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Title: Impact of metal n s 2 lone pair on luminescence quantum efficiency in low-dimensional halide perovskites

Abstract

Based on first-principles calculations, we show that chemically active metal ns2 lone pairs play an important role in exciton relaxation and dissociation in low-dimensional halide perovskites. Here, we studied excited-state properties of several recently discovered luminescent all-inorganic and hybrid organic-inorganic zero-dimensional (0D) Sn and Pb halides. The results show that, despite the similarity in ground-state electronic structure between Sn and Pb halide perovskites, the chemically more active Sn2+ lone pair leads to stronger excited-state structural distortion and larger Stokes shift in Sn halides. The enhanced Stokes shift hinders excitation energy transport, which reduces energy loss to defects and increases the photoluminescence quantum efficiency. Finally, the presence of the ns2 metal cations in the 0D halide perovskites also promotes the exciton dissociation into electron and hole polarons especially in all-inorganic compounds, in which the coupling between metal-halide clusters is significant.

Authors:
 [1]; ORCiD logo [2];  [3]; ORCiD logo [4]
+ Show Author Affiliations
  1. Beihang University, Beijing (China)
  2. East China Normal University, Shanghai (China); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. East China Normal University, Shanghai (China)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1502553
Alternate Identifier(s):
OSTI ID: 1499071
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 3; Journal Issue: 3; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Shi, Hongliang, Han, Dan, Chen, Shiyou, and Du, Mao-Hua. Impact of metal ns2 lone pair on luminescence quantum efficiency in low-dimensional halide perovskites. United States: N. p., 2019. Web. doi:10.1103/PhysRevMaterials.3.034604.
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Shi, Hongliang, Han, Dan, Chen, Shiyou, & Du, Mao-Hua. Impact of metal ns2 lone pair on luminescence quantum efficiency in low-dimensional halide perovskites. United States. https://doi.org/10.1103/PhysRevMaterials.3.034604
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Shi, Hongliang, Han, Dan, Chen, Shiyou, and Du, Mao-Hua. Tue . "Impact of metal ns2 lone pair on luminescence quantum efficiency in low-dimensional halide perovskites". United States. https://doi.org/10.1103/PhysRevMaterials.3.034604. https://www.osti.gov/servlets/purl/1502553.
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@article{osti_1502553,
title = {Impact of metal ns2 lone pair on luminescence quantum efficiency in low-dimensional halide perovskites},
author = {Shi, Hongliang and Han, Dan and Chen, Shiyou and Du, Mao-Hua},
abstractNote = {Based on first-principles calculations, we show that chemically active metal ns2 lone pairs play an important role in exciton relaxation and dissociation in low-dimensional halide perovskites. Here, we studied excited-state properties of several recently discovered luminescent all-inorganic and hybrid organic-inorganic zero-dimensional (0D) Sn and Pb halides. The results show that, despite the similarity in ground-state electronic structure between Sn and Pb halide perovskites, the chemically more active Sn2+ lone pair leads to stronger excited-state structural distortion and larger Stokes shift in Sn halides. The enhanced Stokes shift hinders excitation energy transport, which reduces energy loss to defects and increases the photoluminescence quantum efficiency. Finally, the presence of the ns2 metal cations in the 0D halide perovskites also promotes the exciton dissociation into electron and hole polarons especially in all-inorganic compounds, in which the coupling between metal-halide clusters is significant.},
doi = {10.1103/PhysRevMaterials.3.034604},
journal = {Physical Review Materials},
number = 3,
volume = 3,
place = {United States},
year = {Tue Mar 12 00:00:00 EDT 2019},
month = {Tue Mar 12 00:00:00 EDT 2019}
}
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https://doi.org/10.1103/PhysRevMaterials.3.034604
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