Applications of Ferroelectric Ceramic Materials

Applications of Ferroelectric Ceramic Materials
http://www.rci.rutgers.edu/~ecerg/projects/ferroelectric.html
Ferroelectric Ceramics : Processing, Properties & Applications

Ahmad Safari, Rajesh K. Panda, and Victor F. Janas
Department of Ceramic Science and Engineering, Rutgers University, Piscataway NJ 08855, USA
Keywords:
Ferroelectricity, piezoelectricity, pyroelectricity, dielectrics, ceramics, single crystals, thin films.
Abstract: Ceramic materials and single crystals showing ferroelectric behavior are being used in many applications in electronics and optics. A large number of applications of ferroelectric ceramics also exploit properties that are an indirect consequence of ferroelectricity, such as dielectric, piezoelectric, pyroelectric and electro-optic properties. This review introduces the basic principles and characteristics of ferroelectric materials and lists various materials chosen from single crystals, ceramics, polymers and ceramic-polymer composites which show ferroelectric behavior. Many different applications arising from ferroelectricity and related phenomena in ceramics and thin films have been discussed with their processing techniques.
1 : Introduction :
Ferroelectricity is a phenomena which was discovered in 1921. The name refers to certain magnetic analogies, though it is somewhat misleading as it has no connection with iron (ferrum) at all. Ferroelectricity has also been called Seignette electricity, as Seignette or Rochelle Salt (RS) was the first material found to show ferroelectric properties such as a spontaneous polarization on cooling below the Curie point, ferroelectric domains and a ferroelectric hysteresis loop. A huge leap in the research on ferroelectric materials came in the 1950's, leading to the widespread use of barium titanate (BaTiO ) based ceramics in capacitor applications and piezoelectric transducer
3
devices. Since then, many other ferroelectric ceramics including lead titanate (PbTiO ), lead
3
zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), and relaxor ferroelectrics like lead magnesium niobate (PMN) have been developed and utilized for a variety of applications. With the development of ceramic processing and thin film technology, many new applications have emerged. The biggest use of ferroelectric ceramics have been in the areas such as dielectric ceramics for capacitor applications, ferroelectric thin films for non volatile memories, piezoelectric materials for medical ultrasound imaging and actuators, and electro-optic materials for data storage and displays.
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In the past few decades, many books and reviews have been written explaining the concepts of ferroelectricity in materials [1-12]. In this chapter, an effort is made to introduce the basic principles governing ferroelectricity and list the various materials which exhibit these properties. The processing of ferroelectric ceramics in general, with a few examples are described. Finally, a few important applications of ferroelectric materials are briefly discussed.
2 : General properties of Ferroelectrics :
2.1 : Crystal Symmetry :
The lattice structure described by the Bravais unit cell of the crystal governs the crystal symmetry. Though there are thousands of crystals in nature, they all can be grouped together into 230 microscopic symmetry types or space groups based on the symmetry elements [13,14]. Most of the crystals possess symmetry elements in addition to the repetitions expressed by the crystal lattice. The operation of any single symmetry element of the group leaves the pattern of symmetry unchanged. In studying the physical properties of crystals, only the orientations of the symmetry elements and not their relative positions are important. Hence, if only the orientations of the symmetry elements are taken into account, then the macroscopic symmetry elements in crystals reduce to a center of symmetry, mirror plane, 1-, 2-, 3-, 4- or 6- fold rotation axes and 1-, 2-, 3-, 4- or 6- fold inversion axes. A combination of these symmetry elements gives us the macroscopic symmetry also called as point groups. It can be shown by the inspection of the 230 space groups that there are just 32 point groups. As shown in Table 1, the seven crystal systems can be divided into these point groups according to the point group symmetry they possess.
Table 1 : Point groups for the seven crystal systems.
Crystal Structure
Point Groups
CentroSymmetric
Non-centrosymmetric
Piezoelectric
Pyroelectric
_ Triclinic 1, 1
_ 1 1 1
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Monoclinic
2, m, 2/m
2/m
2, m
2, m
Orthorhombic
222, mm2, mmm
mmm
222, mm2
mm2,
__ Tetragonal 4, 4, 4/m, 422, 4mm, 42m, (4/m)mm 4/m, (4/m)mm
__ 4, 4, 422, 4mm, 42m 4, 4mm
__ Trigonal 3, 3, 32, 3m, 3m
__ 3, 3m 3, 32, 3m 3, 3m
__ Hexagonal 6, 6, 6/m, 622, 6mm, 6m2, (6/m)mm 6/m, (6/m)mm
__ 6, 6, 622, 6mm, 6m2 6, 6mm
_ Cubic 23, m3, 432, 43m, m3m m3, m3m
_ 23, 43m ------
The thirty-two point groups can be further classified into (a) crystals having a center of symmetry and (b) crystals which do not possess a center of symmetry. Crystals with a center of symmetry include the 11 point groups labeled centrosymmetric in Table 1. These point groups do not show polarity. The remaining 21 point groups do not have a center of symmetry (i.e. non-centrosymmetric). A crystal having no center of symmetry possesses one or more crystallographically unique directional axes. All non-centrosymmetric point groups, except the 432 point group, show piezoelectric effect along unique directional axes. Piezoelectricity is the ability of certain crystalline materials to develop an electrical charge proportional to a mechanical stress. It was discovered by the Curie brothers in 1880. Piezoelectric materials also show a converse effect, where a geometric strain (deformation) is produced on the application of a voltage. The direct and converse piezoelectric effects can be expressed in tensor notation as,
P =d
i
ijk jk
(Direct Effect) (1)
e =d
ij
kij
E (Converse Effect) (2)

k
where P is the polarization generated along the i- axis in response to the applied stress s , and
i jk
kij
is the piezoelectric coefficient. For the converse effect, e
ij
is the strain generated in a

i
particular orientation of the crystal on the application of electric field E along the i-axis. [13]
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Out of the twenty point groups which show the piezoelectric effect, ten point groups (including 1, 2, m, mm2, 4, 4mm, 3, 3m, 6, and 6mm) have only one unique direction axis. Such crystals are called polar crystals as they show spontaneous polarization.
2.2 : Spontaneous Polarization and Pyroelectric Effect :
The spontaneous polarization is given by the value of the dipole moment per unit volume or by the value of the charge per unit area on the surface perpendicular to the axis of spontaneous polarization. The axis of spontaneous polarization is usually along a given crystal axis. Although a crystal with polar axes (20 non-centrosymmetric point groups) shows the piezoelectric effect, it is not necessary for it to have a spontaneous polarization vector. It could be due to the canceling of the electric moments along the different polar axes to give a zero net polarization. Only crystals with a unique polar axis (10 out of 21 non-centrosymmetric point groups) show a spontaneous polarization vector P along this axis. The value of the spontaneous polarization depends on the
s
temperature. This is called the pyroelectric effect which was first discovered in tourmaline by Teophrast in 314 B.C. and so named by Brewster in 1824 [15]. The pyroelectric effect can be described in terms of the pyroelectric coefficient p . A small change in the temperature D T, in a crystal, in a gradual manner, leads to a change in the spontaneous polarization vector D P given
s
by,
D P = p D T (3)
s
Figure 1 shows the variation of the spontaneous polarization P with temperature for a BaTiO
s
ferroelectric crystal. An increase in the temperature leads to a decrease in the spontaneous polarization BaTiO has a negative pyroelectric coefficient. The polarization suddenly falls to zero
3
on heating the crystal above the Curie point. [16]
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Fig. 1 : The temperature dependence of spontaneous polarization P crystal. [16]
for BaTiO
ferroelectric
2.3 : Ferroelectric Domains and Hysteresis Loop :
As described above, pyroelectric crystals show a spontaneous polarization P

s
in a certain
temperature range. If the magnitude and direction of P can be reversed by an external electric field, then such crystals are said to show ferroelectric behavior. Hence, all single crystals and successfully poled ceramics which show ferroelectric behavior are pyroelectric, but not vice versa. For example tourmaline shows pyroelectricity but is not ferroelectric. Ferroelectric crystals possess regions with uniform polarization called ferroelectric domains. Within a domain, all the electric dipoles are aligned in the same direction. There may be many domains in a crystal separated by interfaces called domain walls. A ferroelectric single crystal, when grown, has multiple ferroelectric domains. A single domain can be obtained 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 domain, known as domain switching. [17,18] The main difference between pyroelectric and ferroelectric materials is that the direction of the spontaneous polarization in ferroelectrics can be switched by an applied electric field. The polarization reversal can be observed by measuring the ferroelectric hysteresis as shown in Fig. 2. As the electric field strength is increased, the domains start to align in the positive direction giving rise to a rapid increase in the polarization (OB). At very high field levels, the polarization reaches a saturation value (P ). The polarization does not fall to zero when the external field is
sat
removed. At zero external field, some of the domains remain aligned in the positive direction, hence the crystal will show a remnant polarization P . The crystal cannot be completely
r
depolarized until a field of magnitude OF is applied in the negative direction. The external field
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needed to reduce the polarization to zero is called the coercive field strength E . If the field is
c
increased to a more
Fig. 2 : A Polarization vs. Electric Field (P-E) hysteresis loop for a typical ferroelectric crystal. [12]
negative value, the direction of polarization flips and hence a hysteresis loop is obtained. The value of the spontaneous polarization P (OE) is obtained by extrapolating the curve onto the
s
polarization axes (CE).
2.4 : Curie Point and Phase Transitions :
All ferroelectric materials have a transition temperature called the Curie point (T ). At a
c
temperature T > T the crystal does not exhibit ferroelectricity, while for T < T it is ferroelectric.
c c
On decreasing the temperature through the Curie point, a ferroelectric crystal undergoes a phase transition from a non-ferroelectric phase to a ferroelectric phase. If there are more than one ferroelectric phases, the temperature at which the crystal transforms from one ferroelectric phase to another is called the transition temperature. Early research work on ferroelectric transitions has been summarized by Nettleton [19,20]. Figure 3 shows the variation of the relative permittivity e with temperature as a BaTiO crystal is cooled from its paraelectric cubic phase to
r 3
the ferroelectric tetragonal, orthorhombic, and rhombohedral phases. Near the Curie point or transition temperatures, thermodynamic properties including dielectric, elastic, optical, and thermal constants show an anomalous behavior. This is due to a distortion in the crystal as the phase structure changes. The temperature dependence of the dielectric constant above the Curie
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point (T > T ) in ferroelectric crystals is governed by the Curie-Weiss law :

c
e=e
+ C/(T-T ) (4)
o
Fig. 3 : Variation of dielectric constants (a and c axis) with temperature for BaTiO . [21]
3
where e is the permittivity of the material, e

o
is the permittivity of vacuum, C is the Curie

o
constant and T is the Curie temperature. The Curie Temperature T is different from the Curie point T . T is a formula constant obtained by extrapolation, while T is the actual temperature
c o c
where the crystal structure changes. For first order transitions T phase transitions T = T . [5]
o c
< T while for second order

c
3 : Types of ferroelectric materials :

The types of ferroelectric materials discussed in this chapter have been grouped according to their structure. The four main types of structures discussed include the corner sharing oxygen octahedra, compounds containing hydrogen bonded radicals, organic polymers and ceramic polymer composites.
3.1 : Corner Sharing Octahedra :
A large class of ferroelectric crystals are made up of mixed oxides containing corner sharing
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octahedra of O
2-
ions schematically shown in Fig. 4. Inside each octahedron is a cation B

a+ a+ b+ 2-
b+
where
'b' varies from 3 to 6. The space between the octahedra are occupied by A
ions where 'a' varies
from 1 to 3. In prototypic forms, the geometric centers of the A , B and O ions coincide, giving rise to a non-polar lattice. When polarized, the A and B ions are displaced from their geometric centers with respect to the O ions, to give a net polarity to the lattice. These displacements occur due to the changes in the lattice structure when phase transitions take place as the temperature is changed. The formation of dipoles by the displacement of ions will not lead to spontaneous polarization if a compensation pattern of dipoles are formed which give zero net dipole moment. The corner sharing oxygen octahedra discussed in this chapter includes the perovskite type compounds, tungsten bronze type compounds, bismuth oxide layer structured compounds, and lithium niobate and tantalate.
2-
3.1.1 : Perovskites : Perovskite is a family name of a group of materials and the mineral name of calcium titanate (CaTiO ) having a structure of the type ABO . Many piezoelectric (including ferroelectric)
3 3
ceramics such as Barium Titanate (BaTiO ), Lead Titanate (PbTiO ), Lead Zirconate Titanate
3 3
(PZT), Lead Lanthanum Zirconate Titanate (PLZT), Lead Magnesium Niobate (PMN), Potassium Niobate (KNbO ), Potassium Sodium Niobate (K Na NbO ), and Potassium Tantalate Niobate
3 x 1-x 3
(K(Ta Nb
x
1-x
)O ) have a perovskite type structure. Most of the above are discussed in detail
3
below.
(a) Barium Titatate (BaTiO , BT)

3
Barium titanate (BaTiO ) has a paraelectric cubic phase above its Curie point of about 130 C. In
3
the temperature range of 130 C to 0 C the ferroelectric tetragonal phase with a c/a ratio of ~ 1.01 is stable. The spontaneous polarization is along one of the [001] directions in the original cubic structure. Between 0 C and -90 C, the ferroelectric orthorhombic phase is stable with the polarization along one of the [110] directions in the original cubic structure. On decreasing the temperature below -90 C the phase transition from the orthorhombic to ferroelectric rhombohedral phase leads to polarization along one of the [111] cubic directions. The spontaneous polarization on cooling BaTiO below the Curie point T is due to changes in the
3 c
crystal structure. As shown in Fig. 5 the paraelectric cubic phase is stable above 130 C with the center of positive charges (Ba
2+
and Ti
4+
ions) coinciding with the center of
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Fig. 4 : (a) A cubic ABO (BaTiO ) perovskite-type unit cell and (b) three dimensional network of
3 3
corner sharing octahedra of O
2-
ions [12].
Fig. 5 : The crystal structure of BaTiO (a) above the Curie point the cell is cubic; (b) below the
3
Curie point the structure is tetragonal with Ba
2+
and Ti
4+
ions displaced relative to O
2-
ions.
negative charge (O ). On cooling below the Curie point T , a tetragonal structure develops where
c
2-
the center of Ba and Ti ions are displaced relative to the O ions, leading to the formation of electric dipoles. Spontaneous polarization developed is the net dipole moment produced per unit volume for the dipoles pointing in a given direction [22]. Various A and B site substitutions in different concentrations have been tried to see their effect on the dielectric and ferroelectric properties of BaTiO . Sr
3 2+ 2+
2+
4+
2-
substitutions to the A site have been

2+
found to reduce the Curie point linearly towards room temperature. The substitution of Pb
for
Ba raises the Curie point. The simultaneous substitution into both A and B sites with different ions can be used to tailor the properties of BaTiO . The effect of various isovalent substitutions on
3
the transition temperatures of BaTiO ceramic are shown in Fig. 6 [5, 23-25].
3
The dielectric properties of BaTiO are found to be dependent on the grain size [26-28]. Figure 7
3
shows the variation of dielectric constant with temperature for BaTiO ceramics with a fine (~ 1 m
3
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m) and coarse (~ 50 m m) grain size. Large grained BaTiO ( 1 m m) shows an extremely high
3
dielectric constant at the Curie point. This is because of the formation of multiple domains in a single grain, the motion of whose walls increases the dielectric constant at the Curie point. For a BaTiO ceramic with fine grains (~ 1 m m), a single domain forms inside each grain. The
3
movement of domain walls are restricted by the grain boundaries, thus leading to a low dielectric constant at the Curie point as compared to coarse grained BaTiO [29]. The room temperature
3
dielectric constant (e ) of coarse grained ( 10 m m) BT ceramics is found to be in the range of

r
1500-2000. On the other hand, fine grained ( ~1 m m) BT ceramics exhibit a room temperature dielectric constant between 3500-6000. The grain size effect on the dielectric constant at room temperature has been explained by the work of Buessem et. al. [30] and Arlt et. al. [31] Buessem and coworkers proposed that the internal stresses in fine grained BaTiO must be much
3
greater than the coarse grained ceramic, thus leading to a higher permittivity at room temperature. Arlt studied the domain structures in BT ceramics and showed that the room
Fig. 6 : The effect of isovalent substitutions on the transition temperatures of BT ceramic [5].
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Fig. 7 : The variation of the relative permittivity (e ) with temperature for BaTiO ceramics with
r 3
(a) 1 mm grain size and (b) 50 mm grain size. [29]
temperature e reached a peak value at a critical grain size of ~0.7 mm. He concluded that the
r
enhanced dielectric constant was due to the increased 90 domain wall density. The mobility of the 90 domain walls in very fine grained BT is hindered and only less than 25 % of the e was
r o
achieved. As the BT ceramics have a very large room temperature dielectric constant, they are mainly used multilayer capacitor applications. The grain size control is very important for these applications.
(b) Lead Titanate (PbTiO , PT)

3
Lead titanate is a ferroelectric material having a structure similar to BaTiO
with a high Curie
point (490 C). On decreasing the temperature through the Curie point a phase transition from the paraelectric cubic phase to the ferroelectric tetragonal phase takes place. Lead titanate ceramics are difficult to fabricate in the bulk form as they undergo a large volume change on cooling below the Curie point. It is the result of a cubic (c/a = 1.00) to tetragonal (c/a = 1.064) phase transformation leading to a strain of > 6%. Hence, pure PbTiO ceramics crack
3
and fracture during fabrication. The spontaneous strain developed during cooling can be reduced by modifying the lead titanate with various dopants such as Ca, Sr, Ba, Sn, and W to obtain a crack free ceramic. One representative modified lead titanate composition that has been extensively investigated recently is (Pb Ca ) ((Co W ) Ti )O with 2 mol. %
0.76 0.24 0.50 0.50 0.04 0.96 3
MnO added to it. This composition has a decreased c/a ratio and Curie point of 255 C). [32-35]
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(c) Lead Zirconate Titanate [Pb(Zr Ti

x
1-x
)O , PZT]
3
Lead Zirconate Titanate (PZT) is a binary solid solution of PbZrO (orthorhombic structure) and PbTiO
3
an antiferroelectric
a ferroelectric (tetragonal perovskite structure). PZT has a

4+ 4+
perovskite type structure with the Ti and Zr ions occupying the B site at random. The PZT phase diagram is shown in Fig. 8. At high temperatures PZT has the cubic perovskite structure which is paraelectric. On cooling below the Curie point line, the structure undergoes a phase transition to form a ferroelectric tetragonal or rhombohedral phase. In the tetragonal phase, the spontaneous polarization is along the <100> set of directions while in the rhombohedral phase the polarization is along the <111> set of directions. As shown in Fig. 9 most physical properties such as dielectric and piezoelectric constants show an anomalous behavior at the morphotropic phase boundary (MPB). The MPB separating the two ferroelectric tetragonal and orthorhombic phases has a room temperature composition with a Zr/Ti ratio of ~ 52/48. PZT ceramics with the MPB composition show excellent piezoelectric properties. The poling of the PZT ceramic (see Section 4) is also easy at this composition because the spontaneous polarization within each grain can be switched to one of the 14 possible orientations (eight [111] directions for the rhombohedral phase and six [100] directions for the tetragonal phase). Below the Zr/Ti ratio of 95/5 the solid solution is antiferroelectric with an orthorhombic phase. On the application of an electric field to this composition a double hysteresis loop is obtained. This is because of the strong influence of the antiferroelectric PbZrO phase. [5]
3
In order to suit some specific requirements for certain applications, piezoelectric ceramics can be modified by doping them with ions which have a valence different than the ions in the lattice. Piezoelectric PZT ceramics having the composition at the MPB can be doped with ions to form "hard" and "soft" PZT's. Hard PZT's are doped with acceptor ions such as K , Na
3+ 3+ 3+ + +
(for A site) and
Fe , Al , Mn (for B site), creating oxygen vacancies in the lattice [37, 38]. Hard PZT's usually have lower permittivities, smaller electrical losses and lower piezoelectric coefficients. These are more difficult to pole and depole, thus making them ideal for rugged applications. On the other hand, soft PZT's are doped with donor ions such as La (for A site) and Nb , Sb (for B site) leading to the creation of A site vacancies in the lattice [39-42]. The soft PZT's have a higher permittivity, larger losses, higher piezoelectric coefficient and are easy to pole and depole. They can be used for applications requiring very high piezoelectric properties.
3+ 5+ 5+
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Fig. 8 : The PZT phase diagram. [36]
Fig. 9 : The effect of composition on the dielectric constant and electromechanical coupling factor k in PZT ceramics. [5]
p
(d) Lead Lanthanum Zirconate Titanate ((Pb
1-x
La )(Zr
x
1-y
Ti )
y 1-x/4
O V
3
B 0.25x
O , PLZT)
3
PLZT is a transparent ferroelectric ceramic formed by doping La ions on the A sites of lead zirconate titanate (PZT). The PLZT ceramics have the same perovskite structure as BaTiO and
3
3+
PZT. The transparent nature of PLZT has led to its use in electro-optic applications. Before the development of PLZT, the electro-optic effect was seen only for single crystals. The two factors
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that are responsible for getting a transparent PLZT ceramic include the reduction in the anisotropy of the PZT crystal structure by the substitution of La free ceramic by either hot pressing or liquid phase sintering. The (Pb
1-x 3+
and the ability to get a pore
general La )
x 1-0.5x B
formula (Zr
1-y y
for
A
PLZT O
is
given
by
(Pb
1-x
La )(Zr
x
Ti )V
0.5x 3.
The first formula assumes that La
1-y 3+
Ti )
y 1-x/4 3
O V
0.25x 3
and
ions go to the A site and
vacancies (V ) are created on the B site to maintain charge balance. The second formula assumes that vacancies are created on the A site. The actual structure may be due to the combination of A and B site vacancies. The room temperature phase diagram of PLZT system is shown in Fig. 10. The different phases in the diagram are a tetragonal ferroelectric phase (F ), a rhombohedral ferroelectric phase (F ), a
T R
cubic relaxor ferroelectric phase (F ), an orthorhombic antiferroelectric phase (A ) and a cubic

C 0
paraelectric phase (P )
C
The electro-optic applications of PLZT ceramics depends on the composition. Figure 11 shows the hysteresis loops for various PLZT compositions from the phase diagram. PLZT ceramic compositions in the tetragonal ferroelectric (F ) region show hysteresis loops with a very high
T
coercive field (E ). Materials with this composition exhibit linear electro-optic behavior for E < E .
C C
PLZT ceramic compositions in the rhombohedral ferroelectric (F ) region of the PLZT phase
R
diagram have loops with a low coercive field. These PLZT ceramics are useful for optical memory applications.
Fig. 10 : Room temperature phase diagram of the PLZT system. The regions in the diagram are, a tetragonal ferroelectric phase (F ); a rhombohedral ferroelectric phase (F ); a cubic relaxor
T R
ferroelectric phase (F ); an orthorhombic antiferroelectric phase (A ); and a cubic paraelectric

C O
phase (P ). [46]
C
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Fig. 11 : Representative hysteresis loops obtained for different ferroelectric compositions (a) F (b) F (c) F and (d) A
R C O
regions of the PLZT phase diagram. [46]
PLZT ceramic compositions with the relaxor ferroelectric behavior are characterized by a slim hysteresis loop. They show large quadratic electro-optic effects which are used for making flash protection goggles to shield them from intense radiation. This is one of the biggest applications of the electro-optic effect shown by transparent PLZT ceramics. The PLZT ceramics in the antiferroelectric region show a hysteresis loop expected from an antiferroelectric material. These components are used for memory applications. [9, 10, 43-46]
(e) Lead Magnesium Niobate (Pb(Mg
1/3
Nb
2/3
)O , PMN):
3
Relaxor ferroelectrics are a class of lead based perovskite type compounds with the general formula Pb(B ,B )O where B is a lower valency cation (like Mg
1 2 3 2+ 1 5+
, Zn
2+
, Ni
2+
, Fe
3+
) and B is a
2 1/3
higher valency cation (like Nb

/3 3
, Ta
5+
,W
5+
). Pure lead magnesium niobate (PMN or Pb(Mg
Nb
)O ) is a representative of this class of materials with a Curie point at -10 C. The main
differences between relaxor and normal ferroelectrics is shown in Table 2. Relaxor ferroelectrics like PMN can be distinguished from normal ferroelectrics such as BaTiO and
3
PZT, by the presence of a broad diffused and dispersive phase transition on cooling below the Curie point. Figure 12 shows the variation in the dielectric properties with temperature for PMN ceramic. It shows a very high room temperature dielectric constant and a low temperature dependence of dielectric constant. The diffused phase transitions in relaxor ferroelectrics are due to the compositional heterogeneity seen on a microscopic scale. For
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Table 2 : Differences between normal and relaxor ferroelectrics. [47]
Property
Normal Ferroelectric
Relaxor Ferroelectric
Dielectric temperature dependence
Sharp 1 or 2 order transition at Curie point T
st
nd
Broad diffused phase transition at Curie maxima
Dielectric frequency dependence
Weak Frequency dependence
Strong frequency dependence
Dielectric Behavior in paraelectric range ( T > T )

c
Follows Curie - Weiss law
Follows Curie - Weiss square law
Remnant polarization (P )
R
Strong P
Weak P
Scattering of light
Strong anisotropy
Very weak anisotropy to light
Diffraction of X-Rays
Line splitting due to deformation from paraelectric to ferroelectric phase
No X-Ray line splitting
Fig. 12 : Variation of the dielectric properties of PMN with temperature. [11]
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example, there is disorder in the B site for Pb(Mg
1/3
Nb
2/3
)O . The composition of Mg and Nb is

3
not stoichiometric in the microregions, leading to different ferroelectric transition temperatures which broadens the dielectric peak. The relaxors also show a very strong frequency dependence of the dielectric constant. The Curie point shifts to higher temperatures with increasing frequency. The dielectric losses are highest just below the Curie point T . For relaxors which have a second order phase transition, the
c
remnant polarization, P , is not lost at the Curie point but gradually decreases to zero on
r
increasing the temperature beyond T [47-50].

c
The most widely studied relaxor material is the PMN-PT solid solution system. The phase diagram of PMN-PT is shown in Fig. 13. The addition of PT, which has a Curie point of 490 C, shifts the T
o c
of the composition towards higher temperatures. The morphotropic phase boundary composition (0.65 PMN and 0.35 PT) is piezoelectric in nature. Ceramics with this composition are excellent candidates for piezoelectric transducers. Compositions with a Curie point near room temperature (like 0.95 PMN and 0.10 PT) have very large dielectric constants (e > 20,000) which makes them
r
very attractive for multilayer capacitor and strain actuator applications. As opposed to piezoelectric strain (see Section 2.1) the electrostrictive component of strain is proportional to the square of the polarization. Writing the strain in tensor notation,
e =Q
ij
ijkl
P P (5)
k l
P = e e E (6)
o r
where e is the strain, 'Q' is the electrostrictive coefficient and 'P' is the polarization. In eq. (6) e is
o
the permittivity of vacuum, e is the dielectric constant and 'E' is the electric field. As shown in
r
eqs. (5) and (6), the total strain obtained from electrostrictive effect is a (e ) [51].
r
3.1.2 : Tungsten Bronze type Compounds :
The tungsten bronze type ferroelectric crystals have a structure similar to tetragonal tungsten bronze K WO (x<1). Lead niobate (PbNb O ) was one of the first crystals of the tungsten bronze
x 3 2 6
type structure to show useful ferroelectric properties. The site occupancy formula for this type of structure is given by (A ) (A ) (C) (B ) (B ) O . Figure 14 shows the schematic of the
1 2 2 4 4 1 2 2 8 30
projection of the tungsten bronze type structure on the (001) plane. For lead niobate the B and
1
sites are occupied by Nb
5+
ions. The open nature of the structure as compared to the
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perovskite allows a wide range of cation and anion substitutions without loss of ferroelectricity. At present, tungsten bronze family of oxide ferroelectrics, numbers more than 85.
Fig. 13 : Phase diagram for PMN-PT solid solution. [51]
Fig. 14 : Schematic diagram showing a projection of the tungsten-bronze structure on the (001) plane. The orthorhombic and tetragonal cells are shown by solid and dotted lines respectively. [12]
The ferroelectric crystals grown from solid solutions of alkali and alkaline earth niobates have shown great potential for being used as a material for laser modulation, pyroelectric detectors, hydrophones, and ultrasonic applications. The high Curie point (T = 560 C for lead niobate) of
c o
their compounds makes them suitable for high temperature applications.
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It is difficult to fabricate piezoelectric PbNb O
2 6
ceramics because of the formation of a stable temperature. Rapid cooling from the of the rhombohedral phase. Another large volume change due to phase cracking of the ceramic [52-53].
nonferroelectric rhombohedral phase on cooling to room sintering temperature is used to prevent the formation problem associated with this type of materials is the transformation on cooling below the Curie point, leading to
3.1.3 : Bismuth Oxide Layer Structured Ferroelectrics :
The two most important piezoelectric materials with the (Bi O )

2 2
2+
layer structure are bismuth
titanate (Bi Ti O
4 2 4 9
3 12
) and lead bismuth niobate (PbBi Nb O ). As shown in Fig. 15, the structure of
2 2 9 2+ 2 2
PbBi Nb O consists of corner linked perovskite-like sheets, separated by (Bi O )
layers.
The plate like crystal structure of these compounds leads to highly anisotropic ferroelectric properties. The ceramics fabricated from the (Bi O )
2 2 2+
layer compounds do not have very good
piezoelectric properties because of a very low poling efficiency. The piezoelectric properties have been shown to be improved by grain orientation during the processing step. One fabrication method involves the tape casting of plate like Bi Ti O and PbBi Nb O powders. The powders
4 3 12 2 4 9
get aligned during the formation of the green tape. The orientation is further enhanced on sintering. In the other method, the ceramic is hot forged leading to the orientation of the grains along the forged direction. [54-56] The bismuth oxide layer structured ferroelectrics may become important piezoelectric ceramics because of their higher stability, higher operating temperature (T
c
= 550-650 C), and higher
operating frequency. These ceramics are mainly useful for piezoelectric resonators which need to exhibit a very stable resonant frequency.
3.1.4 : Lithium Niobate and Tantalate :
Lithium niobate (LiNbO ) and lithium tantalate (LiTaO ) have similar structures. As shown in Fig.
3 3
16 the LiNbO
structure is actually a variant of the perovskite structure with a much more

3 3
restrictive arrangement. The ferroelectric behavior of LiNbO and LiTaO
was first discovered in

3
1949. Their crystals are very stable with very high Curie points of 1210 C and 620 C for LiNbO and LiTaO
3
respectively. These compounds are mainly used in the single crystal form and have
found applications in piezoelectric, pyroelectric and electro-optic devices [57, 58].
3.2 : Compounds Containing Hydrogen Bonded Radicals :
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Several water soluble ferroelectrics usually made in the single crystal form, have hydrogen bonded radicals in them.
Fig. 15 : One half of the tetragonal (4/mmm) unit cell of PbBi Nb O . A denotes the perovskite
2 2 9
double layer (PbNb O ) ; B is a hypothetical PbNbO and C denotes the (Bi O )

2 7 3 2 2
2-
2+
layers. [36]
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Fig. 16 : Structure of Ferroelectric LiNbO and LiTaO . [36]

3 3
Potassium dihydrogen phosphate (KH PO , KDP) has a tetragonal point group 42m. Hence this
2 4
crystal shows only piezoelectricity and no ferroelectric behavior at room temperature. On decreasing the temperature below the Curie point (T = -150 C) it transforms into a ferroelectric
c
orthorhombic phase. KDP single crystals exhibit very good electro-optical and non-linear optical properties [59, 60]. Triglycine sulfate (NH CH COOH) H SO , TGS) has a ferroelectric monoclinic point group 2 at
2 2 3 2 4
room temperature. On heating the crystal above the Curie point(T
= 49.7 C) the crystal
structure changes from the ferroelectric monoclinic point group to a centrosymmetric monoclinic point group 2/m. The TGS crystals show good pyroelectric properties [61,62]. Rochelle salt (NaKC H O
4 4 6
. 4H O, sodium potassium tantalate tetrahydrate) was the first

2
ferroelectric material to be discovered. Between the two Curie points of -18 C and +24 C, Rochelle salt is ferroelectric with a monoclinic point group 2. In the non-ferroelectric region, Rochelle salt has an orthorhombic point group 222 and hence it shows piezoelectric effect. Single crystals of Rochelle salt are widely used for piezoelectric transducers [2]. These water soluble crystals are still used due to their superiority over other crystals in some properties. Yet these crystals have many deficiencies such as weak ferroelectricity, low Curie point, poor mechanical properties, and deliquescence. For these reasons, KDP, TGS and Rochelle salt single crystals are being gradually replaced by piezoelectric ceramics.
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3.3 : Organic Polymers :
Polyvinylidene fluoride (PVDF, (CH -CF ) ) and copolymers of PVDF with trifluoroethylene
2 2 n
{P(VDF-TrFE)} have found applications as piezoelectric and pyroelectric materials. The piezoelectric and pyroelectric properties of these polymers are due to the remnant polarization obtained by orienting the crystalline phase of the polymer in a strong poling field. Hence the piezoelectric and pyroelectric properties depend on the degree of crystallinity of the polymer and the ferroelectric polarization of the crystalline phase [63, 64]. The piezo-polymers have some properties which make them better suited for use in medical imaging applications. The density of these polymers is very close to that of water and the human body tissues, hence there is no acoustic impedance mismatch with the body. The piezo-polymers are also flexible and conformable to any shape. However, there are also some problems associated with the piezoelectric polymers including the very low dielectric constant (K = 5-10) which could lead to electrical impedance matching problems with the electronics. The dielectric losses at high frequencies are very large for these piezopolymers. The polymers also have a low Curie point and the degradation of the polymer starts occuring at low temperatures (70-100 C). The poling efficiency is very low for polymer specimens with large thickness (>1mm).
3.4 : Ceramic Polymer Composites :
The drive for piezoelectric composites stems from the fact that desirable properties could not be obtained from single phase materials such as piezoceramics or piezopolymers. For example, in an electromechanical transducer, the desire is to maximize the piezoelectric sensitivity , minimize the density to obtain good acoustic matching with water, and make the transducer mechanically flexible to conform to a curved surface. Neither a ceramic nor a polymer satisfies these requirements. The requirement can be optimized by combining the most useful properties of the two phases which do not ordinarily appear together. Piezoelectric composites are made up of an active ceramic phase embedded in a passive polymer. The properties of the composite depend on the connectivity of the phases, volume percent of ceramic, and the spatial distribution of the active phase in the composite. The concept of connectivity developed by Newnham et al. [65] describes the arrangement of the component phases within a composite. It is critical in determining the electromechanical properties of the composite. Figure 17 shows the 10 different types of connectivities possible in a diphasic composite. It is shown in the form A-B where 'A' refers to the number of directions in which the active phase is self connected or continuous. 'B' shows the continuity directions of the passive phase. The density, acoustic impedance, dielectric constant and the piezoelectric properties like the electromechanical coupling coefficient k change with the volume fraction of the ceramic.
t
Optimum material and piezoelectric parameters for medical ultrasound applications are obtained for ~ 20-25 vol. % PZT ceramic in the composite. Many excellent reviews on the processing and properties of piezoelectric / polymer composites have been written in the last few years [66, 67]. The ultrasound imaging application is described in detail in Section 6.1.
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4 : PROCESSING OF FERROELECTRIC CERAMICS :
The final electromechanical properties of ferroelectric ceramic components greatly depend upon the processing conditions of the ceramic. Each step of processing has to be
Fig. 17 : Connectivity patterns for a diphasic solid A-B. The shaded parts represent the A phase while the white parts show the B phase. [66]
carefully monitored and controlled to get the best product. A flowchart for a typical ferroelectric oxide ceramic manufacturing process is shown in Fig. 18. The raw materials (metal oxides or metal carbonates) are first weighed according to the stoichiometric formula of the ferroelectric ceramic desired. The raw materials should be of high purity. The particle size of the powders must be in the submicron range for the solid phase reactions to occur by atomic diffusion. The powders are then mixed either mechanically or chemically. Mechanical mixing is usually done by either ball milling or attrition milling for a short time. Chemical mixing on the other hand is more homogeneous as it is done by precipitating the precursors in the same container. During the calcination step the solid phase reaction takes place between the constituents giving the ferroelectric phase. For example for the calcination of PZT, the starting raw materials PbO, TiO and ZrO are mixed in the molar ratio of 2:1:1, pressed into lumps and then calcined in
2 2
ambient air at 800 C to obtain the perovskite phase. The calcining temperature is important as it influences the density and hence the electromechanical properties of the final product. The higher the calcining temperature, the higher the homogeneity and density of the final ceramic product. However calcining PZT at T > 800 C could lead to lead loss, resulting in a detrimental effect on the electrical properties. So proper calcination at the right temperature is necessary to obtain the best electrical and mechanical properties [68, 69]. After calcining, the lumps are ground by milling. The green bodies should have a certain minimum
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density before they can be sintered. The desired shape and a minimum green density can be provided by various techniques including powder compaction, slip-casting, and extrusion. The choice of the method depends on the type of powder used, particle size distribution, state of agglomeration, desired shape, and thickness of the part
Fig. 18 : Flowchart for the processing of ferroelectric ceramics.
After shaping, the green bodies are heated very slowly to between 500-600 C in order to remove any binder present. The binder burnout rate should be 1-2 C/min in order to allow the gases to come out slowly without forming cracks and blisters in the ceramic part. After the binder burnout is over, the samples are taken to a higher temperature for sintering to take place. The sintering temperature and time should be optimum for proper densification to occur without abnormal grain growth. The sintering of oxide ceramics must be carried out in an oxidizing atmosphere or in air. For lead containing piezoelectric ceramics (PZT, PbTiO , PLZT, etc.) lead loss occurs at
3
temperatures above 800 C. In order to reduce the lead loss during sintering, the samples are kept in a sealed crucible with a saturated PbO vapor in it. The dipoles within a single domain have the same orientation. In ferroelectric ceramics with fine grain sizes (< 1 m m) each grain is a single domain with the domain wall at the grain boundary. If the grain size is larger (> 1 m m) then there could be multiple domains in a single grain. As schematically shown in Fig. 19 (a), when the ferroelectric ceramic is cooled after sintering, it does not show any piezoelectricity because of the random orientations of the ferroelectric domains in the ceramic. Piezoelectric behavior can be induced in a ferroelectric ceramic by a process called "poling". In this process a direct current (dc) electric field with a strength larger than the coercive field strength is applied to the ferroelectric ceramic at a high temperature, but below the Curie point. On the application of the external dc field the spontaneous polarization within each grain gets orientated towards the direction of the applied field, as shown in Fig. 19 (b). This leads to a net polarization in the poling direction. All the domains in a ceramic can never get fully aligned along the poling axis because the orientations of the polarization is restricted by the symmetry. For example, if the material has an orthorhombic perovskite structure then the polarization gets oriented along one of the eight [111] directions. The higher the number of possible orientations, the better is the poling efficiency. The reason for the good poling efficiency of PZT ceramic at the morphotropic phase boundary (MPB) is because of the availability of 14 easy polarization directions for this composition (eight along the [111] set of directions in an orthorhombic phase and six along the [100] set of direction in the tetragonal phase) [29].
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Fig. 19 : Schematic of the poling process in piezoelectric ceramics: (a) In the absence of electric field the domains have random orientation of polarization; (b) the polarization within the domains aligns in the direction of the applied field.
5 : Applications of Ferroelectric Ceramics :
5.1 : Capacitors :
A capacitor consists of a dielectric material sandwiched between two electrodes. The total capacitance for this device is given by
C = (e
0e r
A) / t (7)
where 'C' is the capacitance, e
is the permittivity of free space, e
is the relative dielectric
permittivity, 't' is the distance between the electrodes, and 'A' is the area of the electrodes. To get a high volumetric efficiency (capacitance per unit volume) the dielectric material between the electrodes should have a large dielectric constant, a large area and a small thickness. BaTiO
based ceramics having a perovskite type structure show dielectric constant values as high as 15,000 as compared to 5 or 10 for common ceramic and polymer materials. The high dielectric constant BaTiO ceramic based disk capacitors are simple to make and have captured more than
3
50% of the ceramic capacitor market. The volumetric efficiency can be further enhanced by using multilayer ceramic (MLC) capacitors. As shown in Fig. 20, the MLC capacitor structure consists of alternate layers of dielectric and electrode material. Each individual dielectric layer contributes capacitance to the MLC capacitor as the electrodes terminate in a parallel configuration. Hence the effective equation for capacitance becomes,
C = (ne
0e r
A) / t (8
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Fig. 20 : Schematic of a typical multilayer ceramic (MLC) capacitor.
where n = number of dielectric layers. The advances in tape casting technology have made it possible to make dielectric layers < 20 m m thick. This, combined with the use of a high dielectric constant ceramic like BaTiO , allows large capacitance values to be achieved in relatively small
3
volume capacitor devices. Many good reviews have been written on the state of the MLC capacitor technology and the technical challenges it faces [9, 10, 70, 71]. MLC capacitors are made by the tape casting process. A slurry with a suitable binder/solvent system is first made from the dielectric ceramic powder. Thin green sheets of the ceramic are then made by the tape casting process. An ink consisting of an electrode (Pd, Ag-Pd, etc.) and organics is screen printed on the dielectric sheets and then hundreds of sheets are stacked one on top of the other. A low pressure at a temperature between ~ 50 and 70 C is applied to laminate the sheets. These laminates are then diced to form a monolithic green MLC capacitor. The binder removal is accomplished by heating the green body very slowly to a temperature of ~ 300-400 C. The MLC capacitor is then sintered at a high temperature depending on the type of ceramic. After applying the terminations for the internal electrodes of the MLC capacitors, the capacitor is mounted on the electronic substrate by soldering. The critical steps in the fabrication of the MLC capacitors include the formation of thin uniform green sheets from the ceramic slurry. Any non-uniformity in the thickness could lead to dielectric breakdown during operation of the device. The co-firing of the ceramic tapes and metal electrodes should be compatible and should not lead to any reactions between the two. The high dielectric constants of the relaxors materials such as PMN make them ideal for MLC capacitor applications. Relaxors have various advantages over BaTiO based materials including
3
higher dielectric constants (e
25,000 vs. a maximum e
of 15,000 for BaTiO
based
ceramics). In addition, the temperature dependence of permittivity is much lower for relaxor materials, with no microstructure control needed for getting a shallow peak as in BaTiO . Much
3
finer grain sizes ( 1m m) can be used for relaxor ferroelectrics as compared to BaTiO (2-5m m)
3
to get high dielectric constant with low temperature dependence. The electric field dependence of the dielectric properties is also lower for relaxor dielectrics. Finally, the PbO based relaxors can be
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sintered at T < 1000 C, thus allowing the use of cheaper silver based electrodes instead of palladium based electrodes used with BaTiO based dielectrics which sinter at much higher
3
temperatures. In spite of various advantages of relaxor materials over BaTiO based dielectrics, they have some
3
inherent problems which have to be overcome before large scale production takes place. The dielectric losses for relaxors are the highest just below the Curie point. The permittivity is also highly frequency dependent in this temperature range. The processing of PbO based relaxor powders leads to the formation of a low dielectric constant pyrochlore phase, leading to a decrease in the relative permitivity of the dielectric. Also the relaxor ceramics are mechanically weak and it is difficult to reproduce the same properties from batch to batch, and control of the lead rich atmosphere is needed for proper sintering of the relaxor material [29].
5.2 : Applications of Ferroelectric Thin Films :
Ferroelectric thin films have attracted attention for applications in many electronic and electro-optic devices. Some of the important ferroelectric materials being used for making thin films include the perovskite type materials such as BaTiO , PbTiO , Pb(Zr Ti )O and
3 3 x 1-x 3
Pb(Mg
1/3
Nb
2/3
)O . Some of the non-perovskite materials being studied include Bi Ti O

3 4
3 12
and
(Pb,Ba)Nb O . Applications of ferroelectric thin films utilize the unique dielectric, piezoelectric,
2 6
pyroelectric, and electro-optic properties of ferroelectric materials. Some of the most important electronic applications of ferroelectric thin films include nonvolatile memories, thin films capacitors, pyroelectric sensors, and surface acoustic wave (SAW) substrates. The electro-optic devices being studied include optical waveguides and optical memories and displays.
5.2.1 : Ferroelectric Memories :
Semiconductor memories such as dynamic random access memories (DRAM's) and static random access memories (SRAM's) currently dominate the market. However, the disadvantage of these memories is that they are volatile, i.e. the stored information is lost when the power fails. The non-volatile memories available at this time include complementary metal oxide semiconductors (CMOS) with battery backup and electrically erasable read only memories (EEPROM's). These non-volatile memories are very expensive. The main advantages offered by ferroelectric random access memories (FRAM's) include non-volatile and radiation hardened compatibility with CMOS and GaAs circuitry, high speed (30ns cycle time for read/erase/rewrite) and high density (4(m m) cell size). As described in Section 2.2, ferroelectric materials spontaneously polarize on cooling below the T . The magnitude and direction of polarization can be reversed by the application of an external
c 2
electric field. The FRAM's made from ferroelectric thin films make use of this phenomena to store data. Data is stored by localized polarization switching in the microscopic regions of ferroelectric thin
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films. The FRAM's are non-volatile because the polarization remains in the same state after the voltage is removed (as ferroelectrics have a non-linear hysteresis curve). The radiation hardness of FRAM's allow for the use of devices containing these memories in harsh environments such as outer space [72-75]. The fabrication of ferroelectric thin films is done by three main methods including physical vapor deposition (PVD), chemical vapor deposition (CVD) and sol-gel processing. In PVD, precursors of the desired film composition are vaporized and deposited on the substrate by one of the sputtering techniques (i.e. rf magnetron sputtering, pulsed vapor deposition (PLD) etc.). This process produces films of very high quality. The CVD technique uses volatile chemical precursors which are vaporized on heated substrates. The advantages of this technique include high deposition rates, pinhole free films and good stoichiometric control. The sol-gel method involves the hydrolysis and condensation of organometallic precursors on the substrate. The deposited sol is annealed at low temperatures to crystallize and densify the film. The main advantages of this process include low temperature processing and low cost. Some other thin film deposition techniques that are used include liquid phase epitaxy (LPE), epitaxial growth by melting (EGM), evaporation methods, molecular beam epitaxy (MBE) and laser ablation [29, 76]. There are some critical processing parameters which have to be taken into consideration during the fabrication of ferroelectric thin films. The coercive field (E ) and remnant polarization (P )
c r
govern the hysteresis behavior of ferroelectric materials. PZT thin films are used for FRAM's because of its wide range of switching characteristics (hysteresis) obtained by changing the composition and deposition method. Hence they have to be chosen depending on the properties desired. The film thickness should be small to minimize the switching voltage. For PZT films with a thickness of ~ 200-300 nm the switching can be done at 5V. The interface between the substrate and the PZT film should be minimized to lower the formation of a non-ferroelectric region at the interface. The bottom electrode material should not react with the PZT film at the high temperatures of thin film deposition. For good performance of the device, the ferroelectric thin film should fulfill certain requirements. As the FRAM operates on the basis of polarization switching, the ferroelectric material should have a large remnant polarization and a small coercive field. To obtain it, the PZT composition and the thin film microstructure have to be optimized. One of the problems with ferroelectric memories is the tendency to lose its ability to store data after a certain number of read/write cycles. This phenomena is called fatigue. The PZT thin film FRAM's can withstand 10
15 12
cycles but
a fatigue resistance of 10 cycles is desired if the FRAM's are to replace semiconductor memories completely. The length of time a ferroelectric memory can store information (without switching) is called retention. The aging of polarization with time should be low and retention should be for at least a few years. The prospects of FRAM devices replacing the semiconductor memories in the near future are very bright. A great deal of work still must be done to obtain the optimum composition and microstructure of PZT thin films, and to study the interaction of the PZT film with the electrode material. Finally, the storage device should be reliable.
5.2.2 : Electro-optic Applications :
The requirements for using ferroelectric thin films for electro-optic applications include an optically transparent film with a high degree of crystallinity. The electro-optic thin film devices are
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of two types; one in which the propagation of light is along the plane of the film (optical waveguides) and the other in which the light passes through the film (optical memory and displays). These two types of applications are discussed below.
Ferroelectric Thin Film Waveguides : An optical waveguide controls the propagation of light in a transparent material (ferroelectric thin film) along a certain path. For the waveguide to work properly, the refractive index of the film should be higher that that of the substrate. For light to propagate in the waveguide, the thin film should be optically transparent. This can be achieved by fabricating the film under clean conditions and aiming for a fine grain size with ultra-phase purity and high density. A great deal of work has been done on making ferroelectric thin film waveguides from LiNbO and Li(Nb,Ta)O
3
using LPE, EGM, and MBE methods. PZT and PLZT thin films are even better candidates for optical waveguide applications because of their large electro-optic coefficients [77-79].
Ferroelectric Thin Film Optical Memory Displays: Ferroelectric thin films may replace the use of PLZT bulk ceramics for optical memory and display applications. The advantages offered by thin films for display applications include a simplification of the display device design and lower operating voltages as compared to PLZT ceramic devices. Optical memories using PLZT thin films will also need lower operating voltages. The material requirements for thin film optical memory and displays include large electro-optic coefficients and/or strong photosensitivities for the film. PZT and PLZT thin films show a lot of promise for these optical applications [29].
5.2.3 : Other Ferroelectric Thin Film Applications :
Thin Film Capacitors : As described in Section 5.1 the high dielectric permittivity of ferroelectric ceramics such as BaTiO , PMN and PZT make them very useful for capacitor applications. The MLC capacitors have
3
a very high volumetric efficiency (capacitance per unit volume) because of the combined capacitance of thin ceramic tapes (~ 10-20 m m) stacked one on top of the other. The volumetric efficiency of the MLC capacitor can be further increased if the thickness of the ceramic sheets can be made lower (< 10 m m). Thin film technology can be used to make dielectric layers as thin as 1 m m. BaTiO and PMN are the two important materials being looked at for thin film MLC
3
applications [80].
Pyroelectric Detectors : Pyroelectricity is the polarization produced due to a small change in temperature. Single crystals
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of triglycine sulfate (TGS), LiTaO , and (Sr,Ba)Nb O

3
2 6
are widely used for heat sensing
applications. The use of ferroelectric thin films for pyroelectric devices is advantageous because of the high cost of growing single crystals and also the thin film geometry is convenient for device design. PbTiO , (Pb,La)TiO and PZT have been widely studied for thin film pyroelectric sensing
3 3
applications [81-84]. Surface Acoustic Wave Substrates : As shown in Fig. 21 surface acoustic wave (SAW) devices are fabricated by depositing interdigital electrodes on the surface of a piezoelectric substrate. An elastic wave generated at the input interdigital transducer (IDT) travels along the surface of the piezoelectric substrate and it is detected by the output interdigital transducer. These devices are mainly used for delay lines and filters in television and microwave communication applications. Until recently, only piezoelectric single crystal substrates typically made from LiNbO , or LiTaO
3 3
were used as SAW substrates. Surface acoustic wave propagation in PZT thin films have been reported recently [85-86].
6 : APPLICATIONS OF PIEZOELECTRIC CERAMICS :
6.1 : Medical Ultrasound Applications :
Piezoelectric materials can be used for both active and passive transducer applications. In the passive mode the transducer acts as a sound receiver i.e. there is conversion of sound energy into an electrical signal. The converse piezoelectric effect permits a transducer to act as an active sound transmitter. In the pulse echo mode, the transducer is used to perform both the active and passive functions at the same time. A sound wave is propagated into the medium and a faint echo is received back after a small time gap due to the acoustic impedance mismatch between the interface materials. This principle is used in transducers for ultrasonic medical imaging applications.
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Fig. 21 : Schematic representation of the generation, propagation and detection of surface acoustic waves (SAW) on a piezoelectric substrate with interdigital electrode. A lot of progress has been made in the last twenty years in the area of ultrasonic diagnostic equipment. This is mainly because of the developments in the area of piezoelectric materials used as the vibrator material and instrument electronics. Many reviews in this field have been published in recent years [87-89]. The ultrasound imaging method is superior as the diagnosis can be done without the need of cutting as in surgery. When compared to X-Ray imaging, it is safer at the low power levels used in normal scans. It is also helpful in distinguishing between soft tissues which is not possible with X-Rays. However, X-Ray and ultrasonic imaging can be said to be complementary to each other as the X-Rays can be used to image the bones which is not possible in biomedical imaging. As explained earlier, the principle of ultrasonic imaging is based on the pulse echo mode of operation. The transducer is exited by an electrical signal which in turn produces a vibrational pulse in the medium to be interrogated (in this case the body). If the ultrasonic wave encounters an impedance in the direction of propagation, part of the energy is reflected back towards the transducer. This reflected echo produces a voltage signal which is used to generate the image of the internal organs and tissues in the body. The acoustic impedance difference between one tissue to another is small so the vibrational pulse penetrates to larger depths and gives a good imaging capability. The applications of medical imaging span a wide frequency range (1.5-30 MHz) depending on the organs to be imaged. For example the frequency range of 2-5 MHz is used for abdominal, obstetrical and cardiological applications, 5-7.5 MHz for pediatric and peripheral vascular applications and 10-30 MHz for intravascular, intracardiac and eye imaging. There is a wide frequency range because one of the factors limiting the attainable resolution is the wavelength of the radiation used to form the image.
Wavelength(l) x frequency(f) = velocity of the wave in the medium(v) (9)
As the velocity of sound is 1500 ms in the human body, the resolution varies from l mm - 50mm for the frequency range of 1.5-30 MHz. Thus there is a balance of good resolution obtained with
-1
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high frequency and high penetration got with a lower frequency. The highest frequency that can be used for a given application is limited by frequency dependent attenuation ( 0.5 dB/cm.MHz) within the body [90]. When the ultrasonic wave hits an impedance, for example a tissue, then a fraction R of the incident energy is reflected back.
R= ((Z - Z ) / (Z + Z )) (10)
2 1 2 1
where Z
and Z
are the acoustic impedance of the transducer material and body respectively.
2
The acoustic impedance 'Z' of a medium is defined as the product of density of the medium and the velocity of sound in the medium (Z=rc). The units of acoustic impedance is kg/m .sec and is called as Rayl. Soft PZT ceramics are widely used as transducers for medical imaging. They have an acoustic impedance of 30 MRayl which is very high as compared to the human body with an impedance of only 1.5 MRayl. Hence there is a reflection of the signal at the transducer / body interface. The losses at the interface could be minimized by using matching layers which have an impedance which is the geometric mean of impedances of the transducer material and the body.
6.2 : Other Piezoelectric Applications :
Gas Ignitors : A typical design for a voltage generator for gas ignitors is shown in Fig. 22. It consists of two oppositely poled ceramic cylinders attached end to end in order to double the charge available for the spark. The compressive force has to be applied quickly to avoid the leakage of charge across the surfaces of the piezoelectric ceramic. The generation of the spark takes place in two stages. The application of a compressive force 'F' on the poled ceramic (under open circuit conditions) leads to a decrease in the length by dL . The potential energy developed across the ends must be higher than the breakdown voltage of the gap, for sparking to occur. When the spark gap breakdown occurs the second stage of energy generation starts. The electric discharge across the gap results in a change from open circuit conditions to closed circuit conditions with the voltage dropping to a lower level. The compliance of the material increases and allows further compression of the ceramic by (dL - dL ) where dL is the displacement that would have occurred if the force 'F' had been applied under short circuit conditions. The combination of the strains from the open and short circuit conditions produce more energy that can be dissipated in the spark. Usually PZT ceramic disks are used for this application [11].
E D E D
Displacement Transducers : When force is applied to a long piezoelectric cantilever beam, one side is in tension while the other side will be in compression. No electrical output can be obtained from this
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Fig. 22 : A piezoelectric spark generator.
homogenous body by bending. Bimorphs made with two halves of separate beams with an electrode in between as well as on the top and bottom surfaces is shown in Fig. 23. If the beams are poled in the opposite direction then on the application of a force 'F' the voltage generated on the outer electrodes will be additive (Fig. 23 (a)). If the beams are poled in the same direction, the additive output can be obtained by connecting the outer electrodes and the center electrode as shown in Fig. 23 (b). Conversely the application of a voltage to the bimorph causes it to bend. As shown in Fig. 24. the application of an electric field causes one half of the cantilever beam to expand and the other half to contract. If they are joined in the form of a bimorph it leads to a net displacement on the application of an electric field [11].
Fig. 23 : Cantilever bimorphs with (a) a series connection and (b) parallel connection of beams.
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Fig. 24 : Schematic of a bimorph showing (a) two free halves of the bimorph; (b) teh free halves in an electric field; (c) the two free halves shown in (a) are joined to form a bimorph. Accelerometers : An accelerometer is a device which gives an electrical output proportional to the acceleration. A shear mode accelerometer is shown in Fig. 25. The transducer is a piezoelectric cylinder which is poled along its axis but has its poling electrodes removed and the sensing electrodes applied to its inner and outer surfaces. The cylinder is joined to the fixed central pole on the inside and a cylindrical mass on the outside. When an axial acceleration takes place the cylinder is subjected to a shear force between the outer mass and inner pole. Any motion in the radial direction does not give any output as the d piezocoefficient for PZT ceramic accelerometer is zero. So the
11
device is highly directional [11].
Piezoelectric Transformers : Low voltage to high voltage transformation can be done by using a piezoelectric plate. Fig. 26 shows a flat plate having electrodes on half of it larger face and on an edge. The region between the larger face electrodes and the edge electrode are poled separately. A length mode resonance is excited by applying a low AC voltage source between the larger face electrodes. The step up voltage ration would be proportional to the ratio of the input to output capacitance and the efficiency of the device. This principle has been used for making EHT transformers for miniature television receivers [11].
Impact Printer Head : Dot matrix impact printers driven by multilayer piezoelectric ceramic actuators have been successfully produced on a large commercial scale. As shown in Fig. 27, the printing pin element consists of a piezoactuator, a stroke amplifier operated on the lever principle and a printing wire. When a pulse with a peak voltage of 150 V is applied to the piezoelectric actuator, the printing wire moves by about 400 mm, making the tip of the wire to hit the paper through the ink ribbon. The advantages of the dot matrix printer over the conventional electromagnetic drive printers
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includes a higher printing speed (double the speed because of the presence of 24 printing pin elements) and half the power consumption as compared to the latter printer [91].
Fig. 25 : A shear mode accelerometer.
Fig. 26 : A piezoelectric transformer with the arrows indicating the poling directions.
Precision XYq Stage : Mechanical stages with fine scale movements have been developed using piezo-actuators. They are made up of a linear X-Y stage and a rotational q stage. The linear stage moves independently in the X and Y directions using two piezo-actuators with active feedback control from precision laser interferometeric position sensors. The performance of the XYq stage is given by : X-Y displacement range of 30 x 30 mm and q -rotation of 270 mrad; a linear and angular resolution of 0.01 mm and 0.9 mrad respectively and a time response of < 30 msec. These stages are being used for synchrotron radiation lithography and are expected to be used for Very Large Scale Integration (VLSI) manufacturing in the future [92].
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Fig. 27 : Schematic of a printing pin element.
7 : SUMMARY :
Ceramic materials and single crystals showing ferroelectric behavior are being used in many applications in electronics and optics. In this chapter, an effort has been made to introduce the basic principles governing ferroelectricity and list various materials which exhibit these properties. The processing of ferroelectric ceramics have also been described, as have been a number of the key applications for ferroelectric materials. Finally, a number of applications of ferroelectric ceramics exploiting properties that are an indirect consequence of ferroelectricity, such as dielectrics, piezoelectricity, and pyroelectricity, are described.
REFERENCES :
1. H. D. Megaw, Ferroelectricity in Crystals (Methuen, London, 1957) 2. W. G. Cady, Piezoelectricity (Dover Publications, New York, 1962) 3. M. Deri, Ferroelectric Ceramics (Gordon and Breach, New York, 1969) 4. J. C. Burfoot, Ferroelectrics (Van Nostrand, New York, 1967) 5. B. Jaffe, W. R. Cook Jr., and H. Jaffe, Piezoelectric Ceramics (Academic Press, London, 1971) 6. T. Mitsui, I. Tatsuzaki, and E. Nakamura, An Introduction to the Physics of Ferroelectrics (Gordon and Breach, London, 1976) 7. M. E. Lines and A. M. Glass, Principles and Applications of Ferroelectric and Related Materials (Clarendon Press, Oxford, 1977) 8. J. M. Herbert, Ferroelectric Transducers and Sensors (Gordon and Breach, London, 1982) 9. R. C. Buchanan, ed., Ceramic Materials for Electronics - Processing, Properties and Applications (Marcel Dekker, New York, 1986)
36 of 40
9/12/2011 4:13 PM
10. L. M. Levinson, ed., Electronic Ceramics - Properties, Devices and Applications (Marcel Dekker, New York, 1987) 11. A. J. Moulson and J. M. Herbert, Electroceramics, Materials, Properties, and Applications (Chapman and Hall, London, 1990) 12. Y. Xu, Ferroelectric Materials and their Applications (North Holland, Amsterdam, 1991) 13. J. F. Nye, Physical Properties of Crystals (Clarendon Press, Oxford, 1990) 14. R. E. Newnham, Structure - Property Relations (Springer Verlag, New York, 1975). 15. S. B. Lang, Sourcebook of Pyroelectricity (Gordon and Breach, New York, 1974) 16. W. J. Merz, Phys. Rev. 91, 513 (1953) 17. B. T. Batthais and A. von Hippel, Phys. Rev., 73, 1378 (1948) 18. A. von. Hippel, Rev. Modern Phys., 22, 221 (1950) 19. R. E. Nettleton, Ferroelectrics, 1, 3, 87, 93, 111, 121,127, 207, 221 (1970) 20. R. E. Nettleton, Ferroelectrics, 2, 5, 77, 93 (1971) 21. W. J. Merz, Phys. Rev., 76, 1221 (1949) 22. R. Pepinsky, Y. Okaya and F. Unterleitner, Acta. Cryst., 13, 1071 (1960) 23. W. Jackson and W. Reddish, Nature, 156, 717 (1945) 24. D. F. Rushman and M. A. Strivens, Trans. Faraday Soc., 42A, 231 (1946) 25. T. Matsui and W. B. Westphal, Phys. Rev., 124, 1354 (1961) 26. H. Kneipkamp, and W. Heywang, Z. Angew. Phys., 6, 385 (1954) 27. D. Hennings, and G. Rosenstein, J. Am. Ceram. Soc., 67, 249 (1984) 28. A. J. Bell, Proc. 1994 Int. Symp. Appl. Ferroelectrics, (1994) 29. S. L. Swartz, IEEE Trans. Electrical Insulation, 25, 935 (1990) 30. W. R. Buessem, L. E. Cross, A. K. Goswami, J. Am. Ceram. Soc., 75, 2927 (1966) 31. G. Arlt, D. Hennings and G. de With, J. Appl. Phys., 58, 4 (1985) 32. T. Yamamoto, M.Saho, K. Okazaki, and E. Goo, Jap. J. Appl. Phys., 26-2, 57 (1987) 33. K. M. Rittenmyer, and R. Y. Ting, Ferroelectrics, 110, 171 (1990) 34. K. Takeuchi, D. Damjanovic, T. R. Guraraja, S. L. Jang, and L. E. Cross, Proc. 1986 IEEE Symp. Appl. Ferroelectrics, 402 (1986) 35. Y. Yamashita, K. Yokoyama, H. Honda, and T. Takahashi, Jap. J. Appl. Phys., 20-4, 183 (1981) 36. L. E. Cross, Ferroelectric Ceramics-Tutorial Reviews, Theory, Processing and Applications, N. Setter, and E. L. Colla, ed., 1 (Birkhauser Verlag, Basel, 1993)
37 of 40
9/12/2011 4:13 PM
Hard PZT : 37. T. B. Weston, A. H. Webster, and V. M. McNamara, J. Am. Ceram. Soc., 52, 253 (1969) 38. N. Uchida, and T. Ikeda, Jap. J. Appl. Phys., 6, 1292 (1967) 39. F. Kulcsar, J. Am. Ceram. Soc., 42, 343 (1959) 40. F. Kulcsar, J. Am. Cera. Soc., 48, 54 (1965) 41. R. B. Atkin, R. L. Holman, and R. M. Fularth, J. Am. Ceram. Soc., 54, 113 (1971) 42. H. Banno, and T. Tsunooka, Jap. J. Appl. Phys., 6, 954 (1967) 43. G. H. Haertling and C. E. Land, J. Am. Ceram. Soc., 54, 1 (1971) 44. G. H. Haertling, J. Am. Ceram. Soc., 54, 303 (1970) 45. G. H. Haertling, and C. E. Land, Ferroelectrics, 3, 269 (1972) 46. G. H. Haertling, Ferroelectrics, 75, 25 (1987) 47. L. E. Cross, Ferroelectrics, 76, 241 (1987) 48. G. A. Smolenski, A. I. Agranovskaya, Sov. Phys. Tech. Phys., 3, 1380 (1958) 49. T. R. Shrout and A. Halliyal, Am. Ceram. Soc. Bull., 66, 704 (1987) 50. T. R. Shrout, and J. P. Dougherty, J. Am. Ceram. Soc., 1990 51. T. R. Shrout, and J. F. Fielding, Jr., IEEE Ultrasonics Symp., 711 (1990) 52. G. Goodman, J. Am. Ceram. Soc., 36, 368 (1953) 53. M. H. Francombe and B. Lewis, Acta Cryst., 11, 696 (1958) 54. E. C. Subbarao, J. Am. Ceram. Soc., 45, 166 (1962) 55. S. L. Swartz, W. A. Schulze, and J. V. Biggers, Ferroelectrics, 38, 765 (1981) 56. T. Takenaka and S. Sakata, Jap. J. Appl. Phys., 19, 31 (1980) 57. K. Nassau, H. J. Levinstein, and G. M. Loiacona, J. Phys. Chem. Solids, 27, 983 (1966) 58. (a)S. C. Abraham, W. C. Hamilton, and J. L. Bernstein, J. Phys. Chem. Solids, 27, 997 (1966) (b) S. C. Abraham, W. C. Hamilton, and J. M. Reddy, J. Phys. Chem. Solids, 27, 1013 (1966) (c) S. C. Abraham, H. J. Levinstein, and J. M. Reddy, J. Phys. Chem. Solids, 27, 1019 (1966) 59. B. C. Frazer, and R. Pepinsky, Acta Crystallogr., 6, 273 (1953) 60. G. E. Bacon, and R. S. Pease, Proc. R. Soc. London, A220, 397 (1953) 61. S. Hoshino, Y. Okaya, and R. Pepinsky, Phys. Rev., 115, 323 (1959) 62. M. I. Kay, and R. Kleinberg, Ferroelectrics, 5, 45 (1973) Organic Poly.
38 of 40
9/12/2011 4:13 PM
63. M. G. Broadhurst, G. T. Davis, J. E. McKinney, and R. E. Collins, J. Appl. Phys., 49, 4992 (1978) 64. N. Takahashi, and A. Odaiyama, Ferroelectrics, 32, 49 (1981) 65. R. E. Newnham, L. J. Bowen, K. A. Klicker, and L. E. Cross, Matl. Engg., 2, 107 (1980) 66. A. Safari, J. Phys. III France, 4, 1129 (1994) 67. V. F. Janas, and A. Safari, J. Am. Ceram. Soc., 78, 2945 (1995) 68. Y. Matsuo, and H. Sasaki, J. Am. Ceram. Soc., 48, 289 (1965) 69. D. A. Buckner and P. D. Wilcox, Am. Ceram. Soc. Bull., 51, 218 (1972) 70. H. J. Hagemann, D. Hennings and R. Wernicke, Philips Tech. Rev., 41, 89 (1983/84) 71. J. H. Adair, D. A. Anderson, G. O. Dayton, and T. R. Shrout, J. Matl. Ed., 9, 71 (1987) 72. J. F. Scott, L. Kammerdiner, M. Paris, S. Traynor, V. Ottenbacher, A. Shawabkeh, and W. F. Oliver, J. Appl. Phys., 64, 787 (1988) 73. J. F. Scott, C. A. Aranjo, H. B. Meadows, L. D. McMillan, and A. Shawabkeh, J. Appl. Phys., 1444 (1989) 74. D. Bondurant, and F. Gnadinger, IEEE Spectrum, 30 (1989) 75. J. F. Scott, and C. A. Aranjo, Science, 246, 1400 (1989) 76. L. I. Maissel and R. Glang, ed., Handbook of Thin Film Technology (McGraw Hill, New York, 1970) 77. A. Baudrant, H. Vial, and J. daval, J. Cryst. Growth, 43, 197 (1978) 78. S. Miyazawa and N. Uchida, Opt. and Quantam Electronics, 7, 451 (1975) 79. C. E. Land, J. Am. Ceram Soc., 72, 2059 (1989) 80. I. H. Pratt and S. Firestone, J. Vac. Sci. Tech., 8, 256 (1971) 81. S. G. Porter, Ferroelectrics, 33, 193 (1981) 82. K. Ijima, Y. Tomita, R. Takayama, and I.Ueda, J. Appl. Phys., 60, 361 (1986) 83. R. Takayama, Y. Tomita, K. Ijima, and I. Ueda, J. Appl. Phys., 61, 411 (1987) 84. R. Takayama, and Y. Tomita, J. Appl. Phys., 65, 1666 (1989)
85. A. S. Slobodnik, Jr., Proc. IEEE, 64, 581 (1976) 86. K. Sreenivas, M. Sayer, D. J. Baar, and M. Nishioka, Appl. Phys. Lett., 52, 709, (1988) 87. P. N. T. Wells, Biomedical Ultrasonics (Academic Press, London, 1977) 88. W. A. Smith, Proc. 6
th
Int. Symp. Appl. Ferroelectrics, 249 (1986)
39 of 40
9/12/2011 4:13 PM
89. D. A. Christensen, Ultrasonic Bioinstrumentation (John Wiley, New York, 1988) 90. T. R. Gururaja, Bull. Am. Ceram. Soc., 73, 50 (1994) 91. Takahashi, Ferroelectrics, 91, 293 (1989)
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Ferroelectric Ceramics : Processing, Properties & Applications