Vast Structural and Polymorphic Varieties of Semiconductors AMM′Q4 (A = K, Rb, Cs, Tl; M = Ga, In; M′ = Ge, Sn; Q = S, Se)
Vast Structural and Polymorphic Varieties of Semiconductors AMM′Q4 (A = K, Rb, Cs, Tl; M = Ga, In; M′ = Ge, Sn; Q = S, Se)
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DOI：
10.1021/acs.chemmater.1c02211
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发表时间：
2021-08-05
影响因子：
8.6
通讯作者：
Kanatzidis, Mercouri G.
中科院分区：
文献类型：
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作者：
Friedrich, Daniel;Hao, Shiqiang;Kanatzidis, Mercouri G.
九种新型硫系半导体AInM'Q(4) （A(+) = K+, Rb+, Cs+, Tl+）M'(4+) = Ge4+, Sn4+；采用固态合成法制备了Q(2-) = S2-, Se2-)，并用单晶x射线衍射技术对其结构进行了表征。这些新相填补了这些四元体系中缺失的环节，并以各种二维层状晶型结晶，而含有大M3+和M'（4+）阳离子的组合也采用扩展的三维（3D）网络结构。AMM’q(4)材料的禁带范围较宽，主要为有色硒化物（1.8 eV < E-g < 2.3 eV）和白色硫化物（2.5 eV < E-g < 3.6 eV）。除铊类似物和立方agassse (4)-cP84外，这些相具有直接带隙。电子能带结构的第一性原理理论计算揭示了对这些材料的结构/性质关系的关键见解。通过讨论结晶、结构考虑和互补密度泛函理论（DFT）计算的动力学和热力学因素，研究了这些四相的明显多态性。
Nine new chalcogenide semiconductors AInM'Q(4) (A(+) = K+, Rb+, Cs+, Tl+; M'(4+) = Ge4+, Sn4+; Q(2-) = S2-, Se2-) have been prepared by solid-state syntheses and structurally characterized by single-crystal X-ray diffraction techniques. These new phases fill in the missing links in these quaternary systems and crystallize in various two-dimensional layered polymorphs, while combinations containing large M3+ and M'(4+) cations also adopt an extended three-dimensional (3D) network structure. The AMM'Q(4) materials exhibit a wide range of band gaps with colored selenides (1.8 eV < E-g < 2.3 eV) and mostly white sulfides (2.5 eV < E-g < 3.6 eV). These phases have direct band gaps except for the thallium analogues and the cubic AGaSnSe(4)-cP84. First-principles theoretical calculations of the electronic band structures reveal critical insight into the structure/property relationships of these materials. The distinct polymorphism of these quaternary phases is studied by discussing kinetic and thermodynamic factors responsible for the crystallization, structural considerations, and complementary density functional theory (DFT) calculations.