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

被引:24
作者
Tan, Xiaoyan [1 ,10 ]
Stephens, Peter W. [3 ]
Hendrickx, Mylene [4 ]
Hadermann, Joke [4 ]
Segre, Carlo U. [5 ,6 ]
Croft, Mark [2 ]
Kang, Chang-Jong [2 ]
Deng, Zheng [7 ]
Lapidus, Saul H. [8 ]
Kim, Sun Woo [9 ]
Jin, Changqing [7 ]
Kotliar, Gabriel [2 ]
Greenblatt, Martha [1 ]
机构
[1] Rutgers State Univ, Dept Chem & Chem Biol, Piscataway, NJ 08854 USA
[2] Rutgers State Univ, Dept Phys & Astron, Piscataway, NJ 08854 USA
[3] SUNY Stony Brook, Dept Phys & Astron, Stony Brook, NY 11794 USA
[4] Univ Antwerp, EMAT, Groenenborgerlaan 171, B-2020 Antwerp, Belgium
[5] IIT, Dept Phys, Chicago, IL 60616 USA
[6] IIT, CSRRI, Chicago, IL 60616 USA
[7] Univ Chinese Acad Sci, Chinese Acad Sci, Inst Phys, Sch Phys, POB 603, Beijing 100190, Peoples R China
[8] Argonne Natl Lab, Adv Photon Source, Argonne, IL 60439 USA
[9] Chosun Univ, Dept Chem Educ, Gwangju 61452, South Korea
[10] George Mason Univ, Dept Chem & Biochem, Fairfax, VA 22030 USA
关键词
CRYSTAL-STRUCTURE; MAGNETIC-PROPERTIES; EFFICIENCY;
D O I
10.1021/acs.chemmater.8b04771
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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. The large and indirect band gap suggests that Cs1.17In0.81Cl3 is not a good candidate for photovoltaic application.
引用
收藏
页码:1981 / 1989
页数:9
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