Vibrational studies of crystalline and glassy SiSe2

An analysis of the Raman and Infrared spectra of crystalline and glassy SiSe₂ is presented. A tentative assignment of the vibrational modes of crystalline SiSe₂ is developed which provides a useful framework for understanding the spectrum of glassy SiSe₂. A direct correspondence between the modes of crystalline and glassy SiSe₂ is observed that extends not only to modes associated with the elements of short range order $\text{(Si(Se}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}{}_4$ tetrahedral units) but also to modes that result from correlated motions of extended units (packets of edge-sharing tetrahedral chains). The present results provide strong evidence for a degree of medium range order greater than that previously proposed for the Si-based glasses.     

Multistep deposition of Cu2Si(S,Se)3 and Cu2ZnSiSe4high band gap absorber materials for thin film solar cells

Cu₂ZnSi(S,Se)₄ and Cu₂Si(S,Se)₃ are potential materials to obtain cost effective high band gap absorbers for tandem thin film solar cell devices. A method to synthesize Cu₂SiS₃, Cu₂SiSe₃and Cu₂ZnSiSe₄thin film absorbers is proposed. This method is based on a multistep process, using sequential deposition and annealing processes. X‐ray diffraction analysis performed on the final thin films have confirmed the presence of the Cu₂Si(S,Se)₃ and Cu₂ZnSiSe₄phases. Scanning electron microscopy images revealed the formation of polycrystalline layers with grains size up to 1 µm. The band gap of the ternary Cu₂SiSe₃ and Cu₂SiS₃, and quaternary Cu₂ZnSiSe₄ based thin films as determined from optical and photoluminescence measurements are found to be close to their theoretical values. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Influence of thickness on the optical properties of amorphous GeSe2 thin films: analysis using Raman spectra,Urbach energy and Tauc parameter

An analysis is reported of thickness-induced defects in amorphous GeSe₂ thin films deposited by the vacuum evaporation technique. X-ray diffraction studies confirmed the amorphous nature of the thin films. Optical absorption measurements revealed an indirect transition with an energy gap that increases with film thickness. A blue shift in optical transmittance edges was observed in annealed GeSe₂ thin films. The obtained lower values of Urbach energy (E _U) indicate that as thickness increases more ordered films can be produced. Raman spectra suggest that annealing promotes corner-sharing GeSe_4/2 tetrahedra and edge-sharing Ge₂Se_8/2 bi-tetrahedra bonding and leads to the reduction in disorder in bonding network, which is amply supported by the way of increase in band gap, increase in Tauc parameter (B ^1/2) and reduction in E _U from the analysis of transmittance spectra. Increasing the thickness promotes tetrahedral and bi-tetrahedral bonding through the reduction in bonding defects.     

Structural investigations of GeS2-Ga2S3-CdS chalcogenide glasses using Raman spectroscopy

Raman investigations were carried out for various compositions of chalcogenide glasses in the GeS₂-Ga₂S₃-CdS system. Addition of Ga₂S₃ into GeS₂ results in the formation of metal-metal bonds and edge-shared GaS_4/2 tetrahedra. Ge²⁺ ions may surround [GaS_4/2]¹⁻ tetrahedra acting as charge compensators. Upon the addition of CdS into the GeS₂-Ga₂S₃ system, the number of the metal-metal bonds and edge-shared GaS_4/2 tetrahedra decreases, resulting in the formation of corner-shared tetrahedra with non-bridging sulfurs (NBS). Cd²⁺ ions can be dissolved into the glass network as charge compensators for these NBS and exited few [GaS_4/2]¹⁻ tetrahedra. The high solubility of CdS is ascribed to the dissociation of metal-metal bonds and edge-shared tetrahedra in these Ga-containing glasses.     

Raman scattering study of GeTe and Ge2Sb2Te5 phase-change materials

Structural details of the amorphous binary GeTe and ternary Ge₂Sb₂Te₅ (GST) phase-change materials are investigated with the aid of Raman scattering. In the case of the a-GeTe, a plethora of Raman bands have been recorded and assigned on the basis of a network structure consisting of corner- and edge-sharing tetrahedra of the type GeTe_4−nGe_n (n=0, 1, 2, 3, 4). Significant temperature-induced structural changes take place in this material even at temperatures well below the crystallization temperature. These changes tend to organize the local structure, in particular the coordination number of Ge atoms, so as to facilitate the amorphous-to-crystal transformation. The much simpler Raman spectrum of GST, characterized by one vibrational band, is accounted for by the dominance of the Sb₂T₃ component in Raman scattering; reasons about this explanation, as well as for the lack of any Te–Te bonds are briefly described.     

Diffusion of sodium ions in borosilicate glasses by molecular dynamics method

Molecular dynamics simulations of borosilicate glasses with different sodium oxide content has been carried out. The generated structure indicates that the major number of oxygen atoms introduced as Na₂O consumes in the borate network to convert the BO₃ triangles to BO₄ tetrahedra. The formation of nonbridging oxygen ions in the silica site occurs during the formation of BO₄ tetrahedra with low rate. At higher concentrations of Na₂O, the NBO's increases abruptly. The self diffusion of sodium ions depends essentially on the temperature, composition (number of Na⁺ ions) and the rate of cooling. The phase separation mechanism in borosilicate glasses can be detected by MD simulation since the environment of the B–O, Si–O and B–O–Si can be easily reached.     

Magnetic behavior and structural feature of quasi-one-dimensional BaCu2V2O8 crystal

Magnetic properties of BaCu₂V₂O₈ single crystals obtained by the spontaneous nucleation method using V₂O₅ as a self-flux are investigated. Singlet ground states with spin gaps of 215 and 223 K are observed along the directions parallel and perpendicular to the c-axis of the crystal, respectively, being in good agreement with powder sample measurements. Reinvestigation of the crystal structure reveals that the whole structural framework of BaCu₂V₂O₈ crystal can be described as an assembly of alternating chains, which are built by edge-sharing pairs of CuO₄ square-plaquettes and VO₄ tetrahedra along the c-axis. The magnetic nature of BaCu₂V₂O₈ is well understood based on this structural interpretation.     

Enhanced electrochemical performance of LiMnBO<Subscript>3</Subscript> with conductive glassy phase: a prospective cathode material for lithium-ion battery

LiMnBO₃ has been identified as a promising cathode material for next-generation lithium-ion batteries. In this study, LiMnBO₃ along with glassy lithium borate material (LiMnBO₃ (II)) is synthesized by sol-gel method. X-ray diffraction (XRD) analysis depicts the existence of LiBO₂ glassy phase along with m-LiMnBO₃ phase. Transmission electron microscopy (TEM) analysis confirms the presence of LiBO₂ glassy phase. An enhanced electrical conductivity of 3.64 × 10^?7 S/cm is observed for LiMnBO₃ (II). The LiBO₂ glassy phase is found to promote the Li reaction kinetics in LiMnBO₃ (II). The synthesized LiMnBO₃ (II) delivers a first discharge capacity of 310 mAh g^?1 within a potential window of 1.5–4.5 V at C/10 rate. Further, a discharge capacity of 186 mAh g^?1 at the 27th cycle shows a better cycle performance. The enhanced capacity is due to the presence of LiBO₂ glassy phase and more than one Li-ion transfer in the lithium-rich stoichiometry of LiMnBO₃ (II). Density functional theory calculation reveals the exact electronic structure of m-LiMnBO₃ with a band gap of 3.05 eV. A charge transfer mechanism is predicted for delithiation process of m-LiMnBO₃.     

Li2O-(LiCl)2-B2O3-Al2O3系统玻璃的Raman光谱研究

我们用Raman光谱研究了Li₂O(LiCl)₂B₂O₃-Al₂O₃系玻璃的结构,着重研究了Al₂O₃的影响。对于Li₂O-B₂O₃系玻璃,Li₂O含量增加使玻璃中存在的BO₃三角体转变为BO₄四面体, 关键词：     

The effects of topology on the structural, dynamic and mechanical properties of network-forming materials

The effects of network topology on the static structural, mechanical and dynamic properties of MX(2) network-forming liquids (with tetrahedral short-range order) are discussed. The network topology is controlled via a single model parameter (the anion polarizability) which effectively constrains the inter-tetrahedral linkages in a physically transparent manner. Critically, it is found to control the balance between the stability of corner-?and edge-sharing tetrahedra. A potential rigidity transformation is investigated. The vibrational density of states is investigated, using an instantaneous normal model analysis, as a function of both anion polarizability and temperature. A low frequency peak is seen to appear and is shown to be correlated with the fraction of cations which are linked through solely edge-sharing structural motifs. A modified effective mean atom coordination number is proposed which allows the appearance of the low frequency feature to be understood in terms of a mean field rigidity percolation threshold.     

Selenium adsorption on Cs-covered Si(100) 2×1 surfaces

This report involves the study of Se adsorption on caesiated Si(100) 2×1 surfaces in ultra high vacuum (UHV) using low energy electron diffraction, Auger electron spectroscopy, thermal desorption spectroscopy and work function measurements. Selenium atoms on Cs/Si(100) 2×1 surface adsorb initially on uncaesiated portions of Si and subsequently on the Cs overlayer. The presence of Se increases the binding energy of Cs on Si(100). For Cs and Se coverages above 0.5 ml CsSe and Cs_xSe_ySi_z, compound formation was observed. The coadsorption of Se and Cs induces a high degree of surface disorder, while desorption most probably causes surface etching. The presence of Cs on Si(100) 2×1 surfaces prevents the diffusion of Se into the Si substrate and greatly suppresses the formation of SiSe₂ and SiSe₃, detected when Se is adsorbed on clean Si(100) 2×1 surfaces.     

Structure and optical properties of GeGaS films deposited by thermal evaporation

Amorphous GeGaS thin films have been successfully deposited onto glass slides at room temperature by the thermal evaporation technique. The structural units of the films were studied using Raman spectroscopy. In addition to the basic structural units of GeS₄ tetrahedra, there are some SS and GeGe homopolar bonds which exist in the films. The increase in Ge atoms leads to the replacement of SS bonds by GeGe bonds, and the isolated Ge(Ga)S₄ tetrahedra units transform into corner-sharing or edge-sharing Ge(Ga)S₄ tetrahedra units in the films. The refractive index and optical band gap were derived from transmission spectra of films. The values of optical band gap decrease while the refractive indices increase with increasing Ge content. Composition dependence of optical band gap and refractive index has also been interpreted in terms of the variation in the structure of films based on Raman spectra.     

Orientational disorder,glass/crystal transition and superionic conductivity in nasicon

The relations between the orientational disorder of SiO₄(PO₄) tetrahedra and fast sodium diffusion in superionic NASICON have been studied by conductivity (complex impedance method), DSC, X-ray powder difraction and vibrational spectroscopy (IR and Raman). Sol-gel routes allow to obtain pure glassy NASICON (Na_1+xZr₂Si_xP_3-xO₁₂x≅2) in the 500−700°C temperature range. Tetragonal zirconia nucleates above 700°C and disappears at about 900°C when the isolated tetrahedra framework is formed: a high orientational static disorder of tetrahedra exists and the symmetry is rhombohedral at all studied temperatures (20−600 K). Thermal treatment above 1100°C induces a drastic decrease of the static orientational disorder and nucleation of monoclinic zirconia. The resulting compound exhibits a monoclinic symmetry at R.T. and three phase transitions, two diffuse at about 60 K and 520 K and the 423 K monoclinic-rhombohedral transition associated with the superionic conducting state. An increase in dynamic disorder (broad Rayleigh wing up to 500 cm^-1 is simultaneously observed. The lower the static disorder at low temperature, the higher the dynamic orientational disorder and the phase transitions, and the lower the activation energy of conductivity at high temperature.     

Structure and ionic conduction in solids: VI. Evidence for the non-existence of Na4ZrSi3O10 as a definite crystalline phase

For investigation of phase relations in the NASICON system some compositions of the general formula Na₄Zr_2−xSi₃O_{12 −2x} were prepared by sol-gel technique and the usual method of sintering the oxide mixtures. DTA measurements indicate that unannealed samples in this series must contain a glassy phase. By means of X-ray analysis of a sample of the composition Na₄ZrSi₃O₁₀ it was clearly shown that this sample does not exist as a definite compound, but must be regarded as a composite material consisting of the well known compound Na₄Zr₂(SiO₄)₃ and a glassy phase of the composition Na₄Si₃O₈. This result was proved by high resolution ²⁹Si-magic angle spinning (MAS)-NMR measurements which allow the simultaneous registration of both crystalline and glassy phases and the determination of the relative Si-content of the phases with high accuracy. In this manner the glass composition in the sample was estimated for 1.98 Na₂O·3SiO₂.     

Electrochromic properties of tungsten oxides synthesized from aqueous solutions

Tungsten oxides are known to exhibit interesting electrochemical properties. Ion insertion (Li⁺, H⁺) within the oxide network is highly reversible. It leads to a blue coloration and WO₃ thin films can be used as electrochromic layers in display devices or smart windows. Tungsten oxide thin films can be conveniently deposited from aqueous solutions of tungstic acid. However polytungstic acids are not stable and tend to precipitate into hydrated tungsten oxide WO₃⋅2H₂O. The condensation of polytungstic species can be chemically controlled by adding foreign ions in the solution. Precipitation is no more observed in the presence of H₂O₂. Peroxopolytungstic acids are formed in which chelating [O₂]²⁻ ligands prevent the formation of an oxide network. Such solutions are specially convenient for the deposition of optically transparent thin films. Mixed oxides WO₃-MoO₃ are obtained when condensation is performed in the presence of Mo⁶⁺ cations. This paper shows how the condensation of tungstic acid can be chemically controlled and describes the electrochemical properties of the films deposited from such solutions. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

Structural changes of piezoelectric La3Ga5SiO14 induced by paramagnetic ions revealed by Ga multiple quantum magic angle spinning

Experimental evidence that nuclear magnetic resonance (NMR) can detect structural changes of piezoelectric La₃Ga₅SiO₁₄ induced by dilute paramagnetic ions is presented. Gd³⁺ and Eu³⁺ cations have been incorporated into La₃Ga₅SiO₁₄ monocrystals. As expected, the line-width of the tetrahedral ²⁹Si magic angle spinning (MAS) NMR spectra as well as the inverse of the T₂ relaxation time of ⁷¹Ga increases with the concentration of the paramagnetic ions. A surprising result is shown by ⁷¹Ga multiple quantum (MQ) MAS NMR spectrum, which changes with the concentration of paramagnetic ions. The changes in the ⁷¹Ga MQMAS spectra can be explained by a more ordonated distribution of Ga ions inside the oxygen tetrahedra. The ⁷¹Ga MQMAS NMR spectra allow identification of the one octahedral and two tetrahedral Ga sites.     

High‐pressure polarized Raman spectra of Gd2(MoO4)3: phase transitions and amorphization

Polarized Raman spectra of a single crystal of gadolinium molybdate [Gd₂(MoO₄)₃] were obtained between 1 atm and 7 GPa. Using a mixture of alcohols as the pressure‐transmitting medium, YY, ZZ, XY components of scattering matrices were measured. The ZZ spectra were also obtained in argon. Five phase transitions and amorphization were identified. The first and second transitions are reversible, while amorphization is not. In alcohol, amorphization is observed above 6.5 GPa. With argon as the pressure‐transmitting medium, amorphization is progressive and begins above 3 GPa. The spectral changes with pressure affect the high wavenumber bands attributed to symmetric and antisymmetric MoO₄ stretching modes as well as the very low wavenumber modes such as librations of the tetrahedra. This means that both short‐range and long‐range organizations of the tetrahedra are involved in these phase transitions. The amorphization mechanism and its dependence on the pressure‐transmitting medium are discussed, and the steric hindrance between polyhedra is believed to be the most relevant mechanism. The TO and LO low wavenumber modes of A₁ symmetry, observed in the Y(ZZ)Y and Z(YY)Z geometries, respectively, below 50 cm⁻¹, soften continuously through the first three phases when increasing pressure. The strong A₂ mode observed in the Z(XY)Z spectra exhibits the same anomalous behavior by decreasing from 53 to 46 cm⁻¹ at 2 GPa. The softening of these modes is related to the orientation change of tetrahedra observed by ab initio calculations when the volume of the cell is decreased. These orientation changes can explain the wavenumber decrease of the Mo O stretching modes above 2 GPa, which indicates an increase of Mo coordination. Copyright © 2010 John Wiley & Sons, Ltd.     

Structural,thermal properties and chemical durability of aluminosilicate glasses prepared by Bayer red mud

Two series of glass which are based on the particularity of iron oxide in the Bayer red mud, dolomite, pyrophyllite, quartz powder, fluorite, and industrial Al₂O₃ were prepared. The structure, thermal properties, and chemical durability of the prepared glasses were investigated. X-ray diffraction patterns showed no peaks of crystallization. Result of Fourier transform infrared shows that the existence of ~992 cm^?1 in SF series can be assigned to mixed anion structure of [TO₄] (T = Si, Al) tetrahedra. For the AF series samples, the Si-O network gradually depolymerized as the decrease of Fe₂O₃ when the content of SiO2 remained unchanged. Differential scanning calorimetry analysis shows that, as the content of Si/Fe and Al/Fe increased, the glass-transition temperature of glass approximately showed an increase tendency. From the chemical durability experiment results, the presence of TiO₂, Fe₂O₃, etc. in the Bayer red mud improved the resistance to chemical corrosion (especially in acid and alkali resistance) of the glasses, bringing about corrosion resistance close or be superior to that of E-glass and AR-glass, which can be applied in the preparation of aluminosilicate-based glass fiber.     

EPR study of a ferroelastic phase transition in mixed (Gd,Nd) pentaphosphates

Very accurate EPR measurements have been performed below the critical temperature on Gd³⁺ impurities in NdP₅O₁₄. All experiments are interpreted in terms of a three-dimensional rotation of the principal axes of the D-tensor associated to each Gd³⁺ site. It is shown that this rotation can be associated to the rotations of the PO₄ tetrahedra appearing in the structure of NdP₅O₁₄.     

Structural investigation of Te-based chalcogenide glasses using Raman spectroscopy

Structural changes of metals (Zn, Sb, In, Ga) and metal halides (AgI, ZnI₂, CdI₂, PbI₂, BiI₃) modified GeTe₄ glasses were investigated with the aid of Raman spectroscopy. The Raman spectra of these glasses in the frequency region between 100 cm^?1 and 300 cm^?1 display four main bands at about 124, 140, 159 and 275 cm^?1 which are contributed by Ge–Te, Te–Te, Te–Te and Ge–Ge vibration modes. The intensity of 159 cm^?1 and 275 cm^?1 bands vary with the addition of different glass modifiers. While the relative intensity of the 124 cm^?1 and 140 cm^?1 bands are insensitive to composition changes. Glass modifiers like Zn, In and Sb act as glass network unstabilizer which will disorganize the glass network by opening up the chain structures of Ge–Te and Te–Te. In the case of Ga and metal halides, Ga can open up Ge–(Te–Te)_4/2 tetrahedra and form Ga–(Te–Te)_3/2 triangle. Iodine can form covalent bonds with tellurium and decrease the tendency of microcrystal formation. Thus both Ga and iodine ultimately act as glass network stabilizer.