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)     

An EPR study of local fluctuations in the vicinity of the ferroelectric phase transition in Li2Ge7O15

EPR spectra of Mn²⁺ ions have been studied in the temperature interval containing the ferroelectric transition in crystalline lithium heptagermanate Li₂Ge₇O₁₅. The EPR linewidth and shape were measured as functions of temperature and orientation. It is shown that the critical resonance-line broadening observed to occur in the vicinity of the phase transition is due to fluctuations in the local order parameter with frequencies below 10⁷ Hz.     

Anomalous behavior of dielectric permittivity of Li2Ge7O15 crystals at a phase transition

It is shown that the Curie-Weiss relation describes unsatisfactorily the temperature dependence of dielectric permittivity at the transition from orthorhombic paraphase to polar phase. Fiz. Tverd. Tela (St. Petersburg) 40, 1698–1700 (September 1998)     

Mössbauer diffraction on ferroelectric Li2Ge7O15

Room temperature Mössbauer diffraction experiments on Li₂Ge₇O₁₅ are reported. Due to the presence of additional lattice points near the surface of the Ewald sphere of the used geometry a minimum appears in the inelastically scattered contribution of the 0-0-8 reflection. No elastically scattered intensity is observed at the angular range corresponding to the 0-0-9 reflection supporting Pbcn as space group at room temperature. The calculated ratio of the first order thermal diffuse scattered intensity included, in the background to the total thermal diffuse scattered intensity differs strongly from the experimental results.     

Quadratic crystal field tensors and spin Hamiltonian tensors of Fe3+ in Li2Ge7O15 above and below the phase transition temperature

Dopant Fe³⁺ ions in tetrahedral and octahedral positions of Ge⁴⁺ in the crystal Li₂Ge₇O₁₅ were studied using EPR. Fe³⁺ substitutes for Ge⁴⁺ with a local charge compensation. The octahedral site and the tetrahedral sites significantly differ by the value of the invariant sumS(B ₄) of theB ₄ tensor of the spin Hamiltonian of Fe³⁺. The irreducible tensor products {V ₄ ? V ₄}₄ and {V ₄?V ₄}₂ theV ₄ tensor of the crystal field calculated using the point-charge model for octahedral and tetrahedral complexes provide the predominant contribution of the crystal field to theB ₄ andB ₂ tensors of the spin Hamiltonian of Fe³⁺, respectively. A comparison of the fourth-rank tensorsB ₄ of the spin Hamiltonian and {V ₄?V ₄}₄ of the crystal field determined at 300 K with those determined at 77 K supports the conclusion that the phase transition is accompanied by combined rotation of the [GeO₄] tetrahedra with the [Ge(1)O₆] octahedron almost unaltered. The spectrum lines are narrow and the variety of point defects in the vicinity of the paramagnetic impurity ions Fe³⁺, Cr³⁺ and Cu²⁺ is not detected. These facts are inconsistent with the statistically distributed model for the Li(2) atom. In specific cases at 300 K, when the wings of the two spectrum lines of theM→M+1 and theM+2 →M+3 transitions of Fe³⁺ ions belonging to one system of translationally equivalent positions overlap an extra line appears in the center between these lines. It is suggested that this effect is due to the soft phonon mode above the phase transition temperature.     

EPR Spectra of Cr3+ Ions in Sr3Ga2Ge4O14:Cr Single Crystals

The results of investigations of chromiumdoped Sr₃Ga₂Ge₄O₁₄ single crystals by the EPRspectroscopy method are presented. It is shown that activating chromium ions form Cr³⁺ Ga³⁺ (Ge⁴⁺) substitution centers in the 1aoctahedral positions of the lattice of Sr₃Ga₂Ge₄O₁₄. Depending on the combination of occupation of the 3ftetrahedral positions of the first cationic coordination sphere by Ga³⁺ and Ge⁴⁺ ions, Cr³⁺ centers of two types are formed. Their individual magnetic spectra are characterized by axial and rhombic symmetry. The magnetic multiplicity of the axialsymmetry spectrum is equal to unity. There exist rhombicsymmetry centers of two types differing in the orientation of the principal magnetic axes and the value of the spinHamiltonian parameter E. The magnetic multiplicity of the individual magnetic spectra of rhombic centers of each type is equal to three. The detected EPR spectra of Cr³⁺ ions have been described by the spin Hamiltonian of rhombic symmetry. Its parameters and their spread have been determined.     

Low-frequency polarization relaxation in PMN + 2% Li2O ferroelectric ceramics in the region of diffuse phase transition

Studies of dielectric nonlinearity in lead magnoniobate ceramics doped with lithium show that at a certain value of external field amplitude E, two peaks appear on the temperature dependences of effective dielectric permittivity ?_eff′(T). They are caused by the dynamics of the polar regions in the vicinity of diffuse phase transition and by variation in their volume under the action of field E.     

Studies of local phase transition behavior for Co2+ in CsCaCl3 crystals from EPR data

In this paper, we establish the calculation formulas ofg factorsg _∥,g _⊥ and the hyperfine structure constantsA _∥,A _⊥ for 3d⁷ ions in tetragonal octahedral field from a cluster approach. In these formulas, besides the configuration interaction, the covalency effect due to the admixture between d electrons of 3d⁷ ion and the p electrons of ligands is considered. The parameters used in these formulas (except the core polarization constantsk in the calculation ofA _i) can be obtained from optical spectra of the studied crystal. From these formulas, the local release (or elongation) factork, which is introduced to characterize the release effect of impurity-ligand bond along C₄ axis at the cubic to tetragonal phase transition, is estimated for CsCaCl₃:Co²⁺ crystal by calculating the electronic paramagnetic resonance (EPR) parametersg _i andA _i . These EPR parameters are therefore explained reasonably and the results are discussed.     

EPR and dielectric properties of Pb5Ge3O11 crystals with off-center Cu2+ ions

The electron paramagnetic resonance (EPR) and dielectric properties of Pb₅Ge₃O₁₁ crystals activated by copper ion are investigated. It is shown that Cu²⁺ ions replace Pb²⁺ in trigonal symmetry positions and occupy three off-center positions displaced from a crystal lattice site in a plane perpendicular to the polar axis C. The temperature variation of EPR spectra and dielectric properties indicates the presence of thermally activated jumps of Cu²⁺ ions between off-center positions. The EPR and dielectric data are used to determine the activation energy W=0.24 eV and the eigenfrequency τ ₀ ^?1 ～ 10¹² Hz of local dynamics of Cu²⁺ ions.     

Observation of the ferroelectric phase transition in Pb5Ge3O11 by the chemical potential changes

We observed the transition from the ferroelectric (FE) to paraelectric (PE) phase in the semiconducting, ferroelectric Pb₅Ge₃O₁₁ single crystal with the use of the contact electrode method. To this purpose a thin, metallic layer was placed onto the Pb₅Ge₃O₁₁ crystal surface, forming the contact electrode. At opposite ends of the contact electrode, silver wires were glued and a voltage was applied to the contact electrode in such a way that the electric current could flow only through the attached electrode. The electric resistance R(T) of the electrode was measured as a function of temperature. Two series of measurements were performed. In one of them the ferroelectric c-axis of the investigated crystal was perpendicular to the contact electrode. In the second one the c-axis was parallel to the attached electrode. We used gold as the contact electrode material. The anomaly in the R(T) in a form of a kink at T _kink?=?452?K was found for both c-axis orientations. The measured value of T _kink, appearing in the temperature dependence of contact electrode resistance, corresponds exactly to the phase transition temperature T _C from the FE to PE phase of the investigated Pb₅Ge₃O₁₁ material. This result demonstrates that the contact electrode method, primarily proposed exclusively to find critical temperatures of metallic samples, also works well in the case of ferroelectric and semiconducting materials like Pb₅Ge₃O₁₁. We ascribe the effect of the resistance kink in the temperature dependence of the contact electrode R(T) to thermal excitations of the electrons with different rates below and above T _C due to different electronic activation energies in the FE and PE phases of the investigated Pb₅Ge₃O₁₁ crystal. It, however, means that the phase transition in the electronic subsystem of the Pb₅Ge₃O₁₁ transfers into the electron gas of the contact electrode via the chemical potential relation µ _sample?=?µ _electrode due to the contact between the sample and the electrode. The magnitude of the kink, observed in the R(T) dependence, was higher on heating than on cooling. The additional measurement of the thermally stimulated current (TSC) was carried out on the non-polarised Pb₅Ge₃O₁₁ sample. In this series of measurements, the sample was covered with gold layers sputtered on the two opposite surfaces of the crystal. The TSC anomaly occurred, related to the residual pyroelectric effect, several degrees below the Curie temperature, T _C, and does not disturb the detection of the critical point with the use of the contact electrode method.     

EPR study of the ferroelectric phase transition in chromium-doped DMAAS

X-band electron paramagnetic resonance (EPR) investigations of single crystals of Cr³⁺-doped dimethylammonium aluminium sulphate hexahydrate are presented from 100 K to room temperature. The crystal undergoes a phase transition at 152 K from the ferroelastic to the ferroelectric phase. The spin-Hamiltonian parameters have been determined for both phases. The spin-Hamiltonian parameters in the ferroelectric phase are:g=1.980±0.003,b ₂ ⁰ =(1140±15)·10^?4 cm^?1,b ₂ ² =(214±10)·10^?4 cm^?1. Remarkable EPR line width changes confirm the order-disorder character of the ferroelectric phase transition on a microscopic level and demonstrate that the dimethylammonium reorientation freezing-out is the prime reason for this transition.     

7Li NMR study on Li+ ionic diffusion and phase transition in LixCoO2

The temperature dependence of the spin-lattice relaxation time, T₁ and the line width of the ⁷Li nucleus were measured in delithiated Li_xCoO₂ (x = 0.6, 0.8, 1.0). Two different relaxation behaviors were observed in the temperature dependence of T₁^− 1 in a x = 0.8 sample. These would have arisen from inequivalent Li sites in two coexisting phases; an original hexagonal (HEX-I) and a modified hexagonal (HEX-II) phase in the x = 0.8 sample. We analyzed using a phenomenological non Debye-type relaxation model. Motional narrowing in the line width was observed in each sample, the result revealing that Li⁺ ions begin to move at low temperature in samples with less Li content. It was found that the activation energy associating with Li⁺ ion hopping in the HEX-II phase is smaller than that in the HEX-I phase. These results show that the HEX-II phase produced in the Li deintercalation process would be suitable for Li⁺ ionic diffusion in multi-phase Li_xCoO₂, and it is expected that this would enable fast ionic diffusion. Li⁺ ionic diffusion related to phase transition is discussed from ⁷Li NMR results.     

Diffuse ferroelectric phase transition in Li2Pb2Dy2W2Ti4V4O30

Tungsten–bronze polycrystalline ceramic Li₂Pb₂Dy₂W₂Ti₄V₄O₃₀ was prepared by mixed-oxide method. The preparation conditions were optimized by thermogravimetry analysis and repeated firing. Room-temperature structural analysis confirms the formation of the compound in single phase (orthorhombic). Studies of dielectric parameters () of the compound with temperature at different frequencies suggest the existence of phase transition in the compound. The existence of ferroelectric property (based on dielectric anomaly) of the material was confirmed by polarization study.     

Optical study of the antiferromagnetic-paramagnetic phase transition in chromium oxide Cr2O3

Abstract

Optical effects of the first and second order with respect to the order parameter (1 is antiferromagnetic vector) have been studied in Cr₂O₃ around its phase transition at T_N = 306 K from the antiferromagnetic to paramagnetic state. The magnetic linear birefringence is characterized by a rather large magnitude Δn _sp ? 10^?3 and by a large contribution of fluctuations of the order parameter to the birefringence. The study of the nonreciprocal optical rotation induced by an electric field has shown that the phase transition has a well defined first-order character. This result is also supported by the observation of a nonlinear (quadratic in the electric field) nonreciprocal rotation in a narrow temperature region ΔT = 0.15 K around T_N . The temperature variation of the order parameter l(T) below T_N is well described by a power low l where τ^β = (T_N - T)/T_N and β = 0.355. We also observed a very reproducible effect of the rotation of the optical indicatrix in opposite directions for two types of antiferromagnetic domains. The possible explanation of this effect could be related to the so-called gyrotropic birefringence, an effect related to k_il_i terms in the dielectric permeability.