Zeitz Sabine, Kuznetsova Yulia, Fässler Thomas F
Chair of Inorganic Chemistry with Focus on Novel Materials, School of Natural Science, Technical University of Munich, Lichtenbergstraße 4, D-85747 Garching, Germany.
Molecules. 2024 Aug 28;29(17):4087. doi: 10.3390/molecules29174087.
Due to the high impact of semiconductors with respect to many applications for electronics and energy transformation, the search for new compounds and a deep understanding of the structure-property relationship in such materials has a high priority. Electron-precise Zintl compounds of the composition ( = Li - Cs, = Al - In, = P, As) have been reported for 22 possible element combinations and show a large variety of different crystal structures comprising zero-, one-, two- and three-dimensional polyanionic substructures. From Li to Cs, the compounds systematically lower the complexity of the anionic structure. For an insight into possible crystal-structure band-structure relations for all compounds (experimentally known or predicted), their band structures, density of states and crystal orbital Hamilton populations were calculated on a basis of DFT/PBE0 and SVP/TZVP basis sets. All but three (NaAlP, NaGaP and NaAlAs) compounds show direct or pseudo-direct band gaps. Indirect band gaps seem to be linked to one specific structure type, but only for Al and Ga compounds. Arsenides show smaller band gaps than phosphides due to weaker -As bonds. The bonding situation was confirmed by a Mullikan analysis, and most states close to the Fermi level were assigned to non-bonding orbitals.
由于半导体在电子和能量转换的许多应用中具有重大影响，寻找新化合物并深入了解此类材料的结构-性能关系具有高度优先性。已经报道了组成式为（=Li - Cs，=Al - In，=P，As）的电子精确型津特耳化合物的22种可能元素组合，它们呈现出包含零维、一维、二维和三维聚阴离子子结构的多种不同晶体结构。从Li到Cs，这些化合物系统地降低了阴离子结构的复杂性。为了深入了解所有化合物（实验已知或预测）可能的晶体结构与能带结构的关系，基于DFT/PBE0和SVP/TZVP基组计算了它们的能带结构、态密度和晶体轨道哈密顿布居。除了三种化合物（NaAlP、NaGaP和NaAlAs）外，所有化合物都显示出直接或准直接带隙。间接带隙似乎与一种特定的结构类型有关，但仅适用于Al和Ga化合物。由于As键较弱，砷化物的带隙比磷化物小。通过穆利肯分析证实了键合情况，并且大多数接近费米能级的态被归为非键轨道。
