Photoactivated Preparation and Patterning of Self-Assembled Monolayers with 1-Alkenes and Aldehydes on Silicon Hydride Surfaces

Abstract

Direct lateral patterning in the formation of self-assembled monolayers (SAMs) on silicon was achieved by the photoinduced reaction of aldehydes with Si(111)-H surfaces by using the usual masking techniques (see the schematic illustration; on the right-hand side is a microscopy image of a patterned SAM formed from octadecanal).

Wet chemical routes to the assembly of organic monolayers on silicon surfaces via the formation of Si–C bonds: surface preparation, passivation and functionalization

“…165,166 Initially reported by Terry et al in a study aimed to provide direct evidence of the silicon-carbon bond formation for the reaction of 1-pentene with Si(111)-H, 146 the UV-mediated hydrosilylation reaction of unsaturated hydrocarbons has since seen numerous applications. [50][51][52]113,133,[167][168][169] The process generally affords good hydrocarbon chain surface coverages, 113,133 chemically stable surfaces, 83 and allows for a straightforward light-addressable surface patterning. 51,52,168 For further details on the early body of work on the photochemical hydrosilylation, the reader should consult the comprehensive reviews of Buriak.…”

“…[50][51][52]113,133,[167][168][169] The process generally affords good hydrocarbon chain surface coverages, 113,133 chemically stable surfaces, 83 and allows for a straightforward light-addressable surface patterning. 51,52,168 For further details on the early body of work on the photochemical hydrosilylation, the reader should consult the comprehensive reviews of Buriak. 27,28 Here we will mainly focus our discussion on more recent advances, while trying to bring to the attention of the reader the need for conclusive data to resolve the details of the surface hydrosilylation reaction mechanism, both under illumination and thermal conditions.…”

“…To introduce a pivotal concept to the discussion of the following paragraphs, where an overview will be given of the available derivatization routes toward functional silicon layers, it should be noted that the silicon hydride phase has indeed a broad reactivity and, beside reactions with unsaturated hydrocarbons and halogens, the immobilization of nitriles, 31 alcohols, 44,81 aldehydes, 168 and ketones 198 have all been documented.…”

“…This provides the surface chemist with an array of tools to access either carbon-silicon, 31,87 nitrogen-silicon, 156 or oxygen-silicon 81,139,168,199 bonded organic layers. 27,29 A common feature of most of the early work in this area, and to some extent a limitation of most of the procedures reported in the literature, is a methyl termination at the distal end of the organic films.…”

Photochemical Attachment of Organic Monolayers onto H-Terminated Si(111): Radical Chain Propagation Observed via STM Studies

“…light of < 365 nm) is required. 11,14 Since the visible-light-induced attachment employed here is initiated with photons of significantly less energy, homolytic bond cleavage can be excluded as the starting point for the reaction. Additionally, the 1-decene does not absorb any 447 nm light.…”