Li Yawen, Yang Jingxiu, Zhao Ruoting, Zhang Yilin, Wang Xinjiang, He Xin, Fu Yuhao, Zhang Lijun
State Key Laboratory of Integrated Optoelectronics, Key Laboratory of Automobile Materials of MOE, International Center of Computational Method and Software and College of Materials Science and Engineering, Jilin University, Changchun 130012, China.
Key Laboratory for Comprehensive Energy Saving of Cold Regions Architecture of Ministry of Education and School of Materials Science and Engineering, Jilin Jianzhu University, Changchun 130118, China.
J Am Chem Soc. 2022 Sep 14;144(36):16656-16666. doi: 10.1021/jacs.2c07434. Epub 2022 Aug 29.
Organic-inorganic hybrid semiconductors, of which organometal halide perovskites are representative examples, have drawn significant research interest as promising candidates for next-generation optoelectronic applications. This interest is mainly ascribed to the emergent optoelectronic properties of the hybrid semiconductors that are distinct from those of their purely inorganic and organic counterparts as well as different material fabrication strategies and the other material (e.g., mechanical) properties that combine the advantages of both. Herein, we present a high-throughput first-principles material screening study of the hybrid heterostructured semiconductors (HHSs) that differ entirely from organometal halide perovskite hybrid ion-substituting semiconductors. HHSs crystallize as superlattice structures composed of inorganic tetrahedrally coordinated semiconductor sublayers and organic sublayers made of bidentate chain-like molecules. By changing the composition (e.g., IV, III-V, II-VI, I-III-VI semiconductor) and polymorph (e.g., wurtzite and zinc-blende) of the inorganic components, the type of organic molecules (e.g., ethylenediamine, ethylene glycol, and ethanedithiol), and the thickness of the composing layers across 234 candidate HHSs, we investigated their thermodynamic, electronic structure, and optoelectronic properties. Thermodynamic stability analysis indicates the existence of 96 stable HHSs beyond the ZnTe/ZnSe-based ones synthesized experimentally. The electronic structure and optoelectronic properties of HHSs can be modulated over a wide range by manipulating their structural variants. A machine learning approach was further applied to the high-throughput calculated data to identify the critical descriptors determining thermodynamic stability and electronic band gap. Our results indicate promising prospects and provide valuable guidance for the rational design of organic-inorganic hybrid heterostructured semiconductors for potential optoelectronic applications.
有机-无机杂化半导体，其中有机金属卤化物钙钛矿是典型代表，作为下一代光电子应用的有前途的候选材料，已引起了重大的研究兴趣。这种兴趣主要归因于杂化半导体所具有的新兴光电子特性，这些特性不同于其纯无机和有机对应物的特性，以及不同的材料制造策略和结合了两者优点的其他材料（例如机械）特性。在此，我们展示了一种对杂化异质结构半导体（HHSs）的高通量第一性原理材料筛选研究，其与有机金属卤化物钙钛矿杂化离子取代半导体完全不同。HHSs结晶为超晶格结构，由无机四面体配位半导体子层和由双齿链状分子构成的有机子层组成。通过改变无机成分的组成（例如IV、III-V、II-VI、I-III-VI半导体）和多晶型（例如纤锌矿和闪锌矿）、有机分子的类型（例如乙二胺、乙二醇和乙二硫醇）以及跨越234种候选HHSs的组成层的厚度，我们研究了它们的热力学、电子结构和光电子特性。热力学稳定性分析表明，除了实验合成的基于ZnTe/ZnSe的HHSs之外，还存在96种稳定的HHSs。通过操纵其结构变体，可以在很宽的范围内调节HHSs的电子结构和光电子特性。一种机器学习方法被进一步应用于高通量计算数据，以识别决定热力学稳定性和电子带隙的关键描述符。我们的结果表明了有前景的前景，并为合理设计用于潜在光电子应用的有机-无机杂化异质结构半导体提供了有价值的指导。
