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Reproducible flaws unveil electrostatic aspects of semiconductor electrochemistry
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 posit...
Autores principales: | , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2017
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5727234/ https://www.ncbi.nlm.nih.gov/pubmed/29233986 http://dx.doi.org/10.1038/s41467-017-02091-1 |
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author | Vogel, Yan B. Zhang, Long Darwish, Nadim Gonçales, Vinicius R. Le Brun, Anton Gooding, J. Justin Molina, Angela Wallace, Gordon G. Coote, Michelle L. Gonzalez, Joaquin Ciampi, Simone |
author_facet | Vogel, Yan B. Zhang, Long Darwish, Nadim Gonçales, Vinicius R. Le Brun, Anton Gooding, J. Justin Molina, Angela Wallace, Gordon G. Coote, Michelle L. Gonzalez, Joaquin Ciampi, Simone |
author_sort | Vogel, Yan B. |
collection | PubMed |
description | 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. |
format | Online Article Text |
id | pubmed-5727234 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2017 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-57272342017-12-14 Reproducible flaws unveil electrostatic aspects of semiconductor electrochemistry Vogel, Yan B. Zhang, Long Darwish, Nadim Gonçales, Vinicius R. Le Brun, Anton Gooding, J. Justin Molina, Angela Wallace, Gordon G. Coote, Michelle L. Gonzalez, Joaquin Ciampi, Simone Nat Commun Article 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. Nature Publishing Group UK 2017-12-12 /pmc/articles/PMC5727234/ /pubmed/29233986 http://dx.doi.org/10.1038/s41467-017-02091-1 Text en © The Author(s) 2017 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/. |
spellingShingle | Article Vogel, Yan B. Zhang, Long Darwish, Nadim Gonçales, Vinicius R. Le Brun, Anton Gooding, J. Justin Molina, Angela Wallace, Gordon G. Coote, Michelle L. Gonzalez, Joaquin Ciampi, Simone Reproducible flaws unveil electrostatic aspects of semiconductor electrochemistry |
title | Reproducible flaws unveil electrostatic aspects of semiconductor electrochemistry |
title_full | Reproducible flaws unveil electrostatic aspects of semiconductor electrochemistry |
title_fullStr | Reproducible flaws unveil electrostatic aspects of semiconductor electrochemistry |
title_full_unstemmed | Reproducible flaws unveil electrostatic aspects of semiconductor electrochemistry |
title_short | Reproducible flaws unveil electrostatic aspects of semiconductor electrochemistry |
title_sort | reproducible flaws unveil electrostatic aspects of semiconductor electrochemistry |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5727234/ https://www.ncbi.nlm.nih.gov/pubmed/29233986 http://dx.doi.org/10.1038/s41467-017-02091-1 |
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