掺Sn硫系玻璃的制备及光学特性研究

发布时间：2018-03-28 21:12

本文选题：硫系玻璃　切入点：Ge-Sn-S　出处：《宁波大学》2017年硕士论文

【摘要】：近年来,随着光通信、全光信息和光学计算机等研究工作的飞速发展,光开关、波长转换器、光滤波器等无源器件实用化的需求越来越受到科研工作者的重视,然而要实现全光通信这一美好目标,制备出具有良好非线性性能的超快光子学器件是关键所在。而在非线性光学特性研究中,材料的三阶非线性性能研究是研究的重点所在,原因在于,三阶非线性性能对于光通信网络中全光开关、光参数放大器及全光波长转换器等材料的实际应用有着决定性的影响。在众多的非线性光学材料中,硫系玻璃由于其具有较宽的红外透过范围(3至5微米及8至14微米波段内都拥有较高的透过率)、较高的折射率、良好的热化学稳定性及优秀的三阶非线性性能等优点,特别是在与传统的氧化物玻璃相比较中,其非线性折射率系数的值要比石英玻璃的要高100至1000倍,同时非线性响应时间短于200fs,是实现全光开关最为理想的材料。因此,基于硫系玻璃材料的光学器件的研究与设计已成为目前国际上最为活跃的前沿领域之一。本文的主要目的是通过一系列不同的方法制备得到不同组分的硫系玻璃,通过后续的测试方法对玻璃网络结构、光学特性、三阶非线性性能及三者之间的具体联系做了系统的分析和讨论,最终研究制备得到具有较高非线性性能的光学通信材料。具体内容如下:(1)Ge-Sb-S硫系玻璃的光谱特性及网络结构阈值行为研究。通过对制备所得的玻璃样品的测试,获得了不同组分玻璃的物化及光谱特性,重点结合拉曼光谱从玻璃内部微观结构变化情况来对玻璃光学特性的变化进行了系统分析。利用平均配位数(Z)的模型理论描述了玻璃网络结构的变化趋势,发现当Z值大于2.6时,玻璃的拉曼谱上会出现明显的新峰,说明玻璃的网络结构产生了阈值行为且构成发生了明显变化。玻璃网络中产生的新的结构体改变了玻璃整体键能的大小,进而影响了玻璃的能带结构,光学带隙(E_(opg))值也表征出相应的阈值行为。(2)Ge-Sn-Se微晶化硫系玻璃的制备及光学特性研究。在之前对Ge-Sn-Se基质玻璃的非线性光学特性研究中,确定了非线性性能最佳的玻璃组分为Ge20Sn5Se75,因此将其作为我们后续微晶化处理的基质玻璃。经过相同温度不同时间的热处理操作后,获得一系列不同的测试样品。通过XRD图谱及拉曼光谱测试,确定热处理系列玻璃中的晶体主要为GeSe_2和SnSe_2晶体。玻璃中形成的晶粒的局部场效应导致玻璃样品的光学特性发生变化,如光学^/隙、Urbach能量等,然而,玻璃的红外透过特性却没有发生变化。此外,我们还对该系列样品在1550纳米处的非线性性能进行了Z扫描测试,测试结果表明,玻璃样品中晶粒的形成对非线性性能具有提升作用,最大的非线性折射率达到了5.319′10-16 m~2/W,几乎是基质玻璃的10倍之多。(3)Ge-Sn-S三元体系硫系玻璃的制备及中远红外光学特性研究。通过熔融淬冷的方式制备了三个系列的组分不同的玻璃样品,进而确定了该体系玻璃的玻璃形成区。后续的光谱分析表明,Ge和Sn元素对于玻璃网络结构的影响是类似的,然而Sn元素的加入会减小玻璃的光学带隙能量而增加玻璃在中红外波段内的透过性。测量波长为3.3微米处的Z扫描实验说明,长波段处玻璃的较大的光学带隙能量会使得非线性吸收效应减弱,而玻璃网络内[GeS_4]四面体结构单元的较少会使得非线性折射率的值提高。Sn的加入就起到了减少[GeS_4]结构体数量的作用,从而提升了材料的三阶非线性性能。
[Abstract]:In recent years, with the rapid development of optical communication, optical information and optical, computer etc. the research work of the optical switch, wavelength converter, optical filter requirements of passive devices such as practical more and more attention of researchers, however, to achieve this goal better prepared ultrafast all-optical communications, photonic devices has good nonlinear performance is key. In the study of nonlinear optical properties, is the focus of the study, three order nonlinear properties of materials due to the three order nonlinear properties for all optical communication network switch, have a decisive impact on practical application of optical parametric amplifier and wavelength converter and other materials. In many of the nonlinear optical materials, chalcogenide glass because of its wider infrared transmission range (3 to 5 microns to 14 microns and 8 bands have high transmittance, high fold) The injection rate, good thermal and chemical stability and excellent three order nonlinear performance advantages, especially in comparison with the traditional oxide glass, the nonlinear refractive index value of 100 to 1000 times higher than that of quartz glass, and the nonlinear response time shorter than 200fs, is the most ideal all-optical switch materials. Therefore, the research and design of optical devices of chalcogenide glass materials has become the one of the most active fields. Based on the main purpose of this paper is through a series of different preparation methods of different components of chalcogenide glass, through test method on subsequent glass network structure and optical properties specifically, relations between the three and the three order nonlinear properties of the system were analyzed and discussed, the final preparation of optical communication material has high nonlinear properties. The specific contents are as follows: (1) Ge-Sb-S Study on spectral characteristics and network structure of threshold behavior of chalcogenide glass. The prepared glass samples, obtained the physicochemical and spectral characteristics of different components of glass, focus on the combination of Raman spectra from the changes of microstructure of glass to internal changes on glass optical properties were analyzed. The average coordination number (Z) the theoretical model describes the changing trend of glass network structure, found that when the Z value is greater than 2.6, the glass will appear obvious Raman spectrum shows that peak, the glass network structure had a threshold behavior and had an obvious change. The new structure produced in the glass network changed the whole glass button can the size, thereby affecting the band structure of glass, optical band gap (E_ (OPG)) values represent the corresponding threshold behavior. (2) Ge-Sn-Se ceramics preparation and optical properties of chalcogenide glass in system research. Before the study of nonlinear optical properties of the Ge-Sn-Se glass matrix, to determine the optimum performance of the nonlinear glass component is Ge20Sn5Se75, so as we follow the microcrystalline matrix glass processing. After heat treatment of the same temperature and different time, obtained a series of test samples of different. By the XRD spectrum and Raman spectroscopy sure, heat treatment series in glass crystal is mainly GeSe_2 and SnSe_2 crystal. The local field effect crystal glass leads to the formation of optical properties of glass samples changes, such as optical ^/ gap, Urbach energy, however, the infrared transmittance of glass has not changed. In addition, we are also on the nonlinear properties of the series the samples at 1550 nm by Z scan test, the test results show that the formation of grain in a glass sample has the promotion effect on the nonlinear properties, the largest non line Index reached 5.319 '10-16 m~2/W, is almost 10 times as much of the glass matrix. (3) Ge-Sn-S three element system of chalcogenide glass preparation and infrared optical properties of melt quenching. By way of preparation of a series of three components of different glass samples, then the system of glass forming region. The spectral analysis showed that the Ge and Sn elements is similar to the effect on the glass network structure, but added will reduce the glass optical element Sn band gap energy and increase the glass in the middle infrared band transmission. The wavelength was Z scanned 3.3 micron. Long wavelength glass large optical band gap energy makes the nonlinear absorption effect is weakened, and the glass network [GeS_4] tetrahedron structure less makes the nonlinear refractive index value increased with the addition of.Sn is to reduce [GeS_4] structure The effect of body quantity increases the three order nonlinear properties of the material.

【学位授予单位】：宁波大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ171.1

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