Strong Electron-Phonon Coupling and Self-Trapped Excitons in the Defect Halide Perovskites A3M2I9 (A = Cs, Rb; M = Bi, Sb)

被引:577
作者
McCall, Kyle M. [1 ,2 ]
Stoumpos, Constantinos C. [1 ]
Kostina, Svetlana S. [2 ]
Kanatzidis, Mercouri G. [1 ]
Wessels, Bruce W. [2 ]
机构
[1] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA
[2] Northwestern Univ, Dept Mat Sci & Engn, Evanston, IL 60208 USA
关键词
FERROELASTIC PHASE-TRANSITION; LEAD-FREE; CRYSTAL-STRUCTURE; RAMAN-SCATTERING; BISMUTH IODIDE; BAND; LUMINESCENCE; CS3BI2I9; ABSORPTION; CSPBBR3;
D O I
10.1021/acs.chemmater.7b01184
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
The optical and electronic properties of Bridgman grown single crystals of the wide-bandgap semiconducting defect halide perovskites A(3)M(2)I(9) (A = Cs, Rb; M = Bi, Sb) have been investigated. Intense Raman scattering was observed at room temperature for each compound, indicating high polarizability and strong electron-phonon coupling. Both low-temperature and room-temperature photoluminescence (PL) were measured for each compound. Cs3Sb2I9 and Rb3Sb2I9 have broad PL emission bands between 1.75 and 2.05 eV with peaks at 1.96 and 1.92 eV, respectively. The Cs3Bi2I9, PL spectra showed broad emission consisting of several overlapping bands in the 1.65-2.2 eV range. Evidence of strong electron-phonon coupling comparable to that of the alkali halides was observed in phonon broadening of the PL emission. Effective phonon energies obtained from temperature-dependent PL measurements were in agreement with the Raman peak energies. A model is proposed whereby electron phonon interactions in Cs3Sb2I9, Rb3Sb2I9, and Cs3Bi2I9. induce small polarons, resulting in trapping of excitons by the lattice. The recombination of these self-trapped excitons is responsible for the broad PL emission. Rb3Bi2I9, Rb3Sb2I9, and Cs3Bi2I9 exhibit high resistivity and photoconductivity response under laser photoexcitation, indicating that these compounds possess potential as semiconductor hard radiation detector materials.
引用
收藏
页码:4129 / 4145
页数:17
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