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Title: Anomalous ultrafast dynamics of hot plasmonic electrons in nanostructures with hot spots

Abstract

The interaction of light and matter in metallic nanosystems is mediated by the collective oscillation of surface electrons, called plasmons. After excitation, plasmons are absorbed by the metal electrons through inter- and intraband transitions, creating a highly non-thermal distribution of electrons. The electron population then decays through electron-electron interactions, creating a hot electron distribution within a few hundred femtoseconds, followed by a further relaxation via electron-phonon scattering on the timescale of a few pico-seconds. In the spectral domain, hot plasmonic electrons induce changes to the plasmonic resonance of the nanostructure by modifying the dielectric constant of the metal. Here, we report on the observation of anomalously strong changes to the ultrafast temporal and spectral responses of these excited hot plasmonic electrons in hybrid metal/oxide nanostructures as a result of varying the geometry and composition of the nanostructure and the excitation wavelength. In particular, we show a large ultrafast, pulsewidth-limited contribution to the excited electron decay signal in hybrid nanostructures containing hot spots. The intensity of this contribution correlates with the efficiency of the generation of highly excited surface electrons. Using theoretical models, we attribute this effect to the generation of hot plasmonic electrons from hot spots. Finally, we then developmore » general principles to enhance the generation of energetic electrons through specifically designed plasmonic nanostructures that could be used in applications where hot electron generation is beneficial, such as in solar photocatalysis, photodetectors and nonlinear devices.« less

Authors:
 [1];  [2];  [2];  [3];  [3];  [3];  [2]
  1. Argonne National Lab. (ANL), Argonne, IL (United States); Emory Univ., Atlanta, GA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Ohio Univ., Athens, OH (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1354829
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Nanotechnology
Additional Journal Information:
Journal Volume: 10; Journal Issue: 9; Journal ID: ISSN 1748-3387
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; electronic properties and materials; nanoparticles; nanophotonics and plasmonics

Citation Formats

Harutyunyan, Hayk, Martinson, Alex B. F., Rosenmann, Daniel, Khorashad, Larousse Khosravi, Besteiro, Lucas V., Govorov, Alexander O., and Wiederrecht, Gary P.. Anomalous ultrafast dynamics of hot plasmonic electrons in nanostructures with hot spots. United States: N. p., 2015. Web. https://doi.org/10.1038/NNANO.2015.165.
Harutyunyan, Hayk, Martinson, Alex B. F., Rosenmann, Daniel, Khorashad, Larousse Khosravi, Besteiro, Lucas V., Govorov, Alexander O., & Wiederrecht, Gary P.. Anomalous ultrafast dynamics of hot plasmonic electrons in nanostructures with hot spots. United States. https://doi.org/10.1038/NNANO.2015.165
Harutyunyan, Hayk, Martinson, Alex B. F., Rosenmann, Daniel, Khorashad, Larousse Khosravi, Besteiro, Lucas V., Govorov, Alexander O., and Wiederrecht, Gary P.. Mon . "Anomalous ultrafast dynamics of hot plasmonic electrons in nanostructures with hot spots". United States. https://doi.org/10.1038/NNANO.2015.165. https://www.osti.gov/servlets/purl/1354829.
@article{osti_1354829,
title = {Anomalous ultrafast dynamics of hot plasmonic electrons in nanostructures with hot spots},
author = {Harutyunyan, Hayk and Martinson, Alex B. F. and Rosenmann, Daniel and Khorashad, Larousse Khosravi and Besteiro, Lucas V. and Govorov, Alexander O. and Wiederrecht, Gary P.},
abstractNote = {The interaction of light and matter in metallic nanosystems is mediated by the collective oscillation of surface electrons, called plasmons. After excitation, plasmons are absorbed by the metal electrons through inter- and intraband transitions, creating a highly non-thermal distribution of electrons. The electron population then decays through electron-electron interactions, creating a hot electron distribution within a few hundred femtoseconds, followed by a further relaxation via electron-phonon scattering on the timescale of a few pico-seconds. In the spectral domain, hot plasmonic electrons induce changes to the plasmonic resonance of the nanostructure by modifying the dielectric constant of the metal. Here, we report on the observation of anomalously strong changes to the ultrafast temporal and spectral responses of these excited hot plasmonic electrons in hybrid metal/oxide nanostructures as a result of varying the geometry and composition of the nanostructure and the excitation wavelength. In particular, we show a large ultrafast, pulsewidth-limited contribution to the excited electron decay signal in hybrid nanostructures containing hot spots. The intensity of this contribution correlates with the efficiency of the generation of highly excited surface electrons. Using theoretical models, we attribute this effect to the generation of hot plasmonic electrons from hot spots. Finally, we then develop general principles to enhance the generation of energetic electrons through specifically designed plasmonic nanostructures that could be used in applications where hot electron generation is beneficial, such as in solar photocatalysis, photodetectors and nonlinear devices.},
doi = {10.1038/NNANO.2015.165},
journal = {Nature Nanotechnology},
number = 9,
volume = 10,
place = {United States},
year = {2015},
month = {8}
}

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