Chemical Stability toward O2 and H2O of Si(111) Grafted with —CH3, —CH2CH2CH3, —CHCHCH3, and —CCCH3

The chemical stability of compact monolayers on silicon toward oxidizing agents is a key issue for the use of such monolayers in devices such as solar cells or in the electronics industry. In this work, we investigated the reactivity toward H2O, O2, and OH species of monolayers terminated with a met...

Descripción completa

Detalles Bibliográficos
Autores: Soria, Federico Ariel, Paredes Olivera, Patricia, Patrito, Eduardo Martin
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2014
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/31352
Acceso en línea:http://hdl.handle.net/11336/31352
Access Level:acceso abierto
Palabra clave:Silicon Surfaces
Reactivity
Alkanethiols Monolayers
https://purl.org/becyt/ford/2.10
https://purl.org/becyt/ford/2
id AR_f9cf01e008fc0dcf05cc6a7e52f9be31
oai_identifier_str oai:ri.conicet.gov.ar:11336/31352
network_acronym_str AR
network_name_str Argentina
repository_id_str
dc.title.none.fl_str_mv Chemical Stability toward O2 and H2O of Si(111) Grafted with —CH3, —CH2CH2CH3, —CHCHCH3, and —CCCH3
title Chemical Stability toward O2 and H2O of Si(111) Grafted with —CH3, —CH2CH2CH3, —CHCHCH3, and —CCCH3
spellingShingle Chemical Stability toward O2 and H2O of Si(111) Grafted with —CH3, —CH2CH2CH3, —CHCHCH3, and —CCCH3
Soria, Federico Ariel
Silicon Surfaces
Reactivity
Alkanethiols Monolayers
https://purl.org/becyt/ford/2.10
https://purl.org/becyt/ford/2
title_short Chemical Stability toward O2 and H2O of Si(111) Grafted with —CH3, —CH2CH2CH3, —CHCHCH3, and —CCCH3
title_full Chemical Stability toward O2 and H2O of Si(111) Grafted with —CH3, —CH2CH2CH3, —CHCHCH3, and —CCCH3
title_fullStr Chemical Stability toward O2 and H2O of Si(111) Grafted with —CH3, —CH2CH2CH3, —CHCHCH3, and —CCCH3
title_full_unstemmed Chemical Stability toward O2 and H2O of Si(111) Grafted with —CH3, —CH2CH2CH3, —CHCHCH3, and —CCCH3
title_sort Chemical Stability toward O2 and H2O of Si(111) Grafted with —CH3, —CH2CH2CH3, —CHCHCH3, and —CCCH3
dc.creator.none.fl_str_mv Soria, Federico Ariel
Paredes Olivera, Patricia
Patrito, Eduardo Martin
author Soria, Federico Ariel
author_facet Soria, Federico Ariel
Paredes Olivera, Patricia
Patrito, Eduardo Martin
author_role author
author2 Paredes Olivera, Patricia
Patrito, Eduardo Martin
author2_role author
author
dc.subject.none.fl_str_mv Silicon Surfaces
Reactivity
Alkanethiols Monolayers
https://purl.org/becyt/ford/2.10
https://purl.org/becyt/ford/2
topic Silicon Surfaces
Reactivity
Alkanethiols Monolayers
https://purl.org/becyt/ford/2.10
https://purl.org/becyt/ford/2
description The chemical stability of compact monolayers on silicon toward oxidizing agents is a key issue for the use of such monolayers in devices such as solar cells or in the electronics industry. In this work, we investigated the reactivity toward H2O, O2, and OH species of monolayers terminated with a methyl group to unveil the mechanisms that prevent the oxidation of the underlying silicon. Density functional theory calculations were performed to investigate the reaction pathways for the two competing processes involved: diffusion through the monolayer and reaction with the terminal methyl group. Activation energy barriers for the diffusion of H2O and O2 are very sensitive to the monolayer structure, and they increase in the order —CH2—CH2—CH3 < —C≡C—CH3 < —CH═CH—CH3 with energy barriers of 0.0 kcal/mol (0.0 kcal/mol), 35.0 kcal/mol (42.5 kcal/mol), and 57.0 kcal/mol (64.1 kcal/mol), respectively, for H2O (O2). This agrees with ordering of stabilities reported experimentally for these monolayers. The oxidation of the terminal methyl group by O2 is less affected by steric constraints. The formation of the —CH2OOH species has an energy barrier of 56.5 kcal/mol on the rigid —CH3 monolayer, whereas this barrier decreases to 40.7 kcal/mol on the —C≡C—CH3 monolayer. In the case of the methyl monolayer, the abstraction of a H atom of the —CH3 group has smaller energy barriers with singlet O2 and OH reactants, with values of 38.4 and 3.5 kcal/mol, respectively. The high energy barriers of all of the processes investigated indicate that compact monolayers hinder the oxidation of the underlying substrate. The passivating capability of the monolayers correlates with the steric constraints for H2O and O2 diffusion.
publishDate 2014
dc.date.none.fl_str_mv 2014-12
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
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://hdl.handle.net/11336/31352
Soria, Federico Ariel; Paredes Olivera, Patricia; Patrito, Eduardo Martin; Chemical Stability toward O2 and H2O of Si(111) Grafted with —CH3, —CH2CH2CH3, —CHCHCH3, and —CCCH3; American Chemical Society; Journal of Physical Chemistry C; 119; 12-2014; 284-295
1932-7447
CONICET Digital
CONICET
url http://hdl.handle.net/11336/31352
identifier_str_mv Soria, Federico Ariel; Paredes Olivera, Patricia; Patrito, Eduardo Martin; Chemical Stability toward O2 and H2O of Si(111) Grafted with —CH3, —CH2CH2CH3, —CHCHCH3, and —CCCH3; American Chemical Society; Journal of Physical Chemistry C; 119; 12-2014; 284-295
1932-7447
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/10.1021/jp508728v
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp508728v
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1799196006276923392
spelling Chemical Stability toward O2 and H2O of Si(111) Grafted with —CH3, —CH2CH2CH3, —CHCHCH3, and —CCCH3Soria, Federico ArielParedes Olivera, PatriciaPatrito, Eduardo MartinSilicon SurfacesReactivityAlkanethiols Monolayershttps://purl.org/becyt/ford/2.10https://purl.org/becyt/ford/2The chemical stability of compact monolayers on silicon toward oxidizing agents is a key issue for the use of such monolayers in devices such as solar cells or in the electronics industry. In this work, we investigated the reactivity toward H2O, O2, and OH species of monolayers terminated with a methyl group to unveil the mechanisms that prevent the oxidation of the underlying silicon. Density functional theory calculations were performed to investigate the reaction pathways for the two competing processes involved: diffusion through the monolayer and reaction with the terminal methyl group. Activation energy barriers for the diffusion of H2O and O2 are very sensitive to the monolayer structure, and they increase in the order —CH2—CH2—CH3 < —C≡C—CH3 < —CH═CH—CH3 with energy barriers of 0.0 kcal/mol (0.0 kcal/mol), 35.0 kcal/mol (42.5 kcal/mol), and 57.0 kcal/mol (64.1 kcal/mol), respectively, for H2O (O2). This agrees with ordering of stabilities reported experimentally for these monolayers. The oxidation of the terminal methyl group by O2 is less affected by steric constraints. The formation of the —CH2OOH species has an energy barrier of 56.5 kcal/mol on the rigid —CH3 monolayer, whereas this barrier decreases to 40.7 kcal/mol on the —C≡C—CH3 monolayer. In the case of the methyl monolayer, the abstraction of a H atom of the —CH3 group has smaller energy barriers with singlet O2 and OH reactants, with values of 38.4 and 3.5 kcal/mol, respectively. The high energy barriers of all of the processes investigated indicate that compact monolayers hinder the oxidation of the underlying substrate. The passivating capability of the monolayers correlates with the steric constraints for H2O and O2 diffusion.Fil: Soria, Federico Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Paredes Olivera, Patricia. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Patrito, Eduardo Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaAmerican Chemical Society2014-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/31352Soria, Federico Ariel; Paredes Olivera, Patricia; Patrito, Eduardo Martin; Chemical Stability toward O2 and H2O of Si(111) Grafted with —CH3, —CH2CH2CH3, —CHCHCH3, and —CCCH3; American Chemical Society; Journal of Physical Chemistry C; 119; 12-2014; 284-2951932-7447CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/10.1021/jp508728vinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp508728vinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2024-05-08T14:11:25Zoai:ri.conicet.gov.ar:11336/31352instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982024-05-08 14:11:26.036CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
score 15,812429

Similares en LA Referencia