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Surface modification techniques such as wet chemical etching, oxidizing flames, and plasma treatments (inert ion sputtering and reactive ion etching) have been used to change the surface chemistry of polymers and improve adhesion. With an increase in the use of polyimides for microelectronic applications, the technique of ion sputtering to enhance polymer-to-metal adhesion is receiving increased attention. For this study, the argon-ion bombardment surfaces of pyromellitic dianhydride and oxydianiline (PMDA–ODA) and biphenyl tetracarboxylic dianhydride and phenylene diamine (BPDA–PDA) polyimide films were characterized with x-ray photoelectron spectroscopy (XPS) as a function of ion dose. Graphite and high-density polyethylene were also examined by XPS for comparison of C 1s peak width and binding-energy assignments. Results indicate that at low ion doses the surface of the polyimide does not change chemically, although adsorbed species are eliminated. At higher doses the chemical composition is altered and is dramatically reflected in the C 1s spectra where graphiticlike structures become evident and the prominent carbonyl peak is reduced significantly. Both polyimides demonstrate similar chemical changes after heavy ion bombardment. Atomic composition of PMDA–ODA and BPDA–PDA polymers are almost identical after heavy ion bombardment.

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The chemistry of the Al polyimide interface is examined by x-ray photoelectron spectroscopy sputter profiling. Al deposited on polyimide films without an in situ Ar backsputter shows a clearly defined 50-Å Al2O3 layer just prior to the polyimide. This layer is identified by the O/Al atom ratio at 1.5, and the binding energy of the Al 2p transition. There is a clear separation of the Al/Al2O3/polyimide layers in the sputter profiles. Deposition of Al on polyimide surfaces after Argon backsputtering produces a diffuse Al/polyimide interface with no Al2O3 present. There is evidence in the Al 2p spectra for Al–C or Al–O–C type bonds, while the C 1s spectrum clearly has a metal carbide component. Increased adhesion of Al to polyimide surfaces with Ar backsputtering may be due to the differences in chemistry observed in these two instances.