Ba6Sn6Se13: a new mixed valence selenostannate with NLO property

Abstract

A new ternary selenostannate Ba6Sn6Se13 has been synthesized by a high temperature solid-state method. The compound crystallizes in the non-centrosymmetric orthorhombic space group P2(1)2(1)2(1) and may be represented as Ba6Sn5(2+)Sn(4+)Se13 with mixed valence Sn atoms. Sn(4+) cations lie in a tetrahedral environment, while Sn(2+) cations are found in two kinds of coordination environments: the trigonal pyramid and quadrangular pyramid. SnSe(n) (n = 3, 4, 5) polyhedra are further connected to generate a three-dimensional framework with Ba(2+) residing in cavities. Ba6Sn6Se13 shows moderate nonlinear optical response and is the first reported NLO compound in the Ba-Sn-Se system. In addition, diffuse reflectance spectroscopy measurement indicates that the band gap of Ba6Sn6Se13 is 1.52(2) eV and thermal analysis suggests that the compound melts incongruently. The theoretically calculated SHG response and band gap are in good agreement with experimental results.

Sn2SiS4, synthesis, structure, optical and electronic properties

“…As a result of extensive exploration, many new Sn-containing metal chalcogenides have been discovered, including Ln 2 SnS 5 (Ln = Pr, Nd, Gd and Tb) [2], Ag 6 SnS 4 Br 2 [3], Li 2 CdSnS 4 [4], EuCu 2 SnS [4], Ba 7 Sn 5 S 15 [5], BaSn 2 S 5 [5], Ba 6 Sn 7 S 20 [5], In 4 Pb x Sn y Se 3 [6], Ba 6 Sn 6 Se 13 [7] and SnGa 4 Q 7 (Q = S, Se) [8]. Among them, In 4 Pb x Sn y Se 3 is a promising mid-temperature thermoelectric material candidate [6]; Ba 7 Sn 5 S 15 demonstrates the coexistence of Sn 2 S 3 trigonal-bipyramids and SnS 4 tetrahedra and shows a strong SHG effect [5]; Ba 6 Sn 6 Se 13 has mixed valent Sn 2+ and Sn 4+ cations in 3-fold, 4-fold, and 5-fold coordination environments respectively and shows a moderate NLO effect [7].…”

“…And its coordination environment can range from 3-fold trigonal pyramids, to 4-fold tetrahedra, to 5-fold square pyramids, to 6-fold octahedra, etc. [5,7,8] in chalcogenides. Its mixed valence property and the various coordination environments will certainly increase the stoichiometric and structural diversity of resultant compounds, and hence may lead to interesting properties.…”

“…Among them, In 4 Pb x Sn y Se 3 is a promising mid-temperature thermoelectric material candidate [6]; Ba 7 Sn 5 S 15 demonstrates the coexistence of Sn 2 S 3 trigonal-bipyramids and SnS 4 tetrahedra and shows a strong SHG effect [5]; Ba 6 Sn 6 Se 13 has mixed valent Sn 2+ and Sn 4+ cations in 3-fold, 4-fold, and 5-fold coordination environments respectively and shows a moderate NLO effect [7]. In the meanwhile, Cu 2 ZnSnS 4 , Cu 2 FeSnS 4 and Ag 2 ZnSnS 4 have attracted great interest for their photovoltaic and H 2 production performance [11][12][13][14][15][16].…”

“…Recently, metal chalcogenides containing the group 14 elements, in particular the Sn metal, have received increasing interest [1][2][3][4][5][6][7][8][9][10][11]. Sn atom can be stabilized at both the +2 oxidation state with an electron lone pair and the +4 oxidation states without the lone pair electrons in chalcogenides.…”

Centrosymmetric to noncentrosymmetric structural transformation of new quaternary selenides induced by isolated dimeric [Sn2Se4] units: from Ba8Ga2Sn7Se18to Ba10Ga2Sn9Se22

“…Instead, black crystals of 1, and Ba 6 Sn 6 Se 13 (ref. 35) as a secondary phase together with few red crystals of Ba 5 Ga 2 Se 8 (ref. 36) were produced.…”