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Pentacene films deposited with molecular beam deposition have been fabricated and characterized with respect to structure and morphology using x‐ray diffraction and scanning electron microscopy. Metal‐insulator semiconductor field‐effect transistor devices based on such films were used to study their transport properties. A maximum field‐effect mobility of 0.038 cm-2 V-1 s-1 is reported for devices incorporating pentacene films deposited at room temperature. The structural characterization revealed the coexistence of two phases: the thermodynamically stable single‐crystal phase and the kinetically favored, metastable thin‐film phase. Such mixed phase films were produced when low deposition rates were used in combination with a substrate temperature of 55 °C. Mixed phase films had transport properties inferior to films consisting solely of one phase, while amorphous films deposited at low surface mobility conditions had extremely low conductivity. Use of prepurified pentacene as source material resulted in an order of magnitude lower free‐carrier concentration in the pentacene film as compared to films made with as‐received pentacene. © 1996 American Institute of Physics.