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

Forde, Aaron; Inerbaev, Talgat; Kilin, Dmitri

doi:10.1021/acs.jpcc.8b05392

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

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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 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 attributedmore »« less

Authors:

Forde, Aaron ^[1]; Inerbaev, Talgat ^[2];

^[3]

North Dakota Univ., Fargo, ND (United States)
L.N. Gumilyov Eurasian National Univ., Astana (Kazakhstan); National Univ. of Science and Technology MISIS, Moscow (Russia)
North Dakota State Univ., Fargo, ND (United States)

Publication Date:: Wed Oct 10 00:00:00 EDT 2018

Research Org.:: Lawrence Berkeley National Lab. (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)

OSTI Identifier:: 1543651

Grant/Contract Number:: AC02-05CH11231

Resource Type:: 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

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                    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.

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                    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.  https://doi.org/10.1021/acs.jpcc.8b05392

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                    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.  https://doi.org/10.1021/acs.jpcc.8b05392.  https://www.osti.gov/servlets/purl/1543651.

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@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},

  number       = 45,

  volume       = 122,

  place        = {United States},

  year         = {Wed Oct 10 00:00:00 EDT 2018},

  month        = {Wed Oct 10 00:00:00 EDT 2018}

}

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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

Citation Formats

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