Ellipsometric Determination of the Spectra of Adsorbed Molecules

This paper presents a detailed analysis of the application of ellipsometry to obtaining the optical spectra (principally infrared (i.r.)) of molecules adsorbed on reflecting surfaces. Both external and total internal reflections are considered and the conditions for optimum sensitivity examined. A new empirical quantity, the relative complex optical density, is defined which exhibits thin film properties well, particularly in the case of multiple reflection measurements. An explicit expression is derived for this density function (relating it to the optical constants of the media and other system parameters), which is both reasonably simple and correct to second order terms in the film thickness. It is shown that for thin films, no higher order terms need be included, but that in general the second order term must be retained. Various limiting cases are examined to gain insight into the optical behavior of thin films, and to the same end, model calculations performed for CCl4 physically adsorbed on Ag, Ni, Sb, and Ge. In relation to conventional reflection spectroscopy, ellipsometric spectroscopy is shown to have three major advantages: (1) in general, higher sensitivity to adsorbate properties; (2) very much lower sensitivity to absorption of radiation by the adjacent gas phase; (3) more information, permitting the optical constants and film thickness to be determined. Finally, the practicability of the technique is demonstrated by presenting preliminary results for CH3OH reversibly adsorbed on Ag, showing clearly the C—H stretching bands.