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Title: Parity-Forbidden Transitions and Their Impact on the Optical Absorption Properties of Lead-Free Metal Halide Perovskites and Double Perovskites

Abstract

Using density functional theory calculations, we analyze the optical absorption properties of lead (Pb)-free metal halide perovskites (AB2+X3) and double perovskites (A2B+B3+X6) (A = Cs or monovalent organic ion, B2+ = non-Pb divalent metal, B+ = monovalent metal, B3+ = trivalent metal, X = halogen). We show that if B2+ is not Sn or Ge, Pb-free metal halide perovskites exhibit poor optical absorptions because of their indirect band gap nature. Among the nine possible types of Pb-free metal halide double perovskites, six have direct band gaps. Of these six types, four show inversion symmetry-induced parity-forbidden or weak transitions between band edges, making them not ideal for thin-film solar cell applications. Only one type of Pb-free double perovskite shows optical absorption and electronic properties suitable for solar cell applications, namely, those with B+ = In, Tl and B3+ = Sb, Bi. Our results provide important insights for designing new metal halide perovskites and double perovskites for optoelectronic applications.

Authors:
 [1];  [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [2]
  1. Department of Physics and Astronomy and Wright Center for Photovoltaic Innovation and Commercialization, The University of Toledo, Toledo, Ohio 43606, United States; School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, and Institute for Advanced Studies, Wuhan University, Wuhan 430072, China
  2. Department of Physics and Astronomy and Wright Center for Photovoltaic Innovation and Commercialization, The University of Toledo, Toledo, Ohio 43606, United States
  3. School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, and Institute for Advanced Studies, Wuhan University, Wuhan 430072, China; Science and Technology of High Strength Structural Materials Laboratory, Central South University, Changsha 410083, China
  4. Department of Mechanical Engineering and Materials Science and Department of Chemistry, Duke University, Durham, North Carolina 27708, United States
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Duke Univ., Durham, NC (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC)
OSTI Identifier:
1559769
Alternate Identifier(s):
OSTI ID: 1483858
Grant/Contract Number:  
EE0006712; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 8; Journal Issue: 13; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Meng, Weiwei, Wang, Xiaoming, Xiao, Zewen, Wang, Jianbo, Mitzi, David B., and Yan, Yanfa. Parity-Forbidden Transitions and Their Impact on the Optical Absorption Properties of Lead-Free Metal Halide Perovskites and Double Perovskites. United States: N. p., 2017. Web. doi:10.1021/acs.jpclett.7b01042.
Meng, Weiwei, Wang, Xiaoming, Xiao, Zewen, Wang, Jianbo, Mitzi, David B., & Yan, Yanfa. Parity-Forbidden Transitions and Their Impact on the Optical Absorption Properties of Lead-Free Metal Halide Perovskites and Double Perovskites. United States. doi:10.1021/acs.jpclett.7b01042.
Meng, Weiwei, Wang, Xiaoming, Xiao, Zewen, Wang, Jianbo, Mitzi, David B., and Yan, Yanfa. Fri . "Parity-Forbidden Transitions and Their Impact on the Optical Absorption Properties of Lead-Free Metal Halide Perovskites and Double Perovskites". United States. doi:10.1021/acs.jpclett.7b01042. https://www.osti.gov/servlets/purl/1559769.
@article{osti_1559769,
title = {Parity-Forbidden Transitions and Their Impact on the Optical Absorption Properties of Lead-Free Metal Halide Perovskites and Double Perovskites},
author = {Meng, Weiwei and Wang, Xiaoming and Xiao, Zewen and Wang, Jianbo and Mitzi, David B. and Yan, Yanfa},
abstractNote = {Using density functional theory calculations, we analyze the optical absorption properties of lead (Pb)-free metal halide perovskites (AB2+X3) and double perovskites (A2B+B3+X6) (A = Cs or monovalent organic ion, B2+ = non-Pb divalent metal, B+ = monovalent metal, B3+ = trivalent metal, X = halogen). We show that if B2+ is not Sn or Ge, Pb-free metal halide perovskites exhibit poor optical absorptions because of their indirect band gap nature. Among the nine possible types of Pb-free metal halide double perovskites, six have direct band gaps. Of these six types, four show inversion symmetry-induced parity-forbidden or weak transitions between band edges, making them not ideal for thin-film solar cell applications. Only one type of Pb-free double perovskite shows optical absorption and electronic properties suitable for solar cell applications, namely, those with B+ = In, Tl and B3+ = Sb, Bi. Our results provide important insights for designing new metal halide perovskites and double perovskites for optoelectronic applications.},
doi = {10.1021/acs.jpclett.7b01042},
journal = {Journal of Physical Chemistry Letters},
number = 13,
volume = 8,
place = {United States},
year = {2017},
month = {6}
}

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