1

Ferroic properties of materials at Nano scale

Uppalaiah Erugu
Department of Physics & Astronomy
University of Wyoming
1000E University Dept 3905
Laramie, WY 82071
USA
(Dated: May 14, 2015)

Ferroics are the materials that undergo one or more ferroic transitions. The ferroic phase transition is
characterized by an order parameter which is non-zero below transition temperature and zero above it.
Ferroics are the one of the most promising candidates for catering future technological needs. The
investigation of size effect on ferroic properties in the nano-regime is critical for understanding the physical
phenomena and potential for applications. When the size of ferroic particle is made smaller, four successive
stages of behavior is observed. They are Polydomain, Single domain, Superpara-electric/magnetic/elastic,
and Para-electric /magnetic/elastic. The structural transition is observed to take place at critical size of
ferroic particle. The order parameter (spontaneous polarization or magnetization or strain) of ferroic
nanoparticles decreases with particle size and disappears at critical size. In the vicinity of critical size of
particle (phase transition), the derivatives of order parameters become very large. Domain size in
nanoferroic materials decreases linearly with the square root of film thickness. The variation in the
properties of ferroics in the above four stages provides interesting and multi functionalities, which have
wide applications in science and technology.
CONTENTS
I.
II.

III.

I. INTRODUCTION

Introduction
Ferroic materials
A.
Properties
B.
Thermodynamics of ferroic
phase transition
C.
Classification of ferroics
D.
Multi-ferroics
Ferroic properties at nanoscale
A
ferroics
1.
2.
3.
B

IV.
V.

Size effect on primary

Size effect on Ferroelectrics
Size effect on Ferromagnetic
materials
Size effect on Ferroelastic
materials
Size effect on all ferroics

Conclusions
References

Phase transitions in solids play essential role in

understanding the properties of materials and
their applications. At phase transition point, many
anomalies are observed due to the breaking of
symmetries such as translational, orientational
and time reversal. So, it is useful to categorize
phase transitions in solids in terms of the changes
of symmetry that accompany them. If the initial
and final phase have the same or different spacegroup type, the two phase are said to be
isomorphous or non-isomorphous respectively.
The ferroics term is introduced by Aizu for solids
with non-isomorphous phase transitions and the
change of point symmetry that occurs nondisruptively (Aizu. K, 1970). Non-disruptive
modification means that the new phase can be
obtained from the old one after continuous
distortions, which dont lead to any additional
change of symmetry. Hence, a phase transition is
called a ferroic phase transition if: a) it can be
considered as a non-disruptive modification of a
certain prototype phase (or parent), and b) it

2
involves a loss of one or more point symmetry
elements in the prototype (Widhawan, 2000).
Now, a ferroic material is the one which can
undergo one or more ferroic phase transitions.
These ferroics exhibit different and interesting
properties in the nano-regime as their size is
reduced. This paper presents the review of ferroic
properties of materials at nanoscale.
II. FERROIC MATERIALS
A.

Properties

As a result of occurrence of ferroic phase

transition in materials, they come to possess the
following salient features (Aizu. K, 1962, 1969).
First, one of the characteristic feature of ferroics
is the existence of at least equivalent states which
differ only in their orientations (either of
structure, or of spontaneous electric/magnetic
moment or both) and/ or hardness called
orientation states (Widhawan, 2000).
The
regions where these states occur are called
domains, and the regions separating the domain
are called domain walls. Second, the possibility
of controlling the domain structure by external
fields. The controlling of domain structure results
in the appearance of a hysteresis loop. In other
words, the field dependence of order parameter is
described by hysteresis loop. Third, a crystal
belongs to the primary ferroics, if only one
external field is required to switch it from one
orientation state to another. Ferroelectric,
ferromagnetic and Ferroelastic materials belong
to primary ferroics. Lastly, if two or more
external fields are required for the switching
crystals orientation state, the crystal belongs to
higher order ferroics.
Because of existence of domains, there
is long-ordering with respect to at least one
macroscopic property, which is called an order
parameter (e.g. spontaneous polarization or
magnetization or stain). Ferroic material
undergoes phase transition from ferroic phase to
non-ferroic phase at a certain critical temperature
(Tc). The order parameter is zero in prototype
(non-ferroic) phase and steeply rises from zero as
the temperature is lowered below Tc. That means

domains start to appear from just above Tc. The

temperature dependence of order parameter for
temperatures just below Tc is the characteristic
feature of all ferroics. Another important feature
of ferroics is in the vicinity of a ferroic phase
transition, one or more macroscopic physical
properties, represented as the derivatives of order
parameter, become anomalously large. For
ferroelectrics, the dielectric permittivity becomes
very large. Moreover, ferroics have tendency to
undergo filed-induced phase transitions,
especially in the vicinity of Tc (Glinchuk et al.,
2013)
B.

Thermodynamics of ferroic phase

transition

Lets consider a ferroic crystal in a

particular orientation state S1, under the influence
of an external electric field (Ei), magnetic field
(Hi) and uniaxial stress (ij) (i,j = 1,2,3).
Generalized Gibbs free-energy density of ferroic
crystal is given by
g =

(1)

Where S is entropy, Di is electric displacement, Bi

magnetic field induction, and ij is strain. Di, Bi,
and ij contain a spontaneous part (if any) and an
induced part due to the external fields. If a small
amount of heat dQ is flows into a unit volume of
system, a small amount of work dW is done on it
by the external forces. The work done per unit
volume is
= + +

(2)

The free energy density for this orientation state

can be written as (Widhawan, 2000)
g = (3)
To obtain the free-energy densities g1 and g2 for
orientation states S1 and S2. One can integrate
equation (3). The difference g = g 2 g1
determines whether the crystal switches a state
from S1 to S2 or vice versa under the application
of external fields.
The difference in the domain state free energy

3
1
g = 0 + 0 + 0 +
2
1
1
+ +
2
2
+ +
+
+
(4)
0
0
Here 0 = 2
1
is the difference between
th
the values of the i component of the spontaneous
polarization in the states S1 and S2. kij, ij and sijkl
are the elements of the electric susceptibility
tensor, magnetic susceptibility tensor and the
compliance tensor respectively. ij, dijk and Qijk
are the elements of magnetoelectric, piezoelectric
and piezomagnetic tensors respectively. The
equation (4) serves to define the various types of
ferric materials. A ferroelectric material is
defined as one for which at least one pair of
orientation states exists such that 0 0 for
one or more values of i. Similarly, the
ferromagnetic and ferroelastic materials can be
defined.

C.

Classification of ferroics

Based on the number of external fields

necessary to switch the ferroic from one
orientation state to another and using equation
(4), there are three types of primary ferroics, six
types of secondary ferroics and higher-order
ferroics (Multiferroics). For primary ferroics, the
free-energy difference between at least one pair
of orientation states (domains) involves the first
power of electric, or magnetic, or mechanical
field
g ~ , ,

FIG. 1. Order parameter hysteresis loops of

primary ferroics. Adopted from Glinchuck et al.,
2013.

In secondary and higher order ferroics, no two

orientation states differ in either spontaneous
polarization or spontaneous magnetization or
spontaneous strain. For secondary ferroics, the
difference between orientation states (domains)
thermodynamic potential (g) is proportional
either to square or to the product of external fields
as shown in the table 1.
Free
Name of ferroic
energy
difference
(g)
E2
Ferrobielectric

Example

H2

Ferrobimagnetic

NiO

Ferrobielastic

Quartz

EH

Ferromagnetoelectric Cr2O3

Ferroelastoelectric

NH4Cl

Ferromagnetoelastic

FeCO3

SrTiO3

Table. 1. Secondary ferroics.

For higher-order (third, fourth etc.) ferroics, the
difference of domain states free energy should
be proportional to the third, fourth etc. powers of
external fields. In particular, for the ternary
ferroics
g ~ 3 , 3 , 3 , 2 , 2 , 2 , 2 , , .
The main difference between primary ferroics
and the higher orders is related to the fact that at
least one pair of the domains in the primary
ferroics has opposite direction of order
parameter, while the same pair in the higher-order
ferroics can be induced by corresponding set of
external fields. For example, in ferrobielectric,
the domain pairs have the same orientations of
polarization P, so that field-induced domain
reorientation can be represented via induced
polarization difference as follows:
1
1
g = =
2
2
where is dielectric permittivity tensor.
The most of the secondary and higherorder ferroics fall into four crystallographic
compounds. They are compounds with perovskite
structure (Fiebig.M, 2005), hexagonal structure,
Boracites and BaMF4 compounds. Apart from

4
above types of ferroics, a large number of
multiferroics with other structures are known.
In multiferroics, more than one primary ferroic
order parameter (spontaneous polarization or
magnetization or strain) coexist simultaneously
in single phase. The coupling between these order
parameters, which has numerous applications in
modern electronics, may or may not be present.
One of the multiferroics in which all order
parameters are coupled is Ferromagnetoelectric.
Both spontaneous polarization and magnetization
are strongly coupled to each other. Hence, the
spontaneous polarization (or magnetization) can
be induced and controlled by the application of
external magnetic field (or electric field)
respectively (Kimura et al., 2003; Astrov.D,
1960). Among single-phase crystals, the largest
magnetoelectric effect has been observed in
TbMnO3, BiMnO3 and BiFeO3. In composite
materials, large magnetoelectric effect can be
achieved by coupling of piezomagnetic materials
with piezoelectric ones. When magnetic field is
applied, mechanical deformation is induced in the
magnetic components which in turn induces the
electric polarization via piezoelectric component.

III.
FERROIC
NANOSCALE

PROPERTIES

AT

The properties of ferroics at nanoscale

are of great interest from both fundamental and
application viewpoints. Ferroic phase transition
at nanoscale provides a conceptual and solid
understanding of various physical phenomena
and technological applications. As the particle
size is reduced interesting properties, that do not
exist in bulk, arise as the surface and interfaces
play major role. So, for nanomaterials the
geometric confinement comes from the surfaces
and interfaces. The geometrical confinement in
one (films) or three spatial dimensions
(nanoparticles) lead to essential influence of the
surface on their physical properties in comparison
with unconfined bulk materials. For nanoparticles
with the sizes above around 100 nm, the truly
bulk properties can be found deep inside the
sample, on the other hand for those with the sizes
less than that the properties would never be alike
the bulk materials (Glinchuck et al., 1965).
Because of surface influence the physical

properties, which are spatially homogeneous in

bulk samples, become inhomogeneous in
nanomaterials. Hence, in order to understand the
physical properties of ferroic nanomaterials, the
size effect and spatial inhomogeneity must be
taken into account.
A. SIZE EFFECT
FERROICS

ON

PRIMARY

In this section the theoretical and experimental

investigations of size dependence of ferroic
properties of primary ferroic materials at
nanoscale are reported.
1. Size effect on Ferroelectrics
Ferroelectric material is the one that
undergoes ferroic phase transition from
paraelectric phase to ferroelectric phase. It has
spontaneous polarization (Ps) as order parameter
which can be induced and controlled by the
application of external electric field.
The effect of particle size on crystal structure has
been investigated in barium titanate (BaTiO3) and
lead titanate (PbTiO3) nanopowders (Akdogan et
al., 2005). As the average particle is reduced, the
crystal transforms from tetragonal to cubic at
critical size about 50nm for BaTiO3 (Li. X et al.,
1997) and 20nm for PbTiO3 at room temperature
(Uchino.K et al., 1989).

FIG. 2. The lattice parameters of c and a as

function of BaTiO3 particles size. Adopted From
Li. X et al., 1997.
The surface effects such as surface to volume
ratio and surface tension change the crystal
structure of nanoparticles. At the critical size, the
symmetry breaking, which constitutes the

5
important properties of nanomaterials, occurs as
BaTiO3 and PbTiO3 become cubic. So, the ferroic
phase transition can be arrested below critical
size. The existence of ferroelectricity (Ps)
requires non-centrosymmetric lattice. In other
words, below critical size the crystal becomes a
non-ferroic material as its crystal structure
becomes centrosymmetric (cubic) lattice.
Similarly, the film thickness has same influence
on lattice parameters (Fattuzo.E et al., 1967).
The dielectric permittivity of BaTiO3 powder has
maximum near 70nm, which defines the critical
size. The difference between this value and other
values
obtained
by
lattice
constants
measurements could originate from the influence
of electrodes as well as from different quality of
the samples investigated by different authors. At
critical size 70nm, BaTiO3 undergoes phase
transition from ferroelectric (ferroic phase) to
para-electric (non-ferroic phase) due to crystal
structural transformation. The influence of film
thickness on lattice parameters has been reported
to have same effects as nanoparticles do.
The dielectric permittivity at critical size is
observed to be very high. It is due to the fact that
in the vicinity of ferroic phase transition the
respond function or macroscopic physical

properties ( = )

become large anomalously (Widhawan, 2000).

This manifests how one of the salient features of
ferroic materials depend on particle size.

FIG. 3. The influence of particle size on the

dielectric permittivity of BaTiO3 powder.
Adopted from Wada. S et al., 2003.

Moreover, the spontaneous polarization

decreases with decreasing particle size and
eventually disappears in BaTiO3 and PbTiO3
(Zhong et al., 1994, Ishikawa et al., 1987, Zhong
et al., 1993); i.e., a size-driven phase transition
takes place. The size-driven phase transitions
have the same order as the temperature-driven
phase transitions. The particle size at which longrange (spontaneous polarization) disappears is
called Superparaelectric limit (Rudiger.A et al.,
2005).

FIG. 4. Particle size dependence of spontaneous

polarization of PbTiO3 nanocrystal at room
temperature (25 0C and ferroic phase transition
temperature (Ttr). Adopted from Akdogan et al.,
2005.
The particle or film thickness even affect the
transition temperature (Tc) of ferroelectrics in
nano-regime.
In BaTiO3
and
PbTiO3
nanoparticles, the transition temperature
decreases with decreasing particle size and
reaches zero at the critical size (Uchino.K et al.,
1989). According to Ishikawa et al the transition
temperature Tc (D) in thin films with thickness D
varies as () = () () and
1
() when the depolarization field is

compensated. The calculated size dependence of

spontaneous polarization and Tc for PbTiO3 and
BaTiO3 is in agreement with the experimental
results in the literature (Zhong. W. L et al., 1994).

FIG. 5. The size effect on transition temperature

of PbTiO3 nanoparticles. The full circles are
experimental data and solid curve is theoretical
curve. Adopted from Ishikawa et al., 1987.
The transition temperature of ferroelectric
materials is decided by competition between
dipoledipole interaction of ferroelectricity
active ions in different unit cell and Coulomb
repulsive forces inside a unit cell which tends to
conserve paraelectric order (Ishikawa et al.,
1987). Another factor that decides Ttr is
hydrostatic compression of particles due to their
surface tension.
2. Size on Ferromagnets
Ferromagnetic materials have spontaneous
magnetization as order parameter below
transition temperature (Tc) and undergo ferroic
phase transition from ferromagnetic (or antiferromagnetic or ferromagnetic) phase to
paramagnetic phase.
Similar to ferroelectric materials, the particle size
and film thickness influences the properties of
ferromagnetic
or
anti-ferromagnetic
or
ferrimagnetic
materials.
An
extensive
experimental studies are done on ferromagnetic
materials to see the size effect at nanoscale. For
Fe, Co, and Ni nanoparticles, the coercivity Hc
increases with decrease of particles size whereas
the saturation magnetization Ms decreases with
particle size (Wei Gong et al., 1991).

FIG. 6. The coercivity Hc and saturation

magnetization Ms of Fe dependent on the average
diameter of particles. Adopted from Wei Gong et
al., 1991.
For Fe nanoparticles the coercivity reaches
maximum value around 210, which is the
single-domain size of Fe, and decreases with
particle size. This increase in ferromagnetic
nanoparticles is due to the fact that the effect
magnetic anisotropy of particles is much larger
than that of in bulk. The saturation magnetization
Ms decreases because of the existence of fraction
of superparamagnetism in nanoparticles and
surface effects. Even it has been reported the
increase of permeability of ferromagnetic
materials with grain size (Herzer. G 1990).
The Curie temperature of ferromagnetic materials
(Tc) decreases with particle size due to finite size
scaling and surface effects (Chen. J et al., 1996).
For ferromagnetic nanoparticles of size of 70nm
or more, the decrease in Tc is explained by Valiev
et al., 1990 al that ferromagnetic nanoparticle
with certain critical size has two phases. One
phase consists of particles with Tc of bulk
whereas the other phase has lower Tc. The
reduction in the size of particle results in
transformation into second phase with low T c
(Valiev et al., 1990).
3. Size effect on Ferroelastics
Ferroelastics are the materials where the order
parameter
is
mechanical
deformation
(spontaneous strain) which appears in ferroic
phase when they undergo ferroic phase transition.
When stress is applied to a ferroelastic material,

7
a phase change will occur in material from one
phase to an equally stable phase, either of
different crystal structure or of different
orientation (a twin phase). This stress-induced
phase change results in a spontaneous strain in
material (Widhawan 2000).
The size effect on ferroelastic has not been
investigated experimentally as extensive as for
other primary ferroics. The theoretical and
experimental studies show that the spontaneous
strain decreases with particle size and vanishes at
critical size. Similar to its counterparts, the lattice
parameters of ferroelastic materials decrease with
size which in turn influence the ferroelastic
properties such as domain size and transition
temperature. The size dependence of spontaneous
strain for PbTiO3 is shown fig 7 below.

FIG. 8. Film thickness dependence of domain

size (expressed as domain period) in single
crystal BaTiO3 lamellae. Taken from
Lukyanchuk et al., 2009.
In addition to this, the grain size also affects the
electrical and optical properties of ferroelastic
properties (ref 25 & 26). It is observed that the
reduction in activation energy of nanocrystalline
ZrO2:Y2O3 (YSZ) with grain size results in the
increase in electrical conductivity (Kosacki et al.,
1999). Apart from isolated single crystals of
ferroics, the small-size effects occur in ferroic
ceramics and alloys with very small grains and
ferroic nanocomposites.

FIG. 7. The variation of longitudinal (x33),

transverse (x11) and volumetric (xv) spontaneous
strains with particle size. Adopted from Akdogan
et al., 2005.
As the particle size is reduced, PbTiO3 undergoes
structural transition from tetragonal to cubic and
surface stress (tension) increases. This results in
decrease of the volumetric spontaneous strain.
The domain properties, both ferroelectric and
ferroelastic, of BaTiO3 and PbTiO3 are well
studied at nanoscale. Like other primary ferroics,
the domain size is linearly proportional to the
square root of film thickness or particle size as
shown in figure 8 ( Catalan. C, et al., 2009,
Schilling. A, et al., 2006, and Lukyanchuk et al.,
2009). In thin films, ferroelastic domains appear
even in the absence of extrinsic surface layers,
suggesting an intrinsic origin such as surface
tension (Catalan. C, et al., 2009).

B. SIZE EFFECT ON ALL FERROICS

In this section, we report how the ferroic
properties are affected by size of nanoferroics
materials, including primary, secondary and
higher-order ferroics.
A ferroic crystal is found to undergo four
successive stages as its size is reduced as shown
in figure 9 (Newnham et al., 1998). They are
Polydomain,
Single-domain,
Superparaelectric/magnetic/elastic,
and
Paraelectric/magnetic/ elastic stage.
In the first stage, due to the occurrence of ferroic
phase transition, multiple domains are formed to
minimize the total energy of bulk material in
ferroic phase.

8
larger than that of non-ferroic phase i.e., paraelectric/magnetic/elastic. In the last stage, as the
particle size is reduced to molecular dimensions
all traces of cooperative ferroic ordering
disappear and it undergoes phase transition to
non-ferroic phase. In other words the particle
becomes
para-electric/magnetic/
elastic
(Widhawan 2000).
These different properties in four stages give
ferroic materials exotic and multi functionalities.
The multiple functionalities of ferroic materials
have numerous applications in information
storage, spintronics, sensors and actuators. The
subset of these materials are considered smart
materials for technological applications.
IV. CONCLUSION

FIG. 9. Four stages that a ferroic crystal

undergoes as its size is reduced. Adopted from
Newnham et al., 1998.
As the size of particle is reduced, for sufficiently
small particle sizes the formation of domain walls
is not favored. The trade-off between domain
wall formation energy and the benefit of
decreasing of the depolarizing or demagnetizing
field gets reversed. Hence the whole particle
becomes a single-domain particle. This is
observed experimentally in ferromagnetic iron
(Oppegard et al., 1961), ferroelectric Barium
titanate (Berglund et al., 1967) and ferroelastic
BiFeO3 (Kubel et al., 1990) nanoparticles.
When the particle size is further reduced, the
nanoferroic particle becomes superparaelectric/magnetic/elastic. The energy barrier
opposing a flipping from one easy direction of
magnetization or polarization or strain to another
becomes comparable to KBT and the giant
Superpara-electric/magnetic/elastic moment can
orient as a whole easily.
This stage is
characterized by zero net order parameter
(spontaneous polarization or magnetization or
strain). The susceptibility of particle in this much

The review of ferroic materials and their

properties at nanoscale which are dominated by
surface effects such surface tension and surface
impurities is presented. These materials are very
important from both fundamental and application
viewpoints. The size effect on ferroic properties
at nanoscale provides a strong conceptual
understanding of physical phenomena and
technological applications. Four stages are
observed when the ferroic particle size or film
thickness is reduced: Polydomain, Single
domain, Superpara-electric /magnetic/elastic and
Para-electric / magnetic/ elastic. The crystal
structure of particle is changed at critical size and
particle undergoes phase transition from ferroic
phase to non-ferroic one. The spontaneous
polarization or magnetization or strain decreases
with particle size and vanishes at critical size. The
dielectric constant, magnetic susceptibility,
compliance become anomalously large at the
phase transition point. Moreover, the domain size
in ferroics decreases with grain size or film
thickness. These unique properties of ferroics
make them potential candidate to meet the
technological needs in future.
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