X-ray specular reflection studies of silicon coated by organic monolayers (alkylsiloxanes)

X-ray specular reflectivity has been used to characterize the structure of silicon--silicon-oxide surfaces coated with chemisorbed hydrocarbon monolayer films (alkylsiloxanes). Using synchrotron radiation the reflectivity was followed over 9 orders of magnitude, from grazing incidence to an incident angle of \ensuremath{\varphi}\ensuremath{\approxeq}6.5\ifmmode^\circ\else\textdegree\fi{}, or q=(4\ensuremath{\pi}/\ensuremath{\lambda})sin(\ensuremath{\varphi})=0.8 A${\r{}}^{\mathrm{\ensuremath{-}}1}$, allowing a spatial resolution of features approximately \ensuremath{\pi}/0.8\ensuremath{\approxeq}4.0 A\r{} along the surface normal. Analysis was performed by fitting the data to reflectivities calculated from models of the surface electron density and by calculating Patterson functions directly from the data. Although the measured reflectivities could be equally well described by different sets of model parameters, the electron densities calculated from these different parameters were remarkably alike. Inspection of the electron densities allowed identification of a layer of ${\mathrm{SiO}}_{2}$ (\ensuremath{\approxeq}17-A\r{} thick), a layer of head-group region where the alkylsiloxane adsorbs to the ${\mathrm{SiO}}_{2}$, and the hydrocarbon layer. Fitting the data also required that the various interfaces have different widths. The fact that the same local hydrocarbon density of 0.85 g/${\mathrm{cm}}^{3}$ was observed for both fully formed and partially formed monolayers with alkane chains of varying length excluded a model in which the partially formed monolayer was made up of separated islands of well-formed monolayers. Measurements before and after chemical reaction of a monolayer in which the alkyl chain was terminated by an olefinic group demonstrated the ability to use x-ray reflectivity to characterize chemical changes. The effects of radiation damage on these types of measurements are described.