Reorganization Energy upon Controlled Intermolecular Charge-Transfer Reactions in Monolithically Integrated Nanodevices

Detalhes bibliográficos
Autor(a) principal: Merces, Leandro
Data de Publicação: 2021
Outros Autores: Candiotto, Graziâni, Ferro, Letícia Mariê Minatogau, de Barros, Anerise, Batista, Carlos Vinícius Santos [UNESP], Nawaz, Ali, Riul, Antonio, Capaz, Rodrigo B., Bufon, Carlos César Bof [UNESP]
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Institucional da UNESP
Texto Completo: http://dx.doi.org/10.1002/smll.202103897
http://hdl.handle.net/11449/222542
Resumo: Intermolecular electron-transfer reactions are key processes in physics, chemistry, and biology. The electron-transfer rates depend primarily on the system reorganization energy, that is, the energetic cost to rearrange each reactant and its surrounding environment when a charge is transferred. Despite the evident impact of electron-transfer reactions on charge-carrier hopping, well-controlled electronic transport measurements using monolithically integrated electrochemical devices have not successfully measured the reorganization energies to this date. Here, it is shown that self-rolling nanomembrane devices with strain-engineered mechanical properties, on-a-chip monolithic integration, and multi-environment operation features can overcome this challenge. The ongoing advances in nanomembrane-origami technology allow to manufacture the nCap, a nanocapacitor platform, to perform molecular-level charge transport characterization. Thereby, employing nCap, the copper-phthalocyanine (CuPc) reorganization energy is probed, ≈0.93 eV, from temperature-dependent measurements of CuPc nanometer-thick films. Supporting the experimental findings, density functional theory calculations provide the atomistic picture of the measured CuPc charge-transfer reaction. The experimental strategy demonstrated here is a consistent route towards determining the reorganization energy of a system formed by molecules monolithically integrated into electrochemical nanodevices.
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spelling Reorganization Energy upon Controlled Intermolecular Charge-Transfer Reactions in Monolithically Integrated Nanodevicesdensity functionalelectrochemicalelectron transferhoppingMarcusnanogapnanomembrane origamiIntermolecular electron-transfer reactions are key processes in physics, chemistry, and biology. The electron-transfer rates depend primarily on the system reorganization energy, that is, the energetic cost to rearrange each reactant and its surrounding environment when a charge is transferred. Despite the evident impact of electron-transfer reactions on charge-carrier hopping, well-controlled electronic transport measurements using monolithically integrated electrochemical devices have not successfully measured the reorganization energies to this date. Here, it is shown that self-rolling nanomembrane devices with strain-engineered mechanical properties, on-a-chip monolithic integration, and multi-environment operation features can overcome this challenge. The ongoing advances in nanomembrane-origami technology allow to manufacture the nCap, a nanocapacitor platform, to perform molecular-level charge transport characterization. Thereby, employing nCap, the copper-phthalocyanine (CuPc) reorganization energy is probed, ≈0.93 eV, from temperature-dependent measurements of CuPc nanometer-thick films. Supporting the experimental findings, density functional theory calculations provide the atomistic picture of the measured CuPc charge-transfer reaction. The experimental strategy demonstrated here is a consistent route towards determining the reorganization energy of a system formed by molecules monolithically integrated into electrochemical nanodevices.Brazilian Nanotechnology National Laboratory (LNNano) Brazilian Center for Research in Energy and Materials (CNPEM)Instituto de Física Universidade Federal do Rio de JaneiroInstituto de Química Universidade Federal do Rio de JaneiroInstitute of Chemistry University of CampinasPostgraduate Program in Materials Science and Technology São Paulo State UniversityCenter for Sensors and Devices Bruno Kessler Foundation (FBK)Department of Applied Physics “Gleb Wataghin” Institute of Physics University of CampinasMackenzie Presbyterian UniversityPostgraduate Program in Materials Science and Technology São Paulo State UniversityBrazilian Center for Research in Energy and Materials (CNPEM)Universidade Federal do Rio de Janeiro (UFRJ)Universidade Estadual de Campinas (UNICAMP)Universidade Estadual Paulista (UNESP)Bruno Kessler Foundation (FBK)Mackenzie Presbyterian UniversityMerces, LeandroCandiotto, GraziâniFerro, Letícia Mariê Minatogaude Barros, AneriseBatista, Carlos Vinícius Santos [UNESP]Nawaz, AliRiul, AntonioCapaz, Rodrigo B.Bufon, Carlos César Bof [UNESP]2022-04-28T19:45:20Z2022-04-28T19:45:20Z2021-01-01info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://dx.doi.org/10.1002/smll.202103897Small.1613-68291613-6810http://hdl.handle.net/11449/22254210.1002/smll.2021038972-s2.0-85116125138Scopusreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengSmallinfo:eu-repo/semantics/openAccess2022-04-28T19:45:20Zoai:repositorio.unesp.br:11449/222542Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462024-08-05T20:12:16.586420Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false
dc.title.none.fl_str_mv Reorganization Energy upon Controlled Intermolecular Charge-Transfer Reactions in Monolithically Integrated Nanodevices
title Reorganization Energy upon Controlled Intermolecular Charge-Transfer Reactions in Monolithically Integrated Nanodevices
spellingShingle Reorganization Energy upon Controlled Intermolecular Charge-Transfer Reactions in Monolithically Integrated Nanodevices
Merces, Leandro
density functional
electrochemical
electron transfer
hopping
Marcus
nanogap
nanomembrane origami
title_short Reorganization Energy upon Controlled Intermolecular Charge-Transfer Reactions in Monolithically Integrated Nanodevices
title_full Reorganization Energy upon Controlled Intermolecular Charge-Transfer Reactions in Monolithically Integrated Nanodevices
title_fullStr Reorganization Energy upon Controlled Intermolecular Charge-Transfer Reactions in Monolithically Integrated Nanodevices
title_full_unstemmed Reorganization Energy upon Controlled Intermolecular Charge-Transfer Reactions in Monolithically Integrated Nanodevices
title_sort Reorganization Energy upon Controlled Intermolecular Charge-Transfer Reactions in Monolithically Integrated Nanodevices
author Merces, Leandro
author_facet Merces, Leandro
Candiotto, Graziâni
Ferro, Letícia Mariê Minatogau
de Barros, Anerise
Batista, Carlos Vinícius Santos [UNESP]
Nawaz, Ali
Riul, Antonio
Capaz, Rodrigo B.
Bufon, Carlos César Bof [UNESP]
author_role author
author2 Candiotto, Graziâni
Ferro, Letícia Mariê Minatogau
de Barros, Anerise
Batista, Carlos Vinícius Santos [UNESP]
Nawaz, Ali
Riul, Antonio
Capaz, Rodrigo B.
Bufon, Carlos César Bof [UNESP]
author2_role author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Brazilian Center for Research in Energy and Materials (CNPEM)
Universidade Federal do Rio de Janeiro (UFRJ)
Universidade Estadual de Campinas (UNICAMP)
Universidade Estadual Paulista (UNESP)
Bruno Kessler Foundation (FBK)
Mackenzie Presbyterian University
dc.contributor.author.fl_str_mv Merces, Leandro
Candiotto, Graziâni
Ferro, Letícia Mariê Minatogau
de Barros, Anerise
Batista, Carlos Vinícius Santos [UNESP]
Nawaz, Ali
Riul, Antonio
Capaz, Rodrigo B.
Bufon, Carlos César Bof [UNESP]
dc.subject.por.fl_str_mv density functional
electrochemical
electron transfer
hopping
Marcus
nanogap
nanomembrane origami
topic density functional
electrochemical
electron transfer
hopping
Marcus
nanogap
nanomembrane origami
description Intermolecular electron-transfer reactions are key processes in physics, chemistry, and biology. The electron-transfer rates depend primarily on the system reorganization energy, that is, the energetic cost to rearrange each reactant and its surrounding environment when a charge is transferred. Despite the evident impact of electron-transfer reactions on charge-carrier hopping, well-controlled electronic transport measurements using monolithically integrated electrochemical devices have not successfully measured the reorganization energies to this date. Here, it is shown that self-rolling nanomembrane devices with strain-engineered mechanical properties, on-a-chip monolithic integration, and multi-environment operation features can overcome this challenge. The ongoing advances in nanomembrane-origami technology allow to manufacture the nCap, a nanocapacitor platform, to perform molecular-level charge transport characterization. Thereby, employing nCap, the copper-phthalocyanine (CuPc) reorganization energy is probed, ≈0.93 eV, from temperature-dependent measurements of CuPc nanometer-thick films. Supporting the experimental findings, density functional theory calculations provide the atomistic picture of the measured CuPc charge-transfer reaction. The experimental strategy demonstrated here is a consistent route towards determining the reorganization energy of a system formed by molecules monolithically integrated into electrochemical nanodevices.
publishDate 2021
dc.date.none.fl_str_mv 2021-01-01
2022-04-28T19:45:20Z
2022-04-28T19:45:20Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
format article
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://dx.doi.org/10.1002/smll.202103897
Small.
1613-6829
1613-6810
http://hdl.handle.net/11449/222542
10.1002/smll.202103897
2-s2.0-85116125138
url http://dx.doi.org/10.1002/smll.202103897
http://hdl.handle.net/11449/222542
identifier_str_mv Small.
1613-6829
1613-6810
10.1002/smll.202103897
2-s2.0-85116125138
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv Small
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.source.none.fl_str_mv Scopus
reponame:Repositório Institucional da UNESP
instname:Universidade Estadual Paulista (UNESP)
instacron:UNESP
instname_str Universidade Estadual Paulista (UNESP)
instacron_str UNESP
institution UNESP
reponame_str Repositório Institucional da UNESP
collection Repositório Institucional da UNESP
repository.name.fl_str_mv Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)
repository.mail.fl_str_mv
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