Anomalously large spectral shifts near the quantum tunnelling limit in plasmonic rulers with subatomic resolution

Charlie Readman; Bart De Nijs; Istvan Szabo; Angela Demetriadou; Ryan Greenhalgh; Colm Durkan; Edina Rosta; Oren A. Scherman; Jeremy J. Baumberg

doi:10.1021/acs.nanolett.9b00199

Anomalously large spectral shifts near the quantum tunnelling limit in plasmonic rulers with subatomic resolution

Charlie Readman, Bart De Nijs, Istvan Szabo, Angela Demetriadou, Ryan Greenhalgh, Colm Durkan, Edina Rosta, Oren A. Scherman, Jeremy J. Baumberg

Physics and Astronomy

Research output: Contribution to journal › Article › peer-review

17 Citations (Scopus)

223 Downloads (Pure)

Abstract

The resonance wavelength of a coupled plasmonic system is extremely sensitive to the distance between its metallic surfaces, resulting in “plasmon rulers”. We explore this behavior in the subnanometer regime using self-assembled monolayers of bisphthalocyanine molecules in a nanoparticle-on-mirror (NPoM) construct. These allow unprecedented subangstrom control over spacer thickness via choice of metal center, in a gap-size regime at the quantum-mechanical limit of plasmonic enhancement. A dramatic shift in the coupled plasmon resonance is observed as the gap size is varied from 0.39 to 0.41 nm. Existing theoretical models are unable to account for the observed spectral tuning, which requires inclusion of the quantum-classical interface, emphasizing the need for new treatments of light at the subnanoscale

Original language	English
Pages (from-to)	2051-2058
Number of pages	8
Journal	Nano Letters
Volume	19
Issue number	3
Early online date	6 Feb 2019
DOIs	https://doi.org/10.1021/acs.nanolett.9b00199
Publication status	Published - 13 Mar 2019

Keywords

DFT
Nanocavities
SERS
nanoassembly
phthalocyanines
quantum plasmonics

ASJC Scopus subject areas

Bioengineering
General Chemistry
General Materials Science
Condensed Matter Physics
Mechanical Engineering

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10.1021/acs.nanolett.9b00199Licence: None: All rights reserved

Readman_et_al_Anomalously_large_spectral_shifts_Nano_Letters_2019
Checked for eligibility:16/04/2019 This document is the Accepted Manuscript version of a Published Work that appeared in final form in Nano Latters, 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/10.1021/acs.nanolett.9b00199 DOI: 10.1021/acs.nanolett.9b00199
Accepted author manuscript, 716 KBLicence: None: All rights reserved

Cite this

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title = "Anomalously large spectral shifts near the quantum tunnelling limit in plasmonic rulers with subatomic resolution",

abstract = "The resonance wavelength of a coupled plasmonic system is extremely sensitive to the distance between its metallic surfaces, resulting in “plasmon rulers”. We explore this behavior in the subnanometer regime using self-assembled monolayers of bisphthalocyanine molecules in a nanoparticle-on-mirror (NPoM) construct. These allow unprecedented subangstrom control over spacer thickness via choice of metal center, in a gap-size regime at the quantum-mechanical limit of plasmonic enhancement. A dramatic shift in the coupled plasmon resonance is observed as the gap size is varied from 0.39 to 0.41 nm. Existing theoretical models are unable to account for the observed spectral tuning, which requires inclusion of the quantum-classical interface, emphasizing the need for new treatments of light at the subnanoscale",

keywords = "DFT, Nanocavities, SERS, nanoassembly, phthalocyanines, quantum plasmonics",

author = "Charlie Readman and {De Nijs}, Bart and Istvan Szabo and Angela Demetriadou and Ryan Greenhalgh and Colm Durkan and Edina Rosta and Scherman, {Oren A.} and Baumberg, {Jeremy J.}",

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AU - Readman, Charlie

AU - De Nijs, Bart

AU - Szabo, Istvan

AU - Demetriadou, Angela

AU - Greenhalgh, Ryan

AU - Durkan, Colm

AU - Rosta, Edina

AU - Scherman, Oren A.

AU - Baumberg, Jeremy J.

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Y1 - 2019/3/13

N2 - The resonance wavelength of a coupled plasmonic system is extremely sensitive to the distance between its metallic surfaces, resulting in “plasmon rulers”. We explore this behavior in the subnanometer regime using self-assembled monolayers of bisphthalocyanine molecules in a nanoparticle-on-mirror (NPoM) construct. These allow unprecedented subangstrom control over spacer thickness via choice of metal center, in a gap-size regime at the quantum-mechanical limit of plasmonic enhancement. A dramatic shift in the coupled plasmon resonance is observed as the gap size is varied from 0.39 to 0.41 nm. Existing theoretical models are unable to account for the observed spectral tuning, which requires inclusion of the quantum-classical interface, emphasizing the need for new treatments of light at the subnanoscale

AB - The resonance wavelength of a coupled plasmonic system is extremely sensitive to the distance between its metallic surfaces, resulting in “plasmon rulers”. We explore this behavior in the subnanometer regime using self-assembled monolayers of bisphthalocyanine molecules in a nanoparticle-on-mirror (NPoM) construct. These allow unprecedented subangstrom control over spacer thickness via choice of metal center, in a gap-size regime at the quantum-mechanical limit of plasmonic enhancement. A dramatic shift in the coupled plasmon resonance is observed as the gap size is varied from 0.39 to 0.41 nm. Existing theoretical models are unable to account for the observed spectral tuning, which requires inclusion of the quantum-classical interface, emphasizing the need for new treatments of light at the subnanoscale

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KW - Nanocavities

KW - SERS

KW - nanoassembly

KW - phthalocyanines

KW - quantum plasmonics

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JO - Nano Letters

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Anomalously large spectral shifts near the quantum tunnelling limit in plasmonic rulers with subatomic resolution

Abstract

Keywords

ASJC Scopus subject areas

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