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Title: Defect-induced band-edge reconstruction of a bismuth-halide double perovskite for visible-light absorption

Abstract

In this study, halide double perovskites have recently been developed as less toxic analogs of the lead perovskite solar-cell absorbers APbX3 (A = monovalent cation; X = Br or I). However, all known halide double perovskites have large bandgaps that afford weak visible-light absorption. The first halide double perovskite evaluated as an absorber, Cs2AgBiBr6 (1), has a bandgap of 1.95 eV. Here, we show that dilute alloying decreases 1’s bandgap by ca. 0.5 eV. Importantly, time-resolved photoconductivity measurements reveal long-lived carriers with microsecond lifetimes in the alloyed material, which is very promising for photovoltaic applications. The alloyed perovskite described herein is the first double perovskite to show comparable bandgap energy and carrier lifetime to those of (CH3NH3)PbI3. By describing how energy- and symmetry-matched impurity orbitals, at low concentrations, dramatically alter 1’s band edges, we open a potential pathway for the large and diverse family of halide double perovskites to compete with APbX3 absorbers.

Authors:
 [1];  [2];  [3];  [4]; ORCiD logo [5];  [6];  [7]; ORCiD logo [1]
  1. Stanford Univ., Stanford, CA (United States). Dept. of Chemistry
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States). Dept. of Physics
  3. Delft Univ. of Technology, Delft (The Netherlands). Dept. of Chemical Engineering and Optoelectronic Materials Section; Materials Innovation Institute (M2i), Delft (The Netherlands)
  4. Stanford Univ., Stanford, CA (United States). Dept. of Chemistry; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  6. Delft Univ. of Technology, Delft (The Netherlands). Dept. of Chemical Engineering and Optoelectronic Materials Section
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States). Dept. of Physics; Kavli Energy NanoScience, Berkeley, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab. (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; Sloan Foundation; Alexander von Humboldt Foundation; Netherlands Organization for Scientific Research (NWO); National Science Foundation (NSF)
OSTI Identifier:
1360903
Alternate Identifier(s):
OSTI ID: 1458491
Grant/Contract Number:  
AC02-76SF00515; AC02-05CH11231; DGE-1147470; F71.4.15562a
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 14; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Slavney, Adam H., Leppert, Linn, Bartesaghi, Davide, Gold-Parker, Aryeh, Toney, Michael F., Savenije, Tom J., Neaton, Jeffrey B., and Karunadasa, Hemamala I. Defect-induced band-edge reconstruction of a bismuth-halide double perovskite for visible-light absorption. United States: N. p., 2017. Web. doi:10.1021/jacs.7b01629.
Slavney, Adam H., Leppert, Linn, Bartesaghi, Davide, Gold-Parker, Aryeh, Toney, Michael F., Savenije, Tom J., Neaton, Jeffrey B., & Karunadasa, Hemamala I. Defect-induced band-edge reconstruction of a bismuth-halide double perovskite for visible-light absorption. United States. doi:10.1021/jacs.7b01629.
Slavney, Adam H., Leppert, Linn, Bartesaghi, Davide, Gold-Parker, Aryeh, Toney, Michael F., Savenije, Tom J., Neaton, Jeffrey B., and Karunadasa, Hemamala I. Wed . "Defect-induced band-edge reconstruction of a bismuth-halide double perovskite for visible-light absorption". United States. doi:10.1021/jacs.7b01629. https://www.osti.gov/servlets/purl/1360903.
@article{osti_1360903,
title = {Defect-induced band-edge reconstruction of a bismuth-halide double perovskite for visible-light absorption},
author = {Slavney, Adam H. and Leppert, Linn and Bartesaghi, Davide and Gold-Parker, Aryeh and Toney, Michael F. and Savenije, Tom J. and Neaton, Jeffrey B. and Karunadasa, Hemamala I.},
abstractNote = {In this study, halide double perovskites have recently been developed as less toxic analogs of the lead perovskite solar-cell absorbers APbX3 (A = monovalent cation; X = Br or I). However, all known halide double perovskites have large bandgaps that afford weak visible-light absorption. The first halide double perovskite evaluated as an absorber, Cs2AgBiBr6 (1), has a bandgap of 1.95 eV. Here, we show that dilute alloying decreases 1’s bandgap by ca. 0.5 eV. Importantly, time-resolved photoconductivity measurements reveal long-lived carriers with microsecond lifetimes in the alloyed material, which is very promising for photovoltaic applications. The alloyed perovskite described herein is the first double perovskite to show comparable bandgap energy and carrier lifetime to those of (CH3NH3)PbI3. By describing how energy- and symmetry-matched impurity orbitals, at low concentrations, dramatically alter 1’s band edges, we open a potential pathway for the large and diverse family of halide double perovskites to compete with APbX3 absorbers.},
doi = {10.1021/jacs.7b01629},
journal = {Journal of the American Chemical Society},
number = 14,
volume = 139,
place = {United States},
year = {2017},
month = {3}
}

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Works referencing / citing this record:

CCDC 1567818: Experimental Crystal Structure Determination: NEHTOM : Non-CSD Structure
dataset, August 2017


CCDC 1567819: Experimental Crystal Structure Determination: NEHTUS : catena-(bis(methylammonium) hexakis(μ-bromo)-bismuth-thallium)
dataset, August 2017


CCDC 1567820: Experimental Crystal Structure Determination: OQUTUR01 : catena-(bis(methylammonium) hexakis(μ-bromo)-bismuth-thallium)
dataset, August 2017


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  • Angewandte Chemie International Edition, Vol. 57, Issue 39
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  • Ju, Dianxing; Zheng, Xiaopeng; Liu, Jialiang
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  • DOI: 10.1002/anie.201810481

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  • Wei, Fengxia; Brivio, Federico; Wu, Yue
  • Journal of Materials Chemistry C, Vol. 6, Issue 14
  • DOI: 10.1039/c7tc04798c

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journal, January 2018

  • Li, Tianyue; Wang, Qifei; Nichol, Gary S.
  • Dalton Transactions, Vol. 47, Issue 20
  • DOI: 10.1039/c8dt00864g

Rational design of a triiodide-intercalated dielectric-switching hybrid for visible-light absorption
journal, January 2018

  • Zhang, Weichuan; Kou, Bo; Peng, Yu
  • Journal of Materials Chemistry C, Vol. 6, Issue 45
  • DOI: 10.1039/c8tc04372h

Tunable optical absorption in lead-free perovskite-like hybrids by iodide management
journal, January 2019

  • Kou, Bo; Zhang, Weichuan; Ji, Chengmin
  • Chemical Communications, Vol. 55, Issue 94
  • DOI: 10.1039/c9cc05365d

Small-Band-Gap Halide Double Perovskites
journal, August 2018

  • Slavney, Adam H.; Leppert, Linn; Saldivar Valdes, Abraham
  • Angewandte Chemie, Vol. 130, Issue 39
  • DOI: 10.1002/ange.201807421

Reversible Band Gap Narrowing of Sn-Based Hybrid Perovskite Single Crystal with Excellent Phase Stability
journal, October 2018

  • Ju, Dianxing; Zheng, Xiaopeng; Liu, Jialiang
  • Angewandte Chemie International Edition, Vol. 57, Issue 45
  • DOI: 10.1002/anie.201810481

Synthesis, crystal structure, magnetic and electronic properties of the caesium-based transition metal halide Cs 3 Fe 2 Br 9
journal, January 2018

  • Wei, Fengxia; Brivio, Federico; Wu, Yue
  • Journal of Materials Chemistry C, Vol. 6, Issue 14
  • DOI: 10.1039/c7tc04798c

Extending lead-free hybrid photovoltaic materials to new structures: thiazolium, aminothiazolium and imidazolium iodobismuthates
journal, January 2018

  • Li, Tianyue; Wang, Qifei; Nichol, Gary S.
  • Dalton Transactions, Vol. 47, Issue 20
  • DOI: 10.1039/c8dt00864g

Rational design of a triiodide-intercalated dielectric-switching hybrid for visible-light absorption
journal, January 2018

  • Zhang, Weichuan; Kou, Bo; Peng, Yu
  • Journal of Materials Chemistry C, Vol. 6, Issue 45
  • DOI: 10.1039/c8tc04372h

Tunable optical absorption in lead-free perovskite-like hybrids by iodide management
journal, January 2019

  • Kou, Bo; Zhang, Weichuan; Ji, Chengmin
  • Chemical Communications, Vol. 55, Issue 94
  • DOI: 10.1039/c9cc05365d