Tunable Broad Light Emission from 3D "hollow" Bromide Perovskites through Defect Engineering

Ioannis Spanopoulos, Ido Hadar, Weijun Ke, Peijun Guo, Eve M. Mozur, Emily Morgan, Shuxin Wang, Ding Zheng, Suyog Padgaonkar, G. N. Manjunatha Reddy, Emily A. Weiss, Mark C. Hersam, Ram Seshadri, Richard D. Schaller, Mercouri G. Kanatzidis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

35 Scopus citations


Hybrid halide perovskites consisting of corner-sharing metal halide octahedra and small cuboctahedral cages filled with counter cations have proven to be prominent candidates for many high-performance optoelectronic devices. The stability limits of their three-dimensional perovskite framework are defined by the size range of the cations present in the cages of the structure. In some cases, the stability of the perovskite-type structure can be extended even when the counterions violate the size and shape requirements, as is the case in the so-called "hollow"perovskites. In this work, we engineered a new family of 3D highly defective yet crystalline "hollow"bromide perovskites with general formula (FA)1-x(en)x(Pb)1-0.7x(Br)3-0.4x (FA = formamidinium (FA+), en = ethylenediammonium (en2+), x = 0-0.44). Pair distribution function analysis shed light on the local structural coherence, revealing a wide distribution of Pb-Pb distances in the crystal structure as a consequence of the Pb/Br-deficient nature and en inclusion in the lattice. By manipulating the number of Pb/Br vacancies, we finely tune the optical properties of the pristine FAPbBr3 by blue shifting the band gap from 2.20 to 2.60 eV for the x = 0.42 en sample. A most unexpected outcome was that at x> 0.33 en incorporation, the material exhibits strong broad light emission (1% photoluminescence quantum yield (PLQY)) that is maintained after exposure to air for more than a year. This is the first example of strong broad light emission from a 3D hybrid halide perovskite, demonstrating that meticulous defect engineering is an excellent tool for customizing the optical properties of these semiconductors.

Original languageAmerican English
Pages (from-to)7069-7080
Number of pages12
JournalJournal of the American Chemical Society
Issue number18
StatePublished - 12 May 2021
Externally publishedYes

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