Барична трансформація аномалій діелектричної проникності шаруватих кристалів CuСr0,5In0,5P2S6

Abstract

Наведено результати досліджень температурних залежностей аномалій діелек-тричної проникності шаруватих кристалів CuСr0,5In0,5P2S6 при дії зовнішнього гідростатичного тиску. Встановлено, що дія гідростатичного тиску індукує аномалію діелектричної проникності в кристалах CuСr0,5In0,5P2S6, яка відпові-дає сегнетиелектричному фазовому переходу. Побудована фазова х,Т-діаграма твердих розчинів CuInхСr1-хP2S6

Приведены результаты исследований температурных зависимостей аномалий диэлектрической проницаемости слоистых кристалов CuСr0,5In0,5P2S6 при дей-ствии внешнего гидростатического давления. Установлено, что действие гид-ростатического давления индуцирует аномалию диэлектрической проницаемо-сти в кристаллах CuСr0,5In0,5P2S6, которая соответствует сегнетиэлектрическо-му фазовому переходу. Установлен вид фазовой х,Т-диаграммы кристаллов CuСr1-хIn1-хP2S6.

Purpose: The investigation of the nature of the dipole glass state in ferroelectrics has become one of the most interesting and important areas in solid state physics in recent years. Layered crystals of solid solutions based on CuCrP2S6 and compounds are very convenient materials for studying the effects of freezing relaxation dynam-ics caused by dipole disordering. With the change of the chemical composition of solid solutions, we can observe a transformation from dipole ordering with a long-range order, (a ferroelectric CuInP2S6 in and an anti-ferroelectric in CuCrP2S6) to a state of dipole glass with a relaxation behavior caused by the "freezing" of ferroac-tive ions in the crystal lattice. Based on the investigations of dielectric spectroscopy (10 mHz-3 GHz) in mixed Cu(InxCr1-x)P2S6 crystals, it was found that the phase changing point between the ferroelectric phase and the dipole glass phase lies be-tween x=0.5 and 0.7 , and the corresponding point between the state of the dipole glass and the anti-ferroelectric phase is between x=0.4 and 0.2. The main aim of this study is to investigate the effect of high hydrostatic pressure on the temperature de-pendences of dielectric properties of CuСr0,5In0,5P2S6 crystals, in which the state of dipole glass occurs at atmosphere pressure according to the phase x, T-diagram . Methods: Studied CuСr0,5In0,5P2S6 crystals were grown by the gas transport reaction method. For the dielectric measurement polished plate like crystals were used. All measurements were performed in a direction perpendicular to the layers. The com-plex dielectric permittivity ε∗ was measured using an HP4262A capacitance bridge at the frequency 1 MHz. All measurements have been performed on cooling and heating mode with a temperature rate 0.5 K/min. Silver paste has been used for con-tacting. Hydrostatic pressure was applied a high-pressure chamber, its value being controlled within ±1MPa. Scanning electron microscopy (SEM) studies combined with energy dispersive X-ray spectroscopy (EDX) were performed using a SEM JEOL 7000F microscope. Results: Studies of a complex dielectric permittivity ε* of CuСr0,5In0,5P2S6 crystals with different values of hydrostatic pressure were performed in a wide temperature range 77 K <T <400K and a pressure of 0 MPa <p <600 MPa. In the pressure region p<300MPa for CuСr0,5In0,5P2S6 crystals, no anomaly in the static dielectric permit-tivity indicating a polar phase transition can be detected down to the lowest tempera-ture. The maximum of the real part of the dielectric permittivity shifts to higher tem-peratures with increasing pressure along with the imaginary part of the peak in the whole frequency range. These anomalies of dielectric properties are due to the exist-ence of a state of dipole glass. In the region of pressures p> 300MPa, two anomalies of the real part of the dielectric constant are revealed. One, at lower temperatures. corresponds to the transition to the state of a dipole glass, the other-at higher tem-peratures, is a ferroelectric phase transition induced by hydrostatic pressure. The Value of the baric temperature shift of the ferroelectric phase transition for CuСr0,5In0,5P2S6 crystals induced by high hydrostatic pressure dTc/dp=0,18 K/MPa is close to the similar value of dTc/dp=0,21 K/MPa and dTc/dp =0,29 K/MPa for crys-tals CuInP2S6 and CuСr0,3In0,7P2S6, respectively. Conclusions: Based on the studies of temperature dependences of dielectric permit-tivity of layered crystals at high hydrostatic pressure, the baric behavior of the tem-peratures of the anomalies of dielectric permittivity of crystals CuСr0,5In0,5P2S6 is es-tablished. Hydrostatic pressure induces the appearance of an anomaly of dielectric constant, which corresponds to a ferroelectric phase transition. p,T phase diagram of these crystalls was built, and pressure coefficients for the phase transition temperature shift were determined. The phase transition temperature in crystals CuСr0,5In0,5P2S6 determined by extrapolation of the baric dependence of the temperature of the ferroelectric phase transition to atmospheric pressure is equal to Tc=162K. The phase x,T diagram of Cu(InxCr1-x)P2S6 solid solutions was built. The concentration shift of the temperature of the ferroelectric phase transition for solid solutions of Cu(InxCr1-x)P2S6 can be well described by the equation Тс(х)=314,6-3,5⋅х+0,009⋅х2 (х, mol.%)