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Charge injection at the interface between metallic electrodes and organic semiconductors plays a crucial role in the performance of organic (opto-)electronic devices. This article discusses the current understanding of the formation of the metal–organic contact and the parameters which control the injection current. Organic semiconductors differ significantly from their inorganic counterparts, primarily because they are amorphous van der Waals solids. As a result the electronic states are highly localized, and charge transport is by site-to-site hopping. Organics can also form clean interfaces with many metals, free of interface states in the gap. Nevertheless, there is generally found to be a significant vacuum level offset, the origins of which are not yet fully understood. Organic semiconductors are frequently free of donor and acceptor dopants, and as a result the depletion depth is larger than the organic layer thickness. Thus the Fermi level in the organic and the charge injection barriers depend most directly on the interface offset. The charge injection process is described as thermally assisted tunneling from the delocalized states of the metal into the localized states of the semiconductor, whose energy includes contributions from the mean barrier height, the image potential, the energetic disorder, and the applied electric field. There is no completely satisfactory analytic theory for the field and temperature dependence of the injection current, which, for well characterized interfaces, exhibits behavior relating to both thermionic emission and field-induced tunneling. © 2003 American Vacuum Society.