近日，天津理工大学陈金东团队实现了通过添加相策略合成砷化物红外非线性光学晶体。相关论文发表在2026年5月27日出版的《结构化学》杂志上。

由于缺乏合理的结构设计策略，新型砷化物红外非线性光学晶体的探索仍是一项核心挑战。

通过引入相策略，研究组以具有四面体有序结构的BaSi₇P₁₀为模板相，成功合成了两种新型非中心对称砷化物：BaGa₂Si₇As₁₂（BGSA）和BaIn₂Si₇As₁₂（BISA）。BGSA和BISA表现出巨大的倍频响应（分别为ZnGeP₂的2.6倍和3.7倍）、宽的红外透过范围（截止边达12.2 μm）以及适中的双折射率（0.077和0.096），表明它们是潜在的长波红外非线性光学材料。

它们代表了A-M-As体系四面体有序砷化物的首次成功合成。第一性原理计算揭示，与假想的BaSi₇As₁₀（即BaSi₇P₁₀的同构体）相比，BGSA和BISA同时实现了非线性光学系数和带隙的协同提升。非线性光学系数的增强归因于四面体基团的平均柔度与密度之积（F × n/V）的升高，而带隙的增大则归因于As原子平均配位数的增加。

附：英文原文

Title: BaM2Si7As12 (M = Ga, In): Arsenide infrared nonlinear optical crystals via an adding phase strategy

Author: anonymous

Issue&Volume: 2026-05-27

Abstract: The exploration on novel arsenide infrared (IR) nonlinear optical (NLO) crystals remains a central challenge due to the lack of rational structure design strategies. By adding phase strategy, we successfully synthesized two new non-centrosymmetric arsenides BaGa2Si7As12 (BGSA) and BaIn2Si7As12 (BISA) with tetrahedra-ordered BaSi7P10 as a template phase. BGSA and BISA exhibits giant SHG responses (2.6 and 3.7 × ZGP), broad IR transparency range (cutoff edge up to 12.2 μm), and moderate birefringence (0.077 and 0.096), indicating they are potential long-wave IR NLO materials. They represent the first successful synthesis of tetrahedra-ordered arsenides of A-M-As system. First-principles calculations reveal that both BGSA and BISA achieve a concurrent enhancement in both the NLO coefficients and the band gaps compared to the hypothetical BaSi7As10 (the isomorphism to BaSi7P10). The enhanced NLO coefficients are attributed to the elevated F × n/V, the product of the average flexibility and density of the tetrahedral groups. The enlarged band gaps are attributed to the increased average coordination number of the As atoms.

DOI: 10.1016/j.cjsc.2026.101002

Source: http://cjsc.ac.cn/cms/issues/1066