Instantaneous Functionalization of Chemically Etched Silicon Nanocrystal Surfaces

Remarkable advances in surface hydrosilylation reactions of C=C and C=O bonds on hydride-terminated silicon have revolutionized silicon surface functionalization. However, existing methods for functionalizing hydride-terminated Si nanocrystals (H-SiNCs) require long reaction times and elevated temperatures. Herein, we report a room-temperature method for functionalizing H-SiNC surfaces within seconds by stripping outermost atoms on H-SiNC surfaces with xenon difluoride (XeF₂ ). Detailed analysis of the reaction byproducts by in situ NMR spectroscopy and GC-MS provided unprecedented insight into NC surface composition and reactivity as well as the complex reaction mechanism of XeF₂ activated hydrosilylation.