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Understanding the Impact of Bismuth Heterovalent Doping on the Structural and Photophysical Properties of CH 3 NH 3 PbBr 3 Halide Perovskite Crystals with Near‐IR Photoluminescence
Author(s) -
Meng Rui,
Wu Guangbao,
Zhou Jiyu,
Zhou Huiqiong,
Fang Honghua,
Loi Maria A.,
Zhang Yuan
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201805370
Subject(s) - photoluminescence , doping , halide , perovskite (structure) , dopant , bismuth , chemistry , materials science , analytical chemistry (journal) , crystallography , inorganic chemistry , optoelectronics , organic chemistry , chromatography
A comprehensive study unveiling the impact of heterovalent doping with Bi 3+ on the structural, semiconductive, and photoluminescent properties of a single crystal of lead halide perovskites (CH 3 NH 3 PbBr 3 ) is presented. As indicated by single‐crystal XRD, a perfect cubic structure in Bi 3+ ‐doped CH 3 NH 3 PbBr 3 crystals is maintained in association with a slight lattice contraction. Time‐resolved and power‐dependent photoluminescence (PL) spectroscopy illustrates a progressively quenched PL of visible emission, alongside the appearance of a new PL signal in the near‐infrared (NIR) regime, which is likely to be due to energy transfer to the Bi sites. These optical characteristics indicate the role of Bi 3+ dopants as nonradiative recombination centers, which explains the observed transition from bimolecular recombination in pristine CH 3 NH 3 PbBr 3 to a dominant trap‐assisted monomolecular recombination with Bi 3+ doping. Electrically, it is found that the mobility in pristine perovskite crystals can be boosted with a low Bi 3+ concentration, which may be related to a trap‐filling mechanism. Aided by temperature ( T )‐dependent measurements, two temperature regimes are observed in association with different activation energies ( E a ) for electrical conductivity. The reduction of E a at lower T may be ascribed to suppression of ionic conduction induced by doping. The modified electrical properties and NIR emission with the control of Bi 3+ concentration shed light on the opportunity to apply heterovalent doping of perovskite single crystals for NIR optoelectronic applications.