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Title: Tetragonal Cs1.17In0.81Cl3 : A Charge-Ordered Indium Halide Perovskite Derivative

Abstract

Polycrystalline samples of Cs1.17In0.81Cl3 were prepared by annealing a mixture of CsCl, InCl, and InCl3, stoichiometric for the targeted CsInCl3. Synchrotron powder X-ray diffraction refinement and chemical analysis by energy dispersive X-ray indicated that Cs1.17In0.81Cl3, a tetragonal distorted perovskite derivative (I4/m), is the thermodynamically stable product. The refined unit cell parameters and space group were confirmed by electron diffraction. In the tetragonal structure, In+ and In3+ are located in four different crystallographic sites, consistent with their corresponding bond lengths. In1, In2, and In3 are octahedrally coordinated, whereas In4 is at the center of a pentagonal bipyramid of Cl because of the noncooperative octahedral tilting of In4Cl6. The charged-ordered In+ and In3+ were also confirmed by X-ray absorption and Raman spectroscopy. Cs1.17In0.81Cl3 is the first example of an inorganic halide double perovskite derivative with charged-ordered In+ and In3+. Band structure and optical conductivity calculations were carried out with both generalized gradient approximation (GGA) and modified Becke-Johnson (mBJ) approach; the GGA calculations estimated the band gap and optical band gap to be 2.27 eV and 2.4 eV, respectively. Finally, the large and indirect band gap suggests that Cs1.17In0.81Cl3 is not a good candidate for photovoltaic application.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [3];  [4];  [5]; ORCiD logo [5];  [6];  [7]; ORCiD logo [8]; ORCiD logo [6];  [5]; ORCiD logo [1]
  1. Rutgers Univ., Piscataway, NJ (United States). Dept. of Chemistry and Chemical Biology
  2. State Univ. of New York (SUNY), Stony Brook, NY (United States). Dept. of Physics and Astronomy
  3. Univ. of Antwerp, Antwerp (Belgium). Electron microscopy for Materials science (EMAT)
  4. Illinois Inst. of Technology, Chicago, IL (United States). Dept. of Physics and CSRRI
  5. Rutgers Univ., Piscataway, NJ (United States). Dept. of Physics and Astronomy
  6. Chinese Academy of Sciences and Univ. of Chinese Academy of Sciences (CAS), Beijing (China). Inst. of Physics, School of Physics
  7. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  8. Chosun Univ., Gwangju (South Korea). Dept. of Chemical Education
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Air Force Research Laboratory (AFRL) - Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1510268
Grant/Contract Number:  
AC02-06CH11357; NSF-DMR-1507252
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 6; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Tan, Xiaoyan, Stephens, Peter W., Hendrickx, Mylène, Hadermann, Joke, Segre, Carlo U., Croft, Mark, Kang, Chang-Jong, Deng, Zheng, Lapidus, Saul H., Kim, Sun Woo, Kim, Sun Woo, Kotliar, Gabriel, and Greenblatt, Martha. Tetragonal Cs1.17In0.81Cl3 : A Charge-Ordered Indium Halide Perovskite Derivative. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.chemmater.8b04771.
Tan, Xiaoyan, Stephens, Peter W., Hendrickx, Mylène, Hadermann, Joke, Segre, Carlo U., Croft, Mark, Kang, Chang-Jong, Deng, Zheng, Lapidus, Saul H., Kim, Sun Woo, Kim, Sun Woo, Kotliar, Gabriel, & Greenblatt, Martha. Tetragonal Cs1.17In0.81Cl3 : A Charge-Ordered Indium Halide Perovskite Derivative. United States. https://doi.org/10.1021/acs.chemmater.8b04771
Tan, Xiaoyan, Stephens, Peter W., Hendrickx, Mylène, Hadermann, Joke, Segre, Carlo U., Croft, Mark, Kang, Chang-Jong, Deng, Zheng, Lapidus, Saul H., Kim, Sun Woo, Kim, Sun Woo, Kotliar, Gabriel, and Greenblatt, Martha. Mon . "Tetragonal Cs1.17In0.81Cl3 : A Charge-Ordered Indium Halide Perovskite Derivative". United States. https://doi.org/10.1021/acs.chemmater.8b04771. https://www.osti.gov/servlets/purl/1510268.
@article{osti_1510268,
title = {Tetragonal Cs1.17In0.81Cl3 : A Charge-Ordered Indium Halide Perovskite Derivative},
author = {Tan, Xiaoyan and Stephens, Peter W. and Hendrickx, Mylène and Hadermann, Joke and Segre, Carlo U. and Croft, Mark and Kang, Chang-Jong and Deng, Zheng and Lapidus, Saul H. and Kim, Sun Woo and Kim, Sun Woo and Kotliar, Gabriel and Greenblatt, Martha},
abstractNote = {Polycrystalline samples of Cs1.17In0.81Cl3 were prepared by annealing a mixture of CsCl, InCl, and InCl3, stoichiometric for the targeted CsInCl3. Synchrotron powder X-ray diffraction refinement and chemical analysis by energy dispersive X-ray indicated that Cs1.17In0.81Cl3, a tetragonal distorted perovskite derivative (I4/m), is the thermodynamically stable product. The refined unit cell parameters and space group were confirmed by electron diffraction. In the tetragonal structure, In+ and In3+ are located in four different crystallographic sites, consistent with their corresponding bond lengths. In1, In2, and In3 are octahedrally coordinated, whereas In4 is at the center of a pentagonal bipyramid of Cl because of the noncooperative octahedral tilting of In4Cl6. The charged-ordered In+ and In3+ were also confirmed by X-ray absorption and Raman spectroscopy. Cs1.17In0.81Cl3 is the first example of an inorganic halide double perovskite derivative with charged-ordered In+ and In3+. Band structure and optical conductivity calculations were carried out with both generalized gradient approximation (GGA) and modified Becke-Johnson (mBJ) approach; the GGA calculations estimated the band gap and optical band gap to be 2.27 eV and 2.4 eV, respectively. Finally, the large and indirect band gap suggests that Cs1.17In0.81Cl3 is not a good candidate for photovoltaic application.},
doi = {10.1021/acs.chemmater.8b04771},
journal = {Chemistry of Materials},
number = 6,
volume = 31,
place = {United States},
year = {2018},
month = {6}
}

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Figures / Tables:

Figure 1 Figure 1: Crystal structure of CsInCl3 with space group $I$4/$m$. (a) is the $xy$ layer at $z$ = 0; (b) is the $xy$ layer at $z$ = ½; (c) is a perspective view of the structure viewed along the $y$ axis. Color code: In1 = magenta, In2 = red, In3more » = green, In4 = orange, Cs = grey, and Cl = black.« less

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Works referencing / citing this record:

Pressure-induced semiconductor-to-metal phase transition of a charge-ordered indium halide perovskite
journal, November 2019

  • Lin, Jia; Chen, Hong; Gao, Yang
  • Proceedings of the National Academy of Sciences, Vol. 116, Issue 47
  • DOI: 10.1073/pnas.1907576116

Pressure-induced semiconductor-to-metal phase transition of a charge-ordered indium halide perovskite
journal, November 2019

  • Lin, Jia; Chen, Hong; Gao, Yang
  • Proceedings of the National Academy of Sciences, Vol. 116, Issue 47
  • DOI: 10.1073/pnas.1907576116