray Absorption Spectrum Berlin, 1991.
XFH X-ray Fluorescence Holography 7. A.A. Markowicz, ‘X-ray Physics’, in Handbook
XFY X-ray Fluorescence Yield of X-ray Spectrometry, eds. R.E. Van Grieken, A.A.
Markowicz, Marcel Dekker, New York, 1 – 73,
XMCD X-ray Magnetic Circular Dichroism
1993.
XPD X-ray Photoelectron Diffraction
8. B.L. Henke, E.M. Gullikson, J.C. Davis, ‘X-ray Inter-
XPS X-ray Photoelectron Spectroscopy
actions: Photoabsorption, Scattering, Transmission, and
Reflection at E D 50 – 30 000 eV, Z D 1 – 92’, At. Data
Nucl. Data Tables, 54, 181 – 342 (1993).
RELATED ARTICLES 9. Y. Udagawa (ed.), X-ray Absorption Fine Stru-
cture, Gakkai-Shuppan-Center, Tokyo, 1993 (in
Environment: Water and Waste (Volume 4) Japanese).
X-ray Fluorescence Spectroscopic Analysis of Liquid 10. C.H. Macgillavry, G.D. Rieck, International Tables for
Environmental Samples X-ray Crystallography, Kynoch Press, Birmingham,
Vol. III, 1968.
Surfaces (Volume 10) 11. B.L. Henke, P. Lee, T.J. Tanaka, R.L. Shimabukuro,
Auger Electron Spectroscopy in Analysis of Surfaces ž B.K. Fujikawa, ‘Low Energy X-ray Interaction Coef-
Soft X-ray Photoelectron Spectroscopy in Analysis of ficients: Photoabsorption, Scattering, and Reflection.
Surfaces ž X-ray Photoelectron Spectroscopy in Analysis E D 100 – 2000 eV, Z D 1 – 94’, At. Data Nucl. Data
Tables, 27, 1 – 144 (1982).
of Surfaces
12. B.L. Henke, J.C. Davis, E.M. Gullikson, R.C.C. Perera,
Electroanalytical Methods (Volume 11) ‘A Preliminary Report on X-ray Photoabsorption Coef-
X-ray Methods for the Study of Electrode Interaction ficients and Atomic Scattering Factors for 92 Elements
in the 10 – 10 000 eV Region’, LBL-26259, UC-411,
X-ray Photoelectron Spectroscopy and Auger Electron Lawrence Berkeley Laboratory, University of Califor-
Spectroscopy (Volume 15) nia, Berkeley, CA, 1988.
X-ray Photoelectron and Auger Electron Spectroscopy ž 13. J. Kirz, D.T. Attwood, B.L. Henke, M.R. Howells, K.D.
X-ray Photoelectron Spectroscopy and Auger Electron Kennedy, K.-J. Kim, J.B. Kortright, R.C. Perera, P. Pia-
netta, J.C. Riordan, J.H. Scofield, G.L. Stradling, A.C.
Spectroscopy: Introduction
Thompson, J.H. Underwood, D. Vaughan, G.P. Wil-
X-ray Spectrometry (Volume 15) liams, H. Winick, ‘X-ray Data Booklet’, PUB-490 Rev.,
Energy Dispersive, X-ray Fluorescence Analysis ž Struc- Lawrence Berkeley Laboratory, University of Califor-
ture Determination, X-ray Diffraction for ž Total nia, Berkeley, CA, 1986 (this reference has many printing
errors).
Reflection X-ray Fluorescence ž Wavelength-dispersive
14. J.A. Bearden, ‘X-ray Wavelengths’, Rev. Mod. Phys., 39,
X-ray Fluorescence Analysis ž X-ray Techniques:
78 – 124 (1967).
Overview
15. E.W. White, G.G. Johnson, Jr, X-ray Emission and
Absorption Wavelengths and Two-theta Tables, ASTM
Data Series DS 37A, American Society for Testing and
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by G.A. Lindsay, Oxford University Press, London, Sci. Ups., Ser. IV, 20, 1 – 282 (1967). An extension
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R. Manne, Y. Baer, ESCA Applied to Free Molecules, 34. R. de, L. Kronig, ‘Zur Theorie der Feinstruktur in den
North-Holland, Amsterdam, 1969. Röntgenabsorptionsspektren’, Z. Phys., 70, 317 – 323
17. H. Siegbahn, L. Karlsson, ‘Photoelectron Spectroscopy’, (1931).
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Radiation in Matter I, ed. W. Mehlhorn, Springer, Berlin, Absorptionsspektrums II. Der Einfluss der thermischen-
215 – 467, 1982. Schwingungen des Kristallgitters auf die Feinstrukture’,
18. J.H. Scofield, ‘Theoretical Photoionization Cross-sect- Sci. Rep. Tohoku Univ., Ser. 1, 33, 183 – 194 (1949).
ions from 1 to 1500 keV’, UCRL-51326, Lawrence 36. T. Shiraiwa, T. Ishimura, M. Sawada, ‘The Theory of the
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Absorption Techniques in X-ray Spectrometry

Absorption Techniques in of analyte. X-ray absorption spectrometry is a technique

Encyclopedia of Analytical Chemistry

106 Table 1 Relation between the hole

105 Hole state Electron configuration

where l is the X-ray wavelength, Z is the atomic number,

ing energy, which is used in electron spectroscopy, ESCA

Photoelectron wave Scattered electron wave

Figure 5 Schematic illustration of electron wave propagating

and thus XANES was called the Kossel structure. The

Total electron yield (arbitrary units)

Figure 6 Schematic illustration of X-ray absorption and pho-

3 X-RAY ABSORPTION NEAR-EDGE

2485 well of neighboring atomic potentials, is called the shape

directly represent the mixed-valence components because

portion of the Eu2C and Eu3C states before the X-ray is

special cases. The wave function fk .r/ of a photoelectron 1.0

4.2 Relation to Other Techniques (X-ray Photoelectron

X-ray photoelectron diffraction (XPD).62/ is used to study

5 DATA ANALYSIS AND SOFTWARE

Calc. EXAFS intensity

(a) Photon energy (eV)

1.0 500 600 700 800 900 1000

0.5 (b) Photon energy (eV)

value µ.E/ and normalized according to Equation (11):

Then this is Fourier transformed as shown in Figure 16(c),

Total electron yield

π∗ surface analysis methods, but sometimes interferes with

Table 6 XAFS analysis computer programs

FEFF is the most popular program that is used by EXAFS

6.1 Laboratory Extended X-ray Absorption Fine

Directly Sagittally bent

mechanism. The adjustment of the two crystals should Sample

The intensity of the monochromated X-rays is moni- X-ray

,,,,, ,,,, ,, ,,,,,

Yield window settings

Heat is produced while the sample is irradiated by an

nanobeam techniques are now applicable, as shown in

Figure 31,.89/ where the XFY is measured by a solid-state

, ,,,,,,,,,,,,,,,,,,,, Quartz tube

TV monitor Ionization y stage

Figure 30 Schematic illustration of a liquid cell. (Reproduced Focusing mirror

Piezo translator Sample

To current amplifier To current amplifier

line in the absorption spectra is a measure of the oxidation

3d 3d analysis of EXAFS spectra. The incident X-ray polariza-

mination of the geometry of a reactant and the surface..102/

This society has a close relation to the International Union

resolution, hence chemical state imaging by the chemi- 2500

Intensity (counts per 4 s)

spectra yields an X-ray absorption. Similarly, one set of

SRO Short-range Order 4. A.E. Sandström, ‘Experimental Methods of X-ray Spec-

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