| Energy level alignment is an important factor in efficient charge transfer at an interface between two semiconductors. This topic is explored in model systems that are relevant to quantum dot-sensitized solar cells, inorganic semiconductor nanoparticles adsorbed on single crystal wide band gap oxide substrates, using ultraviolet photoelectron spectroscopy.Cadmium selenide quantum dots are assembled on a ZnO (10 1¯ 0) surface using 3-mercaptopropionic acid linkers. The valence band maximum of the CdSe quantum dots is found to be located at 1.1 +/- 0.1 eV above the valence band maximum of ZnO, nearly independent of the size of the quantum dots (2.1-4.2 nm). This finding suggests that, upon adsorption, there is strong electronic interaction between CdSe quantum dots and the ZnO surface. As a result, varying the quantum dot size mainly tunes the alignment of the conduction band minimum of CdSe with respect to that of the ZnO surface.Sub-monolayer films of PbSe quantum dots are prepared on single crystal substrates, ZnO (10 1 0 ) and TiO2 (110), and exposed to ligand solutions, either hydrazine or 1,2-ethanedithiol (EDT) in acetonitrile. Interfacial energy alignment is measured as a function of quantum dot size, substrate and ligand treatment. The affect of the ligand treatments on the energy alignment is substrate-dependent. The valence band maximum of the dots is size-independent on ZnO due to strong electronic interactions with the substrate in particular, EDT-treated films show significant enhancement of quantum dot valence band intensity due to electronic coupling with the ZnO surface. In contrast, the quantum dot valence band maximum is size-dependent and shows a smaller shift between ligand treatments for films on TiO2, suggesting weaker quantum dot-substrate interactions. In most cases the measured alignment predicts that electron injection from a photoexcited PbSe quantum dot to either ZnO or TiO2 will necessitate the involvement of higher-lying levels above the first excitonic transition. |
