Li2HgMS4 (M = Si, Ge, Sn): New Quaternary Diamond-Like Semiconductors for Infrared Laser Frequency Conversion

Abstract

Abstract:A new family of quaternary diamond-like semiconductors (DLSs), Li 2 HgMS 4 (M = Si, Ge, Sn), were successfully discovered for the first time. All of them are isostructural and crystallize in the polar space group (Pmn2 1 ). Seen from their structures, they exhibit a three-dimensional (3D) framework structure that is composed of countless 2D honeycomb layers stacked along the c axis. An interesting feature, specifically, that the LiS 4 tetrahedra connect with each other to build a 2D layer in the ac plane, is also observed. Experimental investigations show that their nonlinear optical responses are about 0.8 for Li 2 HgSiS 4 , 3.0 for Li 2 HgGeS 4 , and 4.0 for Li 2 HgSnS 4 times that of benchmark AgGaS 2 at the 55-88 µm particle size, respectively. In addition, Li 2 HgSiS 4 and Li 2 HgGeS 4 also have great laser-damage thresholds that are about 3.0 and 2.3 times that of powdered AgGaS 2 , respectively. The above results indicate that title compounds can be expected as promising IR NLO candidates.

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

“…The comparison of the optical properties of some related Li‐containing metal chalcogenides is listed in Table . It is clear that compounds Li 2 MSnS 4 (M=Zn, Cd, Hg) and Li 2 CdMSe 4 (M=Ge, Sn) exhibit much stronger SHG responses than the title compounds owing to the presence of the second‐order Jahn–Teller (SOJT)‐distorted d 10 cations. Nevertheless, the more diffuse nature of the electron orbitals of Sn and/or Se atoms make the SnSe 4 tetrahedra more susceptible to polarization, leading to the stronger NLO response of Li 2 MnSnSe 4 than Li 2 MnMS 4 (M=Ge, Sn) …”

Hg-Based Infrared Nonlinear Optical Material KHg4Ga5Se12 Exhibits Good Phase-Matchability and Exceptional Second Harmonic Generation Response

“…Hence, Hg-based chalcogenides may provide an attractive playground for IR-NLO materials (it should be mentioned that element Hg and most of the Hg-based compounds are extremely toxic and unfriendly to the environment; therefore, all the manipulations should be performed with great care). According to our investigation, only a few Hg-based metal chalcogenides have been reported as promising IR NLO materials including HgGa 2 S 4 , 20 BaHgQ 2 (Q = S, Se), 21,22 Li 2 HgMS 4 (M = Si, Ge, Sn), 23 Li 4 HgGe 2 S 7 , 24 and A 2 Hg 3 M 2 S 8 (A = Na, K; M = Si, Ge, Sn). 25,26 In particular, the [HgSe 3 ] 4− groups in BaHgSe 2 were identified as the first π-conjugated anionic groups with large NLO susceptibilities and stable chemical properties in IR NLO materials.…”

Synthesis, Crystal Structures, Optical Properties and Theoretical Calculations of Two Metal Chalcogenides Ba2AlSbS5 and Ba2GaBiSe5

“…Metal chalcogenides have been used as critical materials in the development of modern science and technology because of their structural complexities and fascinating properties [1][2][3][4][5][6][7][8][9][10][11][12]. Among them, many trivalent cations (such as M III ': As, Sb, or Bi) containing chalcogenides have been discovered and shown to have various application prospects.…”