Previous studies have established that pentacene films deposited on silicon oxide consist of a substrate-induced "thin-film" phase, with the bulk phase of pentacene detected in thicker films only. We show that the bulk phase nucleates as early as the first monolayer, and continues to nucleate as film growth progresses, shadowing the growth of the thin-film phase. Moreover, we find that the transition between the "thin-film" and the bulk phase is not a continuous one, as observed in heteroepitaxial systems, but rather the two phases nucleate and grow independently.

Grazing incidence x-ray diffraction, x-ray reflectivity and atomic force microscopy have been performed to study the structure of pentacene thin films on oxidized Si substrates from submonolayer to multilayer coverages. The volume of the unit cell in the thin film phase is almost identical to that of the bulk phase, thus the molecular packing efficiency is effectively the same in both phases. The structure forming from the first monolayer remains the same for films at least 190Å thick. The in-plane structure of the submonolayer islands also remains unchanged within a substrate temperature range of 0<Tsub<45°C while the island size changes by more than a factor of 4.

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The x-ray standing wave (XSW) technique is used to measure the isotopic mass dependence of the lattice constants of Si and Ge. Backreflection allows substrates of moderate crystallinity to be used while high order reflection yields high accuracy. The XSW, generated by the substrate, serves as a reference for the lattice planes of an epilayer of different isotopic composition. Employing XSW and photoemission, the position of the surface planes is determined from which the lattice constant difference Deltaa is calculated. Scaled to DeltaM = 1 amu we find (Deltaa/a) of -0.36x10(-5) and -0.88x10(-5) for Ge and -1.8x10(-5) and -3.0x10(-5) for Si at 300 and 30 K, respectively.

Real-time synchrotron x-ray scattering in the anti-Bragg configuration was used to monitor the dynamics of pentacene film growth on inert substrates. A distributed-growth model, according to which pentacene molecules adsorbed on the nth layer can either nucleate and contribute to the growth of the ͑n +1͒th layer or transfer downward and contribute to the growth of the nth layer, gave a good description of the data. For molecules adsorbed on the first and second layers, the probability of downward transfer was found to be dependent on the substrate, and independent of temperature within the range from 25 to 60°C. For films grown on SiO 2 , an Ehrlich-Schwoebel barrier of the order of 70 meV dominated downward transfer of pentacene molecules in layers away from the substrate. For films grown on an alkylated self-assembled monolayer, significant desorption of pentacene molecules from the substrate at elevated temperatures forced the growth mode toward the three-dimensional limit.