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Title: Spin–Orbit Interactions Greatly Accelerate Nonradiative Dynamics in Lead Halide Perovskites

Abstract

In this study, we study the role of spin–orbit coupling (SOC) in nonradiative relaxation of hot electrons and holes in methylammonium lead perovskite, MAPbI 3. For this purpose, we have developed the nonadiabatic molecular dynamics method with two-component spinor wave functions that are solutions of the relativistic Kohn–Sham (KS) equations. We find that SOC enhances contributions of Pb(p x) and Pb(p y) orbitals to the conduction and valence bands. As a result, the KS orbitals become more sensitive to nuclear motions, leading to the increased nonadiabatic couplings. Consequently, SOC greatly speeds up the electron and hole relaxation, making the computed relaxation time scales consistent with available experiments. Furthermore, we suggest that the fast hot carrier relaxation facilitated by the SOC allows rapid transition into the long-lived triplet state that extends charge-carrier lifetime and helps achieve high-efficiency perovskite solar cells.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Hunan Agricultural Univ., Changsha (People's Republic of China)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Univ. of Southern California, Los Angeles, CA (United States)
  4. Univ. at Buffalo, The State Univ. of New York, Buffalo, NY (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1480032
Report Number(s):
LA-UR-18-26702
Journal ID: ISSN 2380-8195
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Energy Letters
Additional Journal Information:
Journal Volume: 3; Journal Issue: 9; Journal ID: ISSN 2380-8195
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Material Science

Citation Formats

Li, Wei, Zhou, Liujiang, Prezhdo, Oleg V., and Akimov, Alexey V. Spin–Orbit Interactions Greatly Accelerate Nonradiative Dynamics in Lead Halide Perovskites. United States: N. p., 2018. Web. doi:10.1021/acsenergylett.8b01226.
Li, Wei, Zhou, Liujiang, Prezhdo, Oleg V., & Akimov, Alexey V. Spin–Orbit Interactions Greatly Accelerate Nonradiative Dynamics in Lead Halide Perovskites. United States. doi:10.1021/acsenergylett.8b01226.
Li, Wei, Zhou, Liujiang, Prezhdo, Oleg V., and Akimov, Alexey V. Thu . "Spin–Orbit Interactions Greatly Accelerate Nonradiative Dynamics in Lead Halide Perovskites". United States. doi:10.1021/acsenergylett.8b01226. https://www.osti.gov/servlets/purl/1480032.
@article{osti_1480032,
title = {Spin–Orbit Interactions Greatly Accelerate Nonradiative Dynamics in Lead Halide Perovskites},
author = {Li, Wei and Zhou, Liujiang and Prezhdo, Oleg V. and Akimov, Alexey V.},
abstractNote = {In this study, we study the role of spin–orbit coupling (SOC) in nonradiative relaxation of hot electrons and holes in methylammonium lead perovskite, MAPbI3. For this purpose, we have developed the nonadiabatic molecular dynamics method with two-component spinor wave functions that are solutions of the relativistic Kohn–Sham (KS) equations. We find that SOC enhances contributions of Pb(px) and Pb(py) orbitals to the conduction and valence bands. As a result, the KS orbitals become more sensitive to nuclear motions, leading to the increased nonadiabatic couplings. Consequently, SOC greatly speeds up the electron and hole relaxation, making the computed relaxation time scales consistent with available experiments. Furthermore, we suggest that the fast hot carrier relaxation facilitated by the SOC allows rapid transition into the long-lived triplet state that extends charge-carrier lifetime and helps achieve high-efficiency perovskite solar cells.},
doi = {10.1021/acsenergylett.8b01226},
journal = {ACS Energy Letters},
issn = {2380-8195},
number = 9,
volume = 3,
place = {United States},
year = {2018},
month = {8}
}

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Works referencing / citing this record:

Unraveling photoexcitation dynamics at “dots-in-a-perovskite” heterojunctions from first-principles
journal, January 2019

  • Li, Wei; Zhang, Xu; Lu, Gang
  • Journal of Materials Chemistry A, Vol. 7, Issue 30
  • DOI: 10.1039/c9ta04871e

Unraveling photoexcitation dynamics at “dots-in-a-perovskite” heterojunctions from first-principles
journal, January 2019

  • Li, Wei; Zhang, Xu; Lu, Gang
  • Journal of Materials Chemistry A, Vol. 7, Issue 30
  • DOI: 10.1039/c9ta04871e