Small-Band-Gap Halide Double Perovskites
Abstract
Abstract Despite their compositional versatility, most halide double perovskites feature large band gaps. Herein, we describe a strategy for achieving small band gaps in this family of materials. The new double perovskites Cs 2 AgTlX 6 (X=Cl ( 1 ) and Br ( 2 )) have direct band gaps of 2.0 and 0.95 eV, respectively, which are approximately 1 eV lower than those of analogous perovskites. To our knowledge, compound 2 displays the lowest band gap for any known halide perovskite. Unlike in A I B II X 3 perovskites, the band‐gap transition in A I 2 BB′X 6 double perovskites can show substantial metal‐to‐metal charge‐transfer character. This band‐edge orbital composition is used to achieve small band gaps through the selection of energetically aligned B‐ and B′‐site metal frontier orbitals. Calculations reveal a shallow, symmetry‐forbidden region at the band edges for 1 , which results in long (μs) microwave conductivity lifetimes. We further describe a facile self‐doping reaction in 2 through Br 2 loss at ambient conditions.
- Authors:
-
[1];
[2];
[3];
[4];
[5];
[1]
- Stanford Univ., Stanford, CA (United States)
- Univ. of Bayreuth, Bayreuth (Germany)
- Delft Univ. of Technology, Delft (Netherlands); Materials Innovation Institute, Delft (Netherlands)
- Delft Univ. of Technology, Delft (Netherlands)
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience, Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1475457
- Alternate Identifier(s):
- OSTI ID: 1467925
- Grant/Contract Number:
- AC02-76SF00515; DMR-1708892; ECCS-1542152
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 39; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; absorber; band gap; band structure; doping; halide double perovskite
Citation Formats
Slavney, Adam H., Leppert, Linn, Valdes, Abraham Saldivar, Bartesaghi, Davide, Savenije, Tom J., Neaton, Jeffrey B., and Karunadasa, Hemamala I. Small-Band-Gap Halide Double Perovskites. United States: N. p., 2018.
Web. doi:10.1002/anie.201807421.
Slavney, Adam H., Leppert, Linn, Valdes, Abraham Saldivar, Bartesaghi, Davide, Savenije, Tom J., Neaton, Jeffrey B., & Karunadasa, Hemamala I. Small-Band-Gap Halide Double Perovskites. United States. https://doi.org/10.1002/anie.201807421
Slavney, Adam H., Leppert, Linn, Valdes, Abraham Saldivar, Bartesaghi, Davide, Savenije, Tom J., Neaton, Jeffrey B., and Karunadasa, Hemamala I. Tue .
"Small-Band-Gap Halide Double Perovskites". United States. https://doi.org/10.1002/anie.201807421. https://www.osti.gov/servlets/purl/1475457.
@article{osti_1475457,
title = {Small-Band-Gap Halide Double Perovskites},
author = {Slavney, Adam H. and Leppert, Linn and Valdes, Abraham Saldivar and Bartesaghi, Davide and Savenije, Tom J. and Neaton, Jeffrey B. and Karunadasa, Hemamala I.},
abstractNote = {Abstract Despite their compositional versatility, most halide double perovskites feature large band gaps. Herein, we describe a strategy for achieving small band gaps in this family of materials. The new double perovskites Cs 2 AgTlX 6 (X=Cl ( 1 ) and Br ( 2 )) have direct band gaps of 2.0 and 0.95 eV, respectively, which are approximately 1 eV lower than those of analogous perovskites. To our knowledge, compound 2 displays the lowest band gap for any known halide perovskite. Unlike in A I B II X 3 perovskites, the band‐gap transition in A I 2 BB′X 6 double perovskites can show substantial metal‐to‐metal charge‐transfer character. This band‐edge orbital composition is used to achieve small band gaps through the selection of energetically aligned B‐ and B′‐site metal frontier orbitals. Calculations reveal a shallow, symmetry‐forbidden region at the band edges for 1 , which results in long (μs) microwave conductivity lifetimes. We further describe a facile self‐doping reaction in 2 through Br 2 loss at ambient conditions.},
doi = {10.1002/anie.201807421},
journal = {Angewandte Chemie (International Edition)},
number = 39,
volume = 57,
place = {United States},
year = {Tue Aug 07 00:00:00 EDT 2018},
month = {Tue Aug 07 00:00:00 EDT 2018}
}
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