Raman spectroscopic study of SbxSe100−x phase-separated bulk glasses

The structure of Sb_xSe_100−x bulk glasses is investigated with the aid of Raman scattering over a wide composition range. The Raman spectra of the glasses exhibit unusual features when compared with other structurally similar binary glasses, owing to the phase separation of the present glasses in a certain composition range. The evolution of the Raman spectra and the depolarization ratio of the polarized and depolarized Raman intensities are consistent with the phase separation effect. The present findings are discussed alongside with calorimetric data from the literature that have been used up to now to extract structural information in an indirect way. The capability of Raman scattering as a tool for investigating phase separation in homogeneous media is demonstrated.     

Study of microstructure in Agx(As0.33Se0.67)100−x chalcogenide glasses

Glasses with general formula Ag_x(As_0.33Se_0.67)_100−x were studied by means of modulated differential scanning calorimetry (MDSC), conductivity and permittivity measurements and atomic force acoustic microscopy (AFAM). In the whole range of doping (x = 2–12 at.% Ag) a phase separation was supposed. The proportional amount of the ion-conductive Ag rich phase increased with the Ag content. A rapid increase (almost four orders of magnitude) in the conductivity was observed in the Ag concentration range 4–8 at.%, which could be associated with the interconnection of this ion-conductive phase. The transition from a hole conductivity (at low Ag concentration) to a mixed ionic-hole conductivity at higher Ag concentration was studied by permittivity measurements.     

Rapid quenching and glass formation in chalcogenide glasses: Preparation and properties of Ge–As–Te glasses over an extended composition ranges

In Ge–As–Te system, the glass forming region determined by normal melt quenching method has two regions (GFR I and GFR II) separated by few compositions gap. With a simple laboratory built twin roller apparatus, we have succeeded in preparing Ge_7.5As_xTe_92.5−x glasses over extended composition ranges. A distinct change in T_g is observed at x = 40, exactly at which the separation of the glass forming regions occur indicating the changes in the connectivity and the rigidity of the structural network. The maximum observed in glass transition (T_g) at x = 55 corresponding to the average coordination number (Z_av) = 2.70 is an evidence for the shift of the rigidity percolation threshold (RPT) from Z_av = 2.40 as predicted by the recent theories. The glass forming tendency (K_gl) and ΔT (=T_c−T_g) is low for the glasses in the GFR I and high for the glasses in the GFR II.     

Electrical and optical properties of Sn10Sb20−xBixSe70 (0 x 8) glassy films

Chalcogenide glasses are interesting materials due to their infrared transmitting properties and photo-induced effects exhibited by them. Thin films of the glasses Sn₁₀Sb_20−xBi_xSe₇₀ (0 x 8) prepared by melt quenching technique were evaporated in a vacuum better than 10⁻⁵ mbar. Optical transmission spectra of all the deposited films were obtained in a range 400–2500 nm. The optical band gap and the absorption coefficient were calculated from the transmission data and refractive index was calculated using the swanepoel method. The optical band gap initially increases with increase in Bi content (for x = 2) and then decreases sharply for higher Bi concentrations. The refractive index as well as absorption coefficient decrease with increase in wavelength. The dark activation energy initially increases with increase in Bi content and then decreases with further addition.     

Morphology and structural studies of Ag photo-diffused GeySe1−y thin films prepared by RF-sputtering

Thin films of Ag photo-doped-Ge_ySe_1−y films were prepared by RF co-sputtering technique. A systematic study of the relation existing between the host layer composition and the saturation rate in silver was carried out. Morphology and composition studies before and after chemical etchings were performed by scanning electron microscopy and electron probe micro-analyses, respectively. Raman spectroscopy studies showed the presence of corner-sharing and edge-sharing Ge(Se_1/2)₄ tetrahedra in all thin films. The vibration mode corresponding to Se_n-chains is observed for the Ge-poor host layer and on the contrary, Ge-rich thin films exhibited some tendency to form homopolar Ge–Ge bonds as a part of ethane-like Ge₂Se₆ units. These investigations revealed the amount of Ag that could be incorporated in the host layer. Such an amount strongly depends on the relative ratio Ge/Se in the Ge_ySe_1−y thin film. For the Ge-poor host layer, an incorporation of Ag (54 at.%) was observed but also a drastic increase in the film heterogeneity. On the other hand, the host layers with higher Ge content showed homogeneous surfaces and a saturation level of 32–41 at.% Ag.     

Vibrational modes and structure of (AgI)x (GeS1.5)100−x chalcohalide glasses

We report a structural investigation of bulk Ge-rich Ge–S–AgI chalcohalide glasses. A vibrational spectroscopic study of the quaternary system (AgI)_x (GeS_1.5)_100−x (0  x_AgI  20) has been undertaken using infrared spectroscopy and Fourier transform Raman scattering. It was found that the GeS_1.5 Raman spectrum is compatible with a glass structure composed of corner- and edge-sharing mixed GeS_nGe_4−n (n = 0–4) tetrahedra where units with n = 2–4 dominate, whilst the fraction of corner-sharing units are significantly lower than the corresponding fraction in the stoichiometric GeS₂ glass. The addition of AgI has revealed a subtle but systematic effect in the structure of the Ge-rich glass matrix, manifested by mild decrease of the ES units and the concomitant increase of complex GeS_nI_4−n or GeS_nGe_mI_4-n−m tetrahedra whose vibrational modes form a continuum at low frequencies. Although, AgI seems to cause subtle structural changes due to the formation of Ge–I bonds, it is also evident that AgI does not act as a real modifier that would depolymerize appreciably the Ge–S network structure.     

CuIn1−x GaxS2 wide gap absorbers grown by close-spaced vapor transport

The molecular structure of ranitidine hydrochloride (RAN-HCl) has an important influence on the growth of individual crystals and consequently the physical properties such as bulk solid density. This paper suggests that the correct structure of the nitroethenediamine moiety in the Form 2 RAN-HCl is a mixture of enamine and nitronic acid tautomers. Thermal analysis showed that the difference between the two forms is configurational rather than conformational. It also showed explosive type of degradation at the melting point of both forms. Solid-state NMR studies suggest that Form 2 contains molecular disorder whereas Form 1 may be more ordered. A single crystal X-ray study confirms the disorder in Form 2 but a similar study on Form 1 could not be performed and its suspected order can only be inferred. It was found that significant amounts of strongly polar solvents such as methanol and water would favour the production of Form 2; while anhydrous less polar or non-polar solvents will result in the production of Form 1. Chloride ion acts as the bridge between the individual molecules of RAN-HCl in the crystal structure of Form 2.     

Effect of Al addition on the crystallization of a-AlxSi1−x (0.025 x 0.100) by electron-beam irradiation

Si crystals and nano-rods were formed in Al-added amorphous Si films (a-Al_xSi_1−x; 0.025 x 0.100) by the irradiation of a focused electron-beam; the films were in situ heated to be kept at 400 °C and the current density of the electron-beam was 15.7 pA/cm². The size, shape, and concentration of the Si crystallites were varied sensitively with the Al content as well as the irradiation time. Under the electron-beam irradiation, crystallization occurred to produce polycrystalline phases in the a-Al_0.025Si_0.975 film, while rod-shaped Si nanostructures were formed in the a-Al_0.050Si_0.950 and a-Al_0.100Si_0.900 film. It is evident that the removal of Al and as a result the atomic rearrangements and/or local restructuring in the Al/a-Si film are critically affected by the electron-beam irradiation, which lead to the local crystallization and growth of Si nanocrystallites.     

Glass formation in the MoO3–Nd2O3–La2O3–B2O3 system

In MoO₃–Nd₂O₃–B₂O₃ and MoO₃–Nd₂O₃–La₂O₃–B₂O₃ systems, glasses were obtained in the region between 20 and 30 mol% Ln₂O₃. A liquid-phase separation region was observed near the MoO₃–B₂O₃ side up to 20 mol% Ln₂O₃ (La, Nd). The amorphous phases were characterized by X-ray diffraction (XRD), differential thermal analysis (DTA), UV–VIS and infrared spectroscopy (IR). According to DTA data B₂O₃-rich glasses are stable up to 630 °C while glasses rich in MoO₃ are stable up to 430 °C. The glasses are transparent in the visible region. Structural models for the glasses network were suggested on the basis of IR spectral investigations. It was established that BO₃ (1380 cm⁻¹), BO₄ (1100–950 cm⁻¹) and MoO₄ (860 cm⁻¹) groups build up the glass network. MoO₆ units (band at 880 cm⁻¹) together with BO₃ units participate in the formation of the glass network with a high MoO₃ content (80–90 mol%).     

Structure, electrical, optical and thermal properties of Ge4Sb4Tex (x = 8, 9 and 10) thin films

The crystalline samples of Ge₄Sb₄Te₁₀, Ge₄Sb₄Te₉, and Ge₄Sb₄Te₈ were prepared and their amorphous semiconducting thin films obtained by flash evaporation. Their sheet resistance decreased slowly with temperature up to 147–160 °C with activation energy of electrical conductivity ΔE = 0.40–0.44 eV. Above these temperatures, the sheet resistance drops abruptly by several orders due to crystallization. The drop of resistivity proceeds in two steps. Two steps of phase change were also found on curves of DSC and on the temperature dependence of index of refraction. It pays for slow heating rates, crystallization induced by short (≈30 ns) laser pulses proceeds probably in one step only for all studied samples (as it follows from X-ray diffraction), not only for Ge₂Sb₂Te₅ in which a single phase formation was confirmed. The crystallization temperatures are increasing slightly with decreasing Te content in the series Ge₄Sb₄Te₁₀–Ge₄Sb₄Te₉–Ge₄Sb₄Te₈ from 147 to 160 °C. The X-ray diffractograms revealed that in laser crystallized samples can be found only cubic modification of Ge₂Sb₂Te₅ type (a = 0.6 nm), while the samples annealed (230 °C, 2 h) or annealed after the crystallization with laser pulse, contain also small amounts of hexagonal phase.     

Optical properties of thin films of system (As2Se3)80−x(As2Te3)x(SnTe)20 prepared by PLD

Thin amorphous films from system (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ were prepared by pulsed laser deposition (PLD) from their bulk glasses and their optical properties were studied by spectral ellipsometry. Spectral dependencies of refractive index, absorption and extinction coefficient and optical gap (1.41–1.66 eV for (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ with x = 20 resp. x = 0) were calculated from optical tansmittance, from ellipsometric data by Tauc method. High values of refractive index n₀ (2.49–2.60) and of non-linear χ⁽³⁾ coefficient of index of refraction (4.9–7.5 × 10⁻¹² esu for the glass (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ with x = 0 resp. x = 20) made studied thin films of system (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ promising candidates for application in optics and optoelectronics.     

Growth of single crystals of the new double perovskite Ba2HoRu1−xCuxO6 from high temperature solutions

Single crystals of Ba₂HoRu_1−xCu_xO₆ have been grown from high temperature solutions using PbO–PbF₂ as solvent in the temperature range 1150–1250 °C. Crystals with a six sided plate like morphology measuring up to 3 mm across and 0.5 mm thick and polyhedral habit measuring up to 2 and 1 mm in thick mass were obtained. Powder X-ray diffraction patterns obtained on the crystals were indexed to give a monoclinic space group P2₁/n with lattice parameters a=5.875(2), b=5.874(3), c=8.960(1) and β=89.995(2)°. The crystals with x=0 show a single anomaly at 6.5 K corresponding to an antiferromagnetic phase with . The crystals containing Cu show additional anomalies at 18 and 48 K. The SEM and EDS analysis reveals a 2116 phase.     

The effect of the AlxGa1−xN/AIN buffer layer on the properties of GaN/Si(1 1 1) film grown by NH3-MBE

We describe the growth of GaN on Si(1 1 1) substrates with Al_xGa_1−xN/AlN buffer layer by ammonia gas source molecular beam epitaxy (NH₃-GSMBE). The influence of the AlN and Al_xGa_1−xN buffer layer thickness and the Al composition on the crack density of GaN has been investigated. It is found that the optimum thickness is 120 and 250 nm for AlN and Al_xGa_1−xN layers, respectively. The optimum Al composition is between 0.3<x<0.6.     

NdxLa2−xCaB10O19: Synthesis and characterization

Solid solutions of Nd_xLa_2−xcaB₁₀O₁₉ with different Na³⁺ concentration have been synthesized by substituting Nd ³⁺ for La³⁺ in La₂CaB₁₀O₁₉ Powder X-ray diffraction analysis shows that Nd³⁺ is easy to incorporate into the crystal. Single crystal nd_xLa_2−xCaB₁₀O₁₉ (NLCB) in centimeter size has been grown by Kyropoulos method. The crystal has strong absorption around 580nm and 805nm. The fluorescence spectra indicate that there is an energy transition at 1.06μm. And the SHG of NLCB is about the twice as that of KDP. These favorable features make NLCB a candidate for laser NLO multifunctional materials.     

Characterization of the free volume in a Zr45.0Cu39.3Al7.0Ag8.7 bulk metallic glass by reverse Monte Carlo simulation and density measurements

The absolute contents of free volume in the as-cast and annealed Zr_45.0Cu_39.3Al_7.0Ag_8.7 bulk metallic glass (BMG) samples were quantified by density measurements and reverse Monte Carlo (RMC) simulation using the total structural factors F(Q) determined by X-ray diffraction (XRD) experiments as fitting constraints. The densities of the as-cast, annealed and crystallized samples measured by Archimedes method are 7.319, 7.327 and 7.342 g/cm³ (precision ± 0.003 g/cm³), respectively. A new approach was used in the RMC simulation to define the free volume as the difference between the volume of the Voronoi polyhedron and the volume of the Wigner-Seitz cell of the constituent atoms. Two types of initial configurations were constructed: (1) in configuration A, all types of potential atomic pairs are allowed; (2) in configuration B, Al-Al and Ag-Ag atomic pairs are excluded. The contents of free volume in the as-cast and annealed samples were found to be 0.59% and 0.39% (configuration A), 0.55% and 0.34% (configuration B), respectively (precision ± 0.03%). The probability distribution of the as-calculated free volume can be well-fitted by the equation proposed by Turnbull and Cohen. Finally, it is shown that the contents of free volume determined by density measurements and RMC are comparable, while the discrepancy of the results is discussed.     

Electrical and optical properties of Cd1−xZnxS (0x0.18) grown by chemical bath deposition

Cd_1−xZn_xS films with 0x0.18 were grown by chemical bath deposition technique on glass substrates from an aqueous solution containing cadmium and zinc sulfate, ammonia and thiourea. Microstructural features, obtained from X-ray diffraction and scanning electron microscopy (SEM) measurements, reveal a predominance of Wurtzite structure and an homogenous microstructure formed by densely microcrystallines for all the samples studied. Cd_1−xZn_xS semiconductor was found to be resistive and of n-type. Also, the electron density decreases with increased x and the mobility reaches a maximum around x=0.12. Which means that the Cd_1−xZn_xS films at this composition are of high crystalline quality, i.e. having reduced intrinsic defect concentrations.     

Ternary system Li2O–K2O–Nb2O5: Re-examination of the 30 mol% K2O isopleth and growth of fully stoichiometric potassium lithium niobate single crystals by the micro-pulling down technique

Potassium lithium niobate (KLN) single crystals have attractive properties for non-linear optical applications based on frequency conversion of laser diodes in the blue range. Especially, fully stoichiometric K₃Li₂Nb₅O₁₅ crystals would be capable of doubling a laser light in the near UV range. Using powder X-ray diffraction and DSC experiments, we have re-investigated the 30 mol% K₂O isopleth of the ternary system Li₂O–K₂O–Nb₂O₅ in order to explore the possibility of a limited existence field for this phase. From our results, it was shown that the stoichiometric KLN phase exists between 970 and 1040 °C, temperature at which it undergoes a non-congruent melting. From this conclusion, compositionally homogeneous a-axis oriented single crystals fibers of stoichiometric K₃Li₂Nb₅O₁₅ were successfully grown by the micro-pulling down technique with pulling rates in the range 0.3–0.7 mm min⁻¹. The crystal length was between 10 and 120 mm for an apparent diameter near 500 μm. The fibers, characterized by optical microscopy, X-ray diffraction and Raman spectroscopy, appeared free of macro-defects and of good quality and their stoichiometric composition was also confirmed.     

The effect of mixed alkaline earths on the diffusivity and the incorporation of iron in 5Na2O · xMgO · (15−x)CaO · yAl2O3 · (80−y)SiO2 melts

Diffusion coefficients of iron were measured in glass melts with the basic compositions 5Na₂O · xMgO · (15−x)CaO · yAl₂O₃ · (80−y)SiO₂ with x=5, 10 and y=0, 5, 7.5, 10 and 15. The melts were doped with 0.25 mol% Fe₂O₃ and studied in the temperature range from 1000 to 1600 °C using square-wave voltammetry. The voltammograms exhibited distinct peaks attributed to the reduction of Fe³⁺ to Fe²⁺, from which peak currents mixed diffusion coefficients of iron were calculated. Diffusion coefficients in all melt compositions which did not show crystallization could be fitted to Arrhenius equation. The diffusivities measured in different melt compositions were related to the same viscosity, i.e. not the same temperature. Increasing the alumina concentration from 5 to 10 mol% resulted in an increase of the viscosity corrected diffusivities. At further increasing alumina concentrations, the diffusivities get smaller again. This can be explained by the stabilizing effect of Na⁺ and Ca²⁺ on FeO⁻₄ and AlO⁻₄-tetrahedra, which strengthens the incorporation of Fe³⁺ into the glass structure.     

Solubility of YBa2Cu3O7−δ and Nd1+xBa2−xCu3O7±δ in the BaO/CuO flux

The knowledge of the phase relations and solubilities in the Y–Ba–Cu–O and Nd–Ba–Cu–O systems are of fundamental importance for crystal growth and liquid-phase epitaxy of YBa₂Cu₃O_7−δ (YBCO) and Nd_1+xBa_2−xCu₃O_7±δ (NdBCO). The determination of the solubility curve of YBCO and NdBCO in a BaO/CuO flux containing 31 mol% BaO was done by observation of the formation and dissolution of crystals on the surface of the high-temperature solution. The heat of the solution of YBCO at 1000°C was found to be 34.7 kcal/mol, and for NdBCO at 1060°C, it was found to be 28.1 kcal/mol. The determination of the solubility curves requires special care, and the problems of the time-dependent shift of the solution composition due to the corrosion of the crucible is discussed. The scatter of the solubility data published by different authors could be due to the use of solutions with different Ba : Cu ratios, different determination methods, i.e. different crystallization mechanisms, different crucibles and starting chemicals.     

Synthesis and structure of fullerene halides in the C60-(TiCl4 + Br2) system: Molecular structures of (C60Cl5)2, C60 X 6, C60 X 8, and C60 X 24( X = Cl, Br)

The reactions in the C₆₀-(TiCl₄ + Br₂) system have been performed in ampoules at elevated temperatures. The molecular structure of the fullerene halides (C₆₀Cl₅)₂, C₆₀ X ₆, C₆₀ X ₈, and C₆₀ X ₂₄ (X = Cl, Br) has been determined and refined using single-crystal X-ray diffraction. It has been established that an increase in the bromine concentration results in an increase in the number of halogen atoms attached to the fullerene cage and in an increase in the relative fraction of bromine atoms in mixed halogen derivatives from almost pure chlorides (C₆₀Cl₅)₂ and C₆₀Cl₆ to halides C₆₀ X ₈ and C₆₀ X ₂₄ with a high relative bromine content. Original Russian Text ? S.I. Troyanov, A.V. Burtsev, E. Kemnitz, 2009, published in Kristallografiya, 2009, Vol. 54, No. 2, pp. 268–275.