Oxidation of Hydrogenated Si(111) by a Radical Propagation Mechanism

Autores
Soria, Federico Ariel; Patrito, Eduardo Martin; Paredes Olivera, Patricia
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The reactivity of the hydrogenated Si(111) surface toward H2O and O2 was investigated in order to elucidate the mechanism of oxidation of the first silicon bilayer in air. Density functional theory calculations were performed to identify elementary reaction steps and their corresponding activation energy barriers. The perfect surface is unreactive toward H2O and O2 at room temperature as deduced from the high energy barriers found. However, isolated Si dangling bonds, (Si3)Si·, surrounded by SiH groups, readily react with O2 (but not with H2O), producing a silanone intermediate of the form (Si2O)SiO· where one of the silicon back bonds is oxidized. This intermediate is reached after a series of elementary steps with very small activation energy barriers. In the next step, the oxygen atom of the silanone group inserts into a Si–Si back bond, and the surface silicon dangling bond is regenerated as a (SiO2)Si· moiety in which the silyl group has two oxidized back bonds. This initiates a surface chain reaction in which the oxidized silyl group abstracts a hydrogen atom from a neighboring SiH thus producing a new Si dangling bond that is oxidized by O2 in the next step of the chain reaction. This radical propagation mechanism explains the two-dimensional oxide growth in air and the lack of surface SiOH groups. Therefore, the oxidation of the H–Si(111) surface requires the presence of radicals in air that, upon reaction with the hydrogenated surface, produce silicon dangling bonds where the oxidation begins and propagates by hydrogen abstraction from nonoxidized neighboring SiH groups.
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; Argentina
Fil: 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; Argentina
Fil: Paredes Olivera, Patricia. 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; Argentina
Materia
silicon
radical mechanism
oxidation
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/268449
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/268449
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Oxidation of Hydrogenated Si(111) by a Radical Propagation MechanismSoria, Federico ArielPatrito, Eduardo MartinParedes Olivera, Patriciasiliconradical mechanismoxidationhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The reactivity of the hydrogenated Si(111) surface toward H2O and O2 was investigated in order to elucidate the mechanism of oxidation of the first silicon bilayer in air. Density functional theory calculations were performed to identify elementary reaction steps and their corresponding activation energy barriers. The perfect surface is unreactive toward H2O and O2 at room temperature as deduced from the high energy barriers found. However, isolated Si dangling bonds, (Si3)Si·, surrounded by SiH groups, readily react with O2 (but not with H2O), producing a silanone intermediate of the form (Si2O)SiO· where one of the silicon back bonds is oxidized. This intermediate is reached after a series of elementary steps with very small activation energy barriers. In the next step, the oxygen atom of the silanone group inserts into a Si–Si back bond, and the surface silicon dangling bond is regenerated as a (SiO2)Si· moiety in which the silyl group has two oxidized back bonds. This initiates a surface chain reaction in which the oxidized silyl group abstracts a hydrogen atom from a neighboring SiH thus producing a new Si dangling bond that is oxidized by O2 in the next step of the chain reaction. This radical propagation mechanism explains the two-dimensional oxide growth in air and the lack of surface SiOH groups. Therefore, the oxidation of the H–Si(111) surface requires the presence of radicals in air that, upon reaction with the hydrogenated surface, produce silicon dangling bonds where the oxidation begins and propagates by hydrogen abstraction from nonoxidized neighboring SiH groups.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: 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; ArgentinaFil: Paredes Olivera, Patricia. 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 Society2012-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/268449Soria, Federico Ariel; Patrito, Eduardo Martin; Paredes Olivera, Patricia; Oxidation of Hydrogenated Si(111) by a Radical Propagation Mechanism; American Chemical Society; Journal of Physical Chemistry C; 116; 46; 10-2012; 24607-246151932-7447CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp307798sinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp307798sinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-17T10:55:43Zoai:ri.conicet.gov.ar:11336/268449instacron: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:34982025-09-17 10:55:43.509CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Oxidation of Hydrogenated Si(111) by a Radical Propagation Mechanism
title Oxidation of Hydrogenated Si(111) by a Radical Propagation Mechanism
spellingShingle Oxidation of Hydrogenated Si(111) by a Radical Propagation Mechanism
Soria, Federico Ariel
silicon
radical mechanism
oxidation
title_short Oxidation of Hydrogenated Si(111) by a Radical Propagation Mechanism
title_full Oxidation of Hydrogenated Si(111) by a Radical Propagation Mechanism
title_fullStr Oxidation of Hydrogenated Si(111) by a Radical Propagation Mechanism
title_full_unstemmed Oxidation of Hydrogenated Si(111) by a Radical Propagation Mechanism
title_sort Oxidation of Hydrogenated Si(111) by a Radical Propagation Mechanism
dc.creator.none.fl_str_mv Soria, Federico Ariel
Patrito, Eduardo Martin
Paredes Olivera, Patricia
author Soria, Federico Ariel
author_facet Soria, Federico Ariel
Patrito, Eduardo Martin
Paredes Olivera, Patricia
author_role author
author2 Patrito, Eduardo Martin
Paredes Olivera, Patricia
author2_role author
author
dc.subject.none.fl_str_mv silicon
radical mechanism
oxidation
topic silicon
radical mechanism
oxidation
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The reactivity of the hydrogenated Si(111) surface toward H2O and O2 was investigated in order to elucidate the mechanism of oxidation of the first silicon bilayer in air. Density functional theory calculations were performed to identify elementary reaction steps and their corresponding activation energy barriers. The perfect surface is unreactive toward H2O and O2 at room temperature as deduced from the high energy barriers found. However, isolated Si dangling bonds, (Si3)Si·, surrounded by SiH groups, readily react with O2 (but not with H2O), producing a silanone intermediate of the form (Si2O)SiO· where one of the silicon back bonds is oxidized. This intermediate is reached after a series of elementary steps with very small activation energy barriers. In the next step, the oxygen atom of the silanone group inserts into a Si–Si back bond, and the surface silicon dangling bond is regenerated as a (SiO2)Si· moiety in which the silyl group has two oxidized back bonds. This initiates a surface chain reaction in which the oxidized silyl group abstracts a hydrogen atom from a neighboring SiH thus producing a new Si dangling bond that is oxidized by O2 in the next step of the chain reaction. This radical propagation mechanism explains the two-dimensional oxide growth in air and the lack of surface SiOH groups. Therefore, the oxidation of the H–Si(111) surface requires the presence of radicals in air that, upon reaction with the hydrogenated surface, produce silicon dangling bonds where the oxidation begins and propagates by hydrogen abstraction from nonoxidized neighboring SiH groups.
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; Argentina
Fil: 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; Argentina
Fil: Paredes Olivera, Patricia. 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; Argentina
description The reactivity of the hydrogenated Si(111) surface toward H2O and O2 was investigated in order to elucidate the mechanism of oxidation of the first silicon bilayer in air. Density functional theory calculations were performed to identify elementary reaction steps and their corresponding activation energy barriers. The perfect surface is unreactive toward H2O and O2 at room temperature as deduced from the high energy barriers found. However, isolated Si dangling bonds, (Si3)Si·, surrounded by SiH groups, readily react with O2 (but not with H2O), producing a silanone intermediate of the form (Si2O)SiO· where one of the silicon back bonds is oxidized. This intermediate is reached after a series of elementary steps with very small activation energy barriers. In the next step, the oxygen atom of the silanone group inserts into a Si–Si back bond, and the surface silicon dangling bond is regenerated as a (SiO2)Si· moiety in which the silyl group has two oxidized back bonds. This initiates a surface chain reaction in which the oxidized silyl group abstracts a hydrogen atom from a neighboring SiH thus producing a new Si dangling bond that is oxidized by O2 in the next step of the chain reaction. This radical propagation mechanism explains the two-dimensional oxide growth in air and the lack of surface SiOH groups. Therefore, the oxidation of the H–Si(111) surface requires the presence of radicals in air that, upon reaction with the hydrogenated surface, produce silicon dangling bonds where the oxidation begins and propagates by hydrogen abstraction from nonoxidized neighboring SiH groups.
publishDate 2012
dc.date.none.fl_str_mv 2012-10
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/11336/268449
Soria, Federico Ariel; Patrito, Eduardo Martin; Paredes Olivera, Patricia; Oxidation of Hydrogenated Si(111) by a Radical Propagation Mechanism; American Chemical Society; Journal of Physical Chemistry C; 116; 46; 10-2012; 24607-24615
1932-7447
CONICET Digital
CONICET
url http://hdl.handle.net/11336/268449
identifier_str_mv Soria, Federico Ariel; Patrito, Eduardo Martin; Paredes Olivera, Patricia; Oxidation of Hydrogenated Si(111) by a Radical Propagation Mechanism; American Chemical Society; Journal of Physical Chemistry C; 116; 46; 10-2012; 24607-24615
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/abs/10.1021/jp307798s
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp307798s
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
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
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
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
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score 13.001348

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