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 H3Si(CH2)17CH3, and functional silanes H3Si(CH2)11Br, H3Si(CH2)9CH=CH2, and H3Si(CH2)2(CF2)5CF3 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. Organic trihydridosilanes were grafted to hydrogen-terminated porous Si nanostructures with no catalyst. When intrinsically photoluminescent porous Si films or nanoparticles are used, photoluminescence is retained in the grafted products, thereby indicating that the chemistry does not introduce substantial nonradiative surface traps.