Revisiting the Determination of the Valence Band Maximum and Defect Formation in Halide Perovskites for Solar Cells: Insights from Highly Sensitive Near-UV Photoemission Spectroscopy

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The authors acknowledge funding from the Federal Ministry of Education and Research (BMBF) for funding of the Young Investigator Group Perovskite Tandem Solar Cells within the program “Materialforschung für die Energiewende” (grant no. 03SF0540), the Helmholtz Association within the HySPRINT Innovat...

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Autores: Menzel D., Tejada A., Al-Ashouri A., Levine I., Guerra Torres, Jorge Andrés, Rech B., Albrecht S., Korte L.
Formato: artículo
Fecha de Publicación:2021
Institución:Consejo Nacional de Ciencia Tecnología e Innovación
Repositorio:CONCYTEC-Institucional
Lenguaje:inglés
OAI Identifier:oai:repositorio.concytec.gob.pe:20.500.12390/3049
Enlace del recurso:https://hdl.handle.net/20.500.12390/3049
https://doi.org/10.1021/acsami.1c10171
Nivel de acceso:acceso abierto
Materia:solar cells
defect states
halide perovskites
near-UV spectroscopy
photoemission spectroscopy
https://purl.org/pe-repo/ocde/ford#3.04.02
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network_name_str CONCYTEC-Institucional
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dc.title.none.fl_str_mv Revisiting the Determination of the Valence Band Maximum and Defect Formation in Halide Perovskites for Solar Cells: Insights from Highly Sensitive Near-UV Photoemission Spectroscopy
title Revisiting the Determination of the Valence Band Maximum and Defect Formation in Halide Perovskites for Solar Cells: Insights from Highly Sensitive Near-UV Photoemission Spectroscopy
spellingShingle Revisiting the Determination of the Valence Band Maximum and Defect Formation in Halide Perovskites for Solar Cells: Insights from Highly Sensitive Near-UV Photoemission Spectroscopy
Menzel D.
solar cells
defect states
halide perovskites
near-UV spectroscopy
photoemission spectroscopy
https://purl.org/pe-repo/ocde/ford#3.04.02
title_short Revisiting the Determination of the Valence Band Maximum and Defect Formation in Halide Perovskites for Solar Cells: Insights from Highly Sensitive Near-UV Photoemission Spectroscopy
title_full Revisiting the Determination of the Valence Band Maximum and Defect Formation in Halide Perovskites for Solar Cells: Insights from Highly Sensitive Near-UV Photoemission Spectroscopy
title_fullStr Revisiting the Determination of the Valence Band Maximum and Defect Formation in Halide Perovskites for Solar Cells: Insights from Highly Sensitive Near-UV Photoemission Spectroscopy
title_full_unstemmed Revisiting the Determination of the Valence Band Maximum and Defect Formation in Halide Perovskites for Solar Cells: Insights from Highly Sensitive Near-UV Photoemission Spectroscopy
title_sort Revisiting the Determination of the Valence Band Maximum and Defect Formation in Halide Perovskites for Solar Cells: Insights from Highly Sensitive Near-UV Photoemission Spectroscopy
author Menzel D.
author_facet Menzel D.
Tejada A.
Al-Ashouri A.
Levine I.
Guerra Torres, Jorge Andrés
Rech B.
Albrecht S.
Korte L.
author_role author
author2 Tejada A.
Al-Ashouri A.
Levine I.
Guerra Torres, Jorge Andrés
Rech B.
Albrecht S.
Korte L.
author2_role author
author
author
author
author
author
author
dc.contributor.author.fl_str_mv Menzel D.
Tejada A.
Al-Ashouri A.
Levine I.
Guerra Torres, Jorge Andrés
Rech B.
Albrecht S.
Korte L.
dc.subject.none.fl_str_mv solar cells
topic solar cells
defect states
halide perovskites
near-UV spectroscopy
photoemission spectroscopy
https://purl.org/pe-repo/ocde/ford#3.04.02
dc.subject.es_PE.fl_str_mv defect states
halide perovskites
near-UV spectroscopy
photoemission spectroscopy
dc.subject.ocde.none.fl_str_mv https://purl.org/pe-repo/ocde/ford#3.04.02
description The authors acknowledge funding from the Federal Ministry of Education and Research (BMBF) for funding of the Young Investigator Group Perovskite Tandem Solar Cells within the program “Materialforschung für die Energiewende” (grant no. 03SF0540), the Helmholtz Association within the HySPRINT Innovation lab project, and the HyPerCells joint Graduate School. This research was supported by the joint agreement between the DAAD (German Academic Exchange Service) and FONDECYT (National Fund for Scientific, Technological Development and Technological Innovation) under the agreements 57508544 DAAD and 423-2019-FONDECYT. Further support has been provided by the PUCP vice chancellorship for research (VRI, project no. CAP-2019-3-0041/702). The authors thank Thomas Lußky for technical support, Bor Li for part of the sample preparation, and Norbert Koch, David Cahen, Isaac Balberg and Norbert Nickel for fruitful discussions. I.L. thanks the PEROSEED project and AiF project (ZIM-KK5085302DF0) for financial support.
publishDate 2021
dc.date.accessioned.none.fl_str_mv 2024-05-30T23:13:38Z
dc.date.available.none.fl_str_mv 2024-05-30T23:13:38Z
dc.date.issued.fl_str_mv 2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.uri.none.fl_str_mv https://hdl.handle.net/20.500.12390/3049
dc.identifier.doi.none.fl_str_mv https://doi.org/10.1021/acsami.1c10171
dc.identifier.scopus.none.fl_str_mv 2-s2.0-85115106982
url https://hdl.handle.net/20.500.12390/3049
https://doi.org/10.1021/acsami.1c10171
identifier_str_mv 2-s2.0-85115106982
dc.language.iso.none.fl_str_mv eng
language eng
dc.relation.ispartof.none.fl_str_mv ACS Applied Materials and Interfaces
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONCYTEC-Institucional
instname:Consejo Nacional de Ciencia Tecnología e Innovación
instacron:CONCYTEC
instname_str Consejo Nacional de Ciencia Tecnología e Innovación
instacron_str CONCYTEC
institution CONCYTEC
reponame_str CONCYTEC-Institucional
collection CONCYTEC-Institucional
repository.name.fl_str_mv Repositorio Institucional CONCYTEC
repository.mail.fl_str_mv repositorio@concytec.gob.pe
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spelling Publicationrp08732600rp01802600rp08733600rp08731600rp00710600rp01801600rp01803600rp01800600Menzel D.Tejada A.Al-Ashouri A.Levine I.Guerra Torres, Jorge AndrésRech B.Albrecht S.Korte L.2024-05-30T23:13:38Z2024-05-30T23:13:38Z2021https://hdl.handle.net/20.500.12390/3049https://doi.org/10.1021/acsami.1c101712-s2.0-85115106982The authors acknowledge funding from the Federal Ministry of Education and Research (BMBF) for funding of the Young Investigator Group Perovskite Tandem Solar Cells within the program “Materialforschung für die Energiewende” (grant no. 03SF0540), the Helmholtz Association within the HySPRINT Innovation lab project, and the HyPerCells joint Graduate School. This research was supported by the joint agreement between the DAAD (German Academic Exchange Service) and FONDECYT (National Fund for Scientific, Technological Development and Technological Innovation) under the agreements 57508544 DAAD and 423-2019-FONDECYT. Further support has been provided by the PUCP vice chancellorship for research (VRI, project no. CAP-2019-3-0041/702). The authors thank Thomas Lußky for technical support, Bor Li for part of the sample preparation, and Norbert Koch, David Cahen, Isaac Balberg and Norbert Nickel for fruitful discussions. I.L. thanks the PEROSEED project and AiF project (ZIM-KK5085302DF0) for financial support.Using advanced near-UV photoemission spectroscopy (PES) in constant final state mode (CFSYS) with a very high dynamic range, we investigate the triple-cation lead halide perovskite Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 and gain detailed insights into the density of occupied states (DOS) in the valence band and band gap. A valence band model is established which includes the parabolic valence band edge and an exponentially decaying band tail in a single equation. This allows us to precisely determine two valence band maxima (VBM) at different k-vectors in the angle-integrated spectra, where the highest one, resulting from the VBM at the R-point in the Brillouin zone, is found between -1.50 to -1.37 eV relative to the Fermi energy EF. We investigate quantitatively the formation of defect states in the band gap up to EF upon decomposition of the perovskites during sample transfer, storage, and measurements: during near-UV-based PES, the density of defect states saturates at a value that is around 4 orders of magnitude below the density of states at the valence band edge. However, even short air exposure, or 3 h of X-ray illumination, increased their density by almost a factor of six and ?40, respectively. Upon prolonged storage in vacuum, the formation of a distinct defect peak is observed. Thus, near-UV CFSYS with modeling as shown here is demonstrated as a powerful tool to characterize the valence band and quantify defect states in lead halide perovskites. © 2021 The Authors. Published by American Chemical Society.Consejo Nacional de Ciencia, Tecnología e Innovación Tecnológica - ConcytecengAmerican Chemical SocietyACS Applied Materials and Interfacesinfo:eu-repo/semantics/openAccesssolar cellsdefect states-1halide perovskites-1near-UV spectroscopy-1photoemission spectroscopy-1https://purl.org/pe-repo/ocde/ford#3.04.02-1Revisiting the Determination of the Valence Band Maximum and Defect Formation in Halide Perovskites for Solar Cells: Insights from Highly Sensitive Near-UV Photoemission Spectroscopyinfo:eu-repo/semantics/articlereponame:CONCYTEC-Institucionalinstname:Consejo Nacional de Ciencia Tecnología e Innovacióninstacron:CONCYTEC20.500.12390/3049oai:repositorio.concytec.gob.pe:20.500.12390/30492024-05-30 16:13:29.778http://purl.org/coar/access_right/c_14cbinfo:eu-repo/semantics/closedAccessmetadata only accesshttps://repositorio.concytec.gob.peRepositorio Institucional CONCYTECrepositorio@concytec.gob.pe#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#<Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="94eb499c-f78e-4645-93cf-91f7dbb1b3ef"> <Type xmlns="https://www.openaire.eu/cerif-profile/vocab/COAR_Publication_Types">http://purl.org/coar/resource_type/c_1843</Type> <Language>eng</Language> <Title>Revisiting the Determination of the Valence Band Maximum and Defect Formation in Halide Perovskites for Solar Cells: Insights from Highly Sensitive Near-UV Photoemission Spectroscopy</Title> <PublishedIn> <Publication> <Title>ACS Applied Materials and Interfaces</Title> </Publication> </PublishedIn> <PublicationDate>2021</PublicationDate> <DOI>https://doi.org/10.1021/acsami.1c10171</DOI> <SCP-Number>2-s2.0-85115106982</SCP-Number> <Authors> <Author> <DisplayName>Menzel D.</DisplayName> <Person id="rp08732" /> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> <Author> <DisplayName>Tejada A.</DisplayName> <Person id="rp01802" /> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> <Author> <DisplayName>Al-Ashouri A.</DisplayName> <Person id="rp08733" /> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> <Author> <DisplayName>Levine I.</DisplayName> <Person id="rp08731" /> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> <Author> <DisplayName>Guerra Torres, Jorge Andrés</DisplayName> <Person id="rp00710" /> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> <Author> <DisplayName>Rech B.</DisplayName> <Person id="rp01801" /> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> <Author> <DisplayName>Albrecht S.</DisplayName> <Person id="rp01803" /> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> <Author> <DisplayName>Korte L.</DisplayName> <Person id="rp01800" /> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> </Authors> <Editors> </Editors> <Publishers> <Publisher> <DisplayName>American Chemical Society</DisplayName> <OrgUnit /> </Publisher> </Publishers> <Keyword>solar cells</Keyword> <Keyword>defect states</Keyword> <Keyword>halide perovskites</Keyword> <Keyword>near-UV spectroscopy</Keyword> <Keyword>photoemission spectroscopy</Keyword> <Abstract>Using advanced near-UV photoemission spectroscopy (PES) in constant final state mode (CFSYS) with a very high dynamic range, we investigate the triple-cation lead halide perovskite Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 and gain detailed insights into the density of occupied states (DOS) in the valence band and band gap. A valence band model is established which includes the parabolic valence band edge and an exponentially decaying band tail in a single equation. This allows us to precisely determine two valence band maxima (VBM) at different k-vectors in the angle-integrated spectra, where the highest one, resulting from the VBM at the R-point in the Brillouin zone, is found between -1.50 to -1.37 eV relative to the Fermi energy EF. We investigate quantitatively the formation of defect states in the band gap up to EF upon decomposition of the perovskites during sample transfer, storage, and measurements: during near-UV-based PES, the density of defect states saturates at a value that is around 4 orders of magnitude below the density of states at the valence band edge. However, even short air exposure, or 3 h of X-ray illumination, increased their density by almost a factor of six and ?40, respectively. Upon prolonged storage in vacuum, the formation of a distinct defect peak is observed. Thus, near-UV CFSYS with modeling as shown here is demonstrated as a powerful tool to characterize the valence band and quantify defect states in lead halide perovskites. © 2021 The Authors. Published by American Chemical Society.</Abstract> <Access xmlns="http://purl.org/coar/access_right" > </Access> </Publication> -1
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