Theory of the successive phase transitions in KNbO3

The microscopic mechanism of the successive cubic-tetragonal-orthorhombic-rhombohedral phase transitions in KNbO₃ is discussed quantitatively from the microscopic free energy based upon the mean field approximation where the Nb ions are displaced to create spontaneous deformations. From the calculation of the microscopic free energy, it is shown that the order of the phase transitions and the experimental values of the transition entropy in KNbO₃ are well explained by this model.     

Ferroelectric phase transitions in ultrathin films of BaTiO3

We present molecular dynamics simulations of a realistic model of an ultrathin film of BaTiO3 sandwiched between short-circuited electrodes to determine and understand effects of film thickness, epitaxial strain, and the nature of electrodes on its ferroelectric phase transitions as a function of temperature. We determine a full epitaxial strain-temperature phase diagram in the presence of perfect electrodes. Even with the vanishing depolarization field, we find that ferroelectric phase transitions to states with in-plane and out-of-plane components of polarization exhibit dependence on thickness; it arises from the interactions of local dipoles with their electrostatic images in the presence of electrodes. Secondly, in the presence of relatively bad metal electrodes which only partly compensate the surface charges and depolarization field, a qualitatively different phase with stripelike domains is stabilized at low temperature.     

Investigation of the phase transitions of ferroelectric KIO3 and KNbO3 crystals by optical diffraction

Optical diffraction is reviewed as a technique for investigation of the phase transitions in crystals with a multidomain structure. It has been used to study the phase transitions in KIO₃ and KNbO₃ single crystals. Strong optical diffraction bands resulted from electric domains in KNbO₃ crystals and their change with temperature were observed when a laser beam passed through the crystals. The diffraction patterns observed changed abruptly at 427°C, 223°C, and -50°C respectively, at which KNbO₃ crystals undergo structural phase transitions. It is considered that the change of the diffraction patterns with temperature is due to change of the electric domains in the crystals.     

Structural phase transitions during high-energy ball milling of BaTiO3

Microstructural characterization of ball milled perovskite BaTiO₃ powders has been done by the modeling of X-ray diffraction profiles. The study reveals that on size reduction, BaTiO₃ powders undergo a continuous, displacive, and diffusionless dynamic phase transitions involving tetragonal (T), monoclinic (M), and orthorhombic (O) symmetry via the second-order type [T?→?(T?+?M)?→?(M?+?O)?→?O] when stimulated by a high-power pulse of pressure in a planetary mill. The order parameter, a phenomenological quantity to describe the general behavior of a system going through phase transitions has been estimated using spontaneous strain calculated from lattice parameters or physical distortions derived from atomic coordinates or both. At room temperature, BaTiO₃ nanoparticle achieved an orthorhombic phase when a critical size (<15?nm) has been reached at later stage of milling (≥70?h). Raman's study reveals similar structural phase transitions sequence on size reduction and TEM study reveals the corresponding particle diameter.     

A first-principles study of phase transitions in ultrathin films of BaTiO3

We determine the effects of film thickness, epitaxial strain and the nature of electrodes on ferroelectric phase transitions in ultrathin films of BaTiO₃ using a first-principles effective Hamiltonian in classical molecular dynamics simulations. We present results for polarization and dielectric properties as a function of temperature and epitaxial strain, leading to size-dependent temperature-strain phase diagram for the films sandwiched between ‘perfect’ electrodes. In the presence of non-vanishing depolarization fields when non-ideal electrodes are used, we show that a stable stripe-domain phase is obtained at low temperatures. The electrostatic images in the presence of electrodes and their interaction with local dipoles in the film explain these observed phenomena.      

Determination of the phase transitions in BaTiO3 type crystals by using the theory of symmetry breaking: Etude des transitions de phase dans les cristaux du type BaTiO3 par la theorie des symetries brisees

Crystaks of the BaTiO₃ family showing the following sequence of phase transitions : tetragonal, orthorhombic, rhombohedral, are investigated. From the MASON-MATHIAS model based on a TiO₆ octahedron in which a Ti ion can be displaced along the different pseudo-cubic axes, these different polar structures are found by considering the possible lowering of the O_h symmetry associated with the non polar phase. By the appropriate orientation of the basis of the vector representation connected with the occurence of the polarisation $\text{P}$, the order-parameter of the phase transitions are determined for three cases (O_h → C_4v, C_2v, C_3v). The order of the transition is discussed. These parameters can be used for a thermodynamical investigation of the crystal based on an expansion of its free energy.     

Effect of quantum fluctuations and isotopic substitution on the curie temperature of BaTiO3, PbTiO3, and KNbO3

The Hartree-Fock formalism and density functional theory are used in first-principles calculations of the Landau-Ginzburg free-energy expansion coefficients in the Devonshire-Barrett one-ion model for BaTiO₃, PbTiO₃, and KNbO₃. The Curie temperature T ₀ and the Curie-Weiss constant are calculated. The effect of quantum fluctuations on T ₀ is considered in the approximation of the first quantum correction to the free energy. The quantum shift of the Curie temperature ΔT ₀ ^quant for BaTiO₃, PbTiO₃, and KNbO₃ and the isotopic shift ΔT ₀ ^iso for barium titanate due to the substitution ⁴⁸Ti → ⁴⁶Ti or ⁴⁸Ti → ⁵⁰Ti are calculated.     

Structural phase transitions in KMnF3

The structural transitions of the perovskite KMnF₃ are studied with an energy-dispersive X-ray diffractometer. It is found that the 83 K transition is of first order, though the transition related to the condensation of a M₃-soft phonon mode is considerably affected by crystallographic domain-walls occurring below the 186 K transition. The latter transition is observed at 88.0 K (first-order), and 92.0 K (second-order) in different single crystals, respectively. The difference of the transition temperature and the transition order is interpreted in terms of inner strains appeared in the domain walls.     

Structural phase transitions in CdTiO3

The reconstructive phase transition from the ilmenite-like CdTiO₃ modification to the perovskite modification is investigated thoroughly. It is revealed that the reconstructive transition is determined by size effects, results in the formation of the closest packing of the ilmenite CdTiO₃ structure, and is irreversible with a decrease in temperature. The perovskite CdTiO₃ modification undergoes displacive structural phase transitions at temperatures of 110, 220, and 380°C. The first displacive phase transition is isostructural, whereas the second and third transitions are associated with rotations of oxygen octahedra.     

First-principles study of the temperature-pressure phase diagram of BaTiO3

We investigate the temperature-pressure phase diagram of BaTiO3 using a first-principles effective-Hamiltonian approach. We find that the zero-point motion of the ions affects the form of the phase diagram dramatically. Specifically, when the zero-point fluctuations are included in the calculations, all the polar (tetragonal, orthorhombic, and rhombohedral) phases of BaTiO3 survive down to 0 K, while only the rhombohedral phase does otherwise. This behavior results from a practical equivalence between thermal and quantum fluctuations. Our work confirms the essential correctness of the phase diagram proposed by Ishidate et al. [Phys. Rev. Lett. 78, 2397 (1997)]].     

Emergence of the sub‐THz central peak at phase transitions in artificial BaTiO3/(Ba,Sr)TiO3 superlattices

A prominent central peak in the sub‐THz frequency range was observed in the Raman spectra of BaTiO₃/(Ba,Sr)TiO₃ (BT/BST) superlattice grown on (001)MgO substrate. Both soft and central mode show an anomaly around 200 K and 280 K, which can be correlated with orthorhombic to monoclinic phase transition of BST and BT, respectively. The observed temperature dependence of the central mode enabled us to explain rather broad temperature dependence of the dielectric permittivity previously observed in BT/BST superlattices. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Ferroelectricity and pressure-induced phase transitions in HgTiO3

Using ab initio density functional theory, the ground state of mercury titanate is determined and phase transitions occurring in it at pressures P ?? 210 kbar are analyzed. It is shown that the R3c structure experimentally observed in HgTiO₃ is metastable at P = 0. The ground state structure at T = 0 varies according to the scheme $R3c \to R\bar 3c \to Pbnm$ with increasing pressure in agreement with available experimental data. It is shown that the appearance of ferroelectricity in HgTiO₃ at P = 0 is associated with an unstable soft mode. Some properties of crystals in the $R\bar 3c$ phase are calculated, in particular, the band gap in the GW approximation (E _g = 2.43 eV), which is in better agreement with experimental data than the value obtained in the LDA approximation (1.49 eV). An analysis of the thermodynamic stability explains why the synthesis of mercury titanate is possible only at high pressures.     

Dielectric permittivity and phase transitions in the SrTiO3-KTaO3 system

The dielectric permittivity and losses of the (SrTiO₃)_0.85(KTaO₃)_0.15 solid solution have revealed an unusual behavior at temperatures of 5–300 K and frequencies ranging from 100 Hz to 1 MHz. The dielectric permittivity exhibits a broad maximum at ≈40 K, which obeys the Curie-Weiss law in the high-temperature wing, and the onset of low-temperature relaxation contributions. Besides, while for T>40 K it is a fully ergodic, uniformly ordering system, the uniform polar ordering is replaced with decreasing temperature by two low-temperature phase transitions to a glass-like state. The proposed mechanism for the dielectric relaxation and the observed phase transformations involves reorientation and ordering in the system of electron and hole polarons, which form in the course of charge compensation of the heterovalent ions Sr²⁺, K⁺ and Ti⁴⁺, Ta⁵⁺ distributed randomly in the sublattices. Fiz. Tverd. Tela (St. Petersburg) 39, 2040–2045 (November 1997)     

Anisotropic self-diffraction in KNbO3

Anisotropic diffraction and self-diffraction processes in KNbO₃ crystals are investigated utilizing the large elementr ₅₁ of the electro-optic tensor. Geometrical conditions, polarization changes, phase conjugation, phase doubling and the dynamics of hologram recording are studied theoretically and experimentally. Anisotropic diffraction with equal or different frequencies for recording and reading permits the determination of photo- and dark conductivity. Further material properties are estimated on the assumption that the charge transport is governed by diffusion effects.     

Stress-induced phase transition in ferroelectric domain walls of BaTiO3

The seminal paper by Zhirnov (1958 Zh. Eksp. Teor. Fiz. 35 1175-80) explained why the structure of domain walls in ferroelectrics and ferromagnets is drastically different. Here we show that the antiparallel ferroelectric walls in rhombohedral ferroelectric BaTiO(3) can be switched between the Ising-like state (typical for ferroelectrics) and a Bloch-like state (unusual for ferroelectric walls but typical for magnetic ones). Phase-field simulations using a Ginzburg-Landau-Devonshire model suggest that this symmetry-breaking transition can be induced by a compressive epitaxial stress. The strain-tunable chiral properties of these domain walls promise a range of novel phenomena in epitaxial ferroelectric thin films.     

High-temperature phase transitions in the improper ferroelectric KIO3

The ac conductivity (σ_ac) and dielectric permittivity (?) are determined in the temperature range 300?K?T3 compound. The results indicated that the compound behaves as an improper ferroelectric and undergoes a ferroelectric phase transition from a high temperature rhombohedral phase I to a low temperature monoclinic phase II at T _c?=?(486?±?1)?K. A second structural phase transition was observed around 345?K. The conductivity varies with temperature range and for T?>?428?K intrinsic conduction prevails. Different activation energies in the different temperature regions were calculated. The frequency dependence of σ(ω) was found to follow the universal dynamic response [σ(ω)∝(ω) ^s(T)]. The thermal behaviour of the frequency exponent s(T) suggests the hopping over the barrier model rather than the quantum mechanical tunneling model for the conduction mechanism.