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.     

Linear optical properties of γ-modification of bismuth borate BiB3O6

The refractive index dispersion of the ??-BiB₃O₆ crystal in the wavelength range 0.43?C0.81 ??m has been measured. It has been shown that the principal refractive indices n ₁, n ₂, and n ₃ are on average higher than those of ??-BiB₃O₆, but are slightly lower than those of ??-BiB₃O₆. The temperature dependences of the rotation angle ??(T) of the optical indicatrix and birefringence ??n ₂(T) = (n ₁ ? n ₃)(T) have been studied in the temperature range 100?C963 K. It has been shown that the ??-BiB₃O₆ crystal is stable in this temperature region.     

A study of the effect of gradual substitution NH<Subscript>4</Subscript> → Cs on phase transitions in NH<Subscript>4</Subscript>LiSO<Subscript>4</Subscript> crystals

Solid solutions in the Cs_x(NH₄)_1?xLiSO₄ (0≤x≤0.35) system are grown and investigated. The birefringence (n_a?n_b) and the heat capacity are measured in the temperature range 100–530 K. The (x-T) phase diagram is constructed. It is demonstrated that the substitution of cesium for ammonium in the NH₄LiSO₄ crystal affects the transition temperatures in such a way that the region of the ferroelectric phase increases and the ferroelastic phase disappears at x>0.22. The character of the high-temperature transition remains unchanged (2β=0.24±0.01 for all compositions), but the birefringence anomaly and enthalpy decrease. As the concentration x increases, the low-temperature transition becomes more similar to a first-order transition: the birefringence jump δn and the temperature hysteresis ΔT increase.     

Magneto-optical measurement on the layer type magnet (CH2)2(ND3)2MnCl4

The linear birefringence (LB) of the antiferromagnet (CH₂)₂(ND₃)₂MnCl₄ has been measured as a function of temperature and in magnetic fields up to 100 kOe. The temperature dependence of the LB points to a pronounced two dimensional magnetic behaviour. No anomaly corresponding to the effect of three dimensional ordering could be detected at T_N. In theffield dependent measurements the spin flop at H_SF = 33.6 ± 1 kOe (T = 4K) could clearly be detected.     

Manifestation of quantum statistics in vibrational dynamics of poly(ethylene) crystals

The temperature dependences of the transverse expansion ?_⊥(T) and the longitudinal contraction ?_‖(T) (with respect to the axes of chain molecules) in large-sized poly(ethylene) (PE) crystal grains (100×60×60 nm) are measured using x-ray diffraction in the temperature range 5–380 K. The temperature dependence of the elongation of the molecular skeleton ?_C(T) is obtained by Raman spectroscopy. It is found that the dependences ?_⊥(T), ?_‖(T), and ?_C(T) exhibit a similar specific nonlinear behavior. Analysis of these dependences indicates that the nonlinearity is associated with the quantum statistics of transverse vibrations. The energies and amplitudes of zero-point (at T=0) transverse (torsional and bending) vibrations and the relevant zero-point components ?_‖(0) and ?_C(0) are estimated. It is revealed that the zero-point components make a considerable contribution to the dynamics of the PE crystal up to the melting temperature (～400 K).     

Central peak in the strontium titanate crystal near the tetragonal-to-cubic phase transition

Raman spectra of the SrTiO3 crystal have been measured in wide temperature (22?C316 K) and frequency (2?C1020 cm^?1) ranges. It has been shown that a central peak appears in low-frequency Raman spectra at temperatures above 70 K. In the spectral geometry with polarization rotation near the temperature T _c = 106 K of the cubic-to-tetragonal phase transition, the central peak exhibits properties of the order-disorder phase transition. Such a behavior of the central peak has been explained by the interaction of the low-frequency soft mode E _g with the relaxation mode near T _c .     

Electronic excitations and luminescence of SrMgF4 single crystals

The electronic and crystal structures of SrMgF₄ single crystals grown by the Bridgman method have been investigated. The undoped SrMgF₄ single crystals have been studied using low-temperature (T = 10 K) time-resolved fluorescence optical and vacuum ultraviolet spectroscopy under selective excitation by synchrotron radiation (3.7–36.0 eV). Based on the measured reflectivity spectra and calculated spectra of the optical constants, the following parameters of the electronic structure have been determined for the first time: the minimum energy of interband transitions E _g = 12.55 eV, the position of the first exciton peak E _n = 1 = 11.37 eV, the position of the maximum of the “exciton” luminescence excitation band at 10.7 eV, and the position of the fundamental absorption edge at 10.3 eV. It has been found that photoluminescence excitation occurs predominantly in the region of the low-energy fundamental absorption edge of the crystal and that, at energies above E _g , the energy transfer from the matrix to luminescence centers is inefficient. The exciton migration is the main excitation channel of photoluminescence bands at 2.6–3.3 and 3.3–4.2 eV. The direct photoexcitation is characteristic of photoluminescence from defects at 1.8–2.6 and 4.2–5.5 eV.     

Phase transition in a KPb<Subscript>2</Subscript>Br<Subscript>5</Subscript> crystal

Crystals of the KPb₂Br₅compound are investigated using polarized light microscopy and calorimetry. The birefringence and the angle of rotation of the optical indicatrix are measured in the temperature range 270–620 K. It is found that the KPb₂Br₅ crystal undergoes a first-order ferroelastic phase transition at temperatures T_0↑ = 519.5 K and T_0↓ = 518.5 K with a change in the enthalpy ΔH = 1300 ± 200 J/mol. This transition is accompanied by both twinning and the symmetry change mmm ? P2₁/c. It is revealed that the angle of rotation of the optical indicatrix exhibits an unusual behavior under variations in the temperature due to a strong temperature dependence of the birefringence.     

The role of specific features of the electronic structure in electrical resistivity of band ferromagnets Co<Subscript>2</Subscript>Fe<Emphasis Type="Italic">Z</Emphasis> (<Emphasis Type="Italic">Z</Emphasis> = Al,Si, Ga,Ge, In,Sn, Sb)

The electrical resistivity ρ(T) of the band ferromagnets Co₂FeZ (where Z = Al, Si, Ga, Ge, In, Sn, and Sb are s- and p-elements of Mendeleev’s Periodic Table) has been investigated in the temperature range 4.2 K < T < 1100 K. It has been shown that the dependences ρ(T) of these alloys in a magnetically ordered state at temperatures T < T _C are predominantly determined by the specific features of the electronic spectrum in the vicinity of the Fermi level. The processes of charge carrier scattering affect the behavior of the electrical resistivity ρ(T) only in the vicinity of the Curie temperature T _C and above, as well as in the low-temperature range (at T ? T _C).     

Optical studies of phase transitions in the (NH4)3VO2F4 crystal

(NH₄)₃VO₂F₄ crystals were grown, and polarization-optical studies and measurements of birefringence were conducted on crystal plates of various cuts over a wide temperature range. Phase transitions were detected at temperatures T _1↑ = 417 K, T _3↑ = 211 K, and T _4↑ = 205 K (on heating) and at T _1↓ = 413 K, T _3↓ = 210 K, and T _4↓ = 200 K (on cooling). The transitions are accompanied by anomalies of the birefringence and by twinning. The sequence of changes in the phase symmetry is assumed to be as follows: cubic Fm m ↔ orthorhombic Immm (I222₁) ↔ monoclinic 112/m) ↔ triclinic P . Near temperatures T ₂ ≈ 240–250 K, an additional anomaly of the birefringence is observed, with the crystal retaining the orthorhombic symmetry. Original Russian Text ? S.V. Mel’nikova, A G. Kocharova, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 3, pp. 562–564.     

Galvanomagnetic properties of La0.7Sr0.3Mn0.9Cu0.1O3

La_0.7Sr_0.3Mn_0.9Cu_0.1O₃ ceramic samples have been obtained by the conventional method of the solid-phase reaction, and their resistivity ρ has been investigated in a temperature range from 50 to 300 K in magnetic fields B = 0–20 T. Dependences are typical of perovskite manganites with a maximum at T _max = 140–150 K and an increase in ρ near T _max with increasing external magnetic field B. It has been established that the behavior of resistivity is caused by the variable range hopping conduction mechanism ρ(T) = ρ₀(T)exp[(T ₀/T)^1/4], where ρ₀(T) ～ T ^25/4. The Mott variable range hopping conduction has been observed below the Curie temperature for La_0.7Sr_0.3Mn_0.9Cu_0.1O₃ samples (T _C ～ 300 K) in a temperature range from 300 to 200 K. The influence of Cu doping on the properties of La_0.7Sr_0.3MnO₃ samples is apparently caused by an additional distortion introduced into the crystal lattice of the material and by a weakening of the double-exchange mechanism.     

Phase transitions in orthorhombic oxyfluoride (NH4)2MoO2F4

(NH₄)₂MoO₂F₄ single crystals were grown and studied using polarization-optical methods, and the birefringence was measured in the temperature range 90–350 K. The following sequence of phase transitions is revealed: G ₀ ? G ₁ ? G ₂. It is established that the phase transition at T ₀₁ ≈ 267 K is of the first order and exhibits thermal hysteresis δT ₀₁ ≈ 0.6 K. A weak anomaly is found in Δn(T) at T ₀₂ ≈ 180 K. The crystals are shown to retain the orthorhombic symmetry during the phase transitions.     

Zero-bias tunneling anomaly in a two-dimensional electron system with disorder

The temperature dependence of a zero-bias anomaly in the tunneling conductance of an Al/δ-GaAs tunneling structure with a two-dimensional electron density in the δ-layer of 3.5 × 10¹² cm^?2 has been investigated. It has been shown that the respective drop Δρ(?, T) in the tunneling density of states ρ near the Fermi level E _F of the two-dimensional electron system depends logarithmically on the energy ? within the range of 2.7kT < |?| < ?/τ, where ? is measured with respect to E _F and τ is the momentum relaxation time of two-dimensional electrons. It has been found that the drop depth Δρ(0, T)/ρ is also proportional to ln(kT/?₀) in the temperature range T = 0.1–20 K and saturates below 0.1 K.     

Hysteresis effects at a cooperative high-spin (5T2) ⇌ low-spin (1A1) transition in dithiocyanatobis (4, 7-dimethyl-1, 10-phenanthroline) iron (II)

Hysteresis has been observed at the cooperative high-spin (⁵T₂) ? low-spin (¹A₁) transition in Fe (4, 7-(CH₃)₂-phen)₂(NCS)₂ where phen = 1, 10-phenanthroline. The transition is centered on T_c> = 121.7 K for rising and on T_c< = 118.6 K for lowering of temperature. The observations are in only qualitative agreement with the thermodynamic theory of Slichter and Drickamer.     

Dielectric and optical behaviors in relaxor ferroelectric Pb(In1/2Nb1/2)1−xTixO3 crystal

Dielectric permittivities (ε′,ε″) have been measured as functions of temperature (140-535 K) and frequency (500 Hz-2.0 MHz) in a (001)-cut Pb(In_1/2Nb_1/2)_0.7Ti_0.3O₃ (PINT30%) single crystal grown by the modified Bridgman method with Pb(Mg_1/3Nb_2/3)_0.71Ti_0.29O₃ (PMNT29%) seed crystal. A diffused phase transition was observed in the temperature region of ∼430-460 K with strong frequency dispersion. Above the Burns temperature T_B≅510 K, the dielectric permittivity was found to follow the Curie-Weiss behavior, ε′=C/(T−T_C), with parameters C=3.9×10⁵ and T_C=472 K. Below T_B≅510 K, polar nanoclusters are considered to appear and are responsible for the diffused dielectric anomaly. Optical transmission, refractive indices, and the Cauchy equations were obtained as a function of wavelength at room temperature. The unpoled crystal shows almost no birefringence, indicating that the average structural symmetry is optically isotropic. The crystal exhibits a broad transparency in the wavelength range of ∼0.4-6.0 μm.     

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.     

Antiferromagnetic susceptibility of RbMnF3. Evidence for a temperature dependence of the exchange constant

The perpendicular susceptibility of an RbMnF₃ single crystal has been measured from T = 6?295 K (T_c = 83 K). The data are compared with theoretical predictions for the s.c. Heisenberg model (high-temperature series expansion and spin-wave theory at T = 0). The fit to theory reveals a temperature dependence of the exchange constant, that can be related to the variation of the lattice parameter with temperature as reported in the literature.     

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).     

Specific features of the ferroelastic phase transition in CsLiS1−z CrzO4 solid solutions

Single crystals of the CsLiS_1?z Cr_zO₄ solid solutions (z = 0, 0.1, 0.4, 0.5, 0.9, 1.0) are grown, optical polarization studies are performed, and the birefringence and the angle of rotation of the optical indicatrix φ(T) are measured. A (z?T) phase diagram is constructed in the temperature range from 77 to ～550 K. It is established that substitution of chromium for sulfur has practically no effect on the shape of the optical indicatrix in the initial phase with Pmcn symmetry but produces strong distortions in the monoclinic phase with P112₁/n symmetry. The unusual shape of the curve φ(T) for compositions with z ≈ 1 is accounted for by the interaction of the polarization-constant tensor components a _ij. No radical differences in the patterns of the ferroelastic phase transition between CsLiSO₄ and CsLiCrO₄ are revealed (the critical exponent for the transition parameter is β = 0.33 ± 0.01). These crystals differ only in the magnitudes of the anomalies, which is associated with the large difference between the ionic radii of sulfur and chromium.     

Optical studies of phase transitions in oxyfluoride (NH4)2NbOF5

Polarization-optical studies and measurements of the birefringence Δn and the angle of rotation of the optical indicatrix for the (NH₄)₂NbOF₅ crystal have been carried out in the temperature range 100–350 K. Two anomalies of the birefringence have been revealed at the temperatures T ₀₁ = 258 K and T ₀₂ ≈ 219 K. According to the twinning pattern, the crystal undergoes successive changes in symmetry: orthorhombic ↔ monoclinic 1 ↔ monoclinic 2. The twofold axis of the monoclinic phases (or the normal to the plane) is directed along [001]_or. The effect of the uniaxial compression along [011]_or and the electric field E ≈ 25 kV/cm along [100]_or on the twin structure has been studied. The ferroelastic phase transition at T ₀₁ is due to the appearance of the shear deformation x ₄(T) and is accompanied by significant anomalies of the birefringence. Strong pretransition phenomena mask the jumps in the birefringence Δn(T) and in the angle of rotation of the indicatrix φ(T) at T ₀₁.