高激光损伤阈值的含锡硫属化合物中远红外非线性光学晶体材料的探索

Mid/Far infared nonlinear optical (NLO) crystals play an important role in the frequency conversion of Mid/Far infared laser and are used extensively in military and civilian fields. Up to now, commercial Mid/Far infared NLO materials mainly consist of chalcogenides, like AgGaS2, AgGaSe2 and so on, which possess low laser induced damage thresholds (LIDTs) to greatly hamper their application in high-power laser frequency conversion. So the key scientific problem in this field is the structure design and controllable preparation of Mid/Far infared NLO materials with high LIDTs. We have contributed lots of efforts to do much work in this field for a long period. In this project, we choose the Sn-included chalcogenides as our research system, because there are lots of noncentrosymmetric (NCS) compounds in the system and few of them are reported as NLO materials. We use metal oxides as starting materials to synthesize the Sn-included chalcogenides and design their NCS structures basing on structure chemistry principle. The elements, which frequently coordinate in distorted types, are introduced to induce the synthesis of the NCS compounds. Crystal engineering methods are employed to regulate the components and structures of compounds for the increasing of the LIDT. The Sn-included chalcogenides owning large NLO effects and high LIDTs would be explored for Mid/Far infared NLO crystal materials. 6-8 SCI papers with high impact factors and 2-3 patents are expected to publish in three years.

中远红外非线性光学（NLO）晶体是中远红外激光变频的重要材料，在军事民用各个方面应用广泛。目前，已商业化的中远红外NLO材料主要是硫属化合物，如AgGaS2、AgGaSe2等，但这些材料由于激光损伤阈值（LIDT）低而难以应用在高能激光变频领域，因此，如何结构设计和可控制备高LIDT的中远红外NLO材料成为该领域的关键科学问题。该项目是在对该领域长期研究的基础上提出的，以非心结构众多而NLO效应报道很少的含Sn硫属化合物为研究体系，采用以金属氧化物为起始原料的自主专利技术来制备含Sn硫属化合物，利用结构化学知识设计含Sn硫属化合物的非心结构，通过引入易配位畸变的元素诱导形成非心结构，采用晶体工程的方法调控化合物组分和结构来提高材料的LIDT，从而探索NLO效应大、LIDT高的含Sn硫属化合物基中远红外NLO材料。预期发表高水平SCI论文6-8篇，申请发明专利2-3件。

中远红外非线性光学（NLO）晶体是中远红外激光变频的重要材料，在军事民用哥哥方面应用广泛。目前，已商业化得中远红外NLO材料主要是硫属化合物，如AgGaS2、AgGaSe2等，但这些材料由于激光损伤雨做的（LIDT）低而难以应用在高能激光变频领域。因此，如何结构设计和可控制备高LIDT的中远红外NLO材料成为该领域的关键科学问题。该项目是在对该领域长期研究的基础上提出的，以非心结构众多而NLO效应报道较少的含Sn硫属化合物为研究体系，采用金属氧化物为起始原料的自主专利技术来制备含Sn硫属化合物，利用结构化学知识设计含Sn硫属化合物的非心结构，通过引入易配位畸变的元素诱导形成非心结构，采用晶体工程的方法调控化合物组分和结构来提高材料的LIDT，从而探索NLO效应大、LIDT高的含Sn硫属化合物基中远红外NLO材料。项目期间，在功能结构基因的理论指导下，发现[A3X][Ga3PS8] (A = K, Rb; X = Cl, Br)、BaGeOSe2、A4Ge4Se12 (A = Rb, Cs)等多个具有大NLO效应和高激光损伤阈值的硫属化合物材料。迄今为止，共发表SCI论文13篇，申请中国发明专利3项，美国专利2项。后续研究工作正在进行中。