Semiconductors such as metal oxides, silicon, and diamond lie at the heart of many emerging applications in renewable energy and biotechnology. Through more than 10 years of effort our studies have shown that UV-induced photoemission is a nearly universal way to initiate grafting of molecular monolayers to semiconductor surfaces via 'holey chemistry,' in which UV-induced photoemission leaves behind surface-trapped holes that induce nucleophilic addition reactions to form new, self-terminating surface-to-molecule bonds. When combined with modular chemistry such as 'click' chemistry, this approach can yield highly stable, redox-active and photo-active surfaces with excellent charge-transfer rates. The unique surface bonding structures at metal oxide surfaces also lead to new types of reactions similar to well-known organic reactions, but with distinct differences arising from the unique chemical properties of surface atoms. Finally, a twist on holey chemistry will be presented, leading to a highly unusual type of surface photocatalytic reaction.

Award Address  (ACS Award in Colloid and Surface Chemistry sponsored by The Procter & Gamble Co.). "Holey" chemistry at semiconductor surfaces

243rd National Meeting (2012)

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