We examined the electronic structure of the interfaces formed between pentacene and various metals: Au, Ag, and Ca, using photoemission spectroscopy. For all interfaces, we observed the formation of an interface dipole that varied linearly with the measured metal work function. We observed that the behavior of the interfaces of Ca with pentacene was symmetric with respect to whether Ca was deposited on pentacene or vice versa. On the other hand, the interfaces of Au and Ag with pentacene were asymmetric. For both Au and Ag we saw indications that upon metal deposition, metal penetration resulted in a metallic surface with a work function significantly different from that of pure Au or Ag. This also resulted in different interface dipoles for these interfaces.

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