Single-Particle Emission Spectroscopy Resolves d-Hole Relaxation in Copper Nanocubes

Cai, Yi-Yu; Collins, Sean S.  E.; Gallagher, Miranda J.; Bhattacharjee, Ujjal; Zhang, Runmin; Chow, Tsz Him; Ahmadivand, Arash; Ostovar, Behnaz; Al-Zubeidi, Alexander; Wang, Jianfang; Nordlander, Peter; Landes, Christy F.; Link, Stephan

doi:10.1021/acsenergylett.9b01747

Title: Single-Particle Emission Spectroscopy Resolves d-Hole Relaxation in Copper Nanocubes

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Abstract

Resolving the dynamics of photoexcited d-holes in metallic nanostructures is one step in the rational design of plasmonic photocatalysis. In this work, we track the creation and relaxation of charge carriers in catalytically important plasmonic copper nanocubes using single-particle spectroscopy. We show that interband transitions dominate the absorption and emission of 60–160 nm copper nanocubes, and in contrast to gold nanorods, the LSPR is less important to the emission. Furthermore, we uncover the plasmonic enhancement of emission hidden in ensemble measurements by resolving the size-dependent line shape and quantum yield. Quantum yield analysis reveals the energy dependence of d-hole lifetimes. We demonstrate that the effect of excitation energy on quantum yield is stronger in copper nanocubes than in gold nanocubes of equivalent size due to differences in the band structure and the probabilities of hole scattering. Finally, we establish that emission spectroscopy is useful to understand the physical chemistry of d-holes in plasmonic photocatalysts.

Authors:

^[1]; Collins, Sean S. E. ^[1];

^[1]; Bhattacharjee, Ujjal ^[2]; Zhang, Runmin ^[1]; Chow, Tsz Him ^[3];

^[4]; Ostovar, Behnaz ^[4]; Al-Zubeidi, Alexander ^[1];

^[3];

^[4];

^[4]

Rice Univ., Houston, TX (United States). Lab. for Nanophotonics
Rice Univ., Houston, TX (United States). Lab. for Nanophotonics; Indian Inst. of Engineering Science And Technology (IIEST), Howrah (India)
Chinese Univ. of Hong Kong (China)
Rice Univ., Houston, TX (United States). Lab. for Nanophotonics, Dept. of Electrical and Computer Engineering

Publication Date:: Wed Sep 11 00:00:00 EDT 2019

Research Org.:: Rice Univ., Houston, TX (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); US Air Force Office of Scientific Research (AFOSR); Robert A. Welch Foundation

OSTI Identifier:: 1596110

Grant/Contract Number:: SC0016534; ECCS-1608917; FA9550-15-1-0022

Resource Type:: Accepted Manuscript

Journal Name:: ACS Energy Letters

Additional Journal Information:: Journal Volume: 4; Journal Issue: 10; Journal ID: ISSN 2380-8195

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats


                    Cai, Yi-Yu, Collins, Sean S.  E., Gallagher, Miranda J., Bhattacharjee, Ujjal, Zhang, Runmin, Chow, Tsz Him, Ahmadivand, Arash, Ostovar, Behnaz, Al-Zubeidi, Alexander, Wang, Jianfang, Nordlander, Peter, Landes, Christy F., and Link, Stephan. Single-Particle Emission Spectroscopy Resolves d-Hole Relaxation in Copper Nanocubes.  United States: N. p., 2019. 
Web.  doi:10.1021/acsenergylett.9b01747.

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                    Cai, Yi-Yu, Collins, Sean S.  E., Gallagher, Miranda J., Bhattacharjee, Ujjal, Zhang, Runmin, Chow, Tsz Him, Ahmadivand, Arash, Ostovar, Behnaz, Al-Zubeidi, Alexander, Wang, Jianfang, Nordlander, Peter, Landes, Christy F., & Link, Stephan. Single-Particle Emission Spectroscopy Resolves d-Hole Relaxation in Copper Nanocubes.  United States.  https://doi.org/10.1021/acsenergylett.9b01747

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                    Cai, Yi-Yu, Collins, Sean S.  E., Gallagher, Miranda J., Bhattacharjee, Ujjal, Zhang, Runmin, Chow, Tsz Him, Ahmadivand, Arash, Ostovar, Behnaz, Al-Zubeidi, Alexander, Wang, Jianfang, Nordlander, Peter, Landes, Christy F., and Link, Stephan. Wed .  
"Single-Particle Emission Spectroscopy Resolves d-Hole Relaxation in Copper Nanocubes".  United States.  https://doi.org/10.1021/acsenergylett.9b01747.  https://www.osti.gov/servlets/purl/1596110.

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@article{osti_1596110,

  title        = {Single-Particle Emission Spectroscopy Resolves d-Hole Relaxation in Copper Nanocubes},

  author       = {Cai, Yi-Yu and Collins, Sean S.  E. and Gallagher, Miranda J. and Bhattacharjee, Ujjal and Zhang, Runmin and Chow, Tsz Him and Ahmadivand, Arash and Ostovar, Behnaz and Al-Zubeidi, Alexander and Wang, Jianfang and Nordlander, Peter and Landes, Christy F. and Link, Stephan},

  abstractNote = {Resolving the dynamics of photoexcited d-holes in metallic nanostructures is one step in the rational design of plasmonic photocatalysis. In this work, we track the creation and relaxation of charge carriers in catalytically important plasmonic copper nanocubes using single-particle spectroscopy. We show that interband transitions dominate the absorption and emission of 60–160 nm copper nanocubes, and in contrast to gold nanorods, the LSPR is less important to the emission. Furthermore, we uncover the plasmonic enhancement of emission hidden in ensemble measurements by resolving the size-dependent line shape and quantum yield. Quantum yield analysis reveals the energy dependence of d-hole lifetimes. We demonstrate that the effect of excitation energy on quantum yield is stronger in copper nanocubes than in gold nanocubes of equivalent size due to differences in the band structure and the probabilities of hole scattering. Finally, we establish that emission spectroscopy is useful to understand the physical chemistry of d-holes in plasmonic photocatalysts.},

  doi          = {10.1021/acsenergylett.9b01747},

  journal      = {ACS Energy Letters},

  number       = 10,

  volume       = 4,

  place        = {United States},

  year         = {Wed Sep 11 00:00:00 EDT 2019},

  month        = {Wed Sep 11 00:00:00 EDT 2019}

}

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