Optical coefficients of Hg1 − x − y Cd x Eu y Se crystals

Optical properties of Hg_{1 ? x ? y} Cd _x Eu _y Se crystals grown by the Bridgman method have been investigated based on the independent reflectance and transmittance measurements, which were performed on a Nicolet 6700 spectrometer at T = 300 K in the wavelength range 0.9 ≤ λ ≤ 26.6 μm. The values of refractive index n, absorption index k, and absorption coefficient α have been determined for the crystals studied. Based on the dependences α = f(hν), the presence of direct allowed interband optical transitions in the crystals is established and the band-gap values are determined. The influence of temperature on the transmittance and band gap are investigated in the range T = 114–300 K.     

Local structure and electrochemistry of LiNi y Mn y Co1 − 2y O2 electrode materials for Li-ion batteries

A series of LiNi _x Mn _y Co _z O₂ (x = y, z = 1 − 2y) oxides have been synthesized by “chimie douce” and investigated as positive electrodes in rechargeable lithium batteries. Layered LiNi _y Mn _y Co_1 − 2y O₂ materials with high homogeneity and crystallinity were synthesized using the wet-chemical method assisted by carboxylic acid as the polymeric agent. The long range and local structural properties are investigated with experiments including X-ray diffraction, Fourier transform infrared spectroscopy, and electron paramagnetic resonance spectroscopy. The evolution of the structure is discussed as a function of the cobalt content that confers layer-like behavior on the framework. Electrochemical performance of LiNi _y Mn _y Co_1 − 2y O₂ oxides is tested in cells using nonaqueous 1 M LiPF₆ dissolved in ethylene carbonate–diethyl carbonate. Charge–discharge profiles are investigated as a function of the rate capability and the voltage window. A relation is found between the gravimetric capacity and the cation disorder of the positive electrode as indicated by structural analysis. Fast lithium extraction attributed to the larger interslab space has been observed in the cobalt-rich oxides. Paper presented at the 11th Euro-Conference on Science and Technology of Ionics, Batz-sur-Mer, France, 9–15 Sept. 2007.     

57Fe Mössbauer study of the electrochemical reaction of Li with FeP y (y = 1,2)

A complete ⁵⁷Fe Mössbauer study was undertaken to elucidate the electrochemical mechanism occuring during the cycling of the FeP _x (x?= 1,2)/Li batteries. Upon discharge, for FeP, the conversion reaction FeP + 3Li → Fe + Li₃P was confirmed, whereas for FeP₂, FeP and a disordered magnetic unknown phase A are observed. On charge, the starting material is partially reconstructed only in the case of FeP. Once the first cycle is achieved, the same redox process occurs in both the FeP/Li and FeP₂/Li cells, between LiFeP, FeP, Fe° (or phase A) and Li₃P.     

Growth and Characterization of CdSe1 − y S y Nanofilms Obtained by Chemical Bath Deposition

In this work, the growth and characterization of cadmium selenide sulphur (CdSe_1???y S _y ) deposited by chemical bath deposition (CBD) technique at the reservoir temperature of 20?±?2 °C are presented, varying the thiourea volume added to the growth solution in the range of 0–30 ml. The films chemical stoichiometry was determined by energy-dispersive X-ray spectroscopy (EDS). The X-ray diffraction (XRD) analysis and Raman scattering reveal that CdSe_1???y S _y -deposited films showed hexagonal wurtzite crystalline phase. The average size of the crystalline grain in relation to the sulphur volume varies in the range of 1.48–9.2 nm that was determined by using the Debye-Scherrer equation for the direction (100), which is confirmed by analyzing the grain average diameter by high-resolution transmission electron microscopy (HRTEM). Raman scattering shows that the lattice dynamics is characteristic of bimodal behaviour and the multipeak adjust of the first optical longitudinal mode for the CdSeS denotes, in all cases, the Raman shift of the characteristic peak in the range of 177–181 cm^?1 of the CdSe crystals associated with the sulphur incorporation. CdSe_1???y S _y band gap energy can be varied from 1.86 to 2.11 eV by varying the thiourea volume added in the growth solution measured by transmittance at room temperature.     

Magnetic Parameters of Hg1–x Mn x Se1–y S y and Hg1–x Mn x Te1–y S y Crystals

The magnetic susceptibility of Hg_1–x Mn _x Se_1–y S _y and Hg_1–x Mn _x Te_1–y S _y crystals is investigated by the Faraday method at H = 3 kOe in the temperature interval T = 77–300 K. It is established that the specific features of are due to Mn–S–Mn–S, Mn–Se–Mn–Se, and Mn–Te–Mn–Te clusters and mixed Mn–Se–Mn–S and Mn–Te–Mn–S clusters of different sizes in which the indirect exchange antiferromagnetic interaction between Mn atoms is realized through chalcogen atoms. Based on the dependences 1/_Mn = f(T), the magnetic parameters are determined and their dependences on the crystal composition (x and y) are established.     

Optical properties of GaN x As y P1?x?y semiconductor quaternary solid solutions

The photoluminescence method was used in the temperature range of 15?C300 K to study the optical properties of quantum-dimensional heterostructures based on GaN _x As _y P_(1?x?y) solid solutions, synthesized on the surface of a GaP (100) substrate. The calculations for the band-gap width of the GaN _x As _y P_(1?x?y) solid solution with the use of the band anticrossing model are shown to agree well with experimental data.     

The dependence of photosensitivity on composition for thin films of Ge x As y Se1–x–y chalcogenide glasses

We have prepared twelve Ge–As–Se chalcogenide glass films with different chemical compositions and investigated their stability to exposure with near bandedge light. The evolution of two key parameters, the refractive index at 1550 nm and the bandgap with increasing fluence were fitted with stretched-exponential functions. While most of the films showed photo-bleaching (or photodarkening) behavior, we found that for films with a mean coordination number (MCN) around ≈2.45–2.50, neither the bandgap nor the refractive index changed upon irradiation, demonstrating that photostable glasses exist with a particular chemical composition corresponding to the strongest glass formers. Such photostable glasses are the best choice for applications in photonics.     

Elastic properties of (Pb y Sn1−y )2P2S6 solid solutions

Elastic properties of (Pb _y Sn_1?y )₂P₂S₆ solid solutions were studied using Brillouin scattering technique. Different scattering geometries were used for sound velocities determination that make it possible to find all components of the stiffness tensor. The concentration dependencies of volume compressibility, the Grüneisen parameter and Debye temperature were investigated. The results obtained were used to analyze chemical bonding with substitution of tin by lead at room temperature in the crystals under consideration.     

Photoelectric properties of Pb1−x−y Sn x Ge y Te:In epitaxial films

Pb_1–x–y Sn _x Ge _y Te:In epitaxial films are examined in a wide temperature interval and at various background fluxes. These films have high sensitivity to infrared radiation in the spectral range <20m. The lifetime depends exponentially on temperature and varies from several seconds at T=10 K to 10^–2 s at T=20 K. The two-electron model of Jahn-Teller centers is proposed to explain the results. Multielement photoresistors based on these films are fabricated and D*=1.7×10¹³ cm Hz^1/2 W^–1 at T=25 K is achieved. Noise of the photoresistors is independent of background flux when it varies from 10¹² cm^–2 s^–1 to 10¹⁸ cm^–2 s^–1. As compared with Si:Ga and Ge:Hg photoresistors, the responsitivity is several orders larger at the operating temperature 25–30 K.     

Raman spectra and restructurizations in the system of solid solutions NaTa y Nb1−y O3

By recording the Raman spectra, concentrational restructurizations in the system of solid solutions NaTa_yNb_1−yO₃ were investigated. The regions of relatively stable existence of solid solutions (y<0.2, y>0.8) and the region of a rather high disordering (0.2<y<0.9) with maximum deformation of the elementary cell at y=0.5 have been revealed. It is found that at y=0.5 a concentrational phase transition is observed, and at y ∼ 0.25 and 0.8 concentrational restructurizations occur. It is shown that the octahedral anions of BO₆ are centrosymmetric when y<0.2 and y>0.9, and the system of solid solutions NaTa_yNb_1−yO₃ is antiferroelectric when y<0.2. In the range of concentrations 0.2<y< 0.9, the structure of NaTa_yNb_1−yO₃ is characterized by the presence of polar clusters. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 2, pp. 192–198, March–April, 2000.     

Electron paramagnetic resonance of Gd3+ ions in Ca1 − x − y Y x Gd y F2 + x + y crystals

Electron paramagnetic resonance of Ca_{1 ? x ? y} Y _x Gd _y F_{2 + x + y} single crystals has revealed spectra that are not typical of gadolinium-doped CaF₂ crystals. These spectra have a nearly tetragonal symmetry and are most probably caused by Gd³⁺ ions localized in yttrium clusters. Weak spectra of tetragonal Gd³⁺ centers, whose parameters are close to those of a cubic gadolinium center caused by an isolated Gd³⁺ ion, have been also detected. These centers are attributed to isolated Gd³⁺ ions localized near octahedral rare-earth clusters or their associations.     

Frequency response of the low-temperature ionic conductivity of single crystals R 1 − y M y F3 − y (R = La-Er; M = Ca, Sr, Ba, Cd)

The frequency response (10^?1–10^?7 Hz) of the ionic conductivity σ of R _{1 ? y} M _y F_{3 ? y} single crystals (R is a rare-earth element, and M stands for an alkaline-earth element and Cd) with a tysonite structure is studied over a wide temperature range (114–410 K), which includes (for the first time for these phases) the interval below room temperature. The dependences σ(ν) obtained are discussed within the hopping relaxation model. The characteristics of the relaxation and migration processes and the carrier concentration and mobility are determined.     

Thermoelectric properties of n-Bi2Te3 − x − y Se x S y solid solutions under high pressure

The thermoelectric properties of n-Bi₂Te_{3 ? x ? y} Se _x S _y solid solutions with atomic substitutions in the tellurium sublattice (x = 0.27, 0.3, y = 0, and x = y = 0.09) have been studied under a pressure to 8 GPa. It has been found that the Seebeck coefficient and the resistance decrease with increasing P, and power factor χ increases in all compositions and becomes maximal at pressures of 2–4 GPa. It has been shown that the power factor χ, which is proportional to the product of the effective mass of the density of states m/m m/m ₀ and the charge carrier mobility μ₀ in the form (m/m ₀)^3/2μ₀, increases with increasing pressure mainly due to the increase in the mobility and also depends on the solid solution composition. In the composition with substitution Te → Se + S (x = y = 0.09), the peculiarity of the dependence of m/m ₀ on P in the pressure range corresponding to maximal values of the power factor can be explained by the existence of an electronic topological transition. The increase in the power factor under pressure in n-type Bi₂Te_{3 ? x ? y} Se _x S _y solid solutions combined with similar data for p-type Bi_{2 ? x} Sb _x Te₃ solid solutions obtained earlier, including the estimations of possible changes in the thermal conductivity with increasing pressure, give grounds to design thermoelements with improved value of the thermoelectric figure-of-merit, which can be 50–70% at pressures of 2–4 GPa.     

Mössbauer Study of La1−x Ca x Mn1−y 57Fe y O3 with x=0,0.25; y=0.01

Temperature dependent Mössbauer measurements are done on the samples of La_1–x Ca _x Mn_1–y ⁵⁷Fe _y O₃ with x=0 and 0.25, and y=0.01. With decreasing temperature, the specimen with x=0.25 shows a paramagnetic to ferromagnetic transition around 175 K. In the specimen x=0.0, the temperature dependence of both the center shift () and the recoilless fraction (f) can be fitted very well with the Debye theory with a _D=320±50 K. But for the specimens with x=0.25, f and show distinct deviations from the Debye behavior in the temperature range in which the resistivity shows a sharp decrease. Dips observed in both the f and around the transition temperature suggest that the Jahn–Teller distortion observed in these systems is dynamic in nature.     

Effect of doping with iron on the charge ordering in La0.33Ca0.67Mn1−y Fe y O3 (y = 0, 0.05) manganites

The formation and specific features of the superstructure in La_0.33Ca_0.67Mn_1?y Fe _y O₃ (y = 0, 0.05) manganites doped with iron are investigated using transmission electron microscopy. The electron diffraction patterns of the manganites are studied in the temperature range 90–300 K, and the high-resolution electron microscope images recorded at temperatures of 91–92 K are analyzed. In both manganites, the structural transition that is accompanied by the formation of the superstructure and which is directly observed from the appearance of additional peaks in the electron diffraction patterns occurs at a temperature that is in close agreement with the charge ordering temperature T _CO determined from the temperature dependences of the magnetization M(T). In the temperature range 90 < T < 200 K, the undoped compound has a commensurate superstructure characterized by the vector q = 1/3a* and triple the unit cell «3a × b × c» (where a ≈ b ≈ √2a _c , c ≈ 2a _c , and a _c ～ 3.9 Å is the lattice parameter of a simple perovskite). The doping with iron (5 at. %) brings about a decrease in the charge ordering temperature T _CO by 50 K and the formation of an incommensurate structure for which the magnitude of the vector q is smaller by approximately 15%. The unit cell of the superstructure in the iron-doped compound is not triple the unit cell but involves defects of ordering, such as quadrupling of the unit cell, numerous translations by a _c √2 along the a direction, and dislocation-type defects in the stripe structure of the charge ordering. These pseudoperiodic defects lead to a decrease in the magnitude of the vector q and are responsible for the incommensurability of the structure. A decrease in the charge ordering temperature T _CO due to the doping with iron and the incommensurability of the superstructure correlate with the change in the concentration of Mn³⁺ Jahn-Teller ions as a result of their replacement by Fe³⁺ non-Jahn-Teller ions.     

Preparation and characterization of Li2.9Sc1.9−y Y y Zr0.1(PO4)3 (where y = 0, 0.1) solid electrolyte ceramics

The solid electrolyte Li_2.9Sc_{1.9? y} Y _y Zr_0.1(PO₄)₃ (where y = 0, 0.1) compounds belong to monoclinic symmetry (space group P2₁/n) at room temperature. The Zr 3d, Sc 2p, P 2p, Y 3d, O 1s, and Li 1s core level X-ray photoelectron spectra (XPS) were fitted. The Li ions in ceramics without Y occupy two different positions and in the ceramics with Y they occupy one position in the lattice. The deconvolutions of the Zr 3d, P 2p, Sc 2p, and Y 3d core level XPS are associated with different valence states on the surfaces of the investigated ceramics. Anomalies of enthalpy, change of activation energy of ionic conductivity, anomalies of dielectric permittivity in the temperature range 420–520 K of investigated compounds were found. The phenomena are related to diffuse structure phase transition in the compounds. At temperatures 600 and 900 K, the compounds belong to orthorhombic symmetry (space group Pbcn).     

ODMR Study of Zn1−x Mn x Se/Zn1−y Be y Se and (Cd1−x ,Mn)Te/Cd1−y Mg y Te Diluted Magnetic Semiconductor Quantum Wells

The effects of microwave pumping with a frequency of 60 GHz on the magneto-optical properties of diluted magnetic semiconductors (DMSs) are studied in (Zn,Mn)Se/(Zn,Be)Se and (Cd,Mn)Te/(Cd,Mg)Te quantum wells. Resonant heating of the Mn²⁺ ions in the electron spin resonance conditions leads to an increase in the Mn-spin temperature, which exceeds the bath temperature by up to 5.2 K, as detected by the shift of exciton emission line and decrease of its integral intensity. Nonresonant heating mediated by free carriers is also observed through variation of the polarization degree of emission. Direct measurements of spin–lattice relaxation times for both materials using time-resolved optically detected magnetic resonance (ODMR) technique have been performed. The mechanisms of ODMR in nanostructures of DMSs are discussed.     

Ferromagnetic resonance study of Y3−z Ca z Fe5−x−y Co x Ge y O12 films

Conclusions It has been found that the character of the magnetic anisotropy changes markedly when the Co + Ge YIG films are doped with calcium. For the induced uniaxial and in-plane anisotropy we observe an increasing departure from the predictions based on the two-parameter model and for the cubic anisotropy the constantK ₁ becomes dependent on the growth direction. As a source for the latter effect the octahedral or tetrahedral preference of Co ions depending on the growth direction may be considered. The measured linewidth proportional to frequency indicates the presence of a relaxation mechanism which is, probably, connected with octahedral Co³⁺ ions.The authors express their thanks to Dr. P. Görnert and M. Neviva for preparation of the LPE films and to Dr. P. Novák for valuable discussions.Dedicated to Jan Kaczér DrSc on the occasion of his 65th birthday.     

Synthesis and excess conductivity analysis of TlBa2(Ca3−y Be y )Cu4O12−δ superconductors

TlBa₂(Ca_3?y Be _y )Cu₄O_12?δ (y = 0, 0.5, 1.0, 1.5, 2) samples are synthesized at normal pressure and the influence of doped Be-atoms on the superconductivity parameters at the microscopic level is investigated by carrying out excess conductivity analyses of conductivity data. The samples have shown tetragonal structure and the unit cell volume decreases with increased Be-doping. The onset temperature of superconductivity [T _c(onset)] and zero resistivity critical temperature [T _c(R = 0)] decrease with increased Be, however, the magnitude of diamagnetism is enhanced with Be (except for Be-doping of y = 1.0). The apical oxygen mode of the type Tl–O_A–Cu(2) and CuO₂ planar oxygen mode are softened as observed in FTIR absorption measurements. The FIC analyses of conductivity data have shown an increase in the coherence length along the c-axis and inter-plane coupling. The values of B _c0(T), B _c1(T), J _c(0), τ _φ are improved with the doping of Be. These observations suggested that due to the proximity effect there is less suppression in the value of the order parameter of the Cooper pairs from |ψ|² = 1 value in the CuO₂ planes in Be-doped samples that maintains the density of carriers in the conducting CuO₂ planes [since the |ψ|² = n/2] which promotes enhancement in the magnitude of superconductivity.     

Synthesis and performance of cathode material LiCo0.05Mn1.95O4 − y F y and modify by surface coating with LiCoO2

To investigate the electrochemical properties of LiCo_0.05Mn_1.95O_4???y F _y (y?=?0.025, 0.05, 0.075, 0.1, 0.15) as a cathode material for 4-V class lithium secondary batteries, spinel phases synthesized by sol–gel were examined. X-ray diffraction data reveals that all the materials synthesized are pure spinel structures. The charge–discharge curves demonstrate that LiCo_0.05Mn_1.95O_3.9F_0.1 has the best electrochemical property. LiCo_0.05Mn_1.95O_3.9F_0.1 possesses the initial and stable discharge capacity of 118.3 and 113 mAh/g after 10 cycles at 0.1 C, respectively, while LiCo_0.05Mn_1.95O_3.9F_0.1 possesses the initial and stable discharge capacity of 105.8 and 90.9 mAh/g after 40 cycles at 1 C, respectively. Both the cyclic voltammetry and electrochemical impedance explain the best electrochemical property of LiCo_0.05Mn_1.95O_3.9F_0.1 to some degree. LiCoO₂-coated LiCo_0.05Mn_1.95O_4???y F _y (7 mol%) presents an excellent reversibility than pristine one which possesses the initial and stable discharge capacity of 106.1 and 101.3 mAh/g after 40 cycles at 1 C, respectively.