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题名	ZnGeP2和过渡金属离子掺杂的ZnSe材料的制备及性能研究
作者	张坤
学位类别	硕士
答辩日期	2009
授予单位	中国科学院上海光学精密机械研究所
导师	杭寅
关键词	ZnGeP2 ZnSe 过渡金属离子掺杂 垂直布里奇曼法 热扩散法
其他题名	Preparation and properties of ZnGeP2 and transition-metal ions doped ZnSe materials
中文摘要	近年来，由于中红外固体激光器在军事和民用方面广泛的应用，产生中红外激光输出的非线性光学晶体ZnGeP2和过渡金属离子掺杂的ZnSe晶体都得到了高度重视，成为各国科学家研究的热点，但是高质量晶体难以获得成为制约其发展的主要因素。 本文研究了ZnGeP2晶体和过渡金属离子掺杂的ZnSe晶体的制备工艺，并对生长的晶体进行了性能表征，取得了以下几方面研究结果： 1. 研究了ZnGeP2多晶合成和单晶生长工艺，分析了退火工艺对晶体性能的影响。按照适当的富P和富Zn配料方式，在双温区水平电阻炉中成功合成了质量较好的ZnGeP2多晶料；采用垂直布里奇曼法生长出尺寸为Ф16×36mm3的ZnGeP2单晶；在ZnGeP2粉末和P蒸汽环境下对生长的晶体进行高温退火。 2. 测试并分析了ZnGeP2晶体的结构和热稳定性，结果表明，生长的晶体结晶性能较好，具有完整的四方结构，在20~800℃范围内热稳定性较好；退火后晶体在1.5μm的透过率增大到30.6 %，2.05μm的透过率增大到54.8 %，3μm~8μm的平均透过率在58 %以上。 3. 研究了真空热扩散法制备过渡金属离子掺杂ZnSe晶体的工艺，并制备了Cr2+、Fe2+离子单掺以及Cr2+/Fe2+双掺的ZnSe晶体。 4. 研究了扩散时间对Cr2+: ZnSe晶体掺杂浓度的影响。当扩散温度为950~ 960℃、扩散时间为1~22天时，Cr2+离子的掺杂浓度为0.7~4.8×1019 ions/cm3，对应的峰值(1776nm)吸收系数为7.7~48.9cm-1；Cr2+离子的掺杂浓度和扩散时间(1~22天内)呈近似线性关系。 5. 研究了铥光纤泵浦Cr2+:ZnSe晶体的激光性能。当泵浦功率为23W时，掺杂浓度为1.48×1019 ions/cm3的Cr2+:ZnSe晶体实现了最大3W的连续激光输出，输出中心波长位于2.367μm，带宽为240nm，斜率效率14.1%。 6. 研究了Cr2+/Fe2+:ZnSe 晶体的光谱特性，并分析了Cr2+离子和 Fe2+离子之间的能量转移机理。
英文摘要	With the wide applications of mid-infrared solid state lasers in the military and civilian, the nonlinear optical infrared ZnGeP2 crystals and transition-metal (TM) ions doped ZnSe crystals have drawn a lot of attentions and have been studied extensively for affordable 2~5μm mid-infrared sources in recent years. But the difficulty in preparing of high quality crystals has restrained the development of the lasers. In this paper, we report the preparation of ZnGeP2 crystals and TM2+ doped ZnSe crystals. Furthermore, the performance characterization of the crystals is investigated, and some innovative results are achieved as follows: 1) The synthesis of polycrysralline and the growth process of single crystals are investigated. And, the effects of annealing to crystal properties are analyzed. 100g high-quality polycrystalline materials of ZnGeP2 are synthesized in a horizontal two-temperature-zone tubular furnace according to the stoichiometry of ZnGeP2 with an excess of P and Zn. After that, the ZnGeP2 single crystal with size of 16×36mm3 is grown by vertical Bridgman. Then the as-grown crystals are annealed in high temperature in the conditions of ZnGeP2 powder and P vapor. 2) The structure and thermal stability of the as grown ZnGeP2 crystals have been tested and analyzed. The results show that ZnGeP2 crystals have a complete structure of the tetragonal and good thermal stability in range of 20~800℃. After annealing, the value of ZnGeP2 wafer transmittance with 2mm thickness are 30.6% at 1.5μm and 54.8% at 2.05μm respectively and the infrared transmission is about 58% in the spectral region of 3μm~8μm. 3) The preparation technology of vacuum thermal diffusion method is investigated and TM2+ (Cr2+and Fe2+) singly-doped and Cr2+/Fe2+ co-doped ZnSe crystals are synthesized. 4) The effects of diffusion time to the concentration of doped Cr2+ ions are investigated. With the time of 1~22 days and temperature of 950~960℃, the Cr2+ ions concentration of Cr2+: ZnSe crystals is in the range of 0.7~4.8×1019 ions/cm3 and the corresponding absorption is 7.7~48.9cm-1. The doped Cr2+ ions concentration increases in an approximate linear with the increasement of diffusion time. 5) The mid-infared laser performance of Cr2+:ZnSe crystals with Cr2+ concentration 1.48×1019 ions/cm3 pumped by Tm fiber laser were studied. The maximum average output power of 3W CW output with 14.1% slope efficiency is achieved and the laser spectrum with a widely tuning range of 240nm is centered at 2.367μm. 6) The spectroscopic properties of Fe2+/Cr2+: ZnSe crystals are studied and the energy transfer mechanism between the Cr2+ and Fe2+ doping ions is analyzed.
语种	中文
内容类型	学位论文
源URL	[http://ir.siom.ac.cn/handle/181231/16427]
专题	上海光学精密机械研究所_学位论文
推荐引用方式 GB/T 7714	张坤. ZnGeP2和过渡金属离子掺杂的ZnSe材料的制备及性能研究[D]. 中国科学院上海光学精密机械研究所. 2009.

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