To determine the molecular orientation of rubbed and unrubbed poly[4,4′-oxydiphenylene- pyromellitimide] (PMDA-ODA) films, we have measured the infrared (IR) absorption spectra of PMDA-ODA films on Si substrates as a function of the incident angle. The molecular orientation was determined by fitting the incident angle dependence and the IR dichroic ratio with the theoretical curves. The IR absorption was calculated by a transfer matrix method to take account of the multiple reflection and refraction at the interfaces. The vibrational response of the polyimide film in the IR region was represented by a Lorentz oscillator model. We found that the molecules in a spin-coated polyimide film are oriented parallel to the substrate surface with a standard deviation of 6.5°. For a rubbed film, the polymer chains are oriented along the rubbing direction and are tilted up on average by 8.5° from the surface plane. We observed a blueshift of the C=O asymmetric stretching band at oblique incidence. The blueshift is explained by anomalous dispersion of the dielectric constant of the polyimide film, and is reproduced by our calculation.
%e have made in situ measurements of attenuated total reflection {ATR) and Raman scattering from a layered structure consisting of a glass prism, a thin silver film, an MgF2 spacer, and a liquid mixture whose refractive index is matched to that of MgF2. %'hen the incident angle of the laser beam coincides with the ATR angle, the surface-plasmon polariton (SPP) of the silver film is excited resonantly and the Raman scattering intensity of the liquid shows a maximum. The same effect is observed at the frequency of the Stokes scattered light. By measuring the decrease of the Raman scattering intensity of the liquid with increase of the thickness of the MgF2 spacer layer, we have determined the decay length (lq) of the SPP field into the liquid. The measured value of lq --1539 A agrees with the calculated value, 1534 A.
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