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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; OSTI ID: 1508256
Grant/Contract Number:  
SC0013957; ECC-1542101
Resource Type:
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 = {2017},
month = {5}
}

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

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

Figures / Tables:

Figure 1 Figure 1: B-site cation exchange in thin films. (a) Illustration of the cation exchange process. (b) Absorbance spectra of CH(NH2)2SnI3 thin films reacted with the equivalent molar concentration of Pb shown in the legend. Labels refer to the relative molar amount of Pb in solution compared to the Sn inmore » the film, that is, “1×Pb” refers to an addition of an equivalent number of moles of Pb as Sn in the film. Films were heated at 70 °C for 96 h in the exchange solution. CH(NH2)2PbI3 and CH(NH2)2Sn0.5Pb0.5I3 spectra were measured on non-ion exchanged films of those materials, formed directly from the appropriate solution, as references. (c) Photoluminescence (PL) spectra for three of the films shown in (a). (d) Plot of the estimated bandgap as a function of the relative Pb addition concentration, also showing bandgaps of the reference nonexchanged materials as gray regions.« less

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Works referencing / citing this record:

Scalable Deposition Methods for Large‐area Production of Perovskite Thin Films
journal, June 2019

  • Swartwout, Richard; Hoerantner, Maximilian T.; Bulović, V.
  • ENERGY & ENVIRONMENTAL MATERIALS, Vol. 2, Issue 2
  • DOI: 10.1002/eem2.12043

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.