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.
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Acknowledgements
The authors thank I.R. McNab for critical discussions and reading of the manuscript. The authors also wish to thank the Natural Sciences and Engineering Research Council of Canada (NSERC), Photonics Research Ontario (PRO), an Ontario Centre of Excellence (OCE), the Canadian Institute for Photonic Innovation (CIPI), the Xerox Research Centre Canada (XRCC), Fonds de Recherche sur la Nature et les Technologies (FQRNT) of Quebec and the Canadian Institute for Advanced Research (CIFAR), for their support of this work. H.G. and W.J. are also grateful to Réseau québécois de calcul de haute performance (RQCHP) and Consortium Laval, Université du Québec, McGill and Eastern Quebec (CLUMEQ) for providing computational facilities.
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T.B.L. and J.C.P. planned the experiment. T.B.L. collected and analysed the STM experimental data. H.G. and W.J. performed the DFT and NEB calculations. All authors contributed equally to writing the manuscript.
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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
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DOI: https://doi.org/10.1038/nchem.930
