Acoustic properties of glycine phosphite crystals with an admixture of glycine phosphate

Acoustic and dielectric anomalies in the region of the ferroelectric phase transition in crystals of glycine phosphite (GPI) with a 2 mol % admixture of glycine phosphate (GP) are studied. The acoustic anomalies were found to differ strongly from those observed in nominally pure glycine phosphite crystals. A theoretical analysis of the acoustic and dielectric properties of the crystals was carried out within the model of a pseudoproper ferroelectric phase transition. It is shown that the acoustic anomalies, as well as the temperature dependences of the dielectric constant (for various external electric fields) and pyroelectric current observed in the vicinity of the phase transition in GPI-GP crystals, can be adequately described when the macroscopic polarization present in these crystals above the phase transition temperature is taken into account. The thermodynamic-potential parameters describing electrostriction and the biquadratic relation between the polarization and strain turned out to be close to those characterizing a nominally pure GPI crystal. An irreversible phase transition was observed to occur in GPI-GP crystals at T = 240 K, i.e., above the ferroelectric phase transition temperature.     

Features of the low-frequency polarization response in the region of the ferroelectric phase transition in multiferroic TbMnO<Subscript>3</Subscript>

The unusual behavior of the low-frequency (10 Hz–1 MHz) permittivity in single crystals of ferroelectric multiferroic TbMnO₃ has been experimentally and theoretically studied in detail in the region of the narrow temperature peak of the permittivity, associated with the ferroelectric phase transition (T_C ~ 27.4 K). It has been found that the ε_c^′(ω, T) maximum sharply decreases with increasing measured field frequency, while the temperature position of the maximum is independent of frequency. It has been shown that the observed features of the polarization response can be satisfactorily described within the Landau–Khalatnikov polarization relaxation theory.     

Dielectric properties of betaine phosphite-betaine phosphate solid-solution crystals in the improper ferroelastic phase

Temperature dependences of dielectric permittivity in the improper ferroelastic phase, including the region of the improper ferroelastic phase transition occurring at T=T_c1, were studied in the betaine phosphite-betaine phosphate solid-solution crystals. At a betaine phosphate (BP) concentration of 10%, the phase transition temperature T_c1 was found to shift toward higher temperatures by about 5 K compared to betaine phosphite (BPI) crystals, where T_c1=355 K. The phase transition remains in the vicinity of the tricritical point. As the BP concentration in BPI is increased, the dielectric anomaly at T=T_c1 weakens substantially compared to pure BPI. The nonlinear temperature dependence of reciprocal dielectric permittivity in the improper ferroelastic phase of BPI_xBP_1?x crystals is described in the concentration region 0.9≤x≤1 in terms of a thermodynamic model taking into account the biquadratic relation of the nonpolar order parameter of the improper ferroelastic phase transition to polarization. The decrease in the ferroelectric phase transition temperature T_c1 (or in the temperature of loss of improper ferroelastic phase stability) with increasing BP concentration in the above limits is due to the decreasing effect of the nonpolar mode on the polar instability, which is accompanied by a weakening of the dielectric anomaly at T=T_c1     

Mechanism of the polarization response in the relaxor state of lead scandotantalate single crystals with different levels of ion ordering

The dielectric properties and optical transmission of stoichiometric lead scandotantalate (PST) single crystals in strong electric fields was studied above the temperature of the spontaneous ferroelectric phase transition (T_sp). It is shown that the mechanism of polarization response directly above T_sp is related to induced polarization effects and macrohysteretic behavior only in ac fields above 5 kV/cm. Ananalysis of reciprocal dielectric permittivity carried out over a broad temperature range far above the temperature at which the dielectric permittivity passes through a maximum revealed that specific features of the relaxor behavior manifest themselves up to 400°C even in highly ordered PST crystals.     

Thermooptical and Dielectric Studies of a Calcium-Induced Ferroelectric Phase in a SrTiO<Subscript>3</Subscript> Incipient Ferroelectric

We have examined temperature changes of the light refraction, birefringence, dielectric permittivity, and dielectric hysteresis loops in Sr_{1 – x}Ca_xTiO₃ single crystals with x = 0.014 (SCT-1.4). The dielectric properties of Sr_{1 – x}Ca_xTiO₃ with x = 0.007 (SCT-0.7) have been studied. We have performed ab initio calculations of equilibrium structures and total energies for three low-temperature phases of SrTiO₃ and CaTiO₃, based on which we have determined an expected symmetry of the ground state of their solid solution and spontaneous polarization directions in a calcium-induced ferroelectric phase in Sr_{1 – x}Ca_xTiO₃. In SCT-1.4, we have separated a spontaneous contribution to the light refraction, which arises due to the spontaneous electrooptical effect caused by the spontaneous polarization and its fluctuations. From the spontaneous contribution to the light refraction, based on a previously developed our phenological approach, we have quantitatively determined for the first time the values and temperature dependences of root-mean-square fluctuations of the order parameter—the polarization P_sh = 〈P _fl ² 〉^1/2(short-range, local polar order) in the ferroelectric phase. From optical and dielectric measurements in SCT-1.4, the average value of spontaneous polarization P_s (the contribution from the long-range order) has been determined. We have estimated the values of P_sh and P_s, which characterize the short- and long-range orders in the ferroelectric phase of SCT-0.7. Separate determination of the values and temperature dependences of P_s and P_sh (which considerably exceeds the value of P_s in the ordered phase) has allowed us to reveal on a quantitative level new particular features of the formation of the induced polar phase in Sr_{1 – x}Ca_xTiO₃.     

Specific features of dielectric anomalies in Pb<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te(Ga) near a ferroelectric phase transition

The dielectric properties of Pb_{1 ? x} Ge _x Te(Ga) (x = 0.02, 0.03, 0.05) were studied in the temperature range 77–150 K at frequencies of 10⁴–10⁶ Hz. It is revealed that the ferroelectric phase transition temperature T _c and the permittivity ? of Pb_{1 ? x} Ge _x Te(Ga) increase substantially with the Ge content. The temperature dependence of the permittivity of Pb_{1 ? x} Ge _x Te shows two peaks; the main peak is at the ferroelectric phase transition temperature T _c , and an additional peak is at T ₁ > T _c .     

Electrical instability of LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> crystals

The temperature behavior of I-U curves and the field and temperature dependences of the electrical resistivity and dielectric permittivity of crystals of the LiCu₂O₂ phase have been studied. It was established that the crystals belong to p-type semiconductors and that their static resistivity in the range 80–260 K follows the Mott law ρ=Aexp(T₀/T)^1/4 describing variable-range hopping over localized states. At comparatively low electric fields, the crystals exhibit threshold switching and characteristic S-shaped I-U curves containing a region of negative differential resistivity. In the critical voltage region, jumps in the conductivity and dielectric permittivity are observed. Possible mechanisms of the disorder and electrical instability in these crystals are discussed.     

Optical properties of lithium niobate and lithium tantalate crystals with impurities and defects

The photoinduced and Raman scattering in lithium niobate and lithium tantalate crystals with impurities and defects have been studied. An exciting laser beam propagated either along the ferroelectric Z axis or perpendicular to it. The conditions for exciting transverse and longitudinal polar optical modes in Raman spectra are established. The regularities of the excitation of Raman spectra in several polarization geometries (X(ZZ)Y, Z(XX, Y Y)Z, Z(XX, Y Y)Z, X(ZX)Y, X(ZX)X and X(ZX)X) have been investigated. Additional (extra) spectral lines are interpreted as a manifestation of a biphonon enhanced by the Fermi resonance and the result of violation of selection rules for pseudoscalar modes of the A ₂ type due to the reduction of the point symmetry group caused by the presence of impurities and defects in real crystals. The conditions for exciting coherent longitudinal and transverse modes in lithium niobate and lithium tantalate single crystals upon stimulated Raman scattering are analyzed. The temperature evolution of the spectra recorded in the X(ZZ)Y geometry near the ferroelectric phase transition point is explained based on the concept of effective soft mode and analysis of the isofrequency opalescence effect. Strong photoluminescence is found in copper-doped lithium niobate crystals.     

Lattice dynamics of BiFeO<Subscript>3</Subscript> under hydrostatic pressure

The vibrational frequencies of the BiFeO₃ crystal lattice in the cubic phase (Pm3m) and the rhombohedral paraelectric phase (R3c) are calculated in terms of the ab initio model of an ionic crystal with the inclusion of the dipole and quadrupole polarizabilities. In the ferroelectric phase with the symmetry R3c, the calculated spontaneous polarization of 136 μC cm^?2 agrees well with the experimental data. The dependences of the unit cell volume, the elastic modulus, and the vibrational frequencies on the pressure are calculated. It is found that the frequency of an unstable ferroelectric mode in both the cubic (Pm3m) and rhombohedral (R3c) phases are almost independent of the applied pressure, in contrast to classical ferroelectrics with a perovskite structure, where the ferroelectric instability is very sensitive to a variation in the pressure.     

Raman Scattering on the Effective Soft Mode for Lithium Niobate Crystals

The evolution of Raman spectra in a wide range of temperatures that includes the ferroelectric transition point in lithium niobate single crystals is studied for polarization geometry X(ZZ)Y. In this geometry, the soft mode responsible for the phase transition distinguished by 1A₁(TO)-type symmetry should appear in the spectra. Experimental studies show that the 1A₁(TO) mode interacts resonantly with nonfundamental modes in the low-frequency region of the spectrum. Near the ferroelectric phase transition point, an isofrequency opalescence effect is observed that consists of an abrupt increase in Raman signal intensity at fixed frequencies near the excitation line.     

Possibility of inducing superparaelectricity in strontium bismuth titanate ceramics SrTiO<Subscript>3</Subscript>: Bi

Dielectric strontium bismuth titanate ceramics SrTiO₃: Bi is a complex solid solution consisting of the Sr_1?uBi_2u/3□_u/3TiO₃ perovskite matrix and small planar inclusions related to Aurivillius-type layered ferroelectric compounds with a high Curie temperature T_C (700–950 K). The matrix is characterized by a smeared ferroelectric phase transition in the temperature range 150–200 K and exhibits relaxation dielectric polarization. At temperatures below but close to the Curie temperature T_C, the state of the ceramics can be treated as superparaelectric. The concentration dependence of the temperature corresponding to the maximum of the permittivity is explained.     

Spontaneous ferroelectricity in strained low-temperature monoclinic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>: A first-principles study

As a single-phase multiferroic material, Fe₃O₄ exhibits spontaneous ferroelectric polarization below 38 K. However, the nature of the ferroelectricity in Fe₃O₄ and effect of external disturbances such as strain on it remains ambiguous. Here, the spontaneous ferroelectric polarization of low-temperature monoclinic Fe₃O₄ was investigated by first-principles calculations. The pseudo-centrosymmetric FeB42–FeB43 pair has a different valence state. The noncentrosymmetric charge distribution results in ferroelectric polarization. The initial ferroelectric polarization direction is in the -x and -z directions. The ferroelectricity along the y axis is limited owing to the symmetry of the Cc space group. Both the ionic displacement and charge separation at the FeB42–FeB43 pair are affected by strain, which further influences the spontaneous ferroelectric polarization of monoclinic Fe₃O₄. The ferroelectric polarization along the z axis exhibits an increase of 45.3% as the strain changes from 6% to -6%.     

Phase transitions and spin excitations in new multiferroics with modulated magnetic structure

Coexistence of an antiferromagnetic (modulated) structure and electric polarization has been revealed in single crystals of Eu_{1 ? x} Y_xMnO₃ (0.2 ≤ x ≤ 0.5) and Gd_{1 ? x} Y_xMnO₃ (0 ≤ x ≤ 0.2) manganites. Hence, these compounds can be considered as a new family of multiferroics. Various phase transitions, both spontaneous and induced by magnetic fields up to 250 kOe, accompanied by anomalies in magnetization, magnetostriction, permittivity, and electric polarization, have been found, and phase T-x diagrams have been constructed. In the submillimeter range (8–40 cm^?1), new spin excitations—electromagnons—have been revealed; they are excited by an electric field. It is established that suppression of the modulated structure by a magnetic field leads to the disappearance of electromagnons; this process is accompanied by significant changes in the permittivity in a wide frequency range.     

Long-time relaxation phenomena in Pb<Subscript>0.94</Subscript>Ba<Subscript>0.06</Subscript>Sc<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> (PBSN-6) single crystals

Long-time polarization relaxation in the temperature range where PBSN-6 single crystals reside in the relaxor state was studied. An analysis of the time dependence of the permittivity ε′(t) performed at measuring frequencies from 1 Hz to 1 kHz in weak electric fields E₀ showed that the relaxation (or freezing) times derived by extrapolating relations of the type ε′(t) ～ log(t/t₀) and ε′(t) ～ exp{?[ln(t/t₀)]_β} range from 10⁸ to 10¹¹ min and depend substantially on the bias voltage applied to the sample. A study of the pattern of the dielectric response in moderate and strong infralow-frequency fields revealed that, after a sample was maintained under a bias lower than the coercive force, it no longer exhibited the additional anomalies in the amplitude dependences of the effective loss tangent tan_eff(E₀) than were observed in a thermally recuperated sample.     

Switching of spontaneous electric polarization in the DyMnO<Subscript>3</Subscript> multiferroic

For the DyMnO₃ multiferroic with a modulated magnetic structure, switching of its spontaneous electric polarization (P ‖ c axis) near the ferroelectric transition (T < T _FE ～ 20 K) is revealed by measuring the dielectric hysteresis loops. It is found that the coercive field strongly increases as the temperature decreases (up to 2.6 kV/mm at 17.6 K). The values obtained for the spontaneous polarization are found to agree well with the data obtained from pyroelectric measurements. In addition, anomalies are observed in the temperature dependences of the spontaneous polarization P _c , dielectric constant ? _c , and magnetic susceptibility x _b at T ～ 6 K; these anomalies are attributed to the antiferromagnetic ordering of the Dy³⁺ ions.     

Depolarization field and properties of thin ferroelectric films with inclusion of the electrode effect

The influence of metallic electrodes on the properties of thin ferroelectric films is considered in the framework of the Ginzburg-Landau phenomenological theory. The contribution of the electrodes with different screening lengths l _s of carriers in the electrode material is included in the free-energy functional. The critical temperature T _cl , the critical thickness of the film, and the critical screening length of the electrode at which the ferroelectric phase transforms into the paraelectric phase are calculated. The Euler-Lagrange equation for the polarization P is solved by the direct variational method. The results demonstrate that the film properties can be calculated by minimizing the free energy, which has a standard form but involves the coefficient of the term P². This coefficient depends not only on the temperature but also on the film thickness, the surface and correlation effects, and the electrode characteristics. The calculations of the polarization, the dielectric susceptibility, the pyroelectric coefficient, and the depolarization field show that the ferroelectric state of the film can be destroyed using electrodes from a material whose screening length exceeds a critical value. This means that the electrodes being in operation can induce a transition from the ferroelectric phase to the paraelectric phase. The quantitative criteria obtained indicate that the phase state and properties of thin ferroelectric films can be controlled by choosing the appropriate electrode material.     

Spectral representation for singlet and triplet green's functions

Spectral representations of special Green functions are given explicitly. We consider the density correlation functionG ₂(x ₁ η ₁ x ₂ η ₂,x ₁ ⁺ η ₁ x ₂ ⁺ η′₂) and the functionG ₂(x ₁ η ₁ x ₁ ^? η₂,x ₂ η ₁ ^′ x ₂ ^? η ₂ ^′ Coupling the field operators Ψ^? (x, η), Ψ(x, η) to singlet and triplet operatorsA _{SMs TT3} (x), we obtain spectral representations for theseG-functions. The formulae derived may be of use when studying the system of equations for the Green functions, which describe many particle systems from a microscopic point of view.     

Electrophysical properties of six-component ZTS-based ferrosoft ceramic

The properties of six-component ZTS-based ferrosoft ceramic are studied. The ceramic is found to exhibit properties of a ferroelectric relaxor. The R3c → R3m rhombohedral phase transition is observed in the ferroelectric phase of this composite. Polarization of samples with a constant electric field upon cooling through the Curie point enlarges the temperature range of the R3m phase’s existence, compared to roomtemperature polarization.     

Heat capacity of the Pb<Subscript>5</Subscript>(Ge<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Si<Subscript>x</Subscript>)<Subscript>3</Subscript>O<Subscript>11</Subscript> ferroelectric system

The temperature dependences of the molar heat capacity at constant pressure, C_p, of Pb₅(Ge_1?xSi_x)₃O₁₁ crystals with x=0, 0.39, and 0.45 in the range 5–300 K, as well as of their permittivity, dielectric losses, and the pyroelectric effect, have been measured. Experimental data on the temperature behavior of the heat capacity are presented in the form of a sum of two Debye and one Einstein terms, C_p(T)=0.405C_D1(Θ_D1=160 K, T)+0.53C_D2(Θ_D2=750 K, T)+0.046C_E(Θ_E=47 K, T). Besides a peak in the region of the ferroelectric Curie point T_c=450 K for crystals with x=0, the temperature dependences of the heat capacity did not reveal any other pronounced anomalies.     

Magneto-optical spectroscopy and optical detection of EPR spectra of Yb<Superscript>3+</Superscript> paramagnetic centers with cubic symmetry in single crystals <Emphasis Type="Italic">Me</Emphasis>F<Subscript>2</Subscript> (<Emphasis Type="Italic">Me</Emphasis> = Cd,Ca, Pb)

Cubic paramagnetic centers formed by Yb³⁺ impurity ions in fluorite-type crystals MeF₂ (Me = Cd, Ca, Pb) have been investigated using electron paramagnetic resonance, magnetic circular dichroism, magnetic circular polarization of luminescence, Zeeman splitting of optical absorption and luminescence lines, and optical detection of electron paramagnetic resonance. The g factors of the ²Γ₇ state in the excited multiplet ² F _5/2 of Yb³⁺ ions in Me F₂ crystals, the hyperfine interaction constant ¹⁷¹ A (¹⁷¹Yb) for the excited multiplet ² F _5/2 in the CaF₂ crystal, and the energies and symmetry properties of all energy levels of Yb³⁺ ions in MeF₂ crystals are determined. The crystal-field parameters for the crystals under investigation are calculated.