Hidden electrochemistry in the thermal grafting of silicon surfaces from grignard reagents |
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Authors: | Fellah Samira Boukherroub Rabah Ozanam François Chazalviel Jean-Noël |
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Institution: | Laboratoire de Physique de la Matière Condensée, CNRS-Ecole Polytechnique, 91128 Palaiseau Cedex, France. |
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Abstract: | Covalent grafting of alkyl chains on silicon can be obtained by thermal treatment in Grignard reagents. Alkyl halide present in the Grignard solution as an impurity appears to play a key role in the grafting process. Grafting efficiency is improved when the alkyl halide concentration is increased. It is also enhanced on n-type substrates as compared to p-type substrates and when alkyl bromides are present in solution rather than alkyl chlorides. The grafting reaction involves a zero-current electrochemical step. A reaction model in which simultaneous Grignard oxidation and alkyl halide reduction take place at the silicon surface accounts for all these observations. Alkyl halide reduction is the rate-determining step. Negative charging of the silicon surface lowers the energetic barrier for this reaction, allowing for efficient grafting on n-Si. |
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