Annealed, well ordered Bi(001) films have been used as substrates for the growth of pentacene (Pn). It has been determined using low-energy electron microscope (LEEM) that Pn nucleates on Bi(001) into a highly ordered, crystalline layer, with pentacene molecules "standing up" on the Bi surface. Moreover, the Pn layer is aligned with the bi(001) surface having a "point-on-line" commensurate relation with the substrate. The Pn/Bi(001) films was determined to crystallize in the bulk-like structure directly from the first Pn layer, while formation of the thin-film phase reported for the Pn growth on SiO(2) and other inert substrates is not observed.
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