Understanding the Impact of Bismuth Heterovalent Doping on the Structural and Photophysical Properties of CH3NH3PbBr3 Halide Perovskite Crystals with Near-IR Photoluminescence

Rui Meng, Guangbao Wu, Jiyu Zhou, Huiqiong Zhou, Honghua Fang, Maria A. Loi, Yuan Zhang

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10 Citations (Scopus)

Abstract

A comprehensive study unveiling the impact of heterovalent doping with Bi3+ on the structural, semiconductive, and photoluminescent properties of a single crystal of lead halide perovskites (CH3NH3PbBr3) is presented. As indicated by single-crystal XRD, a perfect cubic structure in Bi3+-doped CH3NH3PbBr3 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 CH3NH3PbBr3 to a dominant trap-assisted monomolecular recombination with Bi3+ doping. Electrically, it is found that the mobility in pristine perovskite crystals can be boosted with a low Bi3+ concentration, which may be related to a trap-filling mechanism. Aided by temperature (7)-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 Bi3+ concentration shed light on the opportunity to apply heterovalent doping of perovskite single crystals for NIR optoelectronic applications.

Original languageEnglish
Pages (from-to)5480-5488
Number of pages9
JournalChemistry
Volume25
Issue number21
DOIs
Publication statusPublished - 11-Apr-2019

Keywords

  • bismuth
  • doping
  • luminescence
  • photochemistry
  • perovskite phases
  • SINGLE-CRYSTALS
  • BANDGAP
  • GROWTH
  • TRANSPORT
  • MAPBI(3)
  • LIFETIME
  • LENGTHS
  • BR
  • CL

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