Electron Irradiation-driven charge state modulation in metal-intercalated SAMs

<p dir="ltr">Metal ion intercalation provides a powerful strategy to modulate the physical and electronic properties of molecular self-assembled monolayers (SAMs), with the charge state of the intercalated metal ions playing a critical role in determining system functionality. Here,...

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Main Author: Yongfeng Tong (3121338) (author)
Other Authors: Manal Alsalama (17316895) (author), Golibjon Berdiyorov (6325997) (author), Hicham Hamoudi (1984285) (author)
Published: 2025
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author Yongfeng Tong (3121338)
author2 Manal Alsalama (17316895)
Golibjon Berdiyorov (6325997)
Hicham Hamoudi (1984285)
author2_role author
author
author
author_facet Yongfeng Tong (3121338)
Manal Alsalama (17316895)
Golibjon Berdiyorov (6325997)
Hicham Hamoudi (1984285)
author_role author
dc.creator.none.fl_str_mv Yongfeng Tong (3121338)
Manal Alsalama (17316895)
Golibjon Berdiyorov (6325997)
Hicham Hamoudi (1984285)
dc.date.none.fl_str_mv 2025-11-03T12:00:00Z
dc.identifier.none.fl_str_mv 10.1016/j.apsusc.2025.165010
dc.relation.none.fl_str_mv https://figshare.com/articles/journal_contribution/Electron_Irradiation-driven_charge_state_modulation_in_metal-intercalated_SAMs/30819815
dc.rights.none.fl_str_mv CC BY 4.0
info:eu-repo/semantics/openAccess
dc.subject.none.fl_str_mv Engineering
Materials engineering
Nanotechnology
Electronic irradiation
Molecular self-assembled monolayer
Metal intercalation
Charge transfer
Molecular diode
dc.title.none.fl_str_mv Electron Irradiation-driven charge state modulation in metal-intercalated SAMs
dc.type.none.fl_str_mv Text
Journal contribution
info:eu-repo/semantics/publishedVersion
text
contribution to journal
description <p dir="ltr">Metal ion intercalation provides a powerful strategy to modulate the physical and electronic properties of molecular self-assembled monolayers (SAMs), with the charge state of the intercalated metal ions playing a critical role in determining system functionality. Here, we demonstrate that electron irradiation can be employed as an external stimulus to control the charge state of metal ions within π-conjugated molecular SAMs on Au (111) substrates. Using copper-intercalated 5,5′-bis(mercaptomethyl)-2,2′-bipyridine (BPD) −based SAMs as a model system, we systematically investigate the effect of electron beam exposure on the valence state of copper ions. X-ray photoelectron spectroscopy reveals a progressive conversion of Cu2<sup>+</sup> to Cu<sup>+</sup> under electron irradiation, attributed to irradiation-induced molecular rearrangements that lower the metal coordination. Density functional theory calculations further indicate that external electrons promote crosslinking patterns stabilizing twofold metal coordination. These findings establish electron irradiation as a versatile tool for post-synthetic charge state modulation in metal-intercalated SAMs, enabling new routes to tailor nanoscale molecular electronic devices.</p><h2>Other Information</h2><p dir="ltr">Published in: Applied Surface Science<br>License: <a href="http://creativecommons.org/licenses/by/4.0/" target="_blank">http://creativecommons.org/licenses/by/4.0/</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.1016/j.apsusc.2025.165010" target="_blank">https://dx.doi.org/10.1016/j.apsusc.2025.165010</a></p>
eu_rights_str_mv openAccess
id Manara2_72d5a1a7ef90856b5b97ac45e406a749
identifier_str_mv 10.1016/j.apsusc.2025.165010
network_acronym_str Manara2
network_name_str Manara2
oai_identifier_str oai:figshare.com:article/30819815
publishDate 2025
repository.mail.fl_str_mv
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rights_invalid_str_mv CC BY 4.0
spelling Electron Irradiation-driven charge state modulation in metal-intercalated SAMsYongfeng Tong (3121338)Manal Alsalama (17316895)Golibjon Berdiyorov (6325997)Hicham Hamoudi (1984285)EngineeringMaterials engineeringNanotechnologyElectronic irradiationMolecular self-assembled monolayerMetal intercalationCharge transferMolecular diode<p dir="ltr">Metal ion intercalation provides a powerful strategy to modulate the physical and electronic properties of molecular self-assembled monolayers (SAMs), with the charge state of the intercalated metal ions playing a critical role in determining system functionality. Here, we demonstrate that electron irradiation can be employed as an external stimulus to control the charge state of metal ions within π-conjugated molecular SAMs on Au (111) substrates. Using copper-intercalated 5,5′-bis(mercaptomethyl)-2,2′-bipyridine (BPD) −based SAMs as a model system, we systematically investigate the effect of electron beam exposure on the valence state of copper ions. X-ray photoelectron spectroscopy reveals a progressive conversion of Cu2<sup>+</sup> to Cu<sup>+</sup> under electron irradiation, attributed to irradiation-induced molecular rearrangements that lower the metal coordination. Density functional theory calculations further indicate that external electrons promote crosslinking patterns stabilizing twofold metal coordination. These findings establish electron irradiation as a versatile tool for post-synthetic charge state modulation in metal-intercalated SAMs, enabling new routes to tailor nanoscale molecular electronic devices.</p><h2>Other Information</h2><p dir="ltr">Published in: Applied Surface Science<br>License: <a href="http://creativecommons.org/licenses/by/4.0/" target="_blank">http://creativecommons.org/licenses/by/4.0/</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.1016/j.apsusc.2025.165010" target="_blank">https://dx.doi.org/10.1016/j.apsusc.2025.165010</a></p>2025-11-03T12:00:00ZTextJournal contributioninfo:eu-repo/semantics/publishedVersiontextcontribution to journal10.1016/j.apsusc.2025.165010https://figshare.com/articles/journal_contribution/Electron_Irradiation-driven_charge_state_modulation_in_metal-intercalated_SAMs/30819815CC BY 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/308198152025-11-03T12:00:00Z
spellingShingle Electron Irradiation-driven charge state modulation in metal-intercalated SAMs
Yongfeng Tong (3121338)
Engineering
Materials engineering
Nanotechnology
Electronic irradiation
Molecular self-assembled monolayer
Metal intercalation
Charge transfer
Molecular diode
status_str publishedVersion
title Electron Irradiation-driven charge state modulation in metal-intercalated SAMs
title_full Electron Irradiation-driven charge state modulation in metal-intercalated SAMs
title_fullStr Electron Irradiation-driven charge state modulation in metal-intercalated SAMs
title_full_unstemmed Electron Irradiation-driven charge state modulation in metal-intercalated SAMs
title_short Electron Irradiation-driven charge state modulation in metal-intercalated SAMs
title_sort Electron Irradiation-driven charge state modulation in metal-intercalated SAMs
topic Engineering
Materials engineering
Nanotechnology
Electronic irradiation
Molecular self-assembled monolayer
Metal intercalation
Charge transfer
Molecular diode