An XPS study of argon ion beam and oxygen RIE modified BPDA-PDA polyimide as related to adhesion

Modification of polymer surfaces by changing the chemical structure, surface energy, and bonding characteristics has considerable technological importance in the area of adhesion. Reactive ion etching (RIE) and ion beam (IB) bombardment were employed to modify the surfaces of fully imidized 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride-p-diaminophenyl (BPDA-PDA)-based polyimide (PI) films. These modification techniques affect only a shallow surface region, approximately 10-20 nm, and the bulk properties of the polymer are unaffected. The angle-resolved X-ray photoelectron spectroscopy (XPS) technique was used to characterize the PI surfaces modified by argon IB bombardment or oxygen RIE treatment. On the argon ion-bombarded surfaces, the XPS spectra indicate that the carbonyl and imide groups are decreased. Oxygen RIE treatment resulted in an increase in the atomic concentration of oxygen. To understand the surface aging effect, the freshly modified PI surfaces were exposed to laboratory air for 1 and 2 days. The changes in composition as a function of the depth of the modified surface region right after treatment and after aging were determined by the angle-resolved XPS technique (ARXPS). Contact angle measurements were used to determine the polar and dispersion components, the sum of which is the surface free energy. The polar component of the surface free energy shows the greatest change, with an increase of 8.0-9.4 times for both the oxygen RIE and ion beam treatments as compared with the as-cured PI surface. Aging of these modified surfaces resulted in a decrease of surface free energy as compared with the just-modified surfaces. In the case of oxygen RIE treatment, the dispersion component of the surface free energy showed little or no change from the as-cured sample. Adhesion of chromium/copper/chromium (Cr/Cu/Cr) films on PI was determined by peel strength measurements. Significant increases in peel strength, by a factor of 10-80, were shown for the modified surfaces. A good correlation between the peel strength and the experimentally determined polar component of surface energy was shown.