Relaxation processes in the incommensurate phase of a crystal with defects

The nature of the relaxation of the incommensurate superstructure of a ferroelectric to the equilibrium state is investigated experimentally. It is shown that near a phase transition the temperature dependence of the relaxation time of the incommensurate phase of the defective crystal is exponential. This law agrees qualitatively with the notion of domain wall motion in an inhomogeneous medium containing “random local phase-transition temperature” type defects. Fiz. Tverd. Tela (St. Petersburg) 41, 513–515 (March 1999)     

Slow stage in the evolution of an incommensurate ferroelectric superlattice

The nature of the slow evolution of a soliton system in an incommensurate phase of a ferroelectric is investigated experimentally. It is shown that the duration of the time interval in which the anomalous permittivity and the corresponding soliton spacings are governed by a logarithmic law increases from a few minutes to several hours as the ferroelectric phase transition is approached. Fiz. Tverd. Tela (St. Petersburg) 40, 2101–2102 (November 1998)     

Incommensurate phase in the layered hexagonal crystal Cs3Bi2I9

An incommensurate phase is observed in a Cs₃Bi₂I₉ crystal, which belongs to the family of layered A₃B₂X₉ structures. Data from ¹²⁷I NQR and x-ray powder diffraction patterns show that the second-order normal phase—incommensurate phase transition at T _i=220 K is accompanied by a P6₃/mmc↔P2₁/m symmetry change and takes place at the center of the Brillouin zone. The nature of the instability leading to the appearance of this little-studied form of incommensurability is discussed. Fiz. Tverd. Tela (St. Petersburg) 39, 1105–1108 (June 1997)     

Interaction of acoustic and optical branches via a Lifshitz-type invariant

It is shown that the interaction of the acoustic and soft optical branches of the spectrum of normal vibrations of a crystal via a gradient invariant of the Lifshitz-invariant type explains the characteristic temperature dependences of these branches as the point of a transition from the initial phase into an incommensurate phase is approached. A comparison is made with the experimental data for betaine calcium chloride dihydrate — BCCD. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 9, 707–710 (10 May 1997)     

Ferroelectric phase transition in Langmuir-Blodgett films of copper phthalocyanine

A ferroelectric phase transition is observed in Langmuir-Blodgett films prepared from substituted copper phthalocyanine molecules. The linear and nonlinear dielectric properties of the films and the switching of their spontaneous polarization are investigated in the temperature range of the phase transition. The observed features can be explained by the Landau-Ginzburg model of a first-order phase transition. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 9, 625–631 (10 November 1999)     

Electric-field-induced phase transition in single-crystal lead zinc niobate

The behavior of lead zinc niobate, a relaxor ferroelectric, in electric fields has been studied by dielectric, optical transmittance, and small-angle light scattering techniques. A field-induced transition from an averaged cubic to macrodomain ferroelectric phase has been found. A comparison is made with the properties of the phase induced in lead magnoniobate, a classical relaxor. Fiz. Tverd. Tela (St. Petersburg) 40, 527–530 (March 1998)     

The intermediate glassy phase in a ferroelectric with dislocations

This paper examines, in the mean-field approximation, the phase transitions in an elasto-isotropic cubic ferroelectric crystal with randomly distributed ring dislocations. It is found that a transition to the dipole-glass phase with chaotic, spontaneous unit-cell dipole moments, characterized by the Edwards-Anderson nonlocal parameter, precedes the transition to the ferroelectric phase. Also determined are the features of the thermodynamic parameters of the crystal at the phase-transition points. Zh. éksp. Teor. Fiz. 116, 986–1000 (September 1999)     

Influence of polytypism on structural phase transformations in TlGaSe2 crystals

The polytypism is found to have a significant influence on the structural transformation of the crystal lattice of the TlGaSe₂ ferroelectric with variations in temperature. In the 2C-polytype, unlike the C-polytype, a first-order structural phase transition, which leads to a change in the translational symmetry along the C axis, is not observed in the temperature range T = 90–300 K and a second-order phase transition due to the formation of an incommensurate phase occurs at a higher temperature.     

Vibronic charge-transfer excitons: Possible nature of the unusual properties of virtual perovskitelike ferroelectrics

A vibronic charge-transfer exciton, which is a pair of Jahn-Teller electron and hole polarons, is considered as a possible cause of the appearance of the Müller phase in the virtual ferroelectric SrTiO₃ and the “green” luminescence in the virtual ferroelectric KTaO₃. The two “green” luminescence bands can be associated with emission from two states of a typical intrinsic defect, viz., a vibronic charge-transfer exciton trapped by an oxygen vacancy and an isolated vibronic charge-transfer exciton. In both cases the “green” luminescence corresponds to the recombination of the electron and the hole in the vibronic charge-transfer exciton, which is accompanied by the emission of light. The properties of the Müller phase can be attributed to mixing of the normal state and states of the vibronic charge-transfer exciton phase when they interact with polarization in the soft SrTiO₃ matrix under the conditions of a pseudo-Jahn-Teller (pseudo-JT) effect on a soft TO mode of the displacement type. In this case the vibronic charge-transfer exciton phase forming the low-lying excited states has “order-disorder” degrees of freedom and exists at temperatures significantly below the point of the order-disorder ferroelectric transition in SrTiO₃ at T=T Q≈37 K. The corresponding lowering of the symmetry of the vibronic charge-transfer exciton phase to polar symmetry leads to the possibility of a long-period incommensurate phase in such excited states, which arises as a result of the appearance of a Lifshitz invariant. The valence-band state making the largest contribution of the pseudo-JT effect corresponds to a wave vector equal to the critical wave vector of the incommensurate vibronic charge-transfer exciton phase. When the temperature is lowered, the pseudo-JT distortion increases down to ∼T _Q and subsequently saturates in accordance with the saturation of the dielectric constant. The basic assumption in the model is that the temperature T=T _Q corresponds to the narrow temperature range for the transition from an intermediate to a strong pseudo-JT effect under the conditions for the realization of polarization tunneling states. The appearance of a significant admixture of states of the modulated ferroelectric vibronic charge-transfer exciton phase to the ground state under the conditions for the realization of polarization tunneling states at low temperatures provides an explanation for the principal properties of the Müller phase. Fiz. Tverd. Tela (St. Petersburg) 40, 907–909 (May 1998)     

Influence of disorder in crystal structure on ferroelectric phase transitions

A new model of ferroelectric phase transitions in disordered crystals is developed. The model takes into account the nonequivalence of the structural environment of identical ions, which alters the balance of forces governing ferroelectric structural instability. In contrast with its predecessors, the new model can be used for qualitative and, in many cases, quantitative predictions of the temperature range of the diffuse ferroelectric phase transition and the value of the disorder-induced shift of the average transition temperature as a function of the degree of disorder and chemical composition. This conclusion is confirmed by a comparison of the theoretical results with an abundance of known experimental facts. Zh. éksp. Teor. Fiz. 111, 1817–1832 (May 1997)     

Phase transitions in the ferroelectrics (Sn1−x In(2/3)x )2P2S6 at high pressures

New ferroelectric solid solutions (Sn_1−x In_(2/3)x )₂P₂S₆ were investigated at high hydrostatic pressures. The range in which the incommensurate structure exists was determined. A dynamic shift of the incommensurate-ferroelectric phase transition temperature with increasing rate of change of temperature and the appearance of “reverse hysteresis” were observed. The characteristic features in the appearance of the latter effect in these crystals are investigated. Fiz. Tverd. Telsa (St. Petersburg) 41, 1276–1278 (July 1999)     

Ferroelectric phase transition in LaBSiO5 crystals from results of thermal and dielectric measurements

The specific heat of the ceramic and the permittivity of a single-crystal sample of LaBSiO₅, a new ferroelectric in the stilwellite family, were measured in a temperature range which includes the phase transition point (T _C=140 °C). The excess entropy of the phase transition ΔS=1.05 J/mol · K and the Curie-Weiss constant C _C-W=3.2×10³ K were determined. The results indicate that the phase transition in this crystal is of a “mixed” nature and exhibits features of a displacement-type transition and an order-disorder transition. Fiz. Tverd. Tela (St. Petersburg) 40, 1310–1312 (July 1998)     

Fluctuation-induced broadening of Mn2+ EPR lines in the incommensurate phase of Rb2ZnCl4 crystals

The EPR spectra of Mn²⁺ ions in Rb₂ZnCl₄ crystals is investigated in the vicinity of the transition from the paraelectric phase to an incommensurate modulated phase. When these crystals are cooled below the transition temperature T _i =304 K, a splitting of the resonance lines is observed in the singular spectrum. A one-harmonic model is used to discuss the contributions that fluctuations in the amplitude and phase of the incommensurate displacement wave make to the local width of the singular spectra. It is shown that anomalies in the local width of the low-temperature singular peaks observed in the vicinity of T _i are caused by amplitude fluctuations. Fiz. Tverd. Tela (St. Petersburg) 41, 1668–1674 (September 1999)     

Magnetic inversion symmetry breaking and ferroelectricity in TbMnO3

TbMnO3 is an orthorhombic insulator where incommensurate spin order for temperature T(N)<41 K is accompanied by ferroelectric order for T<28 K. To understand this, we establish the magnetic structure above and below the ferroelectric transition using neutron diffraction. In the paraelectric phase, the spin structure is incommensurate and longitudinally modulated. In the ferroelectric phase, however, there is a transverse incommensurate spiral. We show that the spiral breaks spatial inversion symmetry and can account for magnetoelectricity in TbMnO3.     

Thermodynamic parameters of diffuse phase transitions in Ag2Te

A differential thermal analysis in vacuum and studies of the coefficients of electrical conductivity and thermal conductivity, and of the thermal emf are made in Ag₂Te in the neighborhood of the structural phase transition. It is shown that these data can be used to calculate the switching factor L(T), determine the region in which the phases coexist within the transition, and calculate the thermodynamic parameters. Prior to and after the main phase transition, additional displacement transitions are observed. It is found that the phase transition takes place roughly according to the scheme α _{385 K}→α′_{405 K}→β′_{420 K}→β _{440 K}. The specific heat C _p, changes in entropy ΔS and transition enthalpy ΔH, as well as the minimum phase fluctuation volume V, and the heat Q of the phase transition are determined. It is shown that excesses of Te and Ag have almost no effect on the transition temperatures T ₀, but have a substantial effect on the thermodynamic parameters. Fiz. Tverd. Tela (St. Petersburg) 40, 1693–1697 (September 1998)     

Ferroelectric phenomena in CdSnO<Subscript>3</Subscript>: A first-principles studies

The phonon spectrum of cubic cadmium metastannate and parameters of the crystal structure of its distorted phases were calculated from first principles within the density functional theory. It is shown that the phonon spectrum and the energy spectrum of the distorted phases in α-CdSnO₃ resemble surprisingly the corresponding characteristics of CdTiO₃. The ground state of α-CdSnO₃ is the ferroelectric Pbn2₁ phase, the energy gain from the phase transition to this phase from the nonpolar phase Pbnm is ∼30 meV, and the spontaneous polarization is 0.25 C/m². The analysis of the eigenvector of the ferroelectric mode in α-CdSnO₃ and the partial densities of states indicates that the ferroelectric instability in this crystal, which does not contain transition d-element atoms, is associated with the formation of a covalent bonding between Cd and O atoms.     

Anomalous behavior of the elastic and inelastic properties in the ferroelectric phase of single-crystal (NH4)2SO4

The anomalous changes of the low-frequency elastic and inelastic properties of single-crystal (NH₄)₂SO₄ accompanying the phase transition from the paraelectric to the ferroelectric phase have been studied by the reverse torsion-pendulum method at 223 K and in the temperature region where the spontaneous polarization changes sign. Fiz. Tverd. Tela (St. Petersburg) 40, 2202–2205 (December 1998)     

Lattice dynamics and the ferroelectric phase transition in ordered Pb2B′B″O6 (B′ = Ga, In, Lu; B″ = Nb, Ta) solid solutions

The lattice vibration spectrum, rf permittivity, and dynamic Born charges have been calculated for ordered Pb₂ B′B″O₃ (B′=Ga, In, Lu; B″=Nb, Ta) solid solutions in terms of the generalized Gordon—Kim model. It has been shown that all compounds exhibit a ferroelectric instability and that the frequencies of “soft” ferroelectric modes are close in magnitude. The ferroelectric phase-transition temperatures and the spontaneous polarization in the ferroelectric phase of the solid solutions under consideration have been calculated by the Monte Carlo method using the model Hamiltonian in the local mode approximation. The transition temperature is found to increase with increasing atomic number of the B′ ion.     

Critical behavior of heat capacity of the SC(NH2)2 ferroelectric in the region of incommensurate phase transition

The anomalous (nonclassical) behavior of heat capacity in the region of the second-order phase transition “initial phase-incommensurate phase” was experimentally observed in the SC(NH₂)₂ ferroelectric. Such a critical behavior of heat capacity above and below the temperature of incommensurate phase transition is shown to be qualitatively consistent with the fluctuation theory of XY-type systems.     

Observation of87Rb NMR satellite transitions in the commensurate and incommensurate phases of Rb2ZnCl4

It is shown that the first order quadrupole split NMR satellite transition frequencies of the⁸⁷Rb nucleus can be detected in the paraelectric, incommensurate and ferroelectric phases of Rb₂ZnCl₄. From rotation patterns the electric field gradient tensor at the Rb sites is determined for the paraelectric phase. The data demonstrate a considerable influence of the structural changes in the incommensurate and ferroelectric phases on the observed NMR transition frequencies. For some crystal orientations the satellite transitions are followed through the incommensurate into the ferroelectric phase. Whereas in the former typical quasi continuous spectra are observed in the latter several sharp lines appear. The results are discussed in relation to the structural changes at the phase transitions.