X
X-Ray Absorption and Scattering
Methods
Dirk L€
utzenkirchen-Hecht
Fachbereich C- Abteilung Physik,
Wuppertal, Germany
Introduction
Studies of the electronic and the atomic structure of
electrodes at the surface and in the bulk material
are of fundamental importance e.g., in corrosion
research, battery technology, electrocatalysis or
electrodeposition. Therefore, a large variety of dif-
ferent in situ and ex situ techniques have been
successfully introduced to the investigation of elec-
trochemical interfaces in the past. Due to possible
changes of the electrode structure related to the loss
of potential control after a removal of the electrode
from the electrolyte, in-situ techniques are in gen-
eral favored compared to ex situ methods such as
photoelectron or Auger-electron spectroscopies
and electron diffraction despite many successful
studies using these vacuum based approaches
(see, e.g. [1]). In contrast, especially photon-in
photon-out techniques using X-rays appear very
promising due to the relatively weak interactions
of hard X-rays and matter – this way the electro-
chemical reactions are not influenced by the X-ray
probe while useful information about the state of
the sample can be achieved. In this contribution,
we will focus on X-ray scattering techniques and
X-ray spectroscopic measurements.
G. Kreysa et al. (eds.), Encyclopedia of Applied Electrochemistry, DOI 10.1007/978-1-4419-6996-5,
# Springer Science+Business Media New York 2014
X-Ray Diffraction (XRD)
The physical basis for X-ray diffraction is Braggs
law, i.e.
nl ¼ 2d cos Y (1)
where l is the X-ray wavelength, d a lattice
spacing in the crystalline sample of interest and
Y the scattering angle between the impinging
radiation and the considered lattice planes.
A constructive interference can thus only occur,
if the optical path difference between the X-rays
which are diffracted from neighboring lattice
planes is equal to an integer multiple of the X-
ray wavelength l. Due to the distribution of the
lattice atoms in the unit cell, each crystal struc-
ture is represented by a set of characteristic lattice
planes, and thus the resulting diffraction pattern
is representative for the considered crystal struc-
ture. In more detail, structure factors Fhkl which
include the positions of the atoms in the crystal
structure under investigation as well as the occu-
pation of these positions by different types of
atoms can be calculated according to
X
Fhkl ¼ f n expð2piQ  Rn Þ (2)
with Rn the lattice vector of the nth atom and Q
the reciprocal lattice vector which represents
scattering processes at the hkl-lattice planes [2].
The summation includes all the atoms in the unit
cell, and fn is the atom form factor, which repre-
sents the scattering power of an individual atom.
X 2154
Basically, fn is determined by the number and the
distribution of the electrons belonging to a single
atom [2]. Values for fn are tabulated e.g. in Ref. [3].
The diffracted intensity then is given by I  |Fhkl|2,
thus not only the positions of the diffraction
peaks are representative for the crystal structure,
but also their intensities. This is in principle
the basis for extremely detailed in-situ investiga-
tions of electrode materials in electrochemical
environments.
As an example, the structure of the passive
layers on iron single crystals formed in slightly
alkaline solution has been studied using synchro-
tron radiation X-ray diffraction [4]. The structure
of those passive layers has been controversially
discussed for decades. While electrochemical
experiments as well as ex-situ surface analytical
experiments using electron diffraction suggest
that the film consists of a duplex structure with
an inner layer of Fe3O4 and an outer layer of
Fe2O3 (maghemite) [5–7], other studies using
e.g. Raman, Mößbauer and X-ray absorption
spectroscopies lead to the conclusion that the
passive film is amorphous or has an extremely
small grain size [8–12]. According to these
experiments, the presence of structures similar
to those of disordered iron hydroxides or
oxyhydroxides seems to be likely, while
a spinel-type structure was deduced from scan-
ning tunnelling microscopy studies [13]. First of
all, the existence of well defined diffraction peaks
in the XRD experiments clearly evidenced the
presence of a well defined crystalline structure,
and a detailed analysis of a large number of
indexed, symmetrically inequivalent diffraction
peaks in terms of their structure factors enabled
the structure identification. In contrast to the
phases described above, a spinel structure with
randomly distributed vacancies on octahedral and
tetrahedral Fe lattice sites and octahedral intersti-
tial sites matches best the experimental data (for
more details see [4]).
Diffraction techniques are of key importance
for the understanding of the functionality and the
improvement of battery materials. In recent
years, numerous studies have appeared making
use of the feasibility to determine the electrode
structure during battery operation using X-ray or
X-Ray Absorption and Scattering Methods
neutron diffraction. Here we will consider an
application of Braggs law using energy disper-
sive X-ray diffraction: While monochromatic
X-rays are used in the conventional setup and
the Bragg angle is varied according to Eq. 1,
a polychromatic X-ray beam combined with
a fixed geometry is used in the case of energy
dispersive diffraction, i.e. the X-ray wavelength
l ¼ hc/E (h, Planck´s constant; c, speed of light;
E, photon energy) is varied instead of the Bragg
angle [14]. Here we will consider the lithium-
titanium-spinel compound Li[Li1/3Ti5/3]O4, the
main feature of which are the minimal variations
of the cubic unit cell that accompany lithium
insertion and extraction, coining the expression
of a zero strain material [15]. This property is of
fundamental impact in any battery application,
because lattice strain is one of the main causes
of electrode capacity fading [16]. In-situ energy
dispersive X-ray diffraction clearly demonstrates
that the positions of the Bragg peaks do not shift
substantially during charge/discharge of the spinel
compound, suggesting that the lithium insertion
processes do not induce any phase transitions
[17]. According to the high-quality diffraction
data, only small variations (<1 %) of the lattice
parameters are resulting [17]. Energy dispersive
diffraction experiments directly profit from the
high intensity and spectral characteristics of syn-
chrotron radiation that are ideal for in situ studies,
making even time-resolved experiments during the
charging/discharging of batteries feasible [17, 18].
Coming back to the detailed analysis of dif-
fraction patterns, we note that such efforts can be
in practice more complicated for real samples for
different reasons. First of all, the crystallites
(grains) inside a polycrystalline sample might
have a preferred orientation (texture), and
accordingly, the Bragg reflexes of all other orien-
tations are extremely suppressed in their intensity
compared to those expected from calculated
structure factors. Such a behavior can be
expected e.g. in the case of epitaxially grown
thin films that adopt the structure or at least the
orientation of the substrate. This is observed e.g.
for the passive films on iron discussed above [4],
and in part also for those on Ni [19] but also for
electrodeposited metal films.
X-Ray Absorption and Scattering Methods
Furthermore, the presence of defects in
a crystal lattice may also alter the diffraction
pattern: Depending on the type and the concen-
tration of the defects, systematic peak broaden-
ing, peak shifts as well as peak splitting may be
observed, and stress and strain may also influence
the diffractograms [20, 21]. Thus the detailed
analysis of measured peak positions, their widths
and intensities can be used for the identification
of the defects existing in a particular sample.
When finite-size effects are included in the
diffraction peak evaluation, the peak widths are
found to be inversely related to the dimension of
the diffracting regions of the crystal; thus, the line
broadening provide information about the parti-
cle size D of small crystallites, for example by
application of the Scherrer formula:
D ¼ Kl=ðDY cos YÞ (3)
where K is the Scherrer constant, which depends
on the shape of the crystallites under investiga-
tion and in most cases is close to 0.9, and DY is
the line width at half maximum (in radians) after
correction for instrumental broadening (see e.g.
[21]). A more sophisticated Fourier analyses of
the line shape may allow determining the particle
size distribution [21, 22]. As a conclusion for the
practical data analysis of real samples, it is by far
not trivial to separate the different contributions.
All the diffraction techniques described so far
are in principle bulk-sensitive techniques only,
and thus the scattering intensities are in general
extremely small if thin surface layers are investi-
gated. Therefore the use of high-intensity syn-
chrotron radiation as well as state-of-the art
detector equipment suited for single photon
counting is recommended in practice. Scattering
contributions from the substrate can substantially
be reduced by using the asymmetric grazing inci-
dence geometry: By using incidence angles
smaller than the critical angle of total reflection,
the penetration depth of the X-rays can be
reduced to some few nm [23], and thus the
scattered intensities are originating from a near-
surface region only [24]. However, the Bragg
peaks related to surface layers still have small
intensities. Furthermore, due to the break of the
2155 X
symmetry at the surface of any single crystal,
there are special Bragg peaks that are sensitive
only to the near-surface structure of the elec-
trodes (surface X-ray scattering, see e.g. [25]).
Moreover, the morphology of the surface sub-
stantially influence the intensity distribution
between the diffraction peaks so that a detailed
picture of electrode surfaces can be gained. For
example, the intensity between the Bragg peaks is
generally smaller for a rough surface compared to
a perfectly sharp interface [25]. A detailed review
on the application of surface X-ray scattering in
electrochemistry has been given recently [26].
Just to mention a few examples, the adsorption
behavior of organic molecules [27], the recon-
struction of metal surfaces under potential varia-
tion in an electrolyte [28] and the distribution of
surface water have been measured [29]. Further
studies deal with electrocatalysis [30] and with
the underpotential deposition of metals – where
the deposition of monolayers may occur for
potentials positive to the thermodynamic equilib-
rium [31, 32].
X-Ray Absorption Spectroscopy
(EXAFS/XANES)
X-ray diffraction experiments are in general
restricted to investigations of crystalline or even
single-crystalline electrode materials, but they
can hardly be used for the investigation of highly
disordered or even amorphous samples. In the
case of corrosion research, species dissolved in
the electrolytes are of particular interest;
especially their valence and coordination (e.g.
complexation) are important to understand corro-
sion or inhibition processes in detail. For those
situations, the X-ray absorption fine-structure
spectroscopy (XAFS) technique may be an alter-
native and complimentary method. In a XAFS
experiment, the absorption of X-rays within the
sample is measured as a function of the X-ray
energy E ¼ hn in the vicinity of an absorption X
edge of an element in the sample, i.e. an
energy, where core electrons can be excited to
unoccupied states above the Fermi or vacuum
level. The energy of the absorption edge is
X 2156
characteristic for the absorbing material and
accordingly the measured edges are signatures
of the atomic species present in a material, with
the intensity of the absorption being directly
linked to the concentration of the considered
element.
Depending on the ligands of the considered
X-ray absorbing atom, the binding energies of
the core electrons are slightly changed, and thus
a precise measurement of the absorption edge
position may yield a sensitive measurement of
the oxidation state of the X-ray absorbing ele-
ment [33, 34]. This is an important characteristic
especially in battery research [35, 36], corrosion
science [37, 38], electrocatalysis and the chemis-
try of fuel cells [39, 40], electrodeposition or
underpotential deposition [41]. As can already
be anticipated from the fact that the transition of
the excited photoelectron can only occur into
unoccupied states, it is clear that the energy
region close to the edge is intimately connected
to the density of unoccupied states of the absorb-
ing element [33, 42]. For higher photon energies,
the photoelectron has enough kinetic energy to
propagate freely through the material, undergo-
ing multiple scattering events at neighboring
atoms. Thereby, the shape of the edge and its
absorption fine structure close to the edge
(XANES) are highly sensitive also to the coordi-
nation of the absorbing atoms [43]. While the
complexity of the involved quantum mechanical
processes makes a full theoretical treatment on an
ab initio basis very difficult [43], it is quite con-
venient to use the XANES as a fingerprint tech-
nique: Near-edge spectra are measured for
a number of standard compounds of the same
element with known valence and crystal structure
and these are compared to the spectrum of the
actual sample [8, 36, 37, 44]. Certain compounds
such as Cr6+ or Mo6+ give rise for distinct pre-edge
peaks so that these species can easily be identified
qualitatively and quantitatively [37, 38].
For samples in an electrochemical environ-
ment, however, the absorber element is typically
present in more than one chemical form.
For example, a battery only consists of a single
phase material if it is fully charged or discharged,
but all intermediate situations are in best case
X-Ray Absorption and Scattering Methods
superpositions of both states [35, 36]. Similarly
only fractions of a catalyst material are modified
during operation, and a metal is in general not
fully present as an oxide or hydroxide during
a corrosion or passivation process. In all those
situations, a quantitative XANES data analysis
may thus be difficult and not straightforward.
For these problems, the application of sophisti-
cated mathematical techniques such as the
principal component analysis (PCA, [45]) is
recommended. A PCA is able to specify whether
or not a chosen reference compound contributes
to the spectrum of the actual sample, and thereby
the application of the PCA yields the number and
type of reference compounds within the sample
[46, 47]. In combination with a least square fit,
the PCA may also provide the concentrations of
all the identified phases [45–48]. This capability
is useful for the investigation of many electro-
chemical reactions, where e.g. reaction interme-
diates have to be identified or the course of
a reaction may be followed quantitatively as
a function of polarization potential or reaction
time [35, 36, 48]. Making use of the extended
X-ray absorption fine structure (EXAFS), even
the detailed atomic configuration in the vicinity
of the X-ray absorbing element can be quantified
irrespective of the state of matter of the sample
[43]. Especially this property makes XAFS an
ideal tool for in situ investigations of all kinds
of electrochemical processes.
Conclusions and Future Directions
Both X-ray scattering and X-ray spectroscopic
methods may provide a detailed, microscopic
picture of the electrode in contact with the elec-
trolyte, and all the information may be obtained
in situ. However, it should be kept in mind that
the described X-ray methods always average over
an extended volume of the investigated samples.
Future efforts should therefore especially include
the use of focussed X-ray beams in order to
combine X-ray scattering and X-ray absorption
techniques with X-ray microscopy, making later-
ally resolved structural investigations feasible.
Using focussing mirrors or X-ray lenses, the
X-Ray Absorption and Scattering Methods
nm domain seems to be accessible, and thus all
localized electrochemical phenomena such as
corrosion, heterogeneous electrocatalysis or the
growth of micro- and nanostructures may be
investigated. Another important aspect is the fea-
sibility of time-resolved experiments: Due to the
large photon flux at modern synchrotron sources,
the time for an individual experiment is not any
more limited by the photon flux of the source.
Thus, extremely fast investigations of dynamic
reactions are possible [48], reaching a resolution
in the ms domain, which is important for many
electrochemical processes.
References
1. Marcus P, Mansfeld F (eds) (2005) Analytical
methods in corrosion science and engineering. CRC
Taylor and Francis, Boca Raton
2. Kittel C (1996) Introduction to solid state physics,
7th edn. Wiley, New York
3. Macgillavry CH, Rieck GD (1962) International
tables for X-ray crystallography, Vol III: mathemati-
cal tables. Kynoch Press, Birmingham
4. Davenport AJ, Oblonsky LJ, Ryan MP, Toney MF
(2000) The structure of the passive film that forms on
iron in aqueous environments. J Electrochem Soc
147:2162–2173. doi:10.1149/1.1393502
5. Haupt S, Strehblow H-H (1987) Corrosion, layer for-
mation and oxide reduction of passive iron in alkaline
solution, a combined electrochemical and surface
analytical study. Langmuir 3:873–885. doi:10.1021/
la00078a003
6. Nagayama M, Cohen M (1962) The anodic oxidation
of iron in a neutral solution. J Electrochem Soc
109:781–790. doi:10.1149/1.2425555
7. Foley CL, Kruger J, Bechtoldt CJ (1967) Electron
diffraction studies of active, passive and transpassive
oxide films formed on iron. J Electrochem Soc
114:994–1001. doi:10.1149/1.2424199
8. Davenport AJ, Sansone M (1995) High resolution in
situ XANES investigation of the nature of the passive
film on iron in a pH 8.4 borate buffer. J Electrochem
Soc 142:725–730. doi:10.1149/1.2048525
9. Long GG, Kruger J, Black DR, Kuriyama M (1983)
Structure of passive films on iron using a new surface-
exafs technique. J Electroanal Chem 150:603–610.
doi:10.1016/S0022-0728(83)80239-3
10. Rubim JC, D€unnwald J (1989) Enhanced Raman
scattering from passive films on silver-coated iron
electrodes. J Electroanal Chem 258:327–344.
doi:10.1016/0022-0728(89)85118-6
11. Gui J, Devine TM (1991) In situ vibrational spectra of
the passive film on iron in buffered borate solution.
2157 X
Corros Sci 32:1105–1124. doi:10.1016/0010-938X
(91)90096-8
12. O’Grady WE (1980) Moessbauer study of the passive
oxide film on iron. J Electrochem Soc 127:555–563.
doi:10.1149/1.2129711
13. Ryan MP, Newman RC, Thompson GE (1995) An
STM study of the passive film formed on iron in
borate buffer solution. J Electrochem Soc 142:
L177–L179. doi:10.1149/1.2050035
14. Giessen BC, Gordon GE (1968) X-ray diffraction:
new high-speed technique based on X-ray spectrog-
raphy. Science 159:973–975. doi:10.1126/sci-
ence.159.3818.973-a
15. Ohzuku T, Ueda A, Yamamota N (1995) Zero-strain
insertion material of Li[Lil/3Ti5/3]O4 for rechargeable
lithium cells. J Electrochem Soc 142:1431–1435.
doi:10.1149/1.2048592
16. Scrosati B (2000) Recent advances in lithium ion
battery materials. Electrochim Acta 45:2461–2466.
doi:10.1016/S0013-4686(00)00333-9
17. Panero S, Reale P, Ronci F, Scrosati B, Perfetti P,
Rossi Albertini V (2001) Refined, in-situ EDXD
structural analysis of the Li[Lil/3Ti5/3]O4 electrode
under lithium insertion-extraction. Phys Chem Chem
Phys 3:845–847. doi:10.1039/B008703N
18. Rowles MR, Styles MJ, Madsen IC, Scarlett NVY,
McGregor K, Riley DP, Snook GA, Urban AJ,
Connolley T, Reinhard C (2012) Quantification of
passivation layer growth in inert anodes for molten
salt electrochemistry by in situ energy-dispersive dif-
fraction. J Appl Crystallogr 45:28–37. doi:10.1107/
S0021889811044104
19. Magnussen OM, Scherer J, Ocko BM, Behm RJ
(2000) In situ X-ray scattering study of the passive
film on Ni(111) in sulfuric acid solution. J Phys Chem
B 104:1222–1226. doi:10.1021/jp993615v
20. Paterson MS (1952) X-ray diffraction by face
centered cubic crystals with deformation faults.
J Appl Phys 23:805–811. doi:10.1063/1.1702312
21. Klug HP, Alexander LE (1974) X-ray diffraction
procedures. Wiley, New York
22. Warren BE, Averbach BL (1952) The separation of
cold-work distortion and particle size broadening in
X-ray patterns. J Appl Phys 23:497. doi:10.1063/
1.1702234
23. Parratt LG (1954) Surface studies of solids by total reflec-
tion of X-rays. Phys Rev 95:359–369. doi:10.1103/
PhysRev.95.359
24. Toney MF, Brennan S (1989) Structural depth profil-
ing of iron oxide thin films using grazing incidence
asymmetric Bragg X-ray diffraction. J Appl Phys
65:4763–4768. doi:10.1063/1.343230
25. Robison IK, Tweet DJ (1992) Surface X-ray diffrac-
tion. Rep Prog Phys 55:599–651. doi:10.1088/0034-
4885/55/5/002 X
26. Nagy Z, You H (2002) Applications of surface X-ray
scattering to electrochemistry problems. Electrochim
Acta 47:3037–3055. doi:10.1016/S0013-4686(02)
00223-2
X 2158
27. Wandlowski T, Ocko BM, Magnussen OM, Wu S,
Lipkowski J (1996) The surface structure of Au(111)
in the presence of organic adlayers: a combined elec-
trochemical and surface X-ray scattering study.
J Electroanal Chem 409:155–164. doi:10.1016/
0022-0728(95)04479-5
28. Ocko BM, Wang J, Davenport A, Isaacs H (1990) In situ
x-ray reflectivity and diffraction studies of the Au(001)
reconstruction in an electrochemical cell. Phys Rev
Lett 65:1466–1469. doi:10.1103/PhysRevLett.65.1466
29. Toney MF, Howard JN, Richer J, Borges GL, Gordon
JG, Melroy OR, Wiesler DG, Yee D, Sorensen LB
(1995) Distribution of water molecules at Ag(111)/
electrolyte interface as studied with surface X-ray
scattering. Surf Sci 335:326–332. doi:10.1016/
0039-6028(95)00455-6
30. Stamenkovic VR, Fowler B, Mun BS, Wang G, Ross
PN, Lucas CA, Marković NM (2007) Improved oxy-
gen reduction activity on Pt3Ni(111) via increased
surface site availability. Science 315:493–497.
doi:10.1126/science.1135941
31. Kondo T, Morita J, Okamura M, Saito T, Uosaki
K (2002) In situ structural study on underpotential
deposition of Ag on Au(111) electrode using surface
X-ray scattering technique. J Electroanal Chem
532:201–205. doi:10.1016/S0022-0728(02)00705-2
32. Tamura K, Wang JX, Adžic RR, Ocko BM
(2004) Kinetics of monolayer Bi electrodeposition
on Au(111): surface X-ray scattering and current
transients. J Phys Chem B 108:1992–1998.
doi:10.1021/jp0368435
33. Lengeler B (1989) X-ray absorption and reflection in
materials science. Adv Solid State Physics 29:53–73.
doi:10.1007/BFb0108007
34. Ressler T, Wong J, Roos J (1999) Manganese
speciation in exhaust particulates of automobiles
using MMT-containing gasoline. J Synchrotron
Radiat 6:656–658. doi:10.1107/S0909049598015623
35. Deb A, Bergmann U, Cairns EJ, Cramer SP
(2004) X-ray absorption spectroscopy study of the
LixFePO4 cathode during cycling using a novel
electrochemical in situ reaction cell. J Synchrotron
Radiat 11:497–504. doi:10.1107/S0909049504024641
36. Wagemaker M, L€ utzenkirchen-Hecht D, van Well
AA, Frahm R (2004) Atomic and electronic bulk
versus surface structure: lithium intercalation in Ana-
tase TiO2. J Phys Chem B 108:12456–12464.
doi:10.1021/jp048567f
37. Schmuki P, Virtanen S, Davenport AJ, Vitus CM
(1996) Transpassive dissolution of Cr and sputter
deposited Cr oxides studied by in situ X-ray near
edge spectroscopy. J Electrochem
143:3997–4005. doi:10.1149/1.1837327
38. L€utzenkirchen-Hecht D, Frahm R (2001) Corrosion of
Mo in KOH: time resolved XAFS investigations. J Phys
Chem B 105:9988–9993. doi:10.1021/jp003414n
39. Russell AE, Rose A (2004) X-ray absorption
spectroscopy of low temperature fuel cell catalysts.
Chem Rev 104:4613–4635. doi:10.1021/cr020708r
X-Ray Diffraction Methods
40. Friebel D, Miller DJ, O’Grady CP, Anniyev T, Bargar
J, Bergmann U, Ogasawara H, Wikfeldt KT,
Pettersson LGM, Nilsson A (2011) In situ X-ray
probing reveals fingerprints of surface platinum
oxide. Phys Chem Chem Phys 13:262–266.
doi:10.1039/c0cp01434f
41. Herrero E, Buller LJ, Abruna HD (2001)
Underpotential deposition at single crystal surfaces
of Au, Pt, Ag and other materials. Chem Rev
101:1897–1930. doi:10.1021/cr9600363
42. Fuggle JC, Inglesfield JE (1992) Unoccupied
electronic states: fundamentals for XANES, EELS,
IPS and BIS, vol 69, Topics in applied physics.
Springer, Berlin
43. Rehr JJ, Albers RC (2000) Theoretical approaches to
x-ray absorption fine structure. Rev Mod Phys
72:621–654. doi:10.1103/RevModPhys.72.621
44. Davenport AJ, Sansone M, Bardwell JA, Aldykiewicz
JA Jr, Taube M, Vitus CM (1994) In situ multielement
XANES study of formation and reduction of the oxide
film on stainless steel. J Electrochem Soc 141:L6–L8.
doi:10.1149/1.2054720
45. Malinowski ER, Howery DG (1980) Factor analysis
in chemistry. Wiley, New York
46. Wasserman SR (1997) The analysis of mixtures:
application of principal component analysis to XAS
spectra. J Phys IV (France) 7:C2-203–C2-205.
doi:10.1051/jp4/1997163
47. Ressler T, Wong J, Roos J, Smith IL (2000) Speciation
of manganese particles in exhaust fumes of cars
utilizing MMT. Environ Sci Technol 34:950–958.
doi:10.1021/es990787x
48. Grunwaldt J-D, L€ utzenkirchen-Hecht D, Richwin M,
Grundmann S, Clausen BS, Frahm R (2001) Piezo
X-ray absorption spectroscopy for the investigation
of solid-state transformations in the millisecond
range. J Phys Chem B 105:5161–5168. doi:10.1021/
jp010092u
X-Ray Diffraction Methods
Deepak Dubal and Rudolf Holze
AG Elektrochemie, Institut f€ur Chemie,
Technische Universit€at Chemnitz, Chemnitz,
Germany
Soc
X-Ray Diffraction
Besides the use of X-ray absorption for the
elucidation of adsorbates and adsorbate-surface
interaction X-ray diffraction is a tool useful in
particular for the determination of structural data
X-Ray Diffraction Methods
on a very high level of precision provided
the presence of a minimum level of structuring.
The advent of synchrotron radiation providing an
intense source of electromagnetic radiation in the
range of X-rays has greatly stimulated the appli-
cation of X-ray diffraction methods. A broad
overview of experimental approaches and recent
results has been provided elsewhere [1–5].
A wave front of electromagnetic radiation
arriving at an array of atoms acting as scattering
centers causes these centers to emit (scatter)
spherical waves of electromagnetic radiation of
the same energy like the incoming radiation.
Depending on the wavelength of the employed
radiation, the a ngle of incidence, and the spatial
arrangement of the scatterers, the emitted
radiation of the different scatterers will interfere
constructively or destructively. With a crystalline
sample containing a considerable number of
scatterers, the conditions for constructive inter-
ference will be fulfilled only when the angle of
incidence relative to the crystallographic plane,
and the scatterers are located in is matched very
precisely. The relationship is given by the Braggs
equation n l ¼ 2 dhkl sin # with n being the order
of the reflection, l the wavelength of the used
radiation, dhkl being the crystallographic spacing,
and # the angle of diffraction (i.e., the angle of
incidence). From the number and intensities
found at different values of values of #, the
crystallographic data of the sample under inves-
tigation can be derived. In order to obtain
a diffractogram a crystal is illuminated with
X-rays of a fixed wavelength l. The angle of
incidence is varied by turning the crystal, and
the diffracted intensity is measured. (for further
details, see [6, 7]).
X-ray diffraction as described above is done
in an angular dispersive way (ADXD). The
diffracted X-ray intensity is displayed as
a function of the scattering angle 2#. This
diffractogram is correct only for the single wave-
length used during its acquisition. Any change of
the incident wavelength causes a nonlinear
stretching of the diffractogram. A more general
display is obtained by displaying the scattered
intensity as a function of the scattering parameter
q. Further details and advantages of this approach
2159 X
have been discussed elsewhere [8, 9]. Conse-
quently two different ways to obtain
a diffractogram are possible: use of light with
a fixed wavelength and measurement of the
diffracted intensity as a function of the scattering
angle or use of polychromatic light (Brems-
strahlung) and detection of the diffracted radia-
tion with a solid-state detector connected to
a multichannel analyzer.
A setup includes a source for X-rays
(usually a fixed or a rotating anode source, more
recently synchrotron radiation has become an
attractive choice as a source of radiation),
a monochromator or at least a filter to select the
desired wavelength, the spectroelectrochemical
cell, and the detector (for an overview on
detectors see [3]).
The cell has to fulfill three general
requirements:
• The path for the incident and the reflected
beam should not be obstructed.
• The number of scattering or absorbing parti-
cles beyond the sample under investigation in
the beam path should be kept at a minimum.
• The electrochemical characteristics of the cell
(like e.g., even current distribution, reliable
potential control, low iR drop) should be as
perfect as possible.
For X-ray diffraction experiments two basic
designs are possible: the Bragg (or reflection) and
the Laue (or transmission) mode. In electrochem-
ical investigations the former is better suited for
studies of adsorbates or of other features parallel
to the electrode surface, whereas the second
mode is suitable for thick films or layers. In
both cases a cell window as transparent as possi-
ble for X-rays with sufficient stability towards
this radiation is needed. Most commonly thin
polymer foils (Mylar ® or Melinex ®) are used.
A typical design of a cell of the Laue type as
depicted below shows the X-ray passing through
two polymer film windows and the electrolyte
solution (Fig. 1).
The working electrode is coated onto one of X
the windows. In order to keep scattering from the
electrolyte solution low, one window is mounted
on the end of a hollow syringe barrel. For
electrochemical measurements it is retracted to
X 2160
provide acceptable current distribution, and for
X-ray measurements the barrel is moved as close
as possible towards the fixed window. An obvi-
ous drawback of the cell design is the poor
electrochemical properties of the cell in the latter
position. A spectroelectrochemical cell of the
Bragg (reflection) type as used for the investiga-
tion of materials which are chemically or
electrochemically deposited onto a gold film
sputtered before onto a porous membrane foil
has been described [10]. The cross-section as
displayed below shows the Prussian blue-coated
membrane assembly with its coating towards
a polyethylene film transparent and amorphous
for X-rays (Fig. 2).
The electrolyte penetrates the porous mem-
brane, via the porous glass body, and the glass
fiber paper connection is provided with the silver
chloride-coated silver plate acting both as
a reference and a counter electrode. The electro-
chemical behavior of the cell as demonstrated
with cyclic voltammetry is fairly close to stan-
dard electrochemical cells. Results show changes
reference electrode compartment
cell window
X-rays
counter electrode
working electrode layer
cell window
X-Ray Diffraction Methods, Fig. 1 Spectroelectro-
chemical cell for X-ray diffraction studies in transmission
mode
to detector
X-Ray Diffraction Methods, Fig. 2 Spectroelectrochemical cell (for better identification of components in exploded
arrangement) for in situ X-ray diffraction studies according to [10]
X-Ray Diffraction Methods
of lattice constants of Prussian blue as a function
of the electrode potential and the transferred
charge. Because of the penetration depth of
X-rays and the need for a minimum of crystallin-
ity, this approach is not exactly surface sensitive;
it probes instead the interphase between the
current collector (i.e., the gold layer) and the
electrolyte solution. Results obtained during
charging/discharging of TiS2 (as proposed
for use in secondary lithium batteries [11])
involving formation of LiTiS2 are displayed
below; the employed cell is depicted thereafter
(Figs. 3 and 4).
Upon discharge lithium is intercalated. This
results in shifts of the (101), (002), and
(100) Bragg peaks. Detailed studies of the vari-
ous shifts as a function of the state of charge/
discharge reveal further information on the mech-
anism of the different phase transitions [12].
Reactions of lithium with S8 in a secondary Li/S
cell have been tracked with in situ X-ray diffrac-
tion [14]. The electrochemical reaction of lithium
with crystalline silicon was monitored [15].
Various LixSiy phases were identified. The tran-
sition from the crystalline into the amorphous
state in the first lithium intercalation was
observed [16]. For alternate cell constructions,
see [17], and for a cell used for studies of ion
insertion into electrode materials, see [18].
A complete cell not modified in any way has
been used with high-energy X-rays from a
synchrotron source for simultaneous measure-
ment of diffraction patterns of cell components
of a lithium ion battery; recorded diffraction
peaks were assigned to cathode and anode
material [19]. A cell particularly suitable for
X-ray in
polyethylene foil
membrane filter
sintered glass
glass fiber
paper
silver plate
cell mount
X-Ray Diffraction Methods
measurements under ultrapure conditions has
been described [20]. Basically the same design
has been employed in a study of the solid-state
electrochemistry of PbO and Pb(OH)Cl
(laurionite) [21]. The particles of red PbO
(litharge) were attached to a paraffin-
impregnated graphite (PIG) rod used as
a working electrode. X-ray diffraction patterns
obtained at various electrode potentials (see
Fig. 5 below) show peaks indicative of PbO,
a mix of PbO and Pb, and finally of Pb as
a function of reduction potential and time
(Fig. 5).
Reflexes of graphite were also observed, they
could be distinguished easily from those of the
electrochemically active material. The reduction
proceeds entirely as a solid state reaction, no
evidence of solution phase intermediates was
observed.
Improved surface specificity can be obtained
by making measurements at grazing angle of inci-
dence. The structure of small two-dimensional
1 Cell designs and examples discussed above
0.8
charged
0.6
l/lo / −
2161 X
clusters and linear nanostructures of copper and
cadmium deposits on Pt(533) at characteristic
electrode potentials in the upd range has been
studied with GIXD combined with GIXAFS [22].
Using X-rays provided by a synchrotron (the
method is now named SR-GIXRD), the corrosion
of mild steel in the presence of carbon dioxide
containing brine electrolyte solutions was studied.
The mechanism of corrosion, in particular
corrosion products present as thin films like
Fe2O2CO3, Fe2O2CO3, and Fe2(OH)2CO3, was
identified with SR-GIXRD [23]. Investigations of
iron chalcogenide glasses suitable for ion-selective
electrodes ISE with a combination of electrochem-
ical impedance measurements and GIXRD have
been reported together with a description of
a suitable electrochemical cell [24, 25]. Selective
dissolution of various crystallographic surfaces
of iron chalcogenides associated with electrode
potential shifts of these materials employed in
ion-selective electrodes has been monitored with
SR-GIXRD [26]; results were found to be in
agreement with those obtained with AFM.
pertain to X-ray diffraction performed in the
angular dispersive mode, i.e., the angle of
incidence is varied by, e.g., turning the electro-

chemical cell with respect to the radiation

0.4 discharged
source.
As already mentioned energy dispersive mea-
0.2 surements are possible with the spectroelectro-
chemical cell staying in place, whereas the
0
28 29 30 31 32 33 34 35 wavelength of the incident radiation is varied.
2 − /⬚ An additional advantage of EDXD is the high
X-Ray Diffraction Methods, Fig. 3 In situ X-ray
intensity of X-ray radiation in the employed
diffraction pattern of TiS2 recorded during charging/ energy range with an upper limit only given by
discharging experiments (Based on data in [12], see the power supply of the X-ray tube. The strong
also [13]) X-ray absorption of standard K- and L-lines in the

Cu Kα radiation

window X
X-Ray Diffraction
Methods, Fig. 4 In situ X- cathode
ray diffraction separator
electrochemical cell anode
(Based on [12])
X 2162
X-Ray Diffraction 1300
Methods, Fig. 5 In situ
X-ray diffraction pattern
of PbO and its reduction
products: before reduction, 1000
at EAg/AgCl ¼ 0.5 V (top);
during reduction at
Intensity / cps
EAg/AgCl ¼ 1 V; after
reduction, at EAg/AgCl ¼
1.3 V (bottom) (Based on 700
data by [21])
400
G
100
26
range of lower energies caused by electrochemi-
cal cell components is no problem, because
usually employed construction materials show
only weak absorption at higher wavelengths [9].
The poor resolution of the solid-state detector
causes a broadening of the peaks in the measured
diffractogram [9]. Results reported so far
deal with intercalation materials as used in
batteries [9].
Application of time-resolved high-energy
X-ray diffraction on platinum nanoparticles in
fuel electrodes have been described [27]. Results
indicate severe surface reconstruction of the
nanoparticle surface showing at least three types
of Pt-O bonds (adsorbed OH, adsorbed atomic
O and amorphous PtOx) under oxidative
conditions.
X-ray diffraction has also been used in studies
of solid electrolytes as reviewed elsewhere [28].
Diffraction techniques (including X-ray as well
as neutron diffraction) as applied in electrolyte
solution studies are described in [29].
Surface X-Ray Diffraction (SXD)
X-ray diffraction discussed so far as applied to
the elucidation of the crystallographic structure
of thick layers, films or other three-dimensional
X-Ray Diffraction Methods
G
G
31 36 41 46
2Θ / ⬚
samples can also be applied to basically
two-dimensional structures on surfaces or at
interfaces based on various instrumental
advances, in particular the use of synchrotron
radiation. The slightly gradual distinction implies
possible overlap between both groups of
methods. This way information on the two-
dimensional periodicity of surface layers can be
obtained. The required surface sensitivity can be
obtained primarily by employing an angle of
incidence less than or in the order of the critical
angle. This results in a significantly reduced
depth of penetration of the X-rays, scattering
from the bulk of the sample is also diminished.
Under these conditions the ratio of the signal
from the surface vs. the signal from the bulk (or
substrate) can be enhanced by a factor of 2/yc
(with yc being the critical angle of total external
reflection in radians.). yc is about 0.5 (or 9 mrad)
at X-ray frequencies typical for metals in contact
with transparent incident phases. These condi-
tions are also known as total reflection Bragg
diffraction [30]. If grazing angle conditions (i.e.
angle of incidence y about 3.5 or lower) are
employed the method is also named grazing
incidence X-ray diffraction GIXRD. Further
enhancement of general and surface sensitivity
can be achieved by applying an electrode poten-
tial modulation procedure combined with an
X-Ray Diffraction Methods
appropriate data treatment. This way only poten-
tial dependent features in the diffractogram will
become visible whereas features (Bragg reflexes)
of the bulk not affected by the electrode potential
will cancel out. Because of fluctuations in the
intensity of the X-ray source and other experi-
mental components it is insufficient to record
complete diffractograms sequentially; instead
a slow potential modulation (with the frequency
set to a value resulting in a time constant
sufficiently longer than that of the occurring
electrochemical process) is applied. Using
computer-based data acquisition the respective
data are stored and treated; for further details
and an overview see [5].
The electrochemical cells described in the
preceding section can be used. A cell design
with a significantly reduced radiation absorption
of the electrolyte solution film as used for specu-
lar X-ray reflectivity measurements can also be
used. Electrode potentials are selected previously
based on standard electrochemical experiments
(e.g. cyclic voltammetry) with respect to
well-defined changes of the electrode/solution
interface (e.g. potential steps between potentials
of complete desorption and maximum adsorp-
tion). Control of the potentiostat and the X-ray
diffractometer as well as data acquisition, storage
and manipulation are done with a suitably
programmed computer.
Typical examples include studies of
underpotential deposition of various metals on
metallic substrates. The structure of the upd
layer [31, 32], the position of adsorbed anions
and water molecules on top of the upd layer and
the respective bond angles and lengths could be
elucidated [33, 34]. Surface reconstruction
caused by e.g. weakly adsorbed hydrogen [35],
surface expansion effects of low-index platinum
and gold surfaces correlated with adsorption/
desorption of solution species [36] and crystallo-
graphic transformations in layers of NiOH2 have
been studied [37]. In a corrosion study of
a Cu3Au(111) alloy single crystal used as
a model system initial stages of corrosion, in
particular structure formation, have been eluci-
dated with surface XRD [38]. Evidence of diffu-
sion of gold atoms into an upd-Te layer on top of
2163 X
a Au(111) has been reported [31]. In a study of
the water layer structure on a Cu(111) electrode
surface during hydrogen evolution combining
SXD and IRRAS showed a closest packing-like
stacked structure with significantly different
inter- and intra-layer specific oxygen-oxygen
nearest neighbor distances [39]; the infrared
spectra indicated the presence of both free and
hydrogen-bonded hydroxyl ions.
Surface Differential X-Ray
Diffraction (SDD)
The scattered X-ray from crystal planes or a thin
metal film can interfere coherently with
scattered X-rays from an adsorbate layer. This
phenomenon is called surface differential dif-
fraction SDD or Bragg peak interference. The
theory has been described elsewhere in detail
[40, 41]. From SDD measurements information
on the relative amount of material in the adsor-
bate layer (coverage) and the distance between
atoms in the top layer of the substrate and in the
adsorbate layer as a function of electrode poten-
tial can be derived.
The experimental setup uses a working
electrode prepared from mica coated with the
metal to be investigated (e.g. silver) by vapor
deposition. Because of the mode of growth
a certain monocrystalline orientation will result
(e.g. (111) in case of silver). The working
electrode is attached to an electrochemical cell
equipped with counter and reference electrode
and the standard ancillary equipment for electro-
chemical measurements. The X-ray of well-
defined wavelength from a standard laboratory
source or from a synchrotron (selected with e.g.
a Si(220) monochromator) impinges on the
working electrode through the mica substrate.
Diffracted intensity is collected with
a multichannel analyzer; it can be done in real
time during electrode potential scans. Investi-
gated systems include predominantly metal X
adlayers (upd layers) on metal surfaces [41, 42].
Data on mode of layer growth, adsorbate-atom
and substrate-atom distance and relaxation of
involved atom layers were obtained.
X 2164
Future Directions
In studies of solid materials like active masses in
electrochemical energy storage and conversion
devices knowledge of structural changes is of
growing importance. Application of X-ray
diffraction methods in particular under in situ
conditions will thus increase.
Cross-References
▶ Insertion Electrodes for Li Batteries
▶ Electrode
▶ Solid State Electrochemistry,
Electrochemistry Using Solid Electrolytes
▶ X-Ray Absorption and Scattering Methods
References
1. (2002) Special issue of Electrochim Acta 47:3035
2. Robinson J (1990) In: Gutiérrez C, Melendres C (eds)
Spectroscopic and diffraction techniques in interfa-
cial electrochemistry, vol 320, NATO ASI series C.
Kluwer, Dordrecht, p 313
3. Robinson J (1988) In: Gale RJ (ed) Spectroelectro-
chemistry. Plenum Press, New York, p 9
4. Holze R (2007) Surface and interface analysis: an
electrochemists toolbox. Springer, Heidelberg
5. Zegenhagen J, Renner F (2006) Nachr Chem 54:847
6. Massa W (1996) Kristallstrukturbestimmung.
Teubner Verlag, Stuttgart
7. Clegg W (2001) Crystal structure analysis. Oxford
University Press, Oxford
8. Caminiti R, Rossi Albertini V (1999) Int Rev Phys
Chem 18:263
9. Rossi Albertini V, Perfetti P, Ronci F, Scrosati
B (2001) Chem Mater 13:450
10. Ikeshoji T, Iwasaki T (1988) Inorg Chem 27:1123
11. Whittingham MS (1976) Science 192:1126
12. Chianelli RR, Scanlon JC, Rao BML (1979) J Solid
State Chem 29:323
13. Chianelli RR, Scanlon JC, Rao BML
(1978) J Electrochem Soc 125:1563
14. Puglisi V, Simoneau M, Geronov Y 210. Electro-
chemical society meeting, Cancun,
29.10.–03.11.2006, Extended abstract #164
15. Li J, Dahn JR 210. Electrochemical society meeting,
Cancun, 29.10.–03.11.2006, Extended abstract #261
16. Li J, Dahn JR (2007) J Electrochem Soc 154:A156
X-Ray Diffraction Methods
17. Nishizawa M, Uchida I (1998) Denki Kagaku 66:991
18. Bergström O, Gustafsson T, Thomas JO (1998) J Appl
Crystallogr 31:103
19. Li ZG, Harlow RL, Gao F, Lin P, Miao R, Liang
L (2003) J Electrochem Soc 150:A1171
20. Koop T, Schindler W, Kazimirov A, Scherb G,
Zegenhagen J, Schulz T, Feidenhans’l R, Kirschner
J (1998) Rev Sci Instrum 69:1840
21. Meyer B, Ziemer B, Scholz F (1995) J Electroanal
Chem 392:79
22. Prinz H, Strehblow HH (2002) Electrochim Acta
47:3093
23. De Marco R, Jiang Z-T, Pejcic B, Poinen E (2005)
J Electrochem Soc 152:B389
24. de Marco R, Pejcic B, Prince K, van Riessen A (2003)
Analyst 128:742
25. De Marco R, Jiang Z-T, Martizano J, Lowe A, Pejcic
B, van Riessen A (2006) Electrochim Acta 51:5920
26. de Marco R, Jiang ZT, Pejcic B, van Riessen A (2006)
Electrochim Acta 51:4886
27. Imai H, Izumi K, Kubo Y, Kato K, Imai Y Extended
abstracts of the 209th meeting of the electrochemical
society Spring Denver, Colorado, USA,
07.05.–11.05.2006, Ext. Abstr. #302
28. Wagner JB Jr (1991) In: Varma R, Selman JR (eds)
Techniques for characterization of electrodes and
electrochemical processes. Wiley, New York, p 3
29. Enderby JE (1991) In: Varma R, Selman JR (eds)
Techniques for characterization of electrodes and
electrochemical processes. Wiley, New York, p 327
30. Marra WC, Eisenberger P, Cho AY (1979) J Appl
Phys 50:6927
31. Kawamura H, Takahasi M, Hojo N, Miyake M,
Murase K, Tamura K, Uosaki K, Awakura Y, Mizuki
J (2002) J Electrochem Soc 149:C83
32. Fleischmann M, Mao BW (1988) J Electroanal Chem
247:297
33. Nakamura M, Endo O, Ohta T, Ito M, Yoda Y (2002)
Surf Sci 514:227
34. Herrero E, Glazier S, Abruna HD (1998) J Phys Chem
B 102:9825
35. Fleischmann M, Mao BW (1988) J Electroanal Chem
247:311
36. Lucas CA (2002) Electrochim Acta 47:3065
37. Fleischmann M, Oliver A, Robinson J (1986)
Electrochim Acta 31:899
38. Renner FU, Stierle A, Dosch H, Kolb DM, Lee T-L,
Zegenhagen J (2006) Nature 439:707
39. Ito M, Yamazaki M (2006) Phys Chem Chem Phys
8:3623
40. Rayment T, Thomas RK, Bomchil G, White JW
(1981) Mol Phys 43:601
41. Chabala ED, Rayment T (1994) Langmuir 10:4324
42. Ramadan AR, Chabala ED, Rayment T (1999) Phys
Chem Chem Phys 1:1591