Shedding Light on the Interfacial Structure of Low-Coverage Alkanethiol Lattices

Autores
Pensa, Evangelina Laura; Azofra Mesa, Luis Miguel; Albrecht, Tim; Salvarezza, Roberto Carlos; Carro, Pilar
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A comprehensive description of the self-assembly process of alkanethiols on Au(111) is presented, focused on the initial formation of the lying down phases. Low-coverage monolayers are prepared by the disintegration of Au₁₄₄(RS)₆₀ nanoclusters on the reconstructed (22 × √3)-Au(111) surface. The method provides a limited number of thiols together with a large excess of gold adatoms. Scanning tunneling microscopy and density functional theory calculations were employed to study the transition between low to high thiolate coverage phases. The process involves different lattices and surface transformations, including thiyl radicals on the herringbone reconstruction, radicalinduced herringbone lifting, and the formation of energetically similar metastable phases formed by RS-Au-RS moieties. Results also show that the transition is slow, and different surface structures can coexist on the same sample. Along the process, the first source of Au adatoms to form the RS-Au-SR moieties is the lifting of the herringbone reconstruction because of the lower energetic cost to extract the extra Au atom. However, for hexanethiol (and shorter alkanethiols) at low coverage, additional Au adatoms must be taken from terraces leading to vacancy islands. This process can be entirely suppressed by growing the lying down phases in the presence of an excess of Au adatoms. Taken together, our results shed light on the elusive initial steps of thiol adsorption on clean reconstructed Au, showing that the RS-Au-SR staple motif is also present at the interface of low-coverage self-assembled monolayers.
Facultad de Ciencias Exactas
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
Materia
Ciencias Exactas
Química
self-assembly process of alkanethiols
alkanethiols
scanning tunneling microscopy
interfacial structure
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/123966

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network_name_str SEDICI (UNLP)
spelling Shedding Light on the Interfacial Structure of Low-Coverage Alkanethiol LatticesPensa, Evangelina LauraAzofra Mesa, Luis MiguelAlbrecht, TimSalvarezza, Roberto CarlosCarro, PilarCiencias ExactasQuímicaself-assembly process of alkanethiolsalkanethiolsscanning tunneling microscopyinterfacial structureA comprehensive description of the self-assembly process of alkanethiols on Au(111) is presented, focused on the initial formation of the lying down phases. Low-coverage monolayers are prepared by the disintegration of Au₁₄₄(RS)₆₀ nanoclusters on the reconstructed (22 × √3)-Au(111) surface. The method provides a limited number of thiols together with a large excess of gold adatoms. Scanning tunneling microscopy and density functional theory calculations were employed to study the transition between low to high thiolate coverage phases. The process involves different lattices and surface transformations, including thiyl radicals on the herringbone reconstruction, radicalinduced herringbone lifting, and the formation of energetically similar metastable phases formed by RS-Au-RS moieties. Results also show that the transition is slow, and different surface structures can coexist on the same sample. Along the process, the first source of Au adatoms to form the RS-Au-SR moieties is the lifting of the herringbone reconstruction because of the lower energetic cost to extract the extra Au atom. However, for hexanethiol (and shorter alkanethiols) at low coverage, additional Au adatoms must be taken from terraces leading to vacancy islands. This process can be entirely suppressed by growing the lying down phases in the presence of an excess of Au adatoms. Taken together, our results shed light on the elusive initial steps of thiol adsorption on clean reconstructed Au, showing that the RS-Au-SR staple motif is also present at the interface of low-coverage self-assembled monolayers.Facultad de Ciencias ExactasInstituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas2020-11-24info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf26748-26758http://sedici.unlp.edu.ar/handle/10915/123966enginfo:eu-repo/semantics/altIdentifier/issn/1932-7447info:eu-repo/semantics/altIdentifier/issn/1932-7455info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.0c07613info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-29T11:29:28Zoai:sedici.unlp.edu.ar:10915/123966Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-29 11:29:28.635SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Shedding Light on the Interfacial Structure of Low-Coverage Alkanethiol Lattices
title Shedding Light on the Interfacial Structure of Low-Coverage Alkanethiol Lattices
spellingShingle Shedding Light on the Interfacial Structure of Low-Coverage Alkanethiol Lattices
Pensa, Evangelina Laura
Ciencias Exactas
Química
self-assembly process of alkanethiols
alkanethiols
scanning tunneling microscopy
interfacial structure
title_short Shedding Light on the Interfacial Structure of Low-Coverage Alkanethiol Lattices
title_full Shedding Light on the Interfacial Structure of Low-Coverage Alkanethiol Lattices
title_fullStr Shedding Light on the Interfacial Structure of Low-Coverage Alkanethiol Lattices
title_full_unstemmed Shedding Light on the Interfacial Structure of Low-Coverage Alkanethiol Lattices
title_sort Shedding Light on the Interfacial Structure of Low-Coverage Alkanethiol Lattices
dc.creator.none.fl_str_mv Pensa, Evangelina Laura
Azofra Mesa, Luis Miguel
Albrecht, Tim
Salvarezza, Roberto Carlos
Carro, Pilar
author Pensa, Evangelina Laura
author_facet Pensa, Evangelina Laura
Azofra Mesa, Luis Miguel
Albrecht, Tim
Salvarezza, Roberto Carlos
Carro, Pilar
author_role author
author2 Azofra Mesa, Luis Miguel
Albrecht, Tim
Salvarezza, Roberto Carlos
Carro, Pilar
author2_role author
author
author
author
dc.subject.none.fl_str_mv Ciencias Exactas
Química
self-assembly process of alkanethiols
alkanethiols
scanning tunneling microscopy
interfacial structure
topic Ciencias Exactas
Química
self-assembly process of alkanethiols
alkanethiols
scanning tunneling microscopy
interfacial structure
dc.description.none.fl_txt_mv A comprehensive description of the self-assembly process of alkanethiols on Au(111) is presented, focused on the initial formation of the lying down phases. Low-coverage monolayers are prepared by the disintegration of Au₁₄₄(RS)₆₀ nanoclusters on the reconstructed (22 × √3)-Au(111) surface. The method provides a limited number of thiols together with a large excess of gold adatoms. Scanning tunneling microscopy and density functional theory calculations were employed to study the transition between low to high thiolate coverage phases. The process involves different lattices and surface transformations, including thiyl radicals on the herringbone reconstruction, radicalinduced herringbone lifting, and the formation of energetically similar metastable phases formed by RS-Au-RS moieties. Results also show that the transition is slow, and different surface structures can coexist on the same sample. Along the process, the first source of Au adatoms to form the RS-Au-SR moieties is the lifting of the herringbone reconstruction because of the lower energetic cost to extract the extra Au atom. However, for hexanethiol (and shorter alkanethiols) at low coverage, additional Au adatoms must be taken from terraces leading to vacancy islands. This process can be entirely suppressed by growing the lying down phases in the presence of an excess of Au adatoms. Taken together, our results shed light on the elusive initial steps of thiol adsorption on clean reconstructed Au, showing that the RS-Au-SR staple motif is also present at the interface of low-coverage self-assembled monolayers.
Facultad de Ciencias Exactas
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
description A comprehensive description of the self-assembly process of alkanethiols on Au(111) is presented, focused on the initial formation of the lying down phases. Low-coverage monolayers are prepared by the disintegration of Au₁₄₄(RS)₆₀ nanoclusters on the reconstructed (22 × √3)-Au(111) surface. The method provides a limited number of thiols together with a large excess of gold adatoms. Scanning tunneling microscopy and density functional theory calculations were employed to study the transition between low to high thiolate coverage phases. The process involves different lattices and surface transformations, including thiyl radicals on the herringbone reconstruction, radicalinduced herringbone lifting, and the formation of energetically similar metastable phases formed by RS-Au-RS moieties. Results also show that the transition is slow, and different surface structures can coexist on the same sample. Along the process, the first source of Au adatoms to form the RS-Au-SR moieties is the lifting of the herringbone reconstruction because of the lower energetic cost to extract the extra Au atom. However, for hexanethiol (and shorter alkanethiols) at low coverage, additional Au adatoms must be taken from terraces leading to vacancy islands. This process can be entirely suppressed by growing the lying down phases in the presence of an excess of Au adatoms. Taken together, our results shed light on the elusive initial steps of thiol adsorption on clean reconstructed Au, showing that the RS-Au-SR staple motif is also present at the interface of low-coverage self-assembled monolayers.
publishDate 2020
dc.date.none.fl_str_mv 2020-11-24
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
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http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://sedici.unlp.edu.ar/handle/10915/123966
url http://sedici.unlp.edu.ar/handle/10915/123966
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/issn/1932-7447
info:eu-repo/semantics/altIdentifier/issn/1932-7455
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.0c07613
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
dc.format.none.fl_str_mv application/pdf
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repository.name.fl_str_mv SEDICI (UNLP) - Universidad Nacional de La Plata
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