Measuring and Controlling Energy Level Alignment at Hybrid Organic/Inorganic Semiconductor Interfaces

Abstract

In this dissertation, I present the results of my research regarding hybrid semiconductor interfaces between organic and inorganic semiconductors. Using photoemission spectroscopy, I elucidate the important role of defect-induced electronic states within the inorganic semiconductor phase. These states significantly affect both the energy level alignment and the charge carrier dynamics at the hybrid interface. I demonstrate that the behavior of these hybrid semiconductor interfaces is complex and not well characterized by current models for organic semiconductor interfaces. Specifically, I show that hybrid interfaces host unique electronic phenomena that depend sensitively on the surface structure of the inorganic semiconductor. I also demonstrate new applications of photoemission spectroscopies that enable the direct analysis of important properties of inorganic semiconductors, including charge carrier behavior near hybrid interfaces and the electronic character of defect-induced energy levels. The research presented here focuses on two different n-type inorganic semiconductors, tin disulfide (SnS₂) and zinc oxide (ZnO). SnS₂ is a layered transition metal dichalcogenide that presents an atomically flat and inert surface, ideal for sensitively probing electronic interactions at the hybrid interface. To probe the electronic structure of the SnS₂ surface, I used a variety of organic molecules, including copper phthalocyanine, vanadyl naphthalocyanine, chloro-boron subphthalocyanine, and C₆₀. ZnO has a complex surface structure that can be modified by simple experimental procedures; it was therefore used as a tunable semiconductor substrate where the effects of altered electronic structure can be observed. By carefully studying the origin of hybrid interfacial interactions, these research projects provide a first step in explicitly elucidating the fundamental mechanisms that determine the electronic properties of hybrid interfaces.