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

Charlie Readman; Bart De Nijs; István Szabó; 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, István Szabó, Angela Demetriadou, Ryan Greenhalgh, Colm Durkan, Edina Rosta, Oren A. Scherman, Jeremy J. Baumberg^*

^*Corresponding author for this work

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

36 Citations (Scopus)

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 bis-phthalocyanine 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
DOIs	https://doi.org/10.1021/acs.nanolett.9b00199
Publication status	Published - 13 Mar 2019

Keywords

DFT
nanoassembly
Nanocavities
phthalocyanines
quantum plasmonics
SERS

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10.1021/acs.nanolett.9b00199

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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 bis-phthalocyanine 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, nanoassembly, Nanocavities, phthalocyanines, quantum plasmonics, SERS",

author = "Charlie Readman and {De Nijs}, Bart and Istv{\'a}n Szab{\'o} and Angela Demetriadou and Ryan Greenhalgh and Colm Durkan and Edina Rosta and Scherman, {Oren A.} and Baumberg, {Jeremy J.}",

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doi = "10.1021/acs.nanolett.9b00199",

language = "English",

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AU - Readman, Charlie

AU - De Nijs, Bart

AU - Szabó, István

AU - Demetriadou, Angela

AU - Greenhalgh, Ryan

AU - Durkan, Colm

AU - Rosta, Edina

AU - Scherman, Oren A.

AU - Baumberg, Jeremy J.

PY - 2019/3/13

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 bis-phthalocyanine 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 bis-phthalocyanine 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.

KW - DFT

KW - nanoassembly

KW - Nanocavities

KW - phthalocyanines

KW - quantum plasmonics

KW - SERS

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DO - 10.1021/acs.nanolett.9b00199

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VL - 19

SP - 2051

EP - 2058

JO - Nano Letters

JF - Nano Letters

IS - 3

ER -

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

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Keywords

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