The atom transfer radical polymerization (ATRP) of styrene and acrylates from silicon wafers modified with an initiator layer composed of 2-bromoisobutyrate fragments is described. In the presence of the proper ratio of activating and deactivating transition-metal species, controlled radical polymerizations of styrene were observed such that the thickness of the layer consisting of chains grown from the surface increased linearly with the molecular weight of chains polymerized in solution in identical, yet separate, experiments. The layer thickness increased linearly with reaction time for ATRP of styrene and methyl acrylate due to both the extremely low initiator concentration relative to monomer and the low monomer conversion. Further evidence for control was observed by the polymerization of blocks of either methyl or tert-butyl acrylate from the polystyrene layer. Modification of the hydrophilicity of the surface layer was achieved by hydrolysis of the poly(styrene-b-tert-butyl acrylate) to poly(styrene-b-acrylic acid) and confirmed by decrease in water contact angle from 86° to 18°. The mechanistic aspects of ATRP in the polymerization process were confirmed by the growth of very thick polystyrene films in the presence of a pure copper(I) complex. Since no deactivator was present, the metal complex served only to facilitate initiation by a redox process. Attempts to extend chain with methyl acrylate under controlled conditions were unsuccessful in those films. The simulation of polymerization of surface layers suggests broader molecular weight and chain end distributions, confirming XPS results on the progressive decrease of Br absorption intensity.

The formation and growth of self-assembled octadecylsiloxane monolayers on native silicon and mica substrates have been studied using atomic force microscopy, ellipsometry, and infrared spectroscopy. Submonolayer ODS films of varying surface coverages were prepared by immersing the substrates into dilute solutions of octadecyltrichlorosilane in toluene for different periods of time, and the submonolayer film structures were compared between mica and silicon substrates for different water contents of the adsorbate solutions and for different time delays between solution preparation and substrate immersion (solution age). It was found that, in general, both a continuous growth (formation of disordered, liquidlike submonolayers) and an island-type growth (formation of organized assemblies with vertically aligned hydrocarbon chains) are involved in the formation of ODS monolayers, whereby the relative contributions depend strongly on the solution properties. With increasing water content or increasing age of the adsorbate solution, island-type growth is strongly favored on both silicon and mica surfaces, which indicates the kinetically controlled formation of larger, preordered aggregates of silanol molecules as the primary hydrolysis products in solution. For identical conditions of film preparation, both the degree of structural order in the submonolayer films and the overall adsorption rate was found to be higher on mica in comparison to silicon. The higher structural order was interpreted as a consequence of the lower hydroxyl group concentration and a correspondingly enhanced surface diffusion rate of weakly bound film molecules on a mica substrate. The enhanced adsorption rate, on the other hand, points to some additional activation of a mica surface with respect to silanol adsorption, which might be related to its ionic composition containing mobile surface charges in contrast to the covalent, neutral character of a native silicon surface.

The formation of alkylsiloxane monolayers O x Si−(CH2) n −Y with different hydrocarbon chain lengths (n = 10, 16, 17) and different terminal substituents (Y = CH3, COOCH3, CN, Br) on native silicon (Si/SiO2) was studied by means of in situ internal reflection IR spectroscopy (ATR) at the interface between a Si ATR crystal and the precursor solution. The growth of the ν(CH2) stretching absorptions of the monolayer films, monitored with s-polarized and p-polarized radiation, provided information on the monolayer formation rates and on structural changes in the course of the growth process. The film molecules adsorb initially in a random, disordered configuration. With increasing coverage, the hydrocarbon chains gradually align and stand up on the surface. Their final orientation in the complete monolayer films depends both on the chain length and on the type of terminal substitution, whereby chain tilt angles between 7° for O x Si−(CH2)17−CH3 and 21° for O x Si−(CH2)16−CN and O x Si−(CH2)16−Br were found. The film growth follows essentially a Langmuir model of irreversible adsorption, from which the adsorption rate constants were derived. Whereas the chain length and the terminal substituent have relatively small influences on the adsorption rates, a higher water content of the precursor solutions strongly accelerates the film formation and, in addition, causes significant deviations from a Langmuir growth model. These findings were interpreted as a consequence of polycondensation of the precursor molecules in solution.

Submonolayers of octadecylsiloxane (ODS) were prepared by adsorption from dilute solutions of octadecyltrichlorosilane (OTS) onto a series of different substrates: mica, native silicon (Si/SiO2), and mica coated with a defined number nSiO of SiO2 monolayers (nSiO ) 1, 2, 4, 6). Atomic force microscopy (AFM) was used to investigate the adsorption rate and the submonolayer island morphology as a function of the substrate composition. Two types of substrate effects were observedsfirst, an abrupt change of the shape, size, and height distribution of the submonolayer islands between mica and SiO2-coated mica or silicon substrates, and second, an exponential decrease of the adsorption rate with nSiO up to a thickness of about 6 SiO2 monolayers. The first effect is independent of the SiO2 film thickness and the nature of the underlying substrate (mica or Si) and is therefore believed to arise from the different surface concentrations of OH groups on mica and SiO2 surfaces. The adsorption rate decrease with nSiO, in contrast, appears to be a long-range, bulk effect of mica and might reflect an electrostatic interaction between the negatively charged mica surface and the polar head groups of the film molecules, which accelerates the adsorption in comparison to that of an uncharged substrate such as silicon.Self-assembled monolayers (SAMs) formed on solid substrates by spontaneous assembly of amphiphilic molecules from dilute solutions are often considered as solidstate analogs to Langmuir-Blodgett (LB) films prepared on a liquid subphase and transferred to a solid support. 1 Despite the striking similarities between these two classes of highly organized, supramolecular systems, regarding the type of film molecules and their uniform, densely packed assembly on the substrate surface, SAM films are generally strongly chemisorbed and often show pronounced, substrate-dependent properties unknown for LB films but rather typical for epitaxial overlayers. Organothiol molecules, for example, adsorb on coinage metal surfaces (Au, Ag, Cu) via specific sulfur-metal bonds onto a predefined coordination site lattice (e.g. 3-fold hollow sites on a Au(111) surface), whereby the lattice spacing and the lattice geometry of the particular metal determine the packing density and the surface orientation of the film molecules. 2 Other classes of SAM films, on the other hand, such as alkylsiloxane monolayers formed from alkylsilanol precursors on a variety of OH-terminated surfaces 3-5 (Si/SiO 2 , Al 2 O 3 , glass, mica, etc.), appear to lack any substrate influences 3,6,7 and are considered as the closest relatives to LB films known to date. 8 One major difference still existssthe covalent linkage between the silanol film molecules and the surface hydroxyl groups under Si-O-Si bond formationswhose role in the film growth process is still under debate. Whereas in some reports a substrate-decoupled growth mechanism was proposed, 7,8 in which the monolayer forms on a thin layer of adsorbed water and is sparsely anchored to the substrate via Si-O-...