Synchrotron X-ray specular scattering measurements confirm microscopically a structural model recently inferred by very-high-resolution ellipsometry of a solid dotriacontane (n-C32H66 or C32) film formed by adsorption from solution onto a SiO2 surface. Sequentially, one or two layers adsorb on the SiO2 surface with the long-axis of the C32 molecules oriented parallel to the interface followed by a C32 monolayer with the long-axis perpendicular to it. Finally, preferentially oriented bulk particles nucleate having two different crystal structures. This growth model differs from that found previously for shorter alkanes deposited from the vapor phase onto solid surfaces. (C) 2003 Elsevier B.V. All rights reserved.