Single-Particle Emission Spectroscopy Resolves d-Hole Relaxation in Copper Nanocubes
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:
-
- 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:
- 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.
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
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.
@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}
}
Web of Science