新型极性结构无机晶态材料的设计合成与倍频效应

To synthesize borogermanates, galloborates, antimony-borates, iodates and phosphites of alkali, alkaline earth and lanthanide ions by high temperature solid state reactions or hydrothermal reactions; to introduce polar structural units such as distorted octahedra of d0-transition metal ions or distorted coordination polyhedra of lone pair containing cations such as Pb(II) into the above systems so as to obtain new types of Second Harmonic Generation (SHG) crystals by additive polarizations from two types of polar groups; to summarize the effects of synthetic conditions, the size of cation and the packing fashions of the polar structural units on the SHG properties of above inorganic crystalline solids through a great number of synthetic experiments and theoretical calculations; to grow large single crystals and study their relevant chemical and physical properties for some compounds with excellent SHG properties we made previously and those will be made in this project; to develop one or two candidates for future applications as new SHG materials. . SHG materials have wide applications in laser and optical communications, this research project involves many branches of sciences such as solid state chemistry, materials chemistry and structure chemistry, hence this study is very important to both basic reseach and applications of new high-tech materials.

以高温固相反应或水热合成方法合成碱金属、碱土金属、稀土或其它金属离子的硼锗酸盐、硼镓酸盐、硼锑酸盐、碘酸盐及亚磷酸盐; 在上述体系中引入d0-过渡金属MO6畸变八面体或孤对电子阳离子如铅（II）的畸变配位多面体等极性结构单元, 利用两种极性结构基团的协同极化效应诱导极性结构的形成，从而获得性能优良的新型倍频(SHG)晶体; 通过大量的合成实验及理论计算, 总结上述无机固体化合物的SHG性能随合成条件、阳离子大小、极性结构单元堆积方式的调控规律; 对前期工作已获得的和本项目即将得到的具有优异SHG性能的部分化合物进行大尺寸晶体的生长, 研究其大尺寸晶体的物化性能, 筛选出一到两种有开发价值的新型倍频晶体材料。.倍频材料在激光及光通讯领域有广泛的应用, 本项目研究属固体化学、材料化学及结构化学等交叉科学, 对于高新技术材料的基础研究与开发应用均有重要意义。

二阶非线性光学材料（也称倍频材料）广泛应用于激光及光通讯领域，倍频材料必须具有非中心对称或极性结构。 在本项目中我们对非中心对称或极性结构无机化合物的设计与合进行了较为系统的研究工作。 我们采用含孤对电子的氧酸盐如亚（硒）碲酸盐、含π共轭电子体系的基团如硼酸（碳酸或硝酸），畸变八面体配位的d0-过渡金属如Ti4+等为构筑单元，利用两种非线性活性基团的复合得到了多种性能优异的新型金属碘酸盐、亚硒（碲）酸盐及硼酸盐NLO晶体。我们通过两种π共轭电子基团的复合得到了SHG系数为9倍于KDP的Pb2(BO3)(NO3)，通过对BiO(IO3)进行不等价取代得到了高倍频系数的BiFSeO3,在碘酸盐中引入氟离子得到了倍频效应为11.5xKDP的Bi(IO3)F2等。在J. Amer. Chem. Soc., Angew. Chem. Int. Ed., Coord. Chem. Rev., Chem. Mater., Chem. Commun., Chem. Eur. J., Inorg. Chem.等重要化学刊物发表SCI论文42篇，论文已被他引321次，项目执行期间获得授权专利15项， 申请专利7项。培养博士毕业生6人， 硕士毕业生5人。