Initial steps of oxidative etching of MoS 2 basal planeinduced by O 2

Autores
Farigliano, Lucas Martín; Paredes Olivera, Patricia; Patrito, Eduardo Martin
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We have investigated the first stages of oxidation of the basal plane of MoS2 with O2. The different intermediates in the energy landscape were found at 0 K with nudged-elastic band calculations, and their reactivity was evaluated at higher temperatures by performing ab initio molecular dynamics simulations. We identified the intermediates and mechanisms leading to the desorption of both SO and SO2 species. The key intermediate consists of an O atom bound on top of an S atom with a second O atom inserted into the S-Mo bond, giving rise to a stable O=S-O-Mo moiety. The mechanisms leading to this intermediate upon adsorption of O2 on the basal plane of MoS2 are discussed. From the O=S-O-Mo intermediate, SO2 may desorb directly generating a single sulfur vacancy on the surface while its decomposition leads to the desorption of SO and leaves substitutional oxygen on the surface. These etching mechanisms were also observed in the ab initio molecular dynamics simulations, in good agreement with energy profiles calculated along the reaction paths. Diffusion of O atoms on top of the sulfur layer and direct desorption of SO groups were never observed in the molecular dynamics simulations because these processes have high energy barriers (2.4 and 3.1 eV, respectively). However, subsurface diffusion of O atoms, involving the formation of both O-S and O-Mo bonds, is a competing process with lower energy barriers.
Fil: Farigliano, Lucas Martín. 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
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
Materia
Desorption
Diffusion
Oxygen
Chemical reactions
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:11336/142572
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/142572
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Initial steps of oxidative etching of MoS 2 basal planeinduced by O 2Farigliano, Lucas MartínParedes Olivera, PatriciaPatrito, Eduardo MartinDesorptionDiffusionOxygenChemical reactionshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We have investigated the first stages of oxidation of the basal plane of MoS2 with O2. The different intermediates in the energy landscape were found at 0 K with nudged-elastic band calculations, and their reactivity was evaluated at higher temperatures by performing ab initio molecular dynamics simulations. We identified the intermediates and mechanisms leading to the desorption of both SO and SO2 species. The key intermediate consists of an O atom bound on top of an S atom with a second O atom inserted into the S-Mo bond, giving rise to a stable O=S-O-Mo moiety. The mechanisms leading to this intermediate upon adsorption of O2 on the basal plane of MoS2 are discussed. From the O=S-O-Mo intermediate, SO2 may desorb directly generating a single sulfur vacancy on the surface while its decomposition leads to the desorption of SO and leaves substitutional oxygen on the surface. These etching mechanisms were also observed in the ab initio molecular dynamics simulations, in good agreement with energy profiles calculated along the reaction paths. Diffusion of O atoms on top of the sulfur layer and direct desorption of SO groups were never observed in the molecular dynamics simulations because these processes have high energy barriers (2.4 and 3.1 eV, respectively). However, subsurface diffusion of O atoms, involving the formation of both O-S and O-Mo bonds, is a competing process with lower energy barriers.Fil: Farigliano, Lucas Martín. 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; 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 Society2020-06info: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/11336/142572Farigliano, Lucas Martín; Paredes Olivera, Patricia; Patrito, Eduardo Martin; Initial steps of oxidative etching of MoS 2 basal planeinduced by O 2; American Chemical Society; Journal of Physical Chemistry C; 124; 24; 6-2020; 13177-131861932-74471932-7455CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpcc.0c02141info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.0c02141info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:00:53Zoai:ri.conicet.gov.ar:11336/142572instacron: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:34982025-09-29 10:00:53.858CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Initial steps of oxidative etching of MoS 2 basal planeinduced by O 2
title Initial steps of oxidative etching of MoS 2 basal planeinduced by O 2
spellingShingle Initial steps of oxidative etching of MoS 2 basal planeinduced by O 2
Farigliano, Lucas Martín
Desorption
Diffusion
Oxygen
Chemical reactions
title_short Initial steps of oxidative etching of MoS 2 basal planeinduced by O 2
title_full Initial steps of oxidative etching of MoS 2 basal planeinduced by O 2
title_fullStr Initial steps of oxidative etching of MoS 2 basal planeinduced by O 2
title_full_unstemmed Initial steps of oxidative etching of MoS 2 basal planeinduced by O 2
title_sort Initial steps of oxidative etching of MoS 2 basal planeinduced by O 2
dc.creator.none.fl_str_mv Farigliano, Lucas Martín
Paredes Olivera, Patricia
Patrito, Eduardo Martin
author Farigliano, Lucas Martín
author_facet Farigliano, Lucas Martín
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 Desorption
Diffusion
Oxygen
Chemical reactions
topic Desorption
Diffusion
Oxygen
Chemical reactions
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We have investigated the first stages of oxidation of the basal plane of MoS2 with O2. The different intermediates in the energy landscape were found at 0 K with nudged-elastic band calculations, and their reactivity was evaluated at higher temperatures by performing ab initio molecular dynamics simulations. We identified the intermediates and mechanisms leading to the desorption of both SO and SO2 species. The key intermediate consists of an O atom bound on top of an S atom with a second O atom inserted into the S-Mo bond, giving rise to a stable O=S-O-Mo moiety. The mechanisms leading to this intermediate upon adsorption of O2 on the basal plane of MoS2 are discussed. From the O=S-O-Mo intermediate, SO2 may desorb directly generating a single sulfur vacancy on the surface while its decomposition leads to the desorption of SO and leaves substitutional oxygen on the surface. These etching mechanisms were also observed in the ab initio molecular dynamics simulations, in good agreement with energy profiles calculated along the reaction paths. Diffusion of O atoms on top of the sulfur layer and direct desorption of SO groups were never observed in the molecular dynamics simulations because these processes have high energy barriers (2.4 and 3.1 eV, respectively). However, subsurface diffusion of O atoms, involving the formation of both O-S and O-Mo bonds, is a competing process with lower energy barriers.
Fil: Farigliano, Lucas Martín. 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
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
description We have investigated the first stages of oxidation of the basal plane of MoS2 with O2. The different intermediates in the energy landscape were found at 0 K with nudged-elastic band calculations, and their reactivity was evaluated at higher temperatures by performing ab initio molecular dynamics simulations. We identified the intermediates and mechanisms leading to the desorption of both SO and SO2 species. The key intermediate consists of an O atom bound on top of an S atom with a second O atom inserted into the S-Mo bond, giving rise to a stable O=S-O-Mo moiety. The mechanisms leading to this intermediate upon adsorption of O2 on the basal plane of MoS2 are discussed. From the O=S-O-Mo intermediate, SO2 may desorb directly generating a single sulfur vacancy on the surface while its decomposition leads to the desorption of SO and leaves substitutional oxygen on the surface. These etching mechanisms were also observed in the ab initio molecular dynamics simulations, in good agreement with energy profiles calculated along the reaction paths. Diffusion of O atoms on top of the sulfur layer and direct desorption of SO groups were never observed in the molecular dynamics simulations because these processes have high energy barriers (2.4 and 3.1 eV, respectively). However, subsurface diffusion of O atoms, involving the formation of both O-S and O-Mo bonds, is a competing process with lower energy barriers.
publishDate 2020
dc.date.none.fl_str_mv 2020-06
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/11336/142572
Farigliano, Lucas Martín; Paredes Olivera, Patricia; Patrito, Eduardo Martin; Initial steps of oxidative etching of MoS 2 basal planeinduced by O 2; American Chemical Society; Journal of Physical Chemistry C; 124; 24; 6-2020; 13177-13186
1932-7447
1932-7455
CONICET Digital
CONICET
url http://hdl.handle.net/11336/142572
identifier_str_mv Farigliano, Lucas Martín; Paredes Olivera, Patricia; Patrito, Eduardo Martin; Initial steps of oxidative etching of MoS 2 basal planeinduced by O 2; American Chemical Society; Journal of Physical Chemistry C; 124; 24; 6-2020; 13177-13186
1932-7447
1932-7455
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpcc.0c02141
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.0c02141
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 13.070432

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