Plasmon-Induced Hot-Carrier Excited-State Dynamics in Plasmonic Semiconductor Nanocrystals

Kuszynski, Jason E.; Fabiano, Catherine J.; Nguyen, Edward T.; Mao, Keyou; Ahuja, Anoushka K.; Schaller, Richard D.; Strouse, Geoffrey F.

doi:10.1021/acs.jpcc.3c05208

Plasmon-Induced Hot-Carrier Excited-State Dynamics in Plasmonic Semiconductor Nanocrystals

Journal Article · Wed Nov 08 00:00:00 EST 2023 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.3c05208· OSTI ID:2514397

^[1]; Fabiano, Catherine J. ^[1]; ^[1]; ^[2]; Ahuja, Anoushka K. ^[1]; Schaller, Richard D. ^[3]; ^[1]

Florida State Univ., Tallahassee, FL (United States)
Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab); FAMU-FSU College of Engineering, Tallahassee, FL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM); Northwestern Univ., Evanston, IL (United States)

The variance of carrier relaxation pathways for WO_3–x plasmonic semiconductor nanocrystals (PSNCs) is monitored by transient absorption spectroscopy following excitation of the localized surface plasmon resonance (LSPR) versus the optical band gap (E_g,opt). Excitation of the LSPR leads to efficient hot carrier population above the Fermi level in WO_3–x via Landau damping, in analogy to noble metal LSPR relaxation mechanisms. Hot carrier depopulation occurs on the femtosecond timescale, observed as the concomitant recovery of an LSPR bleach with the appearance of discrete interband and intraband photoinduced absorption features. Further, by comparison, the direct excitation of E_g,opt results in trion recombination at donor–acceptor sites within the WO_3–x NC, consistent with exciton decay dynamics observed for typical wide-band-gap semiconductor NCs. From the analysis of pump power dependency data, a hot-carrier electron–phonon coupling constant of 1.47 × 10¹¹ J K^–1 s^–1 cm^–3 is extracted. The direct comparison of the decay dynamics following E_g,opt versus LSPR excitation confirms that the observed plasmon in trioctylphosphine oxide passivated, spherical WO_3–x is a resonance state in which hot carriers are generated only from excitation on resonance with the LSPR frequency. This study on WO_3–x PSNCs provides a toolset that can be used to evaluate the role of hot carriers following LSPR excitation of n-type, plasmonic transparent conducting oxide NCs, where enhancement of photocatalysis, photovoltaic performance, and optical enhancement has been reported.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2514397

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 46 Vol. 127; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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