【作者】 肖秀娣；

【导师】 赵修建； 刘启明；

【作者基本信息】 武汉理工大学 ， 材料学， 2007， 硕士

【摘要】 非线性光学材料在未来光通讯领域有潜在应用前景，非线性光学玻璃由于其在光学领域的特殊优势受到人们的重视和研究。微晶掺杂玻璃作为非线性光学玻璃中的一大类，因其具有较大的三阶和二阶非线性系数而受到人们的青睐。而根据前人的研究表明，加入具有大折射率的物质有望提高玻璃的非线性性能，因此本文对Sb₂S₃微晶掺杂SiO₂凝胶玻璃的制备与非线性光学性能进行了系统研究。本文利用综合热分析、X射线衍射、高分辨透射电镜研究了Sb₂S₃微晶掺杂二氧化硅凝胶玻璃的制备工艺，利用紫外可见近红外光谱、荧光光谱、三阶非线性的OKE技术、二阶非线性的Maker条纹法研究了Sb₂S₃微晶掺杂SiO₂凝胶玻璃的非线性光学性能，并获得如下主要结论：制备了含有Sb₂S₃微晶的片状SiO₂凝胶玻璃，Sb₂S₃在SiO₂凝胶玻璃中的理论最大掺杂含量为6wt％，晶粒尺寸在2～5nm之间，并随着热处理温度的升高，时间的延长和掺杂含量的增加而长大；Sb₂S₃微晶掺杂SiO₂凝胶玻璃的紫外截止边随着晶粒的减小而发生蓝移现象，具有明显的量子尺寸效应：该玻璃还具有明显的荧光效应，并随着热处理时间的延长和温度的升高，荧光峰发生红移并且强度降低；Sb₂S₃微晶掺杂的SiO₂凝胶玻璃具有明显的三阶非线性效应，其响应时间为260fs，三阶非线性系数为3.848×10^-13esu，其超快非线性响应归属于半导体微晶中费米面附近电子的带内跃迁和颗粒置入基质结构的区域场增强效应；Sb₂S₃微晶掺杂的SiO₂凝胶玻璃在热电极化和电子束辐射下可以观察到明显的Maker条纹，在入射角±50～60°，SHG强度出现最大值；热电极化的最佳极化温度为170℃；在电子束辐射下，SH强度跟极化条件和微晶的尺寸有很大关系，并随着时间的延长发生缓慢的驰豫，在所研究的条件下，Sb₂S₃微晶掺杂SiO₂凝胶玻璃的二阶非线性系数最大值为2.21pm／V；TSDC测试证明极化层处于样品表面10μm内的区域。更多还原

【Abstract】 Due to the potential application in the optical communication field, nonlinearoptical glasses, as one of nonlinear materials, have attracted great attention in fields ofresearch and application. As one type of nonlinear optical glasses, crystallite dopedglasses also attract people’ sight due to great second and third order nonlinear opticalsusceptibility. According to the previous research, the material with high refractiveindex is helpful to enhance the nonlinear properties. Therefore, a fundamentalresearch on sol-gel preparation and non-linear optical properties of Sb₂S₃ doped silicaglasses was made in this thesis.With the analysis methods of TG-DSC, XRD and HRTEM, the process ofpreparation is systematically conducted. Utilizing the UV-Vis-NIR spectra, PL spectra,OKE and Maker fringe methods, nonlinear properties of these glasses were studied.Main conclusions are as follows:Firstly, the Sb₂S₃ crystallite doped silica glasses has been prepared. Themaximum of the dopant in the glasses is up to 6wt%. The crystallite size in the glassesis about 2～5nm and increases with increasing heat treatment time and temperature.Secondly, the UV cut-off edge of glass shifts towards short wavelength with thedecreasing size of crystallite which shows the quantum size effect. The fluorescence isobserved in the PL spectra. The intensity decreases and the peaks of PL spectra shifttowards long wavelength with increasing heat treatment temperature and time.Thirdly, third order optical nonlinearity is observed in the Sb₂S₃ crystallite dopedsilica glasses. The response time and third order nonlinearity is 260fs and3.848×10^-13esu, respectively, which is ascribed to combination of the intrabandtransition in the semiconductor crystallite and localized charge effect.Lastly, after thermal poling and electron beam irradiation, Maker fringe pattern isobserved and the maximum is around±50～60°of incidence degrees. The optimumtemperature is 170℃during thermal poling. The SH intensity has great dependenceon the irradiation conditions and the size of crystallites. After irradiation, the SHintensity can decrease with delay. The maxiumum of second order nonlinearitysusceptibility is up to 2.21pm/V. The depth of poling domain is under the surface ofthe sample about 10μm after irradiation.更多还原