dc.contributor.author |
Forde, Aaron |
|
dc.contributor.author |
Inerbaev, Talgat |
|
dc.contributor.author |
Hobbie, Erik K. |
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dc.contributor.author |
Kilin, Dmitri S. |
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dc.date.accessioned |
2024-07-15T05:02:23Z |
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dc.date.available |
2024-07-15T05:02:23Z |
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dc.date.issued |
2019 |
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dc.identifier.issn |
0002-7863 |
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dc.identifier.other |
DOI 10.1021/jacs.8b13385 |
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dc.identifier.uri |
http://rep.enu.kz/handle/enu/16078 |
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dc.description.abstract |
Fully inorganic lead halide perovskite nanocrystals (NCs) are of interest for photovoltaic and light-emitting devices due to optoelectronic properties that can be tuned/optimized via halide composition, surface passivation, doping, and confinement. Compared to bulk materials, certain excited-state properties in NCs can be adjusted by electronic confinement effects such as suppressed hot carrier cooling and enhanced radiative recombination. Here we use spinor Kohn-Sham orbitals (SKSOs) with spin-orbit coupling (SOC) interaction as a basis to compute excited-state dissipative dynamics simulations on a fully passivated CsPbBr3 NC atomistic model. Redfield theory in the density matrix formalism is used to describe electron-phonon interactions which drive hot carrier cooling and nonradiative recombination (knonrad). Radiative recombination (krad) is calculated through oscillator strengths using SKSO basis. From krad and krad + knonrad, we compute a theoretical photoluminescence quantum yield (PLQY) of 53%. Computed rates of hot carrier cooling (kcooling ≈ 10-1 1/ps) compare favorably with what has been reported in the literature. Interestingly, we observe that hot electron cooling slows down near the band edge, which we attribute to large SOC in the conduction band combined with strong confinement, which creates subgaps above the band edge. This slow carrier cooling could potentially impact hot carrier extraction before complete thermalization in photovoltaics (PVs). Implications of this work suggest that strong/intermediate confined APbX3 NCs are better suited to applications in PVs due to slower carrier cooling near the conduction band edge, while intermediate/weak confined NCs are more appropriate for light-emitting applications, such as LEDs. |
ru |
dc.description.sponsorship |
The authors acknowledge the use of computational resources at the Center for Computationally Assisted Science and Technology (CCAST) at North Dakota State University. The authors also thank the DOE BES NERSC facility for computational resources via allocation award no. 31857, “Computational Modeling of Photo-catalysis and Photoinduced Charge Transfer Dynamics on Surfaces” supported by the Office of Science of the DOE under contract no. DE-AC02-05CH11231. D.S.K. acknowledges the support of National Science Foundation (NSF) CHE-1800476 for computational methods development. The work of T.I. is performed under the state assignment of IGM SB RAS, and T.I. gratefully acknowledges financial support of the Ministry of Education and Science of the Russian Federation in the framework of the Increase Competitiveness Program of NUST MISIS (no. K3-2018-022) implemented by a governmental decree dated 16 March 2013, N 211. The calculations were partially performed at supercomputer cluster “Cherry” provided by the Materials Modeling and Development Laboratory at NUST “MISIS” (supported by a grant from the Ministry of Education and Science of the Russian Federation, no. 14.Y26.31.0005). E.K.H. acknowledges support from the National Science Foundation (NSF) through CBET-1603445. A.F. and D.S.K. thank S. Tretiak, F. Furche, S. Kilina, Y. Han, L. Johnson, M. Jabed, A. Kryjevski, B. Levine, M. Esch, A. Zunger, D. Micha, and L. Lystrom for discussions. |
ru |
dc.language.iso |
en |
ru |
dc.publisher |
Journal of the American Chemical Society |
ru |
dc.relation.ispartofseries |
Volume 141, Issue 10;Pages:4388 - 4397 |
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dc.subject |
Bromine compounds |
ru |
dc.subject |
Conduction bands |
ru |
dc.subject |
Electron-phonon interactions |
ru |
dc.subject |
Excited states |
ru |
dc.subject |
Hot carriers |
ru |
dc.subject |
Lead compounds |
ru |
dc.subject |
Light emission |
ru |
dc.subject |
Nanocrystals |
ru |
dc.subject |
Passivation |
ru |
dc.subject |
Perovskite |
ru |
dc.subject |
Spin dynamics |
ru |
dc.title |
Excited-State Dynamics of a CsPbBr3 Nanocrystal Terminated with Binary Ligands: Sparse Density of States with Giant Spin-Orbit Coupling Suppresses Carrier Cooling |
ru |
dc.type |
Article |
ru |