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From Nonluminescent to Blue‐Emitting Cs 4 PbBr 6 Nanocrystals: Tailoring the Insulator Bandgap of 0D Perovskite through Sn Cation Doping
Author(s) -
Zou Shenghan,
Liu Caiping,
Li Renfu,
Jiang Feilong,
Chen Xueyuan,
Liu Yongsheng,
Hong Maochun
Publication year - 2019
Publication title -
advanced materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.707
H-Index - 527
eISSN - 1521-4095
pISSN - 0935-9648
DOI - 10.1002/adma.201900606
Subject(s) - band gap , materials science , halide , doping , perovskite (structure) , nanocrystal , optoelectronics , octahedron , photoluminescence , nanotechnology , crystal structure , crystallography , inorganic chemistry , chemistry
All‐inorganic cesium lead halide perovskite nanocrystals (NCs) with different dimensionalities have recently fascinated the research community due to their extraordinary optoelectronic performance such as tunable bandgaps over the entire visible spectral region. However, compared to well‐developed 3D CsPbX 3 perovskites (X = Cl, Br, and I), the bandgap tuning in 0D Cs 4 PbX 6 perovskite NCs remains an arduous task. Herein, a simple but valid strategy is proposed to tailor the insulator bandgap (≈3.96 eV) of Cs 4 PbBr 6 NCs to the blue spectral region by changing the local coordination environment of isolated [PbBr 6 ] 4− octahedra in the Cs 4 PbBr 6 crystal through Sn cation doping. Benefitting from the unique Pb 2+ ‐poor and Br − ‐rich reaction environment, the Sn cation is successfully introduced into the Cs 4 PbBr 6 NCs, forming coexisting point defects comprising substitutional Sn Pb and interstitial Br i , thereby endowing these theoretically nonluminescent Cs 4 PbBr 6 NCs with an ultranarrow blue emission at ≈437 nm (full width at half maximum, ≈12 nm). By combining the experimental results with first‐principles calculations, an unusual electronic dual‐bandgap structure, comprising the newly emerged semiconducting bandgap of ≈2.87 eV and original insulator bandgap of ≈3.96 eV, is found to be the underlying fundamental reason for the ultranarrow blue emission.