Influence of water addition on the structure of plasma-deposited allyl alcohol polymer films

One hundred and fifty nanometre thick polymer films made of allyl alcohol and H2O addition were deposited onto aluminium substrates using the radio-frequency (rf) pulsed plasma mode. The structure–property relationships of polymer films were studied in dependence on the precursor ratio allyl alcohol-water. Both the regularity of structure and composition of such thin films in comparison to chemically polymerized allyl alcohol were investigated using by bulk-sensitive Fourier transform infrared spectroscopy (FTIR) in the spectral range of 4000–500 cm−1 as well as surface-sensitive X-ray photoelectron spectroscopy (XPS). The intention of this work was to increase the yield in OH groups by addition of water to the allyl alcohol precursor. For an unambiguous identification of the functionality of the deposited films, the OH groups were labelled with trifluoroacetic anhydride and subsequently measured by XPS as well as quantitatively by FTIR. As expected, the O/C ratio grew with increasing water admixture by oxidation of both the plasma polymerized allyl alcohol layer to preferably aldehyde and/or carboxylic acid groups. In contrary, the concentration of OH groups in the deposited polymer film decreases dramatically with increasing admixture of water to the allyl alcohol plasma. It has been shown that the additional water has produced preferably higher oxidized C-Ox species with two or three C–O bonds. This fits also very well with the observation that almost no deuterium is introduced into the surface of plasma polymer if D2O was added instead of H2O.