Reproducible flaws unveil electrostatic aspects of semiconductor electrochemistry

Yan B. Vogel, Long Zhang, Nadim Darwish, Vinicius R. Gonçales, Anton Le Brun, J. Justin Gooding, Angela Molina, Gordon G. Wallace, Michelle L. Coote, Joaquin Gonzalez, Simone Ciampi

Research output: Contribution to journalArticlepeer-review

53 Citations (Scopus)
7 Downloads (Pure)


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.

Original languageEnglish
Article number2066
Number of pages9
JournalNature Communications
Issue number1
Publication statusPublished - 12 Dec 2017
Externally publishedYes


  • Electrochemistry
  • Electronic devices
  • Electronic properties and materials


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