GeS2-Ga2S3-PbCl2硫系玻璃光学及析晶特征的研究

采用熔融-淬冷法制备了GeS2-Ga2S3-PbCl2系列样品玻璃,测试了样品从可见到中远红外的透过光谱和不同升温速率下的DTA曲线,用Kissinger法计算了析晶活化能E和晶体生长指数n.结果表明:该系列玻璃具有较宽光谱,引入PbCl2使玻璃的短波截止波长蓝移,长波截止基本不变.玻璃具有较好的热稳定性,以体积晶化一维生长方式.其中,90 (0.85GeS2-0.15Ga2S3) -10 PbCl2玻璃具有最大的析晶活化能E=134.44 kJ·mol-1,可作为研究硫系玻璃基质与微晶玻璃非线性效应的理想材料.     

GeS2-Sb2S3玻璃的三阶非线性研究

采用熔融-急冷法制备了(100-x)GeS2-xSb2S3(x=10%、15%和20%)系列硫系玻璃,测试了样品的折射率、从可见到近红外的透过特性.采用Z-扫描方法测试了样品的三阶非线性特性,分析了Sb2S3的含量对玻璃的线性折射率,透过率和三阶非线性性能的影响.结果表明样品的线性折射率、非线性折射率n2、非线性吸收系数β以及三阶非线性光学极化率χ(3)随着Sb2S3的含量增加而增大,Sb2S3物质的量含量为20%的样品在800 nm处的三阶非线性折射率n2和非线性吸收系数β分别为:n2=3.27×10-10 esu和β= 31.5 cm/Gw.     

氯化铯对GeSe_2-Sb_2Se_3玻璃的析晶及红外透过性能的影响

采用熔融-急冷法制备了20GeSe2-(80-x)Sb2Se3-xCsCl(x-2,4,6,8和10,以摩尔计)系列玻璃样品,用热膨胀仪、棱镜耦合仪、差热分析仪等测试了样品的密度、线膨胀系数、折射率、玻璃转变温度T8和析晶开始温度Tx等.讨论了氯化铯(CsCl)对玻璃的热力学性能和红外光学性能的影响.利用修正的Ozawa方程计算了玻璃的析晶活化能Ec.研究表明:CsCl含量增加使玻璃的密度P和折射率n,Tg,Tx,△T(Tx-Tg)下降,Ec也随之降低;CsCl的引入在一定范围内易导致玻璃析晶;随着CsCl含量的增加,玻璃的近红外短波限产生了略微的蓝移,红外长波截止波长基本无变化.     

Dy3+掺杂Ge-Ga-Sb-S-CsI硫卤玻璃的热学特性及析晶动力学研究

采用熔融急冷法制备了系列Dy3+掺杂的70GeS2-10Ga2S3-5Sb2S3-10CsI硫卤玻璃样品.测试了样品的可见-近红外和红外透过光谱,分析了Dy3+的光谱吸收及杂质吸收.测试了样品的DTA曲线,分析了样品的热学特性.利用修正Kissinger方程分析了玻璃转变活化能Et、析晶活化能Ec,根据Johnson-Mehl-Avrami方法计算了结晶动力学参数n.研究结果表明:随着Dy3+掺杂浓度的增加,玻璃吸收光谱增强,转变活化能和析晶活化能先增加后减小,x=0.3wt%的玻璃样品最稳定.析晶过程中为两维晶体生长.     

GeS_2-Ga_2S_3-AgCl微晶玻璃的制备及其光学性质

用熔融淬冷法制备了一系列GeS2-Ga2S3-AgCl三元系统硫卤玻璃。研究了样品的密度、热稳定性以及折射率随玻璃组分的变化规律。选取了75GeS2-10Ga2S3-15AgCl玻璃组分进行微晶化处理,并且在350℃下热处理得到了可见至红外透明的微晶玻璃样品。X射线衍射和扫描电子显微镜测试显示,玻璃中析出(Ga4Ge)S4和AgCl微晶相,晶粒尺寸为200～400nm。用Z扫描测量了微晶化前后玻璃样品在800nm波长下的三阶非线性特性,结果表明:在热处理后,玻璃的非线性折射率n2和非线性吸收系数β均明显增加,其中微晶玻璃的最大三阶非线性极化率χ(3)为8.619×10-11esu,是基质玻璃的2.2倍。     

Bi2O3-B2O3-BaO系玻璃的光学折射率与带隙

研究了Bi2O3-B2O3-BaO三元系统的玻璃形成区,给出了该三元系统玻璃形成范围.采用熔融淬冷法制备了60Bi2O3-(40-x)B2O3-xBaO(x=5,10,15,20)和65Bi2O3-25B2O3-10BaO(以摩尔计)的5组高Bi2O3含量的Bi2O3-B2O3-BaO玻璃样品.测试了玻璃样品的折射率和吸收光谱,根据经典的Tauc方程计算了间接允许光学带隙和直接允许光学带隙,计算了样品的能量带隙,并估算了它们之间的关系.研究结果表明;随着BaO含量的增加,玻璃样品折射率逐渐增大,但Ba2 对玻璃折射率的影响要远小于Bi3 ;玻璃样品的紫外吸收增强,光学带隙和能量带隙逐渐减小,光学带隙和能量带隙的比值约为1:1.2.     

GeS2-Ga2S3-PbCl2玻璃的三阶非线性光学特性

采用熔融-淬冷法制备了(100-x)(0.8GeS2-0.2Ga2S3)-xPbCl2(x=0,5,10,15,摩尔分数)系列硫卤玻璃,测试了样品的密度、可见-中远红外的透过性以及样品的折射率,并且根据Z扫描测试原理测试了飞秒脉冲下,样品在800 nm波长下的三阶非线性光学特性.结果表明:非线性折射率n2和非线性吸收系...     

Bi2O3-B2O3-Ga2O3玻璃的光学折射率和带隙研究

采用传统熔融淬冷法制备了5组高Bi2O3含量的Bi2O3-B2O3-Ga2O3系统玻璃样品.测试了玻璃样品的密度,折射率和吸收光谱.利用经典的Tauc方程计算了样品的间接允许光学带隙Eopgi,直接允许光学带隙Eopgd和Urbach能量ΔE.根据Duffy等人提出的经验推导公式计算了样品的能量带隙Eg.研究了Ga2O3含量对玻璃样品的密度、折射率、摩尔折射度Rm、金属标准值Mm、光学带隙、能量带隙和Urbach能量的影响,并分析了它们之间的关系.结果表明:随着Ga2O3含量的增加,玻璃样品的密度和折射率逐渐增大,但Ga3+对玻璃折射率的影响要小于B3+;玻璃样品的紫外吸收增强,光学带隙和能量带隙逐渐减小,光学带隙和能量带隙的比值约为1:1.1;Urbach能量逐渐减小,即玻璃中带裂变和缺陷形成的趋势越小.     

新型硫系玻璃热电极化的倍频效应

为探索优良非线性光学玻璃材料,研究了不同磷族元素掺入对GeS2-Ga2S3玻璃结构和性能的影响.利用传统的熔融淬冷技术,制备了0.8GeS2·0.1Ga2S3·0.1X2S3(X=P,As,Sb)3种硫系玻璃.差热分析表明:所制备的3种硫系玻璃的晶化温度和转变温度之差均大于100K,具有较好的成玻性能.Raman光谱、远红外光谱、可见-近红外光谱、Maker条纹等方法对3种硫系玻璃的结构和性能进行了分析.结果表明:玻璃内部存在较多的多面体单元可以导致玻璃在热电极化后出现较大的二阶非线性光学性能,玻璃在可见光波段透过率的不同将会导致在Maker条纹仪记录倍频光强度时出现反射和透射的倍频效应.     

GeS2-Ga2S3-PbCl2玻璃的三阶非线性光学特性

采用熔融-淬冷法制备了(100-x)(0.8GeS2-0.2Ga2S3)-xPbCl2(x=0,5,10,15,摩尔分数)系列硫卤玻璃,测试了样品的密度、可见-中远红外的透过性以及样品的折射率,并且根据Z扫描测试原理测试了飞秒脉冲下,样品在800 nm波长下的三阶非线性光学特性.结果表明:非线性折射率n2和非线性吸收系数β均随着PbCl2含量的增加而增大,特别是x=15的样品的非线性折射率n2=2.812×10-17m2/W,非线性吸收系数β=4.298×10-11m/W,较传统无重金属参杂硫系玻璃的三阶非线性性能明显提高.     

Broadband mid-infrared emission from Cr2+ in crystal-in-glass composite glasses by Hot Uniaxial Pressing

Cr²⁺-doped II-VI crystals have witnessed an excellent gain media for continuously tunable and femtosecond-pulsed lasers. Despite this, major challenges persist toward realizing ultrabroad emission bandwidth and efficient Cr²⁺-doped fiber due to the valence diversity of Cr, especially in chalcogenide glasses. Here, we propose to prepare Cr²⁺:ZnSe/As₂S_3-xSe_x composite glasses by Hot Uniaxial Pressing (HUP), a method that sinters uniformly mixed crystal and glass powders into geometrically designed composite chalcogenide glasses. The densification of the composite glasses reached 99.88%, indicating that a few or none pores remain. Our research shows that Cr²⁺:ZnSe crystals have good performance in chalcogenide glasses, and the composite glasses have the potential to be made into mid-infrared–doped fibers. It was demonstrated by scanning electron microscopy (SEM) and X-ray diffraction (XRD) that the composite glasses have a uniform Cr²⁺:ZnSe distribution and no crystal disintegration. The transmittance of the composite glasses was significantly improved by tailoring the refraction index. The mid-infrared (MIR) fluorescence and decay of the glasses were measured. The lattice constant was measured, calculated, and discussed to reveal the influence of sintering process on lifetime.     

透红外硫系玻璃的被动及主动光学性能研究

概述了近期对透红外硫系玻璃的被动及主动光学性能和应用的研究工作,内容包括若干硫系玻璃新系统,硫系玻璃微晶化处理及性能改进,稀土离子和/或重金属离子掺杂硫系及硫卤玻璃的红外发光性能,硫卤玻璃的非线性光学效应,硫系玻璃的γ射线辐照效应等。     

Electrical conductivity of CuI-Cu<Subscript>2</Subscript>Se-As<Subscript>2</Subscript>Se<Subscript>3</Subscript> chalcogenide films prepared by chemical deposition

The electrical conductivity of CuI-Cu₂Se-As₂Se₃ chalcogenide semiconductor films prepared through the chemical deposition from an organic solvent has been investigated as a function of the temperature and composition of the films. It has been established that the electrical properties of the chalcogenide glasses and related films are characterized by the same values within the limits of the experimental error. This result is in agreement with the model of dissolution of vitreous semiconductors in organic bases (amines), according to which the main properties of bulk (cast) chalcogenide glasses are retained in films prepared from these glasses.     

Dy3+掺杂Ge-Ga-Se硫系玻璃的性质

实验制备了Dy3+掺杂Ge-Ga-Se系统硫系玻璃样品,测试了玻璃的密度、显微硬度、可见-红外透射光谱、荧光光谱以及荧光寿命.根据玻璃的密度计算了玻璃的摩尔体积以及致密度.讨论了玻璃的这些性能随系统平均配位数＜r＞的变化关系.实验结果表明该系统中配位数大于2.67的玻璃在1.3 μm具有较好的发光性能,荧光寿命在440～530μs之间,当玻璃组成位于化学门槛即平均配位数为2.73时玻璃的发光强度最强.     

Effect of doping by transitional elements on properties of chalcogenide glasses

In present work, the results on the influence of doping by transitional elements on thermal, optical, structural and magnetic properties of chalcogenide glasses are presented.Thermal properties (T_g values for undoped and doped glasses) were studied using differential scanning calorimetry technique. Activation energy of glass transition was estimated with the use of Kissinger’s expression. Structural studies were carried with the use of Raman and infrared spectroscopy and X-ray diffraction. Radial electron distribution functions in doped and undoped bulk glasses were obtained and analyzed. In Raman spectra, main observed effect under the introduction of dopants was the change of relative concentration of main and non-stoichiometric structural units characteristic for As₂S₃ glasses. Investigation of influence of transition metals Mn-dopants on the optical properties of As₂S₃ glass was studied in mid-IR region. Pure chalcogenide glasses are diamagnetics. Introduction of transitional and rare earth impurities changes the magnetic properties of investigated chalcogenide glasses.     

高纯透红外硫系玻璃材料的制备

高性能透红我硫系玻璃材料的开发和应用在很大程度上受到杂质对透过性能影响的制约。本综述系统地阐述了存在于不同硫系玻璃中的杂质之种类、来源、形成过程及其对玻璃透过性能的影响，并介绍了旨在有效地消除杂质、降低玻璃的非本质 原料纯化措施和与此相关的硫系玻璃制备新工艺。     

Mechanical properties of SPS sintered chalcogenide glass-ceramics with externally doped crystals

The low mechanical properties limit the application of chalcogenide glasses in the infrared lens. This paper proposes a general method for enhancing the mechanical strength of chalcogenide glasses. A series of GaAs crystal-doped Ge₁₀As₂₀Se₁₇Te₅₃ and ZnS crystal-doped As₂S₅ glass-ceramics were prepared by spark plasma sintering (SPS). The effects of crystal doping on the optical and mechanical properties of glass-ceramics were studied utilizing FTIR, XRD, SEM, ultramicroscopy, and Vickers hardness. The results show that adding GaAs crystal and ZnS crystal significantly improves the hardness and fracture toughness of the chalcogenide glasses. The infrared transmittance and mechanical properties can be further improved by reducing the crystal size.     

Effect of residual chlorine on fluorescence emission of Dy3+ doped chalcogenide glasses with low gallium content

Chlorine or chlorides are usually used as a dehydrating agent for removing the O-H or S(Se)-H in the preparation of high-purity chalcogenide glasses. However, the residual chlorine in some rare-earth ions doped chalcogenide glasses was found to have a great negative impact on fluorescence emission. In this work, the effect of residual chlorine on the fluorescence emission of Dy³⁺ ions in serial (Ge)GaAsSbS glasses was studied quantitatively, and the reasons were discussed. Cl₂ gas and SbCl₃ were used as the source of chlorine and their residual contents were controlled by the post-distillation process and added content, respectively. The results can give some suggestions for how to eliminate the negative effects of chlorine and improve the glass’ optical gain properties.     

Correlation Between Crystallization Behavior and Network Structure in GeS2–Ga2S3–CsI Chalcogenide Glasses

Diagram of the phase transformation behavior of GeS₂–Ga₂S₃–CsI glasses is realized in this article and the structure‐property dependence of the chalcogenide glasses is elucidated using differential scanning calorimetry and Raman spectroscopy. We observe the compositional threshold of crystallization behavior locates at x = 6–7 mol% in (100?x)(0.8GeS₂–0.2Ga₂S₃)–xCsI glasses, which is confirmed by the thermodynamic studies. Structural motifs are derived from the Raman result that [Ge(Ga)S₄], [S₂GeI₂], [S₃GaI], and [S₃Ga–GaS₃] were identified to exist in this glass network. Combined with the information of structural threshold, local arrangement of these structural motifs is proposed to explain all the experimental observations, which provides a new way to understand the correlation between crystallization behavior and network structure in chalcogenide glasses.     

模拟铯废物钛硅酸盐玻璃的化学稳定性研究

熔制了模拟铯废物钛硅酸盐玻璃，用IR研究了玻璃的结构，用产品一致性试验法（PCT）研究了玻璃的化学稳定性，结果表明，所选组成的配料可以在1100℃熔制得玻璃，样品的密度在3．2703．35g/cm^3之间，玻璃中Ti^4 可能以[TiO4]进入玻璃网络，玻璃的结构主要由[SiO4]和[TiO4]组成，产品一致性试验法（PC）实验的浸出液中主要有R＋离子，当配料中n(TiO2):n(SiO2)为0．40－0．35时，浸出液中各种离子的浓度均较低，表明玻璃具有较好的化学稳定性。