Temperature behavior of the photovoltaic and pyroelectric responses of Sn2P2S6 semiconductor ferroelectric films

The electric response of Sn₂P₂S₆ semiconductor ferroelectric films to focused laser radiation (λ = 6328 Å) with a modulation frequency of 24 Hz is studied experimentally. It is shown that the signal involves an initial spike of current (an unsteady component) followed by the relaxation decrease to a certain value (a quasisteady component). The most significant changes in the shape and amplitude of the film response is observed near the Sn₂P₂S₆ monocrystal phase transition point of T _C = 66°C. The behavior of the unsteady component of the response is related to the behavior of the spontaneous polarization. This component decreases with increasing temperature. The quasi-steady component reaches its maximum at T = C _C. It is revealed that the behavior of relaxation processes corresponding to the decreasing response undergoes a change near the phase transition temperature.     

Dielectric relaxation in the weak ferroelectric Li2Ge7O15 near the ferroelectric phase transition

The dielectric permittivity of Ni-doped Li₂Ge₇O₁₅ crystals was studied in the vicinity of the ferroelectric phase transition. Introduction of Ni has been shown to suppress the dielectric anomaly and to reduce substantially the transition temperature. A temperature hysteresis in ɛ (T) has been observed in nominally pure and Ni-doped Li₂Ge₇O₁₅ crystals near the transition point. Measurements performed under cooling from the paraphase reveal dispersion of dielectric permittivity at Debye relaxation frequencies of the order of 10⁴–10⁵ Hz at T _c . It is proposed that the hysteresis phenomena and the low-frequency dispersion are caused by residual defects (of the type of random local fields), which become polarized in the ferroelectric phase and become disordered above T _c . Fiz. Tverd. Tela (St. Petersburg) 40, 2198–2201 (December 1998)     

Critical behaviour of Sn2P2S6 and Sn2P2(Se0.28S0.72)6 crystals under high hydrostatic pressures

Basing on the temperature dependences of optical birefringence for Sn₂P₂S₆ and Sn₂P₂(Se_0.28S_0.72)₆ crystals subjected to hydrostatic pressures, we prove unambiguously that Sn₂P₂S₆ reveals a tricritical point on its (p, T)-phase diagram with the coordinates (p, T) = (4.3 kbar, 259 K), so that the second-order phase transition transforms into the first-order one whenever the pressure increases above 4.3 kbar. We also find that increasing hydrostatic pressure applied to Sn₂P₂(Se_0.28S_0.72)₆ leads to the change in the phase transition character from tricritical to first order. Further increase in the pressure up to ~2.5 kbar imposes splitting of the first-order paraelectric-to-ferroelectric phase transition into two phase transitions, a second-order paraelectric-to-incommensurate one and a first-order incommensurate-to-ferroelectric transition.     

Baric dependence of the fundamental absorption edge in the region of phase transitions of Sn2P2S6-type intrinsic ferroelectrics

The energy position of the fundamental absorption edge in the neighborhood of phase transitions in Sn₂P₂S₆ and (Pb_0.1Sn_0.9)₂P₂S₆ ferroelectric crystals is studied as a function of the temperature and baric dependence on the basis of direct measurements of the isoabsorption relations. Thep, T phase diagram of Sn₂P₂S₆ crystals is constructed. the temperature-dependent variation of the band gap in those crystals is due mainly to electron-phonon interaction. Uzhgorod State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 82–85, August, 1997.     

Effect of ionizing radiation on the dielectric characteristics of TlInSe<Subscript>2</Subscript> and TlGaTe<Subscript>2</Subscript> single crystals

The temperature dependences of the electrical conductivity and the permittivity of TlInSe₂ and TlGaTe₂ crystals unirradiated and irradiated with 4-MeV electrons at a doze of 10¹⁶ cm⁻² have been investigated. It has been established that electron irradiation leads to a decrease in the electrical conductivity σ and the permittivity ɛ over the entire temperature range under study (90–320 K). It has been revealed that the TlInSe₂ and TlGaTe₂ single crystals undergo a sequence of phase transitions characteristic of crystals of this type, which manifest themselves as anomalies in the temperature dependences σ = f(T) and ɛ = f(T). Electron irradiation at a doze of 10¹⁶ cm⁻² does not affect the phase transition temperatures of the crystals under investigation.     

Influence of γ irradiation on the electrical conductivity and dielectric properties of β TlInS2 in the temperature range of the incommensurate phase

The influence of γ irradiation on the electrical conductivity σ, the dielectric permittivity ɛ, and the dielectric loss tangent tanδ of β-TlInS₂ crystals is investigated in the temperature range of the incommensurate phase. It is established that γ irradiation lowers the values of ɛ and tanδ over the entire investigated temperature range and decreases the maxima of the σ(T) and tanδ(T) curves in the vicinity of the transition temperature T _c, but does not alter the transition temperature. Fiz. Tverd. Tela (St. Petersburg) 39, 1088–1090 (May 1997)     

Phase transitions in oxyfluoride (NH4)2WO2F4

(NH₄)₂WO₂F₄ single crystals are grown, and their polarization-optical, calorimetric, and birefringence properties are studied in the temperature range 90–350 K. A first-order structural phase transition is found to occur at T ₀₁↑ = 202 K with thermal hysteresis of ΔT ₀₁ ≈ 6–12 K. The phase transition is accompanied by twinning and modification of the symmetry . An additional weak anomaly in the differential scanning calorimeter signal is found at T ₀₂ ≈ 170 K. The total thermal effect of both anomalies is ∑ΔH _i = 3200 ± 400 J/mol and ∑ΔS _i = 16.5 ± 2.0 J/mol K. The phase transition at T ₀₁ is of the order-disorder type.     

Synthesis, structure, and dielectric properties of KH2PO4 fractal aggregates

Macroscopic fractal aggregates of KH₂PH₄ (KDP) measuring up to 500 μm have been obtained. The fractal structure forms as a result of the precipitation of KDP particles from a supersaturated aqueous solution in the presence of a temperature gradient followed by a diffusioncontrolled mechanism of aggregation. The electron-microscopic analysis performed has shown that the fractals are formed predominantly from crystallites of the tetragonal modification measuring ∼1 μm. The dielectric constant (ɛ) of fractal KH₂PO₄ has been measured in the temperature range 80–300 K. A characteristic anomaly has been discovered on the ɛ(T) curve in the vicinity of 122 K, which attests to a ferroelectric phase transition. The absolute value of ɛ is significantly smaller than the components ɛ ₁₁ and ɛ ₃₃ for KH₂PO₄. Fiz. Tverd. Tela (St. Petersburg) 41, 2059–2061 (November 1999)     

Effect of γ irradiation on the low-temperature electrical conductivity and dielectric properties of TlGaSe2 crystals

Electrical conductivity and dielectric properties of single-crystal TlGaSe₂ have been studied as a function of γ irradiation dose in the 100–280 K range including the existence of an incommensurate phase. Anomalies in the form of maxima have been observed in the σ=f(T), tan δ=f(T), and ɛ=f(T) curves at the points of transition from the paraphase to incommensurate (IC) phase, T _i, and from the IC to commensurate phase, T _c. The increase in the quantities σ, tan δ, and ɛ observed initially with increasing irradiation dose is followed by their strong decrease and disappearance of the anomalies. It has been established that γ irradiation does not affect the phase transition temperatures T _i and T _c. Fiz. Tverd. Tela (St. Petersburg) 40, 1328–1331 (July 1998)     

Magnetic properties and magnetic entropy change in Heusler alloys Ni50Mn35?xCuxSn15

The influence of Cu substitution for Mn on magnetic properties and magnetic entropy change has been investigated in Heusler alloys, Ni₅₀Mn_35−x Cu _x Sn₁₅ (x=2,5 and 10). With increasing Cu content from x=2 to x=5, the martensitic transition temperature, T _M , decreases from 220 K to 120 K. Further increasing Cu up to x=10 results in the disappearance of T _M . For samples Ni₅₀Mn₃₃Cu₂Sn₁₅ and Ni₅₀Mn₃₀Cu₅Sn₁₅, both martensitic and austenitic states exhibit ferromagnetic characteristics, but the magnetization of martensitic phase is notably lower than that of austenitic phase. The magnetization difference, ΔM, across the martensitic transition leads to a considerably large Zeeman energy, μ ₀ΔM⋅H, which drives a field-induced metamagnetic transition. Associated with the metamagnetic behavior, a large positive magnetic entropy change ΔS takes place around T _M . For the sample Ni₅₀Mn₃₃Cu₂Sn₁₅,ΔS reaches 13.5 J/kg⋅K under a magnetic field change from 0 to 5 T.     

Effect of γ irradiation on the hysteresis phenomena at the incommensurate-commensurate phase transition in Rb2ZnBr4

The effect of γ irradiation on the temperature hysteresis in dielectric permittivity ɛ and loss tangent tan δ of crystalline Rb₂ZnBr₄ has been studied in the vicinity of the incommensurate-commensurate phase transition. The ɛ(T) and tan δ(T) curves were found to exhibit anomalies in the form of maxima. Hysteresis was observed in the measured properties, including the transition temperature T _c (ΔT=T _c ^h −T _c ^c ), in both unirradiated and irradiated samples. It is shown that, as the radiation dose increases the extent of the hysteresis ΔT increases, the values of ɛ _max and tan δ _max at the transition point decrease, and the anomalies wash out. Fiz. Tverd. Tela (St. Petersburg) 40, 1911–1914 (October 1998)     

Specific features of the formation of the ferroelectric phase in polytypes of TlGaSe2 crystals

The polytypism of layered crystals of thallium gallium diselenide TlGaSe₂ has been found to substantially affect the temperature of phase transformations and the mechanism of formation of the polar state in these ferroelectrics. In particular, it is shown that the phase transition observed in the C-TlGaSe₂ polytype is an improper ferroelectric phase transition occurring at a temperature T _c ≈ 108 K, whereas the phase transition observed in the 2C-TlGaSe₂ polytype is a proper ferroelectric phase transition occurring at a higher temperature T _c ≈ 111 K. It is concluded that the elucidation of the polytype of a particular sample is a necessary stage of investigation of the TlGaSe₂ crystals.     

Dielectric properties and phase transitions in crystals of TlInS x Se2 − x solid solutions

This paper reports on a study of the dielectric permittivity and electrical conductivity of single-crystal TlInS _x Se_{2 − x} solid solutions as functions of temperature and composition. It has been found that the dielectric permittivity ɛ and electrical conductivity σ decrease with increasing x and increase with growing temperature. The temperature dependences ɛ = f(T) and σ = f(T) for TlInS _x Se_{2 − x} crystals have been demonstrated to reveal anomalies in the form of maxima, which suggests that these crystals undergo phase transitions. The temperatures of the phase transitions increase with increasing x.     

Dielectric properties of solid solutions (1 ? x)(KBi)1/2TiO3-xNa1/4Bi3/4Fe1/2Ti1/2O3 near the morphotropic phase boundary

The dielectric properties of solid solution ceramics (1 − x)(KBi)_1/2TiO₃-(x/2)(NaBi)_1/2TiO₃-(x/2)BiFeO₃ near the morphotropic phase boundary lying near x = 0.75 and separating the compositions with the orthorhombic (x < 0.75) and rhombohedral (x > 0.75) structures have been studied. The solid solutions are shown to undergo a diffuse phase transition with the Curie temperature T _C = 640–650 K. Based on an analysis of the frequency dependence of the imaginary component of the electric modulus in the range T > T _C, it is concluded that the transition of the system of solid solutions near the morphotropic phase boundary (x = 0.75) to the dipole-ordered state is accompanied by the formation of heterophase microregions with different relaxation times of the dielectric polarization. The activation energies of the relaxation of the dielectric polarization (ΔE _M ) in the aforementioned temperature range and of the dc charge carriers (ΔE _dc ) are determined. It is found that ΔE _dc stepwise increases near 570 K in going toward higher temperatures. It is shown that the behavior of the characteristics of the dielectric response of the solid solutions below 400 K corresponds to a relaxor ferroelectric. For the compositions 0.7 ≤ x ≤ 0.8, the estimated freezing temperature of dipole clusters of the relaxation state is about 240 K, and their activation energy decreases with increasing x.     

Investigation of dc hopping conduction in TlGaS2 and TlInS2 single crystals

It is established that variable-range hopping conduction takes place between states localized near the Fermi level in layered TlGaS₂ and TlInS₂ single crystals both along and across their natural layers in a constant electric field at T⩽200 K. The densities of states near the Fermi level and the hopping distances at different temperature are estimated. The occurrence of activationless hopping conduction is established in TlGaS₂ and TlInS₂ single crystals in the temperature range 110–150 K. Fiz. Tverd. Tela (St. Petersburg) 40, 612–615 (April 1998)     

New phase-transformation line and intermediate phase in Sn2P2S6

A study is made of the effect of temperature and hydrostatic pressure on the permittivity, forbidden-band width, electrical conductivity, and photoconductivity of crystals of Sn₂P₂S₆. The empirical results obtained indicate that a new phase-transformation line exists on the p-T diagram of Sn₂P₂S₆ p > 0.17 GPa. This phase transformation is evidently a second-order transition, separating a paraelectric, proportionate phase from an intermediate, possibly nonproportionate phase. The results also indicate similarity of the p-T diagram of Sn₂P₂S₆ to the x-T diagrams of ferroelectric solid solutions of Sn₂P₂(Se_xS_1–x)₆.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 57–60, September, 1985.     

Thermal expansion of Sn2P2S6 crystals

We present the results for thermal expansion coefficients of Sn₂P₂S₆ crystals determined both in the crystallographic system and the system based on eigenvectors of thermal expansion tensor. Peculiarities of temperature evolution of the indicative surface of thermal expansion tensor for Sn₂P₂S₆ are discussed, including the region of their ferroelectric phase transition.     

Phase transitions in the ferroelectrics (Sn1−x In(2/3)x )2P2S6 at high pressures

New ferroelectric solid solutions (Sn_1−x In_(2/3)x )₂P₂S₆ were investigated at high hydrostatic pressures. The range in which the incommensurate structure exists was determined. A dynamic shift of the incommensurate-ferroelectric phase transition temperature with increasing rate of change of temperature and the appearance of “reverse hysteresis” were observed. The characteristic features in the appearance of the latter effect in these crystals are investigated. Fiz. Tverd. Telsa (St. Petersburg) 41, 1276–1278 (July 1999)     

Spectral anomalies of waveguide electromagnetic modes in layered structures

A theoretical study of electromagnetic guided eigenwaves in two-and three-layered plates with metallized surfaces is accomplished. The appropriate dispersion equations are explicitly analyzed using the discretization first introduced by Mindlin in the theory of Lamb acoustic waves. It is shown that the dispersion branches of independent eigenmode families cross each other in the nodes of a grid formed by two infinite series of bond lines. The latter represent the dispersion curves for homogeneous plates with permittivities ɛ₂ or ɛ₂ coinciding with those for the layers of the waveguide. It is proved that, beyond nodes of the grid, the dispersion curves do not intersect bond lines, which thus provides definite “corridors” for these curves. The dispersion lines have a wavy (“zigzag”) form in the grid zone and remain smooth beyond the grid. The crossing branches have coinciding cutoff frequencies. In dimensionless coordinates “slowness (S) vs. frequency (f),” the branches S _l (f) have two asymptotic levels: S = √ɛ₁ and S = √ɛ₂. At the lower level, the spectrum forms a steplike terracing pattern with a progressive closing to the asymptote of a succession of dispersion curves, which change each other at this level with further going up to the next asymptote. An extension to anisotropic waveguides with layers made of uniaxial crystals is considered. The text was submitted by the authors in English.     

Dielectric and photoelectric properties of Pb(Mg1/3Ta2/3O3 crystals

The temperature dependence of the dielectric constant ɛ and the spectral dependence of the photoconductivity of Pb(Mg_1/3Ta_2/3)O₃ crystals are investigated. The width of the band gap (3.4 eV) is determined. It is found that above the temperature of the maximum of the dielectric constant, its reciprocal 1/ɛ varies with temperature first quadratically and then according to a linear law, as is characteristic of ferroelectrics with a smeared phase transition. The smearing parameter of the transition estimated from the experimental data is close to the value calculated assuming the absence of long-range order in the arrangement of the Mg and Ta ions. Fiz. Tverd. Tela (St. Petersburg) 40, 109–110 (January 1998)