Ye Run, Liu Bin-Wen, Jiang Xiao-Ming, Lu Jian, Zeng Hui-Yi, Guo Guo-Cong
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China.
ACS Appl Mater Interfaces. 2020 Dec 2;12(48):53950-53956. doi: 10.1021/acsami.0c15812. Epub 2020 Nov 10.
Exploration of a new nonlinear optical (NLO)-active functional motif is important in the rational design of promising infrared (IR) NLO materials. Compared with typical tetrahedral MQ (M = IIB, III, IV metals; Q = S, Se) motifs, MQ (M = As, Sb) pyramids favor high second-harmonic generation (SHG) efficiency while frequently hindering phase matching (PM) because of excessively large optical anisotropy. The surfactant-thermal method was first adopted to achieve PM in MQ-containing systems and synthesize mixed covalent-ionic IR NLO materials. Two new thioarsenates of AMnAsS (A = Cs, Rb) exhibiting strong PM SHG efficiencies comparable to commercial AGS and laser-induced damage thresholds of one order higher than AGS were obtained. The [AsS] unit in their structures is an unprecedented NLO-active functional motif, which can be useful in designing new IR NLO compounds with large SHG efficiency. In addition, the surfactant-thermal method provides a new general strategy for synthesizing new IR NLO materials.
探索一种新型非线性光学（NLO）活性功能基序对于合理设计有前景的红外（IR）NLO材料至关重要。与典型的四面体MQ（M = IIB、III、IV族金属；Q = S、Se）基序相比，MQ（M = As、Sb）金字塔有利于实现高二次谐波产生（SHG）效率，但由于光学各向异性过大，常常会阻碍相位匹配（PM）。首次采用表面活性剂热法在含MQ的体系中实现相位匹配，并合成混合共价-离子型红外NLO材料。获得了两种新型的AMnAsS硫代砷酸盐（A = Cs、Rb），其表现出与商用AGS相当的强相位匹配SHG效率，且激光损伤阈值比AGS高一个数量级。它们结构中的[AsS]单元是一种前所未有的NLO活性功能基序，可用于设计具有高SHG效率的新型红外NLO化合物。此外，表面活性剂热法为合成新型红外NLO材料提供了一种新的通用策略。
