Thermally Induced Silane Dehydrocoupling on Silicon Nanostructures.

Organic trihydridosilanes can be grafted to hydrogen-terminated porous Si nanostructures with no catalyst. The reaction proceeds efficiently at 80 °C, and it shows little sensitivity to air or water impurities. The modified surfaces are stable to corrosive aqueous solutions and common organic solvents. Octadecylsilane H3 Si(CH2 )17 CH3 , and functional silanes H3 Si(CH2 )11 Br, H3 Si(CH2 )9 CH=CH2 , and H3 Si(CH2 )2 (CF2 )5 CF3 are readily grafted. When performed on a mesoporous Si wafer, the perfluoro reagent yields a superhydrophobic surface (contact angle 151°). The bromo-derivative is converted to azide, amine, or alkyne functional surfaces via standard transformations, and the utility of the method is demonstrated by loading of the antibiotic ciprofloxaxin (35 % by mass). When intrinsically photoluminescent porous Si films or nanoparticles are used, photoluminescence is retained in the grafted products, indicating that the chemistry does not introduce substantial nonradiative surface traps.