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The electronic structures of Alq₃/Si(111) and Alq₃/LiBr/Si(111) interfaces are presented in this report. The studies were carried out in situ in ultrahigh vacuum by ultraviolet photoelectron spectroscopy. Alq₃ and LiBr layers were vapour deposited onto a single crystal of n-type Si(111). The energy level diagrams were prepared for the structures. The formation of the LiBr interfacial layer results in a decrease of the energy barrier at the interface.