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Title: Spinor Dynamics in Pristine and Mn 2+ -Doped CsPbBr 3 NC: Role of Spin–Orbit Coupling in Ground- and Excited-State Dynamics

Abstract

Fully inorganic lead halide perovskite nanocrystals (NCs) are of interest for optoelectronic and light-emitting devices because of their photoluminescence (PL) emission properties, which can be tuned/optimized by (I) surface passivation and (II) doping. (I) Surface passivation of the NC affects PL capabilities, as an underpassivated surface can introduce trap states, which reduces PL quantum yields. (II) Doping NCs and quantum dots with transition-metal ions provides stable optical transitions. Doping perovskite NCs with Mn 2+ ions provides high-intensity 4T 16A 1 optical transitions in addition to the bright intrinsic NC emission. In this study, we use noncollinear density functional theory (DFT) to investigate the roles of surface passivation and doping on the PL emission stability of perovskite NCs. Two models are investigated: (i) a pristine NC and (ii) a NC doped with the Mn 2+ ion. The noncollinear DFT includes spin–orbit coupling (SOC) between different spin states and produces spin adiabatic molecular orbitals. These orbitals are used to calculate the transition dipoles between electronic states, oscillator strengths, radiative transition rates, and emission spectra. It was found that the noncollinear spin basis with SOC slows down hole relaxation in the doped NC by 2 orders of magnitude compared to spin-polarizedmore » basis. This is attributed to “spin-flip” transition from the perovskite NC to the Mn 2+ dopant and low-probability nonradiative d-d transition.« less

Authors:
 [1];  [2]; ORCiD logo [3]
  1. North Dakota Univ., Fargo, ND (United States)
  2. L.N. Gumilyov Eurasian National Univ., Astana (Kazakhstan); National Univ. of Science and Technology MISIS, Moscow (Russia)
  3. North Dakota State Univ., Fargo, ND (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1543651
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 45; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; science & technology - other topics; materials science

Citation Formats

Forde, Aaron, Inerbaev, Talgat, and Kilin, Dmitri. Spinor Dynamics in Pristine and Mn 2+ -Doped CsPbBr 3 NC: Role of Spin–Orbit Coupling in Ground- and Excited-State Dynamics. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b05392.
Forde, Aaron, Inerbaev, Talgat, & Kilin, Dmitri. Spinor Dynamics in Pristine and Mn 2+ -Doped CsPbBr 3 NC: Role of Spin–Orbit Coupling in Ground- and Excited-State Dynamics. United States. doi:10.1021/acs.jpcc.8b05392.
Forde, Aaron, Inerbaev, Talgat, and Kilin, Dmitri. Wed . "Spinor Dynamics in Pristine and Mn 2+ -Doped CsPbBr 3 NC: Role of Spin–Orbit Coupling in Ground- and Excited-State Dynamics". United States. doi:10.1021/acs.jpcc.8b05392. https://www.osti.gov/servlets/purl/1543651.
@article{osti_1543651,
title = {Spinor Dynamics in Pristine and Mn 2+ -Doped CsPbBr 3 NC: Role of Spin–Orbit Coupling in Ground- and Excited-State Dynamics},
author = {Forde, Aaron and Inerbaev, Talgat and Kilin, Dmitri},
abstractNote = {Fully inorganic lead halide perovskite nanocrystals (NCs) are of interest for optoelectronic and light-emitting devices because of their photoluminescence (PL) emission properties, which can be tuned/optimized by (I) surface passivation and (II) doping. (I) Surface passivation of the NC affects PL capabilities, as an underpassivated surface can introduce trap states, which reduces PL quantum yields. (II) Doping NCs and quantum dots with transition-metal ions provides stable optical transitions. Doping perovskite NCs with Mn2+ ions provides high-intensity 4T1 → 6A1 optical transitions in addition to the bright intrinsic NC emission. In this study, we use noncollinear density functional theory (DFT) to investigate the roles of surface passivation and doping on the PL emission stability of perovskite NCs. Two models are investigated: (i) a pristine NC and (ii) a NC doped with the Mn2+ ion. The noncollinear DFT includes spin–orbit coupling (SOC) between different spin states and produces spin adiabatic molecular orbitals. These orbitals are used to calculate the transition dipoles between electronic states, oscillator strengths, radiative transition rates, and emission spectra. It was found that the noncollinear spin basis with SOC slows down hole relaxation in the doped NC by 2 orders of magnitude compared to spin-polarized basis. This is attributed to “spin-flip” transition from the perovskite NC to the Mn2+ dopant and low-probability nonradiative d-d transition.},
doi = {10.1021/acs.jpcc.8b05392},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 45,
volume = 122,
place = {United States},
year = {2018},
month = {10}
}

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