Concentration dependence of radiation-induced changes in the optical properties of Ge<Subscript>x</Subscript>As<Subscript>40−<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>60</Subscript> films

Radiation-induced changes in the optical properties of chalcogenide glasses in the Ge-As-S system are investigated as a function of the concentration. Theoretical calculations are performed with due regard for possible constraints on the range of variation in the number of homobonds and heterobonds upon their switching in the structural network of chalcogenide glasses. The experimental data are obtained upon irradiation of Ge_xAs_40?xS₆₀ thin films with fast electrons (6 MeV). The possible mechanism of structural transformations responsible for the specific features in the concentration dependence of the change in the band gap of chalcogenide glasses is discussed.     

Electrical switching behavior of bulk Cux(AsSe1.4I0.2)100−x glasses: Composition dependence and topological effects

The objective was to study the static current–voltage characteristics and electrical switching properties of the bulk metal chalcogenide glasses Cu_x(AsSe_1.4I_0.2)_100?x (1≤x≤25). The obtained results clearly indicate that all the studied glasses exhibit current-controlled negative resistance behavior and memory switching. The composition dependence of the switching field (E_th) was found to decrease with the increase in copper content and a change in the slope occurs for the compositions with x=5 and 20. The slope change in E_th versus x was identified using two network topological effects, namely, the rigidity percolation threshold and the chemical threshold.     

Influence of the selenium content on thermo-mechanical and optical properties of Ge–Ga–Sb–S chalcogenide glasses

A number of Ge₁₇Ga₄Sb₁₀S_69−xSe_x (x = 0, 15, 30, 45, 60, and 69) chalcogenide glasses have been synthesized by a melt-quenching method to investigate the effect of the Se content on thermo-mechanical and optical properties of these glasses. While it was found that the glass transition temperature (T_g) decreases from 261 to 174 °C with increasing Se contents, crystallization temperature (T_c) peak only be observed in glasses with Se content of x = 45. It was evident from the measurements of structural and physical properties that changes of the glass network bring an apparent impact on the glass properties. Also, the substitution of Se for S in Ge–Ga–Sb glasses can significantly improve the thermal stability against crystallization and broaden the infrared transmission region.     

Study of structural modification of sodium aluminophosphate glasses with TiO2 addition through Raman and NMR spectroscopy

Structural modification of sodium aluminophosphate (NAP) glasses with TiO₂ addition has been investigated using Raman and MAS-NMR (³¹P and ²⁷Al) spectroscopy. TiO₂ incorporated NAP glasses having composition (mol%): 40Na₂O-10Al₂O₃-xTiO₂-(50−x)P₂O₅ (x=0-20), are prepared by conventional melt quench method. The low-frequency Raman spectrum suggests an increase in the average ionic character of phosphate glass network with addition of TiO₂. Raman and ³¹P MAS-NMR revealed that the glasses without TiO₂, consist mainly metaphosphate (Q²) structural units. These are gradually converted into pyrophosphate (Q¹) and orthophosphate (Q⁰) structural units along with the formation of P-O-Ti/P-O-Al linkages. ²⁷Al MAS-NMR revealed the change in coordination of Al from octahedral (AlO₆) to tetrahedral (AlO₄) for TiO₂ above 10 mol%. Raman spectra indicate that TiO₂ enters the network in the form of octahedral (TiO₆) and tetrahedral (TiO₄) structural units and at high concentration of TiO₂, tetrahedral structural units are more favourable. Various thermo-physical properties e.g. density (ρ), molar volume (V_m), glass transition temperature (T_g), microhardness (MH), and thermal expansion coefficient (TEC) have been measured as a function of TiO₂ content. Variations in the thermo-physical properties are correlated with these structural modifications in the phosphate structural units and consequently changes in the average ionic character of phosphate glass network.     

Ge28Sb6S(66－x)Sex玻璃系统光学特性与结构

采用熔融-急冷法制备了系列Ge₂₈Sb₆S_(66－x)Se_xSe_x(x=0,10,20,30摩尔比)硫系玻璃样品.分别测试了样品的密度、折射率、可见-近红外透过光谱、红外透过光谱以及喇曼光谱,并分析了在Ge-Sb-S中引入Se对其物理、光学特性的影响.利用喇曼光谱讨论了玻璃的结构与特性之间的关系.结果表明：随着Se含量的增加,样品的密度和线性折射率都增大,可见和红外截止波长都发生红移,纯硫化物玻璃样品主要由GeS₄四面体和SbS₃三角锥组成,随着Se逐渐代替S,硫-硒混合样品中逐渐出现了GeS_4－xSe_x结构单元以及链状和环状的Se-Se键.     

Optical properties of amorphous films

We have analyzed the optical properties of a-Ge_30-xSb_xS₇₀ chalcogenide glass films (x=0,10,20 and 30 at%); the chalcogenide films were prepared by vacuum thermal evaporation. The optical-absorption data indicate that the absorption mechanism is non-direct transition. We found that the optical band gap, E_opt, decreases from 2.04±0.01 to 1.74±0.01 eV, whereas the refractive index increases with increasing Sb content. Data are analyzed by the Wemple equation, which is based on the single-oscillator model.     

Index of refraction and d. c. electrical conductivity in Ge40−xSbxS60 glasses

The spectral dependence of the index of refraction (n) in Ge_40?xSb_xS₆₀ glasses has been described by a simple one-oscillator approximation using the Wemple-DiDomenico treatment (W-D). The possibility of application of the Moss formula or W-D in some amorphous materials for estimation of the optical gap (E _g) fromn or vice versa has been examined. From the results of optical and d.c. electrical conductivity measurements and bond statistics suggestions it can be concluded that many types of defect states are created in Ge_40?xSb_xS₆₀ glasses, which pin the Fermi level in the vicinity ofE _g/2.     

Thermal conductivity of GexSb(As)ySe100‐x‐y glasses measured by Raman scattering spectra

We systematically measured thermal conductivity of Ge_xSb(As)₁₀Se_90−x, Ge_xSb₁₅Se_85−x, and Ge_xSb(As)₂₀Se_80−x chalcogenide glasses by measuring their Stokes and anti‐Stokes Raman scattering spectra and estimating the temperature raised by laser irradiation via the ratio of Stoke and anti‐Stokes scattering cross‐section. We aimed at demonstrating the viability of Raman scattering method for thermal conductivity measurements, and understanding the role of chemical composition in determining thermal conductivity of the chalcogenide glasses. We found that, while the values of the thermal conductivity measured in the paper are in a range from ~0.078 to 1.120 Wm^‐1K^‐1 that are in agreement with those reported data in the literatures, thermal conductivity increases before it reaches a maximum at the glass with chemically stoichiometric composition, and then decreases with increasing Ge content. We ascribed the threshold behavior of the thermal conductivity to the demixing of the structural units like GeSe₂, As₂Se₃ and Sb₂Se₃ from the main glass network. The present study demonstrated that Raman scattering method is simple and easy to measure thermal conductivity of the material. Copyright © 2014 John Wiley & Sons, Ltd.     

Effect of replacement of Se by S on structural and physical properties of Ge–Sb–As–Se–S chalcogenide glasses

In the present study, the structural and opto-mechanical properties of Ge–Sb–As–Se–S chalcogenide glasses have been investigated. For this purpose, different bulk glasses of Ge₂₀Sb₅As₁₅Se_60?xS_x (0 ≤ x≤50) were prepared by conventional melt quenching technique in quartz ampoule and different characteristics of prepared glasses such as glass transition temperature, density, hardness, transmittance, optical band gap energy and refractive index were determined. The value of hardness and glass transition temperature of prepared glasses were found to increase with increasing the sulfur content as a result of formation of GeS₄ tetrahedral units and increasing the network connectivity and average bonding energy. The optical energy gap (according to Tauc’s relation), transmittance and refractive index of prepared glasses are in direct relation with sulfur content. In this study, the highest value of transmittance (about 70%) and lowest value of refractive index (2–2.3) was achieved in Ge₂₀Sb₅As₁₅Se₄₀S₂₀ and Ge₂₀Sb₅As₁₅Se₁₀S₅₀ glasses, respectively.     

Investigation of nonlinear optical parameters of zinc based amorphous chalcogenide films

Third order nonlinear optical properties of amorphous Zn_x–S_y–Se_100−x−y chalcogenide films have been investigated using single beam transmission z-scan technique at 1064 nm of Nd:YAG laser. Measurement of optical properties of amorphous Zn_x–S_y–Se_100−x−y chalcogenide films prepared by thermal evaporation technique has been made. X-ray diffraction patterns of chalcogenide films confirm the amorphous nature. Optical band gap (E_g) has been estimated using Tauc's plot method from transmission spectra that is found to decrease with increase in content due to valence band broadening and band tailing the system. Nonlinear refractive index (n₂), nonlinear absorption coefficient (β) and third order nonlinear susceptibility (χ³) of chalcogenide films have been estimated. Self-focusing effect has been observed in closed aperture and reverse saturable absorption in open aperture scheme. Limiting threshold and dynamic range have been calculated from optical limiting studies. The increase in nonlinearity with increase in Zn content has been observed that is understood to be due to decrease in band gap on Zn doping. High nonlinearity makes these films a potential candidate for waveguides, fibers and two photon absorption in optical limiters.     

Model fitted and model free approaches for crystallization kinetics in Se85Te15-xBix glasses

In this research work, we have described the model-fitted and model free approaches for the study of crystallization kinetics in Se₈₅Te_15-xBi_x chalcogenide glasses. Se₈₅Te_15-xBi_x bulk alloys were synthesized by melt quenching technique. High Resolution X- Ray diffraction (HRXRD) was used to confirm the amorphous nature of prepared alloys. Non-isothermal Differential Scanning Calorimetry (DSC) measurements were done at heating rates of 5, 10, 15, 20 and 25 K/min for crystallization kinetics studies in Se₈₅Te_15-xBi_x glasses. The various characteristic temperatures, such as glass transition (T_g), on-set crystallization (T_c) temperature, peak crystallization temperature (T_p) and melting temperatures (T_m) have been obtained from various DSC thermograms. The activation energies of glass transition (ΔE_t) were calculated by using Kissinger and Moynihan approaches and found to be minimum for Se₈₅Te₁₂Bi₃ chalcogenide glass which indicates that this alloy has maximum probability to jump into a less configurational energy state and has larger stability. The model-free approaches; Kissinger–Akahira–Sunose (KAS), Flynn-Wall-Ozawa (FWO), Tang and Straink (TS) reveal that the activation energy of crystallization varies with crystallization degree and temperature both. This variation shows that amorphous to crystalline phase transformation in Se₈₅Te_15-xBi_x chalcogenide glasses is a complex process with various nucleation and growth mechanisms.     

新型GeSe2-In2Se3-AgI玻璃性能研究

采用传统熔融-淬冷法制备了一系列新型(100-x) (4GeSe₂-In₂Se₃) -xAgI(x=20,30,40 mol%)硫系玻璃样品.利用X射线衍射分析、差热分析、可见-近红外吸收光谱、红外透过光谱、喇曼分析等技术手段研究了该玻璃系统的组成、结构、热稳定性和光学特性等.利用Tauc方程计算出了样品的间接带隙;测试了部分样品在不同升温速率下的差示扫描量热曲线,并采用Kissinger法计算了玻璃样品的析晶活化能.X射线衍射数据表明,该玻璃体系在较宽的组分范围内有良好的非晶特性,成玻范围较宽;差热分析和析晶动力学研究表明,玻璃样品70(4GeSe₂-In₂Se₃)-30AgI具有较好的热稳定性(ΔT=114℃)和较高的活化能(E_a=320.4 kJ/mol).随着AgI含量的增加,玻璃的短波吸收限蓝移,并且光学带隙有增大的趋势.此外,红外透过光谱分析表明该玻璃体系具有良好的红外透过性能,其红外截止波长不会随着AgI含量的增加而发生明显变化,皆为16μm左右.     

Ga对新型远红外Te基硫系玻璃光学性能的影响

用传统熔融淬冷法制备了新型远红外Te基硫系玻璃(100-x)(GeTe₄)-xGa (x=0, 5, 10 mol%).利用差热分析(DTA)、可见/近红外吸收光谱、红外透射光谱等技术,在GeTe₄玻璃的基础上,通过引入较高配位金属Ga, 研究其对玻璃组成、结构和性能的影响,利用经典的Tauc方程计算了样品光学带隙允许的直接跃迁、允许的间接跃迁及Urbach能量.分析结果表明:在GeTe₄玻璃中引入 关键词： 光学材料 硫系玻璃 光学带隙 红外光谱     

Photo-induced nonthermal melting of amorphous chalcogenides observed by pump and probe x-ray absorption spectroscopy

A new kind of melting phenomenon which is not based on thermal excitation has been observed. X-ray absorption spectroscopy (XAS) experiments under optical pumping provide a “snap-shot” information on the local structure under excitation. We have studied the local structure of chalcogenide glasses such as vitrious selenium and As₂Se₃ under optical excitation and confirmed the local melting phenomenon under light illumination at low temperature. The photo-induced nonthermal melting (PNM) in chalcogenide glasses is interpreted as the result of pairing of excited lone pair electrons during the illumination. Trapped states in this photo-assisted metastable phase result in a local structural disorder which is partially quenched at room temperature. The increased short-range disorder causing Coulomb repulsion is the origin of red shift of the absorption coefficient known as the photodarkening effect. We found that the bond alternation of chalcogens occurs during the photo-excitation.     

Calorimetric study of characteristic temperatures and crystallization behavior in Ge-As-Se-Te glass system

Results of differential scanning calorimetry of high purity Ge_xAs_40−xSe₄₀Te₂₀ (x=0-40) chalcogenide glasses are reported. The glass transition temperatures and crystallization behavior were studied under non-isothermal conditions at different heating rates (2.5-35 K/min). The glass transition temperature changes from 140 °C up to 320 °C with increasing the Ge content in Ge_xAs_40−xSe₄₀Te₂₀ glass. The studied glasses with x≤35 have no exothermal peaks of crystallization, indicating their high glass-forming ability. The glass of Ge₄₀Se₄₀Te₂₀ composition has one-stage glass transition and double-stage crystallization process during phase change. The activation energy of the glass transition (E_g), the activation energy of crystallization (E_c), the Avrami exponent (n), the frequency factor (K₀) and the crystallization criteria of Ge₄₀Se₄₀Te₂₀ glass were determined.     

Phase-change properties related to anharmonicity of local structure

Ge-Sb-Te pseudo-binary compounds are known to be phase-change materials (PCM). Most of these chalcogenide compounds are candidate for future phase-change random access memory (PCRAM) applications since they show abrupt change on crystalline-amorphous phase-change process. For the use in next-generation applications, increase of retention properties and decrease of power needed for phase-change process are required. These phase-change properties depend on various material characteristics, and thermal conductivity is one of them. In this study, to introduce an easier method for evaluating the local structural anharmonicity of phase-change materials, optical pump terahertz (THz) probe experiments were performed. By investigating the phonon behaviours in PCM by this method and comparing them with local structural information extracted from extended X-ray absorption fine structure (EXAFS) on Ge₁Sb₂Te₄ and Ge₂Sb₂Te₅ films, the effects of resonant bonding on lattice anharmonicity and thermal conductivity were determined. As resonant bonding in the local structure get enhanced, local distortion of the system decrease which cause the decrease in anharmonicity. The quantitatively-measured anharmonicity obtained from the optical pump THz probe experiments can be closely related to the structural and electrical properties, thus reflecting well the difference of phase-change properties between Ge₁Sb₂Te₄ and Ge₂Sb₂Te₅ films.     

Crystallization kinetics and thermal stability in Se85-xTe15Sbx chalcogenide glasses

Crystallization process of Se_85-xTe₁₅Sb_x (x = 2.7, 7.5, 10 and 15 at %) chalcogenide glasses has been studied by using differential scanning calorimetry (DSC) with different heating rates. These glasses are found to have a double glasses transition and overlapped crystalline phases for Se₇₀Te₁₅Sb₁₅ glass while single glasses transition and single crystallization stage for other glasses. Glass transition temperature, T_g, onset crystallization temperature, T_c, and peak crystallization temperature, T_p, are found to be dependent on composition and heating rates. Values of various kinetic parameters such as activation energy of glass transition, E_g, activation energy of crystallization, E_c, Hurby number, H_r, thermal stability, S_p, rate constant, K_p, and Avrami exponent, n, are determined for the present systems. Results indicate that rate of crystallization is dependent on thermal stability and glass-forming ability. Crystallization mechanism occurs in two dimensions for studied compositions. Crystalline phases resulting from DSC and scanning electron microscopy have been identified by using X-ray diffraction.     

Effect of B2O3 on the structure and properties of tungsten–tellurite glasses

The elastic properties and Debye temperatures of xB₂O₃–70TeO₂–(30–x)WO₃, (0 ≤ x ≤ 30 mol%) glasses have been investigated using sound velocity measurements at 4 MHz. Ultrasonic and thermal parameters, combined with the results of IR spectroscopic analyses, were employed to explore the effect of B₂O₃ on the structure of tungsten–tellurite glasses. According to IR analysis, there is competition between WO₆ and TeO₄ units to form BO₄ units, and the vibrations of the tellurite structural units are shifted towards lower wavenumbers on the formation of non-bridging oxygens. It is assumed that B₂O₃ acts as a modifier by decreasing the glass-transition temperature T _g and increasing both the thermal stability and glass formation range of the tellurite glasses. The change in density and molar volume with B₂O₃ content reveals that the borate units are less dense than the tellurite structural units. The observed compositional dependence of elastic moduli is interpreted in terms of the effect of B₂O₃ on the coordination number of the tellurite units. A good correlation was observed between experimentally determined elastic moduli and those computed with the Makishima–Mackenzie model.     

Physical,optical and electrical properties of calcium bismuth borate glasses

The variation in physical, optical and electrical properties has been investigated as a function of Bi₂O₃ content in 20CaO?·?xBi₂O₃?·?(80???x)B₂O₃ (0?≤?x?≤?60, in mol%) glasses. The samples were prepared by normal melt-quenching process, and the optical absorption and reflection spectra were recorded in the wavelength range of 400–950 nm. The fundamental absorption edge has been identified from the optical absorption spectra. The optical band gap, E _g, for indirect allowed and indirect forbidden transitions has been determined from the available theories and its value lies between 1.80–2.37 eV and 1.08–2.19 eV, respectively. The theoretical fitting of the optical absorption indicates that the present glass system behaves as an indirect gap semiconductor. The origin of the Urbach energy, ΔE, has been associated with the phonon-assisted indirect transitions. The refractive index and optical dielectric constant have been evaluated from the reflection spectra. The density and molar volume are found to depend on the molar concentration of Bi₂O₃. The values of DC electrical conductivity have been measured from 373 to 623 K and the activation energy has been calculated. Theoretical optical basicity has been reported as a function of the Bi₂O₃ content. The variations have been discussed in terms of structural changes.     

Effect of SnI2 on the thermal and optical properties of Ge–Se–Te glasses

A systematic series of (Ge₂₀Se₁₅Te₆₅)_1?x–(SnI₂)_x (x = 0, 0.05, 0.1, 0.15) chalcogenide glasses have been prepared. The amorphous nature can be confirmed by XRD and SEM. With the SnI₂ content increasing, the indirect optical band gaps are decreased from 0.662 to 0.622 eV according to Tauc laws. The introduction of SnI₂ makes the glasses much easier to prepare and more stable against crystallization, making them drawable as optical fibers. The highest ΔT (130 °C) value for (Ge₂₀Se₁₅Te₆₅)_0.9–(SnI₂)_0.1 glass composition can be obtained. A slight red-shifting of the long-wavelength cutting-off edge from 18.4 to 19.4 μm was shown and it seems that SnI₂ in these glasses offers the improvement in the far-infrared properties.