Three-Dimensional Lead Iodide Perovskitoid Hybrids with High X-ray Photoresponse
Abstract
Large organic A cations cannot stabilize the 3D perovskite AMX3 structure because they cannot be accommodated in the cubo-octhedral cage (do not follow the Goldschmidt tolerance factor rule), and they generally template low-dimensional structures. In this paper, we report that the large dication aminomethylpyridinium (AMPY) can template novel 3D structures which resemble conventional perovskites. They have the formula (xAMPY)M2I6 (x = 3 or 4, M = Sn2+ or Pb2+) which is double of the AMX3 formula. However, because of the steric requirement of the Goldschmidt tolerance factor rule, it is impossible for (xAMPY)M2I6 to form proper perovskite structures. Instead, a combination of corner-sharing and edge-sharing connectivity is adopted in these compounds leading to the new 3D structures. DFT calculations reveal that the compounds are indirect band gap semiconductors with direct band gaps presenting at slightly higher energies and dispersive electronic bands. The indirect band gaps of the Sn and Pb compounds are ~1.7 and 2.0 eV, respectively, which is slightly higher than the corresponding AMI3 3D perovskites. The Raman spectra for the compounds are diffuse, with a broad rising central peak at very low frequencies around 0 cm–1, a feature that is characteristic of dynamical lattices, high anharmonicity, and dissipativemore »
- Authors:
-
[1];
[1];
[2];
[3];
[1];
[2];
[2];
[4];
[5];
[1]
- Northwestern Univ., Evanston, IL (United States)
- Univ. Rennes (France)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Univ. of Crete, Heraklion (Greece)
- Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1755179
- Grant/Contract Number:
- AC02-06CH11357; SC0012541; EAR-1634415; EAR-1531583; ECC-S1542205; DMR-1720139
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 142; 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
Li, Xiaotong, He, Yihui, Kepenekian, Mikaël, Guo, Peijun, Ke, Weijun, Even, Jacky, Katan, Claudine, Stoumpos, Constantinos C., Schaller, Richard D., and Kanatzidis, Mercouri G. Three-Dimensional Lead Iodide Perovskitoid Hybrids with High X-ray Photoresponse. United States: N. p., 2020.
Web. doi:10.1021/jacs.0c00101.
Li, Xiaotong, He, Yihui, Kepenekian, Mikaël, Guo, Peijun, Ke, Weijun, Even, Jacky, Katan, Claudine, Stoumpos, Constantinos C., Schaller, Richard D., & Kanatzidis, Mercouri G. Three-Dimensional Lead Iodide Perovskitoid Hybrids with High X-ray Photoresponse. United States. https://doi.org/10.1021/jacs.0c00101
Li, Xiaotong, He, Yihui, Kepenekian, Mikaël, Guo, Peijun, Ke, Weijun, Even, Jacky, Katan, Claudine, Stoumpos, Constantinos C., Schaller, Richard D., and Kanatzidis, Mercouri G. Mon .
"Three-Dimensional Lead Iodide Perovskitoid Hybrids with High X-ray Photoresponse". United States. https://doi.org/10.1021/jacs.0c00101. https://www.osti.gov/servlets/purl/1755179.
@article{osti_1755179,
title = {Three-Dimensional Lead Iodide Perovskitoid Hybrids with High X-ray Photoresponse},
author = {Li, Xiaotong and He, Yihui and Kepenekian, Mikaël and Guo, Peijun and Ke, Weijun and Even, Jacky and Katan, Claudine and Stoumpos, Constantinos C. and Schaller, Richard D. and Kanatzidis, Mercouri G.},
abstractNote = {Large organic A cations cannot stabilize the 3D perovskite AMX3 structure because they cannot be accommodated in the cubo-octhedral cage (do not follow the Goldschmidt tolerance factor rule), and they generally template low-dimensional structures. In this paper, we report that the large dication aminomethylpyridinium (AMPY) can template novel 3D structures which resemble conventional perovskites. They have the formula (xAMPY)M2I6 (x = 3 or 4, M = Sn2+ or Pb2+) which is double of the AMX3 formula. However, because of the steric requirement of the Goldschmidt tolerance factor rule, it is impossible for (xAMPY)M2I6 to form proper perovskite structures. Instead, a combination of corner-sharing and edge-sharing connectivity is adopted in these compounds leading to the new 3D structures. DFT calculations reveal that the compounds are indirect band gap semiconductors with direct band gaps presenting at slightly higher energies and dispersive electronic bands. The indirect band gaps of the Sn and Pb compounds are ~1.7 and 2.0 eV, respectively, which is slightly higher than the corresponding AMI3 3D perovskites. The Raman spectra for the compounds are diffuse, with a broad rising central peak at very low frequencies around 0 cm–1, a feature that is characteristic of dynamical lattices, high anharmonicity, and dissipative vibrations very similar to the 3D AMX3 perovskites. Devices of (3AMPY)Pb2I6 crystals exhibit clear photoresponse under ambient light without applied bias, reflecting a high carrier mobility (μ) and long carrier lifetime (τ). The devices also exhibit sizable X-ray generated photocurrent with a high μτ product of ~1.2×10-4 cm2 /V and a X-ray sensitivity of 207 μC∙Gy-1∙cm-2.},
doi = {10.1021/jacs.0c00101},
journal = {Journal of the American Chemical Society},
number = 14,
volume = 142,
place = {United States},
year = {Mon Mar 16 00:00:00 EDT 2020},
month = {Mon Mar 16 00:00:00 EDT 2020}
}
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