Chapter 13

Nonstoichiometric Compounds
J.-L. Zhang and G.-Y. Hong
Chinese Academy of Sciences, Changchun, China

In solid-state chemistry, the concept of compound has been performance. The transport properties are affected by the
expanded from the molecular level to the crystal structure concentration of sodium ion vacancies and the thermo-
level. For example, a nonstoichiometric compound is a type electric properties can be improved by addition of dopants
of special solid-state compound with definite structure and such as silver [4]. Their unique properties are determined
thermodynamic characteristics, which differs from its by their solid phase composition, macroscopic thermody-
stoichiometric counterpart. These nonstoichiometric com- namic properties and microscopic crystal defect structure.
pounds characteristically display conductivity, magnetism, Therefore study of the nonstoichiometric compounds has
catalytic nature, color, and other unique solid-state prop- become an active research field in solid-state chemistry and
erties, which have important technological applications. For defect chemistry.
instance, as a promising candidate for next-generation In chemistry, the law of definite proportions states that a
nonvolatile memory devices, the nonstoichiometric stron- chemical compound always contains exactly the same
tium titanate film shows bipolar resistance-switching proportion of elements by mass. An equivalent statement is
properties with enhanced performance and high- the law of constant composition, which states that all
scalability behavior. Experimental and calculated results samples of a given chemical compound have the same
demonstrate that the migration of anion and cation va- elemental composition. The law requires that for every
cancies and the formation of insulating vacancy clusters compound, the proportion of elements by mass should not
near the vicinity of the interface are the fundamental have any change whatever to their origin, existence form,
switching mechanism [1]. Nonstoichiometric In2O2.68 and preparation and determination methods. If a chemical
electrospinning nanowires with below-band gap photo- compound obeys the law of definite proportions, it is called
response and electrical properties would have wide appli- a stoichiometric compound. The stoichiometric compound
cation in the field of energy conversion and fire/flame is also referred to as Daltonides, from John Dalton, who
detection. The dramatically enhanced photoconduction advocated theories of the law of definite proportions in the
under below-band gap light illumination is attributed to the 19th century. Although the law of definite proportions is
transition from defect levels (e.g., oxygen vacancies) [2]. very useful in the foundation of modern chemistry, it is not
As a radar-absorbing material and hyperthermia agent, the universally true. For crystalline compounds the precise
nonstoichiometric zinc ferrite (Zn0.468Fe2.532O4) nano- stoichiometric composition [e.g., dry ice (i.e., solid CO2)
particles with a high room temperature saturation magne- and ice (i.e., solid H2O)] is the exception rather than the
tization of 110 emu g
1 have potential application in the rule because real crystals always contain defects.
military and biomedical fields. The extraordinary magnetic As opposed to the stoichiometric compounds or
property may be derived from the Zn substitution of Fe Daltonides, the nonstoichiometric compounds are also
atoms at the tetrahedral site (A site) in the spinel magnetite known as Berthollides from the name of the chemist Claude
phase [3]. Thermoelectric conversion devices allow for the Louis Berthollet. Nonstoichiometric compounds are
direct conversion of heat to electrical energy and have chemical compounds deviated from stoichiometry, namely,
important remote applications for spacecraft electric power. their elemental composition cannot be represented by a
NaxCoO2 is an important layered cobaltite-based thermo- ratio of well-defined natural numbers, and therefore they
electric material because of its good thermoelectric violate the law of definite proportions. The composition of

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Copyright © 2017 Elsevier B.V. All rights reserved.
330 Modern Inorganic Synthetic Chemistry

a nonstoichiometric compound usually varies in a contin- phase in the range of composition change. Thus the stoi-
uous manner over a narrow range. Wüstite, ferrous oxide, is chiometrically ideal crystal has no special status.
an example of a nonstoichiometric compound. Its chemical A nonstoichiometric solid-state substance may be stated
formula can be written as Fe1
xO, where x may have according to the following two aspects: (1) the non-
values varying from 0.05 to 0.15, and its physical and stoichiometric compound defined by pure chemistry was a
chemical properties will vary somewhat depending on the uniform physical phase in which the nonstoichiometric
value of x [5]. composition can be determined by means of chemical
Nonstoichiometry is very pervasive among the solid analysis, X-ray diffraction analysis, and equilibrium vapor
compounds of transition metals containing lanthanide and pressure; and (2) it is difficult to examine the concentration
actinide metals (e.g., Fe1
xO, TiOx, a-CeO2
x, UO2þx) of the lattice defects by measurement of chemical analysis
[5,6]. In fact, nonstoichiometry is becoming the rule rather or X-ray diffraction analysis because of the small compo-
than the exception and represents a challenge and new sition deviation. But they can be studied by measuring their
opportunity in chemistry. To explore their specific properties optical, electrical, and magnetic properties [8].
and potential applications, it can be foreseen that synthesis Thermodynamically, taking the G (free energy)
x
and characterization of the nonstoichiometric compounds (composition) relation of two component systems at a fixed
are an important task or challenge for us to confront. temperature, for example, we explain the concept of what
In this chapter, definition and classification of the a nonstoichiometric compound is. In the system a non-
nonstoichiometric compounds as well as their point defects stoichiometric phase AB is produced by the coexistence of
are first introduced. Next, some important synthesis two linear phases A2B and AB2, as shown in Fig. 13.1 [9].
methods of the nonstoichiometric compounds will chiefly Dots a and b stand for free energies of the pure phases A
be summarized. Finally, characterization methods of the and B, respectively, and dots c and f are free energies of the
nonstoichiometric compounds are presented. accurately stoichiometric compounds A2B and AB2,
respectively. If the linear phases A2B or AB2 deviate
from their stoichiometric compositions to form an A-rich or
13.1 INTRODUCTION TO B-rich single phase, the corresponding free energies will
NONSTOICHIOMETRIC COMPOUNDS
13.1.1 Definition
In solid-state chemistry, the nonstoichiometric compound
represents a uniform physical phase in which unit cell
parameters vary with their composition in a continuous
manner, and free energy is a function of composition and
temperature of the system. That is to say, “it is to be defined
in strictly operational terms; the criterion is that a crystal-
line compound, in equilibrium with its environment,
behaves as a thermodynamically bivariant system. The
chemical potentials of the components are a continuous
function of the composition of the solid, over an observable
range of composition.” [5] The structural and thermody-
namic criteria of the nonstoichiometric compounds are in
agreement in nature. Structure is related to microcosmic
characteristics, while thermodynamics deals with macro-
scopic systems.
Structurally, though, there exists a broad-range change in
composition for a nonstoichiometric compound, the X-ray
diffraction pattern always possesses the characteristic of
the parent crystallography cell and the unit cell parameters
continuously vary with its composition [7]. This is different
from a crystalline stoichiometric compound or a mixture
composed of crystalline stoichiometric compounds for FIGURE 13.1 Relationship curve of the nonstoichiometric compound
which all have their own characteristic X-ray diffraction AB and the linear phases A2B and AB2. Reproduced with permission from
Y.Q. Zhou, J.Z. Li, Inorganic Phase Equilibrium, Non-Stoichiometric
patterns and unit cell parameters. Compound (Inorganic Chemistry Series), vol. 14, Academic Press,
Schottky and Wagner pointed out that at temperatures Beijing, 1997, pp. 372e376. Copyright 1997 of the Academic Press of
above 0K, every solid-state compound exists in a single China.
 Nonstoichiometric Compounds Chapter | 13 331

become very high, as two sharp wedge-shaped curves formed, and in the second and third cases deviation from
shown in Fig. 13.1. If coexistence of the pure A phase and stoichiometric composition (A:B ¼ 1:1) would result in the
the linear phase A2B is permitted, the corresponding free formation of lattice imperfections. Based on this criterion,
energy will be the simple addition of the G(A) and G(A2B), the nonstoichiometric compounds can be divided into four
which is denoted using a tangent ac. Similarly, the corre- types [14]: (1) anion vacancy type (e.g., TiO2
x, ZrO2
x);
sponding free energy for addition of the G(B) and G(AB2) is (2) cation vacancy type (e.g., Fe1
xO, Cu2
xO); (3) anion
denoted using a tangent bf. Asymmetry line de indicates that interstitialcy type (e.g., UO2þx); and (4) cation interstitialcy
free energy of the nonstoichiometric phase AB gently varies type (e.g., Zn1þxO, Cd1þxO).
with its composition in a continuous manner because of On the basis of composition range, the nonstoichiometric
easy formation of the point defects. But the type of crystal compounds can be classified into two groups: (1) the stoi-
structure in the homogeneity region of existence of the chiometric deviations in nonstoichiometric compounds are
nonstoichiometric compound remains unaltered with change very small, but they are detectable within the range only of
of its composition. This is a key characteristic and general special analytical experiments or of methods based on direct
phenomenon of a nonstoichiometric phase, which is determination of carrier concentrations. Examples are PbSlþx,
produced by the point defects of thermal equilibrium [5]. In Cu2Olþx, ZnOl
x, alkali halides containing F-centers, etc. It is
contrast, some radiation-induced defects [e.g., a pair of reasonable to assume that the stoichiometric deviation is
defects (an anion vacancy and an anion interstitial) in the small enough for the lattice defects to be isolated and
colored NaCl formed after ionizing radiation] are not those randomly distributed. (2) The crystals show gross departure
of thermal equilibrium and disappear upon annealing. from ideal stoichiometry (e.g., the nonstoichiometric rare-
Strictly speaking, such a compound as the colored NaCl is earth oxides, etc.). Their lattice defects are not regarded as
often considered as a defect compound, not a non- randomly distributed because of the existence of the interac-
stoichiometric compound [10]. tion between point defects. The nonstoichiometry is caused
Most nonstoichiometric compounds can be expressed by assimilation of vacancies or interstitial atoms as structure
by such formulas as WO3
x, Co1
xO, or Zn1þxO elements of the crystal [15]. The former are referred to as
(0 < x < 1) because they have compositions that are close narrow-range nonstoichiometric compounds, which deviate
to those of stoichiometric compounds. But in certain cases only slightly from the stoichiometric compounds, while the
apparent nonstoichiometry results from the existence of latter are so-called wide-range nonstoichiometric com-
homologous series of stoichiometric compounds, such as pounds, which grossly depart from ideal stoichiometry [9].
the series of molybdenum oxides having the formulas
MonO3n
1 (n ¼ 8, 9, 10, 11, 12, and 14); a true non- 13.1.3 Point Defects in the
stoichiometric compound MoO3
x would show a contin-
Nonstoichiometric Compounds
uous variation of x within some range of values, and no
discrete species would be detectable [11]. Similarly, the The existence of nonstoichiometric compounds indicates the
niobium oxides NbO2.500, NbO2.4906, NbO2.4800, NbO2.468l, presence of defects in the lattice structures of crystalline
NbO2.4545, and NbO2.467 do not represent compositions substances, such as the absence of ions from sites that would
within some range of stoichiometry, but are a succession of normally be occupied. But it should be noted that there is no
discrete, crystallographically defined compounds Nb28O70 absolute defect-free crystals at T > 0K, so that the presence
(Nb2O5), Nb53O132, Nb25O62, Nb47O116, Nb22O54, and of defects is not by itself an indication of nonstoichiometry.
Nb12O29 [5]. Therefore the term “nonstoichiometric com- For example, a sodium chloride crystal that lacks a sodium
pound” can be occasionally used loosely. ion and a chloride ion is defective but still stoichiometric
because the numbers of sodium ions and chloride ions are
the same; if the sodium ion site, however, is filled by a
13.1.2 Classification
neutral sodium atom, which then gives up its valence
Most of the nonstoichiometric compounds are transition electron to fill the chloride ion site, the crystal defect is
metal oxides, but also include fluorides, hydrides, carbides, remedied, but the crystal is now nonstoichiometric because
nitrides, sulfides, tellurides, and so on [4,12,13]. The non- it contains more sodium ions than chloride ions [11].
stoichiometric compounds existing only in the condensed The defects are mainly crystallographic point defects such
state are often classified in terms of element composition. as interstitial atoms and vacancies resulting from excess or
The simplest way to classify nonstoichiometric deficiency of a component element, respectively. In fact, point
compounds is to consider which element is in excess and defects are an important cause of formation of the non-
how this excess is brought about. For example, a perovskite- stoichiometric compounds. Moreover, ionic and electronic
type nonstoichiometric oxide such as oxygen-deficient point defects determine, to a large extent, the fundamental
ABO3
x, A-deficient A1
xBO3, or B-deficient AB1
xO3 properties of functional materials composed of the non-
often appears. In the first case, an oxygen vacancy would be stoichiometric compounds.
332 Modern Inorganic Synthetic Chemistry

The point defects can be formed by creating vacancy electron or hole trapped at an anion vacancy site. Electrons
and interstitial up to a certain concentration, which leads to in such a vacancy tend to absorb light in the visible
a minimum of free energy. The concepts of vacancy and spectrum such that a material that is usually transparent
interstitial are as follows: if an atom is not present on the becomes colored. The color is the complement of what is
site that it should occupy in a perfect crystal then a vacancy absorbed by the color center. Colors are produced in most
is located at that site, whereas if an atom is present on any of the alkali halides following irradiation with ionizing
site that would be unoccupied in a perfect crystal then that radiation and are characteristic of the crystal not the
atom is an interstitial. radiation source used. Several different types of color
The nonstoichiometric compounds include two types of center have been identified and some of the common ones
important point defects: Frenkel defect and Schottky defect. are illustrated in Fig. 13.3 for the alkali halides [16].
A nearby pair of a vacancy and an interstitial is often called The point defects still employ symbols of the
a Frenkel defect or Frenkel pair. The phenomenon is named KrögereVink defect notation, which has been adopted
after the Soviet physicist Yakov Frenkel, who discovered it by the International Union of Pure and Applied Chemistry
in 1926. When there is a large difference in size between [17]. In this notation, structural elements are denoted as
the cations and anions, the crystals with low coordination SP C . Here S represents the symbol of the point defect, P its
numbers and large interstitial sites will tend to favor position in the lattice, and C the effective charge of the
Frenkel defects by displacing the smaller ion, e.g., Al2O3. defect relative to the perfect crystal lattice. For this part of
For large cations (U4þ, Ce4þ, and Th4þ), the defects the notation, dots ( ), primes (0 ), and (3) represent effective
l

formed in UO2, CeO2, and ThO2 are anion Frenkel defects. positive charges, effective negative charges, and an effec-
A vacancy (or pair of vacancies in an ionic solid) is tive zero charge, respectively. Examples of the symbols of
sometimes called a Schottky defect named after Walter H. intrinsic point defects are:
Schottky. The Schottky defect can be formed when oppo-
l Vacancy V
sitely charged ions leave their lattice sites, creating
l Metal ion (Mþ) vacancy VM
vacancies. Schottky defects in crystals with high coordi-
l Metal ion (Mþ) interstitial Mi $
nation numbers such as MgO are formed easily. Vacancies
l Empty interstitial site Vi 
may also be present on different sites for the same type of
l Oxide ion vacancy Vo $$
ion. For example, NiFe2O4 is an inverse spinel [Fe(NiFe)
l Magnesium ion (Mg2þ) vacancy VMg 00
O4]; Fe3þ ions sit in both tetrahedral and octahedral sites.
l Magnesium ion (Mg2þ) on a regular lattice site MgMg 
Thus we can have Fe3þ vacancies on the tetrahedral or
octahedral sites, but these two types of vacancy are not the
same [16]. Normally, Schottky defects will bring about a
decrease in the density of the crystal. The point defects in
ionic crystal lattice can be illustrated schematically with a
two-dimensional diagram (Fig. 13.2).
For historical reasons, many point defects, especially in
ionic crystals, are called “centers”; e.g., the vacancy in
many ionic solids is called an F-center. The origin of the
name F-center originates from the German Farbzentrum.
An F-center is a type of crystallographic defect in which an
anionic vacancy in a crystal is filled by one or more
electrons, depending on the charge of the missing ion in the
crystal. That is to say, these F-centers are caused by an

FIGURE 13.3 Schematics of color centers in alkali halides. Reproduced

with permission from C.B. Carter, M.G. Norton, Ceramic Materials-
Science and Engineering, Springer Press, New York, 2007, pp.
FIGURE 13.2 Schematic of point defects in an ionic crystal lattice. 181e200. Copyright 2007 of the Springer Press, New York.
 Nonstoichiometric Compounds Chapter | 13 333

defects. The DG minimum corresponds to the equilibrium

concentration of point defects in the crystal. Therefore
formationofanonstoichiometriccompoundcanbeunderstood
from minimization of the free energy (i.e., thermodynamics)
and diffusive equilibrium (i.e., kinetics) of the point
defects as well as microstructure characteristics of component
elements (i.e., micromechanism).
Based on thermodynamics, the point defects in a solid
lattice are a natural tendency caused by increasing the
configuration entropy to minimize the free energy of the
system [8e10,16]. The configurational entropy (kT ln U) is
a driving force behind the vacancy creation, where U [i.e.,
U ¼ (N0 þ n)!/(N0!n!)] is the number of permutations
calculated as n vacancies that can be arranged in the
N0 þ n sites. The Gibbs energy originates from both
entropy and enthalpy contributions because of
FIGURE 13.4 Illustration of defects in the nonstoichiometric Cr2O3 DG ¼ DH
TDS. For formation of n vacancies with a
from chemical reduction (to the left of the center) and oxidation (to the low-vacancy concentration, change of the Gibbs energy is
right) of a pure, stoichiometric Cr2O3. Reproduced with permission from DG ¼ n(DH
TDSv)
kT ln U. The DH deals with the
P. Karen, Nonstoichiometry in oxides and its control, J. Solid State Chem.
enthalpy of the vacancy formation by a net breaking of
179 (2006) 3167e3183. Copyright 2006 of Elsevier.
some bonds, while the DSv is the vibration entropy asso-
ciated with the formation of the vacancy. The DG in the
system depends on two terms: n(DH
TDSv) and kT ln U.
The point defects of a nonstoichiometric compound can These two terms have inverse change tendency with
be created by various ways. To take a concrete example, increase of the defect concentration in the system, as
Cr2O3 is a narrow nonstoichiometric oxide. The defects in shown in Fig. 13.5. It can be seen from the curves that the
the nonstoichiometric Cr2O3 from chemical oxidation and introducing vacancies can make the free energy of the
reduction of a pure, stoichiometric Cr2O3 are illustrated in crystal decrease until an equilibrium concentration corre-
Fig. 13.4 [10]. When the precisely stoichiometric Cr2O3 is sponding to a small equilibrium amount of vacancies (neq)
reduced, a deficit of oxygen or an excess of metal can be is reached. This is because the configurational entropy
created. Upon oxidation, either an excess of oxygen or a
deficit of metal may be produced.
It is the aforementioned defects of the nonstoichiometric
compounds that endow their specific electrical, optical,
magnetic, chemical, and mechanical properties and make
them functional materials.

13.2 SYNTHESIS OF
NONSTOICHIOMETRIC COMPOUNDS
13.2.1 Formation Mechanism
An ideal crystal with a periodic, three-dimensional, and
completely ordered ensemble of particles is only a physical
model of a perfect solid. Real crystals always have various
types of defects. The presence of defects means that an exact
stoichiometric composition of crystalline compounds is
more an exception than a rule [13]. It is the defects in the
crystal that lead to formation of a nonstoichiometric com-
pound. At a given temperature there is an equilibrium con-
FIGURE 13.5 Gibbs energy of formation of n vacancies in an ideal
centration of point defects in a crystal. This means that a
crystal of N0 sites. Reproduced with permission from P. Karen, Non-
crystal containing point defects must have a lower free stoichiometry in oxides and its control, J. Solid State Chem. 179 (2006)
energy (DG) than the corresponding crystal without any 3167e3183. Copyright 2006 of Elsevier.
334 Modern Inorganic Synthetic Chemistry

term is nonlinearity; adding too many vacancies increases the nonstoichiometric compounds are mainly responsible
DG again. The neq value can be evaluated by differentia- for formation of the nonstoichiometric compounds.
tion according to n: Based on kinetics, diffusion that occurs by atomic
  defects moving through the crystal is a thermally activated
d ðN0 þ nÞ!
nDH
nTDSv
kT ln ¼ 0: process. There are four basic mechanisms that can, in
dn N0 !n! principle, occur; these are illustrated in Fig. 13.7 [16]:
For large x the factorial term can be simplified by l Direct exchange (difficult and not energetically
application of the Stirling formula, ln(x!) z x ln x
x: probable)
 
N0 þ neq l Ring mechanism (cooperative motion: possible but
DH
TDSv
kT ln ¼ 0
neq not demonstrated)
l Vacancy mechanism (most common, dominant in
Note that the term involving neq is the inverse of the metals)
fractional concentration of the vacancies formed. A rear- l Movement of interstitials (occurs when you can put
rangement shows that the fractional concentration of interstitials in); an example is Zn in ZnO
vacancies is a sole function of temperature, with two pa-
rameters (DH and DSv) occurring in a mass action-type term: The diffusion coefficient (D) has a strong dependence
  on temperature (T). Here R is gas constant and Q is acti-
neq DSv DH
¼ exp
. vation energy (an activation energy barrier to diffusion).
N0 þ neq k kT Large numbers of experimental results show that the higher
It can be seen from the previous equation that at higher the system temperature, the more remarkable the diffusion
temperatures the equilibrium number of vacancies neq phenomenon; the less the activation energy, the larger the
increases and leads to the formation of the stable non- diffusion coefficient:
stoichiometric phase. This implies that the nonstoichiometric  

Q
phase at relatively higher temperature is more stable than D ¼ D0 exp
RT
one at low temperature because it possesses a lower free
energy in a higher defect concentration (Fig. 13.6). If such The following examples are applied to illustrate special
equilibrium in the crystal without defect clusters is ach- features of diffusion in ceramics:
ieved at a relatively high temperature, the equilibrium
l Zn1þxO is a metal-rich oxide with two different
concentrations of noninteracting point defects can be
charges in which excess zinc is present as interstitials.
treated by the mass action law. Since these defects are in
As the partial pressure of Zn (PZn) increases, the
thermodynamic equilibrium, annealing or other thermal
density of interstitials increases and the diffusion of
treatments cannot remove them. Thus the point defects in
Zn through the structure increases.

FIGURE 13.6 Change of G minimum and the equilibrium concentration of defects in crystal lattices with temperature increase. Reproduced with
permission from http://ocw.nctu.edu.twuploadsschemistrysschemistry_lecturenotesssch-5-1.pdf.
 Nonstoichiometric Compounds Chapter | 13 335

radii of the nonmetal and metal atom, respectively) [19];

and (4) nonstoichiometric compounds are basically highly
ionic compounds because formation of the point defects in
a covalence compound crystal usually needs very high
energy [9]. Many transition metal compounds such as
oxides, fluorites, hydrides, carbides, nitrides, and sulfides
can meet these conditions to form corresponding non-
stoichiometric compounds.

13.2.2 Phase Diagram

A phase diagram enables us to easily choose the appro-
priate temperature (T), composition (x), and pressure (p)
for synthesis of nonstoichiometric compounds. It can give
FIGURE 13.7 Possible mechanisms occurring during diffusion.
the number of nonstoichiometric compounds that may be
(A) Exchange, (B) ring, (C) vacancy, (D) interstitial, (E) knock-on.
Reproduced with permission from C.B. Carter, M.G. Norton, Ceramic formed by the components and the stability limits of
Materials-Science and Engineering, Springer Press, New York, 2007, phases in equilibrium. The synthesis condition of the
pp. 181e200. Copyright 2007 of the Springer Press, New York. nonstoichiometric compound with precise composition for
advanced materials with high performance can be
designed and optimized using a stable region in the phase
l The group of binary oxides with a rock salt structure
diagram. For example, nonstoichiometric fluorite phases
(e.g., FeO, NiO, CoO, and MnO) is metal deficient.
M1
xRxF2þx (M ¼ Ca, Sr, Ba, Cd, Pb; R are rare-earth
The diffusion depends on p(O2) [16]. The most
elements) can be formed in all 80 MF2eRF3 systems.
important of these is Fe1
xO because FeO is unstable
The most phases belong to two structural types: CaF2
and can contain as many as 15 at% vacancies because
(49%) and LaF3 (41%). The fraction of nonstoichiometric
of the equilibrium concentration of Fe3þ cations.
phases with the LaF3 structure increases significantly. The
Fe1
xO is special because point defects are always
reason for this is the stabilization of the tysonite structure
present in FeO and the cation is always present in
with the formation of Berthollide phases. Fig. 13.8 gives
two charge states.
the phase diagrams of SrF2eRF3 (R are rare-earth ele-
l CuO1
x is an example of a group of oxygen-deficient
ments) systems. Nonstoichiometric R1
ySryF3
y phases
oxides, MO1
x, where the nonstoichiometry is
with a tysonite structure are the main ones in the domains
accommodated by oxygen vacancies. With increase
of the SrF2eRF3 systems that are adjacent to RF3. When
of the pO2, the diffusion coefficient will decrease.
R3þ ions are replaced by Sr2þ, the formation of anion
Comparing CuO1
x with Zn1þxO, although both
vacancies will be used to compensate for the difference of
cations exist in the 2þ or 1þ charge state, the crystal
charges. According to the phase diagrams, single crystals of
structures and point defect chemistry are very
nonstoichiometric phases such as Sr1
xLaxF2þx crystals can
different.
be controllably grown [20].
In summary, as long as there exists a concentration Nonstoichiometric oxides of Ce, Pr, and Tb with the
gradient because of inhomogeneous distribution of the oxidation states þIII and þIV, another representative
atoms or ions in a solid, there must exist a chemical example, can also form a number of phases with compo-
potential gradient, which will result in directional flow and sitions all belonging to a homologous series MnO2n
2m, as
mutual mixing of the atoms and ions until diffusion finally shown in Fig. 13.9. All phases in the binary rare-earth
eliminates the chemical potential gradient and reaches intermediate oxides MnO2n
2m have been identified by
uniform distribution of the component concentration in the electron diffraction. The different phases have been named
system [8]. as i (MO1.714), z (MO1.788), ε (MO1.800), d (MO1.818), and b
Based on micromechanism, the following factors are (MO1.833) as well as s (MO1.6e1.7) and a (MO1.72e2.0),
beneficial to the formation of a nonstoichiometric which are disordered nonstoichiometric compounds. These
compound: (1) the energy used for producing point defects phases are oxygen deficient and the structures are fluorite
is not large, namely, change of the free energy brought related. The phase composition depends strictly on tem-
about by the x alteration is small; (2) the metal ion has a perature and oxygen partial pressure [15]. From a Tex
changeable valence state and smaller energy difference phase diagram of PreO system [21], we can easily find the
between various oxidation states; (3) difference of the stability region of the s-phase (Fig. 13.10A) and the
atomic radii between various oxidation states is not too existence of the line phase, PrO1.667. It should be pointed
large (e.g., 0.41 < RX/RM < 0.59, where RX, RM is atomic out that the relationship of the composition, reaction
336 Modern Inorganic Synthetic Chemistry

FIGURE 13.8 Phase diagrams of SrF2eRF3 (R are rare-earth elements) systems [20]. The phases are denoted as follows: (A) nonstoichiometric phases
of fluorite type, (B) nonstoichiometric phases of LaF3 type, and (T, S, R) phases with different distortions of fluorite lattice.

temperature, and gaseous component partial pressure is of plotted in dotted lines for comparison [15]. The curves
vital importance for us to choose synthesis conditions of reveal the relationship of the composition, reaction
nonstoichiometric compounds of transition metals. In temperature, and oxygen partial pressure. Similarly, for
Fig. 13.10B, log p(O2) is plotted against x at different nonstoichiometric nitrides (e.g., cubic titanium nitride
temperatures and the results obtained by Endo et al. are also TiNy used as protective and wear-resistant coating), the
 Nonstoichiometric Compounds Chapter | 13 337

FIGURE 13.9 Phase diagrams for the cerium, praseodymium, and terbium oxygen system. Reproduced with permission from G. Adachi, N. Imanaka,
Z.C. Kang, Binary Rare Earth Oxides, Kluwer Academic Publishers, Netherlands, 2005, pp. 1e7 and 57e93. Copyright 2005 of Kluwer Academic
Publishers, the Netherlands.

relationship of the composition, temperature, and nitrogen Thus we can find optimization parameters of the synthesis
partial pressure of the TiNy in Fig. 13.11 helps us to opti- condition from the foregoing experimental techniques.
mize synthesis conditions of the TiNy [22].
As mentioned previously, the stable nonstoichiometric
13.2.3 Synthesis Methods
phase of a transition metal is usually formed at high tem-
perature and the corresponding defect equilibrium is It is of great interest for us to prepare the nonstoichiometric
established in reasonable time. At the same time, the phase compounds with predetermined composition and structure
composition of the nonstoichiometric compounds depends because of their unique optical, electrical, magnetic,
strictly on reaction temperature and gaseous component thermal, and mechanical properties. It also is necessary for
partial pressure as well as annealing or quenching process. us to design and tailor materials with desirable performance
338 Modern Inorganic Synthetic Chemistry

FIGURE 13.10 (A) Stability region of the s-phase superposed on the phase diagram of a Pr-O system; (B) logarithm of the equilibrium oxygen partial
pressure [log P(O2)] of PrOx as a function of composition (x). Reproduced with permission from J. Nowotny, W. Weppner, Non-Stoichiometric
Compounds-Surfaces, Grain Boundaries and Structural Defects, Netherlands, Kluwer Academic Publishers, 1988, pp. 11e26 and 471e484.
Copyright 1998 of Kluwer Academic Publishers of the Netherlands.

by means of effective and precise control of the composi-

tion, defect, and structure. The synthetic methods of the
nonstoichiometric compounds mainly include dominant
high-temperature synthesis approaches (e.g., solid-state
reaction, thermal decomposition, and high-pressure prepa-
ration at elevated temperatures), electrochemical techniques
(e.g., anodic electrocrystallization and DC electrolysis), and
other technical means (e.g., mechanochemical synthesis
and g-irradiation synthesis, etc.). But then, precursors of
the nonstoichiometric compounds may be prepared by
various chemistry-based synthetic methods such as the
coprecipitation method, solegel techniques, and hydro-
thermal and solvothermal processing.

13.2.3.1 High-Temperature Solid-State

Reaction
13.2.3.1.1 YBa2Cu3O7Lx
The high-temperature superconductor YBa2Cu3O7
x is the
first material to become superconducting above 77K, the
boiling point of nitrogen. All materials developed before
FIGURE 13.11 Nitrogen partial pressure p(N2) in equilibrium with ti-
tanium nitride TiNy at temperatures from 1273 to 2400K: solid lines denote 1986 became superconducting only at temperatures near
calculated isotherms p(N2)-y; (B) and (C) stand for experimental data the boiling points of liquid helium or liquid hydrogen
measured at temperatures 1273 and 1673K, respectively; I and II are the (Tb ¼ 20.28K)dthe highest being Nb3Ge at 23K. Several
positions of the lower boundary of the homogeneity interval of cubic ti- high-temperature superconducting devices used for
tanium nitride TiNv. Reproduced with permission from A.I. Gusev, A.A.
magnetic resonance imaging, magnetic levitation, and
Rempel, A.J. Magerl, Disorder and Order in Strongly Nonstoichiometric
Compounds (Transition Metal Carbides, Nitrides and Oxides), New York, Josephson junctions have realized commercial application.
Springer-Verlag Berlin Heidelberg, 2001, p. 280. Copyright 2001 of The structural feature of YBa2Cu3O7
x is illustrated in
Springer-Verlag of New York. Fig. 13.12 [23]. YBa2Cu3O7
x can be viewed as a variant
 Nonstoichiometric Compounds Chapter | 13 339

FIGURE 13.13 Variation of the oxygen nonstoichiometry x in

YBa2Cu3O7
x with the oxygen partial pressure p(O2) at different tem-
peratures. Reproduced with permission from J. Nowotny, W. Weppner,
Non-Stoichiometric Compounds-Surfaces, Grain Boundaries and Struc-
tural Defects, Netherlands, Kluwer Academic Publishers, 1988, pp. 11e26
and 471e484. Copyright 1988 of Kluwer Academic Publishers of the
Netherlands.

FIGURE 13.12 Structure unit of the superconductor YBa2Cu3O7
x.

Reproduced with permission from http://en.wikipedia.org/wiki/Yttrium_
or by a coprecipitation technique. For the former, high-
barium_copper_oxide.
purity oxide, carbonate, and/or nitrate powders were
mixed in an appropriate ratio, and subsequently heated at a
of the perovskite family of materials. For the cuprates, desirable high temperature for a suitable reaction time in air
Y þ Ba occupy “A sites” whereas Cu occupies the “B [21]. For the latter, three nitric acid solutions of each
sites.” The structure of YBa2Cu3O7
x depends on the constituent metal were mixed in an appropriate ratio. The
oxygen content. When x ¼ 1, the O(1) sites in the Cu(1) ammonium oxalate solution was then used to form the
layer are vacant and the structure is tetragonal YBa2Cu3O6, precipitation from the mixed solution. The precipitates were
which is insulating and does not superconduct. Increasing then filtrated and dried, and subsequently calcined at a
the oxygen content slightly causes more of the O(1) sites to desirable high temperature for a suitable reaction time in
become occupied. For x < 0.65, CueO chains along the air. In the annealing process, the resultant samples were
b-axis of the crystal are formed. Elongation of the b-axis reground, pressed into pellets, and then sintered in air. The
changes the structure to orthorhombic, with lattice param- samples with different oxygen content were prepared by the
eters of a ¼ 3.82, b ¼ 3.89, and c ¼ 11.68 Å. Optimum following method: The sintered pellet samples were
superconducting properties occur when x w 0.07 and all of equilibrated with an oxygen partial pressure for a time,
the O(1) sites are occupied with few vacancies. depending on temperature and oxygen partial pressure, and
As stated earlier, the oxygen in YBa2Cu3O7
x plays a then cooled rapidly to room temperature in an ice bath. The
vital role in the structure and superconductivity of oxygen partial pressure was controlled with O2/air or air/Ar
YBa2Cu3O7
x materials, which are very sensitive to the mixed gases.
value of x (i.e., its oxygen content). In addition, the The samples of YBa2Cu3O7
x superconductor film can
annealing procedure in an oxygen atmosphere is a key to be prepared by a combination of the solegel method and a
obtaining better superconducting properties. For this high-temperature annealed technique. There are two routes
reason, a T-p(O2)
x phase equilibrium diagram, as shown to be used: One is that Y(NO3)3∙5H2O, Cu(NO3)2∙H2O,
in Fig. 13.13 [21], is necessary for us to optimize synthesis and Ba(NO3)2 agents are used as starting materials. First,
parameters of the YBa2Cu3O7
x superconductor. Accord- these chemical agents with an appropriate radio are
ing to the T-p(O2)
x phase equilibrium diagram, the dissolved in ethylene glycol to form a uniform mixed
polycrystalline samples of the YBa2Cu3O7
x supercon- solution. The solution is then refluxed at an appropriate
ductor may be prepared either by a powder-mixing method temperature (e.g., 130e180 C) and the gel is gradually
340 Modern Inorganic Synthetic Chemistry

created as the solvent is vaporized out of the reaction chemisorbed species, such as O
and O2
. Catalytic and
system. After the resultant gel, which may be coated on the photocatalytic properties of oxides are closely related to the
surface of a matrix sintered at a high temperature concentration of these species. At elevated temperatures,
(e.g., 950 C) in oxygen atmosphere with a desirable oxidation of metal oxides results in oxygen incorporation
oxygen partial pressure, a YBa2Cu3O7
x film sample with into the lattice. This leads to a change in the ability of the
orthogonal structure can be obtained. The other route is oxide crystal to donate or accept electrons during chemical
that an organometallic compound Y(OC3H7)3, reactions [25]. The defect diagram for undoped TiO2 at
Cu(O2CCH3)2∙H2O, and Ba(OH)2 with an appropriate 1173 and 1123K is shown in Fig. 13.15. The defect
ratio are dissolved under heating and vigorously stirring in diagram shows the effect of oxygen activity on the con-
ethylene glycol. After formation of a uniform mixed solu- centration of both ionic and electronic defects for TiO2 at
tion, the solvent is vaporized and a gel is produced. The 1173 and 1123K [25,26]. An example of synthesis of the
resultant gel is then coated on the surface of a matrix TiO2
x using a high-temperature solid-state reaction
(e.g., [110] plane of sapphire, [100] plane of SrTiO3 single method can be found in Ref. [27].
crystal, and [001] plane of ZrO2 single crystal). To obtain
10e100 mm of uniform YBa2Cu3O7
x film with good 13.2.3.1.3 LnF2Dx (Ln [ Sm, Yb, Tm) [28,29]
superconducting properties, two annealing methods are Nonstoichiometric fluorides (e.g., LnF2þx) are receiving
employed. In the first method, the film is heated to 400 C in increased attention because of their unique physicochem-
an oxygen atmosphere using a programmed control means ical properties (such as optical characteristics and rather
at the rate of 2 C min
1, then to 950 C at the rate of high unipolar anionic conductivity) with important poten-
5 C min
1, and is subsequently cooled to room tempera- tial applications in various optical and electrochemical
ture at the rate of 3 C min
1. After the step is repeated 2e3 devices. Nonstoichiometric fluorides LnF2þx (Ln ¼ Sm,
times, the film is sintered at 950 C in an oxygen atmo- Yb, Tm) can be prepared by reduction of the corresponding
sphere for 12 h, and finally is cooled to room temperature at trifluorides with the same lanthanide metal by the reaction
the rate of 3 C min
1. In the second method, the film is first (2 þ x) LnF3 þ Ln ¼ 3LnF2þx at various molar ratios in
calcined at 950 C for 10 min in air. Then the film is coated evacuated sealed quartz ampoules. To prevent the reaction
again and is subsequently calcined again. The step is of quartz with fluorides during synthesis, the inner surface
repeated several times. Finally, the film is annealed at of the ampoule was coated with a thin film of lanthanide.
550e950 C in oxygen atmosphere for 5e12 h [24]. The nonstoichiometric fluorides LnF2þx (Ln ¼ Sm, Yb,
Tm) mainly deal with the following synthetic processes:
13.2.3.1.2 TiO2Lx preparation of lanthanide trifluorides, purification pretreat-
Titanium dioxide is often regarded as an oxygen-deficit ment (e.g., removal of the sorbed water and impurities),
nonstoichiometric compound (TiO2
x) whose non- mixing by grinding, and calcination at high temperature.
stoichiometry (x) is closely related to the concentration of The detailed synthetic steps can be found in Refs. [28,29].
both ionic and electronic defects. Studies have shown that Depending on the conditions of synthesis, the resulting
TiO2 may not only exhibit an n-type semiconductor prop- fluorides had different colors: SmF2þx was dark blue but
erty, but may also exhibit a p-type semiconductor property soon turned red; YbF2þx ranged from green to ochroid
(i.e., formula of the p-type TiO2 may be expressed as (the YbF2þx phase crystallizing as a superstructure was
TiO2þx). Therefore the general formula, which represents beige colored); TmF2þx varied from light to dark brown
both n- and p-type TiO2, is TiO2x [25]. Titanium dioxide (Table 13.1).
has been considered the most promising candidate for
photoelectrochemical water-splitting devices and photo- 13.2.3.2 High-Temperature Thermal
catalytic water purification. The structure units of rutile, Decomposition
brookite, and anatase TiO2 are shown in Fig. 13.14.
For oxides the defect-related properties depend on the 13.2.3.2.1 UO2Dx
specimens obtained by following well-known processing When uranium dioxide (UO2), a kind of nuclear fuel, is filled
conditions at elevated temperatures, including the temper- with additional oxygen ions in the lattice, it can form non-
ature, oxygen activity, and rate of cooling. The gas/solid stoichiometric compounds (e.g., UO2þx) whose composition
equilibrium for the oxideeoxygen system (e.g., TiO2eO2 alters with external conditions such as temperature and ox-
system) may be established at elevated temperatures. At ygen partial pressure. The strong tendency of interstitial
lower temperatures, oxidation of metal oxides is mainly oxygen ions in UO2þx to form clusters is related to the
limited to physical adsorption. At moderate temperatures, mixed valence of uranium oxides, allowed by the presence
the physically adsorbed species (molecules and/or atoms) of a partially filled 5f shell in uranium and the possibility for
become ionized, leading to the formation of several a U atom to shift easily among the valences from þ3 to þ6
 Nonstoichiometric Compounds Chapter | 13 341

FIGURE 13.14 Structure units of (A) rutile, (B) brookite, (C) anatase TiO2.

FIGURE 13.15 Defect disorder diagram for undoped TiO2, showing the effect of oxygen activity on the concentration of ionic and electronic defects at
1173 and 1123K, where A corresponds to the equilibrium concentration of titanium vacancies. Reproduced with permission from J. Nowotny, T. Bak, L.R.
Sheppard, M.K. Nowotny, Reactivity of titanium dioxide with oxygen at room temperature and the related charge transfer, J. Am. Chem. Soc. 130 (2008),
9984e9993. Copyright 2008 of the American Chemical Society; L.R. Sheppard, M.K. Nowotny, T. Bak, J. Nowotny, Effect of cooling on electrical
conductivity of TiO2, Phys. Stat. Sol. (b) 245 (2008), 1816e1827. Copyright 2008 of Wiley.

[30]. It can be seen from phase diagrams of the UeO system 13.2.3.2.2 FexO
shown in Fig. 13.16 [30,31] that the nonstoichiometric Iron(II) oxide is a black powder with the chemical formula
species UO2þx as a solid solution can exist at sufficiently FeO. Its mineral form is known as wüstite. This is a typical
high temperatures. According to the phase diagrams, the example of a nonstoichiometric compound with a known
nonstoichiometric UO2þx can be prepared by the direct stability range from x ¼ 0.83 to 0.96 above 560 C and
oxidation of stoichiometric uranium dioxide [30,31]. contains at least 5% vacancies on the cation sublattice.
342 Modern Inorganic Synthetic Chemistry

TABLE 13.1 Preparation Conditions, Phase Composition, and Lattice Parameters of Nonstoichiometric Lanthanide
Fluorides

Synthesis
Structural Type and
Parameters
Molar Ratio LnF3: E Crystal Lattice
(E is Sm, Tm, Yb, Si) Phase Composition Color in Powder Parameters (Å) T (8C) Time (h)
2 SmF2þx Dark blue Not determined 750 2
(a ¼ 5.866 [3])
2 SmF2.01 with oxyfluoride Red Cubic, a ¼ 5.777 750 2
impurity
2.5 SmF2.35 with oxyfluoride Dark red Tetragonal, a ¼ 4.109, 800 3
impurity c ¼ 5.856
2 TmF2.38 Dark brown Hexagonal, a ¼ 3.9546, 820 3
c ¼ 9.4827
2 TmF2.42 Brown Hexagonal, a ¼ 3.9449, 750 3
c ¼ 9.7129
2 YbF1.91 Dark green Tetragonal, a ¼ 5.6078 750 7
2 YbF2.07 Light green Tetragonal, a ¼ 5.5949 890 1
2.5 YbF2.03 Dark green Tetragonal, a ¼ 5.5978
Superstructure Beige Tetragonal, a ¼ 16.7304 750 7.5
YbF2.37 ¼ Yb27F64
3.26 YbF2.37 Ochroid Tetragonal, a ¼ 5.5827 750 7.5

Superstructure Beige Tetragonal, a ¼ 16.7367

YbF2.37 ¼ Yb27F64

Reproduced with permission from N.M. Kompanichenko, A.A. Omel’chuk, A.P. Ivanenko, R.N. Pshenichnyi, E.V. Timukhin, Conductivity of non-
stoichiometric fluorides LnF2þx(Ln ¼ Sm, Eu, Yb), Russ. J. Appl. Chem. 86 (2013), 1835e1841; A.P. Ivanenko, N.M. Kompanichenko, A.A. Omelchuk,
V.F. Zinchenko, E.V. Timukhin, Synthesis and optical properties of non-stoichiometric lanthanide (Sm, Eu, Tm, Yb) fluorides, Russ. J. Appl. Chem. 55
(2010), 841e847.

FIGURE 13.16 Phase diagrams of the UeO system. Reproduced with permission from D. Manara, R. Pflieger, M. Sheindlin, Advances in the
experimental determination of the uraniumeoxygen phase diagram at high temperature, Int. J. Thermophysics 26 (2005), 1193e1206. Copyright 2005 of
Springer Press of New York; R.F. Gould (Ed.), Nonstoichiometric Compounds, the 142st Meeting of the American Chemical Society, Washington, DC,
March 21e23, 1962, pp. 58e65. Copyright 1962 of the American Society of Chemistry.
 Nonstoichiometric Compounds Chapter | 13 343

FIGURE 13.17 The iron oxygen phase diagram. Reproduced with FIGURE 13.18 Structure units of wüstite (FexO). Reproduced with
permission from S. Mrowec, A. Podgórecka, Defect structure and trans- permission from S. Mrowec, A. Podgórecka, Defect structure and trans-
port properties of non-stoichiometric ferrous oxide, J. Mater. Sci. 22 port properties of non-stoichiometric ferrous oxide, J. Mater. Sci. 22
(1987), 4181e4189. Copyright 1987 of Springer. (1987), 4181e4189. Copyright 1987 of Springer.

So the formula should be written as FexO [or better 13.2.3.2.3 ZnxFe3LxO4 [3]
Fe(II)1
2dFe(III)dO]. Fig. 13.17 gives the iron oxygen Magnetic spinel ferrites ðMII FeIII 2 O4 ; M represents Co,
phase diagram [32]. Mn, Ni, Zn or Fe, etc.) with a wide range of technological
FexO has a defect rock salt structure with an ordered applications in magnetic recording, microwave technology,
distribution of iron vacancies (Fig. 13.18) [32]. FexO is and catalytic and biomedical fields can be commonly
paramagnetic at room temperature and antiferromagnetic or described as (M1
xFex)[MxFe2
x]O4, where the round and
weakly ferrimagnetic below the Néel temperature TN of square brackets refer to A sites and B sites, respectively. x
about 183 or 198K, because of a transition from the cubic stands for the inversion degree, defined as the fraction of A
to a rhombohedral or a monoclinic structure. The transition sites occupied by Fe3þ cations. The cation distribution may
is strongly related to the defect structure of wüstite. vary, which decides magnetic properties of spinel ferrites.
For the bulk, wüstite FexO was typically prepared by That is to say, the superexchange interaction that becomes
heating iron and magnetite in sealed vessels based on the strong enough to order the magnetic moments is strongly
iron oxygen phase diagram. This is because it is stable only dependent on the geometry of arrangement such as distance
above 560e570 C, while below this temperature it and angles of cations in the A and B sites. Theoretical
decomposes via a two-step mechanism into a-Fe and prediction shows that Fe2þ, Co2þ, and Ni2þ tend to locate
magnetite, Fe3O4. Redl and coworkers [33] reported the at B sites to form inverse spinel structures, while Zn2þ and
synthesis of nanocrystalline wüstite FexO (0.84 < x < 0.95) Mn2þ tend to locate at A sites to form normal spinel
with controllable size and shape using a high-temperature structures. Thus the control of cation distribution provides a
thermal decomposition method. The method is based on means to tailor their properties. As an example, Fig. 13.19
the decomposition of iron acetylacetonate, iron acetate, and displays the structure unit of spinel ferrite ZnFe2O4.
iron pentacarbonyl precursors in the presence of organic ZnFe2O4 is representative of a normal spinel structure
solvents with high boiling temperatures. Tight control over (Fig. 13.19) and bulk ZnFe2O4 commonly shows para-
temperature allows the syntheses of cubic or faceted FexO magnetism at room temperature. However, the ferrimag-
nanocrystals with narrow size distributions by thermolysis netism has been observed from nanoscale ZnFe2O4 because
of iron(II) acetate or a selective oxidation route of iron of the redistribution of Zn atoms at the A and B sites. The
pentacarbonyl with pyridine N-oxide. The more detailed redistribution of the cations is greatly influenced by the
reaction conditions and results of the products can be found synthetic approach. Although various methods such as
in Ref. [33]. high-temperature calcination, ball milling, coprecipitation,
344 Modern Inorganic Synthetic Chemistry

ones (ZF5) can be obtained, respectively. Moreover, only if

the ratio is less than 0.85 can Zn ferrite nanoparticles with
defined shapes be obtained. In addition, the amount of Fe
precursor rather than zinc precursor is decisive to the
particles’ size. Table 13.2 lists the samples in this work
(ZF0 to ZF7) with different amounts of starting precursors.
Fig. 13.20 gives scanning electron microscope (SEM)
images of as-synthesized samples, and the Zn substitution
of partial Fe atoms at the tetrahedral site (A site) in the
spinel magnetite phase may account for the extra high
saturation. The authors have given a typical preparation
process for a zinc ferrite sample (i.e., ZF3). Briefly, the
mixture including oleic acid (28 mmol), 12 mmol Fe(acac)3
and 6 mmol Zn(acac)2$xH2O) was first dissolved in benzyl
FIGURE 13.19 Structure unit of spinel ferrite ZnFe2O4. ether (20 mL) and the water in the system was then
removed by heating to 120 C and kept for 30 min. Next,
the mixture was heated to 280 C at a rate of 8 C min
1 to
combustion, solegel, and hydrothermal and thermal reflux for 30 min and was cooled down to ambient
decomposition routes have been developed to synthesize temperature naturally. Finally, the grayeblack precipitates
Zn ferrite, it is not easy to control the distribution of Zn were obtained after collecting by magnetic separation and
atoms at either A sites or B sites because of the disorder washing with hexane several times.
induced by the high surface energy of small particles. Ding
et al. [3] reported preparation of nonstoichiometric zinc 13.2.3.3 High-Temperature and High-Pressure
ferrite (ZnxFe3
xO4, x ¼ 0e0.5) nanoparticles with poten- Synthesis
tial application in radar absorption materials and hyper-
thermia agents using the high-temperature thermal 13.2.3.3.1 BaFeO3Lx
decomposition method. Experimental results indicated that Under high-temperature, high-pressure, and rapid cooling
the shape and size of as-synthesized Zn ferrite particles can conditions, it is possible to obtain nonstoichiometric com-
be controlled by the precursor/surfactant ratio, and surfac- pounds possessing nonequilibrium homogeneity regions,
tant oleic acid can control the particle growth and prevent e.g., a BaFeO3
x nonstoichiometric compound with a
interparticle aggregation. When the amount of zinc perovskite-type structure ABO3
d, which contains an
precursor is around 4 mmol or less, 6e8 mmol and equivalent number of A-site and B-site cations as well as
10 mmol, the octahedral-shaped particles (ZF1 and ZF2), oxygen vacancies. The ionic conduction occurs by oxygen
well-faceted polyhedral crystallites (ZF3 and ZF4), and ions “hopping” from one vacant site to a neighboring
nonuniform particles including large cubes and some small vacant site, while the electronic conduction occurs via

TABLE 13.2 The Amounts of Starting Precursors and Some Relevant Experimental Resultsa [3]

Sample Fe(acac)3 Molar Ratio of Zn/Iron Resulting

No. (mmol) Precursors Composition Ms (emu gL1) Lattice Constant (Å)
ZF0 12 0 Fe3O4 85.2 8.396
ZF1 12 0.17 Zn0.189Fe2.811O4 97 8.403
ZF2 12 0.33 Zn0.290Fe2.710O4 106.8 8.408
ZF3 12 0.5 Zn0.387Fe2.613O4 107.2 8.411
ZF4 12 0.67 Zn0.468Fe2.532O4 109.7 8.418
ZF5 12 0.83 Zn0.522Fe2.478O4 104.4 8.420
ZF6 12 1 Zn0.524Fe2.476O4 99.8 8.415
ZF7 12 1.25 Zn0.527Fe2.472O4 94.2 8.410
a
28 mmol oleic acid and 20 mL benzyl ether were used for all the reactions.
 Nonstoichiometric Compounds Chapter | 13 345

FIGURE 13.20 (AeF) Scanning electron microscope (SEM) images of as-synthesized samples. Scale bars ¼ 200 nm. Reproduced with permission from
Y. Yang, X.L. Liu, Y. Yang, W. Xiao, Z.W. Li, D.S. Xue, F.S. Li, J. Ding, Synthesis of nonstoichiometric zinc ferrite nanoparticles with extraordinary room
temperature magnetism and their diverse applications, J. Mater. Chem. C 1(2013), 2875e2885. Copyright 2013 of the Royal Society of Chemistry.

BnþeOeB(nþ1)þ conduction pairs. Its high mixed oxygen/ (2) octahedrally coordinated to oxygen (B site) and is
electronic conductivity has become a promising material occupied by equal numbers of Fe2þ and Fe3þ ions.
for solid oxide fuel cell electrodes and oxygen-permeable Nonstoichiometric magnetite can be represented by the
membranes used for oxygen separation. formula Fe3
xO4, where x can, in principle, range from zero
The BaFeO3
x synthesized by heating in air has two (stoichiometric magnetite) to 0.333 (stoichiometric
stable crystalline phases: one is a high-temperature phase maghemite). The variations in magnetic properties are
with a composition of BaFeO2.5 (x ¼ 0.5) at above 915 C; related to different parameters, such as cationic distribution
the other is a low-temperature phase with a composition of and vacancies, nonstoichiometry, spin canting, or surface
BaFeO2.74 (x  0.26) with a hexagonal system. contribution. If one considers that hopping occurs only
Fig. 13.21A shows the compositionetemperatureepressure between pairs of ferrous and ferric irons, it can also be
phase diagram of BaFeO3
x [34]. As the oxygen pressure represented by the formula [36]:
increases, the low-temperature phase moves toward the  
Fe3þ Fe2þ 1
3x Fe3þ 1
3x Fe3þ 5x Yx O4
high-temperature phase, i.e., at 1412 C (50 atm or 5 MPa);
BaFeO2.74 with a hexagonal phase becomes BaFeO2.5 with Preparation of the nonstoichiometric magnetite nano-
a perovskite-type structure. Obviously, the x change particles (Fe2.95O4) was reported by Daou and coworkers
influences its structure and properties because of oxygen [3]. The nanosized nonstoichiometric magnetite was
vacancies. In addition, it can be seen from Fig. 13.21B that synthesized by coprecipitation at 70 C from ferrous Fe2þ
there is a magnetic transition point at 164 C for the and ferric Fe3þ ions by a (N(CH3)4OH) solution, followed
BaFeO2.95 with minimum oxygen vacancies [35]. by hydrothermal treatment at 250 C. After analyzing and
calculating Mössbauer spectrum data in detail, the authors
13.2.3.3.2 Fe3LxO4 thought that there would be oxidation of Fe2þ on the B site
Fe3O4 belongs to a family of inverse spinel ferrites in Fe3þaccompanied by vacancy formation.
(Fig. 13.22). It consists of a close-packed face-centered cube
of large O2
anions. The smaller cations (Fe2þ and Fe3þ) 13.2.3.3.3 CeO2Lx
are located in the interstitial sites of the anion lattice. All of In recent years, research on synthesis of the ceria
the Fe2þ ions occupy half of the octahedral sites and the (i.e., CeO2
x) nanoparticles has received significant atten-
Fe3þ are split evenly across the remaining octahedral sites tion because of its extensive applications such as excellent
and the tetrahedral sites. That is to say, there exist two kinds automobile exhaust catalysts, additives in ceramics, phos-
of cation sites in the crystal: (1) tetrahedrally coordinated to phors, high-energy efficiency fuel cells, and polishing
oxygen (A site), which is occupied only by Fe3þ ions; and materials [37]. Pure stoichiometric CeO2 has the calcium
346 Modern Inorganic Synthetic Chemistry

FIGURE 13.21 (A) The compositionetemperatureepressure phase diagram of BaFeO3
x. Stippled areas are single-phase regions for high- and low-
temperature forms of BaFeO3
x [34]. (B) Relation of oxygen vacancies and susceptibility (H ¼ 15,300 Oe (Oersted)) [35]. Reprinted with permission
from J.B. MacChesney, J.F. Potter, R.C. Sherwood, H.J. Williams, Oxygen stoichiometry in the barium ferrates; its effect on magnetization and resistivity,
J. Chem. Phys. 43 (1965), 3317e3322. Copyright 1964 of the American Chemical Society.

c
oxide phases of the type CeO2
x with a range of possible
b
a compositions(0  x  0.5)causedbyremovalofoxygenfrom
the ceria,depending onthe partial pressureofoxygen. There are
five different point defect species in the CeO2
x structure: the
reduced cerium ion Ce0Ce ; two types of oxygen vacancies
at different charge states, Vo $ and Vo $$ ; and two types of defect
pairs formed by the association of Ce0Ce with the appropriate
oxygen vacancies, (CeVO)∙ and (CeVO). Fig. 13.24
shows schematically a planner projection of the CeO2 lattice
containing the aforementioned defect species [39].
Fe+3
Fig. 13.25 shows the phase diagram of CeO2
x
Fe+2.50 constructed by M. Mogensen [40]. They concluded that
O-2 CeO2 can be reduced to nonstoichiometric compositions,
CeO2
x, where 1.7  2
x  2. For T > 921K (648 C)
FIGURE 13.22 Structure unit of inverse spinel ferrite Fe3O4. and 2 > 2
x > 1.818, only the a-phase exists. For
T < 722K (449 C), CeO2
x forms a discrete set of com-
positions. The relation between pO2 and x (in CeO2
x)
fluoride (fluorite) type of structure with space group Fm3m
obtained by thermogravimetry in the temperature range
over the temperature range from room temperature to the
900e1400 C is within the a-phase region.
melting point. It consists of a cubic array of fourfold-
The solvothermal/hydrothermal technique has been
coordinated oxygen ions, with the metal ions occupying
used for the synthesis of CeO2
x nanomaterials. During
half of the eightfold-coordinated cationic interstice.
solvothermal treatment, the pressure in the autoclave is able
Fig. 13.23 gives the face-centered crystal cell of the CeO2
to be readily adjusted by using different solvents, which
structure and (100), (110), and (111) planes of the CeO2
have different vapor pressures at a given temperature. There
structure [38]. The relative stability of the low-index ceria
are two examples as follows:
planes abides by the sequence: (111) > (110) > (100),
while the activity follows the opposite order. 1. An alcohothermal method with the addition of bases
When exposed to an O2-deficient atmosphere at high (KOH or NaOH) is used to fabricate uniform ceria
temperatures, ceria can lead to the formation of several cerium nanocrystals with sizes ranging from 2.6 to 6.9 nm.
 Nonstoichiometric Compounds Chapter | 13 347

FIGURE 13.23 (A) Structure unit of face-centered cubic CeO2 and (BeD) (100), (110), and (111) crystal planes of the CeO2 structure. Reprinted with
permission from Z.L. Wang, X.D. Feng, Polyhedral shapes of CeO2 nanoparticles, J. Phys. Chem. 107 (2003), 13563e13566. Copyright 2003 of the
American Chemical Society.

2. The CeO2
x nanotubes were synthesized by two

successive stages: precipitation and aging [37]. In a
typical synthesis, at the precipitation stage, 0.9 g of
cerium nitrate (Ce(NO3)3∙6H2O) was added to
10 mL of deionized water and heated at 100 C.
Once a large amount of vapor formed, 7 mL of 5%
ammonia hydroxide solution was added. Very fine
yellowish precipitates were formed immediately and
started to boil. After 3 min, the solution was quickly
transferred and cooled at 0 C. After 45 days of aging,
FIGURE 13.24 Schematic of a planner projection of the CeO2 lattice the CeO2
x nanotubes were obtained. The formation
containing various species of point defects complexes. Reproduced with of the tubular structure strongly depends on the
permission from S. Ling, High-concentration point-defect chemistry: precipitation temperature and aging time.
statistical-thermodynamic approach applied to nonstoichiometric cerium
dioxides, Phys. Rev. B 49 (1994), 864e880. Copyright 1994 of the
American Physical Society. 13.2.3.4 Electrochemical Techniques
13.2.3.4.1 Anodic Electrocrystallization [41].
The alcohothermal mechanism is investigated to It is well known that the nonstoichiometric fluorite-related
follow a hydrolytic route [37]: (a) the formation of rare-earth oxides of terbium (TbO2
x) are usually prepared
Ce3þ and Ce4þ ions when Ce(III) and Ce(IV) nitrates by annealing the sesquioxides (Tb4O7) under a defined
are dissolved; (b) the formation of polymers of cerium oxygen pressure, but it is very difficult for the synthesis of
hydroxide coordinated with ethanol; (c) the transition larger single crystals using this method. Electro-
of hydroxides to hydrated and alcoholized CeO2
x; crystallization is a powerful tool for the synthesis of highly
and (d) CeO2
x nanocrystals obtained through alco- oxidized metal oxides (e.g., PbO2, MnO2, Ag2O3, Ag3O4,
hothermal treatment. AgO, BiO3, and NaCuO2). Although many limiting
348 Modern Inorganic Synthetic Chemistry

FIGURE 13.25 Phase diagram of CeO2
x. Reproduced with

permission from M. Mogensen, N.M. Sammes, G.A. Tompsett, Physical,
chemical and electrochemical properties of pure and doped ceria, Solid
State Ionics 129 (2000), 63e94. Copyright 2000 of Elsevier.

experimental parameters have hampered its wider applica-

tions, it can synthesize single crystals of the oxygen-
deficient fluorite-related phase TbO2
x (x ¼ 1.75e1.82)
from alkaline hydroxide melts containing TbCl3 because of
the suitable activation energies of TbO2 (EA ¼ 0.50 eV) in
the range from 298 to 507K for electrocrystallization.
Fig. 13.26 gives electrolysis cell and parameters for the
electrocrystallization of TbO2
x. By this electro-
crystallization technique, large crystals (Ø ¼ 0.2 mm) of
TbO2
x as black shiny crystals at the platinum anode can
been obtained by anodic oxidation from alkaline hydroxide
melts. It should be pointed out that electrocrystallization of
TbO2
x was only observed when LiOH was added to the
melt, raising the melting temperature. Probably, LiOH
reduces the solubility of the product in the melt. But no
lithium was incorporated into the electrocrystalline product.
FIGURE 13.26 Electrolysis cell and parameters for the electro-
crystallization of TbO2
x. Reproduced with permission from M. Malchus,
13.2.3.4.2 DC Electrolysis Method [42e45]. M. Jansen, Electrocrystallization of PrO2 and TbO2
x from alkali hy-
The DC electrolysis method is another effective electro- droxide melts and characterization of the fluorite-related TbO2
x, Solid
chemical technique for the synthesis of nonstoichiometric State Sci. 2 (2000), 65e70. Copyright 2000 of Elsevier.
single-crystal TbOx. For example, single crystals of some
nonstoichiometric terbium oxide phases such as TbO1.875 side of the solid electrolyte; (2) M3þ ions migrate succes-
(p-phase), TbO1.833 (b2-phase), and TbO1.818 (d-phase) sively to the cathodic direction because M2(MoO4)3 is the
were synthesized by DC electrolysis of a Tb3þ ion- M3þ ion-conducting material; (3) the M3þ ions arriving at
conducting Tb2(MoO4)3 solid electrolyte and controlling the cathodic surface are successively reduced to a metal
the oxygen partial pressure, the electrolysis temperature, state; and (4) since DC electrolysis is conducted at elevated
and the voltage applied during the electrolysis (Table 13.3 temperatures under the existence of oxygen, the metal
and Fig. 13.27). In fact, this method can be used not only produced on the cathodic surface is immediately
for the single-crystal growth of the ordinary stoichiometric reoxidized. On the other hand, MoO3 produced at the
oxides, but also for the nonstoichiometric and the meta- anodic side immediately evaporates, because the electrol-
stable ones by adjusting the electrolysis conditions. ysis temperature is higher than the vaporization temperature
This method utilizes a unique characteristic of solid of MoO3 (c. 750 C). Accordingly, the reactions during DC
electrolytes: that only one ion species can migrate in the electrolysis can be summarized as follows.
solid. The mechanism of single-crystal growth by this Reaction at the anodic surface:
method (Fig. 13.28) is as follows: (1) by applying a DC
voltage higher than the decomposition one of the 2M2 ðMoO4 Þ3 /4M3þ þ 6MoO3 [ þ 3O2 [ þ 12e

M2(MoO4)3 solid, the M3þ ions are produced at the anodic (13.1)
TABLE 13.3 Textual and Crystallographic Parameters of TbOx Single Crystals
Oxygen Lattice Parameters Average
Partial Phase and Particle Standard
Temperature Voltage Pressure Unit Cell b a b g Size Deviation
(8C) (V) (MPa) Content Space Group a (Å) (Å) c (Å) (degrees) (degrees) (degrees) (mm) (mm)
a
900 11 0.10 p-Tb16O30 Monoclinic 6.4 14.8 7.4 125.2 0.49 0.16

2b
900 11 2.1  10 p-Tb16O30 Monoclinic 6.4 14.8 7.4 125.2 0.46 0.13
900 11 1.0  10
5c b3-Tb48O88 Pn (monoclinic) 6.7 23.2 15.5 125.2 0.47 0.12
900 3 0.10a p-Tb16O30 Monoclinic 6.4 14.8 7.4 125.2 0.64 0.16

2b
900 3 2.1  10 b2-Tb24O44 P 1 (Triclinic) 6.4 12.2 12.2 79.5 100.0 69.6 0.68 0.17

5c
900 3 1.0  10 d1-Tb11O20 P 1 (Triclinic) 6.5 9.83 6.5 99.0 99.9 95.9 0.67 0.13
a
800 11 0.10 p-Tb16O30 Monoclinic 6.4 14.8 7.4 125.2 0.48 0.13

2b
800 11 2.1  10 b3-Tb48O88 Pn (monoclinic) 6.7 23.2 15.5 125.2 0.47 0.13

Nonstoichiometric Compounds Chapter | 13

5c
800 11 1.0  10 b3-Tb48O88 Pn (monoclinic) 6.7 23.2 15.5 125.2 0.48 0.17
800 3 0.10a b3-Tb48O88 Pn (monoclinic) 6.7 23.2 15.5 125.2 0.68 0.18

2b
800 3 2.1  10 b2-Tb24O44 P 1 (Triclinic) 6.4 12.2 12.2 79.5 100.0 69.6 0.66 0.15

800 3 1.0  10
5c d1-Tb11O20 P 1 (Triclinic) 6.5 9.83 6.5 99.0 100.0 95.9 0.68 0.21

a
In pure O2.
b
In air.
c
In standard N2.

349
350 Modern Inorganic Synthetic Chemistry

FIGURE 13.27 Scanning electron microscope (SEM) images and electron diffraction patterns of the nonstoichiometric terbium oxide single crystals
grown by electrolysis for 1 week at 11 V and at 900 C (A) and 800 C (B) under the oxygen partial pressure of 2.1  10
2 MPa (air). Reprinted with
permission from T. Masui, S. Isota, S. Tamura, N. Imanaka, Electrochemical single-crystal growth of nonstoichiometric terbium oxide, Cryst. Growth
Des. 8 (2008), 1035e1038. Copyright 2008 of the American Chemical Society.

13.2.3.5 Other Technical Means

13.2.3.5.1 Mechanochemical Synthesis [46,47]
Mechanochemical synthesis is one of the important modern
methods for production of nanomaterials. It has obvious
advantages for synthesis of nonstoichiometric fluoride
materials at relatively low temperature: (1) to prevent the
incorporation of oxygen into fluorides at pyrohydrolysis
and thus avoid several negative effects such as uncontrol-
lable change of some physical characteristics; (2) to
avoid severe limitations on the choice of fluorides as the
FIGURE 13.28 Schematic illustration of TbOx single-crystal growth by components of complex fluoride materials for high-
the DC electrolysis method. Reproduced with permission from T. Masui, S.
Isota, S. Tamura, N. Imanaka, Electrochemical single-crystal growth of temperature synthesis reaction, such as different melting
nonstoichiometric terbium oxide, Cryst. Growth Des. 8 (2008), points of the components, their vapor pressures, and
1035e1038. Copyright 2008 of the American Chemical Society. thermal decomposition. As a typical representative of the
fluorite phase in the MFmeRFn systems (m < n  4,
Reaction at the cathodic surface: M ¼ Ca, Sr, Ba, Cd, Pb; R are rare-earth elements,
namely, Sc, Y, LaeLu). The nonstoichiometric phases
M3þ þ 3e
/M (13.2) La1
yCayF3
y (y ¼ 0.15, 0.20) with a tysonite (LaF3)
structure from CaF2 and LaF3 single crystals can be
2M þ xO2 /2MOx (13.3) prepared using the mechanochemical synthesis method.
 Nonstoichiometric Compounds Chapter | 13 351

13.2.3.5.2 g-Irradiation Synthesis soluble or insoluble. An example of this type is determi-

Cu2
xSe is a p-type extrinsic semiconductor with an energy nation of any nonstoichiometry above monovalent Cu.
gap of 1.1e1.29 eV, which is near the optimum value for Alternatively, cerimetric analysis is more versatile for
solar cell applications. It is stable over a wide range of similar nonstoichiometry determination. The key technique
departures from stoichiometry (0 < x < 0.15). that makes these titrations simple and applicable to analyses
The g-irradiation technique has become an important of nonstoichiometry in various solid oxides is closed-
room temperature, ambient pressure method to prepare ampoule digestion [10].
nanoscale materials since it can provide high energy and an For the wide-range nonstoichiometric oxides, their
evenly distributed irradiation field. The synthesis of nano- composition with a sufficiently high precision can be ob-
crystalline Cu2
xSe in aqueous solution using sodium sele- tained by the previously mentioned chemical titration
nosulfate as selenium source under g-irradiation in the field methods. However, for the narrow-range nonstoichiometric
of a 2.59  1015 Bq 60Co g-ray source with absorbed dose compounds, it is very difficult and even impossible to
rate of 1  102 Gy min
1 at room temperature and ambient determine their compositions by the chemical titration
pressure was reported by Qiao and coworkers [48]. The methods. This is because the error for the common quan-
effect of pH value of the solutions and the coordination of titative analysis methods is 10
3, while nonstoichiometry
copper ions (Cl
and NH3) on the Cu2
xSe nanocrystals is generally less than 10
3. But then, for some special
were studied in detail, while the mechanism of the formation nonstoichiometric oxides with different oxidizing valence
of nanocrystalline selenide in the g-irradiation process is states such as ZnO1
x (Zn2þO þ Zn0) and FeO1
x
presently not very clear. (Fe2þO þ Fe3þ 2 O3), metal excess or metal deficiency can be
determined using chemical titration methods such as iod-
ometry and cerimetry. In addition, ZnO1
x can also be
13.3 CHARACTERIZATION OF determined by an electroanalysis method [8].
According to the ratio of intensities of two six-line
NONSTOICHIOMETRIC COMPOUNDS
spectra, composing the complex Mössbauer spectrum of
Characterization of nonstoichiometric compounds mainly magnetite depends sensitively on x. Voleník et al. [49] re-
deals with determination of their compositions, substance ported the applicability of Mössbauer spectroscopy and X-ray
phase, and defects. This is because for a solid non- diffraction methods for the determination of the deviation of
stoichiometric compound it is not enough for us to merely magnetite from stoichiometry. The results showed that
consider the composition and we must combine its among the data obtainable by both methods, the ratio of
composition with its structure and properties, which de- intensities of two partial spectra composing the Mössbauer
pends on the defects in the crystal. For example, compo- spectrum of magnetite enables one to evaluate the deviation
sition can be determined by means of chemical analysis; of magnetite from stoichiometry quantitatively. Therefore the
substance phase and structure can be examined through X- measurement of the ratio of intensities of two partial
ray, electron, and neutron diffraction analyses, and rela- Mössbauer spectra is a suitable method for determining the
tionship of the composition, structure, and properties can be deviation x of magnetite from stoichiometry.
detected using various physicochemistry methods. So, we
can categorically confirm that the compound is a non-
stoichiometric compound rather than a stoichiometric
13.3.2 Structure Determination [8,15]
compound. Undoubtedly, X-ray diffraction techniques are some of the
most important methods to confirm phase structure.
A polycrystalline powder sample can be used for determi-
13.3.1 Composition Analysis
nation of the phase structure and unit cell parameters.
Compositions of some nonstoichiometric compounds can A single-crystal sample can directly measure its crystal
be determined through chemical methods. Iodometric and structure and study its crystal integrality. However, it is
cerimetric redox titrations are suitable for determinations of difficult to determine the structures of the homologous
significant levels of nonstoichiometry in metal oxides. series phases (e.g., rare-earth oxides) by X-ray diffraction
There are two types of element nonstoichiometry suitable because of the weak scattering of X-rays by oxygen atoms.
for iodometric analysis: (1) those in highly oxidizing Neutron diffraction turned out to be the best method to
valence states that reduce to stable nonoxidizing ions in determine the structures of these ordered oxygen-deficient
aqueous solutions; this type includes any nonstoichiometry phases. But there exist the following two problems: (1) it
above the following oxidation states such as trivalent Cr, is almost impossible to prepare a sample consisting of a
divalent Mn, divalent Co, divalent Ni, trivalent Ce, trivalent single phase because the oxygen content of the sample will
Tb, and trivalent Pr; and (2) those in valences that reduce easily vary with temperature and oxygen partial pressure;
into states stabilized by formation of an iodide complex, and (2) the refinement of the neutron diffraction data from a
352 Modern Inorganic Synthetic Chemistry

powder sample needs proposed models. These models The electronepositron annihilation method [27,50]
might come from the knowledge of a structural principle for (e.g., positrons injected into a semiconductor become
the homologous series phases. preferentially trapped in features such as vacancies, va-
To overcome these problems, high-resolution electron cancy clusters, and negative charge centers, where they are
microscopy (HRTEM) has become a powerful tool for subsequently annihilated from the trapped state in the
unraveling the structural features in nonstoichiometric defect) is a promising and universally recognized experi-
compounds (e.g., rare-earth oxides). HRTEM is able to mental approach to investigation of solids with point,
give an insight into the real structure of the rare-earth linear, extended, and bulk defects. As an extra merit, this
oxides and therefore overcomes the problem of multido- method of exploring local electronic structure of solids is
mains, even with different compositions. HRTEM opens also sensitive to even very small concentrations of struc-
up the possibility to simultaneously obtain diffraction data tural vacancies in a solid, from 10
6 to 10
3 vacancies per
in the back focal plane and images showing the projection atom. The results obtained by the method identify the
of the arrangement of atoms in a structure at atomic scale in defects contained in a solid and yield information on the
the image plane of the objective lens. The beam size, which presence or absence of structural vacancies in it, establish
can be changed from 100 mm to 1 nm, restricts the area on a the nature of the vacanciesdmonovacancies, divacancies,
sample where the diffraction data and the structure image or clusters of vacanciesdas well as permit estimation of
come from. It is possible to record an electron diffraction their electronic state throughout the volume of the solid
pattern and a structure image at time intervals of 1/16 of a under study.
second. If the sample is located in an environmental cell of It is very difficult to see individual point defects in a
the electron microscope it is possible to record even the material. It is not that they are too small (i.e., transmission
valence variation using electron energy loss spectroscopy electron microscopy has the resolution), but they have to
and a charge-coupled device camera. This means that the be surrounded by atoms, so we tend to see the surrounding
transition of different homologous series phases either at atoms instead [16]! At present, X-ray absorption near-
reduction or oxidation processes can be observed. edge structure spectroscopy is one of the few (and prob-
Therefore HRTEM is a key method to study the higher ably most straightforward) techniques for studies of indi-
oxides of the binary rare earths. vidual cation valences and layer-specific hole
concentrations: it definitely probes local concentration of
holes because the X-ray absorption spectrum is deter-
13.3.3 Defect Detection
mined by electronic transitions from a selected atomic
In principle, all physical properties of a crystal are derived core level to the unoccupied electronic states near the
from its crystal composition and structure. Moreover, some Fermi level [51].
physical properties such as density, electrical conductivity, In addition, electron paramagnetic resonance (EPR)
and optical and optoelectronic properties strongly depend spectra provide detailed structural information about
on kinds and concentration of the defects in the crystal. semiconductor defects, including their symmetry and
Accordingly, we can determine existence and concentration atomic and lattice configurations. EPR is equally useful for
of the defects using the physical properties. For instance, defect clusters because it is for isolated point defects [50].
because Schottky defects can bring about a density Similarly, laser Raman spectroscopy (LRS) is also a
decrease of the crystal, we can combine the density deter- powerful means to investigate the structural information on
mination method with the X-ray diffraction technique the microenvironment of center ions because LRS is
(i.e.,the lattice parameter with a high precision can be sensitive to the slight change of crystalline structure.
determined using X-ray diffraction and the precise lattice- Raman spectroscopy measurements are an efficient way of
parameter method) to confirm concentration of the defects studying the local atomic arrangement change [52].
in the crystal. Also, in situ thermogravimetry is one of the
most universal methods of nonstoichiometry analysis. The
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