Chemically modified elastomer surfaces are important
to many applications,
including microfluidics and soft sensors. Sensitive characterization
of the interfacial chemistry of soft materials has been a persistent
challenge, given their structural and chemical complexity. This article
reports a method to probe local chemical states of elastomer surfaces
that leverages the interference effects observed in micro-Raman spectroscopy.
Unexpectedly, systematic variations of Raman scattering intensity
were observed across a chemical wettability gradient grafted to the
surface of a poly(dimethylsiloxane) (PDMS) film. Specifically, hydrophobic
surface regions with a high graft density of long-chain hydrocarbon
molecules showed suppressed Raman intensity. An optical interference
model that accounts for molecular filling and swelling of an interfacial
glassy layer during chemical modifications of the PDMS surface quantitatively
reproduces experimental observations. This work establishes the spectroscopic
signatures of interfacial chemical modifications on elastomer surfaces
and enables a noncontact optical probe of local chemical states at
the micro- and nanoscale compatible with the complex interfaces of
soft materials.