Optical studies of phase transitions in the (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>Ti(O<Subscript>2</Subscript>)F<Subscript>5</Subscript> crystal

Polarization-optical study of twinning and measurements of the Raman spectra and birefringence in oxyfluoride (NH₄)₃Ti(O₂)F₅ were carried out over the temperature range 90–350 K. Phase transitions were detected at temperatures T ₀₁ = 266 K (second-order transition) and T ₀₂ = 225 K (first order). It is assumed that the crystal symmetry is changed as follows: Fm3m ? I4/mmm ? I4/m. Anomalies of the spectral parameters are established in the frequency range of internal vibrations of ammonium ions and Ti(O₂)F₅ complexes. An analysis of the results shows that the transition at T ₀₁ is likely due to small shifts of the tetrahedral groups from their position on the triad axis and that the transition at T ₀₂ is due to fluorine-oxygen ordering of Ti(O₂)F₅ complexes.     

Piezo-optic effect in Cu<Subscript>6</Subscript>PS<Subscript>5</Subscript>Br crystals

The effect of hydrostatic (P=10–400 MPa) and uniaxial σ=0–5.8 MPa) pressures on birefringence Δn of Cu₆PS₅Br single crystals at the wavelength λ=0.6328 μm has been studied below the temperature of the ferroelastic phase transition (T<268 K). It is found that Δn linearly depends on pressure. The obtained data are analyzed.     

Phase transitions in the oxyfluoride (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>NbOF<Subscript>6</Subscript>

(NH₄)₃NbOF₆ single crystals were grown, polarization-optical studies were performed, and birefringence was measured over the temperature range 90–500 K. A sequence of first-order structural phase transitions was found at temperatures T _1↓ = 259.7 K and T _2↓ = 257.7 K with temperature hysteresis δT ₁ = 0.9 K and δT ₂ = 1.9 K. The transitions are accompanied by twinning and the following change in the crystal symmetry: cubic ? tetragonal ? monoclinic. Optical second harmonic generation is found to occur at room temperature, which indicates that the cubic phase is not centrosymmetric. It is assumed that the phase transitions are ferroelastic and ferroelectric in nature.     

High-resolution spectroscopy of HoFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystal: a study of phase transitions

The transmission spectra of HoFe₃(BO₃) multiferroic single crystals are studied by optical Fourier-transform spectroscopy at temperatures of 1.7–423 K in polarized light in the spectral range 500–10 000 cm^–1 with a resolution up to 0.1 cm^–1. A new first-order structural phase transition close to the second-order transition is recorded at T_c = 360 K by the appearance of a new phonon mode at 976 cm^–1. The reasons for considerable differences in T_c for different samples of holmium ferroborate are discussed. By temperature variations in the spectra of the f–f transitions in the Ho³⁺ ion, we studied two magnetic phase transitions, namely, magnetic ordering into an easy-plane structure as a second-order phase transition at T_N = 39 K and spin reorientation from the ab plane to the c axis as a first-order phase transition at T_SR = 4.7 ± 0.2 K. It is shown that erbium impurity in a concentration of 1 at % decreases the spin-reorientation transition temperature to T_SR = 4.0 K.     

Elastic properties of La<Subscript>0.82</Subscript>Ca<Subscript>0.18</Subscript>MnO<Subscript>3</Subscript> single crystal

The temperature dependences of the velocity of longitudinal sound waves and the internal friction in a La_0.82Ca_0.18MnO₃ single crystal with the Curie temperature T _C = 181 K have been studied. As temperature decreases, the single crystal is shown to undergo the transition from the pseudocubic O* to the Jahn–Teller O’ phase at T ~ 254 K and the reverse transition from O’ to O* phase at T ~ 84 K. The velocity of sound and the internal friction in the O’ phase are found to be significantly smaller than those in the O* phase.     

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.     

X-ray study of [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> at low temperatures

The unit cell parameters a, b, and c of [N(CH₃)₄]₂ZnCl₄ have been measured by x-ray diffraction in the temperature range 80–293 K. Temperature dependences of the thermal expansion coefficients α_a, α_b, and α_c along the principal crystallographic axes and of the unit cell thermal expansion coefficient α_V were determined. It is shown that the a=f(T), b=f(T), and c=f(T) curves exhibit anomalies in the form of jumps at phase transition temperatures T₁=161 K and T₂=181 K and that the phase transition occurring at T₃=276 K manifests itself in the a=f(T) and b=f(T) curves as a break. A slight anisotropy in the coefficient of thermal expansion of the crystal was revealed. The phase transitions occurring at T₁=161 K and T₂=181 K in [N(CH₃)₄]₂ZnCl₄ were established to be first-order.     

Thermophysical study of structural phase transitions in Na<Subscript>0.95</Subscript>Li<Subscript>0.05</Subscript>NbO<Subscript>3</Subscript> solid solution

Temperature dependences of specific heat C_p(T) and coefficient of thermal expansion ;(T) for Na_0.95Li_0.05NbO₃ sodium-lithium niobate ceramic samples are investigated in the temperature range of 100–800 K. The C_p(T) and α(T) anomalies at T₃ = 310 ± 3 K, T₂ = 630 ± 8 K, and T₁ = 710 ± 10 K are observed, which correspond to the sequence of phase transitions N ? Q ? S(R) ? T2(S). The effect of heat treatment of the samples on the sequence of structural distortions was established. It is demonstrated that annealing of the samples at 603 K leads to splitting of the anomaly corresponding to the phase transition Q → R/S in two anomalies. After sample heating to 800 K, the only anomaly is observed in both the C_p(T) and ;(T) dependence. Possible mechanisms of the observed phenomena are discussed.     

Transient optical absorption induced by an electron pulse in KPb<Subscript>2</Subscript>Cl<Subscript>5</Subscript> crystals

The efficiency of formation and time evolution of radiation-induced structural defects and pulsed luminescence in KPb₂Cl₅ crystals under the action of a single electron pulse (E = 250 keV, τ = 20 ns) have been investigated. The spectra (1.1–3.8 eV) and relaxation kinetics (time interval 5 × 10^?8?5 s) of transient optical absorption and the pulsed cathodoluminescence spectra and decay kinetics (1.4–3.1 eV) have been measured in the temperature range 80–300 K. It is revealed that the induced optical density and its time evolution depend strongly on temperature, and the absorption relaxation time contains several components and reaches several seconds at T = 300 K. The decay kinetics of transient absorption and pulsed cathodoluminescence kinetics have different orders and are controlled by different relaxation processes.     

Elastic and kinetic properties of single-crystal La<Subscript>0.75</Subscript>Ba<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript>

An experimental study of the temperature behavior of longitudinal sound velocity, internal friction, electrical resistivity, and thermopower of single-crystal La_0.75Ba_0.25MnO₃ is reported. A structural transition accompanied by a large jump (18%) in the sound velocity was found to occur at T _S ≈170 K. Within the interval 156–350 K, the temperature dependences of the sound velocity and internal friction reveal a temperature hysteresis. An internal-friction peak due to relaxation processes was detected. The metallic and semiconducting regions are separated by a transition domain about 80 K wide lying below the Curie temperature T _C =300 K.     

Optical and dielectric studies of phase transitions in single crystals of NaNbO<Subscript>3</Subscript>-Gd<Subscript>1/3</Subscript>NbO<Subscript>3</Subscript> solid solutions

The temperature dependences of the permittivity ? and the false-color image patterns obtained by the rotating polarizer method for single crystals of (1 ? x)NaNbO_3?x Gd_1/3NbO₃ (x = 0.003, 0.090) solid solutions with different degrees of diffuseness of the phase transition are investigated. A multifractal analysis of the false-color images has revealed anomalies in the temperature dependences of the parameter ?_∞ of the multifractal spectrum. For a sample with a sharp phase transition (x ≈ 0.003), the temperature of this anomaly is in good agreement with the temperature of the jumps in the permittivity ?(T) and birefringence. For an NNG crystal with x ≈ 0.09, which exhibits a diffuse maximum of ?(T), the temperatures of the anomalies of ?_∞(T) differ in the central and peripheral regions, which correlates with the distribution of Gd over the crystal.     

Crystallographic characteristics and phase transitions in the [N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>CdBr<Subscript>4</Subscript> crystal in the low-temperature range

The results of x-ray structural studies of the [N(C₂H₅)₄]₂CdBr₄ crystal at low temperatures are presented. The unit cell parameters and the thermal expansion coefficients along the main crystallographic directions are measured at temperatures in the range from 90 to 320 K. The integrated intensities of the diffraction reflections are investigated as a function of the temperature. It is shown that the curves a = f(T), c = f(T), I ₅₀₀ = f(T), and I ₀₀₆ = f(T) at temperatures T ₁ ≈ 174 K and T ₂ ≈ 226 K exhibit anomalies in the form of abrupt changes in the lattice parameters and the diffraction reflection intensities. This indicates that the [N(C₂H₅)₄]₂CdBr₄ crystal undergo phase transitions at these temperatures. Moreover, there is an anomaly in the form of a small maximum at the temperature T ₃ = 293 K.     

Study of the anisotropy of the dielectric response of Na<Subscript>1/2</Subscript>Bi<Subscript>1/2</Subscript>TiO<Subscript>3</Subscript> relaxor ferroelectric

The dielectric response, conductivity, and domain structure of (Na_1/2Bi_1/2)TiO₃ single crystals are studied in the temperature range of 290–750 K for the [100], [110], and [111] crystallographic directions. It is shown that the region of optical isotropization is observed in polarized light in the temperature range of 570–620 K. In this case, the birefringence (Δn) decreases and disappears (together with the image of the domain structure) for the [100] directions. The region of optical isotropization in the [111] directions is characterized by the disappearance of the image of the domain structure and by the existence of individual regions with partial quenching. The domain structure in the [110] directions remains distinguished against the background of a significant decrease in Δn in the indicated temperature range. The region of isotropization is also manifested in the temperature dependence of the imaginary part of the dielectric response and is determined by the isotropic character of the conductivity in the range of 570–620 K. The bulk conductivity has a thermally activated character with activation energies E _a = 50?60 meV at T < 500 K and E _a = 700?900 meV for T > 620 K. The low-frequency dispersion of the dielectric response is determined by the Maxwell–Wagner mechanism and is due to an increase in the ionic conductivity at temperatures above 620 K. The anisotropy of the susceptibility holds in the entire studied ranges of frequencies (25 Hz–1 MHz) and temperatures.     

Nature of low-temperature phase transitions in CaMn<Subscript>7</Subscript>O<Subscript>12</Subscript>

New data on the specific heat, thermal expansion, and magnetization of the CaMn₇O₁₂ phase require a revision of the current concepts of the sequence of phase transitions in this compound. It is found that a spin-glass phase transition occurs in CaMn₇O₁₂ at T _M = 49 K, whereas the transition at T _S = 89 K exhibits the features of a first-order phase transition and thereby is apparently of structural origin. In the range T _M < T< T _S , the CaMn₇O₁₂ compound exhibits negative thermal expansion, which is also indicative of structural changes.     

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.     

Electron transport,penetration depth,and the upper critical magnetic field in ZrB<Subscript>12</Subscript> and MgB<Subscript>2</Subscript>

We report on the synthesis and measurements of the temperature dependences of the resistivity ρ, the penetration depth λ, and the upper critical magnetic field H_c2, for polycrystalline samples of dodecaboride ZrB₁₂ and diboride MgB₂. We conclude that ZrB₁₂ behaves as a simple metal in the normal state with the usual Bloch-Grüneisen temperature dependence of ρ(T) and with a rather low resistive Debye temperature T_R = 280 K (to be compared to T_R = 900 K for MgB₂). The ρ(T) and λ(T) dependences for these samples reveal a superconducting transition in ZrB₁₂ at T_c = 6.0 K. Although a clear exponential λ(T) dependence in MgB₂ thin films and ceramic pellets was observed at low temperatures, this dependence was almost linear for ZrB₁₂ below T_c/2. These features indicate an s-wave pairing state in MgB₂, whereas a d-wave pairing state is possible in ZrB₁₂. In disagreement with conventional theories, we found a linear temperature dependence, of H_c2(T) for ZrB₁₂ (H_c2(0) = 0.15 T).     

Optical and x-ray diffraction studies of the symmetry of distorted phases of the (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>ZrF<Subscript>7</Subscript> crystal

(NH₄)₃ZrF₇ single crystals were grown, and polarization-optical and x-ray diffraction studies were performed on powders and crystalline plates of various cuts over a wide temperature range. Phase transitions are revealed at temperatures T _1↑ = 280 K, T _2↑ = 279.6 K, T _3↑ = 260–265 K, and T _4↑ = 238 K on heating and at T _1↓ = 280 K, T _2↓ = 269–270 K, T _3↓ = 246 K, and T _4↓ = 235 K on cooling. The sequence of changes in symmetry is established to be as follows: O _h ⁵ (Z = 4) ? D _2h ²⁵ (Z = 2) ? C _2h ³ (Z = 2) ? C _i ¹ (Z = 108) ? monoclinic²(Z = 216).     

Pressure-induced superconductivity and structural transitions in Ba(Fe<Subscript>0.9</Subscript>Ru<Subscript>0.1</Subscript>)<Subscript>2</Subscript>As<Subscript>2</Subscript>

Electrical transport and structural characterizations of isoelectronically substituted Ba(Fe_0.9Ru_0.1)₂As₂ have been performed as a function of pressure up to ～ 30 GPa and temperature down to ～ 10 K using designer diamond anvil cell. Similar to undoped members of the AFe₂As₂ (A = Ca, Sr, Ba) family, Ba(Fe_0.9Ru_0.1)₂As₂ shows anomalous a-lattice parameter expansion with increasing pressure and a concurrent ThCr₂Si₂ type isostructural (I4/mmm) phase transition from tetragonal (T) phase to a collapsed tetragonal (cT) phase occurring between 12 and 17 GPa where the a is maximum. Above 17 GPa, the material remains in the cT phase up to 30 GPa at 200 K. The resistance measurements show evidence of pressure-induced zero resistance that may be indicative of high-temperature superconductivity for pressures above 3.9 GPa. The onset of the resistive transition temperature decreases gradually with increasing pressure before completely disappearing for pressures above ～ 10.6 GPa near the T-cT transition. We have determined the crystal structure of the high-T _c phase of Ru-doped BaFe₂As₂ to remain as tetragonal (I4/mmm) by analyzing the X-ray diffraction pattern obtained at 10 K and 9.7 ± 0.7 GPa, as opposed to inferring the structural transition from electrical resistance measurement, as in a previous report [S.K. Kim, M.S. Torikachvili, E. Colombier, A. Thaler, S.L. Bud’ko, P.C. Canfield, Phys. Rev. B 84, 134525 (2011)].     

The influence of magnetic and structural heterogeneity on thermopower,magnetothermopower, electrical resistivity,and magnetoresistivity of Nd<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> manganite

The thermopower, S, magnetothermopower, ΔS/S, resistivity, ρ, and magnetoresistivity, Δρ/ρ, depending on the temperature T and magnetic field H, have been studied in an Nd_0.5Sr_0.5MnO₃ single crystal consisting of three types of clusters: an antiferromagnetic CE-type with charge-orbital ordering (below the Neel temperature T_NCE ~ 145 K) and an A-type with T_NA ~ 220 K; a ferromagnetic at 234 ≤ T ≤ 252 K, and a ferromagnetic metal phase below the Curie temperature T_C = 248 K. The thermopower was found to be negative, indicating the dominance of the electronic type of conductivity. In the S(T) curves, a sharp minimum is observed in the temperature range of 100 K ≤ T ≤ 133 K, close to T_NCE, where the absolute S value attains 53 μV/K. With a further increase in temperature, the absolute S value decreases rapidly; at 200 K it is equal to 7 μV/K. It then slightly increases, reaching its maximum value of 15 μV/K at a temperature of 254 K, which is close to T_C. The absolute thermopower decreased under the influence of the magnetic field; i.e., a negative magnetothermopower occurs. In {ΔS/S}(T) curves, a sharp minimum is observed at T = 130 K close to T_NCE, where the magnetothermopower reaches a huge value of ~45% at H = 13.23 kOe. A broad minimum in the {ΔS/S}(T) curves is observed near the Curie temperature and its value is also high, viz., ~15% in the maximum measuring magnetic field of 13.23 kOe. The extremely high magnetothermopower values mean that the charge-orbital ordered nanoclusters or ferron type make the main contribution to the thermopower of the entire sample. The behavior of the ρ(T) and {Δρ/ρ}(T) curves is similar to that of the S(T) and {ΔS/S}(T) dependencies, which is in agreement with this conclusion.     

Exponential Increase in the Resistivity upon Cooling and Superconductivity in Indium-Doped Pb<Subscript>0.45</Subscript>Sn<Subscript>0.55</Subscript>Te

We have analyzed the temperature and magnetic-field dependences of resistivity ρ(T, H) of semiconducting compound Pb_0.45Sn_0.55Te doped with 5 at % In under a hydrostatic compression at P < 12 kbar. It is found that the temperature dependence ρ(T) at all pressures at T < 100 K is exponential with the activation energy decreasing upon an increase in pressure; this is accompanied with a superconducting transition on the ρ(T) and ρ(H) dependences at P > 4.8 kbar at T > 1 K (T _c = 1.72 K at a level of 0.5ρ _N at P = 6.8 kbar). We consider the model describing the low-temperature “dielectrization” of the semiconducting solid solution and the formation of the superconducting state upon an increase in the hydrostatic compression P > 4 kbar.