Investigation of GaAs—InyGa1−yPzAs1−z–InxGa1−x-As grading heterojunctions formation

The initial stages of growth of GaAs–InGaAsP_var–In_xGa_1−xAs heterostructures (x = 0.1 and 0.17) were investigated for the equilibrium-cooling method of LPE growth. Similar investigations were carried out for GaAs–InGaAsP_var–In_0.05Ga_0.95As heterocompositions, but for the step-cooling technique. The scheme of growing of In_0.17Ga_0.83As films of GaAs substrates with several intermediate buffler InGaAsP_var layers is represented. These heterostructures were shown to have less than 10⁶ cm⁻² dislocation density on the overall area of the film (> 2 cm²).     

Effect of BaO addition on the structural aspects and thermophysical properties of sodium borosilicate glasses

Sodium borosilicate glasses containing different amounts of BaO were prepared by a conventional melt quench method and characterized for their structural aspects by ²⁹Si, ¹¹B NMR and IR spectroscopy. From ²⁹Si MAS NMR studies, it has been inferred that these glasses consist of Q² and Q³ structural units of silicon and that the addition of BaO results in the marginal conversion of Q³ to Q² structural units. There is no direct interaction between Ba²⁺ ions and boron structural units, as revealed by the identical values of the relative concentration of BO₃ and BO₄ structural units and quadrupolar coupling constant values for the BO₃ structural units. The identical values of glass transition temperature and vibrational frequencies corresponding to Si–O–Si/Si–O–B and B–O linkages of all the samples further support this. As the borosilicate network is unaffected, the systematic increase in the values of thermal expansion coefficient with increase in BaO content has been attributed to the increase in the relative concentration of less rigid Ba–O linkages compared to the more rigid Si–O and B–O linkages in the glass. Such studies will be useful for the development of matrices for the management of nuclear waste generated during the reprocessing of the spent fuel from thoria based reactors.     

Relationship between structure and optical properties in rare earth-doped hafnium and silicon oxides: Modeling and spectroscopic measurements

The SiO₂–HfO₂ binary system is recognized as a promising candidate for Erbium-doped waveguides amplifiers fabrication. Recently, it was demonstrated that Er³⁺-activated 70SiO₂–30HfO₂ planar waveguides with valuable optical and structural properties can be prepared by sol–gel technique with dip-coating processing. The important role played by hafnium in the silica network was evidenced by the particular spectroscopic properties presented by Er³⁺-ions in the silica–hafnia planar waveguides. In this work we present preliminary results on HfO₂–SiO₂ bulk xerogels doped with Eu³⁺ ions, with the aim to go inside the role of hafnium on the rare earth ions local environment. Spectroscopic measurements of the Eu³⁺ photoluminescence emission are given. Numerical simulations by the molecular dynamics method have been performed showing clearly a phase separation for the HfO₂ richer samples. Moreover it is found than the rare earth-doping ions stay preferentially in hafnium rich domains, thus explaining why the rare earth spectroscopic properties are strongly modified.     

Growth,thermophysical and electrical properties of the nonlinear optical crystal BPO4

Bulk BPO₄ crystals have been successfully grown from high temperature solution of BPO₄, Li₂O, and MoO₃ in the molar ratio of 2.3:1:1.3 by the top‐seeded solution growth (TSSG) method using [101]^c orientation seeds. There are no visible scattering centers and impurity of Mo in the as‐grown BPO₄ crystals, whose optical homogeneity reaches up to 1.6×10^–5/cm. BPO₄ possesses a specific heat of 0.50–1.00 J·g^–1·K^–1 in the temperature range from 298 to 698 K and exhibits strong anisotropic thermal expansion behavior with α_a = 14.2 × 10^–6 K^–1 and α_c = ‐4.0 × 10^–7 K^–1. Moreover, the thermal conductivity coefficients are calculated to be κ_a = 62.4 W·m^–1·K^–1 and κ_c = 51.5 W·m^–1·K^–1, which are remarkably larger than those of some commonly used borates. The measured dielectric constants, ε_a and ε_c, are 4.8 and 6.1, respectively, and the ionic conductivity coefficients, σ_a = 4.3 × 10^–8 S/cm and σ_c = 9.5 × 10^–8 S/cm, are several orders of magnitude lower than that of LiB₃O₅ (LBO). (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Laser transition characteristics of Nd3+-doped fluorophosphate laser glasses

Fluorophosphate glasses of composition P₂O₅–K₂O–MgO–Al₂O₃–AlF₃ and P₂O₅–K₂O–MgO–Al₂O₃–BaF₂ were prepared with different Nd³⁺ ion concentrations. The absorption and emission spectra in the UV–VIS–NIR region were measured for these glasses. Judd–Ofelt analysis has been carried out using the absorption spectra of 1.0 mol% Nd³⁺-doped glasses to evaluate the radiative properties for some luminescent levels of the Nd³⁺ ion. The stimulated emission cross-sections of the ⁴F_3/2 → ⁴I_11/2 laser transition for the present glasses are found to be higher than for other Nd³⁺-doped glasses. Branching ratio calculations also revealed the potentiality of the ⁴F_3/2 → ⁴I_11/2 transition for laser action in these glasses. The observed concentration quenching of the lifetime of the ⁴F_3/2 level is explained as a result of cross-relaxation process between the Nd³⁺ ions.     

Synthesis and photoluminescence of Eu3+-doped ZnO–Ga2O3–SiO2 nano-glass-ceramics

Transparent rare-earth Eu³⁺-doped ZnO–Ga₂O₃–SiO₂ nano-glass-ceramics were obtained by a sol–gel method. X-ray diffraction and transmission electron microscopy were used to characterize the as-synthesized materials. Results showed that ZnGa₂O₄ nanocrystals with the size of 5 nm were precipitated from ZnO–Ga₂O₃–SiO₂ system and dispersed in the SiO₂-based glass when the heat-treatment temperature was up to 800 °C. Photoluminescence characterization of Eu³⁺-doped ZnO–Ga₂O₃–SiO₂ nano-glass-ceramics was carried out and the results show that the as-synthesized material display intense emission at 615 nm belonging to ⁵D₀ → ⁷F₂ transition.     

Optical properties and valence change of samarium ions in a sol–gel Al2O3–B2O3–SiO2 glass by femtosecond laser irradiation

10Al₂O₃–5B₂O₃–85SiO₂–xSm₂O₃ glasses were prepared by the sol–gel method. The emission spectra of the glasses indicate that the quench concentration of the Sm³⁺ ions is about 0.2 mol%. The emission spectra of the glasses after high-temperature treatment with H₂ gas exhibit the coexistence of the Sm³⁺ and Sm²⁺ ions. We observed the strong emission line of the Sm²⁺ ions and the emission band of the non-bridging oxygen hole center when the glasses were exposed to a femtosecond laser. It indicates that some Sm³⁺ ions were reduced to Sm²⁺ ions by femtosecond laser pulses and non-bridging oxygen hole centers were formed. The ⁵D₀–⁷F₀ emission line of the Sm²⁺ ions by femtosecond laser irradiation shows a red shift, compared with the emission of the Sm²⁺ ions by reduction with H₂ gas. The strong absorption band and weak, sharp absorption lines in the range from the UV to IR come from charge transfer and the transition from the ⁶H_5/2 state to the various excited states of the Sm³⁺ ions. The reduction mechanism of Sm³⁺ ions is discussed.     

Er3+-doped germanate glasses for active waveguides prepared by Ag+/K+ ↔ Na+ ion-exchange

Planar waveguides were prepared by Ag⁺/K⁺ ? Na⁺ ion-exchange on Er⁺³-doped GeO₂–ZnO–Na₂O–Li₂O glasses obtained by a melting–casting method. Optical parameters of the waveguides were measured at 543.5, 632.8, and 1550 nm by m-line technique as a function of the Ag⁺ ion-exchange time. The optimized planar waveguides show an effective diffusion depth (d) of 2.95 μm and well confined propagating TE₀ and TM₀ modes at 1550 nm. Spectroscopic properties as photoluminescence emission and emission decay time were evaluated for the erbium-doped planar waveguide, indicating that Ag⁺ ? Na⁺ ion-exchange enhance the photoluminescence emissions in the green and infrared regions from erbium ions. The glass system studied is promising to be applied as optical amplifiers in the C-telecom band. Green emission sensitized by Ag⁺ was also observed.     

Role of Te valence on phases crystallized in K2O–Nb2O5–TeO2 glasses

Differences in crystalline phases between glass-ceramics and sintered ceramics in the K₂O–Nb₂O₅–TeO₂ system have been examined, particularly to obtain information on the role of Te valence on crystallization behaviors of TeO₂-based glasses. In glasses or glass-ceramics, the valence of Te⁴⁺ is retained even during heat-treatment up to around 600°C, leading to the formation of crystalline phases containing Te⁴⁺, e.g., the face-centered cubic crystalline phase. In a powder sintering method, Te⁴⁺ is easily oxidized to Te⁶⁺ during sintering at around 600°C in air and compounds such as KNbTeO₆ in which Te⁶⁺ is present are formed.     

Ferromagnetic insulating and reentrant spin glass behavior in Mg doped La0.75Sr0.25MnO3 manganites

In this study, the effect of Mg substitution on structural, magnetic and electrical properties of La_0.75Sr_0.25Mn_1?xMg_xO₃ and La_0.75Sr_0.25?xMg_xMnO₃ (nominal compositions) samples are investigated by XRD, Ac susceptibility and electrical resistivity measurements. It is found that Mg does not replace La in the perovskite lattice. Also the results show that by increasing Mg doping levels, the paramagnetic–ferromagnetic and metal–insulator transition temperatures decrease. The reason for decreasing transition temperatures with increasing Mg concentration is, that the long-range FM order has been destroyed by the Mg, which is randomly occupying Mn site. This leads to the suppression of double-exchange interaction in the Mn³⁺–O–Mn⁴⁺ networks. Also the reentrant spin glass (RSG) state accompanied by FM transition, exists in high doped samples. The RSG state could be understood on the basis of double exchange ferromagnetic interaction in Mn³⁺–O–Mn⁴⁺ and super-exchange antiferromagnetic interaction in the Mn⁴⁺–O–Mn⁴⁺ networks.     

Preparation and some properties of thallium orthothioarsenate single crystals

Growing of large (Ø 25–30 mm, L = 50–60 mm) optically homogenous single crystals of Tl₃AsS₄ using the Bridgman-Stockbarger method is described. Tl₃AsS₄ is orthorhombic (Pnma), a = 8.85 ± 0.03, b = 10.86 ± 0.03, c = 9.18 ± 0.03 Å; z = 4; ϱ_x = 6.15 g · cm⁻³; ϱ_p = 6.15 ± 0,03 g · cm⁻³, T_m = 424 ± 3°C, Moh's hardness = 3, microhardness and ultrasonics velocity along x, y, z are 65–85 kg · mm⁻² and 2.16 – 2.37 · 10⁵ cm · sec⁻¹, respectively. The crystals possess perfect cleavage plane (010). Their transparency range is 0.6–12 microns. – Unsuccessful attempts to obtain Tl₃AsS₄ and its alloys in the vitreous state were taken. The possibilities of glass formation and boundaries of the vitreous region in the system Tl–As–S based on the characteristic features of the melt forming structural units are analyzed.     

Refractive indices of laser nanocrystalline ceramics based on Y3Al5O12

Refractive indices of the nanocrystalline Y₃Al₅O₁₂ ceramic and a garnet single crystal of the same composition have been measured. In the visible and near IR range (0.4–1.064 μm), the prism method was used; in the medium IR range (2–6.2 μm), the interference method with the use of thin plates was applied. The refractive indices of these crystalline materials are practically the same over the entire spectral range studied and are described by the approximate formula proposed earlier for a single crystal. The parameters of the continuos-wave lasing in the nanocrystalline Y₃Al₅O₁₂ ceramic doped with Nd³⁺ and Yb³⁺ ions measured recently are presented.     

Spectroscopic investigation of strain induced by compositional variation in bulk InxGa1–xAs crystal grown by MCZM method

Raman scattering (RS), photoluminescence (PL) and energy dispersive X‐ray (EDX) experiments have been carried out to investigate residual strain and hence to understand breakage issue in bulk In_x Ga_1–x As crystal grown by multi component zone melting (MCZM) method. It is found from a comparison that there is a large discrepancy among the RS, PL and EDX results due to the strain induced by compositional variation in the crystal. The strain induced changes in TO_GaAs and PL peak positions are found to be 4.04 cm^–1 and 0.097 eV, respectively, for the variation of composition from 0.06 to 0.29 from the seed‐end to the tail‐end of the crystal. By assuming a simple one‐dimensional strain distribution, the strain value corresponding to 4.04 cm^–1/ 0.097 eV can be obtained of the order of 10^–2, which is large enough for understanding the breakage issue in the crystal investigated here. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photochromic behavior of Li-stabilized MoO3 sol–gels

Photochromic behavior of Li-doped MoO₃ sol–gels prepared by the peroxo sol–gel method was studied in details using various experimental techniques, including UV–vis, XRD, Raman, EPR, and XPS. The lithium doping has drastically enhanced the stability of the MoO₃ sol–gels. Upon UV-light irradiation from a high-pressure mercury lamp, the Li-doped MoO₃ sol turned from yellowish into deep blue, and the sol in ethanol exhibited much more intense color change than the sol in water. The UV-light exposure has the effect of re-arranging the structural units of MoO₃ and building up short-range order inside the solid. The formation of a blue colored bronze in the photo-irradiated sols because of the reduction of Mo⁶⁺ to Mo⁵⁺ is also evidenced by the experimental data. Based on these data, a mechanism for the photochromic behavior is proposed.     

Glass formation and third-order optical nonlinear properties within TeO2–Bi2O3–BaO pseudo-ternary system

Tellurite glasses from TeO₂–Bi₂O₃–BaO pseudo-ternary system were prepared using a conventional melt-quenching method and its glass-forming region was determined. A series of glasses were selected and their third-order optical nonlinearities (TONL) were measured by employing the Z-scan method at a wavelength of 800 nm with femtosecond laser pulses. The results showed that glass former Te⁴⁺ ions exhibited positive influences on the TONL and glass modifiers Ba²⁺ ions behaved similarly; low concentrated Bi³⁺ ions as glass modifiers weakened the nonlinearities, but an excess amount of Bi³⁺ behaved oppositely. FTIR measurements demonstrated that chemical bonds especially Te–O_eq vibrated at a high energy level remarkably promoted the TONL susceptibility χ⁽³⁾, and the glass sample with the highest Bi₂O₃ content exhibited the largest χ⁽³⁾ value which was due to the presence of BiO₃ polyhedra.     

Temperature‐concentration oscillations as a result of nanoheterophase structure of concentrated aqueous solutions of salts

Detailed precision investigation of aqueous solutions of NaBr·2H₂O, KBr, RbNO₃, and K₂SO₄ salts showed oscillations of crystal‐solution phase equilibria in the temperature range of 15–45 °C. The maximum deviations from the smooth correlation between the saturation temperature and the salt concentration (up to 4% of concentration and up to 10 °C) were found to correspond to simplest salt‐water ratios. Recently, similar trends were observed for NaNO₃, KNO₃ and K₂CrO₄ solutions. Oscillation amplitudes for saturation temperature in the investigated series decreased in the following orders: Na⁺→K⁺, Rb⁺, NH₄⁺ (nitrate systems), CrO₄^2–→SO₄^2– and Br^–→NO₃^– (potassium systems), and NO₃^–→Br^– (sodium systems). Increase in total content of impurities (2‐4‐fold) in solution results in 1.5‐2‐fold elevation of the oscillation amplitudes. A concept of nanoheterophase solution was suggested to account for the observed temperature‐concentration oscillations. The concept is based on the original experimental data on interrelated variation of different properties of aqueous salt solutions depending on their concentrations. Characteristic features of the phase diagrams are discussed and influence of the oscillations on crystal growth is elucidated. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Study of amorphous Ge–SiO2–P+Si tunnel junctions

A new method to determine ac conductivity of amorphous Ge using Al-amorphous Ge–SiO₂–P⁺Si tunnel junctions is presented. Frequency dependence of ac conductivity is found to satisfy the power law in the frequency range between 1 and 50 kHz and the density of localized states at the Fermi level is estimated to be ～ 1.7 × 10²⁰ cm^?3 eV^?1 which decreases to ～ 4.5 × 10¹⁹ cm^?3 eV^?1 after annealing at 175°C.Temperature dependence of tunneling conductance of Al-amorphous Ge–SiO₂–P⁺Si junctions is appreciable only near zero bias. Zero bias conductance of the junctions obeys the $\text{T}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>4</mtext>}}$ law of Mott; the density of localized states obtained from the $\text{T}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>4</mtext>}}$ law is one order of magnitude smaller than that obtained by ac conductivity measurements, being insensitive to annealing. This behavior of the tunnel junctions differes in many respects from those of Al–Al₂O₃-amorphous Ge tunnel juntions.     

Crystal data and some physical properties of Tl2InGaTe4 crystals

The room temperature crystal data, Debye temperature, dark and photoelectrical properties of the Bridgman method grown Tl₂InGaTe₄ crystals are reported for the first time. The X‐ray diffraction technique has revealed that Tl₂InGaTe₄ is a single phase crystal of tetragonal body‐centered structure belonging to the space group. A Debye temperature of 124 K is calculated from the results of the X‐ray data. The current‐voltage measurements have shown the existence of the switching property of the crystals at a critical voltage of 80 V. The dark electrical resistivity and Hall effect measurements indicated the n ‐type conduction with an electrical resistivity, electron density and Hall mobility of 2.49×10³ Ω cm, 4.76×10¹² cm^–3 and 527 cm²V^–1s^–1, respectively. The photosensitivity measurements on the crystal revealed that, the variation of photocurrent with illumination intensity is linear, indicating the domination of monomolecular recombination at room temperature. Moreover, the spectral distribution of the photocurrent allowed the determination of the energy band gap of the crystal studied as 0.88 eV. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Melting enthalpy ΔHm for describing glass forming ability of bulk metallic glasses

A new melting enthalpy ΔH_m criterion for the prediction of glass forming ability (GFA) of alloys is proposed and five Zr–Al–Ni–Cu bulk metallic glasses (BMG) with critical dimension Z_max up to ? 7.5 mm are also developed by us in the light of the optimum ΔH_m of Zr–Al–Ni–Cu alloy system. And then, we researched the relationships between ΔH_m and two GFA parameters (critical cooling rate R_c and Z_max) of five bulk metallic glass (BMG) systems, such as Mg–Ni–Nd, Pd–Cu–Si, La–Al–Ni–Cu, Zr–Al–Ni–Cu and Zr–Ti–Ni–Cu–Be, respectively. The results show that the relationships between ΔH_m and R_c are all concave upward parabolas, and the optimum ΔH_ms for Mg–Ni–Nd, Pd–Cu–Si, Zr–Al–Ni–Cu, Zr–Ti–Ni–Cu–Be and La–Al–Ni–Cu are 10.3960 kJ mol^?1, 21.2202 kJ mol^?1, 19.7146 kJ mol^?1, 18.1455 kJ mol^?1 and 13.1558 kJ mol^?1, respectively. On the contrary, the relationships between ΔH_m and Z_max are all concave downward parabolas, and the optimum ΔH_ms for Mg–Ni–Nd, Pd–Cu–Si, Zr–Al–Ni–Cu, Zr–Ti–Ni–Cu–Be and La–Al–Ni–Cu are 10.5530 kJ mol^?1, 21.0830 kJ mol^?1, 19.6603 kJ mol^?1, 19.7231 kJ mol^?1 and 13.1173 kJ mol^?1, respectively. Furthermore, other BMGs’ R_cs or Z_maxs predicted by above-mentioned relationships satisfactorily agree with the tested results, which indicates that these relationships are reliable. However, the predicted results are reliable only if the main components are similar with the fitted BMGs or the additive is sparkle enough that the alloy’s character does not change. On the whole, the ΔH_m can act as a criterion for quickly predicting the alloy’s GFA and be helpful for the development of new BMGs.     

Comparative infrared lattice vibration study of LiGaO2 and LiInO2 (II). Interatomic force constants

The frequencies of the wurtzite-like modes due to Li–O and Ga–O bond vibrations in LiGaO₂ and of the rocksalt-like mode due to Li–O bond vibrations in LiInO₂ are determined from the infrared reflectivity spectra of the compounds. The force constants for the Li–O and Ga–O bonds in LiGaO₂ follow the same trends as those found for the A^IB^IIIC₂^VI chalcogenides with tetrahedral cordination. The results for LiInO₂ are compared with measurements on the octahedrally coordinated modification of LiAlO₂.