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Title: Tolerance Factor and Cooperative Tilting Effects in Vacancy-Ordered Double Perovskite Halides

Abstract

Lattice dynamics and structural instabilities are strongly implicated in dictating the electronic properties of perovskite halide semiconductors. We present a study of the vacancy-ordered double perovskite Rb2SnI6 and correlate dynamic and cooperative octahedral tilting with changes in electronic behavior compared to those of Cs2SnI6. Though both compounds exhibit native n-type semiconductivity, Rb2SnI6 exhibits carrier mobilities that are reduced by a factor of ~50 relative to Cs2SnI6. From synchrotron powder X-ray diffraction, we find that Rb2SnI6 adopts the tetragonal vacancy-ordered double perovskite structure at room temperature and undergoes a phase transition to a lower-symmetry monoclinic structure upon cooling, characterized by cooperative octahedral tilting of the [SnI6] octahedra. X-ray and neutron pair distribution function analyses reveal that the local coordination environment of Rb2SnI6 is consistent with the monoclinic structure at all temperatures; we attribute this observation to dynamic octahedral rotations that become frozen in to yield the low-temperature monoclinic structure. In contrast, Cs2SnI6 adopts the cubic vacancy-ordered double perovskite structure at all temperatures. Density functional calculations show that static octahedral tilting in Rb2SnI6 results in marginally increased carrier effective masses, which alone are insufficient to account for the experimental electronic behavior. Rather, the larger number of low-frequency phonons introduced by the lowermore » symmetry of the Rb2SnI6 structure yield stronger electron–phonon coupling interactions that produce larger electron effective masses and reduced carrier mobilities relative to Cs2SnI6. Further, we discuss the results for Rb2SnI6 in the context of other vacancy-ordered double perovskite semiconductors, in order to demonstrate that the electron–phonon coupling characteristics can be predicted using the geometric perovskite tolerance factor. This study represents an important step in designing perovskite halide semiconductors with desired charge transport properties for optoelectronic applications.« less

Authors:
ORCiD logo [1];  [2];  [1]; ORCiD logo [2]; ORCiD logo [1]
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  1. Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872, United States
  2. Kathleen Lonsdale Materials Chemistry, Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom, Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, United Kingdom, Thomas Young Centre, University College London, Gower Street, London WC1E 6BT, United Kingdom
Publication Date:
Research Org.:
Colorado State Univ., Fort Collins, CO (United States); Univ. College London (United Kingdom)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Engineering and Physical Sciences Research Council (EPSRC)
OSTI Identifier:
1457590
Alternate Identifier(s):
OSTI ID: 1499116
Grant/Contract Number:  
AC02-06CH11357; SC0016083; EP/L000202; EP/N01572X/1; EP/L015862/1
Resource Type:
Published Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Name: Chemistry of Materials Journal Volume: 30 Journal Issue: 11; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Maughan, Annalise E., Ganose, Alex M., Almaker, Mohammed A., Scanlon, David O., and Neilson, James R. Tolerance Factor and Cooperative Tilting Effects in Vacancy-Ordered Double Perovskite Halides. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.8b01549.
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Maughan, Annalise E., Ganose, Alex M., Almaker, Mohammed A., Scanlon, David O., & Neilson, James R. Tolerance Factor and Cooperative Tilting Effects in Vacancy-Ordered Double Perovskite Halides. United States. https://doi.org/10.1021/acs.chemmater.8b01549
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Maughan, Annalise E., Ganose, Alex M., Almaker, Mohammed A., Scanlon, David O., and Neilson, James R. Wed . "Tolerance Factor and Cooperative Tilting Effects in Vacancy-Ordered Double Perovskite Halides". United States. https://doi.org/10.1021/acs.chemmater.8b01549.
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@article{osti_1457590,
title = {Tolerance Factor and Cooperative Tilting Effects in Vacancy-Ordered Double Perovskite Halides},
author = {Maughan, Annalise E. and Ganose, Alex M. and Almaker, Mohammed A. and Scanlon, David O. and Neilson, James R.},
abstractNote = {Lattice dynamics and structural instabilities are strongly implicated in dictating the electronic properties of perovskite halide semiconductors. We present a study of the vacancy-ordered double perovskite Rb2SnI6 and correlate dynamic and cooperative octahedral tilting with changes in electronic behavior compared to those of Cs2SnI6. Though both compounds exhibit native n-type semiconductivity, Rb2SnI6 exhibits carrier mobilities that are reduced by a factor of ~50 relative to Cs2SnI6. From synchrotron powder X-ray diffraction, we find that Rb2SnI6 adopts the tetragonal vacancy-ordered double perovskite structure at room temperature and undergoes a phase transition to a lower-symmetry monoclinic structure upon cooling, characterized by cooperative octahedral tilting of the [SnI6] octahedra. X-ray and neutron pair distribution function analyses reveal that the local coordination environment of Rb2SnI6 is consistent with the monoclinic structure at all temperatures; we attribute this observation to dynamic octahedral rotations that become frozen in to yield the low-temperature monoclinic structure. In contrast, Cs2SnI6 adopts the cubic vacancy-ordered double perovskite structure at all temperatures. Density functional calculations show that static octahedral tilting in Rb2SnI6 results in marginally increased carrier effective masses, which alone are insufficient to account for the experimental electronic behavior. Rather, the larger number of low-frequency phonons introduced by the lower symmetry of the Rb2SnI6 structure yield stronger electron–phonon coupling interactions that produce larger electron effective masses and reduced carrier mobilities relative to Cs2SnI6. Further, we discuss the results for Rb2SnI6 in the context of other vacancy-ordered double perovskite semiconductors, in order to demonstrate that the electron–phonon coupling characteristics can be predicted using the geometric perovskite tolerance factor. This study represents an important step in designing perovskite halide semiconductors with desired charge transport properties for optoelectronic applications.},
doi = {10.1021/acs.chemmater.8b01549},
journal = {Chemistry of Materials},
number = 11,
volume = 30,
place = {United States},
year = {Wed May 23 00:00:00 EDT 2018},
month = {Wed May 23 00:00:00 EDT 2018}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.chemmater.8b01549
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Citation Metrics:
Cited by: 70 works
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Figures / Tables:

Figure 1 Figure 1: Crystal structures of Rb2SnI6 at T = 295 K and T = 100 K. In (a) and (c), the structures are projected down the c-axis to highlight the octahedral tilting and rotation, while unit cell descriptions are shown in (b) and (d). Rubidium atoms are shown in pink,more » tin atoms in blue, and iodine atoms in purple.« less
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Works referencing / citing this record:

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  • Fedorovskiy, Alexander E.; Drigo, Nikita A.; Nazeeruddin, Mohammad Khaja
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journal, January 2018

  • Butler, Keith T.
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  • DOI: 10.1039/c8tc02976h

Bond valences and anharmonicity in vacancy-ordered double perovskite halides
journal, January 2018

  • Maughan, Annalise E.; Paecklar, Arnold A.; Neilson, James R.
  • Journal of Materials Chemistry C, Vol. 6, Issue 44
  • DOI: 10.1039/c8tc03527j

Advances in modelling and simulation of halide perovskites for solar cell applications
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    Figures / Tables found in this record:

    Figure 1 (p. 4)figure
    Figure 2 (p. 4)figure
    Figure 3 (p. 4)figure
    Table 1 (p. 4)table
    Figure 4 (p. 5)figure
    Figure 5 (p. 5)figure
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    Figure 7 (p. 6)figure
    Figure 8 (p. 6)figure
    Figure 9 (p. 7)figure
    Table 2 (p. 7)table
    Table 3 (p. 7)table
    Table 4 (p. 7)table
    Figure 10 (p. 8)figure
    Table 5 (p. 8)table
    Figure 11 (p. 9)figure
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