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Title: Fluorescence intermittency originates from reclustering in two-dimensional organic semiconductors

Abstract

Fluorescence intermittency or blinking is observed in nearly all nanoscale fluorophores. It is characterized by universal power-law distributions in on- and off-times as well as 1/f behaviour in corresponding emission power spectral densities. Blinking, previously seen in confined zero- and one-dimensional systems has recently been documented in two-dimensional reduced graphene oxide. Here we show that unexpected blinking during graphene oxide-to-reduced graphene oxide photoreduction is attributed, in large part, to the redistribution of carbon sp2 domains. This reclustering generates fluctuations in the number/size of emissive graphenic nanoclusters wherein multiscale modelling captures essential experimental aspects of reduced graphene oxide’s absorption/emission trajectories, while simultaneously connecting them to the underlying photochemistry responsible for graphene oxide’s reduction. These simulations thus establish causality between currently unexplained, long timescale emission intermittency in a quantum mechanical fluorophore and identifiable chemical reactions that ultimately lead to switching between on and off states.

Authors:
 [1];  [2]; ORCiD logo [3];  [1];  [4];  [5];  [5];  [1]
+ Show Author Affiliations
  1. Univ. of Notre Dame, IN (United States). Dept. of Physics
  2. National Taiwan Univ., Taipei (Taiwan). Center for Condensed Matter Sciences
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  4. Max Planck Inst. for the Science of Light, Erlangen (Germany)
  5. Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
University of Notre Dame, IN (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); National Taiwan Univ., Taipei (Taiwan)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Aeronautics and Space Administration (NASA); US Army Research Office (ARO); Univ. of Notre Dame (United States); Ministry of Science and Technology (Taiwan)
Contributing Org.:
Max Planck Inst. for the Science of Light, Erlangen (Germany)
OSTI Identifier:
1364352
Grant/Contract Number:  
AC02-06CH11357; W911NF-12-1-0578; 103-2911-I-002-595
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical physics; materials for optics; photochemistry; two-dimensional materials

Citation Formats

Ruth, Anthony, Hayashi, Michitoshi, Zapol, Peter, Si, Jixin, McDonald, Matthew P., Morozov, Yurii V., Kuno, Masaru, and Jankó, Boldizsár. Fluorescence intermittency originates from reclustering in two-dimensional organic semiconductors. United States: N. p., 2017. Web. doi:10.1038/ncomms14521.
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Ruth, Anthony, Hayashi, Michitoshi, Zapol, Peter, Si, Jixin, McDonald, Matthew P., Morozov, Yurii V., Kuno, Masaru, & Jankó, Boldizsár. Fluorescence intermittency originates from reclustering in two-dimensional organic semiconductors. United States. https://doi.org/10.1038/ncomms14521
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Ruth, Anthony, Hayashi, Michitoshi, Zapol, Peter, Si, Jixin, McDonald, Matthew P., Morozov, Yurii V., Kuno, Masaru, and Jankó, Boldizsár. Wed . "Fluorescence intermittency originates from reclustering in two-dimensional organic semiconductors". United States. https://doi.org/10.1038/ncomms14521. https://www.osti.gov/servlets/purl/1364352.
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@article{osti_1364352,
title = {Fluorescence intermittency originates from reclustering in two-dimensional organic semiconductors},
author = {Ruth, Anthony and Hayashi, Michitoshi and Zapol, Peter and Si, Jixin and McDonald, Matthew P. and Morozov, Yurii V. and Kuno, Masaru and Jankó, Boldizsár},
abstractNote = {Fluorescence intermittency or blinking is observed in nearly all nanoscale fluorophores. It is characterized by universal power-law distributions in on- and off-times as well as 1/f behaviour in corresponding emission power spectral densities. Blinking, previously seen in confined zero- and one-dimensional systems has recently been documented in two-dimensional reduced graphene oxide. Here we show that unexpected blinking during graphene oxide-to-reduced graphene oxide photoreduction is attributed, in large part, to the redistribution of carbon sp2 domains. This reclustering generates fluctuations in the number/size of emissive graphenic nanoclusters wherein multiscale modelling captures essential experimental aspects of reduced graphene oxide’s absorption/emission trajectories, while simultaneously connecting them to the underlying photochemistry responsible for graphene oxide’s reduction. These simulations thus establish causality between currently unexplained, long timescale emission intermittency in a quantum mechanical fluorophore and identifiable chemical reactions that ultimately lead to switching between on and off states.},
doi = {10.1038/ncomms14521},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {Wed Feb 22 00:00:00 EST 2017},
month = {Wed Feb 22 00:00:00 EST 2017}
}
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https://doi.org/10.1038/ncomms14521
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