Silylation of an OH‐terminated self‐assembled monolayer surface through low‐energy collisions of ions: a novel route to synthesis and patterning of surfaces

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Abstract
Using a multi‐sector ion–surface scattering mass spectrometer, reagent ions of the general form SiR3+ were mass and energy selected and then made to collide with a hydroxy‐terminated self‐assembled monolayer (HO‐SAM) surface at energies of ∼15 eV. These ion–surface interactions result in covalent transformation of the terminal hydroxy groups at the surface into the corresponding silyl ethers due to Si—O bond formation. The modified surface was characterized in situ by chemical sputtering, a low‐energy ion–surface scattering experiment. These data indicate that the ion–surface reactions have high yields (i.e. surface reactants converted to products). Surface reactions with Si(OCH3)3+, followed by chemical sputtering using CF3+, yielded the reagent ion, Si(OCH3)3+, and several of its fragments. Other sputtered ions, namely SiH(OCH3)2OH2+ and SiH2(OCH3)OH2+, contain the newly formed Si—O bond and provide direct evidence for the covalent modification reaction. Chemical sputtering of modified surfaces, performed using CF3+, was evaluated over a range of collision energies. The results showed that the energy transferred to the sputtered ions, as measured by their extent of fragmentation in the scattered ion mass spectra, was essentially independent of the collision energy of the projectile, thus pointing to the occurrence of reactive sputtering. A set of silyl cations, including SiBr3+, Si(C2H3)3+ and Si(CH3)2F+, were similarly used to modify the HO‐SAM surface at low collision energies. A reaction mechanism consisting of direct electrophilic attack by the cationic projectiles is supported by evidence of increased reactivity for these reagent ions with increases in the calculated positive charge at the electron‐deficient silicon atom of each of these cations. In a sequential set of reactions, 12 eV deuterated trimethylsilyl cations, Si(CD3)3+, were used first as the reagent ions to modify covalently a HO‐SAM surface. Subsequently, 70 eV SiCl3+ ions were used to modify the surface further. In addition to yielding sputtered ions of the modified surface, SiCl3+ reacted with both modified and unmodified groups on the surface, giving rise not only to such scattered product ions as SiCl2OH+ and SiCl2H+, but also to SiCl2CD3+ and SiCl2D+. This result demonstrates that selective, multi‐step reactions can be performed at a surface through low‐energy ionic collisions. Such processes are potentially useful for the construction of novel surfaces from a monolayer substrate and for chemical patterning of surfaces with functional groups. Copyright © 2002 John Wiley & Sons, Ltd.