The electronic properties of hybrid organic–inorganic semiconductor interfaces depend strongly on the alignment of the electronic carrier levels in the organic/inorganic components. In the present work, we address this energy level alignment from first principles theory for two paradigmatic organic–inorganic semiconductor interfaces, the singlet fission materials tetracene and pentacene on H/Si(111), using all-electron density functional theory calculations with a hybrid exchange–correlation functional. For isolated tetracene on H/Si(111), a type I-like heterojunction (lowest-energy electron and hole states on Si) is found. For isolated pentacene, the molecular and semiconductor valence band edges are degenerate. For monolayer films, we show how to construct supercell geometries with up to 1192 atoms, which minimize the strain between the inorganic surface and an organic monolayer film. Based on these models, we predict the formation of type II heterojunctions (electron states o...

中文翻译：

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并五苯和并四苯分子以及H / Si（111）上的薄膜：基于杂化密度泛函理论的能级对准

杂化有机-无机半导体界面的电子特性在很大程度上取决于有机/无机成分中电子载流子能级的排列。在当前的工作中，我们使用全电子密度泛函理论计算并结合了杂化，从第一原理理论针对两个范式有机-无机半导体界面（单重裂变材料并四苯和并五苯）在H / Si（111）上解决了能级对准问题。交换相关功能。对于在H / Si（111）上分离出的并四苯，发现了I型异质结（Si上的最低能级电子和空穴态）。对于孤立的并五苯，分子和半导体价带边缘是简并的。对于单层膜，我们展示了如何构造具有最多1192个原子的超晶胞几何体，这样可以最大程度地减少无机表面和有机单层膜之间的应变。基于这些模型，我们预测II型异质结的形成（电子态为...