Formation mechanism of metal–molecule–metal junctions: molecule-assisted migration on metal defects

Simple item page
dc.contributor.authorThompson, Damien
dc.contributor.authorLiao, Jianhui
dc.contributor.authorNolan, Michael
dc.contributor.authorQuinn, Aidan J.
dc.contributor.authorNijhuis, Christian A.
dc.contributor.authorO'Dwyer, Colm
dc.contributor.authorNirmalraj, Peter N.
dc.contributor.authorSchönenberger, Christian
dc.contributor.authorCalame, Michel
dc.contributor.funderSeventh Framework Programmeen
dc.contributor.funderScience Foundation Irelanden
dc.contributor.funderNational Research Foundation Singaporeen
dc.date.accessioned2018-08-03T11:02:08Z
dc.date.available2018-08-03T11:02:08Z
dc.date.issued2015-08-05
dc.date.updated2018-08-02T18:39:53Z
dc.description.abstractActivation energies, Ea, measured from molecular exchange experiments are combined with atomic-scale calculations to describe the migration of bare Au atoms and Au–alkanethiolate species on gold nanoparticle surfaces during ligand exchange for the creation of metal–molecule–metal junctions. It is well-known that Au atoms and alkanethiol–Au species can diffuse on gold with sub-1 eV barriers, and surface restructuring is crucial for self-assembled monolayer (SAM) formation for interlinking nanoparticles and in contacting nanoparticles to electrodes. In the present work, computer simulations reveal that naturally occurring ridges and adlayers on Au(111) are etched and resculpted by migration of alkanethiolate–Au species toward high coordination kink sites at surface step edges. The calculated energy barrier, Eb, for diffusion via step edges is 0.4–0.7 eV, close to the experimentally measured Ea of 0.5–0.7 eV. By contrast, putative migration from isolated nine-coordinated terrace sites and complete Au unbinding from the surface incur significantly larger barriers of +1 and +3 eV, respectively. Molecular van der Waals packing energies are calculated to have negligible effect on migration barriers for typically used molecules (length < 2.5 nm), indicating that migration inside SAMs does not change the size of the migration barrier. We use the computational methodology to propose a means of creating Au nanoparticle arrays via selective replacement of citrate protector molecules by thiocyanate linker molecules on surface step sites. This work also outlines the possibility of using Au/Pt alloys as possible candidates for creation of contacts that are well-formed and long-lived because of the superior stability of Pt interfaces against atomic migration.en
dc.description.sponsorshipScience Foundation Ireland (computing resources at the SFI/Higher Education Authority Irish Centre for High-End Computing (ICHEC)); National Research Foundation Singapore (Award NRF-CRP 8-2011-07)en
dc.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationThompson, D., Liao, J., Nolan, M., Quinn, A. J., Nijhuis, C. A., O’Dwyer, C., Nirmalraj, P. N., Schönenberger, C. and Calame, M. (2015) 'Formation Mechanism of Metal–Molecule–Metal Junctions: Molecule-Assisted Migration on Metal Defects', The Journal of Physical Chemistry C, 119(33), pp. 19438-19451. doi: 10.1021/acs.jpcc.5b04383en
dc.identifier.doi10.1021/acs.jpcc.5b04383
dc.identifier.endpage19451en
dc.identifier.issn1932-7447
dc.identifier.issued33en
dc.identifier.journaltitleJournal of Physical Chemistry Cen
dc.identifier.startpage19438en
dc.identifier.urihttps://hdl.handle.net/10468/6573
dc.identifier.volume119en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.projectinfo:eu-repo/grantAgreement/EC/FP7::SP1::NMP/213382/EU/Multi-scale Formation of Functional Nanocrystal-Molecule Assemblies and Architectures/FUNMOLen
dc.relation.projectinfo:eu-repo/grantAgreement/SFI/SFI Starting Investigator Research Grant (SIRG)/11/SIRG/B2111/IE/Engineering Multivalent Proteins for Regenerative Medicine (EMPoRiuM)/en
dc.relation.projectinfo:eu-repo/grantAgreement/EC/FP7::SP1::ICT/318597/EU/SYnaptic MOlecular NEtworks for Bio-inspired Information Processing/SYMONEen
dc.relation.projectinfo:eu-repo/grantAgreement/EC/FP7::SP3::PEOPLE/606728/EU/MOLECULAR-SCALE ELECTRONICS: Concepts, Contacts and Stabilityen
dc.relation.urihttp://pubs.acs.org/doi/abs/10.1021/acs.jpcc.5b04383
dc.rights© 2015 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acs.jpcc.5b04383en
dc.subjectGolden
dc.subjectAtomic-scale calculationen
dc.subjectComputational methodologyen
dc.subjectFormation mechanismen
dc.subjectGold Nanoparticlesen
dc.subjectMetal-molecule-metal junctionsen
dc.subjectMolecular exchangesen
dc.subjectNaturally occurringen
dc.subjectSurface restructuringen
dc.subjectActivation energyen
dc.subjectAtomsen
dc.subjectContacts (fluid mechanics)en
dc.subjectMetal nanoparticlesen
dc.subjectMetalsen
dc.subjectMoleculesen
dc.subjectNanoparticlesen
dc.subjectPlatinum alloysen
dc.subjectSelf assembled monolayersen
dc.subjectVan der Waals forcesen
dc.titleFormation mechanism of metal–molecule–metal junctions: molecule-assisted migration on metal defectsen
dc.typeArticle (peer-reviewed)en
Files
Original bundle
Now showing 1 - 2 of 2
Thumbnail Image
Name:
acs.jpcc.5b04383.docx
Size:
1.56 MB
Format:
Microsoft Word XML
Description:
Author's original
Thumbnail Image
Name:
6636.pdf
Size:
1.19 MB
Format:
Adobe Portable Document Format
Description:
Accepted version
Download
License bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
license.txt
Size:
2.71 KB
Format:
Item-specific license agreed upon to submission
Description:
Download
Collections
Chemistry - Journal Articles
Tyndall National Institute - Journal Articles