We present the results of investigations aimed at understanding the mechanisms by which small, mutually immiscible organic molecules self-assemble into domains during phase separation from liquid solutions in the presence of a solid substrate. As an example system, we investigated molecular mixtures of tetranitro zinc-phthalocyanine (tn-ZnPc), an electron donor, and [6,6]-phenyl-C-butyric acid methyl ester (PCBM), an electron acceptor, in chloroform solution, deposited onto native oxide-covered Si(111) substrates. We found qualitatively different behavior in the formation of domains of the two types of molecules, seemingly because of a large difference in their solubilities in the solvent.
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