Strong Kleinman-Forbidden Second Harmonic Generation in Chiral Sulfide: La₄InSbS₉

Abstract

A new chiral sulfide family, Ln(4)InSbS(9) (Ln = La, Pr, Nd), with its own structure type in space group P4(1)2(1)2 or its enantiomorph P4(3)2(1)2 has been synthesized by solid-state reaction. Remarkably, the La member shows the strongest Kleinman-forbidden second harmonic generation to date, with an intensity 1.5 times that of commercial AgGaS(2) at a laser wavelength of 2.05 μm, and exhibits type-I phase-matchable behavior. Density functional theory calculations and ab initio molecular dynamics simulations suggest that lattice vibrations may be responsible for the origin and magnitude of the strong SHG effect.

Synthesis, Crystal, and Electronic Structure of Ba3Sb2Q7 (Q = S, Se)

“…[18,19] In some cases, the presence of the electron lone pair results in the formation of non-centrosymmetric crystal structures with non-linear optical properties. [19][20][21][22] Centrosymmetric antimony chalcogenides also exhibit prospective thermoelectric [9,10,[23][24][25] and magnetic properties. [26,27] Despite the large number of known ternary, quaternary, and polyternary antimony chalcogenides, only a few compounds in the Ba-Sb-Q (Q = S, Se) systems have been reported: Ba 8 Sb 6 S 17 , [28] BaSb 2 S 4 , [29] Ba 3 Sb 4.67 S 10 , [30] Ba 4 Sb 4 Se 11 , [31] and BaSb 2 Se 4 .…”

Synthesis, Crystal Structure, and Optical Property of the Quaternary Semiconductor La4Cd4In2S13

“…All these La-S distances are close to the normal range as in the related lanthanide sulfides: La 3 Mg 0.5 SiS 7 (2.88-3.11 Å), [19] La 3 FeGaS 7 (2.86-3.46 Å), [20] La 7 Sb 9 S 24 (2.79-3.54 Å), [21] La 4 FeSb 2 S 10 (2.90-3.34 Å), [22] and La 4 InSbS 9 (2.84-3.45 Å). [8] …”

“…In recent years, rare-earth chalcogenides in combination with a triel element have attracted a great deal of attention not only because they can form a large number of structure types but also because of their excellent IR NLO performance, [6][7][8] (RE = Pr, Nd, Sm, Gd -Ho) [6] and Ba 2 InYSe 5 [7] with strong SHG effects in the IR region and RE 4 InSbS 9 (RE = La, Pr, Nd) [8] exhibiting strong Kleinman forbidden NLO coefficients in type I phase-matchable behavior. On the other hand, binary CdS, CdSe, and CdTe are also interesting for their semiconducting, photoconducting, and light-emitting properties, which made them some of the most important members of the II-VI family of solids.…”

“…Moreover, InQ 4 (Q = S, Se) tetrahedra is a typical functional unit for a number of applications such as NLO properties. [7,8] In this paper, our synthetic attempt, intended for Cd analogous of RE 3 MInS 7 (M = Fe, Co, Ni; RE = rare-earth metal), [10] resulted in the isolation of single crystals of another new quaternary rare-earth sulfide, La 4 Cd 4 In 2 S 13 with two-dimensional structure, which represents the example of chalcogenides in quaternary RE/M/N/Q (RE = rare-earth metal; M = Zn, Cd; N = Ga, In; Q = chalcogenides) system. Herein, we report its synthesis, crystal structure, and optical property.…”

Synthesis, Crystal and Electronic Structure, and Optical Property of the Quaternary Selenide: La3Sb0.33SiSe7

“…effects in the IR region and RE 4 InSbS 9 (RE = La, Pr, Nd) [22] exhibiting strong Kleinman forbidden NLO coefficients in type I phase-matchable behavior. In this paper, we extend our exploration to the quaternary RE/Si/Sb/Se (RE = rare earth metal) system, which has not been investigated before.…”