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Title: Tuning the Quantum Dot (QD)/Mediator Interface for Optimal Efficiency of QD-Sensitized Near-Infrared-to-Visible Photon Upconversion Systems

Abstract

Lead sulfide (PbS) quantum dots (QDs) have shown promising performance as a sensitizer in infrared-to-visible photon upconversion systems. To investigate the key design rules, we compare three PbS-sensitized upconversion systems using three mediator molecules with the same tetracene triplet acceptor at different distances from the QD. Using transient absorption spectroscopy, we directly measure the triplet energy-transfer rates and efficiencies from the QD to the mediator and from the mediator to the emitter. With increasing distance between the mediator and PbS QD, the efficiency of the first triplet energy transfer from the QD to the mediator decreases because of a decrease in the rate of this triplet energy-transfer step, while the efficiency of the second triplet energy transfer from the mediator to the emitter increases because of a reduction in the QD-induced mediator triplet state decay. The latter effect is a result of the slow rate constant of the second triplet energy-transfer process, which is 3 orders of magnitude slower than the diffusion-limited value. The combined results lead to a net decrease of the steady-state upconversion quantum yield with distance, which could be predicted by our kinetic model. Our result shows that the QD/mediator interface affects both the first and secondmore » triplet energy transfer processes in the photon upconversion system, and the QD/mediator distance has an opposite effect on the efficiencies of the first and second triplet energy transfer. Lastly, these findings provide important insight for the further rational improvement of the overall efficiency of QD-based upconversion systems.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1];  [2]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
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  1. Emory Univ., Atlanta, GA (United States)
  2. Univ. of California, Riverside, CA (United States)
Publication Date:
Research Org.:
Univ. of California, Riverside, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1773892
Grant/Contract Number:  
SC0018969
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 12; Journal Issue: 32; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; photon upconversion; triplet energy transfer; ultrafast spectroscopy; quantum dot; kinetics; excitons; luminescence; kinetic parameters

Citation Formats

Xu, Zihao, Huang, Zhiyuan, Li, Chenyang, Huang, Tingting, Evangelista, Francesco A., Tang, Ming L., and Lian, Tianquan. Tuning the Quantum Dot (QD)/Mediator Interface for Optimal Efficiency of QD-Sensitized Near-Infrared-to-Visible Photon Upconversion Systems. United States: N. p., 2020. Web. doi:10.1021/acsami.0c10269.
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Xu, Zihao, Huang, Zhiyuan, Li, Chenyang, Huang, Tingting, Evangelista, Francesco A., Tang, Ming L., & Lian, Tianquan. Tuning the Quantum Dot (QD)/Mediator Interface for Optimal Efficiency of QD-Sensitized Near-Infrared-to-Visible Photon Upconversion Systems. United States. https://doi.org/10.1021/acsami.0c10269
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Xu, Zihao, Huang, Zhiyuan, Li, Chenyang, Huang, Tingting, Evangelista, Francesco A., Tang, Ming L., and Lian, Tianquan. Fri . "Tuning the Quantum Dot (QD)/Mediator Interface for Optimal Efficiency of QD-Sensitized Near-Infrared-to-Visible Photon Upconversion Systems". United States. https://doi.org/10.1021/acsami.0c10269. https://www.osti.gov/servlets/purl/1773892.
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@article{osti_1773892,
title = {Tuning the Quantum Dot (QD)/Mediator Interface for Optimal Efficiency of QD-Sensitized Near-Infrared-to-Visible Photon Upconversion Systems},
author = {Xu, Zihao and Huang, Zhiyuan and Li, Chenyang and Huang, Tingting and Evangelista, Francesco A. and Tang, Ming L. and Lian, Tianquan},
abstractNote = {Lead sulfide (PbS) quantum dots (QDs) have shown promising performance as a sensitizer in infrared-to-visible photon upconversion systems. To investigate the key design rules, we compare three PbS-sensitized upconversion systems using three mediator molecules with the same tetracene triplet acceptor at different distances from the QD. Using transient absorption spectroscopy, we directly measure the triplet energy-transfer rates and efficiencies from the QD to the mediator and from the mediator to the emitter. With increasing distance between the mediator and PbS QD, the efficiency of the first triplet energy transfer from the QD to the mediator decreases because of a decrease in the rate of this triplet energy-transfer step, while the efficiency of the second triplet energy transfer from the mediator to the emitter increases because of a reduction in the QD-induced mediator triplet state decay. The latter effect is a result of the slow rate constant of the second triplet energy-transfer process, which is 3 orders of magnitude slower than the diffusion-limited value. The combined results lead to a net decrease of the steady-state upconversion quantum yield with distance, which could be predicted by our kinetic model. Our result shows that the QD/mediator interface affects both the first and second triplet energy transfer processes in the photon upconversion system, and the QD/mediator distance has an opposite effect on the efficiencies of the first and second triplet energy transfer. Lastly, these findings provide important insight for the further rational improvement of the overall efficiency of QD-based upconversion systems.},
doi = {10.1021/acsami.0c10269},
journal = {ACS Applied Materials and Interfaces},
number = 32,
volume = 12,
place = {United States},
year = {Fri Jul 17 00:00:00 EDT 2020},
month = {Fri Jul 17 00:00:00 EDT 2020}
}
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