Infrared reflection spectroscopy of thin films on highly oriented pyrolytic graphite

The properties of highly oriented pyrolytic graphite (HOPG) as a substrate for external reflection infrared spectroscopy in the mid-infrared region were investigated. Clean HOPG substrates, physisorbed hydrocarbon multilayers, and chemisorbed monolayers of p-substituted aryl radicals on HOPG were used as samples, and the experimental spectra were compared and complemented with the results of spectral simulations. From reflectivity measurements of clean HOPG surfaces with polarized light as a function of the light incidence angle and the frequency, the anisotropic optical constants n (refractive index) and k (absorption index) were determined for in-plane and out-of-plane directions with respect to the graphite basal plane. These constants express the semimetallic properties of HOPG, indicated by an intermediate reflectivity between a typical metal and a dielectric substrate and by asymmetric, distorted peak shapes in adsorbate film spectra, which represent a transition state between symmetrical, positive absorptions on metals and inverted, negative peaks on dielectric substrates. Regarding spectral sensitivity and surface selection rules, HOPG behaves much like a metal and is therefore an equally suitable substrate for external reflection infrared (IR) measurements.