RESUMO
Nanoscale organic films are important for many applications. We report on a system of molecular layer deposition that allows for the deposition of conformal organic films with thickness and composition control at the subnanometer length scale. Nanoscale polyurea films are grown on silica substrates in a layer-by-layer fashion by dosing 1,4-phenylene diisocyanate (PDIC) and ethylenediamine (ED) in the gas phase. Ellipsometry measurements indicate that the film growth occurs at a constant growth rate, with film thicknesses consistent with molecular distances calculated using density functional theory. Characterization of the films by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy reveals formation of stable polyurea films with nearly stoichiometric composition, and transmission electron microscopy indicates that the films uniformly coat the substrate surface. Subnanometer control over the film composition was demonstrated using 2,2'-thiobis(ethylamine) (TBEA) as an alternate diamine to vary the composition of the films. By substituting TBEA for ED, blended films, with homogeneous composition through the film, and nanolaminates, with discrete layers of differing film chemistry, were created.
RESUMO
With the rapidly changing materials needs of modern microelectronics, germanium provides an opportunity for future-generation devices. Controlling germanium interfaces will be essential for this purpose. We review germanium surface reactivity, beginning with a description of the most commonly used surfaces, Ge(100) and Ge(111). An analysis of oxide formation shows why the poor oxide properties have hindered practical use of germanium to date. This is followed by an examination of alternate means of surface passivation, with particular attention given to sulfide, chloride, and hydride termination. Specific tailoring of the interface properties is possible through organic functionalization. The few solution functionalization methods that have been studied are reviewed. Vacuum functionalization has been studied to a much greater extent, with dative bonding and cycloaddition reactions emerging as principle reaction mechanisms. These are reviewed through molecular reaction studies that demonstrate the versatility of the germanium surface.