【作者】 张军；

【导师】 陶海征；

【作者基本信息】 武汉理工大学 ， 材料学， 2010， 硕士

【摘要】 硫系玻璃具有宽的红外透过窗口、高的线性和非线性折射率及优异的光敏性,在红外探测、可逆光记录媒体、全光开关、无机光刻等领域具有广阔应用前景。考虑到结构和性能的密切关系,对硫系玻璃微结构的探索有着重要的理论和实际意义。基于玻璃具有组成、性能连续可调的特性,本文系统探索了S或Se取代对Ge(SxSe1-x)2玻璃微结构和光学性能的影响规律,并进而选择Ge(S0.8Se0.2)2玻璃探索了其微晶化规律。针对前人仅分析了Ge(SxSe1-x)2(0=x=0.25)玻璃的拉曼谱演变,本文选用高纯Ge,S和Se(全部5 N)作为原料,采取传统的熔融-淬冷法,通过制备工艺的优化,制备出了组成范围在0≤x≤1的Ge(SxSe1-x)2玻璃。通过拉曼散射技术和正电子湮灭技术探测,表征了Ge(SxSe1-x)2玻璃微结构的演变规律。拉曼研究结果表明S或Se取代并不改变Ge(SxSe1-x)2玻璃的微结构单元构型,仍为四面体单元,即[GeSnSe4-n](n=0,1,2,3,4);但随着S或Se替换,[GeSnSe4-n](n=0,1,2,3,4)四面体在玻璃中的分布发生变化。正电子寿命研究发现当S或Se取代达到某—值时,玻璃的开孔体积最小。折射率表征发现,折射率随组成变化呈现单调线性变化规律；基于Ge(SxSe1-x)2玻璃微结构单元分布演变规律可合理解释该现象。兼顾可见透过和高非线性性能,选择Ge(S0.8Se0.2)2玻璃,通过热处理工艺的剪裁,探索出了一种具有永久二阶非线性光学性能且可见透过的透红外硫系玻璃陶瓷。可见-近红外透过光谱测试表明,为保持样品良好的透过性能,Ge(S0．8Se0．2)2玻璃在470℃(Tg=468℃)热处理的时间不应超过24小时。通过Maker条纹法测试了制备得到的Ge(S0.8Se0.2)2玻璃陶瓷的二次谐波发生性能,计算得Ge(S0.8Se0.2)2玻璃陶瓷的二阶非线性系数χ(2)最高可达到3.54pm/V。更多还原

【Abstract】 Chalcogenide glasses have wide application prospect in the fields of infrared detection、reversible optical recording medi、all-optical switching、inorganic photoresists and so forth due to their wide infrared transmission windows、high linear and nonlinear refractive indices and excellent photosensitivity. Considering the intimate relationship between the properties and structure, micro-structural investigation of chalcogenide glasses has important academic and practical meanings. Based on continuously tunable characteristic of composition and properties for Ge(SxSe1_x)2 glasses, a systemic study on the influence law of S or Se replacement to their microstructure and optical quality was conducted in the present work. Moreover, Ge(S0.8Se0.2)2 chalcogenide glasses were chosen to study the micro-crystallization law.Aiming at the previous analysis of Raman spectra evolvement only for Ge(SxSe1-x)2 (0=x=0.25) glasses, in this study, Ge(SxSe1-x)2 (0=x=1) glasses were prepared by conventional melt-quenching method using high purity Ge, S and Se (all of 5 N) as raw materials through preparation technical optimization. Microstructure evolution law of Ge(SxSe1-x)2 glasses was described by Raman scattering technology and positron annihilation technology. Raman scattering results show that microstructure unit model of Ge(SxSe1_x)2 glasses does not change along with S or Se replacement, tetrahedral unit configuration is preserved, namely [GeSnSe4-n] (n=0,1,2,3,4); but the distributing of [GeSnSe4-n] (n=0,1,2,3,4) tetrahedra in glass changes. Researches on positron annihilation lifetime detect that while S or Se replacement up to a certain value, open volume of the glass is smallest. Refractive index characterization shows that the change of refractive index presents a simple linear evolution which can be reasonably explained base on microstructure unit distributing evolvement law of Ge(SxSe1-x)2 glasses.Give attention to visible transmission and high nonlinear capability, Ge(S0.8Se0.2)2 glasses were chosen to study the second-order optical nonlinearity of obtained glass ceramics. An efficient heat treatment to permanent second-order optical nonlinearity was achieved in Vis-IR transparent chalcogenide glass ceramics. In order to keep the high transmisssion spectra, the time of 470℃(Tg=468℃) heating treating of Ge(S0.8Se0.2)2 glasses should be under 24 hours according to the Vis-NIR spectra. Using Maker fringe method describe SHG performance of prepared Ge(S0.8Se0.2)2 glass ciramics, calculated results show that the highest second harmonic coefficientx(2) of Ge(S0.8Se0.2)2 glass ciramics is up to 3.54pm/V.更多还原