Study of ferroelectric phase transitions in disordered PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> and PbSc<Subscript>1/2</Subscript>Ta<Subscript>1/2</Subscript>O<Subscript>3</Subscript> solid solutions

Ferroelectric phase transitions and thermodynamic properties of disordered PbSc_1/2Ta_1/2O₃ and PbSc_1/2Nb_1/2O₃ solid solutions have been investigated by the Monte Carlo method. The parameters of the effective Hamiltonian were calculated within the generalized Gordon-Kim model. The obtained values of the phase-transition temperatures and spontaneous polarization are in satisfactory agreement with the experimental data.     

Statistical mechanics of cation ordering in PbSc<Subscript>1/2</Subscript>Ta<Subscript>1/2</Subscript>O<Subscript>3</Subscript> and PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> solid solutions

A model Hamiltonian for B cation ordering (Sc-Nb(Ta)) in PbSc_1/2Nb_1/2O₃ and PbSc_1/2Ta_1/2O₃ solid solutions is constructed. The parameters of the model Hamiltonian are determined from the ab initio calculation within the ionic crystal model with allowance made for the deformability and the dipole and quadrupole polarizabilities of the ions. The temperatures of the phase transition due to the ordering of the B cations are calculated by the Monte Carlo method in the mean-field and cluster approximations. The phase transition temperatures calculated by the Monte Carlo method (1920 K for PbSc_1/2Ta_1/2O₃ and 1810 K for PbSc_1/2Nb_1/2O₃) are consistent with the experimental data (1770 and 1450 K, respectively). The thermodynamic properties of the cation ordering are investigated using the Monte Carlo method.     

Local structure of disordered PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> in the region of the diffuse tetragonal phase-rhombohedral phase transition

The local structure of the ferroelectric-relaxor PbSc_1/2Nb_1/2O₃ in the temperature range from 550 to 220 K has been investigated using ⁴⁵Sc nuclear magnetic resonance. It has been found that, in the paraelectric phase at temperatures below 550 K, the crystal consists of regions of an ordered elpasolite structure and inclusions of the disordered tetragonal perovskite phase with displacements along directions of the [001] type. The relative weight of the tetragonal structure in the region of the paraelectric phase is approximately equal to 0.28. Below the temperature of the phase transition from the disordered modification to the polar phase, the relative weight of the tetragonal phase decreases with decreasing temperature. The tetragonal structure is replaced by the trigonal polar structure. In a wide temperature range (∼50 K), there exists a heterophase structure that is characteristic of relaxors. Note that the correlation length of displacements in the tetragonal phase should be very small to explain the absence of indications of the existence of this phase in the diffraction data.     

Ionic displacements and structure of disordered PbFe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript>

A sequence of structural models of unit cells of complex oxides with perovskite-type structure has been constructed to refine the average structure of PbFe_1/2Nb_1/2O₃ (PFN) at temperatures above the ferroelectric Curie point (T _C ～ 110°C). Owing to the analysis of the probability theory considerations, each model is characterized by only two positional fitting parameters. With the use of the intensities of 95 symmetrically independent X-ray reflections from a PFN single crystal at 160°C, a model with the R factor below 3% (K = 2.44%) was chosen. The ravine method has been used to verify the existence of a single minimum for the R factor with respect to the fitting parameter.     

Properties of the ferroelectric ceramics PbSc<Subscript>0.5</Subscript>Ta<Subscript>0.5</Subscript>O<Subscript>3</Subscript> fabricated from an ultradispersed powder

The relaxor ceramics PbSc_0.5Ta_0.5O₃ produced from an ultradispersed powder is studied by X-ray diffraction and dielectric measurements. Before sintering, the powder was subjected to treatment in Bridgman anvils in combination with shear deformation. This method is shown to affect the order parameter and dielectric properties of the ceramics without using long-term high-temperature annealing.     

Acoustic emission and thermal expansion of Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> and Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> crystals

The temperature dependence of the elongation per unit length for Pb(Mg_1/3Nb_2/3)O₃ crystals unannealed after growth and mechanical treatment is investigated in the course of thermocycling. It is revealed that this dependence deviates from linear behavior at temperatures below 350°C. The observed deviation is characteristic of relaxors, is very small in the first cycle, increases with increasing number n of thermocycles, and reaches saturation at n≥3. In the first cycle, a narrow maximum of the acoustic emission activity is observed in the vicinity of 350°C. In the course of thermocycling, the intensity of this maximum decreases and becomes zero at n>3. For (1?x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ crystals, the dependence of the temperature of this acoustic emission maximum on x exhibits a minimum. It is assumed that the phenomena observed are associated with the phase strain hardening due to local phase transitions occurring in compositionally ordered and polar nanoregions.     

Polarization 1/<Emphasis Type=Italic>f</Emphasis> noise in ferroelectric PbFe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> with a diffused phase transition

The dispersion of complex permittivity in ferroelectric PbFe_1/2Nb_1/2O₃ with diffused phase transition at frequencies of 20 Hz-10 kHz was studied. Dielectric measurements revealed that polarization 1/f noise occurs in the region of coexistence of polar and nonpolar phases. It was found that the temperature dependence of parameter α exhibits a singularity when the temperature of the local order parameter rises. Our analysis of the experimental data enables us to say that the source of the noise is the fluctuations of spontaneous polarization.     

Electro-optical polarization mode dispersion in PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript> single crystals

The polarization mode dispersion induced by an external ac electric field in PbMg_1/3Nb_2/3O₃ single crystals is studied experimentally at frequencies of 10⁴–10⁷ Hz. It is established that the discovered electro-optical polarization mode dispersion (EPMD) displays anomalous properties related to the orientation of the induced dipole moments in microregions of the crystal. Analytical expressions describing the peculiarities of the physical properties of relaxors giving rise to the EPMD are obtained.     

Polarization processes in BaBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> and SrBi<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics in infralow-frequency fields

The dielectric nonlinearity in BaBi₂Nb₂O₉ and SrBi₂Ta₂O₉ layered ceramics was studied by measuring their polarization loops and reverse dependences of permittivity. It was shown that the features of the dielectric response of BaBi₂Nb₂O₉ and SrBi₂Ta₂O₉ in strong fields can be explained by glass-like properties and the contribution of the domain structure of the ferroelectric material to repolarization processes, respectively.     

Manifestation of a ferroelectric phase transition in Li<Subscript>0.12</Subscript>Na<Subscript>0.88</Subscript>Ta<Subscript>0.2</Subscript> Nb<Subscript>0.8</Subscript>O<Subscript>3</Subscript> in the Raman spectrum

The ferroelectric-antiferroelectric phase transition in a ceramic solid solution Li_0.12Na_0.88Ta_0.2Nb_0.8O₃ at 350°C was studied using Raman spectroscopy. A considerable broadening of the lines referred to the translational vibrations of the cations in octahedral and cuboctahedral voids and to the vibrations of the oxygen framework, along with a decrease to zero of the intensity of the line corresponding to the bridge stretching mode of the oxygen atoms from the octahedral anion BO₆, was found to take place as the temperature of the solid solution approaches the transition point from below. It is shown that, during the transition, the solid solution loses its ferroelectric properties, probably owing to the preferential increase in the anharmonicity of the vibrations of the cations in the octahedral voids.     

Dielectric dispersion and magnetic properties of Ba-modified Pb(Fe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)O<Subscript>3</Subscript>

The polycrystalline samples of Ba-modified Pb(Fe_1/2Nb_1/2)O₃ (i.e., (Pb_1-xBa_x)(Fe_1/2Nb_1/2)O₃ PBFN, with x=0,0.05,0.07) were synthesized by a mechanosynthesis (i.e., high-energy ball milling) route followed by a mixed oxide method. Structural analysis provides the information on formation of single-phase orthorhombic structure on substitution of a small amount (x=0.07) of Ba at the Pb-site of Pb(Fe_0.50Nb_0.50)O₃ (PFN). The ferroelectric–paraelectric phase transition in PFN was observed at 383 K, which decreases on increasing Ba-concentration in PBFN. Detailed studies of dielectric properties of PBFW show the following: (i) diffuse phase transition, (ii) low loss tangent, (iii) low activation energy, and (iv) low frequency dielectric dispersion. An anomaly in the ac conductivity was found very close to phase transition temperature. The activation energy is found to decrease from 0.19 to 0.01 eV on increasing Ba-concentration to 7% (x=0.07). Temperature field-dependent magnetization measurements of all the samples showed antiferromagnetic transition at ∼15 K (for x=0.07). PBFN sample showed a slight increase in the coercivity (i.e., from 400 Oe (PFN) to 500 Oe (PBFN, for x=0.07) at 2 K. PACS 61.10.Nz; 68.37.Hk; 75.50.Ss; 75.60.Ej; 77.22.Ch; 77.22.Gm     

Heat capacity study of relaxor PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript> in a wide temperature range

Heat capacity of the PbMg_1/3Nb_2/3O₃ compound is measured using the methods of adiabatic and differential scanning calorimetry in the temperature range 80–750 K. Two blurred anomalies on the C _p (T) dependence are observed in wide temperature intervals of 200–400 K and 500–700 K. The results of studies are discussed together with data on the structure and phonon spectrum in the framework of spherical random bond-random field model.     

Effect of the la concentration on the dielectric and optical properties of the transparent ferroelectric ceramics 75PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript>-25PbTiO<Subscript>3</Subscript>

The dielectric, optical, and electro-optical properties of transparent ferroelectric ceramics 75PbMg_1/3Nb_2/3O₃-25PbTiO₃ (75PMN-25PT) with different La concentrations (2, 3, and 4 at %) have been studied. It has been shown that all the samples under study undergo a diffuse phase transition, and the degree of diffuseness increases with an increase in the La concentration. The temperature dependences of the optical transmission in different regimes of applying an electric field and the quadratic electro-optical effect have been investigated. It has been found that, at room temperature, the maximum electro-optical effect is observed in the ceramics with a La concentration of 3 at %. This is explained by the fact that the measurement temperature is close to the Vogel-Fulcher temperature at which the minimum electric field is required to induce ferroelectric states from the relaxor phase.     

The role of the secondary pyroelectric effect in a ferroelectric relaxor 0.72Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>-0.28PbTiO<Subscript>3</Subscript>

The depth profile of the pyroelectric coefficient effective values of a 0.72Pb(Mg_1/3Nb_2/3)O₃-0.28PbTiO₃ (PMN-0.28PT) single crystal is studied. It was shown that owing to high pyroelectric coefficients the secondary pyroelectric effect significally contributes (∼40%) to the total pyroelectric coefficient.     

Heterophase states in 0.10PbTiO<Subscript>3</Subscript>-0.90Pb(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> crystals

A new model of the elastic matching of phases is proposed, and heterophase structures near the morphotropic phase boundary in 0.10PbTiO₃-0.90Pb(Zn_1/3Nb_2/3)O₃ crystals are studied. Unique behavior of the unit cell parameters is found to favor the elastic matching of the ferroelectric tetragonal and orthorhombic phases under the conditions of complete or partial relaxation of internal mechanical stresses at a volume concentration ratio of these phases of about 20/80% and temperatures of T=20–300 K. Interrelations between the volume concentrations of different domain (twin) types and of the coexisting phases are analyzed.     

Nonergodic state of relaxation ferroelectric Cd<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>7</Subscript> in a constant electric field

The temperature dependence of the residual polarization of the nonergodic relaxation state (NERS) obtained from the measurements of pyroelectric current during zero-field heating (ZFH) in the temperature interval from 10 to 295 K is investigated for the Cd₂Nb₂O₇ relaxation system in two cases: (1) after sample cooling in a constant electric field E (FC) from T = 295 K to a preset temperature, which is much lower than the “freezing” temperature of the relaxation state (T _f ≈ 182 K), field removal, and subsequent cooling in zero field (ZFC) to T = 10 K and (2) after ZFC from T = 295 K to the same temperature below T _f , application of the same field, and FC to T = 10 K. The behavior of the P _r ^FC (T) and P _r ^ZFC (T) dependences is analyzed. In the field E < 2 kV/cm, the P _r ^ZFC curves as functions of 1/T have a broad low-intensity peak in the region T ≈ T _f , which vanishes in stronger fields, when the P _r ^FC (1/T) curves intersect at T ≈ T _f and have no anomalies. The difference in the behavior of P _r ^ZFC (T) and P _r ^FC (T) indicates the difference in the nature of NERS formed during ZFC and FC of the system upon a transition through T _f . In the ZFC mode, NERS exhibits glasslike behavior; in the FC regime, features of the ferroelectric behavior even in the weak field. Analogous variations of P _r ^ZFC (T) and P _r ^FC (T) in a classical ferroelectric KDP are also given for comparison.     

Magnetism of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> manganite in structurally ordered and disordered states

The specific features of the crystal structure and the magnetic state of stoichiometric lithium manganite in the structurally ordered Li[Mn₂]O₄ and disordered Li_{1 − δ}Mn_δ[Mn_{2 − δ}Li_δ]O₄ (δ = 1/6) states have been investigated using neutron diffraction, X-ray diffraction, and magnetic methods. The structurally disordered state of the manganite was achieved under irradiation by fast neutrons (E _eff ≥ 1 MeV) with a fluence of 2 × 10²⁰ cm⁻² at a temperature of 340 K. It has been demonstrated that, in the initial sample, the charge ordering of manganese ions of different valences arises at room temperature, which is accompanied by orthorhombic distortions of the cubic spinel structure, and the long-range antiferromagnetic order with the wave vector k = 2π/c(0, 0, 0.44) is observed at low temperatures. It has been established that the structural disordering leads to radical changes in the structural and magnetic states of the LiMn₂O₄ manganite. The charge ordering is destroyed, and the structure retains the cubic symmetry even at a temperature of 5 K. The antiferromagnetic type of ordering transforms into ferrimagnetic ordering with local spin deviations in the octahedral sublattice due to the appearance of intersublattice exchange interactions.     

Dielectric and optical properties of Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)<Subscript>0.8</Subscript>Ti<Subscript>0.2</Subscript>O<Subscript>3</Subscript> (PMNT-0.2) ferroelectric relaxor single crystals

The dielectric and optical (optical transmission, small-angle light scattering, birefringence) properties of PMNT-0.2 single crystals and their variation induced by a dc electric field have been studied. The birefringence was found to increase anomalously at the transition from the rhombohedral ferroelectric to the inhomogeneous relaxor phase (the spontaneous ferroelectric transition temperature T_sp). Below T_sp, the dielectric and optical properties were observed to exhibit anomalies originating from reorientation and growth of domains in size. Unlike ferroelectric relaxors of the type of PbB′_1/3B′_2/3O₃ and PbB′_1/2B′_1/2O₃, in PMNT-0.2 neither induction of the ferroelectric phase by an electric field nor thermally stimulated destruction of the ferroelectric state occurs through the percolation mechanism (i.e., they are not accompanied by anomalously narrow maxima in small-angle light scattering). This is attributed to the inhomogeneous structure of the relaxor phase, as a result of which the phase transition does not take place simultaneously in various regions of the crystal.