We have adapted the microscopic theory of nucleation for the epitaxial growth of inorganic materials to the nucleation of organic small molecules on an inert substrate like the gate dielectric of an organic thin-film transistor. The parameters required to explore the model were calculated with the standard MM3 force field and also include experimentally determined vapor pressure data, as well as film growth data. Sufficient agreement is found between the experimentally determined equilibrium

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... stal shape and heats of sublimation on the one hand and the calculated parameters on the other hand. The growth of pentacene, tetracene, and perylene on inert substrates has been studied in terms of this theory, especially focusing on the two-dimensional ͑2D͒ to 3D nucleation transition. It is demonstrated that 3D nucleation leads to ill-connected grains, while 2D nucleated grains form continuous films suitable for charge transport. The analysis of this transition allows for the experimental determination of the molecule-substrate interactions for a given molecule on a given surface. It was found that the deposition conditions for 2D growth shift to less favorable substrate temperatures and deposition rates as the difference between interlayer interactions and molecule-substrate interactions increase and the intralayer interactions decrease. Moreover, those interactions affect the nucleation rate and therefore the ultimate 2D grain size that can be obtained.