Light Emission Mechanisms in CuInS 2 Quantum Dots Evaluated by Spectral Electrochemistry
Abstract
Luminescent CuInS2 (CIS) quantum dots (QDs) exhibit highly efficient intragap emission and long, hundreds-of-nanoseconds radiative lifetimes. These spectral properties, distinct from structurally similar II–VI QDs, can be explained by the involvement of intragap defect states containing a localized hole capable of coupling with a conduction band electron for a radiative transition. However, the absolute energies of the intragap and band-edge states, the structure of the emissive defect(s), and the role and origin of nonemissive decay channels still remain poorly understood. Here, we address these questions by applying methods of spectral electrochemistry. Cyclic voltammetry measurements reveal a well-defined intragap state whose redox potential is close to that of the Cux defect state (where x = 1+ or 2+). The energy offset of this state from the valence band accounts well for the apparent photoluminescence Stokes shift observed in optical spectra. These results provide direct evidence that Cu-related defects serve as emission centers responsible for strong intragap emission from CIS QDs. We then use in situ spectroelectrochemistry to reveal two distinct emission pathways based on the differing oxidation states of Cu defects, which can be controlled by altering QD stoichiometry (1+ for stoichiometric QDs and 2+ for Cu-deficient QDs).
- Authors:
-
- Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States, Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, Los Angeles, California 90095, United States
- Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States
- UbiQD, LLC, 134 East Gate Drive, Los Alamos, New Mexico 87544, United States
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Advanced Solar Photophysics (CASP)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1413789
- Alternate Identifier(s):
- OSTI ID: 1438124
- Report Number(s):
- LA-UR-18-21643
Journal ID: ISSN 2330-4022
- Grant/Contract Number:
- AC52-06NA25396
- Resource Type:
- Published Article
- Journal Name:
- ACS Photonics
- Additional Journal Information:
- Journal Name: ACS Photonics Journal Volume: 4 Journal Issue: 10; Journal ID: ISSN 2330-4022
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Analytical Chemistry
Citation Formats
Fuhr, Addis S., Yun, Hyeong Jin, Makarov, Nikolay S., Li, Hongbo, McDaniel, Hunter, and Klimov, Victor I. Light Emission Mechanisms in CuInS 2 Quantum Dots Evaluated by Spectral Electrochemistry. United States: N. p., 2017.
Web. doi:10.1021/acsphotonics.7b00560.
Fuhr, Addis S., Yun, Hyeong Jin, Makarov, Nikolay S., Li, Hongbo, McDaniel, Hunter, & Klimov, Victor I. Light Emission Mechanisms in CuInS 2 Quantum Dots Evaluated by Spectral Electrochemistry. United States. https://doi.org/10.1021/acsphotonics.7b00560
Fuhr, Addis S., Yun, Hyeong Jin, Makarov, Nikolay S., Li, Hongbo, McDaniel, Hunter, and Klimov, Victor I. Mon .
"Light Emission Mechanisms in CuInS 2 Quantum Dots Evaluated by Spectral Electrochemistry". United States. https://doi.org/10.1021/acsphotonics.7b00560.
@article{osti_1413789,
title = {Light Emission Mechanisms in CuInS 2 Quantum Dots Evaluated by Spectral Electrochemistry},
author = {Fuhr, Addis S. and Yun, Hyeong Jin and Makarov, Nikolay S. and Li, Hongbo and McDaniel, Hunter and Klimov, Victor I.},
abstractNote = {Luminescent CuInS2 (CIS) quantum dots (QDs) exhibit highly efficient intragap emission and long, hundreds-of-nanoseconds radiative lifetimes. These spectral properties, distinct from structurally similar II–VI QDs, can be explained by the involvement of intragap defect states containing a localized hole capable of coupling with a conduction band electron for a radiative transition. However, the absolute energies of the intragap and band-edge states, the structure of the emissive defect(s), and the role and origin of nonemissive decay channels still remain poorly understood. Here, we address these questions by applying methods of spectral electrochemistry. Cyclic voltammetry measurements reveal a well-defined intragap state whose redox potential is close to that of the Cux defect state (where x = 1+ or 2+). The energy offset of this state from the valence band accounts well for the apparent photoluminescence Stokes shift observed in optical spectra. These results provide direct evidence that Cu-related defects serve as emission centers responsible for strong intragap emission from CIS QDs. We then use in situ spectroelectrochemistry to reveal two distinct emission pathways based on the differing oxidation states of Cu defects, which can be controlled by altering QD stoichiometry (1+ for stoichiometric QDs and 2+ for Cu-deficient QDs).},
doi = {10.1021/acsphotonics.7b00560},
journal = {ACS Photonics},
number = 10,
volume = 4,
place = {United States},
year = {Mon Sep 25 00:00:00 EDT 2017},
month = {Mon Sep 25 00:00:00 EDT 2017}
}
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https://doi.org/10.1021/acsphotonics.7b00560
https://doi.org/10.1021/acsphotonics.7b00560
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