Li₂MnSnSe₄: A New Quaternary Diamond‐Like Semiconductor with Nonlinear Optical Response and Antiferromagnetic Property

Abstract

A new selenide with a diamond-like structure, Li MnSnSe , was synthesized for the first time by using a conventional high-temperature solid-state reaction method. Li MnSnSe crystallizes in the space group Pmn2 (no. 31) of the orthorhombic system. Its three-dimensional framework is constructed by corner-sharing LiSe , MnSe , and SnSe tetrahedra. The title compound has been discovered to have both type I phase-matchable behavior and to exhibit moderate powder second-harmonic generation intensity, about 0.5 times that of commercial AgGaS in the particle size of 200-250 μm at a laser radiation of 2.09 μm. In addition, Li MnSnSe exhibits congruent melting behavior, which makes the bulk single-crystal growth by the Bridgman-Stockbarger method possible. The temperature-dependent susceptibility measurement indicates an antiferromagnetic interaction with a Néel temperature (T ) of 8.6 K for this compound.

Li4HgSn2Se7: The First Second-Order Nonlinear Optical-Active Selenide in the I4–II–IV2–VI7 Diamond-like Family

“…Recently, many quaternary DL metal chalcogenides have been reported as potential IR NLO materials including Li 2 CdMS 4 (M = Ge, Sn), 21 Cu 2 CdSiS 4 , 22 and Li 2 MnSnSe 4 . 23 Unfortunately, these materials are typically limited by low SHG coefficients, although all the MS 4 units are aligned in the same direction. One way to increase the NLO response is to incorporate elements that more easily polarized with chalcogen ligands.…”

Chalcophosphates: A Treasure House of Infrared Nonlinear Optical Materials

“…Chalcogenides with wide IR transparent ranges and great structural diversity have long been regarded as one of the most promising systems for exploring mid-IR NLO crystals. − Researchers have synthesized a good number of metal chalcogenides with excellent NLO performance, such as BaGa 4 S 7 , BaGa 4 Se 7 , Li 2 Ga 2 GeS, LiGaGe 2 Se 6 , BaGa 2 GeSe 6 , Na 2 BaMQ 4 (M = Ge, Sn; Q = S, Se), Li 2 CdGeS 4 , Ba 23 Ga 8 Sb 2 S 38 , NaAsSe 2 , Na 2 Ge 2 Se 5 , Zn 3 P 2 S 8 , SrHgGeSe 4 , Na 2 ZnGe 2 S 6 , PbGa 2 GeSe 6 , AgGa 2 PS 6 , etc. Thereinto, chalcophosphates are interesting and special.…”

Synthesis and Characterization of Ag2MnSnS4, a New Diamond‐like Semiconductor

“…Non‐centrosymmetric, diamond‐like semiconductors are also very interesting materials in the field of non‐linear optics , . Interesting examples in this field are for example GaAs, GaP, AgGa Q 2 ( Q = S, Se),, and quaternary compounds like Li 2 MnSnSe 4 or Li 2 CdGeS 4 …”

“…[11] Non-centrosymmetric, diamond-like semiconductors are also very interesting materials in the field of non-linear optics. [12,13] Interesting examples in this field are for example GaAs, GaP, AgGaQ 2 (Q = S, Se), [13,14] and quaternary compounds like Li 2 MnSnSe 4 [15] or Li 2 CdGeS 4 . [16] Recently, tetrahedral networks deviating from this diamondlike topology (LiGaGe 2 Se 6 , Li 2 In 2 MQ 6 with M = Si, Ge, Q = S, Se) were also reported to have interesting non-linear optical properties.…”