Thermal Excitation Control over Photon Emission Rate of CdSe Nanocrystals
Abstract
Temperature-dependent photoluminescence lifetimes of electron-hole pairs (excitons) in CdSe nanocrystals are governed by the energetic ordering and spacing of slowly emitting, spin-forbidden "dark" exciton states and rapidly emitting "bright" states. Here, infrared pulses that are resonant with hydrocarbon surface ligand vibrational transitions are shown to offer a route to manipulate the instantaneous emission rate of CdSe nanocrystals at cryogenic temperature. Transient heating of the inorganic nanocrystal core is achieved via resonant excitation of ligand vibrations, followed by heat flow to the nanocrystal lattice. Heating of the nanocrystal core is demonstrated using transient absorption spectroscopy, which shows a time-dependent red-shift of the quantum dot electronic absorption resonances, consistent with heating. Transient heating of the nanocrystal above the bath temperature increases the instantaneous radiative rate of the nanocrystals via a combination of thermal occupation of bright states as well as phonon-assisted emission. The lifetime of this infrared pumped, fast-emitting sample condition is dictated by particle thermalization, which is multiple orders of magnitude shorter lived than the dark exciton state. In conclusion, this work demonstrates the feasibility of using heat control pulses to manipulate electronic recombination rates of excitons.
- Authors:
-
- Argonne National Lab. (ANL), Lemont, IL (United States). Center for Nanoscale Materials
- Argonne National Lab. (ANL), Lemont, IL (United States). Center for Nanoscale Materials; Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1531175
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Nano Letters
- Additional Journal Information:
- Journal Volume: 19; Journal Issue: 4; Journal ID: ISSN 1530-6984
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY; exciton; heat transfer; infrared; nanocrystal; photoluminescence
Citation Formats
Diroll, Benjamin T., and Schaller, Richard D. Thermal Excitation Control over Photon Emission Rate of CdSe Nanocrystals. United States: N. p., 2019.
Web. doi:10.1021/acs.nanolett.8b04847.
Diroll, Benjamin T., & Schaller, Richard D. Thermal Excitation Control over Photon Emission Rate of CdSe Nanocrystals. United States. https://doi.org/10.1021/acs.nanolett.8b04847
Diroll, Benjamin T., and Schaller, Richard D. 2019.
"Thermal Excitation Control over Photon Emission Rate of CdSe Nanocrystals". United States. https://doi.org/10.1021/acs.nanolett.8b04847. https://www.osti.gov/servlets/purl/1531175.
@article{osti_1531175,
title = {Thermal Excitation Control over Photon Emission Rate of CdSe Nanocrystals},
author = {Diroll, Benjamin T. and Schaller, Richard D.},
abstractNote = {Temperature-dependent photoluminescence lifetimes of electron-hole pairs (excitons) in CdSe nanocrystals are governed by the energetic ordering and spacing of slowly emitting, spin-forbidden "dark" exciton states and rapidly emitting "bright" states. Here, infrared pulses that are resonant with hydrocarbon surface ligand vibrational transitions are shown to offer a route to manipulate the instantaneous emission rate of CdSe nanocrystals at cryogenic temperature. Transient heating of the inorganic nanocrystal core is achieved via resonant excitation of ligand vibrations, followed by heat flow to the nanocrystal lattice. Heating of the nanocrystal core is demonstrated using transient absorption spectroscopy, which shows a time-dependent red-shift of the quantum dot electronic absorption resonances, consistent with heating. Transient heating of the nanocrystal above the bath temperature increases the instantaneous radiative rate of the nanocrystals via a combination of thermal occupation of bright states as well as phonon-assisted emission. The lifetime of this infrared pumped, fast-emitting sample condition is dictated by particle thermalization, which is multiple orders of magnitude shorter lived than the dark exciton state. In conclusion, this work demonstrates the feasibility of using heat control pulses to manipulate electronic recombination rates of excitons.},
doi = {10.1021/acs.nanolett.8b04847},
url = {https://www.osti.gov/biblio/1531175},
journal = {Nano Letters},
issn = {1530-6984},
number = 4,
volume = 19,
place = {United States},
year = {Fri Mar 22 00:00:00 EDT 2019},
month = {Fri Mar 22 00:00:00 EDT 2019}
}
Web of Science