Synthesis And Micropatterning Of Photocatalytically Reactive Self-Assembled Monolayers Covalently Linked To Si(100) Surfaces Via A Si-C Bond

Selective generation of an amine-terminated selfassembled monolayer bound to silicon wafers via a silicon carbon linkage was realized by photocatalytically reducing the corresponding azide-terminated, self-assembled monolayers (Az-SAMs). The Az-SAM was obtained by thermal deposition of 11-chloroundecene onto a hydrogen-terminated silicon wafer followed by nucleophilic substitution of the chloride with the azide ion in warm N,N'-dimethylformamide (DMF). The presence of the terminal azide group on the SAM was confirmed by reflection absorption infrared spectroscopy (RAIRS), by X-ray photoelectron spectroscopy (XPS), and by detecting the formation of a triazole upon reaction of the azide with an activated alkyne. The desired terminal amine groups were generated by photocatalytic reduction of the Az-SAM with cadmium selenide quantum dots (CdSe Qdots) using lambda > 400 nm. Analysis of the reduced SAM by XPS gave results that were consistent with those obtained with an amine-terminated surface obtained by reducing the Az-SAM with triphenylphosphine. To demonstrate the feasibility of using the Az-SAM for surface patterning, a sample was coated with adsorbed CdSe Qdots and exposed to the output of a diode laser at lambda = 407 nm through a micropatterned mask. Using a SEM, the pattern formed in this manner was revealed after removing the CdSe Qdots and subsequently adsorbing 10 nm gold nanoparticles (AuNPs) to the positively charged terminal-amine groups. The formation of the pattern by CdSe-photocatalyzed reduction of the azide demonstrates a novel route to create features by selective modification of organic monolayers on silicon wafers.