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X‐ray reflection (both specular and off‐specular) and grazing incidence diffraction (GID) have been used to study the structure of alkylsiloxane monolayers (n‐C18H37SiO1.5) formed by self‐assembly from solution on silicon wafers. GID studies of complete monolayers reveal a single ring of scattering associated with the monolayer. The Lorentzian line shape of this ring indicates that the film is characterized by liquidlike order, with a typical translational correlation length of about 45 A. The thermal coefficient of expansion of the monolayer, as determined from the GID peak position, is approximately equal to the value for liquid n‐alkanes. Upon either heating or cooling, the monolayer correlation lengths decrease, suggesting that the differential thermal‐expansion coefficients of the film and substrate figure prominently in thermal changes of the molecular ordering. GID data for incomplete monolayers also reveal a single ring of scattering associated with the monolayer. While both the translational corr...

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.

X‐ray reflectivity has been utilized in a study of the SiO2/Si interfacial structure for dry oxides grown at room temperature on highly ordered Si(001) surfaces. Scattering near (±110) demonstrates the Si lattice termination of the wafers studied is characterized by a highly ordered array of terraces separated by monoatomic steps. Specular reflectivity data indicate the ‘‘native’’ dry oxide thickness is approximately 5 A with a 1‐A vacuum interface width. Residual laminar order in the oxide electron density along the oxide/Si interfacial normal decays exponentially from the oxide/Si interface with a ∼2.7‐A decay length.

X‐ray scattering has been utilized in a study of the SiO2/Si(001) interfacial structure. Scattering data provide evidence for a low coverage 2×1 epitaxial structure at the SiO2/Si interface for dry oxides grown on highly ordered Si surfaces at room temperature. The observed scattering is consistent with distorted dimer models of the interfacial structure. Thermal annealing substantially reduces the order of the 2×1 structure while prolonged exposure to humid air almost eliminates the 2×1 symmetry scattering. These findings suggest that the observed 2×1 order is associated with a metastable, intermediate state of the dry oxidation process.