Journal of Biosphere, 2(1): 55-58, 2013 ISSN 2278 – 3342

Barium titanate as a ferroelectric and piezoelectric ceramics

Surinder Paul, Devinder Kumar, Manokamna and Gagandeep

Abstract: Barium titanate is a member of a large family of compounds with the general formula ABO3 called
perovskites, as the crystal size of barium titanate increases and at critical crystalline size crystal structure of
barium titanate transformed from cubic to tetragonal. Transformation of crystal structure is also take place at
Curi temperature. Cubic structure show paramagenatic behavior while tetragonal is ferroelectric. Differant
methods of synthesis result in to the different crystalline size of barium titanate crystal structure. In ferroelectric
phase barium titanate provide its great importance in the field of technology and have an amount of application
due to its excellent dielectric, ferroelectric and piezoelectric properties. In this review paper, a study on variation
of critical crystalline size of barium titanate and its ferroelectric and piezoelectric behavior is presented.
Key words: Barium titanate ceramics; ferroelectricity; piezoelectricity; structure and phase transitions; synthesis.

1. Introduction
Ferroelectric ceramics were born in the early
Ferroelectric materials have broad applications in 1940s with the discovery of the phenomenon of
transducers, actuators, capacitors, and memories. ferroelectricity as the source of the unusually high
Particularly well studied is BaTiO3, which has dielectric constant in ceramic barium titanate
rhombohedral (R), orthorhombic (O), tetragonal (T), capacitor. Ferroelectrics are materials which show
and cubic (C) phases. The cubic structures are electric polarization in the absence of an external
paraelectric while the tetragonal, orthorhombic and applied electric field and direction of the polarization
the rhombohedra forms are ferroelectric in nature. At may be reversed by an electric field. If the "centers of
the Curie temperature (around 120 ºC) paraelectric gravity" of the positive and negative charge
cubic BaTiO3 transforms into the ferroelectric distributions within a volume of material do not
tetragonal structure, which is important parameter coincide, the material is said to have an electric dipole
relating to its dielectric application. The dielectric and moment. The net dipole moment per unit volume is
ferroelectric properties of BaTiO3 are known to defined as the spontaneous polarization which is
correlate with size, and the technological trend toward magnitude of polarization within a single ferroelectric
decreasing dimensions makes it of interest to examine domain in the absence of an external electric field.
this correlation when sizes are at the nanoscale[1–3]. Spontaneous polarization is a fundamental property of
Due to its high dielectric constant and low loss all pyroelectric crystals, but it is reversible and
characteristics, barium titanate has been used in reorientationable in ferroelectrics only. Most
applications, such as capacitors and multilayer ferroelectric phase originates from a non-polar
capacitors (MLCs). Doped barium titanate has found prototypic phase and all of the polarization is
wide application in semiconductors, PTC thermistors reorientationable. Its magnitude in a single crystal is
and piezoelectric devices, and has become one of the directly related to the atomic displacements that occur
most important ferroelectric ceramics. In this review in ferroelectric reversal and may be calculated from
paper, a study on variation of critical crystalline size the atomic positions within the unit cell if know. The
of barium titanate and its ferroelectric and ferroelectricity disappears above a critical temperature
piezoelectric behavior is presented. Tc, called as Curie temperature, above which it
behave paraelectric. Spontaneous polarization in
ferroelectric state is associated with Spontaneous
electrostrictive strain in the crystal. Ferroelectric state
Surinder Paul( ) and Gagandeep show lower symmetry then paraelectric state. At the
Department of Physics, transition temperature crystal structure is changed[4].
Arni University, H.P, India
Ferroelectric material with high dielectric constant
Email: surinderpaul79@gmail.com
show high volumetric efficiency (capacitance per unit
Devinder Kumar volume). BaTiO3, based ceramics having a perovskite
Department of Physics, type structure show dielectric constant values as high
Govt. M.A.M College, as 15,000 as compared to 5 or 10 for common ceramic
Jammu- 180001, J&K, India.
and polymer materials. The high dielectric constant
Manokamna BaTiO3 ceramic based disk capacitors are simple to
Department of Chemistry, make and have captured more than 50% of the
V.M. University Salem, Salem, India ceramic capacitor market. The volumetric efficiency
can be further enhanced by using multilayer ceramic
 Barium titanate as a ferroelectric and piezoelectric ceramics - Paul et al.

(MLC) capacitors. Ferroelectric thin films have distribution of sizes making these powders highly
attracted attention for applications in many electronic sinterable as well as attractive for the production of
and electro - optic devices. Some of the important thin dielectric layers[8]. Wang et al. [9] used two
ferroelectric materials being used for making thin typical wet-chemistry synthesis methods, stearic acid
films include the perovskite type materials such as gel and acetic acid gel. In the first method, barium
BaTiO3, PbTiO3 etc. Applications of ferroelectric thin acetate, tetrabutyl titanate, isopropyl alcohol and
films utilize the unique dielectric, piezoelectric, glacial acetic acid were starting reagents. 0.1 mol of
pyroelectric sand electro- optic properties of tetrabutyl titanate was dissolved into isopropyl
ferroelectric materials. alcohol at room temperature and then 0.3 mol of
Piezoelectricity refers to the generation of
glacial acetic acid was added and stirred to form a
electricity or of electric polarity in dielectric crystals
titanyl acylate compound. Next, 0.1 mol of barium
when subjected to mechanical stress and conversely,
acetate dissolved in an aqueous solution of acetic acid
the generation of stress in such crystals in response to
an applied voltage. Cady[5] defines piezoelectricity as was dropped into the above compound gradually. The
“electric polarization produced by mechanical strain pH value was between 3.0-4.0 using glacial acetic
in crystals belonging to certain classes, the acid. After stirring the mixture for 30 min., a
polarization being proportional to the strain and transparent sol was obtained. Aging at 95 ºC was
changing sign with it.” In 1880, the Curie brothers performed until a gel formed, followed by drying at
found that quartz changed its dimensions when 120 ºC for 12h in an oven, and finally, the dried gel
subjected to an electrical field and generated electrical was calcined in air at different temperatures to obtain
charge when pressure was applied. Since that time, BaTiO3 nanopowders. The average particle size of this
researchers have found piezoelectric properties in powder was from 50-80 nm. For the second method
hundreds of ceramic and plastic materials. Many also used by Wang et al. [9] starting reagents were
piezoelectric materials also show electrical effects due
barium stearate, tetrabutyl titanate and stearic acid.
to temperature changes and applied, symmetry of
An appropriate amount of stearic acid was first melted
crystal lost, and a net dipole moment is created. This
in a beaker at 73 ºC, and then a fixed amount of
dipole moment forms an electric field across the
crystal. The materials generate an electrical charge barium stearate was added to the melted stearic acid
that is proportional to the pressure applied. They are and dissolved to form a yellow transparent solution.
used widely in sensors and actuators, such as Next, stoichiometric tetrabutyl titanate was added to
microphones, acoustic emitters, ultrasonic sensors and the solution, stirring to form a homogeneous brown
emitters, and actuators. Barium titanate (BaTiO3) sol, naturally cooling down to room temperature, and
show its application in capacitors and piezoelectric drying for 12h to obtain a gel. The gel was calcined at
transducers. Barium titanate ceramic is important for different temperatures in air to obtain nano-crystallites
ultrasonic transducer, mostly for fish finders. It of BaTiO3 with the size of particles from 25-50 nm.
undergoes, in cooling, cubic-to-tetragonal, tetragonal- Wada et al.[10] reported preparation of BT particle
to-orthorhombic, and orthorhombic-to-rhombohedral with various size with a hot uniaxial pressing method
transformations and above the Curie point, the crystal
and Curi point for a grain size 58 nm was found to be
symmetry becomes insufficient for piezoelectricity.
at room temperature. Li et al. synthesized BaTiO3 by
2. Synthesis of Barium titanate the oxalic acid precipitation method which is very
similar to the sol-gel acetate method. Particle size
In proveskite barium titanate, size play important role
prepared by this method was 38.2 nm[11]. Barium
for paraelectric to ferroelectric transition below a
titanate nanoparticles synthesized by oxalic acid
critical size. Barium titanate nanoparticles synthesized
precipitation method which is very similar to the sol-
by solvothermal method in which Precursor
gel acetate method. But acetic acid was replaced by
BaTi(OR)6 was prepared by mixing with Ba(OR)2
the oxalic acid, molar ratio between oxalic acid and
and Ti(OR)4 in benzene. BaTiO3 nanoparticle
tetra butyl titanate was 2.2:1; Ti solution was prepared
prepared with particle size less than 20 nm and XRD
by dissolving the tetra butyl titan ate into the solution
patterns show that tetragonal and cubic phases coexist
of alcohol and oxalic acid. The particle size prepared
in the nanoparticles. Dielectric measurements exhibit
by this method was 38.2 nm[12]. Boulos et al. [2005]
a broad band around 70 ºC due to the low-frequency
reported average particle size for BaTiO3 powders
dielectric dispersion[7]. BaTiO3 powder synthesized by
obtained from TiO2 at 150 ºC or 250 ºC was 40-70
the hydrothermal method at temperatures between
nm[13], Cubic barium titanate powder with particles of
~100-200 ºC by reacting fine TiO2 particles with a
about 20 nm by heat-treating polymeric precursors
strongly alkaline solution (pH>12) of Ba(OH)2. TiCl4,
containing barium and titanium in air at 600 ºC for 8h.
titanium alkoxide and TiO2 gels were used as titanium
An increase in the heat-treatment temperature to 900 ºC
sources at reaction temperatures in the range of 100-
generates grain growth, resulting in BaTiO3 particles
400 ºC. Hydrothermal BaTiO3 powders have a fine
several hundreds of nanometers in size[14].
particle size in the range of 50-400 nm and narrow

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 Barium titanate as a ferroelectric and piezoelectric ceramics - Paul et al.

3. Results and discussion transformation occurs on cooling BaTiO3 below

1460 ºC. Of utmost important parameter relating to its
3.1 Structure and phase transitions:
dielectric application is the ferroelectric – paraelectric
BaTiO3 is member of perovskite family ABO3. Above transition which occurs at the Curie temperature
its Curie point (approximately 130 ºC) the unit cell is (around 130 ºC). At this temperature, paraelectric
cubic. Below the Curie point the structure is slightly cubic BaTiO3 transforms into the ferroelectric
distorted to the tetragonal form with a dipole moment tetragonal structure following an elongation along an
along c direction. Other transformations occur at edge. The tetragonal phase is stable until 0 ºC, where
temperatures close to 0 ºC and -80 ºC: below 0 ºC the it transforms into the orthorhombic phase by
unit cell is orthorhombic with the polar axis parallel to elongation along a phase diagonal. Finally, there is a
a face diagonal and below -80 ºC it is rhombohedral low temperature transition at – 90 ºC where the
with the polar axis along a body diagonal. A typical orthorhombic phase transformed to the rhombohedral
ABO3 unit-cell structure is given in Figure 1. The phase[6].
BaTiO3 unit cell consists of a corner-linked network
of oxygen octahedra with Ti4+ ions occupying sites (B
sites) within the octahedral cage and the Ba2+ ions
situated in the interstices (A sites) created by the
linked octrahedra. When an electric field is applied to
this unit cell, the Ti4+ ion moves to a new position
along the direction of the applied field. Because the
crystallite and, hence, the unit cell is randomly
oriented and the ions are constrained to move only
along certain crystallographic directions of the unit
cell.

Figure 2. Phase diagram of BaTiO3

3.2 Application of BaTiO3 as Ferroelectric materials:

The applications for ferroelectric ceramics are
covering all areas of our workplaces, homes, and
automobiles. One category of applications for
ferroelectric materials is that of high-dielectric-
constant capacitors, particularly Multilayer capacitor
(MLCs). MLCs are extremely important to our
everyday lives in that they are essential to all of our
Figure 1. Perovskite ABO3 unit cell for BaTiO3 illustrating currently produced electronic components, and, as
180° polarization reversal for two of the six possible such, they constitute a significant portion of the
polarization states produced by displacement of the central multibillion dollar electronic ceramics business as a
cation in the tetragonal plane. The views of “polarization
whole. Typical applications include general-use
up” and “polarization down” (representing 180° polarization
reversal) show two of the six possible permanent
discrete capacitors and MLCs, voltage-variable
polarization positions. capacitors, and energy-storage capacitors[15]. Another
application of ferroelectric material is BaTiO3 based
BaTiO3 assumes five different crystal structures PTC ceramic possessing electrically conducting
namely, hexagonal, cubic, tetragonal, orthorhombic, properties at room temperature and rather abruptly
and rhombohedral. The hexagonal and cubic changing to a highly resistive material at some
structures are paraelectric while the tetragonal, elevated temperature at Tc. Applications include
orthorhombic and the rhombohedra forms are switches, sensors, motor starter and controller[16].
ferroelectric in nature. Figure 2 shows hexagonal Ferroelectric materials found applications in
BaTiO3 structure is stable above 1460 ºC. electrooptics and photonics due to their change in
Reconstructive hexagonal phase to cubic phase optical properties and ferroelectric polarization with

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 Barium titanate as a ferroelectric and piezoelectric ceramics - Paul et al.

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