Single crystal polarized Raman spectra of the solid electrolyte Cu2HgI4; attempt frequencies for ion motion in Ag2HgI4

The polarized Raman scattering from small single crystals of Cu₂HgI₄ provided assignments for the more prominent Raman features to specific irreducible representations. The E symmetry assignment, mass dependence, and pressure dependence of the 36 cm^?1 band in Cu₂HgI₄ and 24 cm^?1 band in Ag₂HgI₄ indicate that these features approximate the attempt frequency for ion hopping. The unusually high pre-exponential factor in the Arrhenius expression for ion hopping is discussed in light of the observed attempt frequency; we conclude that despite the high activation energy the conduction mechanism is similar to other heavy-metal solid electrolytes.     

Pressure dependence of transport and optical properties of Ag2HgI4

Silver mercury iodide, Ag₂HgI₄, has been studied to pressures of 75–100 kbar at 25°C. There are now four high pressure phases known. Transport studies indicate predominantly electronic conduction, with the highest pressure phase showing rectification in an asymmetric conductivity cell. Optical studies now corroborate the four high pressure phases. For two of the phases the energy gap shifts to lower energies with increasing pressure.     

Electrical conductivity and composition range of Ag2HgI4 between room temperature and 75°C

The composition range of α- and β-Ag₂HgI₄ near the transformation temperature is determined by X-ray diffraction. The electrical conductivity measured in the α-phase is nearly unaffected by deviation from stoichiometry. This is caused by a compensation of the composition dependences of σ₀ and of the activation energy E_A. From the experimental results the dependences of the entropy and of the Gibbs energy for migration of Ag-ions on temperature and on composition are estimated.     

High pressure X-ray diffraction study of CdAl2Se4 and Raman study of AAl2Se4 (A=Hg, Zn) and CdAl2X4 (X=Se, S)

We report the results of an X-ray diffraction study of CdAl₂Se₄ and of Raman studies of HgAl₂Se₄ and ZnAl₂Se₄ at room temperature, and of CdAl₂S₄ and CdAl₂Se₄ at 80 K at high pressure. The ambient pressure phase of CdAl₂Se₄ is stable up to a pressure of 9.1 GPa above which a phase transition to a disordered rock salt phase is observed. A fit of the volume pressure data to a Birch-Murnaghan type equation of state yields a bulk modulus of 52.1 GPa. The relative volume change at the phase transition at ∼9 GPa is about 10%. The analysis of the Raman data of HgAl₂Se₄ and ZnAl₂Se₄ reveals a general trend observed for different defect chalcopyrite materials. The line widths of the Raman peaks change at intermediate pressures between 4 and 6 GPa as an indication of the pressure induced two stage order-disorder transition observed in these materials. In addition, we include results of a low temperature Raman study of CdAl₂S₄ and CdAl₂Se₄, which shows a very weak temperature dependence of the Raman-active phonon modes.     

Cooperative fluorescence by excitonic resonant pumping in PbI2 and HgI2

The behaviour of the cooperative emission from PbI₂ and HgI₂ at 80 K has been studied at high exciton density by means of a tunable high intensity dye laser pumping. From a comparative analysis of the observed M and S stimulated emission lines from PbI₂ and HgI₂ we find that they strongly depend in two different ways on the pumping photon energy. Then, it is also possible to conclude that exciton-exciton and exciton-electron inelastic scattering are responsible for stimulated emission in PbI₂ and HgI₂ respectively.     

Pressure induced resonance of the Raman linewidth of the A1 mode of Cu3V S4

Investigations of the Raman spectrum of Cu₃V S₄ under pressure up to 60 kbar show a pronounced enhancement of the linewidth of the A₁ mode around 20 kbar. This anomaly is interpreted in terms of a resonance between the A₁ mode and a double phonon structure arising from the combination of F₂ like zone center phonons.     

Magnetic properties for the Cu2MnSnSe4 and Cu2FeSnSe4 compounds

Magnetic susceptibility χ measurements in the range from 2 to 300 K were carried out on samples of the Cu₂FeSnSe₄ and Cu₂MnSnSe₄ compounds. It was found that Cu₂FeSnSe₄ was antiferromagnetic showing ideal Curie-Weiss behavior with a Néel temperature T_N of about 19 K and Curie-Weiss temperature θ=−200 K, while for Cu₂MnSnSe₄ the behavior was spin-glass with a freezing temperature T_f of about 22 K and Curie-Weiss temperature θ=−25 K. The spin-glass order parameter q(T), determined from the susceptibility data, was found to be in agreement with the prediction of conventional spin-glass theory.     

The effect of pressure on the spin density wave transition in the layered cobaltites [Ca2CoO3]0.62[CoO2] and [Ca2Co4/3Cu2/3O4]0.62[CoO2]

In order to investigate the pressure effect on the magnetism in the layered cobaltites, positive muon spin rotation and relaxation μ⁺SR experiments have been carried out up to 1.3 GPa using c-aligned polycrystalline samples of [Ca₂CoO₃]_0.62[CoO₂] and [Ca₂Co_4/3Cu_2/3O₄]_0.62[CoO₂]. A transverse field μ⁺SR experiment indicates that the transition temperature to an incommensurate spin density wave IC-SDW state is independent of hydrostatic pressure up to 1.3 GPa for the both compounds. Furthermore, there are no changes in the spontanious muon precession frequency in zero field at 5 K even under 1.3 GPa. These results strongly suggest that the IC-SDW exists not in the rocksalt-type block ([Ca₂CoO₃] and/or [Ca₂Co_4/3Cu_2/3O₄]) but in the CoO₂ plane.     

Synthesis and characterization of Cu2ZnSnSe4 nanotube arrays on fluorine-doped tin oxide glass substrates

Highly ordered arrays of Cu₂ZnSnSe₄ nanotubes have been successfully synthesized on fluorine-doped tin oxide glass substrate using ZnO nanorod arrays as sacrificial templates. The structure, morphology and optical properties of the Cu₂ZnSnSe₄ arrays were characterized by X-ray diffraction, Raman spectrometry, field-emission scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray, and UV–Vis absorption spectroscopy. The diameter and length of the Cu₂ZnSnSe₄ nanotubes can be adjusted by tuning the diameter and length of the ZnO nanorods. In addition, the effect of the length on the performance of the photoelectrochemical cells was also investigated.     

The solid state reaction between AgI and HgI2

The kinetics of the solid state reaction between AgI and HgI₂ is investigated experimentally by measuring the thickness of the layer of the α-Ag₂HgI₄ product phase as a function of the annealing time and the reaction temperature. A theoretical expression is derived which allows the calculation of the variation of the chemical potentials of the binary components across the product layer considering the variation of the product phase composition. A value of A₀ = 6 kJ/mol is estimated for the standard affinity for the formation of stoichiometric Ag₂HgI₄ from the binary components AgI and HgI₂.     

Raman spectra of TiO2-II,TiO2-III,SnO2, and GeO2 at high pressure

Raman spectra of the orthorhombic (II) and high pressure (III) phases of titanium dioxide at pressures to 372 kbar and effects of temperature and hydrostatic pressure on Raman spectra of the tetagonal cassiterite-like phases of TiO₂, GeO₂ and SnO₂ are described. At room temperature, the TiO₂ II–III transition is sluggish, and metastable coexistence was observed from 200 to 300 kbar. The Raman spectra of TiO₂-III imply that its primitive cell contains at least four formula units; however, the structure could not be established from the Raman spectra and available powder X-ray diffraction patterns.The temperature and pressure dependences of the spectrum of the tetragonal MO₂ phases together with bulk moduli and thermal expansion data were used to evaluate the pure-volume and pure-temperature contributions to the isobaric temperature dependence of the Raman frequencies. Large anharmonicities in TiO₂ are attributed to hybridization of the oxygen p states with the d states of the Ti ion. GeO₂, where p-electron bonding is involved, is much less Enharmonic.     

Investigations on co-evaporated Cu2SnSe3 and Cu2SnSe3-ZnSe thin films

Cu₂SnSe₃ is an important precursor material for the growth of Cu₂ZnSnSe₄, an emerging solar cell absorber layer via solid state reaction of Cu₂SnSe₃ and ZnSe. In this study, we have grown Cu₂SnSe₃ (CTSe) and Cu₂SnSe₃-ZnSe (20%) films onto soda-lime glass substrates held at 573 K by co-evaporation technique. The effect of annealing of these films at 723 K for an hour in selenium atmosphere is also investigated. XRD studies of as-deposited Cu₂SnSe₃ and Cu₂SnSe₃-ZnSe films indicated SnSe as secondary phase which disappeared on annealing. The direct optical band gap of annealed Cu₂SnSe₃ and Cu₂SnSe₃-ZnSe films were found to be 0.90 eV and 0.94 eV respectively. Raman spectroscopy studies were used to understand the effect of ZnSe on the properties of Cu₂SnSe₃.     

Raman scattering from mixed crystals (HgBr2)1−x(HgI2)x

The behavior of long wavelength optic phonons in mixed system HgBr₂-HgI₂ has been investigated in Raman scattering. Different types of behavior, i.e. ‘persistent type’ and ‘amalgamation type’ were observed. Three strong Raman bands were observed for persistent type mode. These correspond to stretching vibration of HgBr₂, HgBrI, HgI₂ molecules. Intensity of these bands showed striking concentration dependence. A model based on nearly free molecular approximation have been proposed to explain the dependence. The analysis indicated that the distribution of anions on the sublattices is essentially random. For amalgamation (one-mode) type behavior, it is suggested that the intramolecular force relevant to the vibration is comparable to the intermolecular force and that the band width of the corresponding phonon branch in the parent crystal is broad enough to be degenerate with impurity mode at the low concentration limit.     

Phases and phase transitions of the superionic conductor Ag2HgI4 in the temperature range between 4.2 K and 370 K detected by diffuse reflectance spectrometry

Diffuse reflectance spectra of the superionic conductor Ag₂HgI₄ powder were recorded between 4.2 K and 370 K and transformed into the Kubelka-Munk function. Six parameters of the spectral band of this function, related to the absorption band of the particular phase, were considered. The graph representing the logarithm of the integrated Kubelka-Munk spectral band versus inverse temperature was most informative. The Arrhenius behaviour of this function, in a temperature interval, was related to the existence of a phase with constant lattice structure. The non-Arrhenius behaviour was tentatively attributed to a temperature sensitive phase. Thus fifteen different crystalline phases were found, only four of them having been, up to now, unquestionably admitted. In particular, evidence was given for the existence of two superionically conducting phases and two room temperature phases. All the graphs representing the chosen parameters versus inverse temperature pointed to the existence of two separate sequences of phases: one generated by cooling gradually the β-phase, stable at room temperature, to low temperatures (β sequence), the other by heating the β-phase above the σ → β (T)₊ transition point and cooling gradually the formed α'′-phase (α′ sequence). The concept of photon absorption thermal activation energy was introduced. Its largest value was of the order of magnitude of the electrical conductivity thermal activation energy of Ag₂HgI₄. Estimates of energy band gaps and their evolution with temperature were made. It is suggested that the polymorphism of the substance is the main reason for the hysteresis loop in the superionic conductivity transition region. The low temperature phases manifested luminescence caused by exciton decay.     

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.     

High-pressure Raman spectroscopic studies on orthophosphates Ba3(PO4)2 and Sr3(PO4)2

By using diamond anvil cell (DAC), high-pressure Raman spectroscopic studies of orthophosphates Ba₃(PO₄)₂ and Sr₃(PO₄)₂ were carried out up to 30.7 and 30.1 GPa, respectively. No pressure-induced phase transition was found in the studies. A methanol:ethanol:water (16:3:1) mixture was used as pressure medium in DAC, which is expected to exhibit nearly hydrostatic behavior up to about 14.4 GPa at room temperature. The behaviors of the phosphate modes in Ba₃(PO₄)₂ and Sr₃(PO₄)₂ below 14.4 GPa were quantitatively analyzed. The Raman shift of all modes increased linearly and continuously with pressure in Ba₃(PO₄)₂ and Sr₃(PO₄)₂. The pressure coefficients of the phosphate modes in Ba₃(PO₄)₂ range from 2.8179 to 3.4186 cm⁻¹ GPa⁻¹ for ν₃, 2.9609 cm⁻¹ GPa⁻¹ for ν₁, from 0.9855 to 1.8085 cm⁻¹ GPa⁻¹ for ν₄, and 1.4330 cm⁻¹ GPa⁻¹ for ν₂, and the pressure coefficients of the phosphate modes in Sr₃(PO₄)₂ range from 3.4247 to 4.3765 cm⁻¹ GPa⁻¹ for ν₃, 3.7808 cm⁻¹ GPa⁻¹ for ν₁, from 1.1005 to 1.9244 cm⁻¹ GPa⁻¹ for ν₄, and 1.5647 cm⁻¹ GPa⁻¹ for ν₂.     

Cation disordering in Ag2HgI4 and Cu2HgI4

The cation order-disorder transitions in Ag₂HgI₄ and Cu₂HgI₄ are first order. This is unusual, since in other superionic conductors the cation disordering is gradual with temperature if there is no structural phase transition. These two materials are also unique in that they have two disordering cations rather than one. A study of a two species lattice gas model shows that this extra degree of freedom is responsible for the first order nature of this transition on the fcc lattice.     

Cu2ZnSnSe4 thin films prepared by selenization of co-electroplated Cu-Zn-Sn precursors

A novel technique for growth of high quality Cu₂ZnSnSe₄ (CZTSe) thin films is reported in our work. The CZTSe thin films were fabricated onto Mo layers by co-electroplating Cu-Zn-Sn precursors followed by annealing in the selenium vapors at the substrate temperature of 550 °C. The morphology and structure of CZTSe thin films were characterized using scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD) and Raman scattering spectrum, respectively. The results revealed that the single phase was in the CZTSe thin films, and the other impurities such as ZnSe and Cu₂SnSe₃ were not existed though they were difficult to distinguish both from EDS and XRD.     

High pressure Raman spectroscopy of spinel-type ferrite ZnFe2O4

An in-situ Raman spectroscopic study was conducted to explore the pressure induced phase transformation of spinel-type ferrite ZnFe₂O₄. Results indicate that ferrite ZnFe₂O₄ initially transforms to an orthorhombic structure phase (CaFe₂O₄-polymorph) at a pressure of 24.6 GPa. Such a phase transformation is complete at 34.2 GPa, and continuously remains stable to the peak pressure of 61.9 GPa. The coexistence of the two phases over a wide range of pressure implies a sluggish mechanism upon the spinel-to-orthorhombic phase transition. Upon release of pressure, the high pressure ZnFe₂O₄ polymorph is quenchable at ambient conditions.     

ESR of Cu2+ in the high pressure form of Cd3(PO4)2

ESR spectra of polycrystalline Cu²⁺ doped samples of the high pressure phase of Cd₃(PO₄)₂ were characteristic of the existence of two different paramagnetic centres. The spin—Hamiltonian constants of both defects were determined. Only two of the three possible substitutional cation sites are occupied by copper ions.