_______________________________________________1

GENERAL VIEW OF FERROELECTRICS

Let us start with the "smartness" of a material. Table 1.1 lists the various effects
relating the input (electric field, magnetic field, stress, heat and light) with the
output (charge/current, magnetization, strain, temperature and light). Conducting
and elastic materials, which generate current and strain outputs, respectively, for the
input, voltage or stress (well-known phenomena!), are sometimes called "trivial"
materials. On the other hand, pyroelectric and piezoelectric materials, which
generate an electric field with the input of heat and stress (unexpected phenomena!),
respectively, are called "smart" materials. These off-diagonal couplings have
corresponding converse effects, the electrocaloric and converse-piezoelectric
effects, and both "sensing" and "actuating" functions can be realized in the same
materials. "Intelligent" materials must possess a "drive/control" or "processing"
function which is adaptive to changes in environmental conditions, in addition to
actuator and sensing functions. Ferroelectric materials exhibit most of these effects
with the exception of the magnetic phenomena. Thus, ferroelectrics are said to be
very "smart" materials.

Tabl e 1.1 Various effects in materials.

INPUT MATERIAL OUTPUT

DEVICE

OUTPUT CHARGE MAGNET- STRAIN TEMPERATURE LIGHT

INPUT CURRENT IZATION

Permittivity Elect.-mag. Converse Elec. caloric Elec.-optic

ELEC. FIELD Conductivity effect piezo-effect effect effect

Mag.-elect. Permeability Magneto- Mag.caloric Mag.optic

MAG. FIELD effect striction effect effect

Piezoelectric Piezomag. Elastic ___ Photoelastic

STRESS effect effect constant effect

Pyroelectric ___ Thermal Specific ___

HEAT effect expansion heat

Photovoltaic ___ ___ Refractive

Photostriction
LIGHT effect index

Diagonal Coupling Sensor

Off-diagonal Coupling = Smart Material Actuator

1
2 Chapter 1

Ferroelectrics are utilized in various devices such as high-permittivity dielectrics,

pyroelectric sensors, piezoelectric devices, electrooptic devices, and PTC (positive
temperature coefficient of resistivity) comp onents. However, ferroelectric devices
often fail to be commercialized in areas of application where competitive materials
exist. Light sensors, for example, typically are manufactured from semiconductive
materials which are superior to ferroelectrics in response speed and sensitivity.
Magnetic devices are much more popular for memory applications, and liquid
crystals are typically used for optical displays. One reason for this is due to the lack
of systematic and comprehensive compilation of knowledge on ferroelectric
materials. In this chapter, we will learn fundamental knowledge on ferroelectricity.

1.1 CRYSTAL STRUCTURE AND FERROELECTRICITY

In the so-called dielectric materials, the constituent atoms are considered to be
ionized to a certain degree and are either positively or negatively charged. In such
ionic crystals, when an electric field is applied, cations are attracted to the cathode
and anions to the anode due to electrostatic interaction. The electron clouds also
deform, causing electric dipoles. This phenomenon is known as electric
polarization of the dielectric, and the polarization is expressed quantitatively as the
sum of the electric dipoles per unit volume [C/m2]. Figure 1.1 shows schematically
the origin of the electric polarization. There are three primary contributions:
electronic, ionic and dipole reorientation-related. The degree to which each
mechanism contributes to the overall polarization of the material depends on the
frequency of the applied field. Electronic polarization can follow alternating fields
with frequencies up to THz-PHz (1012 -1015 cycle/second, higher than visible light
wave) and ionic polarization responds up to GHz-THz (109-10 12 cycle/sec,
microwave region). Thus, you should understand that a famous relation between
the relative permittivity ε and the refractive index n:

E=0 E
-
Electronic
+ - +
Polarization

Ionic
+ - + + - +
Polarization

- +
- + - + - + - + - + - +
Dipole + -
Reorientation - +
+ - - + - + - + - + - +
+ -

Fig. 1.1 Microscopic origins of the electric polarization.

General View of Ferroelectrics 3

ε = n2 (1.1)

is valid only when the applied electric field has a frequency on the order of THz or
higher. Permanent dipole reorientation can follow only up to MHz-GHz (106-109
cycle/sec). This is why ferroelectric materials with permanent dipoles cannot be
used for microwave dielectric materials; their permittivities are typically high at
low frequencies (kHz), but decrease significantly with increasing applied electric
field frequency.

Compared with air-filled capacitors, dielectric capacitors can store more electric
charge due to the dielectric polarization P as shown in Fig. 1.2. The physical
quantity corresponding to the stored electric charge per unit area is called the
electric displacement D, and is related to the electric field E by the following
expression:

D = ε0 E + P = εε0 E. (1.2)

Here, ε0 is the vacuum permittivity (= 8.854x10-12 F/m), ε is the material's relative

permittivity (also simply called permittivity or dielectric constant, and in general is
a tensor property).

Depending on the crystal structure, the centers of the positive and negative charges
may not coincide even without the application of an external electric field. Such
crystals are said to possess a spontaneous polarization. When the spontaneous
polarization of the dielectric can be reversed by an electric field, it is called
ferroelectric.

-
- σf - - - - - -
+ σb
+ + + + +
- - - - -
Dielectric
E + + + + +
- - - - -
- σb

+ σf + + + + + +
σt = σb + σf
+

σ f: Free Charge σb : Bound Charge σt : True Charge

Fig. 1.2 Charge accumulation in a dielectric capacitor.

4 Chapter 1

Table 1.2 Crystallographic classification according to crystal centro-symmetry and

polarity.

Cr ys tal system
Polarity Symmetr y Rhombo- Or tho- Mono-
Cubic Hexagonal Tetr agonal hedral r hombic clinic Tr iclinic

Centr o
m3m m3 6/mmm 6/m 4/mmm 4/m 3 m 3 mmm 2/m
(11)
Non-
polar 432 4 22
622
(22) 23 6 32 2 22
4
43m 6m2 42m
Non-
centro
Polar (21) 2
(Pyr o- 6mm 6 4mm 4 3m 3 mm2 1
electr ic) m
(10)
Inside the bold line ar e piezoelectr ics .

Not every dielectric is a ferroelectric. Crystals can be classified into 32 point

groups according to their crystallographic symmetry, and these point groups can be
divided into two classes, one with a center of symmetry and the other without as
indicated in Table 1.2. There are 21 point groups which do not have a center of
symmetry. In crystals belonging to 20 of these point groups [point group (432)
being the sole exception], positive and negative charges are generated on the crystal
surfaces when appropriate stresses are applied. These materials are known as
piezoelectrics.

Pyroelectricity is the phenomenon whereby, due to the temperature dependence of

the spontaneous polarization, as the temperature of the crystal is changed, electric
charges corresponding to the change of the spontaneous polarization appear on the
surface of the crystal. Among the pyroelectric crystals, those whose spontaneous
polarization can be reversed by an electric field (not exceeding the breakdown limit
of the crystal) are called ferroelectrics. There is some experimental ambiguity in
this definition. In establishing ferroelectricity, it is necessary to apply an electric
field to a pyroelectric material and experimentally ascertain the polarization
reversal.

1.2 ORIGIN OF SPONTANEOUS POLARIZATION

Why is it that crystals which, from a consideration of elastic energy, should be
stable by being non-polar, still experience the shifting of cations and anions and
become spontaneously polarized? The reason is briefly explained below. For
General View of Ferroelectrics 5

simplicity, let us assume that dipole moments result from the displacement of one
type of ion A (electric charge q) relative to the crystal lattice. Consider the case in
which the polarization is caused by all the A ions being displaced equally in a
lattice.

This kind of ionic displacement can be expected through lattice vibrations at a finite
temperature. Figure 1.3 shows some of possible eigen lattice vibrations in a
perovskite-like crystal. (a) shows an initial cubic (symmetrical) structure, (b) is a
symmetrically elongated one, (c) has coherently shifted center cations, and (d)
exhibits an antipolarized shift of the center cations. If one particular lattice
vibration lowers the crystal energy, the ions will shift and stabilize the crystal
structure so as to minimize the energy. Starting from the original cubic structure
(a), if (b) is stabilized, only oxygen octahedra are distorted without generating
dipole moments (acoustic mode). On the other hand, when (c) or (d) is stabilized,
dipole moments are generated (optical mode). The final stabilized states (c) and (d)
correspond to ferroelectric and antiferroelectric states, respectively. If this
particular mode becomes stabilized, with decreasing temperature, the vibration
mode frequency decreases (soft phonon mode), and finally at a certain phase
transition temperature this frequency becomes zero.

It follows that, at any individual A ion site, there exists a local field from the
surrounding polarization P, even if there is no external field. The concept of the
local field is shown schematically in Fig. 1.4. It can be shown that:

Eloc = E0 + Σ [3(pi.r i)r i - ri2 pi ] / 4πε0 ri5 .

i
= (γ/3ε0 )P. (1.3)

(a) (b) (c) (d)

Fig. 1.3 Some possible eigen lattice vibration modes in a perovskite crystal.
6 Chapter 1

+ + + Equipotential
- - -
E-Line

r1
+ pi
ri -

Eo

+ + +
- - - Dielectric Material

Fig. 1.4 Concept of the local field. Eloc is given by

Eloc = E0 + Σ [3(pi.r i)r i - r i2 pi] / 4πε0 r i5.
i

This local field is the driving force for the ion shift. Here γ is called the Lorentz
factor. For an isotropic cubic system, it is known that γ = 1.1) ε0 is the permittivity
of vacuum and is equal to 8.854x10-12 F/m. If the ionic polarizability of ion A is α,
then the dipole moment of the unit cell of this crystal is:

µ = (αγ/3ε0 )P (1.4)

The energy of this dipole moment (dipole -dipole coupling) is

wdip = - µ . Eloc = -(αγ 2/9ε0 2 )P2 (1.5)

Defining N to be the number of atoms per unit volume:

W dip = Nwdip = -(Nαγ2/ 9ε0 2)P2 (1.6)

Furthermore, when the A ions are displaced from their nonpolar equilibrium
positions, the elastic energy also increases. If the displacement is u, and the force
constants k and k', then the increase of the elastic energy per unit volume can be
expressed as:

W elas = N[(k/2)u 2 + (k'/4)u4 ] (1.7)

Here, k' (> 0) is the higher-order force constant. It should be noted that in
pyroelectrics, k' plays an important role in determining the magnitude of the dipole
moment. By rewriting Eq. (1.7) using:
General View of Ferroelectrics 7

P = Nqu , (1.8)

where q is the electric charge, and combining with Eq. (1.6), the total energy can be
expressed as follows (see Fig. 1.5):

W tot = W dip + W elas

= [(k/2Nq 2 ) - (Nαγ2/9ε0 2)] P2 + [k'/4N3q 4] P4 (1.9)

From this, one can see that if the coefficient of the harmonic term of the elastic
energy is equal to or greater than the coefficient of the dipole-dipole coupling, then
P = 0; the A ions are stable and remain at the non-polar equilibrium positions.
Otherwise, a shift from the equilibrium position (P2 = [(2Nαγ2/ 9ε0 2) - (k/Nq 2)]/
[k'/N3q 4]) is stable. Spontaneous polarization can occur more easily in perovskite
type crystal structure (e.g. barium titanate) due to a higher value of Lorenz factor γ
(= 10)2) than found for other crystal structures. Note also that the polarizability is
sensitive to temperature, leading to the phase transition. Suppose that the ionic
polarizability of ion A, α, increases with decreasing temperature, even if [(k/2Nq 2) -
(Nαγ2/9ε0 2)] > 0 (paraelectric!) at a high temperature, this value may become
negative with decreasing temperature, leading to a ferroelectric phase transition.
Considering a first approximation, a linear relation of the α with temperature, the
well-known Curie-Weiss law is derived, which will be discussed in detail in Section
2.2(1).

Wdip Welas

P
(a) Dipole interaction (b) Elastic energy
Wdip = - (Nαγ2/9 ε0 2)P2 Welas = (k/2Nq2)P2 + (k'/4N3 q4 )P4

Wtot

(c) Total energy

Wtot = Wdip + Welas
Fig. 1.5 Energy explanation of the origin of spontaneous polarization.
8 Chapter 1

Example Problem 1.1_________________________________________________

BaTiO 3 exhibits ionic displacements as illustrated in Fig. 1.6 at room temperature.

Calculate the magnitude of the spontaneous polarization. The lattice constants are c
= 4.036 A and a = 3.992 A.

0.061 A

Ti4+ O2-
Ba 2+
Ba 2+ 0.036 A

Ti4+
0.12 A
O2-

Fig. 1.6 Ionic displacements in BaTiO3 .

Hint

P = N µ (N: number of the dipole moments included in a unit volume)

Solution

The dipole moment is calculated by taking the product of the charge magnitude and
its displacement. The total dipole moment in a unit cell is calculated by summing
the Ba 2+, Ti4+, O2- related dipoles (notice the fractional contribution of each atom,
i. e. 1/8 for corner atoms and 1/2 for face-centered atoms);

p = 8(2e/8)(0.061x10-10 m) + 4e(0.12x10-10 m) + 2(-2e/2)(-0.036x10-10 m)

= 0.674x10-10e m
= 1.08x10-29 Cm , (P1.1.1)

where e = 1.602 x 10-19 C. The unit cell volume is given by

General View of Ferroelectrics 9

v = a2c = (3.992)2(4.036) x 10-30 m3

= 64.3 x 10-30 m3. (P1.1.2)

The spontaneous polarization is defined as the polarization (total dipole moment)

per unit volume:

PS = p/v = 1.08 x 10-29 Cm/64.3 x 10-30 m3

= 0.17 C/m2 (P1.1.3)
The experimental value of P S is about 0.25 C/m2.
___________________________________________________________________

1.3 ORIGIN OF FIELD INDUCED STRAIN

Solids, especially ceramics (inorganic materia ls), are relatively hard mechanically,
but still expand or contract depending on the change of the state parameters. The
strain (defined as the displacement ∆L/ initial length L) caused by temperature
change and stress are known as thermal expansion and elastic deformation,
respectively. In insulating materials, the application of an electric field can also
cause deformation. This is called electric field induced strain.

Generally speaking, the word "electrostriction" is used in a general sense to

describe electric-field induced strain, and hence frequently also implies the
"converse piezoelectric effect." However, in solid state theory, the converse
piezoelectric effect is defined as a primary electromechanical coupling effect, that
is, the strain is proportional to the electric field, while electrostriction is a secondary
coupling in which the strain is proportional to the square of the electric field. Thus,
strictly speaking, they should be distinguished. However, the piezoelectricity of a
ferroelectric which has a centro-symmetric prototype (high temperature) phase is
considered to originate from the electrostrictive interaction, and hence the two
effects are related. The above phenomena hold strictly under the assumptions that
the object material is a mono-domain single crystal and that its state does not
change under the application of an electric field. In a practical piezoelectric
ceramic, additional strains accompanied by the reorientation of ferroelectric
domains are also important.

Why a strain is induced by an electric field is explained herewith.3) For simplicity

let us consider an ionic crystal such as NaCl. Figures 1.7(a) and 1.7(b) show a one-
dimensional rigid-ion spring model of the crystal lattice. The springs represent
equivalently the cohesive force resulting from the electrostatic Coulomb energy and
the quantum mechanical repulsive energy. Figure 1.7(b) shows the
centrosymmetric case, whereas Fig. 1.7(a) shows the more general non-
centrosymmetric case. In (b), the springs joining the ions are all the same, whereas
in (a), the springs joining the ions are different for the longer and shorter ionic
distances, in other words, hard and soft springs existing alternately are important.
10 Chapter 1

Next, consider the state of the crystal lattice (a) under an applied electric field. The
cations are drawn in the direction of the electric field and the anions in the opposite
direction, leading to the relative change in the inter-ionic distance. Depending on
the direction of the electric field, the soft spring expands or contracts more than the
contraction or expansion of the hard spring, causing a strain x (a unit cell length
change) in proportion to the electric field E. This is the converse piezoelectric
effect. When expressed as

x = d E, (1.10)

the proportionality constant d is called the piezoelectric constant.

On the other hand, in Fig.1.7(b), the amounts of extension and contraction of the
spring are nearly the same, and the distance between the two cations (lattice
parameter) remains almost the same, hence, there is no strain. However, more
precisely, ions are not connected by such idealized springs (those are called
harmonic springs, in which force (F) = spring constant (k) x displacement (∆)
holds). In most cases, the springs possess anharmonicity (F = k1 ∆ − k2∆2 ), that is,
they are somewhat easy to extend but hard to contract. Such subtle differences in
the displacement causes a change in the lattice parameter, producing a strain which
is independent of the direction of the applied electric field (+E or -E), and hence is
an even-function of the electric field. This is called the electrostrictive effect, and
can be expressed as

x = M E2 , (1.11)

where M is the electrostrictive constant.

Lattice constant Lattice constant

E E

- + - + - + - +

Ion pair potential energy Ion pair potential energy

δ1 δ2 δ1 δ2

(a) Piezoelectric Strain (b) Electrostriction

Fig. 1.7 Microscopic explanation of the piezostriction and electrostriction.

 General View of Ferroelectrics
11
The one-dimensional crystal pictured in Fig. 1.7(a) also possesses a spontaneous
bias of electrical charge, or a spontaneous dipole moment. The total dipole moment
per unit volume is called the spontaneous polarization. When a large reverse bias
electric field is applied to a crystal that has a spontaneous polarization in a particular
polar direction, a transition "phase" is formed which is another stable crystal state in
which the relative positions of the ions are reversed. (In terms of an untwinned
single crystal, this is equivalent to rotating the crystal 180° about an axis
perpendicular to its polar axis. This is also understood from the potential double
minima in Fig.1.5.) This transition, referred to as polarization reversal, also causes
a remarkable change in strain. This particular class of substances is referred to as
ferroelectrics, as mentioned in Section 1.1. Generally, what is actually observed as
a field-induced strain is a complicated combination of the three basic effects just
described.

Figure 1.8 shows typical strain curves for a piezoelectric lead zirconate titanate
(PZT) based and an electrostrictive lead magnesium niobated (PMN) based
ceramic.4) An almost linear strain curve in PZT becomes distorted and shows large
hysteresis with increasing applied electric field level, which is due to the
polarization reorientation. On the other hand, PMN does not exhibit hysteresis
under an electric field cycle. However, the strain curve deviates from the quadratic
relation (E2) at a high electric field level.

We described the converse piezoelectric effect above. Then, what is the normal or
direct piezoelectric effect? This is the phenomenon whereby charge (Coulomb per
unit area) is generated by applying an external stress (force per unit area). Note that
the same piezoelectric coefficient d is used as used in Eq.(1.10), in the relation

P = d X. (1.12)

Fig. 1.8 Typical strain curves for a piezoelectric lead zirconate titanate (PZT)
based (a) and an electrostrictive lead magnesium niobate (PMN) based ceramic (b).
12 Chapter 1

Example Problem 1.2_________________________________________________

One of the lead zirconate titanate (PZT) ceramics has a piezoelectric constant of d 33
= 590 x 10-12 C/N with a dielectric constant ε3 = 3400 and an elastic compliance
s 33 = 20 x 10-12 m2/N.

(a) Calculate the induced strain under an applied electric field of E3 = 10 x 105
V/m. Then, calculate the generative stress under a completely clamped
condition.

(b) Calculate the induced electric field under an applied stress of X3 = 3 x 107
N/m2. The induced field does not coincide with the above-mentioned 10 x
105 V/m. Explain the reason, taking account of electromechanical
coupling factor k.

Hint

We will introduce the tensor quantities in Chapter 2. However, try to solve the
problems by neglecting the subscripts at the moment.

x=dE (P1.2.1)
P=dX (P1.2.2)

k2 = d 2 / (s ε0 ε) (P1.2.3)

Solution

(a) x3 = d 33 E3 = (590 x 10-12 C/N)(10 x 10 5 V/m)

= 5.9 x 10 -4 (P1.2.4)

Under a completely clamped condition,

X3 = x3 / s 33 = 5.9 x 10-4 /20 x 10-12 m2/ N

= 3.0 x 10 7 N/m2 (P1.2.5)

(b) P3 = d 33 X 3 = (590 x 10 -12 C/ N) (3 x 10 7 N/m2)

= 1.77 x 10-2 C/m2 (P1.2.6)
E3 = P 3/ ε0 ε = (1.77 x 10 C/m )/(3400 x 8.854 x 10
-2 2 -12 F/m)
5
= 5.9 x 10 V/m (P1.2.7)

The induced field is only 59% of the field in the case of (a); this is explainable by
the electromechanical coupling factor k.
 General View of Ferroelectrics
13
When electric energy is supplied to a piezoelectric sample and some part is
transduced into mechanical energy, the electromechanical coupling factor k is
defined by

k2 = (Stored mechanical energy)/(Input electrical energy).

= (1/2)(x2/ s)/(1/2)(ε0 εE2) = (1/2)((d E)2/ s)/(1/2)(ε0εE2 )
= d 2 / s ε0ε (P1.2.8)

On the other hand, when mechanical energy is supplied to the sample and some part
is transduced into electrical energy, k is also defined (notice the same result!) by

k2 = (Stored electrical energy)/(Input mechanical energy).

= (1/2)(P2/ ε0ε)/(1/2)sX2 = (1/2)((d X) 2/ε0 ε)/(1/2)sX2
= d 2 / s ε0ε (P1.2.9)

In the above case,

k33 2 = d 33 2/ s 33 ε0 ε3
= (590 x 10-12 C/N)2/(20 x 10-12 m2/N)(3400 x 8.854 x 10-12 F/m)
= 0.58 (P1.2.10)

The reason why the induced field in (b) is about k2 of the 10 x 105 V/m of (a) is this
transduction ratio; that is, each energy transduction ratio accompanying the E --> M
and M --> E processes is k2. Thus (last electrical energy)/(initial electrical energy)
= k4, leading to (last induced field)/(initial applied field) = k2 .
___________________________________________________________________

1.4 ELECTROOPTIC EFFECT

Since light is an alternating electromagnetic wave with electric and magnetic field
vibration directions mutually perpendicular to one another, the electric field induces
an electric polarization in a dielectric crystal and the light itself is influenced by the
crystal. The alternating frequency of the light is so high (PHz =1015 Hz) that only
the electronic polarization can follow the electric field change, and the relative
permittivity of an optically transparent crystal is small, not exceeding 10. The
relative permittivity ε at this high frequency is related to the refractive index n by
the following equation:

ε = n 2. (1.13)

When an external electric field is applied to the crystal, ion displacement is induced,
deforming the shape of the electron cloud, and consequently the refractive index is
changed. This phenomenon is called the electrooptic effect.
14 Chapter 1

Generally, the refractive index is treated as a symmetrical second-rank tensor

quantity and is represented geometrically by the optical indicatrix which is
described by
x2 y2 z2
__ + __ + __ = 1, (1.14)
2 2
n1 n2 n3 2

where n1, n2 and n 3 are the principal refractive indices. With the application of an
electric field, the change in refractive index is given by an expansion expression:
1/nij2(E) - 1/nij2(0) = Σ rijk Ek + Σ RijklEk El . (1.15)

Here n(E) and n(0) (n 0) are the refractive indices at E and zero field, respectively,
and rijk is the primary electrooptic coefficient (Pockels effect) and Rijkl is the
secondary coefficient (Kerr effect).

Considering the paraelectric phase of a perovskite crystal (m3m) as an example, the

Kerr coefficients are represented in the following matrix:

R 11 R 12 R 12 0 0 0
R 12 R 11 R 12 0 0 0
R 12 R 12 R 11 0 0 0
0 0 0 R 44 0 0
0 0 0 0 R 44 0
0 0 0 0 0 R 44

so that the refractive indicatrix under an electric field applied along the z direction is
expressed as:
x2 + y 2 z2
____________________ + ____________________ = 1 . (1.16)
n 02(1 - (n 0 2/2)R 12 Ez2 ) 2 n 0 2(1 - (n 02/2)R 11 Ez2 )2
The refractive index change under an external electric field is explained intuitively
as follows. When an electric field Ez is applied to a cubic perovskite crystal, the
crystal is elongated along the z-axis and contracted along both the x and y axes.
Consequently, the material's density or compactness will be decreased along the z
axis and densified along the x and y axes, leading to a decrease in the refractive
index nz and an increase of the indices n x and n y . (Note that the refractive index is
proportional to the electron density or ion compactness along the polarized light
electric field direction which is perpendicular to the light propagation direction.)

When light is transmitted along the y direction, the phase retardation Γy between
the ordinary and extraordinary waves is given by
 General View of Ferroelectrics
15

Fig. 1.9 Optical phase retardation through an electrooptic crystal. Notice the
crossed polarizer configuration.

Γy = (2π/λ) (n 0 3/2) (R11 - R12) L (Vz/d) 2, (1.17)

where d is the electrode gap and L is the optical path length (See Fig. 1.9). Placing
the crystal between crossed polarizers arranged at a 45o angle with respect to the z-
axis, the output light intensity is modulated as a function of applied voltage
according to:

I = I 0 sin 2 (Γy /2) = (1/2) I 0 (1 - cosΓy ) . (1.18)

This is the principle behind the operation of a light shutter/valve, and the voltage
required for the first intensity maximum (i.e., Γy = π) is an important characteristic
called the half-wave voltage.

Example Problem 1.3_________________________________________________

A paraelectric La-doped PZT (PLZT) sample with a rectangular shape (optical

pathlength: L) is put between two crossed polarizers arranged at 45° with respect to
the z-axis (Fig. 1.9). Assuming a voltage Vz is applied to the sample with an
electrode gap d, and light with a wavelength of λ (incident intensity: I0) is
transmitted through it, derive the output light intensity I(Vz) by neglecting light
absorption in the PLZT. Other parameters are listed below:
16 Chapter 1

refractive index at E = 0 : n 0
electrooptic Kerr coefficients : R11, R 12
phase retardation: Γy
reflectance at the crystal surface : Re = [(n - 1)/(n + 1)]2

Hint

The initial spherical indicatrix will be deformed into an ellipsoidal one under an
applied electric field Ez:
x2 + y 2 z2
____________________ + _____________________ = 1. (P1.3.1)
n 02(1 - (n 0 2/2)R 12 Ez2 ) 2 n 0 2(1 - (n 02/2)R 11 Ez2 )2

The output light intensity is reduced twice, once at the inlet and once again at the
outlet crystal surfaces by a factor of (1 - Re)2.

Also you should notice that the incident light (after passing through the first
polarizer) has ordinary and extraordinary light components of equal magnitudes.

Solution

In a cubic structure, the refractive index change under an external electric field
along z-axis is expressed by the following two equations:
1/nz2(Ez) - 1/n0 2 = R11 Ez2 , (P1.3.2)
1/n x2 (Ez) - 1/n0 2 = R12 Ez2. (P1.3.3)

Taking into account the relation, d(1/n2) = - (2/n3 ) dn,

n z(Ez) = n 0 - (1/2) n 03 R11 Ez2 , (P1.3.4)

n x(Ez) = n 0 - (1/2) n 03 R12 Ez2 , (P1.3.5)
where R11 > 0 and R12 <0 in most cases.

Since the wavelengths of the extraordinary (polarized along z-direction) and the
ordinary (polarized along x) waves are described as

λz = λ0 / n z, (P1.3.6)
λx = λ0 / n x, (P1.3.7)

where λ0 is the vacuum wavelength of the incident light, and the numbers of waves
existing in the crystal with an optical pathlength of L are L/ λz and L/ λx,
respectively, the phase difference between these waves (retardation Γy ) is given by
 General View of Ferroelectrics
17
Γy = 2p (L/ λx - L/λy )
= (2p/λ0 ) L (1/2) n 0 3 (R 11 - R12) (Vz / d) 2. (P1.3.8)

When we describe the linearly polarized light incident on the PLZT in terms of its
electric field vector as

ex __ sin[(2π/λ 0 ) y - ω t]
= √ I0 , (P1.3.9)
ez sin[(2π/λ 0 ) y - ω t]

the output light from the PLZT can be described as

ex __ sin[(2π/λ 0 ) y - ω t + φ]
= (1 - Re) 2 √ I0 , (P1.3.10)
ez sin[(2π/λ 0 ) y - ω t + φ − Γ y ]

Through the polarizer arranged at the - 45o orientation, the electric field component
in this direction is represented by
_ _ ____
e x /√2 - e z /√2 = (1 - Re) √I 0 /2
2
. [sin[(2p/λ )y - ωt + φ] - sin[(2p/λ )y - ωt + φ − Γ ]
0 0 y
____
= (1 - Re)2 √I 0 /2 [(1 - cosΓy ) sin[(2p/λ0 )y - ωt + φ]
+ sinΓy sin[(2p/λ0)y - ωt + φ]]. (P1.3.11)

Light
Intensity
(1 - R)2 I 0

0 Vz, λ/2
Applied Voltage

Fig. 1.10 Variation in the light intensity of an electrooptic shutter with applied
voltage.
18 Chapter 1

Thus, the output intensity through the 2nd polarizer is obtained:

I = (1/2) (1 - Re)2 (I0 /2) [(1 - cosΓy )2 + (sinΓy )2]
=(1/2) I 0 (1 - cosΓy ) (P1.3.12)

Figure 1.10 shows the output intensity I as a function of applied voltage Vz. The
half-wave voltage, which is defined as the minimum voltage required to produce the
first maximum in the transmitted light intensity, is given by
___________________
Vz,λ/ 2 = d √λ0/ L n 03 (R11 - R12 ) . (P1.3.13)
___________________________________________________________________

1.5 EXAMPLE OF FERROELECTRICS

A typical ceramic ferroelectric is barium titanate, which is used here as an example
to illustrate some properties of ferroelectrics. As shown in Fig. 1.11, BaTiO3 has a
perovskite crystal structure. In the high temperature paraelectric phase (non - polar
phase) there is no spontaneous polarization (the symmetry is Oh - m3m). Below the
transition temperature TC called the Curie temperature (about 130o C), spontaneous
polarization occurs, and the crystal structure becomes slightly elongated, that is,
tetragonal (C4v - 4mm). Figure 1.12 shows schematically the temperature
dependence of the spontaneous polarization PS and permittivity ε. PS decreases with
increasing temperature and vanishes at the Curie temperature, while ε tends to
diverge near TC. Also, the reciprocal (relative) permittivity 1/ ε is known to be
linear with respect to the temperature over a wide range in the paraelectric phase
(so-called Curie-Weiss law),

ε = C / (T - T 0) , (1.19)
where C is the Curie-Weiss constant and T0 is the Curie-Weiss temperature. T0 is
slightly lower than the exact transition temperature TC .

It is also known that the spontaneous polarization Ps and the spontaneous strain xs
follow the relationship

xs = QPs 2, (1.20)

and xs decreases almost linearly with increasing temperature. In the case of

BaTiO3 , it exhibits the piezoelectric effect in the ferroelectric phase, while in the
paraelectric phase, it is non-piezoelectric and exhibits only the electrostrictive
effect. With decreasing temperature from room temperature, however, barium
titanate undergoes a series of complicated phase transitions. Figure 1.13 illustrates
these successive phase transitions.
 General View of Ferroelectrics
19

Ti 4+

Ba 2+

O 2-

T>T C T<TC

T C : Curie temperature

Fig. 1.11 Crystal structures of BaTiO 3.

(a) Capacitor

Permittivity ε

Spontaneous P s

(b) Memory Inverse permittivity 1/ ε

(c) Pyro sensor

T c (Curie Temp.)
Temperature

(e) Piezoelectric transducer (d) Electrooptic device

(f) Electrostrictor

Fig. 1.12 Temperature dependence of the spontaneous polarization and

permittivity in a ferroelectric material. (a) - (f) indicate the temperature ranges for
each application. In other words, if we can shift such temperature range closer to
room temperature, a practical material is obtained.
20 Chapter 1

Rhom bohedral Orthorhombic Tetragonal Cubic

Ps Ps
10,000 Ps
Dielec tr ic c onstant

5,000 εa

εc
0

-150 -100 -5 0 0 50 100 15 0

Te mpera ture ( C)

Fig. 1.13 Various phase transitions in barium titanate.

1.6 APPLICATIONS OF FERROELECTRICS

Ferroelectric materials, especially polycrystalline ceramics, are very promising for a

variety of applications such as high permittivity capacitors, ferroelectric memories,
pyroelectric sensors, piezoelectric/electrostrictive transducers, electrooptic devices
and PTC thermistors.

For capacitor dielectrics, the peak dielectric constant around the transition (Curie)
temperature is utilized, while for memory applications, the material must be
ferroelectric at room temperature (refer to Fig. 1.12). A large temperature
dependence of the spontaneous polarization below TC is sought for pyroelectric
sensors. Piezoelectric materials are used as sensors and actuators, where the TC
should be above room temperature. Pressure and acceleration sensors are now
commercially available in addition to conventional piezo-vibrators. Precision
positioners and pulse drive linear motors have already been installed in precis ion
lathe machines, semiconductor manufacturing apparatuses and office equipment.
Recent enthusiastic development is found in ultrasonic motors. Electrooptic
materials will become key components in displays and optical communication
systems in the future. For thermistor applications, semiconductive ferroelectric
ceramics with a positive temperature coefficient (PTC) of resistivity due to a
junction effect have been developed from barium titanate based materials.
 General View of Ferroelectrics
21
CHAPTER ESSENTIALS_________________________________
1. Category:
Dielectrics > Piezoelectrics > Pyroelectrics > Ferroelectrics

2. Ferroelectric materials are very promising for a variety of applications:

high permittivity capacitors,
ferroelectric memories,
pyroelectric sensors,
piezoelectric/electrostrictive transducers,
electrooptic devices,
PTC thermistors.

3. Origin of spontaneous polarization:

dipole coupling with the local field -- driving force of ionic displacement
elastic anharmonic term -- impeding ionic displacement

4. Field-induced strains:
piezoelectric strain -- x = d E in an asymmetric crystal
strain associated with polarization reorientations
electrostriction -- x = M E2 in a symmetric crystal
Piezostriction: the difference of the harmonic term of the two equivalent
springs
Electrostriction: anharmonicity of the equivalent springs

5. Electrooptic effect: refractive index change with an external electric field. The
secondary Kerr effect is frequently used. Devices making use of this effect
require a pair of crossed polarizers arranged at a 45o angle with respect to
the electric field direction.
___________________________________________________________________

CHAPTER PROBLEMS

1.1 Consider a 1-dimensional infinite chain of two kinds of ions +q and -q,
arranged alternately over a distance a. Calculate the Coulombic potential
energy at one +q ion, and obtain the Madelung energy.

Hint

Remember U = - (1/4πε0 ε) (q 2 / r).

Use an expansion series of log(1 + x) = x - x2/2 + x3/3 - x4/4 + ...

1.2 Pottasium tantalate niobate K(Ta0.65Nb 0.35 )O3 is cubic at room

temperature. By applying an electric field Ez along a perovskite [100]
22 Chapter 1

axis, it exhibits an induced polarization P3 , electrostrictive strains x3 =

Q11P32 and x1 = Q12P32, and refractive index changes ∆n 3 = - (1/2)
n 03g 11P32 and ∆n 1 = - (1/2) n03g 12P32. Experimental values of these are:
Q11 = 0.090 m4 C-2, Q12 = - 0.035 m4 C-2; g11 = 0.136 m4 C-2, g 12 = -
0.038 m4 C-2. Comparing the absolute values between Q and g and the
ratios Q11/ Q12 and g11/g 12 , discuss similarities in terms of the crystal
lattice compactness along and perpendicular to the electric field.

REFERENCES
1) C. Kittel: Introduction to Solid State Physics 6th edition, Chap.13, John Wiley &
Sons, New York (1986)
2) W. Kinase, Y. Uemura and M. Kikuchi: J. Phys. Chem. Solids, 30, 441 (1969)
3) K. Uchino and S. Nomura: Bull. Jpn. Appl. Phys. 52, 575 (1983); K. Uchino, S.
Nomura, L. E. Cross, R. E. Newnham and S. J. Jang: Electrostrictive Effect in
Perovskites and Its Transducer Applications, J. Mater. Sci., 16, 569 (1981).
4) K. Uchino: Electrostrictive Actuators: Materials and Applications, Bull. Amer.
Ceram. Soc. 65, No.4, 647 (1986).