Progress in Growth of Calcium Copper Titanate and Related Perovskites

Progress in Crystal Growth and Characterization of Materials 60 (2014) 15–62
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Progress in Crystal Growth and

Characterization of Materials
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Full length article
Progress in the growth of CaCu3Ti4O12 and

related functional dielectric perovskites
Laxman Singh a, **, U.S. Rai a, K.D. Mandal b, *, N.B. Singh c
a
Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi 221005, U.P., India
b
Department of Chemistry, Indian Institute of Technology, Banaras Hindu University, Varanasi 221005, U.P.,
India
c
Department of Chemistry and Biochemistry, University of Maryland Baltimore County, Baltimore,
MD 21250, USA
a b s t r a c t
Keywords: Calcium copper titanate, CaCu3Ti4O12, (CCTO), a potential electro-

Calcium copper titanate ceramic is a member of a very important perovskite family and
Electro-ceramic has been found to a show dielectric constant of the order of 104–
XRD
105. It has a remarkable ability to undergo a series of cationic
EDX
exchange reactions resulting in corresponding isomorphs. In the
Chemical synthesis
Dielectric properties past decade there has been immense activity in the search of an
isomorph of CCTO with high dielectric constant and low loss which
enables its use as capacitor material for the storage of energy and
miniaturization of electronic based equipment. Despite intensive
research in the area there is no source of any literature that gives
all the possible relevant information regarding various synthetic
methods, characterizations, effect of sintering parameters (tem-
perature, duration, and atmosphere). This review article is an effort
to review the synthesis, grain growth, morphological evolution,
effect of impurities, substitution and interface anisotropy on the
dielectric constant, resistivity and other materials parameters.
Ó 2014 Elsevier Ltd. All rights reserved.
* Corresponding author. Tel.: þ91 542 6702868 (office); fax: þ91 542 2368428.
** Corresponding author.
E-mail addresses: laxmanresearcher84@gmail.com (L. Singh), kdmandal.apc@itbhu.ac.in (K.D. Mandal).
http://dx.doi.org/10.1016/j.pcrysgrow.2014.04.001
0960-8974/ Ó 2014 Elsevier Ltd. All rights reserved.
16 L. Singh et al. / Progress in Crystal Growth and Characterization of Materials 60 (2014) 15–62
1. Introduction
A family of ACu3Ti4O12 (A ¼ Ca, Ba, Sr) compounds was discovered in 1967 [1] and their accurate
structures were determined in 1979 [2]. ACu3Ti4O12 type oxides have a complex perovskite structure
and are well known for their ability to produce high dielectric constants which has led to many
important applications. Presently we use BaTiO3 or relaxor ferroelectrics such as Pb(Mg1/3Nb2/3)O3
[PMN], Pb(Zn1/3Nb2/3)O3 [PZN] and Pb1xLax(Zr1yTiy)O3 [PLZT] [3] which are not environmentally
friendly as capacitor materials, dielectric constant (εr w1000–20,000). Problems with BaTiO3 are that it
is a ferroelectric perovskite which is quite unstable and shows phase transitions. Its dielectric constant
is highly unstable and shows a variation with temperature (T) and it is not suitable for use at high
temperature. High dielectric ferroelectric materials exhibiting the phase transition near the Curie
temperature are not the ultimate choices. For this reason, a high dielectric calcium copper titanate,
CaCu3Ti4O12 (CCTO) which belongs to ACu3Ti4O12 family, first discovered by Subramanian et al., (2000)
[4,5] is the best choice. CCTO has a pseudo-cubic perovskite structure with the space group of Im3 and
the lattice parameter of 7.391 A [2]. The very high dielectric constant (w104) value exhibited by (CCTO),
which is nearly constant in the temperature range of 100–600 K makes it a promising material for
many important industrial applications in microelectronics and memory devices as static dielectric
constant of a material ultimately decides the degree of miniaturization. It may widely be used in the
electronic industries to manufacture electronic components such as multilayer capacitor (MLCC),
dynamic random access memory (DRAMs), microwave devices, electronic devices in automobiles and
aircrafts [6–9]. Despite the fact that much theoretical and experimental research work has been done
to reveal the nature and origin of the giant dielectric constant of CCTO ceramics, it is still controversial
and as yet unsolved. At present, an internal grain boundary barrier layer capacitance (IBLC) model at
the grain boundaries between semiconducting grains [10,11], is widely accepted by the researchers.
Although several investigations have been reported on the dielectric properties of polycrystalline and
single crystal CCTO ceramics, their high loss tangent (tan d >0.05 at 1 kHz) is still the most serious
problem for applications based on capacitive components. Therefore, creation of a lead-free high
dielectric material with high dielectric constant and low loss tangent (tan d), and good stability in wide
temperature and frequency ranges are highly desired. Recently, varieties of methods [12–14] have been
reported by several researchers to prepare this giant dielectric material. Among these the most adopted
and traditional solid state reaction method lacks in terms of homogeneity of precursor materials. As a
consequence, the process requires higher sintering temperature and longer sintering time for solid
state diffusion to result single phase-formation. Therefore, suitable chemical methods for good
homogeneity and lower sintering temperature for shorter sintering time are the demand of current
time. In the present review, we report the recent progress in synthesis, characterization and applica-
tions of CCTO ceramic and its isomorphs. As such, it is essential to reveal its influence and find the
proper processing parameters to obtain CCTO ceramics with optimized properties. With a view to
understand and improve the dielectric properties of the ceramics, the effect of different parameters
such as sintering temperature, sintering duration, ceramic compositions, different processing methods
and their dielectric and electrical behavior dependence on temperature and frequency, among others,
are summarized in this review.
The recent past has witnessed the study on novel dielectric materials and their isomorphs for the
development of small size capacitor for the miniaturization of electronic devices. Dielectric material is
a substance that is a poor electrical conductor but an efficient supporter of electrostatic field. There has
always been requirement of new, innovative and easily obtainable dielectric materials that produce
high dielectric permittivity with very low dielectric loss. New ideas and designs to implement these
materials in microwave devices and structures with the most efficiency and performance are also of
equal importance. The appropriate materials and method of synthesis were utilized in the preparation
of the new type of dielectric ceramic substrate materials. Materials exerting a high dielectric constant
w103 have gained a great deal of attention. Since the discovery of ferro-electricity in a single crystal of
Rochelle salt in 1921, there have been many attempts to find new materials that possess a high
dielectric constant (εr). The urgent demand for ceramic capacitors having high dielectric constants has
been a key issue leading to the development of ceramic capacitor technology. However, the most
notable achievement in high εr dielectrics (materials having dielectric constants higher than 1000) was
L. Singh et al. / Progress in Crystal Growth and Characterization of Materials 60 (2014) 15–62 17
not gained until the unusual dielectric constant of barium titanate (εr w1100) based on the work of
Thurnauer was first observed in 1941. But the dielectric permittivity of the barium titanate being
strongly temperature dependent can pose limitations in its wide application in electronic industries
[15,16]. In view of this the scientist and technologist are seriously involved to obtain its alternative
showing thermally stable high εr and giving constant value in the wide frequency region, 104–106 Hz
and in the temperature range, 100–600 K. The perovskites have shown the above desired properties.
2. Perovskite oxides (a general overview)
A perovskite is a material with the same crystal structure as that of the natural mineral, calcium
titanium oxide (CaTiO3), originally found in the ural mountains of Russia in 1839 by Gustav Rose. This
mineral was named after the Russian mineralogist, L.A. Perovski. Perovskites have the general formula
ABO3, where A and B are cations of different sizes (A larger than B) and O is the anion. The B ions can be
3d, 4d or 5d transition metal ions taking an octahedral coordination. It is considered an FCC-derivative
structure in which the larger A cation and oxygen together form an FCC lattice while the smaller B
cation occupies the octahedral interstitial sites in the FCC array. There is only the oxygen being B
cation’s nearest neighbor. The perovskite structure is displayed by many oxides, several of which have
technological applications. The properties required for such applications are strongly dependent on the
coordination and connectivity of ions in the perovskite structure, making it important to be well un-
derstood. Many perovskite oxides and ceramic oxides having high dielectric constant are used for
making capacitors. The requirement for the manufacture of high energy storage capacitors is that they
have a high dielectric constant with low dielectric loss. There is a large numbers of ABO3 type and
complex perovskite oxides possessing high dielectric constant. A list of perovskite oxides and their
dielectric constant is shown in Table 1.
As mentioned earlier, oxides which are structurally analogous to the naturally occurring mineral
perovskite CaTiO3 are known as perovskite. Perovskites have the general formula, ABO3, where A and B
are metal cations. In ideal perovskite structure the larger A cations occupy 8 corner positions, B ions the
body center position and oxygen ions occupy the centers of six faces (Fig. 1). Goldschmidt in 1926 [17]
framed some empirical rules for the stability of ABO3 perovskites.
According to him the geometrical requirement for the formation of perovskite structure is that the
ionic radii rA, rB and rO of cations A, B and anion O, respectively, must satisfy the relation
ðr þ rO Þ
t ¼ pffiffiffi A ; (1)
2ðrB þ rO Þ
where t is the tolerance factor, which describes the range of relative sizes for which the perovskite
structure is stable. The structure will be cubic, if 0.95 < t 1.0. Compounds having tolerance factor in
Table 1
ABO3 type perovskite oxides and their dielectric constant.
Perovskite oxides Dielectric constant
BaTiO3 (ABO3) 200–3000

CaTiO3 100
SrTiO3 320
Ba (TiZr)O3 10,000Pb (Mg1/3Nb2/3)O3 18,000
Pb (Fe0.5Nb0.5)O3 100,000
CaCu3Ti4O12 10,000
CdCu3Ti4O12 409
La2/3Cu3Ti4O12 418
Sm2/3Cu3Ti4O12 1665
Na1/2La1/2Cu3Ti4O12 3560
Na1/2Sm1/2Cu3Ti4O12 1426
Na1/2Yb1/2Cu3Ti4O12 2048
LaCu3Ti3FeO12 44
CaCu3Ge4O12 34
Fig. 1. A unit cell of ABO3 type cubic perovskite [17].
the range 0.75 t 0.95 are non-ferroelectric with distorted structure while those with 1.0 are
ferroelectric [18–20]. If t < 0.75, the compound does not crystallize in perovskite structure.
They also have some empirical rules for the stability of ABO3:
a) An ion has a radius, which does not vary by more than a few percent in different structures in which
it occurs.
b) When a cation and the surrounding anions are given with their correct radii, all the anions must
touch the cation.
From literature the following points were found regarding geometry and electronic configuration:
a) The rA:rO should be approximately 1 or slightly higher.

b) The tolerance factor for the perovskite structure, using Pauling corrected radii should be
approximately 1.05.
c) Ionization potential of B should be 40 kJ/mol or higher.
d) Electro-negativity of O2 ion should be 2.5 or higher.
Perovskite oxides can be categorized into five types on the basis of valences m and n of cations A
and cations B in AþnBþmO3, respectively [21,22]. The only criterion is that the sum of the valences’
(m þ n) of the cations must be equal to that of anions to maintain charge neutrality. If A and B ions in
the structure have even valence, then all the ions in the structure should have 8 electrons in their
shells. If either A or B ions have odd valence, then the ions in the structure may have more than 8
electrons in their outer shells. Therefore, there are only three following categories of perovskite
oxides, which actually exist. If cation A belongs to first group elements and cation B belongs to the
fifth group elements of the periodic table, some important perovskite oxides of the type A1þB5þO3 are
LiNbO3, KNbO3, AgNbO3, AgTaO3 and KTaO3. Most of the compounds are either ferroelectrics or anti-
ferroelectrics [23].
a) If cation A belongs to second group and cation B belongs to the fourth group of the periodic table,
some examples of this group are A2þB4þO3 where A is a divalent ion (Ca, Sr or Ba) and B is a
tetravalent ion (Ti, Zr or Sn). Among these perovskite, the most widely studied materials are MTiO3
where M ¼ Ba, Sr, Ca and Pb. BaTiO3, CaTiO3, SrTiO3 and PbTiO3 are the important perovskite of this
category. These perovskites are used as dielectric and piezoelectric materials.
b) If cation A and cation B both belong to the third group of the periodic table, the compounds
belonging to this category have a rare earth or yttrium ion at A site and a trivalent transition metal
ion on B site i.e. A3þB3þO3 type oxides. These are of particular interest for technical applications as
functional materials in many fields because of their interesting properties such as mixed conduc-
tivity by both ions and electrons or holes migration [24].
Out of these perovskites, the category (b) and category (c) are of prime importance for this review.
2.1. Substitutions in perovskite
Oxides with the perovskite structure are well stabilized by their high dielectric constants (K) which
lead these classes of materials to a large number of technological applications [25]. The perovskites are
technologically important materials even in un-doped form and also its doping with different cations
modifies their properties [26–32]. The general doping is classified as interstitial and substitution.
Perovskites have close packed structure, therefore, interstitial substitution is difficult to make. There is
a lot of flexibility of substitution on A or B site of perovskite. ABO3 is made use by modifying their
properties. The following factors affect the substitution modifications:
a) Size: If the size of two ions differs by less than 15%, the condition is favorable.
b) Chemical affinity: The greater the chemical reactivity of the two crystalline materials, the more
restricted the solid solubility.
c) Structure: For complete solid solubility the two end members must have the same crystal
structure.
d) Valence: If the added ion has a valence different from the host ion, substitution is limited.
The substitution in perovskite oxides can be of the following types:
i) Isovalent substitution
ii) Heterovalent substitution
iii) Valence compensated substitution
(i) Isovalent substitution: In isovalent substitutions, the substituent ion and the ion which it
replaces, have the same valence. This substitution may be on either A site or B site or simulta-
neously on A and B site. In BaTiO3, substitution of Ca, Sr or Pb at Ba site are examples of isovalent
substitution at A site whereas replacement of Ti ion by Zr, Sn or Hf ions are examples of B site
isovalent substitution.
(ii) Heterovalent substitution: The substituent ion and the ion which is being substituted, have
different valences. A defect structure will be produced in order to compensate the extra charge
resulting from this substitution. The substitution also may be on either A site or B site. This
substitution is of two types:
1. Acceptors substitutions: An impurity ion that has a lower valence than that of the cation it
replaces in solid compound is called an acceptor impurity. This creates holes due to less
contribution of electrons from the substituent ion, which it replaces or it generates oxygen
vacancies e.g. substitution of Naþ on Ba2þ and Co3þ on Ti4þ site in BaTiO3.
2. Donors substitutions: A positive ion replacing another ion of lower valence on A or B site is called
a donor. The impurity thus bears an effective positive charge relative to the lattice of the host
oxide and charge compensation requires a species having an effective negative charge e.g.
electrons or cation vacancy e.g. La3þ or Y3þ on Ba2þ [33] and Nb5þ on Ti4þ site in barium titanate
separately.
3. Valence compensated substitution: Simultaneous substitution of a combination of ions at A and B
sub-lattice sites is such that total electrical charge neutrality in the crystal is maintained
internally. Simultaneous valence compensated substitutions are of two types (a) simultaneous
substitution of isovalent ions on A and B sub-lattice site (e.g. Pb1xBaxTi1xSnxO3) and (b)
simultaneous substitution of hetero-valent ions on A and B sub-lattice sites so that the charge
balance is maintained internally without requiring the change in the oxidation state of an ion or
creating vacancies in A, B or O sub-lattices such as M1xLaxTi1xM/xO3 (M ¼ Ca2þ, Sr2þ, Ba2þ or

Pb2þ and M/¼ Co3þ, Ni3þ, Fe3þ etc.) [34–36]. Such solid solutions are known as valence
compensated solid solutions (VCSS); e.g. La3þ ion on Ba2þ site and Co3þ on Ti4þ site simulta-
neously in BaTiO3: Ba1xLaxTi1xCoxO3. In this case there is a little chance of defect creation.
3. Synthetic routes for perovskite oxides
3.1. Dry method
The perovskite oxides are generally synthesized by conventional solid-state route or dry route. In
this route, oxides of various cations with suitable liquid (acetone or ethanol) are mixed in stoichio-
metric ratio and ground to fine powder using a pestle-mortar. Dried mixed powder is calcined at a
particular temperature for a certain period of time to remove volatile impurities. The calcined powder
is ground again and converted in to fine powder. An optimum amount of a suitable binder (PVA) is
added to powder and mixed uniformly then it is pressed in to a suitable shape. The resulting product is
first heated slowly to a particular temperature to burn off the binder and then the temperature of the
sample is increased to a particular value and maintained at this value for certain duration for annealing.
After annealing the sample is cooled under controlled rate of cooling. The final resulting product is
achieved by diffusion of metal ions at high temperature. A systematic flow chart is shown in Fig. 2.
3.2. Wet methods
Although the dry method is used for the synthesis of CCTO this procedure involves tedious work,
relatively long reaction times and formation under high temperature conditions. In addition, some
other secondary phases also appear during synthesis because of limited atomic diffusion through
micrometer sized grains. Therefore, repeated grinding, mixing and annealing is required at high
temperatures in attempting to attain chemical homogeneity. However, this does not necessarily lead to
chemical homogeneity at micro level in the end product. On the other hand, wet chemical methods
provide atomic level mixing of individual components and can result in the formation of nano-
crystalline materials at much lower temperature compared to solid state reactions. There are many
chemical methods, such as, sol–gel, co-precipitation, precursor solution techniques and hydrothermal
processes [12,37,38] which have been used for the synthesis of these ceramics.
3.2.1. Pechini’s method

Pechini’s method was developed by Pechini (Pechini, 1967) for the synthesis of titanates and nio-
bates for the capacitor industry. The modified Pechini method referred as the citrate gel process or the
amorphous citrate gel process has been used for the preparation of a wide variety of ceramic oxide
powders. The technique involves mixing of solutions of a metal precursor and an organic poly-
functional acid possessing at least one hydroxyl group and one carboxylic acid group such as citric
acid, glycine, tartaric acid and glycerol which results in complexation of the metal by the poly-
carboxylic acid. The solutions are heated to evaporate water and after its complete removal the
highly viscous resin is formed. The resin is then heated to decompose the organic constituents, ground
and finally calcined to produce the powder. The Pechini route achieves very good chemical homoge-
neity due to mixing of the metal cations on the atomic scale during the polymerization process and this
is maintained in the formation of the resin. If none of the constituents volatilizes during the calcination
step, the cation composition remains identical to that of the original solution. The disadvantage of the
above method is that the material formed from the decomposition of resin is not in the form of a fine
powder but consists of charred lumps. These lumps have to be ground and then calcined to produce
the final powder. Care should be taken that the grinding step may not introduce impurities into the
powder. As such the resulting calcination step produces hard agglomerates.
3.2.2. Glycine gel method

The glycine gel nitrate process is one of the types of combustion methods for the synthesis of
ceramic powders. A highly viscous mass formed by evaporation of a solution of metal nitrates and
Fig. 2. Flow chart for the synthesis of materials by solid state route.
glycine is ignited to produce the powder [39]. Glycine is a complexing agent and prevents the pre-
cipitation of the metal ions as the water is evaporated. It can form complex with cation at both the
carboxylic end and the amino group end as illustrated in Fig. 3. Glycine also serves another important
function and it provides a fuel for the ignition step of the process as it is oxidized by the nitrate ions.
The reactions occurring during ignition are highly explosive and extreme care is required during this
step. Normally, only small quantities should be ignited at a time. Under well controlled conditions, a
loose mass of very fine crystalline powder is obtained after ignition, so, in contrast to the Pechini
method, no grinding is required. The very fine size and crystalline nature of the powder are believed to
be direct result of short exposure to high temperature during the ignition step.
Glycine gel nitrate process, therefore, offers a relatively/inexpensive route for the synthesis of very
fine chemically homogeneous powder. It has been used for the synthesis of simple oxides as well as
complex oxides e.g. manganites, chromites, ferrites and oxide superconductors.
3.2.3. Semi wet method

This route is a modified sol–gel technique. It is also named as a citrate–nitrate gel chemical method
which is a type of combustion synthesis technique. Combustion synthesis is generally used to obtain
multi-component single phase material. The combustion technique is based on a redox reaction be-
tween a fuel and oxidant present in the precursor solution. Generally, citric acid, urea, ethylene glycol
etc. are used as a fuel and nitrates of different metals are used as an oxidant. The chelating agents like
EDTA, acetic acid etc. can form complex with metal ions present in the precursor solution and act as
fuel. This complex, on dehydration, produces a viscous gel which on further heating self-ignites with
the evolution of huge amount of gases. This leads to the development of porous floppy ash. Fine phase
pure powder can be obtained on further calcinations of the ash at high temperature. In a semi-wet
route, TiO2 suspension was developed in our laboratory with citric acid solution. All the metal cat-
ions were taken as nitrate except TiO2 which was taken as solid. Citric acid was used as the fuel. A
probable complex of metal cations and the citric acid is shown in Fig. 4.
In this route, standard solutions of nitrates of each metal ion were prepared using distilled water.
Solutions of metal nitrates in stoichiometric amounts were mixed in a beaker. Stoichiometric amounts
of solid TiO2 and aqueous solution of citric acid (equivalent to metal ions) were added to the solution.
The solution was then heated on a hot plate using a magnetic stirrer at 70–80 C to evaporate water.
Dehydration of the homogeneously mixed solution during heating caused the development of a gel.
This gel on further heating self-ignites followed by its swelling. This ignition product ash was volu-
minous and floppy in nature.
This ash was calcined in air at 800 C for 8 h in a muffle furnace. The resultant mixtures were ground
into fine powder using a pestle and mortar and mixed using few drops of 2% PVA binder.
Fig. 3. Zwitterionic glycine molecule complexing Mnþ.

Fig. 4. A probable structure of metal–citrate complex.
The cylindrical pellets were made using a hydraulic press and were sintered at 950 C for 12 h for
dielectric measurements. A flow chart indicating the various steps for the preparation of these ma-
terials by this method is shown in Fig. 5.
4. Principle of dielectrics
Dielectrics and insulators can be defined as materials with high electrical resistivity. A good
dielectric is, of course, necessarily a good insulator, but the converse is by no means true [40]. Dielectric
properties, dielectric constant, dielectric loss factor, dielectric resistivity, and dielectric strength will be
interpreted in the following sections:
4.1. Dielectric properties
The dielectric properties of perovskites have been studied in detail since the discovery of ABO3
perovskites such as BaTiO3 and PbTiO3 [41] and possess unusually high dielectric constants. This
feature is desired for, amongst other things, capacitive components in microelectronics. The high
dielectric constant of PbTiO3 and BaTiO3 is based on collective polar displacements of the metal ions
(on the B site of the perovskite) with respect to the oxygen sub-lattice and hence is linked to ferro-
electricity. Another group of perovskite-structured materials which exhibit large dielectric constants
of practical interest are known as relaxor ferroelectrics. These are examples of disordered solid solu-
tions, such as (1 x)PbZn1/3Nb2/3O3$xPbTiO3 (PZN-PT) [42] and (1 x)PbMg1/3Nb2/3O3$xPbTiO3(PMN-
PT), which not only show large dielectric constants but also pronounced frequency dispersion and a
variation of the dielectric constant as a function of temperature. Giant dielectric constant materials
have now found great importance for use in device implementation e.g. as metal-oxide semi-con-
ducting field effect transistors (MOSFET’s). In such cases the dielectric constant will ultimately
determine the miniaturization of such components. The complex perovskite, CaCu3Ti4O12, [1] currently
displays the largest known dielectric constant of w104–105 in the series of ACu3Ti4O12 [4,5,43]. The
mechanism behind this property is not yet clear; the barrier layer capacitor model being one of the
possible origins has been claimed in the literature. Another example is the Li-ion conductor compound
La0.67Li0.25Ti0.75Al0.25O3 [44].
It is well known that a dielectric substance is defined as a material with a high electrical resistivity
[45] but an efficient supporter of electrostatic field. If the flow of current between opposite electric
poles is kept to a minimum while the electrostatic flux lines are not impeded or interrupted, energy can
be stored by an electrostatic field. This property is useful in capacitors and can find applications in
virtually any electricity-driven devices [46]. As a familiar example, recent technological developments
in wireless telecommunication are based in part on the fabrication of superior dielectrics [47]. Many
capacitor formulations are based on BaTiO3, PbMg1/3Nb2/3O3x [PMN], PbZn1/3Nb2/3O3x [PZN], and
Pb1xLax(Zr1yTiy)O3 [PLZT] dielectric materials which possess the perovskite structure.
Fig. 5. Flow chart for the synthesis of materials by semi-wet route.
Dielectric properties of ceramic materials are of great interest in electronic ceramic industry. The
principal applications for ceramic dielectrics are as capacitive elements in electronic circuits and as
electrical insulators. Modified BaTiO3, CaTiO3 and SrTiO3 ceramics are frequently used as barrier layer
capacitor materials [48]. In real dielectric materials in an alternating field, the response lags behind the
applied field. Therefore, the dielectric constant of the ceramic material becomes a complex quantity, ε*
and can be represented by equation (2):
ε ¼ ε0r jε00r ; (2)

where εr0 and εr00
are the real and imaginary parts of dielectric constant of ceramic materials. In an ideal
capacitor, the dielectric charge adjusts itself simultaneously to any change in applied voltage. In
practice, however, there is inertia to this change that shows up as a loss in the electrical circuit. In an
alternating field, the time required for polarization shows up as a phase retardation of the charging
current. Instead of being 90 advanced, it is advanced only by (90 d) , where d is the loss angle. The
dissipation factor or loss tangent is given by:
ε00r
tan d ¼ ; (3)
ε0r
The dissipation factor is one of the important parameters for the application of a dielectric. The
dielectric has a low dielectric loss and low dielectric constant in use as an insulator and high dielectric
constant and low loss factor is desirable in use as a capacitor component. The response of a dielectric
material in an electric field is defined by a polarization parameter, which is the dipole moment per unit
volume of the material. There are various possible mechanisms of polarization viz. (i) electronic po-
larization, (ii) atomic or ionic polarization, (iii) orientation polarization, (iv) space charge polarization.
The ability of the dielectric materials to store energy is attributed to the polarization, i.e. electric field-
induced separation and alignment of the electric charges, which can result in an increase in capaci-
tance. There are several molecular mechanisms associated with this polarization, including electronic,
ionic, molecular (dipole) and interfacial (space-charge) polarization. For a given material, the sum of
the contributions from each mechanism determines the net polarization (P) of the dielectric material.
P ¼ Pelectronic þ Pionic þ Pmolecular þ Pinterfacial (4)
The typical response of the total polarizability of a crystal as a function of electric field frequency is
shown in Fig. 6 [49].
Electronic polarization occurs in neutral atoms when the electric field displaces the positive nucleus
with respect to the electrons around it, thus inducing a dipole moment. It occurs in all materials.
Magnitude of this mechanism is usually very small compared to other polarization mechanisms since
the moment arms of these dipoles are very short. This mechanism would result in low dielectric
constant, up to 2–4, and can respond to very high frequencies around 1015 Hz.
Ionic polarization occurs in materials made up of more than one type of non-ionic atoms as the
shifting of electron cloud toward the more electronegative atoms results in a permanent dipole under
Fig. 6. Typical response of the total polarizability of a crystal as a function of electric field frequency [49].
an applied electric field. The aligning of the permanent dipoles in a direction with the field creates
enhanced capacitance. Therefore, εr is a function of the material’s structure and lattice flexibility as well
as its composition.
Molecular or dipolar polarization occurs in substances containing permanent dipole moment
resulting from unbalanced sharing of electrons by atoms of a molecule. The rotations of the permanent
dipoles to align with the external electric field cause orientation polarization to occur at around 1011 to
1012 Hz.
Space charge or interfacial polarization occurs in heterogeneous systems such as multi-component
materials or incompatible chemical substance containing materials when translating charge carriers
are accelerated by an applied field until they are impeded by and trapped at the physical barriers in
these heterogeneous systems. This build-up of charge dictates the polarization of the material. Grain or
phase boundaries and free surfaces are common barriers. The typical frequency range for this polar-
ization is around 103 to 103 Hz.
Ideally, the dielectric constant should be constant with regard to frequency, temperature, voltage
and time. However, each polarization mechanism has a characteristic relaxation frequency. Therefore,
εr values of most of the materials show a dependence on the frequency because slower mechanisms fail
to respond and contribute to the dielectric storage when the frequency becomes large. The εr values of
dielectric materials can also vary with temperature, bias, impurity and crystal structure.
4.1.1. Dielectric constant

Dielectric constant is the factor by which the capacitance of a parallel-plate capacitor is increased by
inserting a dielectric in place of a vacuum. Insulators are materials with low conductivity. This low
conductivity of roughly 20 orders of magnitude (compared with typical metals) is the result of energy
band gaps greater than 2 eV (compared to zero for metals). These low conductivity materials are an
important part of the electronics industry. It (ε) is a physical quantity that describes the ability of a
material to polarize in response to the field, and thereby reduce the total electric field inside the
material [50,51].
4.1.2. Dielectric loss

The dielectric loss is a measure of energy loss in the dielectric during a cooperation, which is a
material property and does not depend on the geometry of capacitor. Usually the dielectric loss,
expressed as the loss tangent (tan d) or dissipation factor (Df) can be mathematically defined as
equation (5)
ε00 s
tan d ¼ þ (5)
ε0 2pf ε0
where ε0 , ε00 are the real and imaginary part of the dielectric permittivity and s is the electrical con-
ductivity of the materials, respectively, and f is the frequency. In general, dielectric loss of a dielectric
material results from distortional, dipolar, interfacial, and conduction loss. The distortional loss is
related with electronic and ionic polarization mechanisms. The interfacial loss originates from the
excessive polarized interface induced by the fillers and specifically the movement or rotation of the
atoms or molecules in an alternating electric field. The conduction loss is attributed to the dc electrical
conductivity of the materials, representing the flow of actual charge through the dielectric materials.
The loss factor is the primary criterion for the usefulness of a dielectric as an insulator material which is
given by equation (6):where ε0 is dielectric constant defined above, while tan d is the dissipation factor.
For this purpose it is desirable to have a low dielectric constant and particularly a very small loss angle.
In general, dielectric loss of the dielectric material results from distortional, dipolar, interfacial and
conduction loss. The distortional loss is related with electronic and ionic polarization mechanisms. The
interfacial loss originates from the excessive polarized interface induced by the fillers and specifically
the movement or rotation of the atoms or molecules in an alternating electric field. The conduction loss
is attributed to the DC electrical conductivity of the materials, representing the flow of actual charge
through the dielectric materials. The energy loss in dielectric materials results from three processes
[52] as follows:
i) Long range electronic or ionic migration losses (i.e. DC conductivity)

ii) Relaxation losses for dipole reorientation due to ionic jump and
iii) Ion vibration and deformation losses.
ε00 ¼ tan d=ε0 (6)
The energy loss (W) refers to the energy dissipated in a dielectric material and is proportional to the
dielectric loss tangent, which can be determined by the following equation:
W ¼ pε0 x f tan d
2
(7)
where x is the electric field strength and f is the frequency. Therefore, a low dielectric loss is preferred in
order to reduce the energy dissipation and signal losses, particularly for high frequency applications.
Generally, a dissipation factor under 0.1% is considered to be quite low and 5% is high. Very low
dissipation factor is desired for radio frequency (RF) applications to avoid signal losses, but much
higher values can be tolerated for energy storage applications such as decoupling.
The presences of oxygen vacancies are important in the high temperature region. The rapid increase
of dissipation factor is caused by free carrier conductivity and the concentration of free carriers de-
pends on doping and temperature. The loss factor (tan d) is inversely proportional to frequency in this
temperature range.
Polycrystalline titanates are appreciably reduced at the temperatures used in firing ceramic
capacitors. On cooling, rapid re-oxidation occurs above 1100 C but effectively stops at some tem-
perature between 600 C and 900 C. As a consequence, the outside of the sample and to some extent,
the outside of each grain is well oxidized, but the interior of the grains remains oxygen deficient.
Oxygen vacancies carry an effective charge of þ2e, which are neutralized by 3d electrons on the ti-
tanium atoms, forming two Ti3þ ions for every oxygen vacancy. At low temperatures, the oxygen va-
cancies and Ti3þ ions are bound by a small energy of 0.10–0.20 eV which is sufficiently large so that only
a few of the defects are separated. Electrons associated with the unattached Ti3þ ions are responsible
for conduction making use of the narrow 3d conduction band. Alternatively the conduction process can
be described as electron hopping via Ti3þ 4 Ti4þ þ e transfer. Unattached oxygen vacancies also
contribute to the conductivity but their mobility is much smaller than that of electrons [53].
Neutralized bound defects do not participate directly in the conduction process but experience a torque
tending to align the dipole moment with the applied field. This in turn creates dielectric polarization
and dielectric loss.
5. ABO3 type high dielectric constant perovskites
ABO3 type perovskite materials display a wide spectrum of physical properties of technical
importance such as ferro-electricity, anti-ferroelectricity, piezo-electricity, insulating behavior, semi-
conducting, metallic, super-conducting, ferromagnetic, anti-ferromagnetic behavior. Perovskite
ceramics like CaTiO3 and SrTiO3 after suitable modification become technologically important electro-
ceramics and hence are widely used as dielectric thermistors and barrier layer capacitors (BLC). These
oxides form a large group of dielectric materials having ferroelectric, anti-ferroelectric and paraelectric
behavior at room temperature. The perovskite family includes many titanates used in various electro-
ceramic applications, for example, electronic, electro-optical, and electromechanical applications of
ceramics. Barium titanate, perovskite structure, is a common ferroelectric material with a high
dielectric constant, widely utilized to manufacture electronic components such as mutilayer capacitors
(MLCs), PTC thermistors, piezoelectric transducers, and a variety of electro-optic devices [54]. Because
of people’s demands, dielectric (essentially non-conducting) characteristics of ceramics materials are
increasing rapidly. At the same time researcher and technologists are attempting to reduce the size of
all communication devices to be as small and as light as possible. Due to this trend, high dielectric
constant materials such as barium titanate (BaTiO3) and strontium titanate (SrTiO3) and their iso-
morphs obtained by different substitutions now a day’s become more and more important in ceramics
materials. The rapid development of the microelectronic devices such as capacitors, resonators and
filters not only accelerates the miniaturization of passive components but also increases the active
demands of the high dielectric permittivity materials. Dielectric properties of these ceramics are useful
for applications in capacitors and memory devices. The applications of perovskites materials are shown
in Table 2.
5.1. Barium titanate (BaTiO3)
BaTiO3 is a ferroelectric perovskite (ABO3) with a high value of dielectric constant (w200–3000) at
room temperature. In BaTiO3, both barium and oxygen ions have radii of about 1.40 A and together they
make up a face centered cubic array. Octahedrally coordinated titanium ions located at B-site, the body
center of a perovskite unit cell, are the active ions promoting ferro-electricity. The low-lying d-orbital
of titanium lead to an eccentric atomic arrangement and large electrical polarizability. On cooling from
high temperature, BaTiO3 undergoes three ferro-electric phase transitions. All the three transitions are
displaceable in nature involving atomic movements of 0.10 A or less. The direction of spontaneous
polarization changes from one ferroelectric phase to another. At temperature above 1450 C, it
transforms to non-ferroelectric hexagonal form [15]. Below 1450 C, it exists in the cubic form, which is
para-electric. At room temperature BaTiO3 is tetragonal with axial ratio c/a z1.012 [55]. The poly-
morphic phase transitions at lower temperatures are found to occur as:
90 C 5 C 130 C
Rhombohedral 4 Orthorhombic4Tetragonal 4 Cubic:
with the direction of spontaneous polarization (Ps) as <111>, <110> and <001> in rhombohedral,
orthorhombic and tetragonal structure, respectively. Therefore, BaTiO3 shows a strong temperature
dependence of the dielectric constant near its curie temperature and therefore limits its application to
high temperatures.
5.2. Calcium-titanate (CaTiO3)
It is a para-electric material at room temperature with no interesting dielectric properties in the

pure form. Donor doping in CaTiO3 gives rise to boundary layer effects with enhanced permittivities.
Calcium titanate when doped with 0.75 mol% yttrium sintered in N2 atmosphere was found to give
rise to anomalously high dielectric constants with relaxor behavior [56]. It has a distorted cubic
structure [57,58]. It has been reported that calcium titanate has an orthorhombic symmetry at room
temperature and the structure becomes tetragonal at 600 C, which changes to cubic at 1000 C. Study
of optical density on the single crystal of CaTiO3 has shown that the band gap is 3.4 eV at 0 K. The
electrical conductivity of this compound at 130 C, after exposing to oxidizing atmosphere, was found
Table 2
Applications of the perovskite oxides.
Application
BaTiO3 Multilayer capacitor

Pb (ZrxTi1x)O3 Piezoelectric transducer
BaTiO3 P. T. C. Thermistor
(Pb, La) (Zr, Ti)O3 Electrooptical modulator
LiNbO3 Switch
BaZrO3 Dielectric resonator
BaRuO3 Thick film resistor
Pb (Mg1/3Nb2/3)O3 Elecrostrictive actuator
Ba (Pb, Bi) O3 layered cuprates Superconductor
GdFeO3 Magnetic bubble memory
YAlO3 Laser host
(Ca, La)MnO3 Ferromagnet
LaCoO3 Refractory electrode
KNbO3 Second harmonic generator
to be p-type [59]. CaTiO3 can be converted to n-type semiconductor either by reduction at elevated
temperature or by doping with donors [56].
5.3. Strontium titanate (SrTiO3)
SrTiO3 has attracted much attention for its potential applications such as substrate for epitaxial
growth of high temperature superconductor thin films [60] in photolysis of water, as an oxygen sensor
and in magneto-hydrodynamics operations [61,62], photo-chromic and cathode-chromic materials,
which are also used in memory devices, optical processors etc [63,64]. It exhibits n-type conductivity
due to formation of oxygen vacancies [65]. At room temperature it is cubic having a band gap of 3.2 eV
[66–68] and is para-electric [69]. Strontium titanate does not possess interesting properties in the pure
form. At room temperature, strontium titanate is a cubic perovskite and a para-electric [70]. Its prop-
erties can be modified by various substitutions which are important from a device point of view. Doping
polycrystalline strontium titanate with several mol% bismuth or trivalent rare-earth ions has been
found to result in relaxor behavior and a high dielectric constant. For example the room temperature
dielectric constant for strontium titanate is w300 whereas the dielectric constant is raised to w18,000
by doping with 0.75–1.0 mol% Yttrium. Other important donor dopants are La3þ, Ce3þ, Sb5þ etc.
6. ACu3Ti4O12 type of materials
High dielectric constants are found in perovskite oxides of the type ACu3Ti4O12 (A ¼ Ca, Sm, Dy, Y
and Bi) which has led to many important applications in microelectronics and memory devices since
the static dielectric constant of a material ultimately decides the degree of miniaturization. The
dielectric constant of a material is related to polarizability, a, in particular, the dipole polarizability
which arises from structures with a permanent electric dipole that can change orientation in an applied
electric field. In general, a value of a dielectric constant of over 1000 is related to either a ferroelectric
that exhibits dipole moment in absence of applied electric field or to a relaxor characteristic.
Ferroelectrics respond under high electric fields at low temperatures but no macroscopic sponta-
neous polarization. However, both classes of materials show a peak in plot of εr as a function of tem-
perature that is undesirable for many applications. For example capacitors need to have thermally
stable values to operate properly over a wide range of temperatures. If εr has strong temperature
dependence, then the device may not be robust and may fail. Recently, the perovskite related bcc
materials of type ACu3Ti4O12 (A ¼ Ca, Sm, Dy, Y and Bi) revealed extraordinarily high permittivity at
room temperature, when A ¼ Ca we have the much more important pervsokite, CaCu3Ti4O12 pos-
sessing high dielectric constant which is frequency independent (104–106) in the range 100–600 K [4].
This is very important from a device point of view. In addition to CaCu3Ti4O12 many other perovskite
materials also have a large dielectric constant, e.g., Bi2/3Cu3Ti4O12 (BCTO), Y2/3Cu3Ti4O12 (YCTO) and
La2/3Cu3Ti4O12 (LCTO). All these large dielectric constant materials have similar dielectric behavior, i.e.,
they all exhibit a Debye-like relaxation and their dielectric constants are nearly independent of fre-
quency and temperature well below the relaxation frequency. Among these, CaCu3Ti4O12, has exhibited
an extraordinarily high dielectric constant at room temperature of about 104 to 105 and good tem-
perature stability in a wide temperature range from 100 to 600 K. Scientists have been working to
improve dielectric properties particularly to minimize the dielectric loss of high dielectric constant
perovskite oxide (CaCu3Ti4O12) by substitution with-trivalent or divalent metal ions on A and B site,
respectively. The dielectric response of this material was found to be very sensitive to the micro-
structure (such as grain size) and the processing condition [71] as well as doping [72,73]. People have
applied various methods for the synthesis of this material and various cationic substitutions at the Cu
site, Ti site and both sites for the purpose of increasing the high dielectric constant and decreasing low
dielectric losses needed for the miniaturization of devices in the modern age.
6.1. Crystal structure of CaCu3Ti4O12 materials
The structure of CCTO has been determined using XRD and neutron powder diffraction studies. It
has been found that CCTO crystallizes in a perovskite structure of the type (A0 A00 )(BO3), where Ca2þ and
Cu2þ ions share the A site and Ti4þ at the B site. The crystal structure of CCTO is cubic in the Im3 space
group (No. 204) [74] with two formula units per unit cell because TiO6 doublets are present in the
structure [5]. The lattice parameter of this unit cell was found to be 7.391 A. The structure remains
centro-symmetric cubic up-to very low temperatures. The structure of a unit cell of this composition is
shown in Fig. 7. Here the TiO6 octahedra are tilted to produce a square planar environment for the Cu2þ
ions. Each copper atom is bonded to four oxygen atoms and the large Ca atoms are in corner and body
centered positions. Ti4þ ions occupy the centro-symmetric position in the octahedral sites.
The tilt angle of the TiO6 octahedra is large enough (141 ) to accommodate local distortion, which, in
turn, would effectively rule out pure ferroelectric behavior [75]. In CaCu3Ti4O12 the observed Ca–O
distance is equal to 2.604 A, which is less than the 2.720
A predicted on the basis of the ionic radii. Thus
the site is too small for the A2þcations and they push out to expand the lattice. This places Ti–O under
tension and increases the polarizability of the structure. On substituting donors and acceptors on Ca2þ
and Ti4þ sites, respectively, their different ionic radii as compared to the host ions cause increased or
decreased tension. This will result in a lower or higher value of polarizability and hence dielectric
constant as is observed experimentally.
6.2. Sudden increase in the interest on CCTO
The urgency of finding alternative energy sources and the means to store them has undergone
phenomenal resurgence. New materials and novel engineering approaches are needed to overcome the
challenges facing the society to minimize its dependence on fossil fuel. Perovskite CCTO (CaCu3Ti4O12)
appears to be ideally suited for high energy density storage medium owing to its colossal dielectric
constant >104 and its excellent temperature and frequency dependence. Since its discovery in 2000 it
has been investigated for miniaturized capacitor devices for large scale energy storage systems as well
as for advanced microelectronics. But neither the materials nor the engineering conditions have been
solved satisfactorily.
The discovery of the unusual high dielectric constant in CaCu3Ti4O12 (CCTO) [4] has opened a new
field of materials research. CaCu3Ti4O12 exhibits the most exceptional behavior, and shows a high
dielectric constant of about 12,000 at 1 kHz that is nearly constant from room temperature to 300 C
and is frequency independent (102–106 Hz). CCTO does not show ferroelectric transition behavior due
to its unusual dielectric property and nonlinear electric varistor behavior [76]. It is well known that
Fig. 7. The unit cell of body-centered cubic CaCu3Ti4O12, which consists of two formula units. The Ti atoms sit at the center of canted
TiO6 octahedra (the tilt angle is nominally 141 ), with bridging Cu atoms and large Ca atoms sitting at the center and corners of the
unit cell [4].
there is potential demand for high dielectric constant ceramic materials. At the same time people are
attempting to reduce the size of all communication devices to be as small and as light as possible. Due
to this trend, high dielectric constant materials, such as barium titanate have currently become more
and more important in ceramic materials. There is continuous demand for miniaturization of electronic
devices (cell phones, digital cameras, note book, computers, TV etc.). There is continuous interest to
develop capacitor materials with high dielectric constant and low loss for application to microelec-
tronics, microwave, memory and capacitance based energy storage devices. CCTO can meet these re-
quirements. These are the advantageous features of CCTO compared to the high dielectric constant
ferroelectric materials which have applications to the miniaturization of electronic devices except for
the limitation that they can exhibit a high dielectric loss. An ideal capacitor material requires a high
dielectric constant 102–106 and low dielectric loss (0.01–0.0001). The dielectric constant should not
vary with frequency of current in any region. Dielectric materials require high thermal stability from
room temperature to 500 C.
Presently, we use relaxor ferroelectrics such as Pb(Mg1/3Nb2/3)O3 [PMN], Pb(Zn1/3Nb2/3)O3 [PZN],
and Pb1xLax(Zr1yTiy)O3 [PLZT] which are not environmentally friendly as capacitor materials. BaTiO3
is a ferroelectric perovskite which is used in ceramic industry as a capacitor material.
6.2.1. Special properties of CaCu3Ti4O12 (CCTO)
(i) It is non-ferroelectric with a very high dielectric constant (for polycrystalline – 104, for single
crystal – w105, Depending on processing – w102–106).
(ii) High dielectric loss (tan d ¼ w0.1)
(iii) No phase transition till w800 C.
(iv) Dielectric constant is stable between 100 and 600 K. Below 100 K it drops suddenly to w100.
(v) Dielectric constant is stable in low frequency region 102–105 Hz.
BaTiO3 is one of the most important materials in the family of alkaline earth titanates. It is a
ferroelectric a perovskite with a dielectric constant of 2000–3000 at room temperature and low
dielectric loss (tan delta w0.01–0.2). Dielectric constant is highly unstable with temperature and it is
not suitable for use at high temperature.
7. What is the origin of the very high dielectric constant in CaCu3Ti4O12?
CCTO exhibits an enormously large low-frequency dielectric permittivity (ε) of the order of 104 in
both forms of single crystals and polycrystalline ceramics at room temperature and is almost constant
at low frequencies over the temperature range from 100 to 380 K. The dielectric constant (ε) drops
rapidly to a value of about 100 with decreasing temperature or increasing frequency and shows the
Debye-type relaxation behavior [14]. The characteristic relaxation frequency follows approximately the
Arrhenius law [43]. Such dielectric behavior is scientifically interesting and technologically intriguing.
So, the origin of large dielectric permittivity of CaCu3Ti4O12 (CCTO) has attracted much attention. So far,
several models have been proposed to explain the dielectric behavior which is quite controversial. The
mechanism for the giant dielectric constant of CCTO is still questionable and investigators are studying
it in an effort to understand whether the giant dielectric constant is intrinsic to a perfect crystal or
extrinsic where it originates from defects, in homogeneities, etc.
7.1. Intrinsic factors: atomic structure aspects
There has been substantial debate about the intrinsic and extrinsic electrical properties of CaCu3-
Ti4O12 since the original report by Subramanian et al. The central question is whether the large
dielectric response is intrinsic to a perfect crystal of CaCu3Ti4O12 or extrinsic in that it originates with
defects, in homogeneities, etc. “Intrinsic” means that the large dielectric response would be present in a
perfectly stoichiometric, defect-free, single-domain crystal of CaCu3Ti4O12. The CaCu3Ti4O12 structure
is much more constrained than other ABO3 type perovskites. The structure of unit cell is shown in
Fig. 7; here the TiO6 octahedra are tilted to produce a square planar environment for the Cu2þ ions. If
the Ti–O and Cu–O distances are 1.96 A then the Ti–O octahedron is not distorted for distortion to occur
the unit cell edge and Ca–O distance must be 7.383 A and 2.61 A, respectively. The experimentally
determined values of a ¼ 7.391 A and Ca–O distance ¼ 2.604 A. The Ca–O distance is much less than
2.72 A which is predicted based on ionic radii. Thus, in CCTO the A2þ ion is at a site too small for it. As it
pushes out to expand the lattice, it places the Ti–O bonds under tension and increases the polarizability
of the Ti–O octahedra. Thus in CCTO, the dielectric constant and polarizability are enhanced by tension
in Ti–O bonds. Subramanian et al. had interpreted the high permittivity in terms of its intrinsic crystal
structure, i.e., arising from the local dipole moments which are associated with off center displacement
of Ti ions, but the transition to a ferroelectric state is frustrated by the TiO6 octahedral tilt being
required to accommodate the Cu2þ square planar coordination. However, noticing the existence of a
high degree of twinning with small domains in the single crystal, they also suggested that these twin
boundaries might act as the barrier layer capacitance, thus offering a possible extrinsic explanation for
the observed giant dielectric property. Ramirez et al. [5] found that the high dielectric constant was
temperature independent over 100–400 K. However, the dielectric constant dropped by the factor of
100 at temperatures below 100 K along with a broad peak in the loss tangent. Dielectric constant (εr)
and dielectric loss (tan d) as a function of temperature revealed a strong frequency dependence and an
increasing trend in the characteristic frequency (uo) over temperature. Raman scattering data
measured at the different temperatures showed a temperature independent gap frequency (28 meV),
which is analogous to the thermal activation energy of the dielectric constant at the low frequency
region. Considering that uo can be defined as the jump rate for an electron between two lattice sites, its
change as a function of temperature indicates that the anomalous dielectric responses in CCTO might
be linked to a Debye-like relaxation behavior. Also, the gap frequency correlated with the energy
difference between those sites suggests the possibility of highly polarizable relaxation modes. Lun-
kenheimer and coworkers [77] suggested that the intrinsic properties of CCTO are due to charge
transport via hopping of localized charge carriers. They measured frequency dependent conductivity of
CCTO at various temperatures. They found that the intrinsic conductivity increases with frequency at
low temperature, which is generally observed in transition-metal oxides due to indicative hopping
conduction of localized charge carriers [78,79]. Homes et al. [43] have suggested that the large change
in dielectric constant at low temperature may be due to a relaxor like dynamical slowing down of
dipolar fluctuations in nano-sized domains, based on their optical measurement.
7.2. Extrinsic factors: microstructural aspects
In view of the experimental and theoretical difficulties associated with an intrinsic explanation,
many puzzling aspects of the behavior of CaCu3Ti4O12 become easier to understand if one assumes that
the large observed static dielectric response arises from extrinsic mechanisms, such as point, line, or
planar defects, or other crystal imperfections or more generally, with sample microstructure,
morphology, domain boundaries and boundary layers [80–82]. Although we can rationalize the high
dielectric constant of CCTO based on its atomic structure, there is good reason to suspect that the
dielectric constant is enhanced by its microstructure and other external parameters.
Extrinsic:
(a) Single crystal (domains and its domain boundaries)

(b) Electrically heterogeneous – Internal Barrier Layer Capacitance (IBLC)
(c) Electrode/sample contact effects
(d) Interfacial polarization effect: Maxwell–Wagner model.
7.2.1. Single crystal (grains and its domain boundaries)

The giant dielectric constants were also reported in single crystal CaCu3Ti4O12. It would be con-
tradictory for the giant dielectric response of CaCu3Ti4O12 to have the dielectric response mechanism
with different kinds of the origins, namely, the internal boundaries for the single crystal but the grain
boundaries for the polycrystalline CaCu3Ti4O12. The insulating barrier layer of single crystals, locally
planar twin boundaries, anti-phase and compositional-ordering domain boundaries were proposed to
be the possibilities for the barrier layers [83,84]. The recent discovery of internal domains inside the
grains has indeed solved this contradiction, which also strongly suggested that the origin of the giant
dielectric response of CaCu3Ti4O12 is related to the barrier layer mechanism. Fang et al. observed
internal domains inside grains [85]. They proposed the possible existence of both domain boundaries
and grain boundaries as the barrier layers to contribute the extraordinary dielectric response in
CaCu3Ti4O12 [86]. The discovery of the internal domains inside the grains of the polycrystalline
CaCu3Ti4O12 not only solves the contradictory explanation of the dielectric response between poly-
crystalline and single-crystal, but also justifies the extrinsic effect of the enhancement of the dielectric
response of CaCu3Ti4O12.
7.2.2. Internal barrier layer capacitor (IBLC) model

Internal barrier layer capacitance (IBLC) has been considered as the widely accepted mechanism to
explain the observed giant dielectric response [87]. A barrier layer structure with semiconducting areas
encircled by insulating layers was established to explain the very large capacitance behavior of both
polycrystalline and single crystal CaCu3Ti4O12 [72,88]. The dielectric responses of such a structure
essentially are characterized by the so-called interfacial polarization. For polycrystalline materials, the
barrier layers are presumably located at the interface between the sample and contact, or at grain
boundaries [89,90]. Sinclair et al. [91] used impedance spectroscopy to demonstrate that CaCu3Ti4O12
ceramics were electrically heterogeneous, consisting of semiconducting grains (with dielectric con-
stant <100) and insulating grain boundaries. A simplified equivalent circuit can be thus obtained,
which consists of two parallel RC elements connected in series, one RC element, RgCg, representing the
semiconducting grains and the other, RgbCgb, representing the insulating grain boundary regions [92].
The equivalent circuit is shown in Fig. 8(a). The schematic diagram of atypical impedance complex
plane plot obtained at various temperatures for CaCu3Ti4O12 ceramics is shown in Fig. 8(b).
In Fig. 8(a) the equivalent circuit used to represent the electrical properties of grain and grain-
boundary effects is shown. Herein, Rg (Rgb) and Cb (Cgb) are resistivity and capacitance of grain
(grain-boundary), respectively. In Fig. 8(b), the corresponding schematic impedance spectra according
Fig. 8. (a) Equivalent circuit of the Cole–Cole plot. (b) Impedance complex plane plot, Z* at w104, 115 and 130 K, for CaCu3Ti4O12
ceramics [92].
to equivalent circuit (a) are shown [74]. In this case, the complex impedance plot should in principle
reveal two semicircles, corresponding to the contributions of grain and grain boundary, respectively
(Fig. 8(b)). In some cases, the electric response (the semicircle corresponding to the grain (bulk) at
higher frequencies is missing or only partially appearing due to the limitation of the frequency range of
the instrument. This study by impedance spectroscopy reveals the electrically inhomogeneous
structure of the sample, which is a typical combination of the semiconducting grains with the insu-
lating grain boundaries. This investigation supports the extrinsic IBLC model as the origin of the high
permittivity of CaCu3Ti4O12 and also reconciled the intrinsic properties of CaCu3Ti4O12. The barrier
layers are supposed to be the grain-boundaries. The influence of average grain size on the electrical
properties of CaCu3Ti4O12 ceramics has been reported [73]. Extremely high grain boundary permittivity
value of w280,000 was obtained in the large grained (w100–300 mm) ceramics, which provided
further support for the extrinsic IBLC mechanism of the dielectric response in CaCu3Ti4O12 ceramics.
The heterogeneous materials such as varistors and barrier layer capacitors have properties that are
controlled exclusively by the detailed chemistry and structure of “interfacial regions” at grain
boundaries and grain surfaces [93]. It may be less important to achieve high density ceramics in such
cases. For the characterization of electro-ceramics, it is useful to distinguish between the ceramic
microstructure that is seen by direct observation using electron microscopy and the electrical micro-
structure that is determined indirectly by techniques such as impedance spectroscopy [94]. Grains,
especially at grain surfaces, may show small variations in composition that are responsible for the
characteristic properties of varistors and barrier layer capacitors. Whereas it may be extremely difficult
to detect such compositional variations by electron microscopy, these features are clearly present in the
electrical microstructure and indeed, may dominate the overall electrical properties [10,95]. As stated
earlier, for the extrinsic mechanism, the barrier-layer model has been considered as the most favorable
mechanism to explain the giant dielectric response in CaCu3Ti4O12 material. According to the internal
barrier layer capacitance model, the apparent εr of such an electrically heterogeneous ceramics can be
approximated from
tg þ tgb
εr ¼ εgb (8)
tgb
where εgb is the dielectric constant of the grain boundary layer, tg and tgb are the thickness of the grains
and grain boundary layers, respectively. Therefore, even a small εgb could lead to a giant εr if the ratio
(tg þ tgb)/tgb is large [96,97]. Accordingly, it can be easily understood that the bigger grains (larger tg)
with thinner grain boundaries (smaller tgb) in the samples give higher dielectric constants (higher εr).
The development of insulating barrier layers at grain boundaries is widely accepted. The microstructure
model [98] for the enhancement of the dielectric response of CaCu3Ti4O12 has been schematically
illustrated in Fig. 8(a). The series-connected conduction path can be simulated by the equivalent circuit
of Fig. 8(b). In this case, the stained and composition disordered domain boundaries could make up large
energy barriers for hopping and be assumed to be insulating. Though the origin of such dielectric
behavior is still open to debate, an internal barrier layer capacitor is generally considered as the most
probable mechanism [99,100]. Guillemet-Fritsch et al. investigated dielectric properties of CaCu3Ti4O12
based multiphase ceramics [101]. They proposed the presence of a copper oxide phase besides
CaCu3Ti4O12 for enhancing the dielectric property. Kobayashi et al. investigated the dielectric properties
of two phase composites of CaCu3Ti4O12 and CaTiO3 [54]. A high εr (z1800) with a low tan d (0.02)
below 100 kHz was obtained at CaCu3Ti4O12:CaTiO3 ratio of 2:1. A barrier layer of CaTiO3 on the surface
of the CaCu3Ti4O12 grains was proposed to be the possible contribution of the high dielectric perfor-
mance. Chung et al. [102] used a combination of scanning Kelvin probe microscopy with a lateral bias
and I–V measurements on pellets and across individual grain boundaries (using micro-contact elec-
trodes on individual grains) to demonstrate the presence of electrostatic barriers at the grain boundaries
in CaCu3Ti4O12 ceramics. The grain size-dependent breakdown voltage supports the IBLC mechanism.
7.2.3. Electrode/sample contact effects

The high dielectric constant in CaCu3Ti4O12 is related to the ceramic itself and from the electrode/
sample contact effects depend on the surface resistivity of the sample. There will be no mobile space
charges when the surface resistivity is as high as 1.2 108 U so the dielectric properties of the sample
are inert to the different metal electrodes and various sample thickness. Under this condition, the
dielectric constant was found to be nearly 2000 at 10 kHz at room temperature, as reported by
Yang et al., 2005 [103]. When the surface resistivity was decreased to 3.1 107 U via post annealing the
sample in a N2 atmosphere at 750 C, the dielectric sample became sensitive to different types of
contact because space charges can be observed. Measurement of the dielectric constant of the sample
using platinum (Pt) electrode shows a significant change when the dielectric constant increased to
5000 at 10 kHz compared to a silver (Ag) electrode. Fig. 9(a) shows the frequency dependence of the
dielectric constant at room temperature for the CaCu3Ti4O12 ceramic coated with various metal
electrodes. There are slight changes for the dielectric constant of the sample with different contacts in
the frequency region of 100 Hz and 1 MHz. From the figure, the dielectric constant for silver paint
and evaporated silver are same. This result indicated that the dielectric constant of the sample is inert
to the different types of contacts. Lunkenheimer et al., in 2004 [77] stated that the dielectric properties
of CaCu3Ti4O12 is sensitive to metal contact because the high dielectric constant exhibited by
this material is due to the formation of the Schottky barriers between the electrodes and the sample.
In order to reduce the resistivity of the sample to form the Schottky barriers, the samples were
annealed. Fig. 9(b) shows that the dielectric constant of CaCu3Ti4O12 samples is sensitive to the
different contacts.
Fig. 9. (a) Frequency dependence of the dielectric permittivity for CCTO-based pellets with evaporated Au, Cu, Al, Ag and coated Ag
electrodes. (b) Frequency dependence of the dielectric losses for CCTO-based pellets with evaporated Au, Cu, Al, Ag and coated Ag
electrodes [116].
7.2.4. Interfacial polarization effect: Maxwell–Wagner model

Interfacial polarization occurs in electrically inhomogeneous systems. When an electric current
passes through interfaces between two different dielectric media, because of their different conduc-
tivities, surface charges pile up at the interfaces, and give rise to a Debye-like relaxation process
[104,105] under an external alternating voltage. A detected Debye-like relaxation response is therefore
not necessarily the result of dipole relaxation in the system; sometimes it originates from the het-
erogeneity of the system [106]. For example, grains, grain boundaries or the electrodes and the sample
having a different conductivity can also produce the effect. This effect could be conveniently described
by an equivalent circuit and has been widely used to account for dielectric relaxations in many het-
erogeneous materials. The IBLC model was considered as the most favorable mechanism for the other
materials with similar dielectric response, e.g. Li or Ti doped NiO [107], CuO, etc. although the location
of the barrier layers is still open to scientific debate and needs further confirmation.
In summary, the giant dielectric constants have been variously attributed to: (i) the barrier layer
capacitance arising at twin boundaries (ii) disparity in electrical properties between grain interiors and
grain boundaries [91,108,109], (iii) space charge at the interfaces between the sample and the electrode
contacts [110] and [77], (iv) polarizability contributions from lattice distortions [111], (v) differences in
electrical properties due to internal domains [98], (vi) dipolar contributions from oxygen vacancies
[112] and [113], (vii) the role of Cu off-stoichiometry in modifying the polarization mechanisms [83],
(viii) cations disorder induced planar defects and associated in-homogeneity [114] or (ix) nano-scale
disorder of Ca/Cu substitution giving rise to electronic contribution from the degenerate eg states of
Cu occupying the Ca site contributing to the high dielectric constant [115]. To date, the IBLC explanation
of extrinsic mechanism is comparatively widely accepted.
None of the approaches explains all the experimental findings satisfactorily.
8. High dielectric constant and low loss CCTO
It has been previously reported that the dielectric properties of CCTO are largely influenced by
factors such as different synthetic routes, cationic substitutions at A-site, B-site, simultaneously A-site
and B-site as well as stoichiometric variations. The dielectric constant (εr) and loss tangent (tan d) of
CCTO are strongly dependent upon the processing conditions such as sintering temperature, sintering
time, cooling rate and partial pressure of sintering atmosphere.
8.1. Different synthetic methods for CCTO
CaCu3Ti4O12 prepared using a mortar and pestle is known as a conventional ceramic solid state
reaction processing technique. Z.A. Ahmad et al. prepared CCTO samples by a solid state method.
Stoichiometric ratios of the raw materials were mechanically ball milled for 1 h. XRD confirmed the
single CCTO phase of the sample sintered in air at 1050 C for 24 h. The sintering parameters then were
modified using the temperature range of 950–1050 C for 3–12 h with a heating rate of 5 C/min. They
concluded that it is crucial to adequately control sintering temperature and times to obtain the desired
microstructure and dielectric properties. The sample sintered at 1050 C for 24 h shows melting and
abnormal grain growth. Increasing sintering temperature enhances the density. A clear grain and dense
microstructure were observed for the samples sintered at 1000 and 1030 C for 12 h, and for the
samples sintered at 1040 C for 3, 6 and 10 h. The melting grains in the sample sintered at 1050 C for
12 h show the existence of a new phase, CuO. The highest εr with clear uniform grain was obtained by
the sample sintered at 1040 C for 10 h.
B.A. Bender et al. [71] prepared CaCu3Ti4O12 using conventional ceramic solid state reaction pro-
cessing techniques. Stoichiometric amounts of raw materials were mixed either by attrition milling
(AM1 and AM2) or mortar and pestle (MP1). The resultant slurries were then attrition-milled for 1 h
and dried at 90 C. AM1 was calcined for 8 h at 1000 C then 930 C for 4 h and 970 C for 4 h. AM2 was
calcined at 970 C for 8 h and then at 940 C for 4 h. The pellets were then placed on platinum foil and
sintered in air at different temperatures (990–1100 C) for various dwell times (3–16 h). The standard
sintering conditions were considered to be 1100 C for 3 h. Multiple pellets were sintered at the same
time and used for subsequent characterization and thermal annealing. Thermal annealing was carried
out in flowing argon at 1000 C for 6 h.
B. Barbier et al. [116] had reported synthesis and dielectric properties of CCTO based ceramics and
thick films (e w50 mm) prepared from powders synthesized by a chemical route. The characteristics of
pellets and thick films were compared. The pellets exhibited high values of dielectric permittivity (εr
w1.4 105) and relatively small dielectric losses (tan d w0.16) at 1 kHz and room temperature shown
in Fig. 9(a) and (b).
These properties are independent of the nature of the metallization of the electrodes. In addition,
the dielectric permittivity decreases when the diameter of the electrodes of the pellets increases while
the losses remain constant. This is strongly related to the nature of the dielectric material in between
the electrodes which constitutes a strong indication that the high dielectric permittivity values
observed in this material are not related to an interfacial related mechanism but is in an internal barrier
layer capacitor type.
L. Singh et al. [117] have collected the data on magnesium doped calcium copper titanate
CaCu2.90Mg0.10Ti4O12 (CCMTO), electro-ceramic, synthesized by a semi-wet route (SWR), ball milled
route (BMR) and a solid state route (SSR) and characterized by TG/DTA, XRD, SEM, EDX and TEM
techniques. XRD confirmed the formation of single-phase in the CCMTO ceramic. The CuO phase
present at grain-boundaries in SWR shown by SEM micrograph was verified by EDX. The grain size for
the ceramics synthesized by SWR, BMR and SSR routes were found to be in the range of 15–20 mm, 1–
3 mm and 1–2 mm, respectively, as shown in Fig. 10. The CCMTO ceramic synthesized by SWR exhibited
dense microstructure with large grains having flat and curved morphology and clear grain boundary
whereas those of BMR and SSR showed their agglomeration. The grain size of BMR and SSR is smaller
than that of SWR where the lower sintering duration and temperature lead to less grain growth. The
TEM image of SWR shows the nano-crystalline particles in the range 80 20 nm. The value of
dielectric constant of SWR (εr w20,091) ceramic is higher than those of BMR and SSR (εr w1247)
ceramics at 1 kHz at 450 K. A dielectric relaxation has been observed in the frequency range of 100 Hz–
100 kHz.
The impedance and modulus studies show the highest grain-boundary resistance for a BMR ceramic
shown in Fig. 11(a) and (b). The high-temperature (450 K) dielectric dispersion shows one large low-
frequency response; two Debye-type relaxations were also seen Fig. 11(b).
Jianjun Liu et al. [37] have reported synthesis of fine crystalline CCTO powder a using wet chemistry
method at relatively low temperatures and a shorter reaction time. The pure phase sample was ob-
tained at 800 C for 0.5 h and the grain size of a pellet sample sintered at 1030 C for 4 h has a ho-
mogeneous distribution in the range 0.4–1.5 mm. This method starts with a homogeneous liquid
solution of the cation ingredients mixed in stoichiometric ratio on the atomic scale. Therefore, pure
samples at the nanometer scale could theoretically be obtained at lower temperature and shorter
reaction time than that afforded by solid state reactions. In this method metal oxides are formed in the
first heat treatment step and CCTO is produced by a subsequent solid state reaction.
Jianjun Liu et al. [14] have also synthesized the giant dielectric constant material CCTO by pyrolyzing
an organic solution containing stoichiometric amounts of the metal cations at lower temperature and a
shorter reaction time than that for a conventional solid state reaction. CCTO has a giant dielectric
constant up to 105 at room temperature and great potential for technological application. In this work,
two wet chemistry methods are reported to synthesize CCTO at a relatively lower temperature and
shorter reaction time. The pure phase sample was obtained at 800 C for 0.5 h and the grain size of a
pellet sample sintered at 1030 C for 4 h has a homogeneous distribution in the range 0.4–1.5 mm. The
sample exhibits a giant dielectric constant of 11,500. However, this method still has the disadvantage
that it involves handling chemicals in a glove box and refluxing of solutions.
Mandal et al. [31] has developed a novel method to synthesize samples in the
Ca1xLaxCu3Ti4xCoxO12 system (x ¼ 0.10, 0.20 and 0.30) using solid TiO2 powder and metal nitrate
solutions. X-ray powder diffraction analysis confirms the formation of single phase at 900 C. SEM
micrographs of the system confirmed the average grain size in the range 1–2 mm. Transmission electron
microscopy has been employed to characterize the structure of the resulting materials. Energy
dispersive X-ray analysis (EDX) confirms the stoichiometry of the synthesized materials. Dielectric
constant and dielectric loss of the composition were found to be 2000 and 0.50 respectively at room
Fig. 10. SEM micrographs of (a) SWR, (b) BMR and (c) SSR synthesized by diverse routes sintered at 950 C for 12 h [117].
Fig. 11. (a) Impedance plane plots (Z00 versus Z0 ) for SWR, BMR and SSR synthesized by diverse routes; The inset shows an expanded
view of the high-frequency data close to origin. (b) Electric modulus plots (a) real M0 and imaginary M00 (b) imaginary electric
modulus (M00 ) as a function of frequency at 450 K for SWR, BMR and SS [117].
temperature (1 kHz). AC conductivity of Ca1xLaxCu3Ti4xCoxO12 sample increases with increasing

temperature, which shows semiconducting behavior of the materials.
Shuhua Jin et al. [13] synthesized CCTO by a sol–gel method. The nano ultrafine powders for the
preparation of CCTO ceramics were prepared by the sol–gel method and citrate auto-ignition method.
The relative dielectric constant of the ceramic sintered at 1000 C was measured with a magnitude of
more than 104 at room temperature which was approaching to those of Pb containing complex
perovskite ceramics and the loss tangent were also compared with that of CCTO ceramics prepared by
other reported method. Such CCTO ceramic prepared by the sol–gel processes with ideal electrical
properties is expected to find applications in electric devices.
Kim et al. [118] studied the micro-structural evolution and dielectric properties of SiO2 doped CCTO
ceramics. The abnormal grain growth behavior of un-doped and SiO2 doped CCTO ceramics were
investigated. With the addition of 2 wt.% SiO2 the abnormal grain growth triggering temperature
decreased from 1100 to 1060 C and the temperature for obtaining a uniform and coarse micro-
structure decreased from 1140 to 1100 C see Fig. 12. The lowering of the abnormal grain growth
temperature by SiO2 addition was attributed to the formation of a CuO–SiO2 rich inter granular phase at
lower temperatures. The apparent dielectric permittivity of coarse SiO2 doped CCTO ceramics was w10
times higher than that of the fine SiO2 doped CCTO ceramics at the frequency of 103–105 Hz.
The doping of CCTO ceramics with SiO2 provides an efficient route of improving the dielectric
properties via grain coarsening. The correlation between the microstructure and apparent permittivity
suggests the presence of a barrier layer near the grain-boundaries.
Wang et al. [119] has reported a Maxwell–Wagner relaxation in CCTO/Ag composites. CCTO/Ag
composites with different Ag weight fractions were prepared by sintering thoroughly mixed CCTO and
Ag2O powders at 1050 C in air. The samples were found to consist of Ag deficient insulating surface
layers and Ag rich more conductive inner parts. Dielectric measurements reveal that apart from the
distinct dielectric features for pure CCTO another dielectric relaxation appears near room temperature.
This relaxation has been interpreted based on the Maxwell–Wagner model due to the discontinuity of
the charge concentration across the interfaces between the surface and inner layers.
Zhu et al. [120] fabricated CCTO by an oxalate co-precipitation method which was formed at a lower
temperature and a shorter reaction time than that for a conventional solid state reaction. The

Fig. 12. Microstructures of the 2 wt.% SiO2 doped-CCTO ceramics sintered at (a) 1060 C, (b) 1080 C, and (c) 1100 C for 12 h [118].
precipitate containing the stoichiometric amounts of the metal cations was calcined to achieve single
phase CCTO. DTA/TGA was carried out on the dried precipitate to study the thermal decomposition
process. The microstructure and dielectric properties of the sample were characterized by X-ray
diffraction, Scanning electron microscopy and impedance analyzer.
Hutagalung et al. [121] synthesized CCTO by microwave an assisted solid state reaction technique.
Processing involved the preparation of raw materials, mixing and milling, calcinations, pellet forming
and a sintering process. Conventional furnace and microwave assisted sintering processes were
employed in order to improve phase structure, morphology and dielectric properties of CCTO ceramics.
Surface and fracture SEM analysis showed that microwave assisted sintered CCTO produced better
densification and more uniform grain size compared to conventional sintered sample. The highest εr
value was obtained in this study and measured at room temperature was about 2800, whereas the
lowest dielectric loss is about 0.08 as observed from Fig. 13. The dielectric loss is slightly decreased with
increasing sintering duration, even though a minimum value or better dielectric loss property was
found for samples sintered for 90 min.
Thomas et al. [122] synthesized nano-particles of CCTO using the precursor route. A method pre-
paring nano particles of CCTO with a crystallite size varying from 30 to 200 nm is optimized at a
temperature as low as 680 C from the exothermic thermal decomposition of an oxalate precursor
CaCu3(TiO)4(C2O4)8$9H2O which is shown in Fig. 14.
The phase singularity of the complex oxalate precursor is confirmed by wet chemical analyses, X-ray
diffraction, FT-IR and DTA/TGA analyses. The UV reflectance and ESR spectra of CCTO powders indicates
that the Cu(II) coordination changes from distorted octahedral to nearly flattened tetrahedral to square
planar geometry with increasing annealing temperature. The HRTEM images have revealed that the
evolution of microstructure in nano-scale is related to changes of Cu(II) coordination around the
surface regions for the chemically prepared powder specimens. The nearly flattened tetrahedral
geometry prevails for CuO4 in the near surface regions of the particles whereas square planar CuO4
groups are dominant in the interior regions of the nano-particles. The powders derived from the ox-
alate precursor route have excellent sinter ability resulting in high density ceramics which exhibit a
high dielectric constant up to 40,000 (1 kHz) at 25 C accompanied by low dielectric loss (<0.07).
Chivalrat Masingboon et al. [38] have synthesized nano-sized powders of CCTO by a polymerized
complex method and calcined them at 600, 700 and 800 C in air for 8 h. The diameter of the powders
was found in the range 30–100 nm and is shown in Fig. 15. The CCTO powders were characterized by X-
ray diffraction, FT-IR, DTA/TGA, SEM and TEM. Sintering of the powders was carried out in air at 1100 C
for 16 h. The XRD results indicated that all the sintered samples have a typical perovskite CCTO
structure with some amount of CaTiO3 and Cu2O. SEM micrographs of the sintered ceramics showed a
grain size of 10–15 mm. The samples exhibit a giant dielectric constant of 10,000–20,000. It is found that
the dielectric constant was independent of frequency and weakly dependent on temperature.
Maxwell–Wagner model is used to explain the giant dielectric constant present in these materials. It is
also found that in all three sintered ceramic the activation energy for MW relaxation of grains is
0.116 eV.
Fig. 13. Effect of MW sintering duration on the dielectric constant and dielectric loss of CCTO [121].
Fig. 14. Bright field TEM images of phase-pure CCTO obtained at 680 C (a–c) particle dimensions ranging from 30 to 200 nm and (d)
weakly agglomerated particles [122].
On the other hand the values of activation energy of the grain-boundaries were found to be 0.219,
0.391 and 0.641 eV for CCTO ceramic prepared by the CCTO powders calcined at 600, 700 and 800 C,
respectively.
Jha et al. [12] synthesized CCTO by a polymeric citrate precursor route. Using citric acid and ethylene
glycol a polymeric precursor of the above compound was obtained at low temperature (135 C) which
on subsequent heat treatments led to pure CCTO at 1000 C. On sintering further at 1000 C (20 h) the
pellets show high density (98%) and a dielectric constant of the order of 3000 at 1 kHz. The dielectric
loss varied between 0.30 and 0.35 at 100 kHz beyond that it increases sharply from 0.35 to 0.7 with
frequencies of 100–500 kHz.
Smith et al. [123] synthesized a low loss colossal dielectric CCTO by an anion substitution route. An
anion substitution route was utilized for lowering the dielectric loss in CCTO by partial replacement of
oxygen by fluorine. This substitution reduced the dielectric loss and retained a high dielectric constant
that was essentially temperature independent from 25 to 200 C. In particular CaCu3Ti4O11.7F0.3
exhibited a giant dielectric constant over 6000 and low dielectric loss below 0.075 at 100 kHz within a
temperature range of 25–200 C. Fluorine analysis confirmed the presence of fluorine in all samples
measured.
L. Singh et al. [124] synthesized CaCu2.90Zn0.10Ti4O12 (CCZTO), nano-crystalline electro-ceramics by
a solution-wet route (SR) as well as by a semi-wet route using citric acid (SWR1) and glycine (SWR2)
separately, and characterized them by TGA/DTA, XRD, TEM, SEM and EDX techniques. The crystallite
Fig. 15. Bright field TEM images with corresponding selected-area electron diffraction (SAED) patterns of CCTO powders calcined in
air for 8 h: (a) 600 C; (b) 700 C; (c) 800 C, respectively [38].
sizes of the ceramics obtained by XRD were found to be in the range of 45–90 nm is in good agreement
with those observed by TEM analysis shown in Fig. 16. The grain sizes for the ceramics SWR1, SWR2 and
SR observed by SEM were found in the range of 10–15 mm, 1–4 mm, and 2–4 mm, respectively. Thermal
studies showed that single phase CCZTO ceramic was formed in the single step combustion reaction
SWR2 while in the case of SWR1 and SR they were obtained in multi-step reactions. SWR2 route shows
more effective solid state reaction for the formation of nano-crystalline CCZTO single phase at a much
lower sintering temperature.
Fig. 16. TEM images of (a) SWR1, (b) SWR2 and (c) SR synthesized by diverse routes sintered at 950 C for 12 h [124].
Liu et al. [90] prepared electrically heterogeneous CCTO by a sol gel method using tetrabutyl
titanate, calcium nitrate and copper nitrate and a gel of these compounds was obtained at room
temperature which on subsequent heat treatments at 900 C for 1 h led to CCTO powder. On sin-
tering further at 1060 C for 48 h the dielectric constant of CCTO ceramics was above 35,000 at 1 kHz
and it displays a good tune behavior as shown in Fig. 17. Their dielectric constant is above 28,000
over a wide frequency range between 100 Hz and 1 MHz. Their dielectric loss is below 0.1 from
100 Hz to 100 kHz. The giant dielectric constant values for CCTO ceramics are associated with the
presence of either thin, re-oxidized grain boundary regions on the outer surfaces of the large sem-
iconducting grains or to a secondary phase at the grain boundaries which confirm the IBLC mech-
anism present in these ceramics. Impedance spectroscopy on CCTO ceramics demonstrates that they
are electrically heterogeneous and consist of semiconducting grains with insulating grain boundaries.
The dc bias experiment demonstrates clearly that the grain boundary response is consistent with a
Schottky barrier response. Therefore, CCTO ceramics display an internal barrier layer capacitor (IBLC)
behavior.
Subramanian et al. [125] reported valence degeneracy in CCTO. The synthesis of CCTO has been
accomplished at a pressure of 60 kbar. Analysis of single crystal X-ray diffraction data demonstrates
that this compound is isostructural with CCTO. The electrical resistivity data for CCTO show metallic
behavior, and the magnetic susceptibility indicates delocalized electrons for both Cr and Cu. The Cu–O
Fig. 17. Dielectric properties (A) and SEM micrograph (B) of sintered pellets 1100 C for 3 h from MS and CS powders [6].
and Cr–O bond distances give fractional valences of Cu (2.45) and Cr (3.66), thus indicating both Cu and
Cr 3d states at the Fermi level.
Chiodelli et al. [72] reported electric and dielectric properties of pure and doped CCTO perovskite
materials. AC impedance spectroscopy measurements were performed in the 15–700 K temperature
range on pure and Ni, Fe and Co doped CCTO materials. Capacitance values were also confirmed by
direct current measurements at room temperature. Thermoelectric power measurements showed that
the electrons are involved in the conduction process of the semiconducting bulk region. The IS results
evidenced a dielectric behavior in the grain boundary region giving a permittivity of about 3400 for the
pure sample and so CCTO can be considered an internal barrier layer capacitance (IBLC) material. The
giant permittivity of CCTO can be strongly increased to a value of 15 104 by Co doping on Ti site. IBLC
behavior together with giant permittivity offer the opportunity to combine capacitance and resistance
values in RC circuits and provide evidence for the applicability of this material as an integrated reso-
nant element for the electronics industry.
Yu et al. [6] synthesized single phase cubic perovskite CCTO powders using microwave heating with
relatively low energy consumption and a short time compared to conventional synthesis. The ceramics
from microwave synthesized (MS) powder were found to have higher dielectric constants than that
from conventional synthesized (CS) powder under the same sintering conditions. The relative
dielectric constant from MS powder was found to be w21,400, at 1 kHz which was higher than that of
CS powder (w10,240, at 1 kHz) at room temperature sintered at 1100 C for 3 h, as shown in Fig. 17(A).
The higher dielectric constants of MS powder compared with CS powder is attributed to the fact
that MS ceramics have larger grains than those from CS ceramics as in Fig. 17(B) and it is based on the
internal barrier layer capacitor model.
Hutagalung et al. [121] studied microwave assisted sintering of CCTO. CCTO electro-ceramics, pre-
pared by a microwave assisted solid state reaction technique from CaCO3, CuO and TiO2 powders.
Processing involved the preparation of raw material, mixing and milling, calcinations, pellet forming
and sintering processes. Conventional furnace and microwave assisted sintering processes were
employed in order to improve phase structures, morphology and dielectric properties of CCTO ceramics.
FESEM analysis of fractured surfaces showed that the microwave assisted sintered CCTO products have
better densification and more uniform grain size as compared to the conventional sintered sample.
Hutagalung et al. [126] studied the role of tin oxide addition on the properties of microwave treated
CCTO. A microwave (MW) irradiation process was performed to pre-sintered CCTO. A conventional
furnace was used for calcination as well as for the sintering processes while a domestic microwave
oven was employed for MW irradiation in order to produce better morphology, improved phase
structures and dielectric properties of CCTO products. SEM analysis shows that the microstructures of
MW irradiated samples are denser with larger grain size if compared to the untreated samples.
Dielectric properties have also been improved by MW treatment with higher dielectric constant and
lower dielectric loss. Meanwhile the addition of tin-oxide (SnO2) to CCTO provides strong effects on the
dielectric constant of MW samples with and without irradiation. It was found that the dielectric
constant of CCTO decreases exponentially with mole percentages of SnO2. However, the addition of
SnO2 shows better dielectric loss properties of CCTO.
Tselev et al. [127] investigated the dielectric response of CCTO thin films grown epitaxially on
LaAlO3 (001) substrates by pulsed laser deposition. The dielectric response of the films was found to be
strongly dominated by a frequency power law typical of materials with localized hopping charge
carriers in contrast to the Debye like response of the bulk material. The film conductivity decreases
with annealing in oxygen and it suggests that oxygen deficiency is a cause of the relatively high film
conductivity. With increase of the oxygen content, the room temperature frequency response of the
CCTO thin films changes from a response indicating the presence of some relatively low conducting
capacitive layers to a purely power law and then toward a frequency independent response with a
relative dielectric constant εr w102. The film conductance and dielectric response decrease upon
decrease of the temperature with dielectric response being dominated by the power law frequency
dependence. Below 80 K the dielectric response of the films is frequency independent with εr w102.
The results provide another piece of evidence for an extrinsic Maxwell Wagner type origin of the
colossal dielectric response of the bulk CCTO material connected with electrical in homogeneity of the
bulk material.
Shao et al. [128] prepared CCTO ceramics by the conventional solid state reaction method under
various sintering temperatures from 1000 to 1120 C at intervals of 10 C. Microstructures and crys-
talline structures were examined by scanning electronic microscopy and X-ray diffraction, respectively.
It has been reported that the morphologies change significantly with the sintering temperature.
Ceramic specimens prepared by this method have a good polycrystalline structure in spite of the
different microstructures. The dielectric permittivity increases with the sintering temperature and is
closely related to the polycrystalline microstructure particularly to the grain size. This suffers from the
disadvantages of inhomogeneity and it also requires repetitive grinding and firing at high temperatures
and a long reaction time.
8.2. Effects of sintering parameters
Fang and Kai [129] reported that the value of dielectric constant is however dependent on annealing
time and temperature. CCTO samples sintered at 1035 C for 8 h give dielectric constant w3000
whereas those sintered at 20 h show dielectric constant of w18,000 (see Fig. 18). It is evident that the
values of dielectric increase with an increase in duration of sintering.
Below w100 K, the dielectric constant drops rapidly to a value of w100, but it is not accompanied by
any structural phase transition. Powder neutron diffraction data show that the structure remains cubic
and centro-symmetric. It has been reported that at temperatures above 100 K, pairings of positive and
negative electric charges, called dipoles, can flip around quickly independent of one another.
L. Singh et al. [130] synthesized nano-structured CaCu2.90Zn0.10Ti4O12 (CCZTO) electro-ceramic by
semi-wet route. The pellets were sintered at 950 C for 6 h, 8 h and 12 h in air. The ceramics exhibit high
dielectric constant of 1.35 104 at 1 kHz. The crystallite size of the CCZTO ceramic, obtained by XRD
using Debye Scherrer formula, range from 38 to 74 nm which is in good agreement with the particle
size observed by TEM analysis.
It was observed clearly that the grain size significantly increased with an increase in sintering
duration which is shown in Fig. 19. The dielectric constant increases with increasing sintering time and
dielectric loss decreases. It is suggested that the longer sintering time may lead to more defect
structures. The size of the particle increases with increasing sintering time shown in Fig. 20. It is mainly
due to formation of large size particles as a result of loss of grain boundaries of small size particles.
These changes lead to stability of the large size particles due to loss of grain boundaries.
Prakash et al. (2007) [131] showed that the different times of sintering also lead to change in
permittivity. The dielectric constant of CCTO increased drastically with increase in sintering temper-
ature and duration as a consequence of significant changes in the microstructural and compositional
Fig. 18. Temperature dependence of the dielectric constant for CCTO sintered at 1035 C for different times measured at 1 kHz and
prepared by a solid-state route [129].
Fig. 19. SEM images of CCZTO ceramics sintered at 950 C for (a) 6 h, (b) 8 h and (c) 12 h [130].
Fig. 20. TEM images of CCZTO ceramics sintered at 950 C for (a) 6 h, (b) 8 h and (c) 12 h [130].
heterogeneity. Fig. 21 shows the dielectric dispersion at 225 K of CaCu3Ti4O12 sintered at 1100 C for
2.5, 5, 7.5, 10 and 15 h. The dielectric behavior of the ceramics was explained based on the Maxwell–
Wagner relaxation arising mostly from the interfaces between grains and the grain boundaries.
Increasing the sintering duration enhanced the dielectric constant and it remains nearly constant
till 100 kHz for the entire sample before it drops to lower values that are below 100. The dielectric
constant for the sample sintered at 1100 C for 2.5 h is only 2400 at 10 kHz. When the sintering
duration was increased to 5 h, the dielectric constant improved to 13,000 at 10 kHz.
They described this variation because of the remarkable change in the microstructure in which
some grains show abnormal growth and Cu-rich smaller grains occupy the intermittent regions.
Further increase in the sintering duration to 15 h increased the dielectric constant to more than 24,000.
When CaCu3Ti4O12 sample was annealed in flowing argon at 1000 C, the dielectric constant was close
to one million at room temperature.
Kwon Seunghwa et al. [132] studied the structure–property relationships of the CaCu3Ti4O12
ceramics processed via a conventional solid-state method in terms of the different sintering duration.
X-ray diffraction patterns of the tenorite (CuO) and cuprite (Cu2O) secondary phases found on the
unpolished and polished surfaces of CaCu3Ti4O12 were explained by the reduction/re-oxidation reac-
tion as a function of sintering time. Based on the microstructures, grain growth of CaCu3Ti4O12
continued from 0.5 to 4 h sintering while the further growth was limited to the small-sized grains after
8 h sintering. The change of dielectric constant and tan d were shortly discussed with regard to the
secondary phases and the microstructures of the different sintering hours. The dielectric constant of
CCTO samples increased with the sintering time at frequencies over 10 kHz.
Yang et al. [133] studied CCTO ceramics, sintered in air and in oxygen, under oxygen pressures of
1 atm and 3 atm, respectively. The results on the dc electrical conduction and dielectric measurements
showed that for the CCTO ceramics sintered in oxygen, leakage, grain conductivity and the low-
frequency dielectric constant are greatly reduced; these changes in electrical properties may be
attributed to the enhancement of activation energies for electrical conduction in the grains. In addition,
for the CCTO ceramics sintered in oxygen, in the spectra of dielectric loss strong peaks appear in the
low-frequency range, which may be attributed to the contact-electrode effect on the ceramic surface.
Marques et al. [134] studied calcium copper titanate (CaCu3Ti4O12) ceramic varistors, prepared by
the solid-state method. The samples were heat treated several times in vacuum and the evolution of
electrical characteristics was monitored by current density versus electric field measurements and
impedance spectroscopy. Repeated heat treatments at 900 C in vacuum lead to desorption of oxygen
adsorbed at the grain boundaries and consequently to a degradation of the varistor properties. During
Fig. 21. Plots of the dielectric constant versus frequency of the polished CCTO samples with different sintering time at 1115 C [131].
further successive heat treatments some oxygen from the grain interior moves to the grain boundaries
thereby partially restoring the varistor properties.
Fang et al. [135] studied the electrical properties and microstructure relations of the as-deposited
and post-annealed polycrystalline CCTO films prepared on Pt/Ti/SiO2/Si (100) substrates by pulsed-
laser deposition (PLD). Their results demonstrated that the as-deposited polycrystalline CCTO film
was made of insulating grain boundaries with semiconducting grains, indicating that the high
dielectric-constant can be attributed to barrier layer capacitor (BLC) effects. The simple resistor–
capacitor (RC) equivalent circuit and the modified constant phase element (CPE) circuit were used to
describe the impedance spectroscopy, and excellent agreement between the calculated and measured
curves was obtained in the CPE circuit. The resistance and capacitance of the grains and grain
boundaries can be tuned by changing the annealing atmosphere and temperature. Under an oxygen-
absent annealing atmosphere, the electric resistances of the grain boundaries changed greatly but
the resistance of the grains showed almost no change. While under an oxygen annealing atmosphere,
the reverse process occurred. On the basis of this result, it is demonstrated that the origin of the semi-
conductivity of the grains in CCTO polycrystalline films arises from their oxygen-loss, while the grain
boundaries are close to oxygen-stoichiometry.
Li et al. [136] investigated experimentally the effects of heat treatments in high vacuum on the
microstructures and electrical properties of CCTO. Two conditions of heat treatment, i.e., calcinations at
950 C for 10 h and then sintering at 1100 C for 20 h, and calcination at 900 C for 2 h in a 104 Pa
vacuum level were used. It was found from the X-ray diffraction (XRD) that for the former condition,
single phase of CCTO based on the perovskite structure was formed, whereas for the later condition,
multiple phases were detected due to the decomposition of CCTO. The electrical responses of both the
conditions, monitored using dielectric spectroscopy, revealed that varistor voltage increased remark-
ably due to the heat treatments at high vacuum.
8.3. Effects of substitutions on CCTO electro-ceramic
Prakash and Varma [28] examined the effect of La3þ doping on Ca2þ sites in CaCu3Ti4O12 (CCTO),
synthesized via the conventional solid state reaction route. A remarkable decrease in grain size from
50 mm to 3–5 mm was observed on La3þ substitution. The dielectric constant of CaCu3Ti4O12 decreased
drastically on La3þ doping. The impedance spectroscopy showed that La3þ substitution at the Ca2þ site
resulted in an increase in the resistance of the grains and a decrease in grain boundary resistance,
consequently, a decrease in the grain boundary internal barrier layer effect.
Mandal et al. [31] synthesized samples in the Ca1xLaxCu3Ti4xCoxO12 system (x ¼ 0.10, 0.20 and
0.30) using solid TiO2 powder and metal nitrate solutions. Dielectric constant and dielectric loss of the
composition was found to be 2000 and 0.50, respectively, at room temperature (1 kHz) shown in
Fig. 22.
Dielectric constant for the composition x ¼ 0.30 is higher than the other two compositions over the
measured frequency range. AC conductivity of Ca1xLaxCu3Ti4xCoxO12 samples increases with
increasing temperature and shows semiconducting behavior.
Hong et al. [137] prepared pure and Nb-substituted CaCu3Ti4xNbxO12x/2 (CCTO, x ¼ 0.05, 0.02, 0.1,
0.2, 0.4) ceramics by a conventional solid-state method. Single-phase Nb doped CCTO was obtained up
to a composition x ¼ 0.2 Nb substitution, and the lattice parameter increased with Nb concentration.
The grain size and the resistivity decreased with Nb substitution. The dielectric constant increased with
Nb substitution, and the highest value of εr w420,000 was observed in the x ¼ 0.2 Nb-substituted
specimen at 10 kHz.
Chen et al. [138] synthesized Ca1xSrxCu3Ti4O12 (x ¼ 0, 0.1, and 0.2) ceramics and studied their
dielectric properties. It was found that on Sr doping the dielectric constant significantly decreased with
the increase of Sr content in the low temperature region 250 K and remained almost unchanged in the
high temperature region above 250 K as observed in Fig. 23.
Three sets of relaxation peaks were observed in electric modulus plots, which were considered to be
associated with grains, domain boundaries, and grain boundaries, respectively. Through the analysis of the
heights and calculated activation energies of the relaxation peaks, it is strongly believed that the decrease
in the value of the dielectric constant is related to the change of domain boundaries with Sr doping.
Fig. 22. Plots of (a) dielectric constant (εr) and (b) dielectric loss (tan d) versus log f for Ca1xLaxCu3Ti4xCoxO12 (x ¼ 0.10, 0.20 and
0.30) at room temperature (310 K) [31].
Cai et al. [139] present a remarkable effect of Mn doping on the dielectric and nonlinear electric
properties of CaCu3Ti4O12 ceramics. The results indicate that only 2.5 at.% Mn doping can suppress the
dielectric permittivity in CaCu3Ti4O12 by up to two orders of magnitude from 104 to 102, and the
nonlinear varistor characteristics disappear completely, which is mainly ascribed to the decrease of
potential barrier height at the grain boundary and charge compensation for the conduction electrons
caused by the Mn doping.
Kwon et al. [140] studied the substitution of the alio-valent dopant Cr2O3 on the Ti site in terms of
the effects on the dielectric properties at doping levels ranging from 0.1 to 1.0%. No evidence of sec-
ondary phases was observed from XRD analysis, but both the permittivity and dielectric loss of 1%
Fig. 23. Dielectric constant as a function of temperature for various frequencies of 102, 102.5, 103, 103.5, 104, 104.5, 105, 105.5, and 106 Hz
for Ca1xSrxCu3Ti4O12 (x ¼ 0, 0.1, and 0.2) [138].
Cr2O3 doped CaCu3Ti4O12 were improved with K z 19,000 and tan d z0.049 at 1 kHz as shown in
Fig. 24(a) and (b).
Also, 1% Cr2O3 doping was effective in maintaining the high K up to 150 V. From these results, it can
be inferred that Cr2O3 doping is an efficient method to achieve a high-K and low loss.
Mu et al. [141] studied the effect of Fe3þ substituted CaCu3Ti4xFexO12 (CCTFO, 0 x 0.2) ceramics
prepared by solid-state reaction. Three new relaxation processes were discovered by means of
dielectric properties spectra measurements. These rare multiple dielectric relaxation processes urge us
exploring the fascinating origin of the giant dielectric constant in CaCu3Ti4xFexO12 ceramics.
Impedance measurement results show that the resistivity of grains and grain boundaries increased
while the dielectric constant decreased dramatically in the frequency range of 1 kHz to 1 MHz with
increasing Fe content.
Mandal et al. [142] studied the effect of doping at Ti4þ site by Ce3þ using CaCu3Ti3.90Ce0.10O12
synthesized by a citrate-gel route. DTA/TG analysis of the dry powder gives pre-information about the
formation of final product around 850 C. XRD analysis confirmed the formation of the CaCu3Ti3.90-
Ce0.10O12 phase of the ceramic sintered at 950 C for 12 h. Microstructures, studied using Scanning
Electron Microscopy (SEM) confirmed the average grain size in the nano range 200 nm–400 nm in the
system. The nature of relaxation behavior of ceramic was also rationalized by using impedance and
modulus spectroscopy. The bulk conductivity indicates an Arrhenius-type thermally activated process.
The ac conductivity spectrum obeyed the Jonscher power law. The complex impedance diagrams of the
ceramic exhibited a significant contribution from the grains, grain boundaries and electrode. The
activation energies calculated from the grain-boundary relaxation time constant was found to be
0.49 eV which confirmed the Maxwell–Wagner type of relaxation present in the ceramic.
Fig. 24. (a) Dielectric constant and (b) dielectric loss versus frequency for CaCu3Ti4O12with undoped, 0.5% ZrO2 doped, and 1.0%
Cr2O3 doped [140].
Singh et al. [143] have demonstrated repeatedly dielectric constants higher than 100,000 and very
small effects of voltage on the variation of dielectric constant of CCTO. They have performed the
synthesis and grain growth of pure CaCu3Ti4O12 (CCTO) compound and its derivatives by substituting
silicon CaCu3SixTi4xO12 (CCSTO) to determine the effect on dielectric properties and resistivity. They
observed significant increases in the resistivity even with a small concentration of silicon. Concen-
tration above 5% did not produce any significant advantages. We observed a similar increase in re-
sistivity when we doped the CCSTO with nickel. In a separate experiment, we soaked the CCSTO before
grain growth in an organic melt. Soaking also increased the resistivity by several orders of magnitude.
We observed almost three orders of magnitude higher resistivity in CCSTO compared to CCTO material
processed under identical conditions. The resistivity for pure CCSTO was 3.8 108 U-cm which is at
least two orders of magnitude higher than pure CCTO. For a typical CCSTO, they observed the results of
the dielectric constant as shown in Fig. 25.
Shao et al. [144] examined the effect of La on the Cu site with nominal compositions of CaCu3xLa2x/
3Ti4O12. It was found that these ceramics show high dielectric permittivity and sufficiently low
dielectric loss. In particular, CaCu2.9La0.2/3Ti4O12 ceramics sintered at 1050 C for 20 h showed the high
dielectric permittivity of 7500 with weak frequency dependence below 1 MHz. The low dielectric loss,
less than 0.05 in the wide frequency range of 120 Hz–200 kHz with the a 0.012 at 20 kHz shown in
Fig. 26, suggest that the presence of a CaTiO3 secondary phase due to Cu deficiency. La doping plays
important roles in the observed excellent dielectric properties in CaCu3xLa2x/3Ti4O12 ceramics. The
results indicated that they are a very promising class of high-permittivity materials for practical
applications.
Choi et al. [145] studied the substitution effect of Al-doped CaCu3Ti4xAlxO12-x/2 (CCTO, x ¼ 0.05–
0.1) ceramics. They showed reduced remarkably dielectric loss while maintaining a high dielectric
constant. It was found that for the composition x ¼ 0.06, the loss tangent (tan d) was below 0.06 over
the frequency range of 102–104 Hz, and the dielectric constant was 41,000 at 10 kHz. Impedance spectra
indicated that Al doping increased the resistivity of the grain boundary by an order of magnitude. The
improvement of the dielectric loss in Al-doped CCTO was attributed to enhanced grain boundary
resistivity.
Mandal et al. [146] have studied the effects of Coþ2 doping at Cuþ2 and Tiþ4 sites in calcium copper
titanate. The doped compositions CaCu3xCoxTi4O12 and CaCu3Ti4xCoxO12 (x ¼ 0.10) ceramics were
prepared by a novel semi-wet route. In this method calcium, copper, cobalt salts were taken in solution
form and TiO2 was used in solid form. XRD analysis confirmed the formation of single-phase materials.
Structure of CaCu3Ti4O12 does not change on doping with cobalt either on Cu-site or Ti-site and it
remains cubic. Scanning electron micrographs (SEM) show that the average grain size of CaCu2.9-
Co0.1Ti4O12 is larger than CaCu3Ti3.9Co0.1O12 ceramic. Energy dispersive X-ray spectroscopy (EDX)
studies confirmed the purity of parent and Co-doped CaCu3Ti4O12 ceramics. Dielectric constant (εr) and
dielectric loss (tan d) of CaCu2.9Co0.1Ti4O12 is comparatively higher than that of CaCu3Ti3.9Co0.1O12
ceramic at all measured frequencies and temperatures.
Hutagalung et al. [147] have studied the effect of zinc dopant on the dielectric properties of
CaCu3Ti4O12 at lower frequencies and it was found that the dielectric constants had a minimum value
at 1.5 mol% Zn. A minimum dielectric loss was observed at 5 mol% Zn. At 1 kHz, the dielectric loss
decreases from 30% (un-doped) to a minimum value of 18% at 5 mol% Zn dopant. This result indicates
that certain Zn dopant concentrations can be used to improve the dielectric loss properties of
CaCu3Ti4O12.
Rai et al. [148] prepared the un-doped CaCu3Ti4O12 and cobalt doped CaCu3Ti4xCoxO12 (CCTCO)
with x ¼ 0.10, 0.20 and 0.30 by a semi-wet route for the first time using solid TiO2 powder and metal
nitrate solutions. XRD analysis confirmed the formation of single-phase material in the samples sin-
tered at 900 C for 6 h. Structure does not change on doping with cobalt and it remains cubic in all the
three compositions studied. Lattice parameter increases slightly with cobalt doping. SEM micrographs
of the CaCu3Ti4xCoxO12 samples show that the grain size is in the range of 2–8 mm for these samples.
EDX studies show the percentage of elements along with the grain and grain boundary, which confirm
Fig. 25. Dielectric constant of NiO doped CCSTO [143].

Fig. 26. Frequency dependence of εr and tan d for the various CCTO and CCLTO ceramics at room temperature. The inset in b shows
the enlarged view of low frequency data forCCLTO-01-20 h [144].
the rich phase of copper oxide at grain boundaries. Dielectric properties have been measured as a
function of temperature and frequency.
Rai et al. [149] have examined nickel doped CaCu3Ti4O12 (CCTO) samples, i.e. CaCu2.9Ni0.1Ti4O12
(CCNTO) and CaCu3Ti3.9Ni0.1O12 (CCTNO) prepared by a semi-wet route using TiO2 powder and metal
nitrate solutions. According to them both the stoichiometry and structure do not change on doping
with nickel and it remains cubic. Scanning electron micrographs (SEM) show that the grain size for
both doped samples is in the range of 10–50 mm. Energy dispersive X-ray spectrometer (EDX) studies
confirmed the presence of a copper rich phase at the grain boundaries. X-ray photoelectron spec-
troscopy (XPS) studies confirm the presence of Cu2þ and Ti4þ in both the samples of nickel doped CCTO
ceramics. The dielectric constant (εr) and dielectric loss (tan d) of Ni doped samples in CCTO on the
copper site is comparatively more than Ni doping on the titanium site. Since the microstructure is
directly related to the performance of the material, a detailed investigation was performed to deter-
mine the effect of microstructure on the dielectric constant and resistivity. In some cases there was a
significant change in the shapes of grains and its effect. In addition some dopants produced faceted to a
non-faceted transition.
Singh et al., [150] performed experiments to study the role of anisotropy in interfacial energy during
the coarsening of CaCu3Ti4O12 (CCTO) material system. When they altered the interface anisotropy,
they observed that the evolution and sizes of spherical grains completely altered to facetted cubes.
When the interface became anisotropic, crystal growth appears to occur by the surface attachment/
detachment rate, the motion of ledges, and the nucleation of new layers. Observations showed that
new layers grew by a screw dislocation mechanism. This suggests that nucleation limited coarsening is
occurring by the development of a transient bimodal grain size distribution consisting of large step
growth of grains. In presence of PbO they observed the development of a shaped nucleus which grew
larger. Sometimes very complex shaped crystals grew as a meta-stable shape. These shapes became
uniform as the growth progressed and size of grains became larger. This process produces smaller
grains that act as a source of material for the growth of large less defective larger grains. Fig. 27 shows
the morphology of un-doped CCTO grains processed for 24 and 96 h. There was no sign of faceting at
any stage in pure CCTO stoichiometry. It is clear from the observed morphologies that as we processed
the sample longer, grain growth occurred and gaps between the grains filled as grains merged to
become larger in size. Occasionally we observed smaller grains on the top of later grains which dis-
solved and disappeared. Careful observations of small and large grains both indicated that there was no
faceted grain in pure CCTO. Effect of addition of PbO in the range 1%–20% was very dramatic. Fig. 28
shows the early stage of the coarsening and transformation of the non-faceted to faceted shapes.
This happens in several stages. First material starts sintering and in presence of PbO it forms small
segregated precipitates. These precipitates transform into shaped nuclei. At some spots liquids were
still present in the matrix. As shown in Fig. 28 there were some places where particles/precipitates
were covered with PbO-rich liquid. As shown in Fig. 28, after sintering of materials, small nuclei with
shaped faces generated and grew larger as a function of time. This type of faceted morphology was
never observed for pure CCTO or copper-rich CCTO.
Sen et al. [151] report the effect of vanadium doping on the dielectric and electrical properties of
giant dielectric material CaCu3Ti4O12 (CCTO), The X-ray photoelectron spectroscopic studies confirmed
vanadium doping with V4þ replacing Ti4þ at its lattice site. The morphology of the un-doped sample is
characterized by grain size of the order of 5–30 mm with the bigger grains dominating the feature
which decreases with increasing vanadium content as shown in Fig. 29.
As x increased to 0.1 and 0.3, loosely linked grains having clear grain boundaries with mean grain
size ranging from 3 to 6 mm were observed with some holes. The influence of the above features has
been visualized by monitoring the dielectric properties of various V-doped CCTO ceramics. The grain
boundary resistivity was found to decrease monotonically with the percentage increase of V doping as
revealed by impedance spectroscopic measurement and furthermore the grain size was found to follow
the similar trend.
Li et al. [152] reported the effects of the Mg doping on the dielectric properties of CaCu3Ti4O12 in the
frequency range of 200 Hz–200 kHz and in the temperature range of 58–473 K. It was found that the
incorporation of Mg2þ resulted in an increase in the dielectric constant by 12%–20% and a decrease in
the dielectric loss by 41%–64% with the minimum of 0.042 for CaCu2.7Mg0.3Ti4O12 at room temperature
and at 1 kHz. The x-ray photoemission spectroscopy measurements reveal that the content of Cu3þ
increases with the increasing concentration of Mg2þ. The enhanced dielectric response may be related
to the influence of Cu3þ and/or Mg2þ.
Fig. 27. Morphology of undoped CCTO processed for 24 h for the grain growth. There is no sign of faceting in the un-doped CCTO
[150].
Fig. 28. After sintering the materials starts shaping as it starts coarsening and in presence of PbO transform into a shaped nucleus
[150].
Zheng et al. [153] prepared pure and chromium-doped CCTO ceramics by a conventional solid-state
reaction method. Scanning electron microscopy (SEM) results showed that doping effectively
enhanced grain growth or densification, which should increase the complex permittivity. The dielectric
constant reached a value as high as 20,000 (at 1 kHz) at a chromium-doping concentration of 3%. The
Fig. 29. The SEM images of CaCu3Ti4xVxO12 ceramics (a) x ¼ 0, (b) x ¼ 0.1, (c) x ¼ 0.3 and (d) x ¼ 0.5 sintered at 1040 C for 10 h
[151].
obtained activation energy associated with the electrical relaxation, determined from the electric
modulus spectra, was in the range of 0.50–0.60 eV, which was very close to the value of the activation
energy for dc conductivity (0.50 0.05 eV). These results suggest that the movement of oxygen
vacancies at the grain boundaries is responsible for both the conduction and relaxation processes.
A.K. Rai et al. [154] prepared CaCu2.90Fe0.10Ti4O12 (CCFTO) by a novel semi-wet route and studied its
dielectric properties in the temperature range 300–500 K. It was found that the dielectric constant (ε)
decreases drastically in the frequency range 100 Hz to 1 MHz. Complex plane impedance and modulus
analysis were carried out to understand this drastic decrease in ε. Oxidation state of various ions was
studied using X-ray photoelectron spectroscopy (XPS). The decrease in the permittivity of CCFTO can be
attributed by two factors: first the suppression of the Ca/Cu disorder and second the absence of the
grain boundary internal barrier layer capacitance mechanism in CCFTO ceramic.
L. Singh et al. [155] studied Zn substitution at the Cu-site in undoped CCTO and zinc doped
CaCu3xZnxTi4O12 samples with x ¼ 0.10, 0.20 and 0.30 prepared by the semi-wet method for the first
time using solid TiO2 powder in metal nitrate solutions. The SEM images of the sintered CaCu3xZnx-
Ti4O12 ceramics showed average grain size in the ranges of 2–6, 8–13, 12–16 and 14–20 mm for x ¼ 0.00,
0.10, 0.20 and 0.30, respectively. Energy dispersive X-ray spectroscopy studies confirm the purity of
parent and Zn doped CCTO ceramics. At room temperature, the dielectric constants of Zn doped CCTO
are always higher than pure CCTO. CaCu3xZnxTi4O12 (x ¼ 0.20) ceramic has the maximum value of ε
w4347 along with the minimum value of tan d ¼ 0.14 at 1 kHz.
L. Singh et al. [156] studied the effect of doping of Mg2þ at the Cu2þ site in CaCu3Ti4O12. XRD analysis
confirmed the formation of single-phase material, and the structure does not change on doping with
Mg and it remains cubic similar to CaCu3Ti4O12 (CCTO). The average particle size in sintered powder of
the ceramic obtained from XRD and transmission electron microscopy (TEM) was found to be
59 05 nm and 90 25 nm, respectively. SEM image shows the presence of bimodal grains while EDX
analysis confirmed a copper oxide rich phase at the grain boundaries. We found exceptionally a very
high dielectric constant ε w86,084 at 500 K on partially substituted Mg2þ at Cu-site in CCTO ceramic at
1 kHz. The nature of relaxation behavior of the ceramic was also rationalized by impedance and
modulus spectroscopic analysis. Modulus spectroscopic studies confirmed the Maxwell–Wagner
relaxation arising due to the interfaces between grain and grain boundaries.
Acknowledgment
Authors are grateful to Prof. Om Parkash, Department of ceramic Engineering and Prof. R.K. Mandal,
Department of Metallurgical Engineering IIT Banaras Hindu University for their fruitful discussions
about SEM and TEM analyses.
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Dr. Laxman Singh (L. Singh) was born on July 15, 1984 and did his Ph.D. under the supervision of Prof.
U.S. Rai and Co-Supervision of Prof. K.D. Mandal in 2013 from Department of Chemistry, Faculty of
Science, Banaras Hindu University (B.H.U.), Varanasi, India and presently he is working as postdoctoral
fellow in the field of rechargeable lithium–ion based electrode nano-materials at Department of
Chemistry, University of Ulsan, Ulsan, Republic of Korea. Dr. Singh during his Ph.D., he has worked on
synthesis and characterization, especially on nano-materials, energy-related materials, metals, mixed
metal oxide (Perovskite oxides, spinels) and ceramics for energy storage devices. He has developed
several CaCu3Ti4O12 based nano-materials adopting the chemical solution synthesis (sol–gel, com-
bustion, and co-precipitation etc.), high-temperature solid-state method, planetary ball mill, and spin
coating etc. and some of the materials have shown promising desirable dielectric properties might get
potential significance for cost-effective technological applications in microelectronic devices. He has
published more than a dozen papers and several papers are in process of publications.
Prof. U.S. Rai was born on May 03, 1951 and received his graduation, post-graduation and Ph.D. degree
from Chemistry Department, Banaras Hindu University (BHU), Varanasi, India. He joined BHU as fac-
ulty in 1972 and was promoted as Reader and Professor in the University in 1987 and 1998, respec-
tively. He is specialized in physical chemistry and has experience of working in solid state chemistry, in
general, and chemistry of hydroxylapatites, chemistry of organic eutectics and monotectics, ESR of
radical anions and cations, polymer matrix composites, nano-materials and calcium copper titanate.
Prof. Rai worked as Research Associate in Leicester University, U.K. from September 1991 to September
1993 and Research Scientist in Jackson State University, Jackson, USA, from May 2007 to May 2008.
Prof. Rai has published more than 128 papers in reputed International Journals. He has attended
several international conferences in USA; Gordon Research Conference on Crystal Growth in PlyMouth,
NH, USA during July 15–19, 1985, ASM 2003 Materials Solution Conference in Pittsburgh, USA, during
October 13–15, 2003, Laser Induced Breakdown Spectroscopy-2011 in ClearWater Beach, Florida, USA
during July 18–20, 2011 and 11th Computational Chemistry and Materials Science conference in
Jackson State University, Jackson, USA, in July 28–29, 2011.
Prof. K. D. Mandal received B.Sc (Chem. Hons.1979) and M.Sc (Chemistry) degree from Bhagalpur
University (1981) and Ph.D. in Chemistry from Banaras Hindu University, Varanasi (1989). After
postdoctoral studies, he became a Lecturer in Chemistry at North Eastern Regional Institute of Science
and Technology(NERIST), Itanagar, Arunachal Pradesh in 1995 after serving nine years at NERIST, he
was shifted to Institute of technology presently known as Indian Institute of technology, Banaras Hindu
University in 2004 and promoted to Reader (2005) and Associate Professor (2008). His current research
interests include synthesis, characterization and applications of nano-materials, oxide based electro-
ceramics and graphene-based composites for energy storage devices.
Prof. N. B. Singh, FASM, FSPIE, FOSA of the Department of Chemistry and Biochemistry University of
Maryland Baltimore County (UMBC) is a Fellow of American Society of Materials (ASM) International, a
Fellow of SPIE-The International Society of Optics and Photonics, and a Fellow of OSA –the Optical
Society of America (OSA). He is internationally recognized for his researches in the area of materials
research and technology focused for Lasers and Electro-Optics, RF and Wide band gap and radiation
sensors. He held the position of Senior Consulting Engineer until December 30, 2011, the highest
technical position in the Northrop Grumman Electronic Systems at Baltimore Maryland. Dr. Singh has
been honored by many local chapters and international awards including the American Association of
Crystal Growth (AACG) Mid-Atlantic Chapter, the Pittsburgh Chapter and the Capital Chapter of Crystal
Growth with “Senior Crystal Growth Award”, the “R&D star” to watch by R&D magazine, the “2010
Engineering Materials Achievement Award” of the ASM International. He has published extensively
in journals and conference proceedings, has twenty one issued patents, more than two hundred
company trade secrets and invention awards. Dr. Singh has been Associate Editor of the journal,
Progress in Crystal Growth and Characterization and has been editor of several proceedings of the conferences and two books.
Dr. Singh served as an Executive Committee member of the American Association for Crystal Growth for 12 years. He is a very
active member of the, SPIE, Optical Society of America (OSA), American Ceramic Society (ACeS) and ASM International, and has
served on the organizing and advisory committees of many national and international conferences. He was chairman of the
Gordon Conference on “Gravitational Effects on Materials” in 1993. Dr. Singh is the founder of the Northrop Grumman Ma-
terials Corporate Forum which focuses on critical materials and device technologies.

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Progress in Crystal Growth and Characterization of Materials 60 (2014) 15–62

Contents lists available at ScienceDirect

Progress in Crystal Growth and

Full length article

Progress in the growth of CaCu3Ti4O12 and

Keywords: Calcium copper titanate, CaCu3Ti4O12, (CCTO), a potential electro-

2. Perovskite oxides (a general overview)

Perovskite oxides Dielectric constant

BaTiO3 (ABO3) 200–3000

Fig. 1. A unit cell of ABO3 type cubic perovskite [17].

a) The rA:rO should be approximately 1 or slightly higher.

2.1. Substitutions in perovskite

The substitution in perovskite oxides can be of the following types:

creating vacancies in A, B or O sub-lattices such as M1xLaxTi1xM/xO3 (M ¼ Ca2þ, Sr2þ, Ba2þ or

3. Synthetic routes for perovskite oxides

3.1. Dry method

3.2. Wet methods

3.2.1. Pechini’s method

3.2.2. Glycine gel method

3.2.3. Semi wet method

Fig. 3. Zwitterionic glycine molecule complexing Mnþ.

Fig. 4. A probable structure of metal–citrate complex.

4.1. Dielectric properties

Fig. 5. Flow chart for the synthesis of materials by semi-wet route.

ε ¼ ε0r jε00r ; (2)

P ¼ Pelectronic þ Pionic þ Pmolecular þ Pinterfacial (4)

4.1.1. Dielectric constant

4.1.2. Dielectric loss

i) Long range electronic or ionic migration losses (i.e. DC conductivity)

ε00 ¼ tan d=ε0 (6)

5. ABO3 type high dielectric constant perovskites

5.1. Barium titanate (BaTiO3)

5.2. Calcium-titanate (CaTiO3)

It is a para-electric material at room temperature with no interesting dielectric properties in the

BaTiO3 Multilayer capacitor

5.3. Strontium titanate (SrTiO3)

6. ACu3Ti4O12 type of materials

6.1. Crystal structure of CaCu3Ti4O12 materials

6.2. Sudden increase in the interest on CCTO

6.2.1. Special properties of CaCu3Ti4O12 (CCTO)

7. What is the origin of the very high dielectric constant in CaCu3Ti4O12?

7.1. Intrinsic factors: atomic structure aspects

7.2. Extrinsic factors: microstructural aspects

(a) Single crystal (domains and its domain boundaries)

7.2.1. Single crystal (grains and its domain boundaries)

7.2.2. Internal barrier layer capacitor (IBLC) model

7.2.3. Electrode/sample contact effects

7.2.4. Interfacial polarization effect: Maxwell–Wagner model

8. High dielectric constant and low loss CCTO

8.1. Different synthetic methods for CCTO

temperature (1 kHz). AC conductivity of Ca1xLaxCu3Ti4xCoxO12 sample increases with increasing

8.2. Effects of sintering parameters

8.3. Effects of substitutions on CCTO electro-ceramic

Fig. 25. Dielectric constant of NiO doped CCSTO [143].

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ε ¼ ε0r jε00r ; (2)