Surface-mediated chain reaction through dissociative attachment
Author: ["Tingbin Lim","John C. Polanyi","Hong Guo","Wei Ji"]
Publication: Nature Chemistry
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Abstract
Chain reactions on a surface offer an important route to linear nanopatterning. We recently reported cooperative reactions on a silicon surface in which the reaction of one halogen atom with a silicon atom of a silicon dimer induced the halogenation of its neighbouring silicon atom through surface-mediated charge transfer. The reaction was unable to propagate further but here we describe how, by chemically bridging the gaps between the rows of these silicon dimers, this mechanism is able to form extended chains. The agents for chain growth are CH3Cl molecules that dissociatively attach CH3 groups and chlorine atoms to silicon atoms from different dimers. By means of charge transfer through the surface, this gives rise to dangling bonds adjacent to the CH3 groups and chlorine atoms (in effect, ‘free radicals’) that dissociate further incoming CH3Cl molecules, thereby providing the growing points for chains of indefinite length. This versatile mechanism of chain growth is examined in experiments and using ab initio theory. Chain-reactions could provide an alternative method for surface patterning. Now the chain reaction of CH3Cl molecules on a silicon surface has been observed to create lines that are made up of alternating CH3 groups and Cl atoms. The reactions are propagated through surface-mediated charge-transfer and have been studied using microscopy and ab initio theory.
Cite this article
Lim, T., Polanyi, J., Guo, H. et al. Surface-mediated chain reaction through dissociative attachment. Nature Chem 3, 85–89 (2011). https://doi.org/10.1038/nchem.930
