Structure and crystallization behavior of mixed potassium-lithium niobiosilicate glasses

Potassium-lithium niobiosilicate (KLiNS) glasses with a composition of (27 ? x)K₂O · xLi₂O · 27Nb₂O₅ · 46SiO₂ (x = 0, 3, 12 and 20) have been synthesized by a melt-quenching method. The glass structure and devitrification behavior have been studied by Raman spectroscopy, DTA, and XRD. By increasing the lithium content, less distorted niobium octahedra increase, indicating a niobium clustering. This change strongly affects the crystallization behavior. In the glasses x = 0 and x = 3, just above T_g, only nanocrystals of an unidentified phase are formed, while for x = 12 and x = 20 potassium lithium niobate (KLN) solid solutions with tetragonal tungsten–bronze structure crystallize by bulk nucleation. In these glasses, LiNbO₃ crystallizes at higher temperature by surface nuclei. Ultimately, it is possible to produce nanostructured glasses based on KLN nanocrystals, by partial replacement of K by Li.     

Single crystal growth from the melt and magnetic properties of hexaferrites–aluminates

Single crystals of aluminum substituted barium hexaferrite were grown by the floating zone method with optical heating. Single crystals were produced from a melt of stoichiometric composition. The process was carried out under a pressure of 50 atm of oxygen. In the system BaO–(x)Al₂O₃–(6?x)Fe₂O₃ the region of single phase crystal growth from the melt is limited by the value x=3. For higher substitutions single-phase crystallization is not observed. The grown single crystals are cylindrical boules with a diameter of 4–5 mm and with lengths up to 50 mm. To avert cracking the crystals have been annealed during the process of growth at 1100 °C. The content of FeO in the composition of single crystals of barium hexaferrite, grown by zone melting under an oxygen pressure of 50 atm, is approximately 0.3 wt%. In the system of hexaferrite–aluminates the macroscopic magnetic moment of the material disappears at x=3.     

Evaluation of basic physical parameters of quaternary Ge–Sb-(S,Te) chalcogenide glasses

New quaternary chalcogenide Ge_xSb_40?xS₅₀Te₁₀ (x = 10, 20 and 27 at.%) and Ge_xSb_40?xS₅₅Te₅ (x = 20 and 27 at.%) glasses have been synthesized and the compositions have been characterized applying prompt gamma-ray activation analyses, neutron diffraction, and material density measurements. Using the experimental data, the basic physical parameters, such as average atomic volume, packing density, compactness, average coordination number, number of constrains, average heat of atomization and cohesive energy, of the synthesized glasses are evaluated and the results are discussed in a function of glass composition.     

Evolution of nanocrystalline BaBi2Nb2O9 in Li2B4O7–BaO–Bi2O3–Nb2O5 glass system

Transparent glasses and glass nano crystal composites (GNCs) of various compositions in the system (100 − x)Li₂B₄O₇–x(BaO–Bi₂O₃–Nb₂O₅) (where x = 10, 20, and 30 in molar ratio) were fabricated via splat-quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses. X-ray powder diffraction and transmission electron microscopic (TEM) studies confirmed the formation of layered perovskite BBN via a fluorite like phase. TEM studies revealed the presence of 10 nm sized spherical crystallites of fluorite like BaBi₂Nb₂O₉ phase in the glassy matrix of Li₂B₄O₇ (LBO). The influence of composition on the dielectric and the optical properties (transmission, optical band gap) of these samples has been investigated.     

Effect of Pb impurity on the localized states of Se–Ge glassy alloy

Space charge limited conduction (SCLC) is investigated in vacuum evaporated thin films of (Ge₂₀Se₈₀)_1−xPb_x (x = 0, 0.02, 0.04, 0.06). I–V characteristics have been measured at various fixed temperatures. At high fields (∼10⁴ V cm⁻¹), current could be fitted to the theory of space charge limited conduction in case of uniform distribution of localized states in the mobility gap of these materials. Using the above theory, the density of localized states near Fermi level is calculated. A reversal in density of localized states is obtained at 4 at.% of Pb.     

Preparation and ionic conductivity of transparent glass−ceramics containing a large quantity of lithium−mica

In order to crystallize a large quantity of the lithium?mica in glass?ceramics, 5.1 mass% MgF₂ was added to the starting materials of the parent glasses having chemical compositions of Li_(1+x)Mg₃AlSi_3(1+x)O_10+6.5xF₂ (x = 0.5 and 1.0). Transparent glass?ceramics, in which a large quantity of lithium?mica with particle size of <50 nm was separated, could be prepared from the MgF₂-added parent glass with x = 0.5. While the parent glass, which had a binodal phase separation structure, did not exhibit electrical conductivity, the transparent glass–ceramic was given conductivity by the formation of an interlocking structure of mica. As the separated mica formed a tighter interlocking structure, the conductivity increased and reached a value of 2.0 × 10^?3 S/cm at 600 °C. The MgF₂-added parent glass with x = 1.0 was not transparent because of coarse spinodal phase separation. The conductivity was 4.3 × 10^?4 S/cm at 600 °C but was significantly decreased by the separation of mica.     

Preparation of transparent lithium-mica glass-ceramics

In order to fabricate transparent and machinable mica-type glass-ceramics, parent glasses having chemical compositions corresponding to Li_(1+x)Mg₃AlSi_3(1+x)O_10+6.5xF₂ (x = 0.15, 0.5, 0.65, 1.0 and 1.2) were crystallized. Lithium-micas were precipitated in all the specimens as the main crystal at 650 °C though the content was little. And the micas were changed from trisilicic type to tetrasilicic type as the x increased. After the precipitation of the micas, a large amount of β-eucryptite solid solution was precipitated as the main crystal at higher temperatures and even at 650 °C after a certain period of time. The parent glasses having the spinodal phase separation, of which the x was 1.0 and 1.2, were transparent and colored in light blue. And at 650 °C, the fine mica crystals with size of about 20 nm were precipitated in one continuous glass phase of the spinodal phase separation, which made the phase separation structure become finer. Consequently, the heated specimens showed higher transmittance of visible ray and became colorless. Moreover, because the mica crystals formed the continuous phase, the specimens showed the machinability.     

Te-rich Ge–As–Se–Te bulk glasses and films for future IR-integrated optics

Ge₁₅As₁₅Se_70−xTe_x materials with x = 56, 60 and 63, of potential use in IR-integrated optics, were prepared by the classical melt-quenching method. A macroscopic phase separation was observed with a crystalline phase on the top and an amorphous one at the bottom. The glasses from the bottom were transparent from 1.9 to 16 μm without any purification of the elemental precursors Ge, As, Te and Se. The higher the Te/Se content in the glasses the lower their glass transition temperature and thermal stability. Films 7–12 μm thick of the above stated compositions were deposited by thermal evaporation. The higher the tellurium content, the larger the optical band gap shift of the films in the infra-red and the higher the refractive index.     

Growth and characterization of InxBi2−xTe3 single crystals

The V–VI group narrow band gap compounds are known to have important photoconductivity and thermoelectric properties. Among these, Bi₂Te₃ is the most potential material for thermoelectric devices having a direct band gap of 0.16 eV. There has been ample study reported on crystal growth and polycrystalline thin films of both pure and indium doped Bi₂Te₃ pertaining to its basic semiconducting, optoelectronic and thermoelectric properties. It has been shown that on exceeding certain limiting concentration of indium in Bi₂Te₃, the conductivity changes from p-type to n-type. However, there is hardly any work reported in literature on crystal growth, dislocation etching and optical band gap of In_xBi_2?xTe₃ (x=0.1, 0.2, 0.5) single crystals. The authors have grown their single crystals using the zone melting method. The freezing interface temperature gradient of 70 °C/ cm^?1 has been found to yield the best quality crystals obtainable at the growth rate of 0.4 cm/h. The as-grown crystals have been observed to exhibit certain typical features on their top free surfaces. The crystals have been characterized using XRD technique. A chemical dislocation etchant has been used for estimating perfection in terms of dislocation density in the crystals. The optical absorption was measured in the wave number range 500 to 4000 cm^?1. The transitions in all the cases were observed to be allowed direct type. The detailed results are reported in the paper.     

Electromechanical and electro-optic properties of xBiScO3–yBiGaO3–(1−x−y)PbTiO3 single crystals

Single crystals in the xBiScO₃–yBiGaO₃–(1−x−y)PbTiO₃ (BS–BG–PT) system were grown by the high temperature solution method using Pb₃O₄ and Bi₂O₃ as the flux. The dielectric permittivity (ε_r) at room temperature for unpoled tetragonal crystals was determined to be 500–600 with dielectric loss tangents less than 0.3%. The Curie temperature was found to be around ∼420–450°C, with a dielectric maximum, exhibiting relaxor behavior. The longitudinal piezoelectric coefficient (d₃₃) was found to be ∼300 pC/N for 〈0 0 1〉 oriented tetragonal crystals with electromechanical coupling factor (k₃₃) of 75%, with a shear mode, d₁₅∼290 pC/N and k₁₅∼45%, lateral mode, d₃₁∼−55 pC/N and k₃₁∼−37%. The remnant polarization (P_r) was 46 μC/cm² with a coercive field (E_c) of 43 kV/cm at 1 Hz and DC field of 60 kV/cm. The linear electro-optic (E-O) coefficients of poled crystals determined using an automated scanning Mach–Zehnder interferometer method at room temperature and wavelength of 632.8 nm were r₃₃=36 and r₁₃=4 pm/V, respectively.     

Optical properties of Ge–Se–Te wedge-shaped films by using only transmission spectra

Amorphous Ge₁₀Se_90?xTe_x (with x = 0, 5, 10 and 15 at.%) thin films were prepared by thermal evaporation method. The optical transmission spectra of these films were measured in the wavelength range of 500–2500 nm in order to drive the refractive index and the absorption coefficient of these films. Applying the analytical expressions proposed by Swanepoel, enabling the calculations of optical constants of thin films with non-uniform thickness with high accuracy. Furthermore, the dispersion of the refractive index is discussed in terms of the single-oscillator Wemple and DiDomenico model. It was found that, the mechanism of the optical absorption follows the rule of the allowed non-direct transition. The optical band gab, E_g, and the oscillator energy, E_o, decrease while the dispersion energy, E_d, increases by increasing Te content. The relationship between the obtained results and the chemical compositions of the Ge₁₀Se_90?xTe_x thin films were discussed in terms of the chemical bond approach, the excess of Se–Se homopolar bonds and the cohesive energy (CE).     

Growth optimization and characterization of lattice-matched Al0.82In0.18N optical confinement layer for edge emitting nitride laser diodes

We present the growth optimization and the doping by the metal organic chemical vapor deposition of lattice-matched Al_0.82In_0.18N bottom optical confinement layers for edge emitting laser diodes. Due to the increasing size and density of V-shaped defects in Al_1?xIn_xN with increasing thickness, we have designed an Al_1?xIn_xN/GaN multilayer structure by optimizing the growth and thickness of the GaN interlayer. The Al_1?xIn_xN and GaN interlayers in the multilayer structure were both doped using the same SiH₄ flow, while the Si levels in both layers were found to be significantly different by SIMS. The optimized 8×(Al_0.82In_0.18N/GaN=54/6 nm) multilayer structures grown on free-standing GaN substrates were characterized by high resolution X-ray diffraction, atomic force microscopy and transmission electron microscopy, along with the in-situ measurements of stress evolution during growth. Finally, lasing was obtained from the UV (394 nm) to blue (436 nm) wavelengths, in electrically injected, edge-emitting, cleaved-facet laser diodes with 480 nm thick Si-doped Al_1?xIn_xN/GaN multilayers as bottom waveguide claddings.     

Growth improvement and characterization of AgGaxIn1−xSe2 chalcopyrite crystals using the horizontal Bridgman technique

AgGa_xIn_1?xSe₂ single crystals with x=0.4 have been grown by the horizontal Bridgman technique for nonlinear optical application requires phase matching. High purity polycrystalline synthesis of AgGa_xIn_1?xSe₂ was carried out at 850 °C, which is a relatively lower temperature compared to those in earlier reports, thus reducing secondary phase formation. An average Ga:In ratio of 62:38 (±3%) was measured using energy dispersive spectroscopy (EDS). As grown, a single crystal shows very high IR transmission of ～65% in the spectral range of 4000–600 cm^?1. There was no significant change in its IR transmission after annealing it at 500 °C for 20 days in vacuum in the presence of AgGa_xIn_1?xSe₂ powder. This indicates a low concentration of defects in the crystal. The results demonstrate that the improved new synthesis method for crystal growth was promising and that the quality of the crystal was good.     

Crystallization of NANOPERM-type amorphous alloys

In the present work, we have investigated progress of crystallization in the Fe_91?xMo₈Cu₁B_x (x = 12, 15, 17, 20) alloy as a function of annealing temperature. This material belongs to the family of the Fe–M–B–(Cu) alloys (transition metal M = Zr, Nb, Hf, Mo, …) called also NANOPERM. The alloy was found to contain small amounts (<5%) of bcc Fe(Mo) and Mo₂FeB₂ nanocrystallites (<2 nm) located on the surface of the ribbon-shaped samples already in the as-quenched state. Depending upon composition, the nanocrystallites are formed on the air and/or wheel side of the ribbon. They are characterized by atomic force microscopy, conversion electron Mössbauer spectroscopy, and by X-ray diffraction of synchrotron radiation. Fast detection (every 10 s) of the latter during continuous heating of as-quenched specimens enabled an in situ observation of the evolution of the crystallization. For x = 12, the crystallization starts earlier at the wheel side of the ribbon but its progress is more rapid at the opposite, i.e. air side.     

Temperature dependent blue second harmonic generation in Ba5Li2Ti2Nb8O30 microcrystals embedded in TeO2 glass–matrix

The as-quenched samples in the system (100 ? x) TeO₂-(x) Ba₅Li₂Ti₂Nb₈O₃₀ (2 ? x ? 8) were found to be embedded with 10–20 μm sized crystallites of the polar phase Ba₅Li₂Ti₂Nb₈O₃₀ (BLTN). Blue (400 nm) second harmonic generation (SHG) was observed in transmission mode when 800 nm laser light was allowed to pass through the individual crystallites. The blue SHG signal was temperature dependent and its intensity was maximum at ～175 °C which was tentatively attributed to the concomitant changes associated with the refractive indices of the BLTN crystallites. The SHG intensity attained a minimum value around the Curie temperature of BLTN crystals.     

Enhanced spectral response by silicon nitride index matching layer in amorphous silicon thin-film solar cells

We employed the low temperature hydrogenated amorphous silicon nitride (a-SiN_x:H) prepared by plasma-enhanced chemical vapor deposition as a refractive index (n) matching layers in a silicon-based thin-film solar cell between glass (n = 1.5) and the transparent conducting oxide (n = 2). By varying the stoichiometry, refractive index and thickness of the a-SiN_x:H layers, we enhanced the spectral response and efficiency of the hydrogenated amorphous silicon thin-film solar cells. The refractive index of a-SiN_x:H was reduced from 2.32 to 1.78. Optimizing the a-SiN_x:H thickness to 80 nm increased the J_SC from 8.3 to 9.8 mA/cm² and the corresponding cell efficiency increased from 4.5 to 5.3%, as compared to the cell without the a-SiN_x:H index-matching layer on planar substrate. The a-SiN_x:H layers with graded refractive indices were effective for enhancing the cell performance.     

Absorption and luminescence in amorphous SixGe1-xO2 films fabricated by SPCVD

Optical absorption and photoluminescence of Ge-doped silica films fabricated by the surface-plasma chemical vapor deposition (SPCVD) are studied in the 2–8 eV spectral band. The deposited on silica substrate films of about 10 μm in thickness are composed as x·GeO₂-(1-x)·SiO₂ with x ranging from 0.02 to 1. It is found that all as‐deposited films do not luminesce under the excitation by a KrF (5 eV) excimer laser, thus indicating lack of oxygen deficient centers (ODCs) in them. After subsequent fusion of silicon containing (x < 1) films by a scanning focused CO₂ laser beam absorption band centered at 5 eV as well as two luminescence bands centered at blue (3.1 eV) and UV (4.3 eV) wavelengths arise, highlighting the formation of the ODCs. The excitation of unfused SPCVD films by an ArF (6.4 eV) excimer laser yields a luminescence spectrum with two bands typical for the ODCs, but with a faster decay kinetics. Intensities of these bands grow up with samples cooling down to a temperature of 80–60 K. Unfused films excited by the ArF laser also demonstrate luminescence due to recombination of a trapped charge resulted from the excitation of localized electron states of the glass network. In the unfused GeO₂ film luminescence related to a self-trapped exciton (STE) typical for GeO₂ crystals with α-quartz structure is observed. The observed STE luminescence can be indicative of the crystalline fraction availability in the film. Whereas GeO₂ crystals are known as not containing twofold coordinated germanium, a polycrystalline inclusion in the SPCVD GeO₂ film serves as a factor explaining the absence of any spectroscopic manifestation of this type of defects in it even after fusion. On the other hand, lack of STE luminescence in other unfused films with x < 1 testifies truly amorphous state of the matter in them.     

Thermally reversing window in Ge15Te85 − xInx glasses: Nanoindentation and micro-Raman studies

Nanoindentation studies on Ge₁₅Te_85 ? xIn_x glasses indicate that the hardness and elastic modulus of these glasses increase with indium concentration. While a pronounced plateau is seen in the elastic modulus in the composition range 3 ≤ x ≤ 7, the hardness exhibits a change in slope at compositions x = 3 and x = 7. Also, the density exhibits a broad maximum in this composition range. The observed changes in the mechanical properties and density are clearly associated with the thermally reversing window in Ge₁₅Te_85 ? xIn_x glasses in the composition range 3 ≤ x ≤ 7. In addition, a local minimum is seen in density and hardness around x = 9, the chemical threshold of the system. Further, micro-Raman studies reveal that as-quenched Ge₁₅Te_85 ? xIn_x samples exhibit two prominent peaks, at 123 cm^? 1 and 155 cm^? 1. In thermally annealed samples, the peaks at 120 cm^? 1 and 140 cm^? 1, which are due to crystalline Te, emerge as the strongest peaks. The Raman spectra of polished samples are similar to those of annealed samples, with strong peaks at 123 cm^? 1 and 141 cm^? 1. The spectra of lightly polished samples outside the thermally reversing window resemble those of thermally annealed samples; however, the spectra of glasses with compositions in the thermally reversing window resemble those of as-quenched samples. This observation confirms the earlier idea that compositions in the thermally reversing window are non-aging and are more stable.     

Effect of the substitution of S for Se on the structure and non-linear optical properties of the glasses in the system Ge0.18Ga0.05Sb0.07S0.70−xSex

Glasses in the system Ge–Ga–Sb–S/Se have been elaborated with different S/Se ratios in order to increase the non-linear optical properties of these glasses. We report results of a systematic study examining the relationship of the physical properties to the structure of the glasses in the system Ge_0.18Ga_0.05Sb_0.07S_0.70−xSe_x with x = 0, 0.02, 0.05, 0.10, 0.20, 0.30 and 0.40 where the replacement of S by Se has been made. The non-linear refractive index has been measured using the Z-scan technique, with picosecond pulses emitted by a 10 Hz Q-switched mode-locked Nd-Yag laser at 1064 nm under conditions suitable to characterize ultrafast non-linearities. The decrease of the glass transition temperature, the increase of the non-linear refractive index and of the density with the progressive replacement of S by Se have been correlated along with the red shift of the absorption band gap, to associated structural reorganization. A corresponding progressive decrease of corner-sharing GeS_4/2 and the formation of mostly two edge-sharing Ge₂S₄S_2/2, S₃Ge–S–GeS₃ as well as mixed GeS_4−xSe_x units have been identified by Raman spectroscopy.     

Topology and chemical order in AsxGexSe1 − 2x glasses: A high-resolution X-ray photoelectron spectroscopy study

The evolution of topology and chemical order along the As_xGe_xSe_1 ? 2x composition-line within the As–Ge–Se glass-forming region is studied by high-resolution X-ray photoelectron spectroscopy. It is shown that cation–cation bond formation becomes a dominant process for the compositions with x > 0.09. The results explain the peculiarities observed around this composition recently in the temperature-modulated differential scanning calorimetry data. Substitution of two selenium atoms within constituent structural units (pyramids and/or tetrahedra) by corresponding cations explains a second peculiarity point at x > 0.16 compositions observed recently with the above technique. The present observations show segregation of As and then Ge at high concentrations of cations in the system (x > 0.20).