Intrinsic and Extrinsic Exciton Recombination Pathways in AgInS 2 Colloidal Nanocrystals
Abstract
Ternary I-III-VI 2 nanocrystals (NCs), such as AgInS 2 and CuInS 2 , are garnering interest as heavy-metal-free materials for photovoltaics, luminescent solar concentrators, LEDs, and bioimaging. The origin of the emission and absorption properties in this class of NCs is still a subject of debate. Recent theoretical and experimental studies revealed that the characteristic Stokes-shifted and long-lived luminescence of stoichiometric CuInS 2 NCs arises from the detailed structure of the valence band featuring two sublevels with different parity. The same valence band substructure is predicted to occur in AgInS 2 NCs, yet no experimental confirmation is available to date. Here, we use complementary spectroscopic, spectro-electrochemical, and magneto-optical investigations as a function of temperature to investigate the band structure and the excitonic recombination mechanisms in stoichiometric AgInS 2 NCs. Transient transmission measurements reveal the signatures of two subbands with opposite parity, and photoluminescence studies at cryogenic temperatures evidence a dark state emission due to enhanced exchange interaction, consistent with the behavior of stoichiometric CuInS 2 NCs. Lowering the temperature as well as applying reducing electrochemical potentials further suppress electron trapping, which represents the main nonradiative channel for exciton decay, leading to nearly 100% emission efficiency.
- Authors:
-
[1];
[1];
[1];
[6];
[1]
- Dipartimento di Scienza dei Materiali, Università degli studi di Milano-Bicocca, via Roberto Cozzi 55, 20125 Milano, Italy
- Dipartimento di Energia, Politecnico di Milano, Via Ponzio 34/3, 20133 Milano, Italy
- Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy
- Dipartimento di Scienza dei Materiali, Università degli studi di Milano-Bicocca, via Roberto Cozzi 55, 20125 Milano, Italy, Glass to Power SpA, Via Fortunato Zeni 8, 38068 RoveretoItaly
- Beijing Key Laboratory of Construction-Tailorable Advanced Functional Materials and Green Applications, School of Materials Science &, Engineering, Beijing Institute of Technology, Beijing 100081, China
- Dipartimento di Energia, Politecnico di Milano, Via Ponzio 34/3, 20133 Milano, Italy, IFN-CNR, Piazza Leonardo da Vinci 32, 20133 MilanoItaly
- National High Magnetic Field Laboratory, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); Italian Ministry of Education, University and Research (MIUR); National Natural Science Foundation of China (NSFC)
- OSTI Identifier:
- 1909317
- Alternate Identifier(s):
- OSTI ID: 1804374
- Report Number(s):
- LA-UR-21-21348
Journal ID: ISSN 2692-7640; 2021/1959321
- Grant/Contract Number:
- 89233218CNA000001; DMR-1644779; 2015WTW7J3; 51872030; 51631001
- Resource Type:
- Published Article
- Journal Name:
- Energy Material Advances
- Additional Journal Information:
- Journal Name: Energy Material Advances Journal Volume: 2021; Journal ID: ISSN 2692-7640
- Publisher:
- American Association for the Advancement of Science (AAAS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; high magnetic field science
Citation Formats
Zaffalon, Matteo L., Pinchetti, Valerio, Camellini, Andrea, Vikulov, Sergey, Capitani, Chiara, Bai, Bing, Xu, Meng, Meinardi, Francesco, Zhang, Jiatao, Manna, Liberato, Zavelani-Rossi, Margherita, Crooker, Scott A., and Brovelli, Sergio. Intrinsic and Extrinsic Exciton Recombination Pathways in AgInS 2 Colloidal Nanocrystals. United States: N. p., 2021.
Web. doi:10.34133/2021/1959321.
Zaffalon, Matteo L., Pinchetti, Valerio, Camellini, Andrea, Vikulov, Sergey, Capitani, Chiara, Bai, Bing, Xu, Meng, Meinardi, Francesco, Zhang, Jiatao, Manna, Liberato, Zavelani-Rossi, Margherita, Crooker, Scott A., & Brovelli, Sergio. Intrinsic and Extrinsic Exciton Recombination Pathways in AgInS 2 Colloidal Nanocrystals. United States. https://doi.org/10.34133/2021/1959321
Zaffalon, Matteo L., Pinchetti, Valerio, Camellini, Andrea, Vikulov, Sergey, Capitani, Chiara, Bai, Bing, Xu, Meng, Meinardi, Francesco, Zhang, Jiatao, Manna, Liberato, Zavelani-Rossi, Margherita, Crooker, Scott A., and Brovelli, Sergio. Mon .
"Intrinsic and Extrinsic Exciton Recombination Pathways in AgInS 2 Colloidal Nanocrystals". United States. https://doi.org/10.34133/2021/1959321.
@article{osti_1909317,
title = {Intrinsic and Extrinsic Exciton Recombination Pathways in AgInS 2 Colloidal Nanocrystals},
author = {Zaffalon, Matteo L. and Pinchetti, Valerio and Camellini, Andrea and Vikulov, Sergey and Capitani, Chiara and Bai, Bing and Xu, Meng and Meinardi, Francesco and Zhang, Jiatao and Manna, Liberato and Zavelani-Rossi, Margherita and Crooker, Scott A. and Brovelli, Sergio},
abstractNote = {Ternary I-III-VI 2 nanocrystals (NCs), such as AgInS 2 and CuInS 2 , are garnering interest as heavy-metal-free materials for photovoltaics, luminescent solar concentrators, LEDs, and bioimaging. The origin of the emission and absorption properties in this class of NCs is still a subject of debate. Recent theoretical and experimental studies revealed that the characteristic Stokes-shifted and long-lived luminescence of stoichiometric CuInS 2 NCs arises from the detailed structure of the valence band featuring two sublevels with different parity. The same valence band substructure is predicted to occur in AgInS 2 NCs, yet no experimental confirmation is available to date. Here, we use complementary spectroscopic, spectro-electrochemical, and magneto-optical investigations as a function of temperature to investigate the band structure and the excitonic recombination mechanisms in stoichiometric AgInS 2 NCs. Transient transmission measurements reveal the signatures of two subbands with opposite parity, and photoluminescence studies at cryogenic temperatures evidence a dark state emission due to enhanced exchange interaction, consistent with the behavior of stoichiometric CuInS 2 NCs. Lowering the temperature as well as applying reducing electrochemical potentials further suppress electron trapping, which represents the main nonradiative channel for exciton decay, leading to nearly 100% emission efficiency.},
doi = {10.34133/2021/1959321},
journal = {Energy Material Advances},
number = ,
volume = 2021,
place = {United States},
year = {Mon Apr 05 00:00:00 EDT 2021},
month = {Mon Apr 05 00:00:00 EDT 2021}
}
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