The formation of thin polyimide films from vapor phase deposited 4,4 Oxydianiline (ODA) and Pyromellitic dianhydride (PMDA) was studied by X‐ray photoelectron spectroscopy and vibrational spectroscopies. Codeposition of ODA and PMDA onto polycrystalline copper substrates at room temperature, follyowed by heating in vacuum, led to polymerization and the formation of thermall stable (T≤723 K) polyimide films. Films with thicknesses ranging from ultra‐thin (12–30 Å) to several hundred nanometers thick were prepared by this method. Adhesion of the polymer to the surface involve chemical bonding to fragments of PMDA and ODA initially chemisorbed on the clean metal surface.

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