X-RAY-SCATTERING STUDIES OF THIN-FILMS OF PHOTOSENSITIVE POLYIMIDES

Using the techniques of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS), the morphology of polyimide thin films thermally imidized from several photosensitive polyimide (PSPI) precursors has been investigated and compared with that of the thin films prepared from the corresponding poly(amic acid) precursors: poly(4,4'-oxydiphenylene pyromellitimide) (PMDA-ODA), poly(p-phenylene biphenyltetracarboximide) (BPDA-PDA) and poly(4,4'-oxydiphenylene benzophenonetetracarboximide) (BTDA-ODA). The WAXD results indicate that regardless of the precursor origin, the BTDA-ODA polyimide is amorphous, whereas the other polyimides exhibit a molecular order. For both the PMDA-ODA and the BPDA-PDA, the molecular order is relatively higher in the films prepared from the PSPI precursors than in those from the corresponding poly(amic acid)s, indicating that during thermal imidization, the photosensitive groups play an important role to improve the mobility of the polymer chains, which may be critically needed to make better molecular packing, in spite of their bulkiness having the potential to hinder the molecular packing. In Lorentz-corrected SAXS analyses, a long period (130-156 angstrom mean periodicity) was observed for all the polyimides except the PMDA-ODA. In particular, the microstructure in the BPDA-PDA could be described by an extended chain-based two-phase (ordered and less ordered phase) model with diffuse boundaries because of its high chain rigidity. In addition, the Guinier SAXS analyses indicate the presence of voids in all the polyimide films, regardless of the precursor origin. The size of voids was 251-349 angstrom in radius, depending upon the type of polyimide.