Luo Ling, Wang Linan, Bai Chen, Zhou Jiazheng, Wei Lai, Su Xin
School of Physical Science and Technology, Yili Normal University, Yining 835000, China.
Xinjiang Laboratory of Phase Transitions and Microstructures of Condensed Matter Physics, Yi Li Normal University, Yining 835000, China.
Dalton Trans. 2022 Mar 22;51(12):4903-4908. doi: 10.1039/d2dt00295g.
A Ga-enriched ternary alkali-metal sulfide NaGaS has been synthesized by a high temperature solid-state reaction. It crystallizes in the centrosymmetric (no. 61) space group with cell parameters = 13.5260(4) Å, = 11.4979(3) Å, = 29.9592(9) Å, and = 8, and exhibits a three-dimensional (3D) network structure constructed from unique [GaS] 12-membered rings, one-dimensional [GaS] chains, individual [GaS] units and Na ions. The experimental band gap of NaGaS was measured as ∼3.57 eV. Theoretical calculations indicate that the title compound is a direct band gap compound and the band gap is mainly determined by [GaS] units. Meanwhile, statistical analysis shows that the atomic ratio N (N = AA/Ga, where A = alkali-metal, A = alkaline earth-metal) can be used to regulate the connection of [GaS] units from zero-dimensional (0D) isolated groups, one-dimensional (1D) chains, and two-dimensional (2D) layers to 3D frameworks in Ga-containing alkali- and/or alkaline earth-metal chalcogenides. The results enrich the diversity of alkali-metal sulfides and give an insight into the structural regulation of alkali- and/or alkaline earth-metal chalcogenides.
通过高温固态反应合成了一种富镓三元碱金属硫化物NaGaS。它结晶于中心对称（编号61）空间群，晶胞参数a = 13.5260(4) Å，b = 11.4979(3) Å，c = 29.9592(9) Å，Z = 8，并呈现出由独特的[GaS] 12元环、一维[GaS]链、单个[GaS]单元和Na离子构成的三维（3D）网络结构。NaGaS的实验带隙测量值约为3.57 eV。理论计算表明，该标题化合物是一种直接带隙化合物，其带隙主要由[GaS]单元决定。同时，统计分析表明，原子比N（N = AA/Ga，其中A = 碱金属，A = 碱土金属）可用于调控含镓碱金属和/或碱土金属硫族化合物中[GaS]单元从零维（0D）孤立基团、一维（1D）链、二维（2D）层到三维（3D）框架的连接方式。这些结果丰富了碱金属硫化物的多样性，并为碱金属和/或碱土金属硫族化合物的结构调控提供了见解。
