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=20,30,40mol%)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(Ea=320.4kJ/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.     

Investigation of GeSe2-In2Se3-AgI Chalcogenide Glasses

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) -30 AgI具有较好的热稳定性(△T-114℃)和较高的活化能(Ea=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.     

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.     

GeS2-Ga2S3-CsI硫系玻璃的析晶行为及其组成依赖研究

硫系玻璃晶化过程中析出晶相的控制是硫系玻璃陶瓷制备中的一个重要环节. 在制得的65GeS₂·25Ga₂S₃·10CsI(GGC25)和70GeS₂·20Ga₂S₃·10CsI(GGC20)玻璃和玻璃陶瓷基础上, 利用可见—近红外透过光谱, SEM, XRD, Raman光谱等测试技术表征了其透过性能、晶粒尺寸、晶相类型等信息. 研究发现在这两组玻璃样品中少量的组分差别就能导致其显著的析晶行为改变: GGC20玻璃在热处理过程中析出的是GeS₂晶体; GGC25样品则拥有两步析晶过程, 其率先析出Ga₂S₃, 而后才有GeS₂晶体出现. 此外, 研究讨论了这种析晶行为与组成的依赖关系及其与玻璃网络结构之间联系, 可为今后硫系玻璃的可控晶化研究提供实验依据和理论指导.     

Er3+/Ce3+共掺TeO2-Bi2O3-TiO2玻璃的热稳定性和光谱特性研究

用高温熔融法制备了Er³⁺/Ce³⁺共掺新型碲酸盐玻璃(TeO₂-Bi₂O₃-TiO₂).采用差热分析方法研究了玻璃的热稳定性,测试并分析了不同Ce³⁺离子掺杂浓度下Er³⁺离子的吸收光谱、上转换光谱和荧光光谱特性.研究结果表明,制备的碲酸盐玻璃具有很好的热稳定性,玻璃析晶温度Tx与玻璃转变温度Tg之差(ΔT=Tx-Tg)达到了185 ℃,高于其它文献的报道|同时,Ce3+离子共掺引入的能量转移(Ce³⁺∶2F5/2+Er³⁺∶4I11/2→Ce³⁺∶2F7/2+Er³⁺∶4I13/2)有效地抑制了Er³⁺离子上转换发光并显著增强了1.53 μm波段荧光强度,而发射截面随着Ce³⁺离子掺杂浓度相应增大.优异的热稳定性以及光谱性能揭示Er³⁺/Ce³⁺共掺碲酸盐玻璃是一种潜在的制备宽带掺铒光纤放大器的理想增益介质.     

远红外Ge-Te-AgI硫卤玻璃光学性能

用传统熔融淬冷法制备了一系列(100－x)(GeTe4.3)－xAgI (x=5,10,20,30)硫卤玻璃.并通过阿基米德法、XRD衍射、差热分析、可见/近红外吸收光谱、红外透射光谱等手段研究了该硫卤玻璃的热稳定性和光学特性.研究表明随着AgI含量的增加,玻璃的密度从5.591 g·cm－3递增到6.314 g·cm－3|折射率从3.73上升到5.70|XRD衍射数据表明该玻璃体系在较宽的组分范围内没有微晶析出,说明成玻范围较宽|差热分析表明当x=5时玻璃有着最高的转变温度206 ℃|AgI含量增多时短波截止限发生红移,红外截止波长基本不变（均超过25 μm）,表明此硫卤玻璃材料在远红外领域有很大的潜在应用前景.     

Ge20Sb15Se65硫系玻璃光子晶体光纤的中红外色散特性

硫系玻璃与石英玻璃相比具有高折射率(2.0~3.5)、低声子能量 (<350 cm^-1)、优良的中远红外透过性能(可至25 μm)等特性.本文制备了一种在中红外具有优良透过特性的无As环保型Ge₂₀Sb₁₅Se₆₅硫系玻璃材料,以此为基质材料设计了一种三层空气孔结构光子晶体光纤,利用多极法对光纤的中红外色散特性进行了数值模拟,系统研究了结构参量孔径d、孔间距Λ 以及d/Λ 对其色散特性的影响.分析表明:通过改变包层空气孔直径d或空气孔间距Λ,可灵活的调节光子晶体光纤的零色散波长向短波或长波方向移动.通过优化结构参量发现,当Λ=3 μm,d/Λ=0.35 附近变化时,可获得3~5 μm色散平坦,且色散值小于5 ps·nm^-1·km^-1的光子晶体光纤.     

Al2O3对氟氧化物玻璃微结构和析晶的影响

采用红外, Raman, X射线衍射测试分析方法, 研究了Al₂O₃对氟氧化物玻璃微结构和析晶的影响.结果表明, Al³⁺主要以[AlO₄]的形式与[SiO₄]以顶角相连的方式构成基本网络骨架, Al₂O₃含量的增加, 使氧化物玻璃基质的网络向单体和二聚体结构转变, 并使氟化物微晶尺寸有一个先变小后增大的趋势, 但不影响微晶结构.     

GeS2-Ga2S3-CsCl玻璃的三阶非线性光学性能研究

用传统的熔融急冷法制备了组分为(100-2x) GeS₂-xGa₂S₃-xCsCl (x= 15, 20, 25 mol%)系列硫卤玻璃, 测试了样品玻璃的吸收光谱. 采用Z-扫描方法测试了样品的三阶非线性光学特性. 分析了激光光子能量与玻璃三阶非线性光学特性的关系,并研究了组分变化对玻璃的三阶非线性性能的影响. 研究结果表明,光子能量的少许改变可以使非线性吸收系数在一个较大的范围内变化,随着光子能量的增大, 玻璃的非线性吸收系数β 增大;当光子能量趋近于0.5E_g时, β值趋近于0,玻璃有最佳的品质因子; 玻璃样品中CsCl含量的增加使得玻璃的光学带隙E_g增大,短波截止边蓝移,非线性吸收系数β 减小. 但是由于结构与带隙对光学非线性的影响相反,非线性折射率γ 值变化不大. 该结果表明样品的光学非线性性能由光学带隙和结构两方面因素共同决定,对今后研究全光开关用硫系玻璃具有一定的指导意义和参考价值.     

二维GaTe/Bi2Se3异质结：一类有潜力的Z型光解水催化剂

本文基于第一性原理方法，计算了二维GaTe/Bi₂Se₃异质结的电子结构、界面电荷转移、静电势分布、吸收光谱及光催化性质. 计算结果表明异质结是一个小能隙的准直接半导体，能有效捕获太阳光. 由于相对较强的界面內建极化电场和带边轻微弯曲，导致异质结中的光生电子和空穴分别有效分离在GaTe单层和Bi₂Se₃薄片上，可用于析氢和产氧. 这些理论计算结果意味着二维GaTe/Bi₂Se₃异质结是一类有潜力的Z型太阳能全解水催化剂.     

Third-order nonlinear optical properties of GeSe2-Ga2Se3-PbI2 glasses

The third-order nonlinear optical (NLO) properties of new selenium-based GeSe₂-Ga₂Se₃-PbI₂ glasses have been measured using the optical Kerr effect (OKE) technique, with picosecond and femtosecond laser pulses. The 0.70GeSe₂-0.15Ga₂Se₃-0.15PbI₂ glass has the largest third-order optical nonlinear susceptibility in GeSe₂-Ga₂Se₃-PbI₂ glass system with χ⁽³⁾ of 5.28×10¹² esu. In addition, the response time of glasses is sub-picosecond, which is predominantly associated with electron cloud. Local structure of the glasses has been identified by using Raman studies, while the origins of the observed nonlinear optical response are discussed. The [Ge(Ga)Se₄] tetrahedral and lone-pair electrons from highly polarizable Pb atom in glasses play an important role in enhanced NLO response. These results as well as their good chemical stability indicate that GeSe₂-Ga₂Se₃-PbI₂ glasses are promising materials for photonic applications of third-order nonlinear optical signal processing.     

Crystallization behavior of GeSe2-Ga2Se3-CsI glasses studied by Differential Thermal Analysis

GeSe₂-Ga₂Se₃-CsI chalcohalide glasses had been prepared by the melt-quenching technique. With the addition of CsI, the short wavelength cut-off edge of the glasses shifts to the short wavelength gradually, while the long wavelength cut-off edge located at ∼16 μm is nearly unchanged. Thermal properties were measured by Differential Thermal Analysis (DTA). From the heating rate dependence of crystallization temperature, the activation energy for crystallization (E) and the order parameter (n) were calculated by the Kissinger equation. The results show that the activation energy of crystallization decreases dramatically with increasing of CsI content, and the most probable crystallization mechanism is volume controlled one-dimensional growth.     

Optical absorption spectrum of Cu2O-CaO-P2O5 glasses

Homogeneous CaO-P₂O₅ and Cu₂O-CaO-P₂O₅ glasses were prepared using a melt-quenched method under controlled conditions. The binary glasses were found to be colourless and transparent while the ternary glasses changed from light green to dark green as the Cu₂O content increased. From the absorption edge studies, the values of the optical band gap, E_opt and Urbach energy, ΔE were evaluated. The position of the absorption edge and hence the optical band gap were found to depend on the glass composition. Analysis of the optical band gap shows that for the binary glasses, the value increases as the content of CaO decreases, while for the ternary glasses, the value of the optical band gap increases as the content of the Cu₂O decreases. The density of the glasses was also measured and was found to increase with the increase in CaO and Cu₂O contents.     

Effect of Bi2O3 content on physical and optical properties of 15Li2O-15K2O-xBi2O3-(65−x) B2O3: 5V2O5 glass system

Multi-component bismuth borate glasses doped with vanadium ions 15Li₂O-15K₂O-xBi₂O₃-(65−x) B₂O₃: 5V₂O_5, (x=3, 5, 7, 10, 12 and 15) have been prepared using conventional melt quench technique. Characterization of the prepared glasses has been done using X-ray diffraction, differential scanning calorimetry and density measurements. The effect of Bi₂O₃ content on the optical properties of the present glass system is studied from the optical absorption spectra recorded in the wavelength range 200-800 nm. The fundamental absorption edge has been identified from the optical absorption spectra. The values of optical band gap for indirect allowed transitions have been determined using available theories. The origin of the Urbach energy is associated with the phonon-assisted indirect transitions. The density and molar volume studies indicate that Bi₂O₃ in these glasses is acting partly as network modifier and partly as network former. The variations in the optical band gap energies, density and molar volume with Bi₂O₃ content have been discussed in terms of changes in the glass structure. Values of the theoretical optical basicity, average crosslink density and the average electronic polarizability are also reported.     

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     

Optical properties of Sm-doped CaF2 bismuth borate glasses

Sm³⁺-doped calcium fluoride bismuth borate glasses were prepared and characterized optically and the oscillator strengths and Judd–Ofelt parameters for the glass containing 1.5 mol% of Sm₂O₃ were calculated. Density and optical absorption, transmission and the emission spectra were measured. The values of Judd–Ofelt parameters suggested an increase in the degree of asymmetry the local ligand field at Sm³⁺ sites. The optical band gap energy, band tailing parameter and Urbach's energy were calculated for all glass samples. It was found that with increasing the concentration of Sm₂O₃ content the values of the optical band gap energy decrease whereas Urbach's energy increases. Absorption and excitation spectra indicate that commercial UV and blue laser diodes, blue and bluish-green LEDs and Ar⁺ optical laser are powerful excitation sources for Sm³⁺ visible fluorescence in the glass.     

Influence of gallium and alkali halide addition on the optical and thermo–mechanical properties of GeSe<Subscript>2</Subscript>-Ga<Subscript>2</Subscript>Se<Subscript>3</Subscript> glass

A systematic compositional study of a new family of chalcogenide glasses, transparent from the visible range up to 16 μm has been performed. Numerous glass forming regions were explored in the GeSe₂-Ga₂Se₃-MX system (MX = alkali halide) in order to understand the role of alkali halides and the effect of Ga substitution for Sb in the glass structure. To that avail, several ternary diagrams were investigated, and optical and thermo-mechanical measurements were performed. It is shown that the introduction of an alkali halide in the GeSe₂-Ga₂Se₃ glasses increased the band-gap energy E_g by stabilizing electrons from the lone pairs of selenium. However, the glass hardness was lowered due to a decrease in the glass network reticulation. The chemical resistance was studied in a glass containing high CsCl content. Significant corrosion occurred when the glass was exposed to hot water for several hours. There is a great deal of interest in these glasses for use in thermal imaging devices, as they permit the alignment of infrared optical systems with visible red light. Furthermore, the low cost of raw materials and the possibility of shaping these glasses into lenses by molding could extend their utilization from defense to civilian applications. PACS 61.43.Fs; 62.20.-x; 81.05.-t     

Temperature induced band gap shrinkage in Cu2GeSe3: Role of electron-phonon interaction

The ternary semiconducting compound Cu₂GeSe₃ has been investigated for optical properties with photoacoustic spectroscopy. Optical absorption spectra of Cu₂GeSe₃ is obtained in the range of 0.76-0.81 eV photon-energy at temperatures between 80 and 300 K. The thermal variation of band gap energy has been examined from the optical absorption spectra at different temperatures. The temperature induced band gap shrinkage has been explained on the basis of electron-phonon interaction. Varshni's empirical relation in conjunction with Vina and Passler model is taken into consideration for data fitting. The Debye temperature was calculated approximately as 240 K. The acoustic phonons with a characteristic temperature as 160 K corresponding to effective mean frequency have been attributed to the thermal variation of the energy gap.