Chapter -1

Ferroelectric Materials - A Review

A brief discussion on the general characteristics of the ferroelectric materials is

presented m this chapter The classification of ferroelectric materials and various

physical properties of ferroelectric crystals are described m brief The reviews of

the work carried out by the various investigators m modifying the properties of

the TGS crystals are presented Aims and objectives of the present work are also

discussed
 Ferroelectric Materials: A Review

11 CRYSTALS

"Crystals are fascinating substances" and man has admired crystals ever
since he realized their beauty and rarity (Dr. A.K.Batra)[l] A single crystal is a
regular array of atoms repeated with the same orientation m three dimensions
and without interruption throughout the sample The study of growth and
characterization of single crystals is receiving increasing importance for both
academic research and technology Dr M.D.Aggarwalfl] calls crystals "The
unacknowledged pillars of the world of modern technology" Well
characterized smgle crystals are necessary m fundamental research as well for
device fabrication The growth of bulk size crystals without defects is a
challenging task for crystal growers. Crystal growth is a multi disciplinary field,
which demands collaboration of physicists, crystallographers, chemical and
process engineers, electrical and mechanical engineers, instrumentation engineers,
material scientists and numerical simulation specialists Modern solid-state
electronics is based on a crystal growth revolution that has now made possible the
growth of large dislocation free crystals of silicon and gallium arsemde, the
production of rods and laser materials like ruby and sapphire, epitaxial growth,
integrated circuit technology, the production of magnetic materials and piezo
electrics like quartz Highly perfect crystals of materials like sodium chloride,
lithium fluoride are needed for optical and x-ray spectroscopy. In the fields of
conversion of solar energy, information storage and manipulation m large
capacity digital computers, crystal bubble memories and improved artificial
sensors, improved communication, single crystal may find extensive applications
Crystals are used in almost all electronic gadgets such as computers, video
recorders, Blue ray technology and several other devices that have made our lives
so comfortable.

1
Chapter I

12 GENERAL CHARACTERISTICS OF FERROELECTRIC MATERIALS

Ferro electricity is a property of certain non-conducting crystals, or

dielectrics, that exhibit spontaneous electric polarization that can be reversed in
direction by the application of an appropriate electric field All ferroelectric
crystals are necessarily both pyroelectric and piezoelectric. Many lose these polar
properties at the transition or Curie temperature Tc A nonpolar phase above Tc is
the so-called paraelectric phase Ferroelectricity, though initially considered to be
a rarity m nature, was later observed to be of frequent occurrence Ferroelectricity
was first discovered m 1920 by J Valasek [2], during an investigation of the
anomalous dielectric properties of Rochelle salt. A second ferroelectric material,
KDP, was found m 1935 by Busch and Scherrer and was followed by some of its
isomorphs The third major substance, BaTiCb, was reported by A von Hippel m
1944. Smce then, this small group has been joined by large number of pure
materials and many more mixed crystal systems Even though ferroelectricity was
first recognized m Rochelle salt by Valasek the theoretical development of the
phenomenon began with the phenomenological theories by Mueller m 1940,
Ginzburg m 1945 and by Devonshire m 1949 [3]. The microscopic understanding
of the phenomena came through gradually m 1960 with the recognition of the
fundamental relationship between lattice dynamics and ferroelectricity by
Anderson and Cochran [3]

1.2.1 Classification of ferroelectric materials:

According to elements of symmetry all crystals can be divided into 32

different classes or point groups [4] These point groups, according to the point
group symmetry they possess, are shown m table 11 These 32 point groups are
sub divisions of the seven basic crystal systems, which, m the order of ascending
symmetry, are triclmic, monoclimc, orthorhombic, tetragonal, trigonal, hexagonal

2
 Ferroelectric Materials: A Review

and cubic. Out of 32 point groups, eleven are characterized by the existence of a

center of symmetry; they are thus called eentrosymmetric The remaining twenty-

one crystal classes do not have a center of symmetry, they are non-centnc The

absence of a center of symmetry makes it possible for crystals m these classes to

have one or more polar axes. 20 out of these are piezoelectric as they have the

property that a polarization can be induced by an applied mechamcal stress One

class, (cubic class 432) although lackmg a centre of symmetry, is not piezoelectric

because of its combined symmetry elements The schematic tree of different

classes of crystal systems and their property classifications are shown m the figure

11
......................................... 1. TRICLINIC
CRYSTAL i 2- MONOCLINIC
*- 7 3. ORTHORHOMBIC
SYSTEMS [ 4. TETRAGONAL
........ 5. TRIGONAL
6. HEXAGONAL
7. CUBIC

NO CENTER OF SYMMETRY
21 POINT GROUPS
32 POINT GROUPS

1- - - - - - - - - - - - - - - --------------------- ,
CENTER OF SYMMETRY
11 POINT GROUPS

!——,
1
PIEZOELECTRIC NON PIEZOELECTRIC
20 POINT GROUPS 1 POINT GROUP

j—————I
j
POLAR or PYROELECTRIC NON PYROELECTRIC
10 POINT GROUPS 10 POINT GROUPS

1- - - - - - - - - - - - - - - ■

FERROELECTRIC NON FERROELECTRIC

Figure 1.1 The schematic tree of different classes of crystal systems [5]

Out of the twenty piezoelectric classes ten are characterized by the fact that

they have a unique polar axis. These crystal classes exhibit the property that a

finite and permanent value- of the polarization, known as spontaneous

polarization, exists m the absence of an applied field or stress, and such dielectric

materials are known as polar materials or pyroelectric materials

3
Chapter I

The polar materials m which the spontaneous polarization can be reversed

i

and reoriented by an application of an external electric field are known as

ferroelectric materials. Ferroelectrics are a sub-group of pyroelectric materials

which m turn is a subgroup of the piezoelectric materials Hence, the ferroelectrics

possess both the piezo and pyroelectric properties m addition to their umque

ferroelectric properties.

Crystal Centro- Non-centrosymmetnc

Pomt groups
structure symmetric
Piezoelec tnc Pyroelectric

Tricbmc 1,1 1 1 1

Monocknic 2, m, 2/m 2/m 2, m 2, m

Orthorhombic 222, mm2, mmm mmm 222, mm2 mm2,

4,4,4/m, 422,
4/m, 4, 4,422,
Tetragonal 4mm, 42m, 4, 4mm
(4/m)mm 4mm, 42m
(4/m)mm

Trigonal 3, 3, 32, 3m, 3m 3, 3m 3, 32, 3m 3, 3m

6, 6, 6/m, 622,
6/m, 6, 6, 622,
Hexagonal 6mm, 6m2, 6,6mm
(6/m)mm 6mm, 6m2
(6/m)mm

23, m3, 432,

Cubic m3, m3m 23,43m
43m, m3m

Table 1.1 Point groups for the seven crystal systems.

1.2.2 Ferroelectric Phase transitions:

As the temperature is increased a ferroelectric undergoes a phase transition

which is accompanied by the disappearance of spontaneous polarization and by a

change m the symmetry of the crystal lattice. This temperature is called the Curie

temperature, denoted byTc Above Tc the material becomes paraelectric. This

phase with the highest symmetry is called the prototype phase. In most, but not
4
 Ferroelectric Materials: A Review

all cases, this phase is non-polar and occurs m the highest temperature phase The
phase transitions can be divided into two types First order phase transition and
second order phase transition First-order (or discontinuous) phase transitions are
those that involve latent heat; i.e, during such a transition a system either absorbs
or releases a certain amount of energy In a first order structural phase transition
there is a discontinuity m order parameter, enthalpy, entropy, volume through
the phase transition temperature and at the transition point the two phases can
coexist m equilibrium First order transitions are also often accompanied with a
region where one phase is stable and the other metastable [3]. Accordingly,
thermal hysteresis [6], where the Curie point is different upon heating and
cooling, is commonly observed m ferroelectric perovskites. First order phase
transitions usually occur by a mechanism of nucleation and growth of the new
phase within the old

p*

Ps(0)

0 Te T

Figure 1.2 Schematic representation of spontaneous polarization Ps upon cooling

through a ferroelectric phase transition* (a) First order phase transition (b)
Second order phase transition

Second order (or continuous) phase transitions, m contrast, do not mvolve

the transfer of latent heat Upon cooling through a second order structural
transition temperature the order parameter increases continuously from zero at
the phase transition temperature There is no discontinuity m enthalpy, entropy
or volume and continuous phase transitions are not accompamed by regions of
metastabihty; even at the phase transition temperature only one phase can exist
In mixtures of vapour and liquid phases, for some special combination of
5
Chapter I

temperature and pressure, the first order phase transition can become second
order This pomt is known as the critical point at this point the fluid is sufficiently
hot and compressed that the distinction between the liquid and gaseous phases
becomes almost nonexistent [7]. Importantly, the excess free energy (or dnvmg
force) AG goes continuously to zero at the phase transition regardless of the order
of the transition The two types of phase transition are shown schematically m
figure 12 for ferroelectric materials where the spontaneous polarization is
proportional to the order parameter A discontinuous "jump" m polarization is
characteristic of a first order ferroelectric phase transition (figure 1 2(a))

1.2.3 Spontaneous polarisation, Domains and Domain Wall:

Pyroelectric crystals show spontaneous polarization Ps m certain

temperature range. If the magnitude and direction of Ps can be reversed by an
external electric field, then sue„h crystals are said to show ferroelectric behavior
Hence, all single crystals which show ferroelectric behavior are pyroelectric, but
not vice versa
Ferroelectric crystals typically exhibit separate regions with uniform
polarisation called "domains" which differ m their spontaneous polarization
direchon Within a domain all the electric dipoles are aligned m the same
direction. The number of distinct spontaneous polarization directions m a
ferroelectric depends on its pomt group symmetry. When two domains with
distinct polarization directions Ps meet commensurately within a crystal, they
form domain walls that separate the two domains The walls that separate
domains with oppositely oriented polarization are called 180° walls and those that
separate regions with mutually perpendicular polarization are called 90° walls
(figure 1.3). In the domain-wall region, the polarization changes from one domain
to another continuously but steeply [8] The ferroelectric domain walls are
therefore much narrower than the domam walls m ferromagnetic materials
6
 Ferroelectric Materials: A Review

Observations with transition electron microscopy show that the width of the
domain walls m ferroelectric materials is of the order of 1-10 nm [3,8,9]. The width
of the domains increases with increasing temperature, as the phase transition is
approached [10]. There may be many domains m a crystal A ferroelectric smgle
crystal, when grown, has multiple ferroelectric domains A smgle domam can be
obtamed by domain wall motion made possible by the application of an
appropriate electric field A very strong field could lead to the reversal of the
polarization in the domam, known as domam switching [11,12] For all the
uniaxial ferroelectric crystals, and the biaxial orthorhombic ferroelectncs, the
polarization, Ps can exist only along their crystallographic c-axis. For the
monoclmic ferroelectncs, the polarization can exist either along the 2-fold rotation
axis, b (as in pomt group 2), or m any direction within the mirror plane, a-c (as m
pomt group m) There is no restriction on the direction of polarization m a triclimc
system. For a polarization m direction +P, there can a polarization m the
direction-P, forming at least two degenerate polarization states Additional
degeneracies can come from the number of distinct polarization directions
possible m a crystal system.
The domam walls (figure 1 3) are also restricted by symmetry to distinct
crystallographic planes within the crystal depending on the nature of the walls.
All ferroelectncs can possess 180° domain walls (or antiparallel domam walls)
that separate +P and -P polarization domains For uniaxial trigonal and
hexagonal materials, only 180° walls can exist Controlling and patterning these
domain walls m uniaxial ferroelectric materials such as lithium mobate and
lithium tantalate is extremely important for many electro-optic and frequency
conversion devices For tetragonal systems, 90° walls can also exist, where the
latter refers to walls separating two perpendicular polarization directions, which
is an eqmvalent of crystallographic twinning

7
Chapter I

180° 90°

Figure 1.3 Some common types of ferroelectric domain walls Arrows mdicate the
direction of polarization Ps, m each domain and the hatched plane mdicates
the domam wall [5]

Example materials include ferroelectric barium titanate, lead titanate, and

strontium barium mobate Orthorhombic crystal systems such as potassium
mobate and potassium titanyl phosphate can have 60°, 90°, 120°, and 180° domam
walls. The domain wall orientations become more numerous and complex for
monoclimc and triclimc systems [13]. The most common symmetries among
materials m nature are the low symmetries such as monoclimc, triclimc, and
orthorhombic systems [14].

1.2.4 Polarisation reversal and hysteresis loop:

The pyroelectric materials that are ferroelectric are distinguished by the fact
that the polarization direction in a ferroelectric can be changed, at least partially,
by an externally applied electric field The polarization reversal can be observed
by measuring the ferroelectric hysteresis as shown m figure 14 As the electric
field strength is mcreased, the domains start to align m the positive direction
giving rise to a rapid mcrease m the polarization (AC) At very high field levels,

the polarization reaches a saturation value Ps(max). The polarization does not fall to

zero when the external field is removed At zero external fields, some of the
domains remain in their switched state hence the crystal will show a remanent
polarization PR.
8
 Ferroelectric Materials: A Review

oooooooooo
Polarization (pC/cm 2 )

.50 E2-------x.----------- 1------------ —-------- t—-------1------------ -

•300 -200 -100 0 100 200 300
Electric field (kV/cm)

Figure 1.4 Polarization vs Electric Field (P-E) hysteresis loop for a typical ferroelectric
crystal [15]

The crystal cannot be completely depolarized until a field of magnitude AF

is applied m the negative direction. The external field needed to reduce the

polarization to zero is called the coercive field strength Ec. If the field is increased

to a more negative value, the direction of polarization flips and hence a hysteresis

loop is obtained. The value of the maximum spontaneous polarization ps(max) is

obtained by extrapolating the linear portion of the curve CD onto the polarization

axes. The hexagons with gray and white regions m figure 14 represent

schematically repartition of two polarization states m the ferroelectric material at

different fields.

The phenomenological theory of polarisation reversal was proposed by

Pulvari and Kuebler [16]. There are a lot of experimental and theoretical works on
the mechanism of polarization reversal and domain dynamics. Both direct

microscopic observations of domains during switchmg and electrical

measurements on the bulk crystals have yielded information on these Some of

the earlier investigations are on TGS [17, 18] The theory gives expressions for

9
Chapter I

crystal polarization P, electric field dependence of tmax (the time correspondmg

to the maximum switching current, imax) and imax Considering that the current is

proportional to the rate of change of polarization, a differential equation for

polarization reversal is obtained as

dP + 7TL~(p-ps)=°
..11
dt xmax

t=0,P=-Ps and the equation 11 integrates to

t
=l-2e maxj .. 1.2

The field dependence of tmax was obtained from the plot of l/tmax verses E and
is given by
——=yEe_a/E ......................................... 13
lmax

Where a is the activation field, and is related to the threshold field needed to
initiate nucleation and y is proportional to the displacement mobility Both a and
y depend on temperature, crystal thickness and the impurity content. The above
equation takes care of both the low field and high field switchmg behavior of the
process. At low fields, the exponential term is prominent representing the"
nucleation of domains and at high field strengths when E>a, the field
dependence is linear similar to the expression derived by Merz [19].

= y [e—<x] 14
xmax

From expressions 12 and 13, one obtains the following expression that describes
the switchmg dynamics as observed by experiments

P _I ytEe' •a,:/E)
—=l-2e 2 1.5

10
 Ferroelectric Materials: A Review

From expression 1 2, the expression for the current transient is expressed as

dP
i=A—=2APS t
-y-—e 2[tmaxJ
—f . .16
dt
Ul t2
‘-max

where A is the electroded area of the crystal Maximum current iraax occurs at

t= tmax/ therefore equation 1 6 becomes

2AP _I
—-e ^ .1.7
max t
max

Using equation 13, the equation 1.7 is rewritten as

_I
i = 2e 2APvEe' -ot/E ...... 18
max s

This phenomenological model successfully explains the switching dynamics m

BaTiOa [16] and TGS [20]

From equation 1.7 the polarisation from the switchmg transient is expressed as

p _ 1max ^max
19
s 2e“*A

Polarization calculated from the switching transient is well m agreement

with the values obtamed from the hysteresis loop measurements for BaTiCb [16]

and TGS and TGFB crystals [20]

1.2.5 Piezoelectricity:

"Piezo" originates from the Greek word "piezem" meaning to press or to

squeeze Smce the discovery of the piezoelectric effect by Pierre and Jacques Curie

m 1880, piezoelectric materials have been utilized in a wide variety of sensor and

actuator applications [21]. Piezoelectricity is the ability of certam non-

centrosymmetric crystals to develop an electric charge proportional to applied

mechanical stress This is the direct piezoelectric effect [6,21] Conversely, when

11
Chapter I

an electric field is applied along certain directions m a piezoelectric crystal, the

crystal is strained by an amount proportional to the applied field This is called
the converse piezoelectric effect The class of the piezoelectric materials includes
ferroelectrics
The direct piezoelectric effect is described by a linear relationship between
stress X,k applied to a piezoelectric material and the resulting charge density D,.
n direct y
ui—aijk ik .110

where dtJk is the third-rank tensor of piezoelectric coefficients, measured m

[C/N], The converse piezoelectric effect is described by a linear relationship

between the strain X9 developed m a piezoelectric material and the applied

electric field Ek •

X,=d—E„ =(<£"/.......................... 1.11

where t denotes the transposed "matrix". The unit of the converse piezoelectric
coefficient is [m/V] The piezoelectric coefficients for the direct and converse
piezoelectric effects are thermodynamically identical 1 e dconverse = ddtrect. Because

the strain and the stress are symmetrical tensors, the tensor of the piezoelectric
coefficients is symmetrical with respect to the correspondmg indices, dIJk=dlkJ

The piezoelectric coefficient measured m the direction of the applied field is

usually called the longitudinal coefficient, and that measured m the direction
perpendicular to the field is known as the transverse coefficient [21] Other
piezoelectric coefficients are denominated shear coefficients

I—....- ........ VP.«................. '"I |

r=.............
Figure 1 5 (a) Piezoelectric crystal sample

For a thin piezoelectric disc of the type shown m figure 1 5(a), where the
diameter-to thickness ratio is greater than 10, the shear components of stress and

12
 Ferroelectric Materials: A Review

strain can be ignored [22]. In this context, the significant piezoelectric strain
constants are the 6si and d33 components
A

Y o
UJ
u-

A
d33
V

Figure 1 5 (b) Piezoelectric coefficients

The d3i coefficient describes the radial expansion and contraction of a poled
piezoelectric disc when an electric field is applied across the thickness of the disc
and the d33 coefficient describes the expansion or contraction through the
thickness of the disc when the electric field is applied across the thickness of a
poled piezoelectric disc [23], as shown m the figure 1.5(b) In the piezoelectric
strain coefficient (d) the two subscripts, first of which refers to the electrical
direction (electric field or dielectric displacement) and the second refers to the
mechamcal direction (stress or strain) For example m cbi coefficient the first
subscript i e 3 is displacement or electric field direction and the second subscript
i.e. 1 is stress or strain direction

1.2.6 Dielectric Properties:

The dielectric properties of a polar material can be described m terms of the

electric field (E), polarization (P) and displacement field (D) and are connected by
the relation [24]
D=s0 E + P . ................. 112

where £0 = 8.854 xlO'12 C/Vm is the permittivity of free space The polarization (P)

can also be expressed as

13
Chapter I

P=S0%E.........................................................113
and therefore equation 1.12 becomes

D=s0(l+X)E .......................................... 114

where % is the dielectric susceptibility of the material. The dielectric permittivity

of the material is defined as
s=s0(1+x) 1-15

and therefore equation 114 becomes

D=sE.................. . .116

The ratio of the permittivity of a material to the permittivity of free space is called
the relative permittivity, or the relative dielectric constant e'
?'= £/
1.17

This ratio can be the charge stored on a set of electrodes separated by a given
material to the charge stored on an identical set of electrodes separated by the
same distance m vacuum when placed m an identical electric field [25] The value
of the dielectric constant can vary depending on the conditions of the material.
The clamped value of the dielectric constant (sdamp) is always smaller than the free

dielectric constant (s’free) The relationship between the clamped and free relative

dielectric constants is given by:

^clamp (i ^ )^free " ' •«••• • .. ••••••••••. 4.43

where k is the electromechanical coupling coefficient of the piezoelectnc material

[26]. The capacitance C of a capacitor filled with a dielectric is

c=s0e'A/ 149

where A is the area of the two parallel plates and d is the spacing between them
When ac voltages are applied to a piezoelectric material, there is some charge loss
due to resistive leakages and dielectric absorption. The dissipation factor or loss

14
 Ferroelectric Materials; A Review

tangent (tan 6), is used to characterize the amount of this loss tan8=s"/s' where e"

and s' are the imaginary and real components of the complex permittivity [25].

12.7 Pyroelectric Effect:

Spontaneous polarisation of a pyroelectric material can be changed by a

change m temperature [27, 28] The pyroelectric effect is the generation of a
current or voltage caused by a temperature change m a pyroelectric material.
When a pyroelectric crystal is heated or cooled, the internal or external electrical
conduction generally cannot provide enough current to compensate for the
change m polarisation with temperature, and the crystal develops an electric
charge on its surface If the Crystal sample is electroded and the external
resistance is connected across it, the current flow is a pyroelectric current. This
effect can be used for detecting radiation via thermal effects once it is absorbed.
The pyroelectric effect is only found m polar crystals The mechanism of
pyroelectric infrared detection is as follows Usually, the surface charge of a
pyroelectric crystal is neutralized by free carriers from the interior and exterior of
the crystal. The average time needed for interior free carriers to neutralize surface
charge is xE=s/o, where e is the dielectric constant and a is the conductivity of
the crystal. When an infrared radiation of frequency / is made to fall on the
pyroelectric crystal the light will be absorbed by the crystal and temperature of
the crystal rises. The change m temperature alters the lattice spacing of the
pyroelectric crystal and produces a change in spontaneous polarization An
electric current is generated to balance the polarization change and, thus, the
surface charge of the crystal will also be modulated with frequency /. If f> l/tE,

free carriers from the interior of the material do not have enough time to ,
compensate for the alternating surface charge An alternating current will
therefore flow m an external resistance connected to the pyroelectric crystal The
magnitude of this current is given by

15
Chapter I

( dPs^ YdP.'lfdT^l A „ ( dT
IP=A =A —- 120
l dt J IdT j l dt j l dt
where A is the area of electrodes, dPs/dt is the rate of change of spontaneous

polarization, dT/dtis the heating rate, and dPs/dT is the pyroelectric coefficient X
When the temperature change AT is small, the pyroelectric coefficient can be
considered to be a constant Then, the magnitude of signal current Ipis
proportional to dT/dt. The materials for pyroelectric applications should have
large dT/dt. A large dT/dt can be achieved with materials that have a large IR
absorption coefficient, a small specific heat (cp), low density, and small physical
dimensions High Curie temperatures (Tc), high pyroelectric coefficients (A,) as

well as low dielectric constants (s) and low dielectric loss are desirable material
properties for pyroelectric infrared detectors especially for high frequency
applications The performance of a pyroelectric detector is strongly dependent on
its material properties The various figures of merits for pyroelectric materials can
be expressed as [29-31]
FV = %' " Figure of merit for high voltage responsivity...................1 21

Fvld = Vo “ figure of merit for vidicon application.........................1.22

Fd = Yrr, - Figure of merit for high detectivity ..............................1.23

where X is the pyroelectric coefficient and e' is the real part of the dielectric
permittivity and e" is the imaginary part of the dielectric permittivity
Improvements m the pyroelectric properties of triglycme single crystals are
of considerable interest. It has been observed that TGS shows a tendency to
depolarize with time, and is a drawback associated with these crystals [32] Efforts
to tailor the properties of TGS crystals for practical design requirements led to
numerous studies on TGS doped with rare earths, organic and inorganic dopants
with various metal ions [30-32, 41-93] Efforts made m the present investigation
are discussed m the chapter VI.

16
 Ferroelectric Materials: A Review

1.3 TRIGLYCINE SULPHATE CRYSTALS

1 3.1 Structural Characteristics:

Matthias, Milks & Remeika first reported the ferroelectric behavior m TGS
in 1956 [33] The crystal structure of TGS single crystal was reported by Hoshino
et all [34] The chemical formula for triglycine sulphate single crystal is
(NH2CH2COOH)3 H2S04. Crystallographic data for triglycme sulphate,

(nh2CH2COOH)3 H2S04, were reported by Wood and Holden [4] is as follows

a’ = 9.15 A; b' = 12.69A; c' = 5.73 ± 0.03 A; (3 = 105°40' + 20'

The space group at room temperature is P2,, the experimental density is

p=1.69g/cm3 and the unit cell volume is 640(Aj A detailed structural

investigation of the polar room-temperature phase was carried out by Hoshino et

al. [34] using three-dimensional X-ray diffraction data

a = 9.42 A; b = 12.64 A; c = 5.73A; p = 110°23'

It has three glycine molecules and one sulphuric acid molecule The
chemical formula of glycine is NH2CH2COOH. In glycme, the molecule exists in

the zwitter-iome form NH3CH2COO", where the His removed from the hydroxyl

group of carboxylic group and re-attached to the amine (NH2) group to form

(nh3) [35]. The analysis of the crystal structure [34] shows that the two H atoms

of the sulphuric acid is protonated to the carboxylic groups of two glycme

molecules and there by the name of Glycine3 H2S04 becomes "Glycme di-

Glycimum sulfate" having the formula (NH3CH2C00_)(NH3CH2C00H)2(S04_).

The monoprotonated glycines I and III takes the planar configuration, while the
glycme IE takes the zwitter-ion configuration and the sulphate ion has lost both
of its protons. Thus glycme I and III are designated as glycimum ions, while the
zwitter-ion glycme II is simply designated as glycme.

17 i
Chapter I

TGS is a ferroelectric crystal having a typical second order phase transition

at the Curie temperature 49 °C Below the Curie temperature TGS exists m a

ferroelectric phase and ferroelectric is found along the two fold polar axis (b-axis)
[4,36] The X-ray analysis has shown that the crystal symmetry of TGS is

monoclimc with the space group P2i m the ferroelectric phase and in the
paraelectric phase the structure exhibits two mirror planes at y = V4 and y = %

and the space group becomes P2i/m

Tnglycme Sulphate (TGS) crystal is an important pyroelectric material used

for developmg detectors for fourier-transform Infrared spectrometry (FTIR),

environmental analysis monitors, earth observation cameras, astronomical

telescopes, military systems, pyroelectric bolometers and target faces vidicons

based on the pyroelectric effects [37,38], This crystal is one of the potential

detector materials for pyroelectric infrared sensors by virtue of its high

pyroelectric coefficient, reasonably low dielectric constant and large figures of

merit [39,40] TGS detectors have the great advantage over electronic detectors m

that they operate at room temperature and do not require cryogenic cooling [38]

TGS crystals have a maximum pyroelectric sensitivity at room temperature and

therefore do not require the coolmg for detection of temperature changes, TGS

exhibit a large spontaneous electrical polarization below their Curie point The

spontaneous polarization is measured m terms of dipole moment per unit

volume, or, with reference to the charges induced on the surfaces perpendicular
to the polarization, m terms of charge per unit area. Research and development
efforts have been mainly directed towards the further improvements m the

pyroelectric properties of TGS using a wide variety of dopants Many

modifications were made to TGS without changing the basic crystal structure

13 2 Influence of dopant on Triglycine Sulphate crystal properties;

Generally it is considered that the dipole moment m TGS crystals is mainly

due to the glycine molecules [41], Therefore any other molecule similar to glycine

18
 Ferroelectric Materials: A Review

molecule but with a larger contribution m terms of dipole moment is incorporated

into TGS, improved pyroelectric properties of the crystal are expected. Effects of
several organic dopants on TGS such as alanine, Urea, Thiourea, Aniline, Serine,
Guanidine, L-lysme, L-cystme, L-asparagme, L-tyrosme, Threonine, L-valme and
Sarcosine were extensively studied [31,32,41-82] Table 1 2 summarizes the effect
of various dopants on the properties of the TGS single crystals.
Alanine is one of the dopant studied extensively by various authors (42-59)
Doping of L-a-alanme into TGS improves the pyroelectric properties, but the
doped crystals develop a large internal stress and the crystals crack durmg
polishing [32]. The growth of TGS with alanine doping, growth mechanisms, the
domam structures, spontaneous polarisation and change m the mtemal bias field
is studied by various authors [32,43- 44, 48-57]. It is found that large mtemal bias
field is mduced m grown crystals. Several authors have studied the pyroelectric
properties of alanine doped TGS, pyroelectric detector performance and figure of
merits [31,42,47,54,57,58] and the figure of merits was found improved.
J.E Lorenzo et.al.[45] studied thermal hysteresis and relaxation effects near the
transition temperature and found there is a shift m the transition temperature
during the coolmg and the heating run m the measurements of dielectric
constant The temperature dependence of internal bias field m LATGS crystals
found mdependent of temperature near Tc [46]. Dagmar Barasova [59] measured
various piezoelectric coefficients and also studied the temperature dependence of
the piezoelectric coefficient da ‘ The Urea doped TGS crystals exhibited better
growth yield and pyroelectric properties [29,60] and the figure of merit was
increased nearly 5 times compared to undoped TGS [29] 15 wt% thiourea doped
TGS crystals showing higher pyroelectric coefficient and smaller piezoelectric
coefficient compared to pure TGS [61]. The pyroelectric coefficients and figure of
merits are found increased m aniline family of molecules doped TGS crystals
[41,62-64]. S C.Mathur et al. studied the temperature dependence of dc

19
Chapter I

conductivity [62] of mtroamline doped TGS crystals and found dopant supports
the conduction process and the conductivity is much more than the alanine
doped TGS crystals The influence of serine admixture on the internal bias field,
permittivity and P-E hysteresis were studied [49,65-67] Bias field, permittivity
and coercive field are found increased where as spontaneous polarisation is
decreased. Guanidine doped TGS crystals exhibited better pyroelectric properties
[68]. L-lysine doped TGS crystals showing excellent pyroelectric properties and
higher internal bias field compared to 1-alanme doped TGS crystals [70,71]. In
these crystals growth rate m the positive b-side of the crystal is higher than in the
negative b-side [69]. The transition temperature of the L-cystme [72] doped TGS
crystals increased by 3.5 °C compared to pure TGS crystals and dielectric
permittivity and hardness found decrease There are not many improvements m
the properties of the pure TGS crystal due to the doping of L-asparagme [73,74]
and L-tyrosme [75,76] Morphology changes observed m the L-asparagme doped
TGS and small increase m the coercive field of the L-tyrosme doped TGS are
insignificant TGS crystals have been admixtured with L-threomne, DL-threomne
and L-methiomne [77] and the grown crystals exhibit some interesting properties
From the dielectric and the pyroelectric studies of these crystals it has been found
that L-threonme (10 wt%) addition to TGS yields the highest value of the
pyroelectric coefficient amongst the ammo acids The dielectric studies of these
crystals shows that there is a decrease m the dielectric permittivity with increased
transition temperature [77-79] but transition temperature is found decrease with
the mcrease m doping concentration [78] The decrease m spontaneous
polarisation and increase m coercive field is observed with the increasing doping
concentration [78]. The role of L-valme on the nucleation process is studied [55].
Nonyuki Nakatam found the L-vahne [49] doped TGS crystals shows no bias
field and observed same domain structure as undoped TGS but bias field is found
m sarcosme doped TGS crystals [49,82]. However S.Erdei et al. found 0.1 kV/cm

20
 Ferroelectric Materials: A Review

and 0.18 kV/cm internal bias field m 10 and 20 mol% L-Valine doped TGS and
high pyroelectric and dielectric constant values at both the phase transition and
room temperatures [80,81]
Inorganic acids whose radical structures and lomc radii are similar to S04-
can be used as dopants to substitute H2S04 [83] C.S Fang et.al doped the TGS

crystals with the inorganic dopants like HC104, HBF4, H3B03 H3As04 andH3P04and

studied its pyroelectric properties [41]. Doping TGS with HC104 or HBF4 or H3B03

do not improve the pyroelectric properties but dopants like H3As04andH3P04

exhibited a significant enhancement m the pyroelectric properties of TGS

through partial substitution of S04" by As04-andP04- respectively. Effect of
phosphoric acid (H3P04) doping was studied by various authors [52,58,84-86].

High figure of merit with larger values of transition temperature (Tc= 57.5 °C) is
observed m deuterated ATGSP crystals [87]
There are few investigations about the modifications on the properties of
TGS crystals doped with metal ions Metallic ions like Fe3+ and Cr3+ ions modify
the morphology of TGS but decrease the pyroelectric coefficient and spontaneous
polarization [89], Mg2+ and Cu2+ modify growth habit but marginally mcrease the
pyroelectric material figure of merit [89]. Li+ and Mn2+ produced high
pyroelectric coefficient and high dielectric constant, so there is little change m
material figure of merit [90]. The absorption spectra and optical parameters are
studied for the TGS crystals doped with Cu2+, Mn2+ and Ni2+[91]. Nickel (Ni2+)
doped crystals do not show any improvements m the growth characteristics [92]
TGS crystals doped with Cobalt (II) phosphate show higher values of coercive
field [93]. The rare earths dopants like samarium sulfate, ytterbium sulfate and
terbium sulfate changed the morphology of TGS crystals and decreased dielectric
constant, pyroelectric coefficient and figure of merit [30]. Hardness and
piezoelectric coefficient is found increased.

21
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Chapter I

14 AIMS AND OBJECTIVES OF THE PRESENT WORK

In recent years there has been a renewed interest m the efficient pyroelectric
materials because of their great potential as pyroelectric thermal detectors for
infrared detection and imaging. Infrared detectors and detector arrays are used m
many fields of application today, both civilian and defence oriented Triglycine
sulphate (TGS) crystals have been the subjects of intensive investigations as a
material havmg superior optical memory and utilizing pyroelectric effects m
infrared detectors. However TGS crystal has a disadvantage of depolarization as
time elapses The depolarization effect can be reduced by doping the crystal with
optically active molecules and also by irradiating the crystals with graded l

dosages of electron energy. A large number of researchers at the international and

national level are engaged m improving the physical characteristics of triglycme
sulphate crystals by dopmg it with suitable organic dopants. Therefore, studies
dealing with the influence of irradiation as well as of dopmg TGS crystal on their
physical properties are of particular interest. In recent years, the interest m
studying pure, irradiated and doped TGS crystals has increased because of their
promise m various devices. Krajewski et.al. observed that the molecules of higher
dipole moment produces higher pyroelectric coefficient [63] However,
M.A.Gaffer et al. measured higher pyroelectric coefficient for the dopants of lower
dipole moment [94]. Keeping this m view, the present investigation will be
carried out with the growth of four new TGS crystals doped with
4-(dimethylamino) benzaldehyde [(CH3)2NC6H4CHO] (dipole moment 0.1976D),

iminodiacetic acid [HN(CH2COOH)2] (dipole moment 24092D), n-bromo

succinimide [C4H4BrN02] (dipole moment 6 1924D), and Succinic acid

[(CH2COOH)2] (dipole moment 3.6933D), by slow evaporation method at ambient

/ constant temperature These organic dopants are not tried so far and these large
molecular dopants may improve the physical properties of TGS The present

24
 Ferroelectric Materials: A Review

investigation aims at the study of optical and electrical parameters of pure and
doped TGS crystals and the effect of electron irradiation on these parameters.
Such a study might be promising since the individual effect of dopants and
irradiation on TGS crystals is quite valuable.
A comparative study is also planned, to investigate the role of organic
dopant molecules of different character m identical concentration m the solution
of growth and with nearly the same growth conditions on optical, dielectric,
pyroelectric and piezoelectric properties of TGS crystals
The effect of pulsed electron beam irradiation on optical properties of pure
and doped TGS single crystals is also planned. One of the most effective and
informative methods to investigate the nature of the pulsed electron beam
interaction with a sample is IR spectroscopic study Dielectric and pyroelectric
properties of electron irradiated pure and doped TGS crystals have not yet been

investigated. It is planned to include the temperature dependence of dielectric

constant, pyroelectric coefficient and dc conductivity of electron irradiated pure
and doped TGS crystals

Objectives:

1. To grow pure and doped single crystals of triglycme sulphate.

2. To characterize the grown crystals using powder x-ray diffraction, Fourier
transform infrared spectroscopy, Vickers micro hardness and morphology
3. To study the optical (UV-visible) and electrical (dielectric, pyroelectric,
piezoelectric, P-E hysteresis, dc conductivity, scanning electron microscopy)
characteristics of pure and doped triglycme sulphate crystals.
4 To mvestigate the effect of electron irradiation on the electrical and optical
characteristics of pure and doped triglycme crystals.

25
Chapter I

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Chapter I

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