Liu Chang, Mukta Musiha Mahfuza, Kang Byungkyun, Zhu Qiang
Department of Physics and Astronomy, University of Nevada, Las Vegas, Nevada 89154, United States.
International Center for Computational Methods & Software, College of Physics, Jilin University, Changchun, Jilin 130012, China.
ACS Omega. 2025 Jan 6;10(1):1635-1642. doi: 10.1021/acsomega.4c09513. eCollection 2025 Jan 14.
Electrides are ionic crystals, with electrons acting as anions occupying well-defined lattice sites. These exotic materials have attracted considerable attention in recent years for potential applications in catalysis, rechargeable batteries, and display technology. Among this class of materials, electride semiconductors can further expand the horizon of potential applications due to the presence of a band gap. However, there are only limited reports on semiconducting electrides, hindering the understanding of their physical and chemical properties. In recent work, we initiated an approach to derive potential electrides via selective removal of symmetric Wyckoff sites of anions from existing complex minerals. Herein, we present a follow-up effort to design semiconducting electrides from parental complex sodalites. Among four candidate compounds, we found that a cubic CaAlO structure with the -43 space group symmetry exhibits perfect electron localization at the sodalite cages, with a narrow electronic band gap of 1.8 eV, making it suitable for use in photocatalysis. Analysis of the electronic structures reveals that a lower electronegativity of the surrounding cations drives greater electron localization and promotes the formation of an electride band near the Fermi level. Our work proposes an alternative approach for designing new semiconducting electrides under ambient conditions and offers guidelines for further experimental exploration.
电子化合物是离子晶体，其中电子作为阴离子占据明确的晶格位置。近年来，这些奇特的材料因其在催化、可充电电池和显示技术方面的潜在应用而备受关注。在这类材料中，电子化合物半导体由于存在带隙，能够进一步拓展潜在应用的范围。然而，关于半导体电子化合物的报道有限，这阻碍了对其物理和化学性质的理解。在最近的工作中，我们开创了一种通过从现有复杂矿物中选择性去除阴离子的对称韦科夫位置来推导潜在电子化合物的方法。在此，我们展示了一项后续工作，即从母体复杂方钠石设计半导体电子化合物。在四种候选化合物中，我们发现具有-43空间群对称性的立方CaAlO结构在方钠石笼中表现出完美的电子定位，其电子带隙窄至1.8 eV，适用于光催化。对电子结构的分析表明，周围阳离子较低的电负性会导致更大程度的电子定位，并促进费米能级附近电子化合物能带的形成。我们的工作提出了一种在环境条件下设计新型半导体电子化合物的替代方法，并为进一步的实验探索提供了指导。
