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1、_大学硕士学位论文题名:新型掺镱钼酸盐类激光晶体的生长及发光特性研究新型掺镱钼酸盐类激光晶体的生长及发光特性研究The Research on Growth and Optical Property of Novel Molybdate Laser Crystal Doped with Ytterbium摘摘 要要掺镱(Yb3+)钼酸盐类激光晶体材料是目前国内外研究的热点,它具有飞秒激光器所需要的大的发射截面和宽的吸收、发射带宽,有 Yb3+高浓度掺杂所需的结构无序性,还有双折射自调谐的特征,引起了众多科研工作者极大的兴趣。但是,该类材料也存在分层结构、生长困难和热性能差等缺点。本文在综述国内
2、外钼酸盐晶体研究成果的基础上,利用钨酸根离子和磷酸根离子改性钼酸盐来生长复合酸盐型激光晶体。通过研究分析取得以下成果:1.利用熔盐加热炉和单晶提拉炉生长了五种新型的二倍钼酸钨酸盐、二倍钼酸磷酸盐以及四倍钼酸钨酸盐多晶和单晶材料;2.对五种材料进行了 XRD 结构和物相分析、DSC-TG 热性能分析、吸收光谱特性分析、荧光光谱特性和荧光寿命的计算分析;3.利用钨酸根离子改性的方法可以非均匀增宽材料的吸收带宽,最宽可以达到 80nm,并且其吸收谱与 980nmLD 泵浦激光器的发射谱非常吻合,可以间接的改善晶体的热效应;4.复合钼酸钨酸盐都属于四方晶系的 I41/a 空间群,而二倍钼酸磷酸盐晶体则
3、属于正交晶系的 Ibca 空间群;5.二倍钼酸磷酸盐晶体材料的荧光寿命达到了 ms 量级,具有高储能的特点;6.多晶材料主要利用高温固相合成和顶部籽晶法来合成生长,而单晶材料主要利用提拉法来生长,其中四倍钼酸盐 Na5La(MoO4)4最易结晶,利用提拉法生长出了小尺寸的单晶材料;7.在固相合成的过程中,伴随有中间产物 Na2MoO4的生成,使固相反应原料失配,但它也起到了助熔剂的作用;8.通过实验结果分析,提出了下一步的工作方案。关键词:关键词:激光晶体;钼酸盐;掺镱复合酸盐;晶体生长;光谱特性ABSTRACTAt present, the molybdate is on focus in
4、the area of laser crystal. Because it has big emission cross-section and wide absorption, emission bandwidth for femto-second laser, the disordered structure for high concentration doped with Yb3+, and the feature of self-tuning by birefringent. Though, these excellent properties interested lots of
5、scientist, it also has the problem of layered structure, difficult to grow and bad thermal property etc.In this paper, we concluded the research results of molybdate at home and abroad. In order to modify the property of molybdate, we made the research plan of using the WO42-and PO43- to synthesis t
6、he compound-acid ions material. Then we gain some important conclusions: 1.we have grown five types of double-molybdate-tungstate, double-molybdate-phosphate and quadruple-molybdate-tungstate polycrystalline materials and crystal by heating furnace and czochralski furnace; 2.we characterize the five
7、 materials respectively by XRD for structure and chemical phase, DSC-TG for melting point and thermal property, absorption and emission spectrum; 3.the WO42- can inhomogeneous broaden the absorption bandwidth, which can reach to 80nm, and the absroption spectrum contains the emission spectrum of 980
8、nm LD pumped source. It can impove the thermal property of molybdate indirectly; 4.the compound-acid molybdate-tungstate belongs to I41/a space group of tetragonal system and the compound-acid molybdate- phosphate belongs to Ibca space group of orthorhombic system; 5.the fluorescence lifetime of com
9、pound-acid molybdate- phosphate can reach to 1002.5s, with the property of high energy storage; 6.the polycrystalline materials is synthesized by melting and TSSG and the crystal was grown by CZ method. And the Na5La(MoO4)4 is easy to crystallize; 7.during the course of solid state reaction, the mid
10、dle product Na2MoO4 is produced, and it can be used as fluxing agent; 8. the future work plan is presented. Key words: Laser crystal; Molybdate; Compound-acid ions material doped with ytterbium; Crystal growth; Spectrum property目录目录摘要摘要 .IABSTRACT.II目录目录.III第一章第一章 绪论绪论.11.1 激光晶体材料的研究发展概况.1 1.2 钼酸盐类激
11、光晶体的研究现状概述.7 1.3 选题依据和研究的主要内容.9第二章第二章 钼酸盐类激光晶体的特点与研究方法钼酸盐类激光晶体的特点与研究方法.112.1 晶体结构及其物理、化学性质.11 2.2 钼酸盐晶体生长原理和技术.17 2.3 材料性能测试分析方法.19第三章第三章 掺镱二倍钼酸钨酸盐激光多晶材料掺镱二倍钼酸钨酸盐激光多晶材料.243.1 多晶材料 Yb3+:NaBi(WO4)(MoO4)的固相合成.24 3.2 Yb3+:NaBi(WO4)(MoO4)的性能测试与分析.25 3.3 本章小结.29第四章第四章 掺镱二倍钼酸磷酸盐激光多晶材料掺镱二倍钼酸磷酸盐激光多晶材料.304.1 未掺杂 Na2La(PO4)(MoO4)的制备和性能研究.30 4.2 Yb3+:Na2Bi(PO4)(MoO4)的制备和性能研究.