Fermi level equilibration at the metal-molecule interface in plasmonic systems
File(s)
Accepted version
Author(s)
Type
Journal Article
Abstract
We highlight a new metal–molecule charge transfer process by tuning the Fermi energy of plasmonic silver nanoparticles (AgNPs) in situ. The strong adsorption of halide ions upshifts the Fermi level of AgNPs by up to ∼0.3 eV in the order Cl– < Br– < I–, favoring the spontaneous charge transfer to aligned molecular acceptor orbitals until charge neutrality across the interface is achieved. By carefully quantifying, experimentally and theoretically, the Fermi level upshift, we show for the first time that this effect is comparable in energy to different plasmonic effects such as the plasmoelectric effect or hot-carriers production. Moreover, by monitoring in situ the adsorption dynamic of halide ions in different AgNP–molecule systems, we show for the first time that the catalytic role of halide ions in plasmonic nanostructures depends on the surface affinity of halide ions compared to that of the target molecule.
Date Issued
2021-07-22
Date Acceptance
2021-07-01
Citation
Nano Letters: a journal dedicated to nanoscience and nanotechnology, 2021, 21 (15), pp.6592-6599
ISSN
1530-6984
Publisher
American Chemical Society
Start Page
6592
End Page
6599
Journal / Book Title
Nano Letters: a journal dedicated to nanoscience and nanotechnology
Volume
21
Issue
15
Copyright Statement
© 2021 American Chemical Society
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000685244900031&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Subjects
Science & Technology
Physical Sciences
Technology
Chemistry, Multidisciplinary
Chemistry, Physical
Nanoscience & Nanotechnology
Materials Science, Multidisciplinary
Physics, Applied
Physics, Condensed Matter
Chemistry
Science & Technology - Other Topics
Materials Science
Physics
Photocatalysis
catalysis
Fermi level
charge transfer
SERS
COLLOIDAL SILVER NANOPARTICLES
METHYLENE-BLUE
SINGLE-MOLECULE
CHARGE-TRANSFER
GOLD
NANOSTRUCTURES
REDUCTION
ALIGNMENT
FILMS
Publication Status
Published
Date Publish Online
2021-07-22