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dc.contributor.authorAsyuda, Andika
dc.contributor.authorde la Morena, Rodrigo Ortiz
dc.contributor.authorSauter, Eric
dc.contributor.authorTurner, Kelly
dc.contributor.authorMcDonald, Kirsty
dc.contributor.authorBuck, Manfred
dc.contributor.authorZharnikov, Michael
dc.identifier.citationAsyuda , A , de la Morena , R O , Sauter , E , Turner , K , McDonald , K , Buck , M & Zharnikov , M 2020 , ' Electron-induced modification of self-assembled monolayers of aromatic carboxylic acids ' , Journal of Physical Chemistry C , vol. 124 , no. 45 , pp. 25107-25120 .
dc.identifier.otherPURE: 271330914
dc.identifier.otherPURE UUID: 289960d1-1e4d-499f-8298-55563823827f
dc.identifier.otherRIS: urn:DABDE08858CD2F5A96AFC783A88E8544
dc.identifier.otherScopus: 85095805678
dc.identifier.otherORCID: /0000-0003-1225-7607/work/83889270
dc.identifier.otherWOS: 000598992900055
dc.descriptionA.A. acknowledges the financial support by the DAAD-Aceh Scholarship of Excellence. Financial support by EPSRC via doctoral training grants (R.O.d.l.M.) and the EPSRC Center for Doctoral Training in Critical Resource Catalysis (CRITICAT) (PhD studentship to K.T.) is gratefully acknowledged.en
dc.description.abstractThe effects of low-energy electrons on aromatic self-assembled monolayers (SAMs) with carboxylic acid (CA) docking groups were studied with a focus on the dose range below 5 mC/cm2. The SAMs were prepared on an underpotentially deposited Ag bilayer and comprised nonsubstituted and CA-substituted monolayers with a rod-like biphenyl backbone and a monolayer of a Y-shaped, CA-substituted molecule, 1,3,5-benzenetribenzoic acid (H3BTB), formed either as a single-component film or as a binary one by mixing with adamantane-CA (Ad-CA). X-ray photoelectron and near-edge X-ray absorption fine structure spectra suggest high proneness of the CA groups to electron irradiation at both SAM/substrate and SAM/ambient interfaces. Cleavage of the carboxylate-substrate bond results in substantial molecular desorption at the initial stage of irradiation until electron-induced cross-linking gradually takes over. The CA groups at the outer SAM interface undergo substantial chemical changes, indicating that they participate in the cross-linking chemistry. The electron-induced processes are accompanied by molecular reorientation. Disordering for the SAMs formed by the rod-like molecules is contrasted by the H3BTB-based systems where changes also occur but some molecular order is preserved as explained by a proposed model invoking conformational changes. In SAMs of H3BTB mixed with Ad-CA, the latter shows higher proneness to irradiation-induced desorption than the former, as well as an influence on the cross-linking chemistry. The results of the present study suggest that CA-based SAMs on Ag offer additional options for cross-linking in SAMs and, as exemplarily demonstrated by the generation of Cu patterns on structured H3BTB templates, can be efficiently used for lithography and nanofabrication.
dc.relation.ispartofJournal of Physical Chemistry Cen
dc.rightsCopyright © 2020 American Chemical Society. This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at
dc.subjectQD Chemistryen
dc.titleElectron-induced modification of self-assembled monolayers of aromatic carboxylic acidsen
dc.typeJournal articleen
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.contributor.institutionUniversity of St Andrews. EaSTCHEMen
dc.description.statusPeer revieweden

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