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Title: Spatially defined molecular emitters coupled to plasmonic nanoparticle arrays

Abstract

This paper describes how metal–organic frameworks (MOFs) conformally coated on plasmonic nanoparticle arrays can support exciton–plasmon modes with features resembling strong coupling but that are better understood by a weak coupling model. Thin films of Zn-porphyrin MOFs were assembled by dip coating on arrays of silver nanoparticles (NP@MOF) that sustain surface lattice resonances (SLRs). Coupling of excitons with these lattice plasmons led to an SLR-like mixed mode in both transmission and transient absorption spectra. The spectral position of the mixed mode could be tailored by detuning the SLR in different refractive index environments and by changing the periodicity of the nanoparticle array. Photoluminescence showed mode splitting that can be interpreted as modulation of the exciton line shape by the Fano profile of the surface lattice mode, without requiring Rabi splitting. Compared with pristine Zn-porphyrin, hybrid NP@MOF structures achieved a 16-fold enhancement in emission intensity. Our results establish MOFs as a crystalline molecular emitter material that can couple with plasmonic structures for energy exchange and transfer.

Authors:
ORCiD logo; ; ; ; ; ; ORCiD logo; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1498799
Grant/Contract Number:  
SC0004752
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 116 Journal Issue: 13; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Liu, Jianxi, Wang, Weijia, Wang, Danqing, Hu, Jingtian, Ding, Wendu, Schaller, Richard D., Schatz, George C., and Odom, Teri W. Spatially defined molecular emitters coupled to plasmonic nanoparticle arrays. United States: N. p., 2019. Web. doi:10.1073/pnas.1818902116.
Liu, Jianxi, Wang, Weijia, Wang, Danqing, Hu, Jingtian, Ding, Wendu, Schaller, Richard D., Schatz, George C., & Odom, Teri W. Spatially defined molecular emitters coupled to plasmonic nanoparticle arrays. United States. doi:10.1073/pnas.1818902116.
Liu, Jianxi, Wang, Weijia, Wang, Danqing, Hu, Jingtian, Ding, Wendu, Schaller, Richard D., Schatz, George C., and Odom, Teri W. Fri . "Spatially defined molecular emitters coupled to plasmonic nanoparticle arrays". United States. doi:10.1073/pnas.1818902116.
@article{osti_1498799,
title = {Spatially defined molecular emitters coupled to plasmonic nanoparticle arrays},
author = {Liu, Jianxi and Wang, Weijia and Wang, Danqing and Hu, Jingtian and Ding, Wendu and Schaller, Richard D. and Schatz, George C. and Odom, Teri W.},
abstractNote = {This paper describes how metal–organic frameworks (MOFs) conformally coated on plasmonic nanoparticle arrays can support exciton–plasmon modes with features resembling strong coupling but that are better understood by a weak coupling model. Thin films of Zn-porphyrin MOFs were assembled by dip coating on arrays of silver nanoparticles (NP@MOF) that sustain surface lattice resonances (SLRs). Coupling of excitons with these lattice plasmons led to an SLR-like mixed mode in both transmission and transient absorption spectra. The spectral position of the mixed mode could be tailored by detuning the SLR in different refractive index environments and by changing the periodicity of the nanoparticle array. Photoluminescence showed mode splitting that can be interpreted as modulation of the exciton line shape by the Fano profile of the surface lattice mode, without requiring Rabi splitting. Compared with pristine Zn-porphyrin, hybrid NP@MOF structures achieved a 16-fold enhancement in emission intensity. Our results establish MOFs as a crystalline molecular emitter material that can couple with plasmonic structures for energy exchange and transfer.},
doi = {10.1073/pnas.1818902116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 13,
volume = 116,
place = {United States},
year = {2019},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1818902116

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Works referenced in this record:

A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n
journal, February 1999


Electromagnetic fields around silver nanoparticles and dimers
journal, January 2004

  • Hao, Encai; Schatz, George C.
  • The Journal of Chemical Physics, Vol. 120, Issue 1, p. 357-366
  • DOI: 10.1063/1.1629280

Plasmonics for improved photovoltaic devices
journal, February 2010

  • Atwater, Harry A.; Polman, Albert
  • Nature Materials, Vol. 9, Issue 3, p. 205-213
  • DOI: 10.1038/nmat2629

Enhancement and Quenching of Single-Molecule Fluorescence
journal, March 2006

  • Anger, Pascal; Bharadwaj, Palash; Novotny, Lukas
  • Physical Review Letters, Vol. 96, Issue 11, Article No. 113002
  • DOI: 10.1103/PhysRevLett.96.113002

Large single-molecule fluorescence enhancements produced by a bowtie nanoantenna
journal, October 2009

  • Kinkhabwala, Anika; Yu, Zongfu; Fan, Shanhui
  • Nature Photonics, Vol. 3, Issue 11, p. 654-657
  • DOI: 10.1038/nphoton.2009.187

Exploitation of Localized Surface Plasmon Resonance
journal, October 2004