A versatile modular setup is described which incorporates ellipsometry, surface plasmon spectroscopy, waveguide modes, their corresponding imaging techniques and Brewster angle microscopy in a single instrument. The important design criteria are discussed with special emphasis given to the requirements imposed by imaging under an oblique angle of incidence. Several experimental examples demonstrate the power of the instrument. Imaging nullellipsometry of a patterned monolayer on a highly reflecting support demonstrates a lateral resolution of approximately 1 μm and an accuracy in the thickness determination in the sub-nm region. The localization of the evanescent field of a surface plasmon was exploited to characterize adsorption layers in turbid and thus highly scattering solutions. An example of how an anisotropic sample can be characterized with the aid of waveguide modes is provided.

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In the widely accepted Stern model, an adsorption layer of an ionic surfactant at the air-water interface consists of a charged topmost amphiphilic monolayer, a so-called compact Stern layer of directly adsorbed counterions, and the Gouy-Chapman layer characterized by a diffuse ion distribution. The crux of Stern's treatment is the estimation of to what extent ions enter the compact layer and reduce the surface potential. This issue is addressed in this paper by optical means. Surface second harmonic generation, ellipsometry, and surface tension measurements have been used for an investigation of the prevailing ion distribution. Each technique probes different structural elements of the interfacial architecture, and their combination yields a deeper insight into the internal composition of the interface. The amphiphile 1-dodecyl-4-dimethylaminopyridinium bromide, C12-DMP, was used as a cationic soluble surfactant and the comparison with the experimental data obtained with the closely related nonionic betaine 2-(4′dimethylaminopyridinio)-dodecanoate provided evidence for the correctness of our interpretation of the data. A strikingly different ion distribution with increasing bulk concentration is observed and the underlying mechanism is discussed. Furthermore we are able to clarify the current discussion about the meaning of ellipsometric measurements for adsorption layers of soluble surfactants (with thickness < 2 nm). The dilemma is the impossibility of obtaining on the basis of Fresnel theory (i.e., the solution of Maxwell's equations) a one to one correspondence between measured quantities and the structural data of the monolayer. Commonly it is assumed that ellipsometry measures at least the surface excess but a recent publication questioned this [Teppner et al., Langmuir 1999, 15, 7002.]. Our simulations reveal that the effect of optical anisotropy within the layer on the ellipsometric signal is negligible as compared to the effect of a changing ion distribution. This analysis combined with the experimental results on both model systems give us the means to precisely state under which experimental prerequisites ellipsometry directly measures the surface excess as defined by Gibbs.

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