Formation of a new class of layered, microcrystalline polymers from a simple hydrolytic polycondensation of n-alkyltrichlorosilanes in water is demonstrated. The structure of the polymeric condensate, determined from a combination of spectroscopic, diffraction, and thermal analysis techniques, consists of highly uniform, pillared microcrystallites in which the inorganic siloxy backbones are present in periodic layers, each containing a monomolecular layer of intercalated water, separated by crystalline assemblies of alkyl chains. The alkyl-chain organization shows a remarkable resemblance to that in highly organized, self-assembled monolayers formed from the precursor silane molecules on hydrophilic substrates and this parallel lends support to the critical importance of water in monolayer self-assembly of silanes.

Highly organized monolayers formed from the self-assembly of octadecyl derivatives on oxide-covered Si and Ti substrates have been exposed to electron beam impact under typical conditions used in lithographic patterning. A combination of X-ray photoelectron spectroscopy, ellipsometry, infrared spectroscopy, and liquid drop contact angle measurements show that the major effect of irradiation is the loss of H, Via cleavage of C-H bonds, to form a carbonaceous residue with a surface containing oxygenated functional groups.

Dots demonstrating critical resist dimensions of approximately 5 to 6 nm were formed in an octadecylsiloxane monolayer on silicon by electron beam exposure using a digital scanning electron microscope at 20 keV beam energy. The patterned dots were observed by imaging with an atomic force microscope (AFM). The electron beam size was measured to confirm that it is not the limiting factor in the exposure resolution. The limit that prevents the observation of smaller structures is either the small contrast in the AFM imaging for smaller dots or an intrinsic material limit caused by the secondary electron range.

Stable, nanometer-scale thickness films of −(CH2) x − have been observed to form by the surface-catalyzed decomposition of CH2N2 on evaporated Au film substrates. In the early stages, growth occurs in the form of isolated clusters at defect regions in the {111} textured surfaces. As the average thickness increases beyond ∼20 nm, growth spills out onto the {111} terraces with eventual coverage of the entire surface. At all coverages, the dominant structure is highly trans, extended polymethylene chains packed in an orthorhombic lattice, similar to the typical structure of crystalline, bulk-phase polyethylene but containing more conformational defects than well-formed bulk crystals. Chain melting occurs at ∼135 °C, and cooling to room temperature results in differing extents of ordering as a function of the total film coverage, an indication that the structures of the growing films are constrained in metastable forms by the presence of adjacent gold surface defect features. The polymerization mechanism appears to involve surface-catalyzed decomposition of the diazomethane at gold defect sites to produce methylidene adsorbate species, which subsequently initiate the formation of linear polymers via a free radical propagation process. This process provides a useful limiting case of the surface-catalyzed formation of linear hydrocarbons from C1 intermediates on transition metals.