903

Ferroelectrics
Ferroelectric crystals (especially oxides in the form of ceramics) are important basic materials for technological applications in capacitors and in piezoelectric, pyroelectric, and optical devices. In many cases their nonlinear characteristics turn out to be very useful, for example in optical second-harmonic generators and other nonlinear optical devices. In recent decades, ceramic thinlm ferroelectrics have been utilized intensively as parts of memory devices. Liquid crystal and polymer ferroelectrics are utilized in the broad eld of fast displays in electronic equipment. This chapter surveys the nature of ferroelectrics, making reference to the data presented in the LandoltBrnstein data collection Numerical Data and Functional Relationships in Science and Technology, Vol. III/ 36, Ferroelectrics and Related Substances (LB III/ 36). The data in the gures in this chapter have been taken mainly from the LandoltBrnstein collection. The LandoltBrnstein volume mentioned above

4.5. Ferroelectrics and Antiferroelectrics

4.5.1 Denition of Ferroelectrics and Antiferroelectrics ......................... 903 4.5.2 Survey of Research on Ferroelectrics ..... 904 4.5.3 Classication of Ferroelectrics .............. 906 4.5.3.1 The 72 Families of Ferroelectrics 909 4.5.4 Physical Properties of 43 Representative Ferroelectrics ..................................... 4.5.4.1 Inorganic Crystals Oxides [5.1, 2] 4.5.4.2 Inorganic Crystals Other Than Oxides [5.3] ............ 4.5.4.3 Organic Crystals, Liquid Crystals, and Polymers [5.4] .................. 912 912 922 930

References .................................................. 936

consists of three subvolumes: Subvolume A [5.1, 2], covering oxides; Subvolume B [5.3], covering inorganic crystals other than oxides; and Subvolume C [5.4], covering organic crystals, liquid crystals, and polymers.

Part 4 5

Matter consists of electrons and nuclei. Most of the electrons generally are tightly bound to the nuclei, but some of the electrons are only weakly bound or are freely mobile in a lattice of ions. The physical properties of matter can be considered as being split into two categories. The properties in the rst category are determined directly by the electrons and by the interaction of the electrons with lattice vibrations. Examples are the metallic, magnetic, superconductive, and semiconductive properties. The properties in the second category are only indirectly related to the electrons and can be discussed as being due

to interaction between atoms, ions, or molecules. In this category we have, for example, the dielectric, elastic, piezoelectric, and pyroelectric properties; we have the dispersion relations of the lattice vibrations; and we have most of the properties of liquid crystals and polymers. The important properties of ferroelectrics are linked to all the latter properties, and they exhibit diverse types of phase transitions together with anomalies in these properties. These specic modications convey information about cooperative interactions among ions, atoms, or molecules in the condensed phase of matter.

4.5.1 Denition of Ferroelectrics and Antiferroelectrics

A ferroelectric crystal is dened as a crystal which belongs to the pyroelectric family (i. e. shows a spontaneous electric polarization) and whose direction of spontaneous polarization can be reversed by an electric eld. An antiferroelectric crystal is dened as a crystal whose structure can be considered as being composed of two sublattices polarized spontaneously in antiparallel directions and in which a ferroelectric phase can

904

Part 4

P Ps Pr Ecrit Ec E

Ecrit

Fig. 4.5-1 Ferroelectric hysteresis loop. Ps , spontaneous polarization; Pr , remanent polarization; E c , coercive eld

Fig. 4.5-2 Antiferroelectric hysteresis loop. E crit , critical

eld

be induced by applying an electric eld. Experimentally, the reversal of the spontaneous polarization in ferroelectrics is observed as a single hysteresis loop (Fig. 4.5-1), and the induced phase transition in antiferroelectrics as a double hysteresis loop (Fig. 4.5-2), when a low-frequency ac eld of a suitable strength is applied. The spontaneous polarization in ferroelectrics and the sublattice polarizations in antiferroelectrics are analogous to their magnetic counterparts. As described above, however, these polarizations are a necessary

but not sufcient condition for ferroelectricity or antiferroelectricity. In other words, ferroelectricity and antiferroelectricity are concepts based not only upon the crystal structure, but also upon the dielectric behavior of the crystal. It is a common dielectric characteristic of ferroelectrics and antiferroelectrics that, in a certain temperature range, the dielectric polarization is observed to be a two-valued function of the electric eld. The denition of ferroelectric liquid crystals needs some comments; see remark l in Sect. 4.5.3.1.

Part 4 5.2

4.5.2 Survey of Research on Ferroelectrics

The ferroelectric effect was discovered in 1920 by Valasek, who obtained hysteresis curves for Rochelle salt analogous to the B H curves of ferromagnetism [5.5], and studied the electric hysteresis and piezoelectric response of the crystal in some detail [5.6]. For about 15 years thereafter, ferroelectricity was considered as a very specic property of Rochelle salt, until Busch and Scherrer discovered ferroelectricity in KH2 PO4 and its sister crystals in 1935. During World War II, the anomalous dielectric properties of BaTiO3 were discovered in ceramic specimens independently by Wainer and Solomon in the USA in 1942, by Ogawa in Japan in 1944, and by Wul and Goldman in Russia in 1946. Since then, many ferroelectrics have been discovered and research activity has rapidly increased. In recent decades, active studies have been made on ferroelectric liquid crystals and high polymers, after ferroelectricity had been considered as a characteristic property of solids for more than 50 years. Figures 4.5-3, 4.5-4, and 4.5-5 demonstrate how ferroelectric research has developed. Figure 4.5-3 indicates the number of ferroelectrics discovered each year for oxide (Fig. 4.5-3a) and nonoxide ferroelectrics (Fig. 4.5-3b). Figure 4.5-4 gives the total number of ferroelectrics known at the end of each year. At present more than 300 ferroelectric substances are known. Figure 4.5-5 indicates the number of research papers on ferroelectrics and related substances published each year. Advanced experimental methods (e.g. inelastic neutron scattering and hyper-Raman scattering) have been applied effectively to studies of ferroelectrics, and several new concepts (e.g. soft modes of lattice vibrations and the dipole glass) have been introduced to understand the nature of ferroelectrics. Ferroelectric crystals have been widely used in capacitors and piezoelectric devices. Steady developments in crystal growth and in the preparation of ceramics and ceramic thin

Ferroelectrics and Antiferroelectrics

5.2 Survey of Research on Ferroelectrics

905

a) Number of oxide ferroelectrics

10 9 8 7 6 5
Gd2(MoO4)3 Pb5Ge3O11 Bi4Ti3O12 YMnO3 Ba2NaNb5O15

4 3 2 1 0

O3 LiNbO LiNb

Li2 Ge7O15

hexagonal BaTiO3

cubic BaTiO3

Cd2Nd2O7 PbNb2O6

Sr2Ta2O7

64

67

61

52

43

58

70

79

82

85

40

46

49

55

73

76

88

91

19

19

19

19

19

19

19

19

19

19

94 19

19

19

19

19

19

19

19

19

Year of discovery

19

97

GdMn2O5

Li2Ge4O9

SrTeO3

Part 4 5.2

b) Number of non-oxide ferroelectrics

25 CsCoPO4, HAOBAMBC K2SeO4, BaMgF4

TGS, (NH4)2SO4 Alum

20

LiNH4C4H4O6 H2O

NaNO2, KNO3

15

Rb2ZnCl4, DOBAMBC (CH2CF2)n

(CH3NH3)6 Bi2Cl11

Sn2P2S6, PbHPO4

10 Rochelle salt

KDP

KIO3

0 1920

1930

1940

1950

1960

1970

1980

1990 Year of discovery

Fig. 4.5-3a,b Number of ferroelectric substances discovered in each year. Representative ferroelectrics are indicated at their year of discovery. (a) Oxide ferroelectrics. Only pure compounds are taken into account. (b) Nonoxide ferroelectrics.

Gray bars stand for nonoxide crystals, counting each pure compound as one unit. Brown bars stand for liquid crystals and polymers, counting each group of homologues (cf. Chaps. 71 and 72 in [5.4]) as one unit. The gure was prepared by Prof. K. Deguchi using data from LB III/36

TIS

(CH3)NH2H2PO4

SbSI

HCl

Ferroelectrics and Antiferroelectrics

5.4 Physical Properties of 43 Representative Ferroelectrics

913

Dielectric constant 5000 f = 10 kHz E = 500 Vm 4000

1

3850

3845 3000 3840 2000 3835 1000 3830 0 100 200 300 400 500 Temperature T ( C) 0 1 2 3 4 5 6 7 T (K)

0 200 100

Fig. 4.5-12 KNbO3 . Dielectric constant versus tempera-

Fig. 4.5-14 KTaO3 . Real part of dielectric constant ver-

ture T KTaO3 (LB Number 1A-5). KTaO3 is cubic at all temperatures, and its dielectric constant becomes very large at low temperatures without a phase transition (Fig. 4.5-14). It is generally believed that this behavior is related to the zero-point lattice vibrations. Replacement of Nb by Ta generally lowers drastically the ferroelectric Curie temperature , as seen by comparing Fig. 4.5-14 with Fig. 4.5-12. (This effect is well demonstrated later in Figs. 4.5-39 and 4.5-40). SrTiO3 (LB Number 1A-8). This crystal is cubic at room

sus T . f = 1 kHz

1.50 1.25 1.00 0.75

p (1012 Hz)

Part 4 5.4

temperature and slightly tetragonal below 105 K. The phase transition at 105 K is caused by softening of the lattice vibration mode at the (1/2, 1/2, 1/2) BrilPs (102 C m2) Ec (102 V m1)

0.50 0.25

40 30 20

0 100 120 140 160 180 200 220 240 T (K)

Ps 2000 Ec 1000 250 300 350 0 400 T ( C)

Fig. 4.5-15 SrTiO3 . P versus T . P is the frequency of the

R25 (25 ) optical phonon

10 0 100 150 200

Fig. 4.5-13 KNbO3 . Ps and E c versus T . Measurements were made by applying the electric eld parallel to the pseudocubic [100] direction

louin zone corner (Fig. 4.5-15) without an appreciable dielectric anomaly. At very low temperatures, the dielectric constants become extraordinarily high without a phase transition (Fig. 4.5-16), owing to softening of the optical phonon at the origin of the Brillouin zone (Fig. 4.5-17). It is generally believed that the absence of a low-temperature transition is related to zero-point lat-

Ferroelectrics and Antiferroelectrics

5.4 Physical Properties of 43 Representative Ferroelectrics

915

BaTiO3 (LB Number 1A-10). BaTiO3 is the most exten-

sively studied ferroelectric crystal. It is ferroelectric below about 123 C, where the crystal symmetry changes from cubic to tetragonal. Further phase transitions take place from tetragonal to orthorhombic at about 5 C and to rhombohedral at about 90 C (Figs. 4.5-18 to 4.5-20). It is believed that the ferroelectric transition
Ps (102 C m2) 30 20 10 0 140 120 100 80 60 40 20 0 20 T (C)

4.840

(1012 Hz) T= 230 C 430 C [ 00] LA

3.872

2.904 TA 1.936 TO 0.968

Zone boundary

Fig. 4.5-20 BaTiO3 . Ps[001] versus T below 20 C, where

Ps[001] is the component of the spontaneous polarization parallel to the c axis in the tetragonal phase

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8 0.9 (1)

'' (arb. units)

40 0 10

20 20

40

60

80

100

/ c (cm1) 120 140

10
8 6 4 2

Fig. 4.5-22 BaTiO3 . Phonon dispersion relation determined by neutron scattering along the [100] direction in the cubic phase. is the phonon frequency. LA, longitudinal acoustic branch; TA, transverse acoustic branch; TO, transverse optical branch. The frequency of the TO branch is lower (softer) at 230 C than at 430 C, indicating mode softening

Part 4 5.4

T = 408 K T = 423 K T = 473 K T = 553 K

1
8 6 4 2

101
8 6 4 2

10

66

12

18

24

30

36 42 (1011 Hz)

Fig. 4.5-21 BaTiO3 .

versus . Parameter: T . is the imaginary part of obtained from the hyper-Raman spectrum. Curves: calculations based upon the classical dispersion oscillator model. c: light velocity

is caused by softening of an optical mode at the center of the Brillouin zone. Hyper-Raman scattering studies support this model (Figs. 4.5-21 and 4.5-22). The results of neutron scattering studies favor this model (Fig. 4.5-23), but the measurement was not easy owing to the intense elastic peaks (Fig. 4.5-24a). These elastic peaks indicate marked cluster formation in the vicinity of the Curie point. As discussed in Sect. 4.5.3, there seem to be two components contributing to the dielectric constant measured in the vicinity of the Curie point: a component due to the soft mode and another one due to the motion of the cluster boundaries. Presumably the two components suggested by infrared and hyper-Raman scattering data correspond to these two components. For theoretical studies of the phase transitions, readers should refer to [5.7]. Solid solutions of BaTiO3 are the most useful ferroelectrics in ceramic condensers and as thin lms in memory devices. When the temperature is raised above 1460 C, cubic BaTiO3 performs another phase transition to a hexagonal structure. This hexagonal phase can be quenched

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