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Title: Air-Stable Direct Bandgap Perovskite Semiconductors: All-Inorganic Tin-Based Heteroleptic Halides Ax SnClyIz (A = Cs, Rb)

Abstract

Semiconducting halide perovskites are a group of materials with exciting photoelectronic properties. Compared to the widely studied hybrid organic–inorganic perovskites, the all-inorganic derivatives are less well understood even as they promise high inherent stability. At the moment, such materials are limited due to the fact that there is a very narrow choice of inorganic cations that can stabilize the desirable perovskite structure. Herein we report on the synthesis and characterization of novel all-inorganic tin-based perovskites and perovskitoids that can be stabilized by the heteroleptic coordination of chloride and iodide anions, Cs2SnCl2I2 (1) and Cs2.38Rb1.62Sn3Cl8I2 (2), consist of two-dimensional (2D) layers of [SnCl4I2]4– octahedra with different connectivity modes. Compound 1 is an n = 1 Ruddlesden–Popper type perovskite adopting the tetragonal archetype structure (I4/mmm space group; a = 5.5905(3) Å, c = 18.8982(13) Å), while compound 2 crystallizes as an orthorhombic modification (Cmcm space group; a = 5.6730(11) Å, b = 25.973(5) Å, c = 16.587(3) Å) with corrugated layers. The crystal chemistry changes drastically when Cs+ is replaced by the smaller Rb+ cation which leads to the isolation of the low dimensional compounds Rb3SnCl3I2 (3a), Rb3SnCl2.33I2.67 (3b) and Rb7Sn4.25Cl12I3.5 (4), thus illustrating the importance of the A-cation size in themore » formation of perovskites. The 2D perovskites show wide band gaps and relatively large resistivities, associated with their chemical stability against the oxidation of Sn2+. The chemical stability is coupled with remarkable electronic properties that derive from the perovskite structure. DFT calculations suggest that both compounds are direct band gap semiconductors with large bandwidths, consistently with the experimentally determined band gaps of Eg = 2.62 and 2.81 eV for 1 and 2, respectively. The combination of stability and favorable electronic structure in heteroleptic-halide perovskites presents a new direction toward the realization of functional devices made exclusively from inorganic perovskites.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [2];  [3]; ORCiD logo [2];  [2]; ORCiD logo [2];  [4]; ORCiD logo [2]
+ Show Author Affiliations
  1. Tsinghua Univ., Beijing (China); Northwestern Univ., Evanston, IL (United States)
  2. Northwestern Univ., Evanston, IL (United States)
  3. Northwestern Univ., Evanston, IL (United States); Seoul National Univ. (Korea, Republic of)
  4. Tsinghua Univ., Beijing (China)
Publication Date:
Research Org.:
Univ. of California, Santa Barbara, CA (United States); Univ. of California, Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Science Foundation (NSF); National Natural Science Foundation of China (NSFC); Keck Foundation; Chinese Scholarship Council (CSC)
OSTI Identifier:
1599735
Grant/Contract Number:  
SC0012541; NNCI-1542205; DMR-1121262; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 14; Journal ID: ISSN 0897-4756
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

Li, Jiangwei, Stoumpos, Constantinos C., Trimarchi, Giancarlo G., Chung, In, Mao, Lingling, Chen, Michelle, Wasielewski, Michael R., Wang, Liduo, and Kanatzidis, Mercouri G. Air-Stable Direct Bandgap Perovskite Semiconductors: All-Inorganic Tin-Based Heteroleptic Halides Ax SnClyIz (A = Cs, Rb). United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.8b02232.
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Li, Jiangwei, Stoumpos, Constantinos C., Trimarchi, Giancarlo G., Chung, In, Mao, Lingling, Chen, Michelle, Wasielewski, Michael R., Wang, Liduo, & Kanatzidis, Mercouri G. Air-Stable Direct Bandgap Perovskite Semiconductors: All-Inorganic Tin-Based Heteroleptic Halides Ax SnClyIz (A = Cs, Rb). United States. https://doi.org/10.1021/acs.chemmater.8b02232
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Li, Jiangwei, Stoumpos, Constantinos C., Trimarchi, Giancarlo G., Chung, In, Mao, Lingling, Chen, Michelle, Wasielewski, Michael R., Wang, Liduo, and Kanatzidis, Mercouri G. Wed . "Air-Stable Direct Bandgap Perovskite Semiconductors: All-Inorganic Tin-Based Heteroleptic Halides Ax SnClyIz (A = Cs, Rb)". United States. https://doi.org/10.1021/acs.chemmater.8b02232. https://www.osti.gov/servlets/purl/1599735.
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@article{osti_1599735,
title = {Air-Stable Direct Bandgap Perovskite Semiconductors: All-Inorganic Tin-Based Heteroleptic Halides Ax SnClyIz (A = Cs, Rb)},
author = {Li, Jiangwei and Stoumpos, Constantinos C. and Trimarchi, Giancarlo G. and Chung, In and Mao, Lingling and Chen, Michelle and Wasielewski, Michael R. and Wang, Liduo and Kanatzidis, Mercouri G.},
abstractNote = {Semiconducting halide perovskites are a group of materials with exciting photoelectronic properties. Compared to the widely studied hybrid organic–inorganic perovskites, the all-inorganic derivatives are less well understood even as they promise high inherent stability. At the moment, such materials are limited due to the fact that there is a very narrow choice of inorganic cations that can stabilize the desirable perovskite structure. Herein we report on the synthesis and characterization of novel all-inorganic tin-based perovskites and perovskitoids that can be stabilized by the heteroleptic coordination of chloride and iodide anions, Cs2SnCl2I2 (1) and Cs2.38Rb1.62Sn3Cl8I2 (2), consist of two-dimensional (2D) layers of [SnCl4I2]4– octahedra with different connectivity modes. Compound 1 is an n = 1 Ruddlesden–Popper type perovskite adopting the tetragonal archetype structure (I4/mmm space group; a = 5.5905(3) Å, c = 18.8982(13) Å), while compound 2 crystallizes as an orthorhombic modification (Cmcm space group; a = 5.6730(11) Å, b = 25.973(5) Å, c = 16.587(3) Å) with corrugated layers. The crystal chemistry changes drastically when Cs+ is replaced by the smaller Rb+ cation which leads to the isolation of the low dimensional compounds Rb3SnCl3I2 (3a), Rb3SnCl2.33I2.67 (3b) and Rb7Sn4.25Cl12I3.5 (4), thus illustrating the importance of the A-cation size in the formation of perovskites. The 2D perovskites show wide band gaps and relatively large resistivities, associated with their chemical stability against the oxidation of Sn2+. The chemical stability is coupled with remarkable electronic properties that derive from the perovskite structure. DFT calculations suggest that both compounds are direct band gap semiconductors with large bandwidths, consistently with the experimentally determined band gaps of Eg = 2.62 and 2.81 eV for 1 and 2, respectively. The combination of stability and favorable electronic structure in heteroleptic-halide perovskites presents a new direction toward the realization of functional devices made exclusively from inorganic perovskites.},
doi = {10.1021/acs.chemmater.8b02232},
journal = {Chemistry of Materials},
number = 14,
volume = 30,
place = {United States},
year = {Wed Jun 20 00:00:00 EDT 2018},
month = {Wed Jun 20 00:00:00 EDT 2018}
}
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https://doi.org/10.1021/acs.chemmater.8b02232
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    Works referencing / citing this record:

    Strong thickness-dependent quantum confinement in all-inorganic perovskite Cs 2 PbI 4 with a Ruddlesden–Popper structure
    journal, January 2019

    • Ding, Yu-Feng; Zhao, Qian-Qi; Yu, Zhuo-Liang
    • Journal of Materials Chemistry C, Vol. 7, Issue 24
    • DOI: 10.1039/c9tc02267h
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