Paraelectric properties

Although the superconducting properties of these materials are of major interest at this time, future applications of these materials may depend upon utilization of the dramatic changes in electrical properties accompanying stoichiometric changes in these solid solutions. Particularly interesting are the ferro-, ferri-, piezo- and paraelectric properties displayed by the insulating phases in BaPbx ... 

Historically, materials based on doped barium titanate were used to achieve dielectric constants as high as 2,000 to 10,000. The high dielectric constants result from ionic polarization and the stress enhancement of k associated with the fine-grain size of the material. The specific dielectric properties are obtained through compositional modifications, ie, the inclusion of various additives at different doping levels. For example, additions of strontium titanate to barium titanate shift the Curie point, the temperature at which the ferroelectric to paraelectric phase transition occurs and the maximum dielectric constant is typically observed, to lower temperature as shown in Figure 1 (2). 

Crystals with one of the ten polar point-group symmetries (Ci, C2, Cs, C2V, C4, C4V, C3, C3v, C(, Cgv) are called polar crystals. They display spontaneous polarization and form a family of ferroelectric materials. The main properties of ferroelectric materials include relatively high dielectric permittivity, ferroelectric-paraelectric phase transition that occurs at a certain temperature called the Curie temperature, piezoelectric effect, pyroelectric effect, nonlinear optic property - the ability to multiply frequencies, ferroelectric hysteresis loop, and electrostrictive, electro-optic and other properties [16, 388],... 

The phase transiton from a paraelectric to a ferroelectric state, most characteristic for the SbSI type compounds, has been extensively studied for SbSI, because of its importance with respect to the physical properties of this compound (e.g., J53, 173-177, 184, 257). The first-order transition is accompanied by a small shift of the atomic parameters and loss of the center of symmetry, and is most probably of a displacement nature. The true structure of Sb4S5Cl2 106), Bi4S5Cl2 194), and SbTel 108,403) is still unknown. In contrast to the sulfides and selenides of bismuth, BiTeBr 108) and BiTel (JOS, 390) exhibit a layer structure similar to that of the Cdl2 structure, if the difference between Te, Br, and I (see Fig. 36) is ignored. 

The semiconducting properties of the compounds of the SbSI type (see Table XXVIII) were predicted by Mooser and Pearson in 1958 228). They were first confirmed for SbSI, for which photoconductivity was found in 1960 243). The breakthrough was the observation of fer-roelectricity in this material 117) and other SbSI type compounds 244 see Table XXIX), in addition to phase transitions 184), nonlinear optical behavior 156), piezoelectric behavior 44), and electromechanical 183) and other properties. These photoconductors exhibit abnormally large temperature-coefficients for their band gaps they are strongly piezoelectric. Some are ferroelectric (see Table XXIX). They have anomalous electrooptic and optomechanical properties, namely, elongation or contraction under illumination. As already mentioned, these fields cannot be treated in any detail in this review for those interested in ferroelectricity, review articles 224, 352) are mentioned. The heat capacity of SbSI has been measured from - 180 to -l- 40°C and, from these data, the excess entropy of the ferro-paraelectric transition... 

At high temperatures, ferroelectric materials transform to the paraelectric state (where dipoles are randomly oriented), ferromagnetic materials to the paramagnetic state, and ferroelastic materials to the twin-free normal state. The transitions are characterized through order parameters (Rao Rao, 1978). These order parameters are characteristic properties parametrized in such a way that the resulting quantity is unity for the ferroic state at a temperature sufficiently below the transition temperature, and is zero in the nonferroic phase beyond the transition temperature. Polarization, magnetization and strain are the proper order parameters for the ferroelectric. 

T = 140 °C. Here, during solidification, the H increase from 140 °C down to about 100 °C is the result of a double contribution of (a) the crystallization of the fraction of molten crystals and (b) the thermal contraction of the nonpolar phase crystals. The hysteresis behavior is also found in other mechanical properties (dynamic modulus) derived from micromechanical spectroscopy [66, 67], where it is shown that the hysteresis cycle shifts to lower temperatures if the samples are irradiated with electrons. It has also been pointed out that the samples remain in the paraelectric phase, when cooling, if the irradiation dose is larger than 100 Mrad. 

The effects of pressure on the properties of perovskite fes and rls are manifestations of the influence of pressure on the soft fe mode frequency of the host lattice [14,24], This frequency is determined by a delicate balance between short-range and long-range forces, and these forces exhibit markedly different dependences on interatomic separation, or pressure. Specifically, pressure increases the soft-mode frequency at constant temperature, which reduces the polarizability of the host lattice, thereby reducing Ac. The result is a shift of the transition temperature, Tc (or Tm), to lower temperatures and a suppression of the e (T) response in the high temperature paraelectric phase [14,24],... 

Ferroelectric behaviour is limited to certain materials and to particular temperature ranges for a given material. As shown for barium titanate in Section 2.7.3, Fig. 2.40(c), they have a Curie point Tc, i.e. a temperature at which the spontaneous polarization falls to zero and above which the properties change to those of a paraelectric (i.e. a normal dielectric). A few ferroelectrics, notably Rochelle Salt (sodium potassium tartrate tetrahydrate (NaKC406.4H20)) which was the material in which ferroelectric behaviour was first recognized by J. Yalasek in 1920, also have lower transitions below which ferroelectric properties disappear. 

The P,T) phase diagram for the system has been prepared (Fig. 6.6) using a combination of data from neutron scattering, NQR, vibrational spectroscopy and conductivity measurements (Cailleau et al. 1997). The neutral phase is paraelectric, while the ionic phase has paraelectric and ferroelectric regions. The nature and mechanism of the phase transition has been reviewed and treated, as well as a number of other physical properties (Le Cointe et al. 1996 Cailleau et al. 1997). 

Ceramic capacitors are prepared with their chemical compositions placing them close to a ferroelectric-paraelectric phase boundary, where the dielectric permittivity is anomalously high. These materials are commonly based on BaTiOs which is similar in structure and properties to the piezoelectric ceramics. 

The two features are attributable to the same type of paraelectric center and correspond to its relaxation and resonance interactions with the alternating electric field. Pirc and Dick first gave a unified theoretical treatment of both peaks. Their treatment applied primarily to crystalline media and is qualitatively applicable to glasses if paraelectric centers are assumed to have a distribution of energy splittings and relaxation times instead of fixed values. In the case of glasses, the theory of low-energy excitations was initially formulated to explain their low-temperature thermal properties Pure vitreous silica apparently contains... 

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