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Title: B-Site Metal Cation Exchange in Halide Perovskites

Abstract

Here, we demonstrate exchange of the B-site metal cation in hybrid organic-inorganic halide perovskite thin films. We exchange tin in formamidinium tin triiodide (NH 2) 2SnI 3' or FASnI 3) with lead at controllable levels, forming (CH- (NH 2) 2SnI xPB 1-xI 3 alloys with partial substitution and fully converting the film to CH(NH 2) 2PbI 3 with a large excess of Pb 2+. We observe no evidence for phase segregation or bilayered films, indicating that conversion is uniform throughout the film. This facile technique provides a new way to control composition independently from the crystallization processes, allowing formation of the black phase of CH(NH 2) 2PbI 3 at much lower temperatures than those previously reported while also opening the door to new morphology-composition combinations. The surprising observation that the B-site metal cations are mobile may also provide insight into the nature of transient processes in these materials, suggesting that they may be involved in ionic conduction, and will be a critical consideration for long-term stability.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Washington Research Foundation, Seattle, WA (United States); National Science Foundation (NSF); National Institutes of Health (NIH)
OSTI Identifier:
1361564
Alternate Identifier(s):
OSTI ID: 1425734
Grant/Contract Number:
SC0013957; ECC-1542101
Resource Type:
Journal Article: Published Article
Journal Name:
ACS Energy Letters
Additional Journal Information:
Journal Volume: 2; Journal Issue: 5; Journal ID: ISSN 2380-8195
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Eperon, Giles E., and Ginger, David S. B-Site Metal Cation Exchange in Halide Perovskites. United States: N. p., 2017. Web. doi:10.1021/acsenergylett.7b00290.
Eperon, Giles E., & Ginger, David S. B-Site Metal Cation Exchange in Halide Perovskites. United States. doi:10.1021/acsenergylett.7b00290.
Eperon, Giles E., and Ginger, David S. Tue . "B-Site Metal Cation Exchange in Halide Perovskites". United States. doi:10.1021/acsenergylett.7b00290.
@article{osti_1361564,
title = {B-Site Metal Cation Exchange in Halide Perovskites},
author = {Eperon, Giles E. and Ginger, David S.},
abstractNote = {Here, we demonstrate exchange of the B-site metal cation in hybrid organic-inorganic halide perovskite thin films. We exchange tin in formamidinium tin triiodide (NH2) 2SnI3' or FASnI3) with lead at controllable levels, forming (CH- (NH2)2SnIxPB1-xI3 alloys with partial substitution and fully converting the film to CH(NH2)2PbI3 with a large excess of Pb2+. We observe no evidence for phase segregation or bilayered films, indicating that conversion is uniform throughout the film. This facile technique provides a new way to control composition independently from the crystallization processes, allowing formation of the black phase of CH(NH2)2PbI3 at much lower temperatures than those previously reported while also opening the door to new morphology-composition combinations. The surprising observation that the B-site metal cations are mobile may also provide insight into the nature of transient processes in these materials, suggesting that they may be involved in ionic conduction, and will be a critical consideration for long-term stability.},
doi = {10.1021/acsenergylett.7b00290},
journal = {ACS Energy Letters},
number = 5,
volume = 2,
place = {United States},
year = {Tue May 02 00:00:00 EDT 2017},
month = {Tue May 02 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acsenergylett.7b00290

Citation Metrics:
Cited by: 9works
Citation information provided by
Web of Science

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  • Here, we demonstrate exchange of the B-site metal cation in hybrid organic-inorganic halide perovskite thin films. We exchange tin in formamidinium tin triiodide (NH 2) 2SnI 3' or FASnI 3) with lead at controllable levels, forming (CH- (NH 2) 2SnI xPB 1-xI 3 alloys with partial substitution and fully converting the film to CH(NH 2) 2PbI 3 with a large excess of Pb 2+. We observe no evidence for phase segregation or bilayered films, indicating that conversion is uniform throughout the film. This facile technique provides a new way to control composition independently from the crystallization processes, allowing formation ofmore » the black phase of CH(NH 2) 2PbI 3 at much lower temperatures than those previously reported while also opening the door to new morphology-composition combinations. The surprising observation that the B-site metal cations are mobile may also provide insight into the nature of transient processes in these materials, suggesting that they may be involved in ionic conduction, and will be a critical consideration for long-term stability.« less
  • Organic-inorganic hybrid halide perovskites are a promising class of materials for photovoltaic application with reported power efficiencies over similar to 22%. However, not much is known about the influence of the organic dipole rotation and phase transitions on charge carrier dynamics. Here, we report substantial changes in mobility and lifetime of charge carriers in CH 3NH 3PbI 3 after the low-temperature tetragonal (beta) to orthorhombic (gamma) phase transition. By using microwave conductivity measurements, we observed that the mobility and lifetime of ionized charge carriers increase as the temperature decreases and a sudden increment is seen after the beta-gamma phase transition.more » For CH 3NH 3PbI 3, the mobility and the half-lifetime increase by a factor of 36 compared with the values before the beta-gamma phase transition. We attribute the considerable change in the dynamics at low temperature to the decrease of the inherent dynamic disorder of the organic cation (CH 3NH 3+) inside the perovskite crystal structure.« less
  • We reveal here a key aspect of the inorganic framework of hybrid halide perovskites that potentially impacts the electronic, thermal, and dielectric properties.
  • We employed multiwavelength anomalous X-ray dispersion to determine the relative cation occupation at two crystallographically distinct metal sites in Fe 2+-, Cu 2+-, and Zn 2+-exchanged versions of the microporous metal–organic framework (MOF) known as MnMnBTT (BTT = 1,3,5-benzenetristetrazolate). By exploiting the dispersive differences between Mn, Fe, Cu, and Zn, the extent and location of cation exchange were determined from single crystal X-ray diffraction data sets collected near the K edges of Mn 2+ and of the substituting metal, and at a wavelength remote from either edge as a reference. Comparing the anomalous dispersion between these measurements indicated that themore » extent of Mn 2+ replacement depends on the identity of the substituting metal. We contrasted two unique methods to analyze this data with a conventional approach and evaluated their limitations with emphasis on the general application of this method to other heterometallic MOFs, where site-specific metal identification is fundamental to tuning catalytic and physical properties.« less