Ultraviolet photoemission spectroscopy (UPS) was employed to investigate the electronic structure upon deposition of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) on differently treated n-GaAs(100) surfaces. Interface dipoles are found to form according to the electron affinities (EA) of the substrates and PTCDA films at the interfaces and, consequently, the vacuum level alignment rule does not hold. The results demonstrate that the energy offset between the conduction band minimum of n-doped inorganic semiconductors and the lowest unoccupied molecular orbital of organic molecular films at the interfaces can be obtained using UPS by systematically varying the EA of substrates with a known band gap.

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