Bulk and Surface Contributions to Ionisation Potentials of Metal Oxides
Bulk and Surface Contributions to Ionisation Potentials of Metal Oxides
复制标题
金属氧化物的体积和表面对电离势的贡献
DOI：
10.1002/ange.202308411
复制
发表时间：
2023
影响因子：
--
通讯作者：
Zhang X
中科院分区：
文献类型：
--
作者：
Zhang X
确定固体材料中的绝对带边位置对于优化其在包括电子器件和电子器件在内的广泛应用中的性能至关重要。然而，获得绝对能量是具有挑战性的，如在CeO2中所看到的，其中实验测量显示电离电位（IP）的实质性差异。在这里，我们结合了几种理论方法，从经典的静电学量子力学，阐明了金属氧化物的IP的体积和表面的贡献。我们已经确定了一个理论的批量贡献的IP化学计量CeO2的只有5.38 eV，而表面取向的结果在固有的IP变化范围从4.2 eV到8.2 eV。 在TiO 2、ZrO 2和HfO 2中也发现了高度可调谐的IP，其中表面极化在长程能级移动中起着关键作用。我们的分析，除了合理化观察到的范围内的实验结果，氧化物能带结构的实验和计算研究的未来解释提供了坚实的基础。
Determining the absolute band edge positions in solid materials is crucial for optimising their performance in wide‐ranging applications including photocatalysis and electronic devices. However, obtaining absolute energies is challenging, as seen in CeO2, where experimental measurements show substantial discrepancies in the ionisation potential (IP). Here, we have combined several theoretical approaches, from classical electrostatics to quantum mechanics, to elucidate the bulk and surface contributions to the IP of metal oxides. We have determined a theoretical bulk contribution to the IP of stoichiometric CeO2of only 5.38 eV, while surface orientation results in intrinsic IP variations ranging from 4.2 eV to 8.2 eV. Highly tuneable IPs were also found in TiO2, ZrO2, and HfO2, in which surface polarisation plays a pivotal role in long‐range energy level shifting. Our analysis, in addition to rationalising the observed range of experimental results, provides a firm basis for future interpretations of experimental and computational studies of oxide band structures.