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
- Institución
- Universidad Nacional de La Plata
- OAI Identificador
- oai:sedici.unlp.edu.ar:10915/123966
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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 |
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format |
article |
status_str |
publishedVersion |
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http://sedici.unlp.edu.ar/handle/10915/123966 |
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http://sedici.unlp.edu.ar/handle/10915/123966 |
dc.language.none.fl_str_mv |
eng |
language |
eng |
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