Microwave dielectric dispersion in ferroelectric telluric acid ammonium phosphate

The paper presents the results of the investigation of dielectric dispersion in monoclinic telluric acid ammonium phosphate crystal over the frequency range 1 MHz to 77 GHz. It is shown that ferroelectric dispersion of the Debye type along the direction perpendicular to the plane (101) occurs in the frequency range 10⁸ to 10¹¹ Hz and is caused by a single relaxational soft mode. The relaxational soft mode is caused by the flipping motion of protons between two potential minima in a hydrogen bond. The frequency of the flipping proton mode in the paraelectric phase varies according to v_s = 0.94 (T – T_o ) GHz and decreases to 1.75 GHz at T_c = 317.3 K. The relaxational mode gives the main contribution to the high static dielectric permittivity of this crystal which fits the Curie-Weiss law. The results confirm the order-disorder nature of a proper ferroelectric phase transition of second order.     

Acoustic attenuation in ferroelectric Sn<Subscript>2</Subscript>P<Subscript>2</Subscript>S<Subscript>6</Subscript> crystals

The temperature and frequency dependencies of sound attenuation for the proper uniaxial ferroelectric Sn₂P₂S₆, which has a strong nonlinear interaction of the polar soft optic and fully symmetrical optic modes that is related to the triple well potential, were studied by Brillouin spectroscopy. It was found that the sound velocity anomaly is described in the Landau-Khalatnikov approximation with one relaxation time. For explanation of the observed temperature and frequency dependencies of the sound attenuation in the ferroelectrric phase, the accounting of several relaxation times is needed and, for quantitative calculations, the mode Gruneisen coefficients are more appropriate as interacting parameters than are the electrostrictive coefficients. Relaxational sound attenuation by domain walls also appears in the ferroelectric phase of Sn₂P₂S₆ crystals.     

Dielectric properties of thin ferroelectric Sn<Subscript>2</Subscript>P<Subscript>2</Subscript>S<Subscript>6</Subscript> films deposited by thermal evaporation

The structure, microstructure, and temperature and field dependences of the dielectric properties of thin (0.5–8.0μm) Sn₂P₂S₆ ferroelectric films deposited onto glass and aluminum foil substrates by thermal vacuum evaporation in a quasi-closed volume are studied. The film-thickness and frequency dependences of the dielectric properties and the unipolarity of the C–V characteristics are explained by the presence of near-surface Schottky-type barrier layers.     

Soft modes and phonon interactions in studied by neutron scattering

The low frequency lattice dynamics and its relationship to the second order paraelectric-to-ferroelectric transition in Sn₂P₂S₆ is studied. The dispersion branches of the acoustic and lowest lying optical phonons in the a^*-c^* plane have been obtained in the ferroelectric phase, for x-polarized phonons. Close to the phase transition a considerable softening is found for the lowest optical mode (P_x), comparable to the behaviour observed in previous Raman investigations. As found previously in Sn₂P₂Se₆, a strong coupling between the TO(P_x) and TA(u_xz) phonons is observed, although, apparently, not strong enough to lead to an incommensurate phase. The soft TO(P_x) mode at the zone center is observed. The temperature dependence of its frequency and damping shows that the transition is not entirely displacive. At low temperatures an unusual apparent negative LO-TO splitting is observed which is shown to arise from the coupling of the x-polarized soft mode to the nearby z-polarized optical phonon. For comparison, the soft TO(P_x) dispersion in the a^*-b^* plane is measured in both the paraelectric and ferroelectric phases. Consistent frequency changes and LO-TO splitting are observed, revealing a significant interaction between the TA(u_yx) and LA(u_xx) acoustics branches and the TO and LO soft optic branches, respectively. In contrast, the nearby y-polarized optic branch shows almost no temperature dependence. Finally, the influence of piezoelectric effects on the limiting acoustic slopes in the ferroelectric phase is discussed. Received: 11 May 1998 / Revised and Accepted: 15 June 1998     

Phase transitions sequence in pyrochlore Cd2Nb2O7 studied by IR reflectivity

The infrared reflectivity of Cd₂Nb₂O₇ single crystal was studied in the temperature interval of 10-540 K, together with complementary dielectric measurements. A ferroelectric soft mode was revealed above the ferroelectric phase transition at T _c = 196 K coupled with a central-mode type dispersion in the near-millimetre range. This proves the mixed displacive and order-disorder nature of the transition. Below T _c many new modes were detected due to lowering of the symmetry, especially below the previously suggested incommensurate transition at 85 K. Discussion of the possible phase transitions based on symmetry considerations is presented with the conclusion that the ferroelectric transition is proper with the F_1u symmetry of the order parameter, whereas the intermediate ferroelastic transition is improper and triggered by the coupling with the ferroelectric order parameter. Received 17 July 2000     

Pinning effect on microwave dielectric properties and soft mode in TlInS2 and TlGaSe2 ferroelectrics

This paper presents the results of an investigation of microwave dielectric dispersion in the proper semiconductive ferroelectrics TIInS₂ and TIGaSe₂ with an incommensurate structure modulation. In these crystals there is a strongly overdamped soft ferroelectric mode, whose frequency in the vicinity of the phase transitions drops to the millimetre wave region and causes dielectric microwave dispersion plus a high contribution to the static dielectric permittivity. Within the incommensurate phase crystal defects, such as impurities, cause pinning of the soft mode. Because of this pinning effect the phason frequency increases. Pinning also changes the dynamical dielectric properties and the contribution of the phason and amplitudon to the static permittivity.     

Splitting of the phase transition in ferroelectric solid solutions Sn2P2(SexS1−x)6 at high pressures

The influence of the temperature and hydrostatic pressure on the forbidden band width and dielectric permittivity of the ferroelectric solid solutions Sn₂P₂(Se_xS_1–x)₆ (x=0.04, 0.20, 0.30) is investigated. A change in the species and splitting of ferroelectric phase transition lines are detected for p = 0.140 and 0.026 GPa, respectively, for the solid solutions Sn₂P₂(Se_0.04S_0.96)₆ and Sn₂P₂(Se_0.20S_{0.80 6}, which is due to the existence of a Lifshits critical point separating the transitions into codimensional and noncodimensional phases on the p, T diagram. Shift coefficients with the pressure of the phase transition temperature are found for the solid solutions investigated.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 28–32, February, 1988.     

Dielectric relaxation in ferroelectric (CH3)2NH2AL(so4)2 · 6H2O crystal

Abstract

This paper presents the results of the investigation of dielectric dispersion and ultrasonic velocity in the ferroelectric (CH₃)₂NH₂Al(SO₄)₂ · 6H₂O crystal. The crystal shows a critical slowing down process of polarization with an extremely long relaxation time of the dipole system (τ = 1.6 · 10^?7s at the phase transition point). The dielectric response over the frequency range up to 56 GHz in the paraelectric phase can be well described in terms of a monodispersive Debye-type formula. The activation energy of dipoles in the paraelectric phase is 0.11 eV = 8.5 kT_c . The results show that the proper ferroelectric phase transition is nearly critical and of the order-disorder type.     

La诱导(Pb(1-3x/2)Lax)(Zr0.5Sn0.3Ti0.2)O3反铁电介电弛豫研究

采用标准电子陶瓷工艺制备了(Pb_(1-3x/2)La_x)(Zr_0.5Sn_0.3Ti_0.2)O₃(PLZST,0.00≤x≤0.18)反铁电陶瓷,利用X射线衍射、不同频率下弱场介电温谱、强场下的极化强度-电场(P-E)测试研究了材料相结构和电学性能.实验结果发现,随La含量x增大,室温下材料由铁电三方相(关键词： 反铁电陶瓷 介电频率色散 相变弥散 介电弛豫     

Coexistence of glass and ferroelectric order in deuterated betaine phosphate0.05 betaine phosphite0.95 crystals

The dielectric spectra of ferroelectric hydrogen bonded betaine phosphate_0.05 betaine phosphite_0.95 (DBP_0.05DBPI_0.95) was investigated in the very wide temperature (300–20 K) and frequency (20–35 GHz) regions. The dielectric dispersion was analyzed in terms of distribution of relaxation times, using Tichonov regularization method. Strongly asymmetric and broad distribution of relaxation times below ferroelectric phase transition temperature T _c?≈?253 K clearly differs from the one that is usually observed in ferroelectrics. The observed disorder in deuterons system close to ferroelectric phase transition temperature is an embryo of coexistence ferroelectric order and dipolar glass disorder observed at low temperatures.     

Dielectric spectroscopy of a high-polarization ferroelectric liquid crystal

Dielectric spectroscopy investigations in the frequency range 50?Hz to 1?MHz have been carried out on a new ferroelectric liquid-crystalline material (S-(-)-4-(2-n-hexylpropionyloxy)biphenyl-4′-(3-methyl-4-decyloxy)benzoate) possessing a relatively large spontaneous polarization (P _s?～?240?nC?cm^?2) and containing a lateral methyl group on the aromatic ring of the alkoxybenzoate unit. The effect of temperature on the dielectric relaxation modes has been investigated in the SmC* and N* phases. From dielectric dispersion data, relaxation frequency and dielectric strength of all detected relaxation modes have been evaluated and discussed. A new surface-like mode of relaxation frequency ～11?kHz and dielectric strength 3.8, is seen to appear in the SmC* phase.     

The soft mode properties in Raman spectra of improper ferroelastics Hg2Cl2 and Hg2Br2

The temperature dependence of the frequency and intensity of the soft mode line appearing in the Raman spectra of Hg₂Cl₂, Hg₂Br₂ below the critical point T_c was studied. A proportionality between the scattering cross section of the soft mode and the square of its frequency v_sm was established. A strong stress-induced increase of the intensity and frequency of the soft mode line was observed near T_c, the relative shift of v_sm being ～30% at ～0.5 kg/mm² stress and T_c?T=5°K.     

Transient short-circuit photocurrent in ferroelectric semiconductor Sn2P2S6 films

Transient short-circuit photocurrents in films of the ferroelectric semiconductor Sn₂P₂S₆ are studied in a temperature range that includes the phase transition point. The influence of an external electric field and white-light illumination on the photoelectric response of samples is discussed.     

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.     

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.     

Millimetre-wave investigation of the soft mode in ferroelectric PbHPO4

The complex dielectric function along the a axis of PbHPO₄ single crystals is determined from reflection measurements at frequencies between 70 and 225 GHz in the paraelectric and the ferroelectric phase near the transition temperature T_c = 310 K. The data are complemented by a remeasurement of the properties of the lowest far-infrared mode. The mm-wave data can be described by a simple Debye formula. The relaxation time exhibits critical slowing down, and the corresponding relaxation frequency varies between about 2 and 60 GHz near T_c. Proton tunneling appears to play no essential role in this dielectric mechanism related to proton ordering.     

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)     

Thickness dependence of the soft ferroelectric mode in SrTiO3 thin films deposited on MgO

We have measured the complex dielectric constants of SrTiO₃ thin films deposited on MgO substrate, by using the broadband terahertz time-domain spectroscopy. The dielectric dispersion of SrTiO₃ thin films with thickness of 1046, 460 and 55 nm has been observed in the frequency range from 0.1 to 8 THz. The dispersion mainly consists of the TO1 ferroelectric soft mode with a slight absorption of the TO2 phonon mode. From the analysis of the obtained dispersion, we found that the soft mode frequency hardens as the thickness of the film becomes thinner, and is extremely large compared with the bulk crystals. The damping of the soft mode is also larger than that of bulk SrTiO₃, which suggests the extrinsic nature of the broadening of the soft mode dispersion. In the thinnest film of 55 nm, even the shape of the dielectric dispersion changes, which may be related to integrated defects near the interface.     

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.     

Band structure and model of the paraelectric structure of the Sn2P2S6 crystal

Since a variety of choices exist in the literature for the symbol of the space group of crystals of the type Sn₂P₂S₆, hindering the use of a group-theoretic analysis to determine the properties of the band spectrum and phonon spectrum, identified this symbol is identified with the known coordinates of the atoms of the given crystals. It is shown that the different arrangements P2₁/c and P2₁/n lead to permutations of the points in the Brillouin zone and correspondingly to a change in the irreducible representations. Calculating the spectra of Sn₂P₂S₆ and Sn₂P₂Se₆ by the method of pseudopotentials fitted to the width of the bandgap confirms the double degeneracy at the X, Y, Z points of the Brillouin zone, which was not expected for the X point in the arrangement P2₁/c. We have detected the previously predicted minimal band complexes in the band spectrum, which are the same as for In₄Se₃ of the group D _2h ¹² . Fiz. Tverd. Tela (St. Petersburg) 39, 1219–1222 (July 1997)