Sn₇Br₁₀S₂: The First Ternary Halogen‐Rich Chalcohalide Exhibiting a Chiral Structure and Pronounced Nonlinear Optical Properties

Abstract

Infrared nonlinear optical (IR NLO) materials are significant in laser technology for civil and military uses. Here, we report the synthesis, structural chemistry and NLO properties of a halogen‐rich chalcohalide Sn7Br10S2. Its noncentrosymmetric (NCS, P63) structure can be considered as partially aliovalent anion substitution of SnBr2 (P63/m) induced centrosymmetric (CS) to NCS structural transformation. The 3D ∞[Sn(1)6Sn(2)6Br6X6]6− (X=Br/S) channel framework consists of Sn(1)BrX2 and Sn(2)X3 trigonal pyramids. It exhibits excellent NLO performance, including a strong phase‐matchable NLO response of 1.5 × AgGaS2and high laser‐induced damage threshold of 6.3 × AgGaS2.Investigation of the structure–NLO performance relationship confirms that the effective arrangement of Sn(1)BrX2 and Sn(2)X3 units predominantly contributes to the large SHG response. These results indicate Sn7Br10S2 is a potential IR NLO candidate and provides a new feasible system for promising NLO materials.

Influence of Proton Ion Irradiation on the Linear–Nonlinear Optoelectronic Properties of Sb40Se20S40 Thin Films at Different Fluences for Photonic Devices

“…The observed nonlinear optical values are quite close to those obtained in other related studies. 2, 21,52 The χ (3) values are higher than those of well-known SiO 2 glass (2.8 × 10 −14 esu), As 2 S 3 glass (1.48 × 10 −12 esu), GeS 2 glass (1 × 10 −12 esu), 63 and several heavy metal oxide glasses. 64 Furthermore, the χ (3) and n 2 obtained for Sb 2 Se 3 and Ge−Se−Te−Sb thin films were both in the range of 10 −11 to 10 −10 esu, which are close to our estimated values.…”

“…According to Miller's rule, χ (1) and χ (3) are evaluated by 61,52 = [ ] = where n o is the static refractive index for hυ → 0 and A is a constant with a value of ∼1.7 × 10 −10 [for χ (3) measured in esu]. Additionally, the nonlinear refractive indices (n 2 ) of the films have been estimated by using Ticha−Tichy and Miller's rule by 62 = n n 2 12 (3) o . The estimated χ (1) , χ (3) , and n 2 values of the investigated films are listed in Table 3.…”

“…Additionally, the nonlinear refractive indices (n 2 ) of the films have been estimated by using Ticha−Tichy and Miller's rule by 62 = n n 2 12 (3) o . The estimated χ (1) , χ (3) , and n 2 values of the investigated films are listed in Table 3. χ (3) and n 2 were found to decrease with ion dose.…”

“…The estimated χ (1) , χ (3) , and n 2 values of the investigated films are listed in Table 3. χ (3) and n 2 were found to decrease with ion dose. The spectral dependency of χ (3) on wavelength is shown in Figure 9a.…”

“…(2) 2 (3) 3 (11) where χ (1) is the linear susceptibility and χ (2) and χ (3) are the second-and third-order nonlinear susceptibilities, respectively. In this case, χ (2) is 0 (with center of inversion symmetry); thus, only the non-zero χ (3) term plays an influential role in all glassy compounds.…”