In the age when the miniaturization trend that has driven the semiconductor industry is reaching its limits, organic modification of semiconductors is emerging as a field that could give much-needed impetus. We review the current state of understanding of the functionalization of C(100), Si(100), and Ge(100) surfaces through chemisorption of alkenes and alkynes, focusing on adsorbate structural control. While reactions on C(100) show most of the properties expected for concerted cycloaddition reactions such as [2+2] and [4+2] (Diels–Alder) processes, reactions on Si(100) present a wide range of variant behavior, including in some cases the prominence of non-cycloaddition products. More general stepwise free-radical addition processes are seen to provide a better description of reactions on Si(100), their prominence being attributed to either the non-existence or ineffectiveness of π bonding within surface silicon dimers. The investigations of these systems provide not only insight into driving mechanisms for chemisorption but also motivation for the development of new techniques of organic functionalization on semiconductors.
