Controlled organic functionalization of silicon surfaces as integral part of semiconductor technology offers new perspectives for a wide range of applications. The high reactivity of the silicon dangling bonds, however, presents a major hindrance for the first basic reaction step of such a functionalization, i.e., the chemoselective attachment of bifunctional organic molecules on the pristine silicon surface. We overcome this problem by employing cyclooctyne as the major building block of our strategy. Functionalized cyclooctynes are shown to react on Si(001) selectively via the strained cyclooctyne triple bond while leaving the side groups intact. The achieved selectivity originates from the distinctly different adsorption dynamics of the separate functionalities: A direct adsorption pathway is demonstrated for cyclooctyne as opposed to the vast majority of other organic functional groups. The latter ones react on Si(001) via a metastable intermediate which makes them effectively unreactive in competition with the direct pathway of cyclooctyne's strained triple bond.Comment: 16 pages, 5 figures, TOC figur

The dynamics of ethylene adsorption on the Si(001) surface was investigated by means of molecular beam techniques. A constant decrease of initial sticking probability s(0) was observed with increasing kinetic energy indicating a non-activated adsorption channel. With increasing surface temperature, s(0) decreases as well, pointing towards adsorption via a precursor state. Quantitative evaluation of the temperature dependence of s(0) via the Kisliuk model was possible for surface temperatures above 250 K; below that value, the temperature dependence is dominated by the adsorption dynamics into the precursor state. Maximum surface coverage was found to be reduced with increasing surface temperature, which is discussed on the basis of a long lifetime of the precursor state at low temperatures.

The key parameters of the potential energy curve of organic molecules on semiconductor surfaces, binding energy of the intermediate state and dissociation barrier, were experimentally investigated for the model system of diethyl ether (Et2O) on Si(001). Et2O adsorbs via a datively bonded intermediate from which it converts via ether cleavage into a covalently attached final state. This thermally activated conversion into the final state was followed in real-time by means of optical second-harmonic generation (SHG) at different temperatures and the associated energy barrier ϵa = 0.38 ± 0.05 eV and pre-exponential factor νa = 10(4±1) s(-1) were determined. From molecular beam experiments on the initial sticking probability, the difference between the desorption energy ϵd and ϵa was extracted and thus the binding energy of the intermediate state was determined (0.62 ± 0.08 eV). The results are discussed in terms of general chemical trends as well as with respect to a wider applicability on adsorbate reactions on semiconductor surfaces.

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