Photoacoustic determination of low absorption coefficients in CdI2 layered semiconductor

Photoacoustic spectra in thin samples of CdI₂ layered semiconductor have been measured in the region of energies near the fundamental energy gap. By means of this technique it was possible to obtain the spectrum of the low values of the absorption coefficient in the range between 3.12 and 3.26 eV, where the absorption coefficient varied from 5 to 100 cm^-1. The experimental results are sound with respect to the indirect nature of the optical gap of the CdI₂.     

New compounds with incommensurate phases: Cs2CdI4 and Cs2ZnI4

Abstract

In this paper the results of birefringence studies and of optical observations in polarized light in a wide temperature region are presented for crystals Cs₂CdI₄ and Cs₂ZnI₄. There is the following sequence of phases: commensurate orthorhombic Pnma ? incommensurate ? monoclinic ferroelastic P2₁/n ? triclinic ferroelastic PT. A correlation was observed between the peculiarities of birefringence and NQR spectra temperature dependence. An assumption is made, that in Cs₂ZnI₄ crystal in a broad pre-transition region (T - T _i = 100 K) precursor clusters exist, which manifest themselves as coexistence of NQR spectra of two phases and as deviation of birefringence from the linear temperature dependence (“tail”).     

Thermal,Electrical and Optical Studies of Phase Transitions in Ag2CdI4 Solid Electrolyte

The article deals with the preparation method of bulk Ag₂CdI₄ superionic material and with investigations of structural phase transitions (PT) which take place in the 100÷450 K temperature range. The phase transitions were studied by thermal, electrical and luminescence methods. The temperature dependencies of thermal expansion, heat capacity, thermal conductivity, electric conductivity and excitation luminescence spectra show that in the temperature range 100 ÷ 450 K Ag₂CdI₄ possesses a sequence of structural changes at 180 ÷190 K, 320 ÷ 330 K, 350 ÷ 370 K and at T>400K. The nature and mechanisms of the observed structural changes are discussed.     

Time dependence of the luminescence intensity in CdI2-Cd and CdI2-Ag crystals

The decrease in the luminescence intensity (luminescence ??fatigue??) of long-wavelength emission bands with time in CdI₂-Cd (??_max = 700 nm) and CdI₂-Ag (??_max = 680 nm) crystals upon exposure to light in the fundamental absorption region has been studied. The process parameters, i.e., the capture cross section ?? and the fraction ?? of centers disappeared during interband irradiation, have been determined. The model of electronic processes has been proposed, within which experimental data have been consistently explained.     

Structural and transport properties of CdI2 doped silver ion conducting system

The glass system xCdI₂-(100−x)[2Ag₂O-(0.7V₂O₅-0.3B₂O₃)] with different amount of dopant salt have been prepared by melt quenching technique. The sample obtained were pulverized and characterized by XRD, DSC, and FTIR. The electrical conductivity studies of the samples have been carried out at different temperatures and frequencies. Conductivity of the glasses increased with the increase in the CdI₂ contents and attains a value of 7.76×10⁻⁴ S/cm at room temperature for the composition having x=30 mol% of CdI₂. Infrared spectroscopic studies on these glasses indicated that the oxyanion network was not affected by the addition of CdI₂. The transport number of the silver ion determined by emf method is nearly unity. The frequency dependence of electrical conductivity for various glass compositions at different temperature has been analyzed in terms of Jonscher's Universal expression. In the present CdI₂ doped system, the conduction is due to the Ag⁺ ions attached to the AgI which is formed due to the exchange reaction between CdI₂ and Ag₂O.     

A study of formation of solid ionic conductors in the mixed system (CdI2)b[(Ag2O)·(CrO3)]100-b (20≤b≤80)

Using Wagner's polarization technique and EMF method the joinic and silver ionic transport number measurements of various compositions of the mixed system CdI₂-Ag₂O-CrO₃ have been made. The presence of AgI in these materials has been inferred from the typical β → α phase transition of AgI, which is characterized by an endothermic peak at around 420 K in the DSC traces of these specimens. While the structural analysis performed by means of powder X-ray diffraction has revealed the formation of ionic phases involving polycrystalline compounds, the Fourier transform infrared (FTIR) spectroscopic results have indicated the presence of ionic species thus confirming the ionic nature of the products. The complex impedance studies carried out in the frequency range 20 Hz - 1 MHz and over the temperature range 294 – 442 K have revealed that the best conducting composition, namely 55%(CdI₂) – 45%(Ag₂O·CrO₃), would exhibit a silver ionic conductivity of 1.3×10⁻⁵Scm⁻¹ at 294 K.     

The absorption spectrum and excitons in an Ag2CdI4 ionic conductor

The electron absorption spectrum of thin stochiometric Ag₂CdI₄ films produced by thermal vacuum deposition on a quartz substrate in is investigated. The spectrum shape is sensitive to the method of preparation (the substrate temperature and deposition rate). Under optimal preparation conditions, the films are free of AgI and CdI₂ impurities and the fundamental absorption edge is at 3.28 eV. The long-wavelength exciton A band at 3.31 eV (90 K) is associated with the excitation of excitons in the AgI sublattice of the compound. An investigation of the temperature dependence of the spectral position and half-width of the A band in the range 90–430 K revealed that the exciton-phonon interaction makes the major contribution to the broadening of the band at T ≤360 K. At higher temperatures, the contribution associated with the generation of Frenkel defects with activation energy U _F=0.200±0.025 eV appears.     

Phonon density of states of CdI2 deduced fro,the fine structure of the 3A2g → 1Eg electronic transition of CdI2:Ni2+

The absorption and MCD spectra of the ³A_2g → ¹E_g transition of CdI₂:Ni²⁺ at about 12,500 cm^?1 have been measured. The unusual vibronic fine structure is explained by the coupling of the phonons of the CdI₂ lattice to the electronic states of Ni²⁺. The dispersion curves for the acoustical and optical branches in the Brillouin Zone of CdI₂ are deduced.     

Impedance and Modulus studies of the solid electrolyte system 20CdI2–80[xAg2O–y(0.7V2O5–0.3B2O3)], where 1 ≤x/y ≤ 3

In the present work, an evaluation of the transport properties of super ion conducting quaternary system 20CdI₂–80[xAg₂O–y(0.7V₂O₅–0.3B₂O₃)], where 1 ≤ x/y ≤ 3, in steps of 0.25, to study the effect of changing the modifier to former ratio on the conduction phenomena has been undertaken. Electrical conductivity measurements were made using complex impedance method. The electrical conductivity and conductivity relaxation of the system were studied in the temperature range from 303 K to 333 K and in the frequency range from 100 Hz to 10 MHz. The highest conductivity at room temperature is obtained for the system with modifier to former ratio 1.75. Impedance and modulus analyses had indicated the temperature independent distribution of relaxation times and the non-Debye behavior in these materials. The co-operative motion due to strong coupling between the mobile Ag⁺ ions is assumed to give rise to non-Debye type of relaxation. The silver ionic transport number (t_Ag+) obtained by the emf technique suggested the occurrence of silver ion conduction in the CdI₂-doped Ag₂O–V₂O₅–B₂O₃ system.     

Raman and infrared spectra of CdIn2S4 and ZnIn2S4

Four one-phonon Raman lines have been found in CdIn₂S₄ (ZnIn₂S₄) spinels at 92 (72) cm^-1, 186 (184) cm^-1, 246 (253) cm^-1, and 367 (372) cm^-1 for incident photon energies well below the energy gap E_G ～ 2.4 (2.2) eV at 300 K. For photon energies close to E_G, the 367 cm^-1 mode underwent a resonant enhancement in CdIn₂S₄ and four infrared active but Raman forbidden F_1u modes appeared in the CdIn₂S₄ and ZnIn₂S₄ Raman spectra: TO modes at 226 (221) cm^-1 and 309 (312) cm^-1, and LO modes at 274 (272) cm^-1 and 340 (342) cm^-1.     

XRD, conductivity and FTIR studies on LiI-Li2WO4-Li3PO4 prepared by low temperature sintering

Different amounts of Li₃PO₄ were mixed to a fixed ratio of LiI:Li₂WO₄, ground and pelletised before subjected to sintering at 70°C for 7 days. XRD shows that the product formed after sintering process is most likely Li₆P₄W₈O₃₂ due to peaks present at 10.6°, 22.4°, 24.0°, 24.4, 26.2°, 32.4° and 34.0°. Conductivity studies show that the sample with 25 wt.% Li₃PO₄ exhibits the highest room temperature conductivity of 3.42×10⁻³ Scm⁻¹. Conductivity is expected to occur through channel-like structures which could have formed due to corner or edge sharing of polyhedra. FTIR studies have shown the existence of WO₄ tetrahedra and WO₆ octahedral at 850 cm⁻¹ and 952 cm⁻¹, and phosphate tetrahedral at 564 cm⁻¹, 700 cm⁻¹, 890 cm⁻¹ and 1030 cm⁻¹.     

The polarized reflectance spectrum of a novel organic conductor (BEDT-TTF)2ClO4(C2H3Cl3)0.5

The polarized reflectance spectrum of a novel organic conductor, (BEDT-TTF)₂ClO₄(C₂H₃Cl₃)_0.5 was measured at room temperature over the spectral region from 340 cm^-1 to 25000 cm^-1. The reflectance spectrum provided an evidence for the anisotropic two-dimensional character of this material. The optical conductivity spectrum exhibits the existence of an optical band gap of about 0.2 eV, suggesting that this material is a semimetal rather than a metal.     

Magnetic excitations in the two dimensional planar antiferromagnets K2FeF4 and Rb2FeF4

The magnetic excitation spectrum of K₂FeF₄ and Rb₂FeF₄, two K₂NiF₄-structure planar antiferromagnets with rather large anisotropy and spins perpendicular to the c-axis, has been measured by Raman and FIR-spectroscopy. One of the two predicted one-magnon transitions and the two-magnon mode have been observed in K₂FeF₄ (Rb₂FeF₄) at 48.5 cm^-1 (37.6 cm^-1) and 182.0 cm^-1 (160.5 cm^-1) respectively. The magnetic field and temperature dependence of the spectra are reported too. The data are discussed on the basis of an easy plane spin model Hamiltonian. In K₂FeF₄: Mn²⁺ a low lying magnetic impurity mode is observed at 40.5 cm^-1.     

Die Eigenschwingungen des Metall-Hydratkomplexes in BeSO4·4H2O und BeSO4·4D2O

Infrared reflection spectra of single crystals of BeSO₄·4H₂O and BeSO₄·4D₂O have been obtained in polarized light at 300°K and at 14°K in the region between 4000 cm^?1 and 300 cm^?1. By a Kronig-Kramers analysis, the frequencies of the infrared active transitions have been calculated. These transitions are attributed to internal vibrations of the water molecules and sulfate ions and, in the region between 1000 cm^?1 and 300 cm^?1, especially to internal and external vibrations of the tetrahedral Be⁺⁺·4aqu-complexes. The vibrational modes of these complexes consist of a superposition of translational and librational modes of the water molecules and translational modes of the central Be⁺⁺-ion. The vibrational frequencies and normal modes of this complex have been calculated in a central-force model, and force-constants have been determined by fitting the calculated frequencies to the observed spectra. The calculations have shown that the modes, which comprise mainly translational motions of the water molecules, are strongly coupled with librational motions of the water molecules. On the other hand, there exist pure librational modes with practically no admixture of translational motions. The optimum sets of force constants for the BeSO₄·4H₂O crystal and the BeSO₄·4D₂O crystal differ in a manner which can be understood under the assumption that the dimensions of the Be(D₂O)₄ complex are about 0.1 Å larger than those of the Be(H₂O)₄ complex. Some arguments supporting this conclusion will be discussed.     

Spectral and kinetic characteristics of CdI<Subscript>2</Subscript> and CdI<Subscript>2</Subscript>:Pb scintillators

We have studied the effect of lead dopant on the optical absorption, photoluminescence, and x-ray luminescence spectra, and the scintillation characteristics of CdI₂ at room temperature. The crystals for the study were grown by the Stockbarger-Bridgman method. Activation of CdI₂ from the melt by the compound PbI₂ leads to the appearance in the absorption spectra in the near-edge region of an activator band at 395–405 nm, which is interpreted as an A band connected with electronic transitions from the ¹S₀ state to the ³P₁ levels in the Pb²⁺ ion. For x-ray excitation, CdI₂:Pb²⁺ crystals with optimal dopant concentration (∼1.0 mol%) are characterized by a light yield with maximum in the 570–580 nm region that is an order of magnitude higher than for CdI₂ crystals in the 490–500 nm band. For α excitation, the radioluminescence kinetics for cadmium iodide is characterized by a very short (∼0.3 nsec) rise time and fast decay of luminescence, with τ₁ ≈ 4 nsec and τ₂ = 10–76 nsec. Depending on the conditions under which the crystals were obtained, the fast component fraction is 95%–99%. The crystal is characterized by a similar scintillation pulse in the case of excitation by x-ray pulses. The radioluminescence pulse shape for CdI₂:Pb in the decay stage is predominantly exponential, with luminescence decay time constants τ₁ ≈ 10 nsec and τ₂ = 200–250 nsec. This system is characterized by low afterglow, at the level for the Bi₄G₃O₁₂ scintillator. We have demonstrated the feasibility of using CdI₂:Pb as a scintillator for detecting α particles. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 825–830, November–December, 2008.     

Photoluminescence of cobalt in CdIn2S4

The photoluminescence of cobalt (0.05 mol %) doped CdIn₂S₄ has been measured in the range 8500–16500 cm^-1. Luminescence is observed from both tetrahedrally and octahedrally coordinated Co²⁺ ions in the partially inverted spinel. Vibrationally assisted transitions from the ²E(G) state of both of these sites are identified. The ⁴A₂(F) level of the tetrahedrally coordinated Co²⁺ is found to be 1927 cm^-1 above the CdIn₂S₄ valence band and the spin-orbit splitting factor is measured to be λ = -133 cm^-1.     

新型激光晶体Yb:KY(WO4)2的结构与光谱

采用顶部籽晶提拉法，以K₂W₂O₇为助溶剂，生长了Yb:KY(WO₄)₂新型激光晶体.经热重-差热分析，确定晶体熔点为1045℃，相变温度为1010℃.X射线粉末衍射测试，验证所生长的晶体为β-Yb:KY(WO₄)₂.晶体结构分析确定Yb:KY(WO₄)₂晶体由WO₆八面体连接而成，WO₆八面体是由双氧桥(WOOW)及单氧桥(WOW)构成.晶体粉末样品室温下的红外及拉曼光谱测试，确定WO₆原子基团、双氧桥及单氧桥的振动频率.晶体的吸收峰位于940nm，980nm，发射峰位于989nm—1030nm. 关键词： 晶体结构 光谱 晶体生长     

Vibration-rotation energies of harmonic and combination levels in tetrahedral XY4 molecules: Analysis of the 2ν2 and ν2 + ν4 bands of 12CH4

The theory and the extrapolation method described in the previous paper are used to analyze the v₂ = 2 and v₂ = v₄ = 1 levels of ¹²CH₄. In addition to the well-known parameters of the ground, v₂ = 1, and v₄ = 1 states, the computation of energy levels involves only 6 new parameters for 2ν₂ and 13 for ν₂ + ν₄ up to the fourth order of approximation. These parameters have been determined from Raman and infrared data. Forty-four Raman lines observed by Berger in the region from 3060 to 3090 cm^?1 have been assigned to the 2ν₂ band. The standard deviation obtained by fitting 39 of these transitions with the 6 corresponding parameters is 0.025 cm^?1. The calculated frequencies of ν₂ + ν₄ are compared with moderate resolution ir spectra recorded in our laboratory and the recent spectra of Hunt et al. Totally polarized weak Raman lines observed by Berger in the region from 2850 to 2900 cm^?1 have been assigned to the ν₂ + ν₄ band arising through a second-order Coriolis interaction with the ν₁ band. A project of a comprehensive treatment of the energy levels of methane between 2550 and 3650 cm^?1 is discussed.     

UV absorption spectra of thin films of Cs<Subscript>2</Subscript>CdI<Subscript>4</Subscript> and Rb<Subscript>2</Subscript>CdI<Subscript>4</Subscript> ferroelectrics

Thin films of M₂CdI₄ ferroelectrics (M=Cs, Rb) of orthorhombic structure were synthesized, and their electronic optical spectrum was studied. It was established that both compounds belong to direct-gap dielectrics and that their low-frequency excitons are localized on a sublattice made up of (CdI₄)^2? tetrahedra. The temperature dependence of the exciton band parameters was studied for Cs₂CdI₄ within the temperature interval 90–420 K. The phase transitions occurring in this interval manifest themselves as breaks in the temperature behavior of the band spectral positions and weak peaks in the halfwidth and oscillator strength.     

Infrared spectra of paraelectric and ferroelectric CsH2PO4

ir spectra are reported for polycrystalline CsH₂PO₄ above and below the transformation temperature, 153 K. Three absorption bands at 1760 cm^-1 2350 cm^-1 and 2800 cm^-1 are assigned to -OHO- vibrations. Whilst the 2350 cm^-1 band remains essentially unaltered, the 1760 cm^-1 band splits into multiplets and the 2800 cm^-1 band shifts to lower frequency on cooling below 153 K. A broad band centred at 3240 cm^-1 is found to exist in the ferroelectric phase and is associated with the -OHO- mode involving the H(2) proton ordered below the transition.