Isoabsorption and spectrometric studies of optical absorption edge in Cu6AsS5I superionic crystal

Cu₆AsS₅I single crystals were grown using chemical vapour transport method. Two low-temperature phase transitions (PT) are observed from isoabsorption studies: a first-order PT at Т_?=153±1 K and a second-order PT in the temperature interval T_?I=260–280 K. At low temperatures and high absorption levels an excitonic absorption band was revealed in the range of direct optical transitions. At Т>Т_?, the absorption edge has an exponential shape and a characteristic Urbach bundle is observed. The influence of the cationic P→As substitution on the parameters of the Urbach absorption edge, parameters of exciton–phonon interaction, and phase transitions temperatures are studied.     

Electrical and optical absorption studies of Cu7GeS5I fast-ion conductor

Electrical conductivity and fundamental absorption spectra of monocrystalline Cu₇GeS₅I were measured in the temperature ranges 95-370 and 77-373 K, respectively. A rather high electrical conductivity (σ_t=6.98×10⁻³Ω⁻¹ cm⁻¹ at 300 K) and low activation energy (ΔE_a=0.183 eV) was found. The influence of different types of disordering on the Urbach absorption edge and electron-phonon interaction parameters were calculated, discussed and compared with the same parameters in Cu₇GeS₅I, Cu₆PX₅I (X=S,Se) and Ag₇GeX₅I (X=S,Se) compounds. We have concluded that the P→Ge and Cu→Ag cation substitution results in an increase of the electrical conductivity and a decrease of the activation energy. Besides, P→Ge substitution, results in complete smearing and disappearance of the exciton absorption bands and in blue shift of the Urbach absorption edge, an increase of the edge energy width and an electron-phonon-interaction enhancement.     

Relaxation of Dielectric Loss Peak over Intermediate Temperature Range in Bi5TiNbWO15 Intergrowth

A dielectric loss peak with relaxation-type characteristic is observed in Bi5TiNbWO15 over 200-400℃. The modified Cole-Cole relation by introducing relaxation strength as another important fitting parameter is used to describe this temperature-dependent behaviour of dielectric relaxation process. This peak is considered to be associated with the oxygen vacancies inside the grains and with its activation energy by relaxation determined to be 0.76eV. The obtained broadening factor α is around 0.4, which indicates a strong correlation between those relaxation units. It is confirmed that the behaviour of this peak is due to the combined effects of the dielectric relaxation and electrical conduction by the thermal motion of oxygen vacancies. These results axe further confirmed in Bi5TiNbWO15 samples through oxidization atmosphere treatment and Nd modification respectively.     

On the Urbach rule in sulphur-implanted Cu6PS5I superionic conductors

Cu₆PS₅I superionic crystals, grown using chemical vapour transport, were implanted by sulphur ions. The ion implantation effect on the phase transitions is studied by temperature isoabsorption investigation of the optical absorption edge. For the implanted crystals the optical absorption edge shape is studied in the temperature range 77-320 K, the parameters of exciton-phonon interaction, resulting in the Urbach behaviour of the optical absorption edge, are determined, the temperature dependences of the optical pseudogap and Urbach energy are obtained. The implantation effect on the ordering-disordering processes in Cu₆PS₅I superionic conductors is studied.     

Dependence of the laser-induced voltages on the oxygen content in normal state YBa2Cu3O7−δ films

Our investigation on the relation between oxygen content and the laser-induced voltages of the YBa₂Cu₃O_7−δ films in normal-state shows that deoxygenation of the superconducting films reduces the laser-induced voltages greatly, even reverses the sign of the signals at large oxygen deficiency. The absolute value of the negative signal at large oxygen deficiency can be greater than that of the positive signal.     

The electrical properties and phase transformation of PLZST 2/85/13/2 antiferroelectric thin films on different bottom electrode

Pb_0.97La_0.02(Zr_0.85Sn_0.13Ti_0.02)O₃ (PLZST 2/85/13/2) antiferroelectric thin films were deposited on Pt(111)/Ti/SiO₂/Si and LaNiO₃(LNO)/SiO₂/Si substrates through a modified sol-gel process. The phase structure and microstructure of PLZST 2/85/13/2 antiferroelectric thin films were analysed by x-ray diffraction (XRD), scanning electron microcopy (SEM) and field-emission SEM (FE-SEM). The antiferroelectric nature of the PLZST 2/85/13/2 thin films on two electrodes was demonstrated by the C-V (capacitance-voltage) and P-E (polarization-electric field) measurement. The maximum polarizations for PLZST 2/85/13/2 films on Pt and LNO electrodes were 42 and 18 μC/cm², respectively. The temperature dependence of the dielectric property of the PLZST 2/85/13/2 films was measured under different dc electric fields. Also, the phase transformation of the PLZST 2/85/13/2 films was studied in detail as a function of temperature and dc electric field.     

Fermi-level engineering of BaTiO3 by alkali codoping: increasing the near-infrared absorption by rhodium

Using electron paramagnetic resonance, optical absorption, and fast spectroscopy of light-induced absorption changes, it is shown that codoping BaTiO₃:Rh with Na_Ba acceptors raises the charge state of Rh³⁺ to Rh⁴⁺. Subsequent oxidation under high oxygen pressures can lower the Fermi level to Rh^4+/5+, leading to increased infrared absorption. The light-induced charge transfer in such specimens is characterised by “one center” behaviour. Received: 18 November 1998 / Revised version: 23 December 1998 / Published online: 7 April 1999     

Optical absorption spectrum and local symmetry of Tm ion in TmAl3(BO3)4 crystal

With the help of group theory analysis of absorption spectra of the transition ³H₆ → ³F₃ of Tm³⁺ ion in TmAl₃(BO₃)₄ crystal, measured at several temperatures from 1.8 till 293 K, it has been shown, that the local symmetry of the Tm³⁺ environment is C₃ and it decreases to C₁ at a low temperature. Effective selection rules and polarizations of lines at high enough temperatures (when the line-width is larger than the splitting in C₃ symmetry) have been obtained.     

Critical currents and the critical state in superconductors with magnetic ions

The critical state model is used to derive equations that relate the additional magnetic moment (ΔM) produced by the flux pinning to the critical current density (J_c) measured in transport measurements. The equations derived for conventional superconductors can be used for superconductors that contain magnetic ions, if ΔM is replaced by ΔM/(1 + χ′(H)) where χ′(H) is the differential susceptibility. In the critical state, the field gradient has contributions from both the macroscopic supercurrents and the Amperian currents from the magnetic ions. Magnetic measurements are sensitive to both contributions. Transport measurements only characterise the macroscopic supercurrents. For superconductors which contain rare-earth elements, the J_c values calculated using hysteretic magnetisation measurements without including the term χ′(H), can be in error by factors of 7.     

Temperature induced band gap shrinkage in Cu2GeSe3: Role of electron-phonon interaction

The ternary semiconducting compound Cu₂GeSe₃ has been investigated for optical properties with photoacoustic spectroscopy. Optical absorption spectra of Cu₂GeSe₃ is obtained in the range of 0.76-0.81 eV photon-energy at temperatures between 80 and 300 K. The thermal variation of band gap energy has been examined from the optical absorption spectra at different temperatures. The temperature induced band gap shrinkage has been explained on the basis of electron-phonon interaction. Varshni's empirical relation in conjunction with Vina and Passler model is taken into consideration for data fitting. The Debye temperature was calculated approximately as 240 K. The acoustic phonons with a characteristic temperature as 160 K corresponding to effective mean frequency have been attributed to the thermal variation of the energy gap.     

Dramatic effects of excess oxygen on physical properties and crystal structure of La0.95Sr0.05MnOy single crystal

We have examined the effects of excess oxygen on the magnetization, electrical transport properties and crystal structure of La_0.95Sr_0.05MnO_y. An antiferromagnetic insulator phase confirmed in the as-grown crystal at low temperatures changed to a ferromagnetic insulator phase after the introduction of excess oxygen. The ferromagnetic transition temperature, T_C, systematically increased with increasing oxygen content, y, due to an increase in the mean valence of manganese. However, the T_C of crystals with excess oxygen was lower than that of the La_1−xSr_xMnO_3.00 having identical manganese valence. This is considered to be a result of the competition among the mean valence of manganese, the concentration of cation vacancies, and the mean ionic radius of cations at the A-site.     

Influence of phase transitions on the spontaneous voltage in P(VDF/TrFE) copolymers

Spontaneous voltages were observed in a structure made of poly(vinylidene fluoride-trifluoroethylene) copolymers films sandwiched by metals evaporated onto both surfaces. Open voltages and short-circuit currents were measured as a function of the temperature using different combinations of evaporated metals as electrodes: aluminum, gold, nickel and copper. The ferroelectric-to-paraelectric transition was also observed in such structures for 60:40, 70:30 and 80:20 of VDF/TrFE molar ratios, including the temperature hysteresis characteristic of the first-order transition. Received: 9 February 2000 / Accepted: 28 March 2000 / Published online: 9 August 2000     

EPR study of the low temperature ferroelectric phase transition in Cu doped Rb2ZnCl4 single crystals

Temperature dependent EPR measurements on copper doped Rb₂ZnCl₄ single crystals allowed us to evidence and study the P2₁cn↔C1c1 structural phase transition that takes place in this compound at 74.6 K. From the two types of Cu²⁺ centers localized at different anionic sites, called Cu²⁺(I) and Cu²⁺(II), which are formed in this compound, only the Cu²⁺(II) centers exhibit observable changes in their EPR spectra, attributable to the symmetry lowering. The observed changes have been related to the soft-mode responsible for the structural phase transition.     

Magnetic studies on electrodeposited Cu1−xCox alloy films

Six Cu_1−xCo_x alloy films were prepared by an electrodeposition technique. The compositions of the films were determined to be , 0.13, 0.17, 0.19, 0.21, 0.26 by an atomic absorption spectrophotometer. The crystal structure is FCC-Cu for all films but a shift in the diffraction lines is observed with increasing Co content. The giant magnetoresistance effect was determined in some of the films below 200 K. Magnetisation curves showed no saturation at 10 kOe and the curves of the samples which have a large magnetoresistance value are inclined more than the curves of the other low magnetoresistance samples. This may be due to the degree of magnetic moment distribution in these samples.     

Dependence of high electric-field-induced strain on the composition and orientation of Pb(Mg1/3Nb2/3)O3-PbTiO3 crystals

Electric-field-induced strain behavior of (1−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (PMNT) crystals with different orientations and compositions was investigated for use as electromechanical actuators. Crystallographically, high strains with low hysteresis were achieved for 〈001〉 oriented rhombohedral crystals (29%≤x≤31%) near a morphotropic phase boundary, rather than 〈110〉 and 〈111〉. Domain instability could explain inferior strain levels and large hysteresis for 〈110〉 and 〈111〉 oriented crystals. Ultrahigh strain levels up to 1.8% could be achieved for 〈001〉 oriented PMNT crystals, being related to an E-field induced phase transition. −2 kV/cm negative E-field can be applied to PMNT ferroelectric material with low hysteresis. High strain with low hysteresis makes PMNT crystals promising candidates for high performance solid-state actuators.     

Investigations of structural, dielectric and ferroelectric behavior of europium substituted SrBi2Ta2O9 ferroelectric ceramics

Europium substituted samples of the compositions Sr_1−xEu_xBi₂Ta₂O₉ (x=0.0,0.025,0.050,0.10 and 0.20) were synthesized by solid state reaction method and studied for their structural, dielectric and ferroelectric properties. The X-ray diffractograms confirmed the formation of single phase layered perovskite structure in all the samples. The temperature variation of dielectric constant shows that the Curie temperature (T_c) decreases on increasing concentration of europium. The dielectric loss reduces significantly with europium addition. The P-E studies of the Eu-substituted SBT ceramics show that the remanent polarization increases with increasing concentration of europium.     

Modification of the charge ordering transition in the quasi-one-dimensional conductor (TMTTF)2SbF6 under pressure

We have measured the temperature dependences of the conductance G and the dielectric permittivity ε′ of the (TMTTF)₂SbF₆ compound under a moderate pressure. The maximum of G(T) associated with the Mott-Hubbard localization disappears under pressure. With increasing pressure the peak in ε′(T), corresponding to the charge ordering (CO) phase transition, shifts to lower temperatures and broadens. At pressures above 0.24 GPa, ε′(T) becomes strongly frequency dependent. These modifications are explained in the frame of the extended Hubbard model and a slowing down behavior.     

Crystal structure and structural transition caused by charge-transfer phase transition for iron mixed-valence complex (n-C3H7)4N[FeFe(dto)3] (dto=C2O2S2)

(n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] shows a new type of first order phase transition called charge-transfer phase transition around 120 K, where the charge transfer between Fe^II and Fe^III occurs reversibly. Recently, we have succeeded in obtaining single crystals of the title complex and determined the crystal structure at room temperature. Crystal data: space group P6₃, Z=2. Moreover, we have investigated the structural transition caused by the charge-transfer phase transition by means of powder X-ray diffraction measurement. When the temperature is decreased, the a-axis, which corresponds to the hexagonal ring size in two-dimensional honeycomb network structure of [Fe^IIFe^III(dto)₃]_∞, contracts by 0.1 Å at the charge-transfer transition temperature (T_CT), while the c-axis, perpendicular to the honeycomb network layer, elongates by 0.1 Å at T_CT. Consequently, when the temperature is decreased, the unit cell volume decreases without noticeable anomaly around T_CT, which is responsible for the quite small vibrational contribution to the entropy change, compared with usual spin crossover transition. Thus, the charge-transfer phase transition around 120 K for (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] is regarded as spin entropy driven phase transition.     

Structure and magnetostriction of RFex (1.6 ? x ? 2.0) and R(Fe1−yTiy)1.8 (y ? 0.2) alloys (RDy0.65Tb0.25Pr0.1)

Structure, Curie temperature and magnetostriction of RFe_x (1.6 ? x ? 2.0) and R(Fe_1−yTi_y)_1.8 (y ? 0.2) alloys (RDy_0.65Tb_0.25Pr_0.1) have been investigated using optical microscopy, X-ray diffraction, AC initial susceptibility and standard strain gauge techniques. The homogenized RFe_x alloys are found to be essentially single phase in the range of 1.8 ? x ? 1.85. The second phase is a rare-earth-rich phase when x ? 1.8, and (Dy, Tb, Pr)Fe₃ phase when x ? 1.85. X-ray diffraction indicates that the R(Fe_1−yTi_y)_1.8 alloys contain a small amount of Fe₂Ti phase when y ? 0.05, which increases with the increment of Ti content. The Curie temperature of R(Fe₁−_yTi_y)_1.8 alloys slightly enhances with increasing Ti concentration when y ? 0.05, then remains almost unchanged in the range of 0.05 ? y ? 0.20. The magnetostriction of RFe_x alloys is improved when x ? 1.80 and reduced by increasing Fe content when x ? 1.85. The magnetostriction of R(Fe_1−yTi_y)_1.8 alloys is lowered by increasing Ti content.     

Effects of composition on phase structure and electrical properties of (K0.5Na0.5)0.90Li0.06Sr0.02Nb(1−x)SbxO3 ceramics

Lead-free (K_0.5Na_0.5)_0.90Li_0.06Sr_0.02Nb_(1−x)Sb_xO₃ (KNLSN-Sb_x) ceramics were synthesized by ordinary sintering technique. The compositional dependence of phase structure and electrical properties of the ceramics was systematically investigated. All samples possessed pure perovskite structure, showing room temperature symmetries of orthorhombic at x<0.01, coexistence of orthorhombic and tetragonal phases at x=0.01, and tetragonal at 0.02≤x≤0.05. The temperature of the polymorphic phase transition (PPT) was shifted to lower temperature and dielectric relaxor behavior was induced by increasing Sb content. The samples near the coexistence region (x=0.01) exhibited enhanced electrical properties: d₃₃∼145 pC/N, k_p∼38% and P_r∼20.4 μC/cm².