Rb3InCl6: A Monoclinic Double Perovskite Derivative with Bright Sb3+-Activated Photoluminescence
- 22 September 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 59 (19), 14478-14485
- https://doi.org/10.1021/acs.inorgchem.0c02248
Abstract
Here, we present the synthesis and crystal structure of Rb3InCl6 prepared from air stable reagents via a two-step process that proceeds through the intermediate Rb2InCl5·H2O. Rb3InCl6 crystallizes with the Rb3YCl6 structure type (C2/c), which can be derived from the double perovskite structure by noncooperative tilting of isolated [InCl6]3– octahedra. Despite this lowering of symmetry, the optical properties are similar to the cubic double perovskite Cs2NaInCl6. Partial substitution of In3+ with Sb3+ in Rb3InCl6 results in intense cyan-green photoluminescence originating from localized 5s2 to 5s15p1 electronic transitions of [SbCl6]3– polyatomic anions. In comparison with the cubic double perovskite phosphor Cs2NaInCl6:Sb3+, the octahedral tilting distortion increases the electronic isolation of the In/Sb-centered octahedra thus facilitating electron and hole localization on Sb3+ sites, leading to bright photoluminescence. The distorted crystal structure also leads to a larger Stokes shift (1.29 eV) and a corresponding red shift of the emission peak (λmax = 522 nm) compared to the more symmetric Cs2NaInCl6:Sb3+ (Stokes shift ≈ 0.94 eV, λmax = 445 nm).Keywords
Funding Information
- Division of Materials Research (DMR-2003793)
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