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Reproducible flaws unveil electrostatic aspects of semiconductor electrochemistry

Journal Article


Abstract


  • Predicting or manipulating charge-transfer at semiconductor interfaces, from molecular electronics to energy conversion, relies on knowledge generated from a kinetic analysis of the electrode process, as provided by cyclic voltammetry. Scientists and engineers encountering non-ideal shapes and positions in voltammograms are inclined to reject these as flaws. Here we show that non-idealities of redox probes confined at silicon electrodes, namely full width at half maximum < 90.6 mV and anti-thermodynamic inverted peak positions, can be reproduced and are not flawed data. These are the manifestation of electrostatic interactions between dynamic molecular charges and the semiconductor's space-charge barrier. We highlight the interplay between dynamic charges and semiconductor by developing a model to decouple effects on barrier from changes to activities of surface-bound molecules. These findings have immediate general implications for a correct kinetic analysis of charge-transfer at semiconductors as well as aiding the study of electrostatics on chemical reactivity.

Authors


  •   Vogel, Yan Boris (external author)
  •   Zhang, Long (external author)
  •   Darwish, Nadim A. (external author)
  •   Goncales, Vinicius R. (external author)
  •   Le Brun, Anton P. (external author)
  •   Gooding, J Justin. (external author)
  •   Molina, Angela (external author)
  •   Wallace, Gordon G.
  •   Coote, M L. (external author)
  •   Gonzalez, Joaquin (external author)
  •   Ciampi, Simone (external author)

Publication Date


  • 2017

Citation


  • Vogel, Y. B., Zhang, L., Darwish, N., Goncales, V. R., Le Brun, A., Gooding, J. Justin., Molina, A., Wallace, G. G., Coote, M. L., Gonzalez, J. & Ciampi, S. (2017). Reproducible flaws unveil electrostatic aspects of semiconductor electrochemistry. Nature Communications, 8 (1), 2066-1-2066-9.

Scopus Eid


  • 2-s2.0-85037721583

Start Page


  • 2066-1

End Page


  • 2066-9

Volume


  • 8

Issue


  • 1

Place Of Publication


  • United Kingdom

Abstract


  • Predicting or manipulating charge-transfer at semiconductor interfaces, from molecular electronics to energy conversion, relies on knowledge generated from a kinetic analysis of the electrode process, as provided by cyclic voltammetry. Scientists and engineers encountering non-ideal shapes and positions in voltammograms are inclined to reject these as flaws. Here we show that non-idealities of redox probes confined at silicon electrodes, namely full width at half maximum < 90.6 mV and anti-thermodynamic inverted peak positions, can be reproduced and are not flawed data. These are the manifestation of electrostatic interactions between dynamic molecular charges and the semiconductor's space-charge barrier. We highlight the interplay between dynamic charges and semiconductor by developing a model to decouple effects on barrier from changes to activities of surface-bound molecules. These findings have immediate general implications for a correct kinetic analysis of charge-transfer at semiconductors as well as aiding the study of electrostatics on chemical reactivity.

Authors


  •   Vogel, Yan Boris (external author)
  •   Zhang, Long (external author)
  •   Darwish, Nadim A. (external author)
  •   Goncales, Vinicius R. (external author)
  •   Le Brun, Anton P. (external author)
  •   Gooding, J Justin. (external author)
  •   Molina, Angela (external author)
  •   Wallace, Gordon G.
  •   Coote, M L. (external author)
  •   Gonzalez, Joaquin (external author)
  •   Ciampi, Simone (external author)

Publication Date


  • 2017

Citation


  • Vogel, Y. B., Zhang, L., Darwish, N., Goncales, V. R., Le Brun, A., Gooding, J. Justin., Molina, A., Wallace, G. G., Coote, M. L., Gonzalez, J. & Ciampi, S. (2017). Reproducible flaws unveil electrostatic aspects of semiconductor electrochemistry. Nature Communications, 8 (1), 2066-1-2066-9.

Scopus Eid


  • 2-s2.0-85037721583

Start Page


  • 2066-1

End Page


  • 2066-9

Volume


  • 8

Issue


  • 1

Place Of Publication


  • United Kingdom