离子热合成在红外区具有非线性光学活性的金属硫属化物 MAgSbS（M = Rb，Cs）。

Ionothermal Synthesis of Metal Chalcogenides MAgSbS (M = Rb, Cs) Displaying Nonlinear Optical Activity in the Infrared Region.

机构信息

China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical and Material Engineering , Jiangnan University , Wuxi 214122 , P. R. China.

School of Chemical Science and Engineering , Tongji University , Shanghai 200092 , P. R. China.

出版信息

Inorg Chem. 2019 Oct 7;58(19):12582-12589. doi: 10.1021/acs.inorgchem.9b01262. Epub 2019 Sep 25.

DOI:10.1021/acs.inorgchem.9b01262

PMID:31553591

Abstract

Two interesting non-centrosymmetric metal chalcogenides, RbAgSbS and CsAgSbS, were synthesized by an ionothermal approach. Crystals of compounds RbAgSbS and CsAgSbS possess isomorphic configuration, consisting of two-dimensional (2D) anionic networks [AgSbS], which are split by alkali-metal M cations. The band gaps are 2.11 and 2.02 eV for RbAgSbS and CsAgSbS, respectively. Second-harmonic generation (SHG) studies revealed that RbAgSbS affords a powder SHG performance of ∼0.5 × AgGaS with type-I phase matching, while CsAgSbS shows a slightly stronger SHG performance of ∼0.6 × AgGaS with type-I phase matching. Both compounds possess broad transparency ranges (∼0.6-20 μm), suggesting their potential as infrared (IR) nonlinear optical (NLO) materials. The laser damage thresholds (LDTs) of both RbAgSbS and CsAgSbS are about 2.3 × AgGaS. The calculated birefringence indexes Δ are 0.1885 and 0.1944 at 1.064 μm, respectively, which are sufficiently large enough to achieve phase matching. Theoretical studies using density functional theory have been implemented to further understand the relationship between their NLO properties and band structures.

摘要

两种有趣的非中心对称金属硫属化物 RbAgSbS 和 CsAgSbS 通过离子热法合成。化合物 RbAgSbS 和 CsAgSbS 的晶体具有同构配置，由二维（2D）阴离子网络[AgSbS]组成，这些网络被碱金属 M 阳离子分裂。RbAgSbS 和 CsAgSbS 的能带隙分别为 2.11 和 2.02 eV。二次谐波产生（SHG）研究表明，RbAgSbS 具有约 0.5 × AgGaS 的粉末 SHG 性能，具有 I 型相位匹配，而 CsAgSbS 则具有约 0.6 × AgGaS 的稍强 SHG 性能，同样具有 I 型相位匹配。两种化合物都具有较宽的透明范围（约 0.6-20 μm），表明它们可能作为红外（IR）非线性光学（NLO）材料。RbAgSbS 和 CsAgSbS 的激光损伤阈值（LDT）约为 2.3 × AgGaS。在 1.064 μm 处，计算得到的双折射指数Δ分别为 0.1885 和 0.1944，足够大以实现相位匹配。使用密度泛函理论进行了理论研究，以进一步了解它们的 NLO 性质和能带结构之间的关系。