On confocal Raman spectroscopy of semicrystalline polymers: the effect of optical scattering

A series of semicrystalline polymers has been prepared through morphological control. Each of these has an identical refractive index but a different, well-defined, scattering behavior. From existing geometrical optical theories of confocal Raman spectroscopy, these materials should behave identically. Initially, the extent of scattering in each system was assessed quantitatively, from the near-infrared through the visible wavelength range, by UV/visible spectroscopy. The effect of optical scattering on the variation of intensity of the Raman scattered radiation with subsurface position was then examined in all four materials; the effect of surface roughness was also considered in the highest clarity system. Where surface effects are removed through careful sample preparation and the materials are interrogated using identical optical systems to mitigate against the impact of refractive index mismatch and other optical effects, the Raman response is strongly affected by the scattering characteristics of each material. A simple empirical relationship has been determined that adequately described all our specimens.