Raman Scattering from Confined Liquid Films in the Sub-Nanometre Regime

Abstract

Raman spectroscopy has been used to study the confinement of octamethylcyclotetrasiloxane (OMCTS) and n-hexadecane between a prism and a lens at contact pressures of 40 MPa. Both lens and prism surfaces were optically smooth but not atomically flat. A total internal reflection geometry was employed to provide the sensitivity needed to detect liquid films of sub-nanometre thickness. For both liquids, the thickness of the residual film under load corresponded to less than a monolayer of liquid. The Raman spectra of the confined liquids were identical or very similar to that of the bulk liquid. Similar results were obtained for hexadecane confined between two surfaces coated with a Langmuir-Blodgett monolayer of a fatty acid. We infer that the liquids do not form a boundary layer under these conditions but rather they are squeezed out of the contact under the modest pressure applied. We ascribe the residual signal to liquid trapped in scratches or other defects on the surfaces.