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

Abstract

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 APbX3absorbers.

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. https://doi.org/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. https://doi.org/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. https://doi.org/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 = {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 APbX3absorbers.},
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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