Roles of Pseudo-Closed s2 Orbitals for Different Intrinsic Hole Generation between Tl–Bi and In–Bi Bromide Double Perovskites
Abstract
Although metal halide double perovskites A2B(I)B(III)X6 are expected as nontoxic alternatives for lead halide perovskites, recent studies have shown that only Tl(I)–Bi(III) and In(I)–Bi(III) bromides are thermodynamically stable and possess optoelectronic properties suitable for photovoltaic absorbers. In this work, we show, through density functional theory calculations, that Tl–Bi and In–Bi bromide double perovskites exhibit significantly different semiconducting behaviors due to the different energy levels of the highest-occupied pseudoclosed s2 orbitals of Tl(I) and In(I). While Tl–Bi double perovskites can exhibit semiconducting $$p$$-type properties, In–Bi bromide double perovskites exhibit metallic $$p$$-type ones regardless of the synthesis condition due to the extremely low formation energy of In vacancy. Such difference makes Tl–Bi bromide double perovskites suitable for optoelectronic applications, but not In–Bi bromide double perovskites. Furthermore, there is a high probability for In to substitute a Bi site, forming a local In–In bromide double perovskite structure with a lower local conduction band minimum, detrimentally affecting the open circuit voltage of In–Bi bromide double perovskite-based thin film solar cells.
- Authors:
-
[1];
[2];
- Tokyo Inst. of Technology (Japan). Materials Research Center for Element Strategy
- Univ. of Toledo, OH (United States). Dept. of Physics and Astronomy and Wright Center for Photovoltaics Innovation and Commercialization (PVIC)
- Tokyo Inst. of Technology (Japan). Materials Research Center for Element Strategy and Lab. for Materials and Structures
- Publication Date:
- Research Org.:
- Duke Univ., Durham, NC (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE); Ministry of Education, Culture, Sports, Science and Technology (MEXT); National Science Foundation (NSF)
- OSTI Identifier:
- 1593889
- Grant/Contract Number:
- EE0006712; CHE-1230246; DMR-1534686
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 1; 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
Xiao, Zewen, Yan, Yanfa, Hosono, Hideo, and Kamiya, Toshio. Roles of Pseudo-Closed s2 Orbitals for Different Intrinsic Hole Generation between Tl–Bi and In–Bi Bromide Double Perovskites. United States: N. p., 2017.
Web. doi:10.1021/acs.jpclett.7b02949.
Xiao, Zewen, Yan, Yanfa, Hosono, Hideo, & Kamiya, Toshio. Roles of Pseudo-Closed s2 Orbitals for Different Intrinsic Hole Generation between Tl–Bi and In–Bi Bromide Double Perovskites. United States. https://doi.org/10.1021/acs.jpclett.7b02949
Xiao, Zewen, Yan, Yanfa, Hosono, Hideo, and Kamiya, Toshio. Thu .
"Roles of Pseudo-Closed s2 Orbitals for Different Intrinsic Hole Generation between Tl–Bi and In–Bi Bromide Double Perovskites". United States. https://doi.org/10.1021/acs.jpclett.7b02949. https://www.osti.gov/servlets/purl/1593889.
@article{osti_1593889,
title = {Roles of Pseudo-Closed s2 Orbitals for Different Intrinsic Hole Generation between Tl–Bi and In–Bi Bromide Double Perovskites},
author = {Xiao, Zewen and Yan, Yanfa and Hosono, Hideo and Kamiya, Toshio},
abstractNote = {Although metal halide double perovskites A2B(I)B(III)X6 are expected as nontoxic alternatives for lead halide perovskites, recent studies have shown that only Tl(I)–Bi(III) and In(I)–Bi(III) bromides are thermodynamically stable and possess optoelectronic properties suitable for photovoltaic absorbers. In this work, we show, through density functional theory calculations, that Tl–Bi and In–Bi bromide double perovskites exhibit significantly different semiconducting behaviors due to the different energy levels of the highest-occupied pseudoclosed s2 orbitals of Tl(I) and In(I). While Tl–Bi double perovskites can exhibit semiconducting $p$-type properties, In–Bi bromide double perovskites exhibit metallic $p$-type ones regardless of the synthesis condition due to the extremely low formation energy of In vacancy. Such difference makes Tl–Bi bromide double perovskites suitable for optoelectronic applications, but not In–Bi bromide double perovskites. Furthermore, there is a high probability for In to substitute a Bi site, forming a local In–In bromide double perovskite structure with a lower local conduction band minimum, detrimentally affecting the open circuit voltage of In–Bi bromide double perovskite-based thin film solar cells.},
doi = {10.1021/acs.jpclett.7b02949},
journal = {Journal of Physical Chemistry Letters},
number = 1,
volume = 9,
place = {United States},
year = {Thu Dec 21 00:00:00 EST 2017},
month = {Thu Dec 21 00:00:00 EST 2017}
}
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Works referencing / citing this record:
From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives
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