On the structure of amorphous GexTe1−x systems

Calculations have been made for the quadrupole splitting of a $\text{3}\text{2}$ spin state of Te¹²⁵ in an amorphous Ge_xTe_1?x system. The results favour the existence of a threefold coordinated black phosphorus structure with an excess of TeTe chains for x-values between o and 0.5; beyond 0.5, threefold coordinated GeTe and an excess of amorphous Ge coexist.     

Devitrification characteristics of GexSe1−x glasses

Amorphous Ge_xSe_1?x compounds have been prepared and carefully characterized in the range 0 ? x ? 0.43 (density and micro-hardness measurements and DTA experiments). By heating samples from the amorphous phase, the crystallization process has been investigated for 0.15 ? x ? 0.30. An immiscibility gap in the vitreous region is determined by optical microscopy, from phase-separation observations; moreover, a new metastable crystalline phase appearing as an intermediate step between phase separation and stable GeSe₂ is described.     

Effect of annealing on an amorphous GexTe1−x matrix with Te cristallites

Annealing shows very different behaviour for Te crystallites in an amorphous Ge_xTe_1?x matrix as a function of x (x = 0.1 … 0.5). For x ? 0.2, annealing at increasing temperatures increases the number (size) of the Te crystallites with subsequent GeTe + Te crystallization. However for x ? 0.3 there is first a disappearance of Te crystallites, then an appearance of GeTe crystallites, and subsequently GeTe + Te crystallization. Crystallites of either Te or GeTe act as extrinsic defects which add to the intrinsic ones. Activatioon energy decreases (increases) and conductance increases (decreases) as the number of defects increases (decreases). In all cases the final metallic state is obtained only when both GeTe and Te crystallites are present.     

Change of short-range order with temperature and composition in liquid GexSe1−x as shown by density measurements

Density measurements were performed on melts of the binary chalcogenide system Ge_xSe_1?x (0 ? x ? 0.5) up to 1000°C. The isotherm of molar volumes V_m at 750°C shows a relative maximum near GeSe₂. Molar volumes of the system behave linearly between GeSe and Se at 1000°C. V_m's of melts between x = 0.30 and x = 0.35 decrease at high temperatures on heating. The anomalous density behaviour of the melts clearly shows a change of short-range order from a less to a more densely packed structure, caused by the development of a pσ-bonding system. Within the composition range $\text{0 ? x ?}\text{1}\text{3}$ the short-range order at lower temperatures is determined mainly by $\text{GeSe}{}_{\mathrm{<mtext>4</mtext><mtext>2</mtext>}}$ tetrahedra linked directly corner-to-corner or via Se atoms. At higher temperatures pσ bonds arise more and more, even in melts rich in selenium. Within the composition range $\text{1}\text{3}\text{? x ? 0.5}$ the short-range order is mainly determined by a distorted octahedral configuration, even at lower temperatures. From the short-range orders of melts and from crystalline structures of GeSe₂ and GeSe, the tendency of glass formation from the melt is discussed in detail.     

X-ray investigation of the crystallization of chalcogenide glasses of the type (As2Se3)1−x:(Tl2Se)x

Amorphous and crystalline states of As₂Se₃, (As₂Se₃)₃ : Tl₂Se and As₂Se₃ : Tl₂Se have been studied using X-ray diffraction techniques. Structural changes arise during the process of annealing in the temperature range between their softening and melting points are reported and their rates investigated. The crystallization temperatures were found to be 105 ± 5 °C, 135 ± 5 °C and 180 ± 5 °C respectively. The unit cell parameters are identified for each of the three resulting crystalline phases, that for As₂Se₃ : Tl₂Se being orthorhombic while the other two are monoclinic.     

ac Conductivity of 4.5 TiO2−x · 2 P2O5

The ac conductivity of a member of the family of glasses 4.5 TiO_2?x · 2 P₂O₅ has been measured between 77 and 300 K, and up to 100 kHz. The dc conductivity was measured over only part of this temperature range. The measured ac conductivity can be represented by σ_ac = σ₀ + σ₁ω^s, with s < 1, and temperature dependent. A similar equation describes the ac dielectric constant, ?_ac = ?₀ + ?₁ω^s?1, where $\text{?}{}_1\text{= σ}{}_1\text{tan}\text{1}\text{2}\text{sπ}$. A simple proportionality of s to temperature holds at low temperature; at the higher temperatures, the T-dependence of s is no longer simple. The observed behaviour of the ac properties of this glass is in general accordance with a recently proposed model for systems where transport occurs by hopping. The over-all behaviour is comparable to other transition metal glasses.Using the model and treating the carriers as polarons yields an expression for s in terms of temperature. Values for the polaron radius and the effective dielectric constant are then extracted from the measurements. These values are in good agreement with values for similar systems obtained by other means.     

A thermodynamic and kinetic investigation of amorphous (1−x)As2Se3 · xSb2Se3 alloys

The heats of formation of amorphous (1?x)As₂Se₃ · xSb₂Se₃ (x = 0 to 0.4) referred to crystalline As₂Se₃ and Sb₂Se₃ were measured by liquid metal solution calorimetry. The values of heats of formation of amorphous (1?x)As₂Se₃ · xSb₂Se₃ decreased from 1.39 ± 0.03 kcal · (g-at)^?1 at x = 0 to 1.27 ± 0.04 kcal · (g-at)^?1 at x = 0.4.The glass transition temperature and the temperatures of the maximum rates of crystallization and fusion were measured by differential scanning calorimetry. The glass transition temperature increased and the temperatures of the maximum rates of crystallization and fusion decreased with increasing Sb₂Se₃ content.The relaxation process in amorphous (1?x)As₂Se₃ · xSb₂Se (x = 0.3) was investigated by measuring changes in microhardness, small-angle X-ray scattering and heat capacity with time of annealing at several temperatures ranging from room temperature to 413 K. With increasing annealing time the microhardness, the height and the temperature of the glass transition peak increased whereas the intensity of small-angle X-ray scattering decreased. These changes reflect relaxation towards a more stable structure of smaller molecular mobility. The changes in the enthalpy with annealing time and the activation energy spectra for relaxation were derived from the heat capacity data. The effects of temperature and time of annealing on the various properties are explained in terms of structural changes and relaxation kinetics.     

Raman and infrared spectra of As2Sx chalcogenide glasses with x ⩽ 3

Raman laser and far infrared spectra of As₂S_x glasses with x ? 3 are given and discussed. The purpose of the work is to bring a vibrational spectroscopic contribution to the study of these glasses and to the hypothesis, still under discussion in the literature, that they might be constituted either by a homogeneous vitreous phase or by a mixture of As₂S₃ and As₄S₄.Our results confirm a phase separation, with formation of ß-As₄S₄, below a certain value of x, which depends not only on the preparation method of the samples but also on other factors such as melting time. Laser irradiation of ß-As₄S₄ modifies its Raman spectrum. Such a phenomenon is attributable to two principal factors, either a partial polymerization or formation of a species richer in arsenic. A structural and formation model of the As₂S_x glasses is given, starting from a more generalized structural model of vitreous As₂S₃ which is an accord with the vibrational results and those by the diffraction method in the literature.     

AlxGa1−xN bulk crystal growth: Crystallographic properties and p–T phase diagram

The recent results on the growth of the Al_xGa_1−xN bulk single crystals (0.22≤x≤0.91) from solution in liquid Ga under high nitrogen pressure are discussed. We focus on the influence of temperature and the choice of the Al source on the crystal growth. The experiments involving different sources of aluminum such as Al metal, pre-reacted polycrystalline Al_yGa_1−yN and AlN powder are compared. The best results were achieved using pre-reacted polycrystalline Al_yGa_1−yN or/and AlN. Single-crystal structure refinement data of these Al_xGa_1−xN crystals are presented. We also update the p–T phase diagram of (Al,Ga)N compound at high N₂ pressure for various Al content, which is the basis for (Al,Ga)N synthesis.     

Infrared studies of Se-based polynary chalcogenide glasses (II): YxZxSe100−2x (Y = Ge,As; Z = As,Te)

The infrared (IR) absorption spectra for Y_xZ_xSe_100?2x glasses (Y = Ge, As;Z = As, Te), x = 2.5 and 5.0 are measured in the wavenumber region 700-60 cm^?1 at room temperature. These IR spectra are explained by comparing with the IR spectra already reported for the binary glasses such as Ge–Se, As–Se and Se–Te. In Ge_xAs_xSe_100-2x glasses (x ? 5.0), the main spectral features as well explained by both the spectra of Ge_xSe_100?x and As_xSe_100?x glasses. Main structural units in these glasses are considered to be GeSe₄ tetrahedra and AsSe₃ pyramids, and Se₈ rings and Se_n chains which are the units in pure glassy Se. In Ge_xTe_xSe_100?2x glasses (x ? 5.0) and IR band which cannot be explained by either the spectra of Ge_xSe_100?x or Se_100?xTe_x glasses appears at 210 cm^?1. This band is considered to be due to Ge–Te bonds. The IR spectra of As_xTe_x Se_100?2x glasses (x ? 5.0) are well explained by both the spectra of As_xSe_100?x and Se_100?xTe_x glasses. It is concluded that As and Te atoms combine with Se atoms in the forms of AsE₃ pyramids and Se₅Te₃ mixed rings, respectively.     

Change of bonding system in liquid SexTe1−1 alloys as shown by density measurements

Density measurements have been performed on melts in the binary chalcogenide system Se_xTe_1?x up to a temperature of 950°C. Anomalous behaviour of the density was observed. At higher temperatures the density increased on raising the temperature up to a maximum whose position shifts to lower temperatures with increasing concentration of tellurium. This anomalous density behaviour clearly shows an increase of the average coordination number of atoms in the melt. This increase of CN is caused by a change of the bonding system because of the tendency of Te to form pσ bondings. It was assumed that there exist two distinct structures in thermodynamical equilibrium at each temperature according to a law of mass action, for which cooperation effects have to be taken in account. At low temperatures Te atoms easily accept a loosely packed structure I with the aid of selenium. At high temperatures even Se atoms develop a more densely packed structure II with the aid of Te.     

Dependence of the surface topology and raman scattering spectra of Ge x Si1−x /Si films on the composition variation over the layer thickness

The surface topology and Raman scattering spectra of Ge _x Si_{1 ? x} /Si(100) films are investigated in dependence of the composition variation over the film thickness. It is shown that the character of the Ge content variation in the Ge _x Si_{1 ? x} alloy at the constant cumulative Ge fraction in the film (x _int = 0.5) affects the surface morphology of the grown Ge _x Si_{1 ? x} /Si layer. The heterostructures were grown by molecular-beam epitaxy.     

Effect of Cd1−xZnxS/ZnS core/shell quantum dot on the optical response and relaxation behaviour of ferroelectric liquid crystal

Dielectrics, polarizing optical microscopic and electro-optical measurements have been carried out on a core/shell quantum dot Cd_1?xZn_xS/ZnS dispersed ferroelectric liquid crystal (FLC). In the present study, quantum dots were dispersed into two different concentrations of 0.1 and 0.25 wt./wt.% in pure FLC. The electro-optical parameters of pure and QDs dispersed FLC were carried out as a function of applied voltage. A significant improvement in optical response time of QDs dispersed FLC system is one of the major finding of the present study which may be useful for fabrication of faster liquid crystal system.     

Ab initio calculation on the (Si2O7)6− bitetrahedra

The total energy surface of the (Si₂O₇)^6? ion is calculated from the bend and torsion angles in the SiOSi axis. The results are discussed and compared with the experimental data. The ab initio calculation of (SiO₄)^4?, as well as the calculation of the charge distributions for all species were made and discussed.     

Structural and magnetic properties of ZnO and Zn1−xMnxO nanocrystals

Chemical precipitation of metal-ions from aqueous solution has been successfully used to produce Zn_1?xMn_xO nanocrystals, in the form of nano-powder. X-ray diffraction (XRD) measurements reveal that the as-prepared samples are single-phase materials and their lattice constant changes with the variation of Mn-concentration, which indicates the incorporation of Mn²⁺ into the hosting ZnO. These findings are corroborated by the observation of the well defined six hyperfine lines of Mn²⁺ ion in the electron paramagnetic resonance (EPR) spectra of the samples with a low Mn-concentration, and of a broad EPR line, which manifests the onset of Mn–Mn exchange interaction, in the samples with an elevated value of x.     

Crystal and magnetic structures of the Bi1 ? xSrxFeO3 ? δ and Bi1 ? xAxFe1 ? xMnxO3 (A = Sr, Ca) solid solutions

Bi_{1 − x} Sr _x FeO_{3 − x/2} (I), Bi_{1 − x} Sr _x Fe_{1 − x} MnxO₃ (II), and Bi_{1 − x} Ca _x Fe_{1 − x} Mn _x O₃ (III) solid solutions have been obtained. Their magnetization has been measured by X-ray and neutron diffraction and M?ssbauer spectroscopy. According to the M?ssbauer spectroscopy data, iron ions are in the trivalent state in system I. Near the concentration x ≈ 0.2, rhombohedral distortions (sp. gr. R3c) are transformed into tetragonal (P4/mmm). The symmetry of system II changes at x > 0.2 (R3c → R3c), whereas orthorhombic distortions (R3c → Pbnm) arise in system III at x > 0.2. The magnetic structure is antiferromagnetic (of G type). The samples of systems II and III exhibit weak ferromagnetism at x > 0.2 due to the Dzyaloshinski-Moriya interaction.     

Growth and structural properties of Zn1−xCrxTe crystals

Single crystals of Zn_1?xCr_xTe were grown by vapour phase growth method in the composition range of 0?x?0.005. Chemical analysis, surface morphology, structural and microhardness studies were carried out by EDAX, SEM, XRD and Vicker's indentation techniques, respectively. Microscopic variations between the target and actual compositions were noticed. Morphology studies revealed that dislocation aided growth is active in the present crystals. XRD studies showed that samples of all compositions crystallized in zinc blende structure, and the lattice parameters varied linearly with x following Vegard's law. Vicker's hardness (H_v) decreased exponentially with x.     

Thermal decomposition of energetic materials. 44. Rapid thermal decomposition of the propyl-1,3-diammonium salts of NO 3 − and ClO 4 − , and the crystal structure of the ClO 4 − salt

The temperature dependence of the IR spectra of the condensed phase (dT/dt=5°C min^–1) and the fast thermolysis (dT/dt100°C sec^–1) of propyl-1,3-diammonium dinitrate (PDD) and diperchlorate (PDP) are compared. Rapid-scan FTIR/temperature profiling shows that PDP explodes on heating while PDD decomposes with much less energy. HNO₃(g) is formed by deneutralization in the initial decomposition of PDD, but HClO₄(g) is not detected from PDP. PDP is unique among the compounds studied by this technique in that a solid-solid phase transition can be detected during rapid heating. The initial phase of PDP has been characterized by X-ray crystallography: monoclinic,P2₁/c,a=7.316(2),b=14.428(2),c=9.742(2) Å,=96.81°,V=1021.1(3) ų,Z=4,D=1.789 g cm^–3,R(F)=0.034,R(wF)=0.040.     

Glass formation and structure of glasses in the ZnO―Bi2O3―WO3―MoO3 system

The glass formation region in the ternary ZnO―Bi₂O₃―WO₃ system is determined by melt quenching technique (cooling rates 10¹-10² K/s). New original glasses are obtained in a narrow concentration range with high WO₃ content (60-75 mol%). Homogeneous glasses of the composition (100 − x)[0.2ZnO·0.3Bi₂O₃·0.5WO₃]xMoO₃, were obtained between 20 and 60 mol% MoO₃. Characterization of the amorphous samples was made by x-ray diffraction (XRD), differential thermal analysis (DTA) and infrared spectroscopy (IR). The thermal stability of glasses decreases with the increasing of MoO₃ content. The glass transition temperature, T_g, varies between 340-480 °C, while the crystallization temperature, T_x, varies between 388-531 °C. The tungstate glasses possess higher crystallization temperature (T_x over 500 °C) in comparison with the other vanadate and molybdate non-traditional glasses. The glass network is realized by transformation of three-dimensional structure of WO₃ into a layered one, consisting mainly of WO₆ units. We supposed that the network of quaternary glasses is built up by MoO₄, MoO₆ and WO₆. At low concentration ZnO and Bi₂O₃ facilitate the disorder in the supercooled melts, while at high concentration stimulate crystallization processes. These oxides belong to the intermediate ones.