Signal Enhanced FTIR Analysis of Alignment in NAFION Thin Films at SiO₂ and Au Interfaces

Spin-cast NAFION samples were prepared on silicon native oxide and gold substrates with film thicknesses ranging from 5 to 250 nm. The influence of NAFION film thickness on the infrared spectrum of the polymer was investigated in substrate overlayer attenuated total reflection (SO-ATR) geometry at incident angles between 60° and 65°. In the grazing angle SO-ATR geometry, the thickness of the film significantly affected the position and absorbance of characteristic peaks in the FTIR spectrum of NAFION. Two major peaks in the NAFION spectrum at 1220 cm^-1 (predominantly v_as(CF₂) and v_as(SO₃^-)) and 1150 cm^-1 (predominantly v_as(CF₂)) appeared to systematically blueshift to 1256 and 1170 cm^-1, respectively, as the thickness of the film decreased from 250 to 5 nm. The changes in the NAFION thin film FTIR spectrum can be attributed to two factors; (1) ordering of NAFION at the interface during spin coating and film formation and (2) the increase in the p-polarization character of the infrared evanescent wave as the polymer film became thinner between the internal reflection element and the film substrate overlayer. The increase in p-polarization resulted in an increase in characteristic peak absorbances of dipoles aligned normal to the substrate due to the overlayer enhancement of the electric field with NAFION films on Si or Au film substrates. These results show that the specific thin film sampling geometry, especially in internal reflection experiments, must be considered to rationally quantify changes in NAFION thin film infrared spectra.