Transformation of Sintered CsPbBr 3 Nanocrystals to Cubic CsPbI 3 and Gradient CsPbBr x I 3– x through Halide Exchange

Hoffman, Jacob B.; Schleper, A. Lennart; Kamat, Prashant V.

doi:10.1021/jacs.6b04661

Title: Transformation of Sintered CsPbBr ₃ Nanocrystals to Cubic CsPbI ₃ and Gradient CsPbBr _x I _{3– x} through Halide Exchange

Journal Article · Thu Jun 30 00:00:00 EDT 2016 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.6b04661· OSTI ID:1259934

Hoffman, Jacob B. ^[1]; Schleper, A. Lennart ^[1]; Kamat, Prashant V. ^[1]

Radiation Laboratory, †Department of Chemistry and Biochemistry, and §Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, Indiana 46556, United States

All-inorganic cesium lead halide (CsPbX₃, X = Br^–, I^–) perovskites could potentially provide comparable photovoltaic performance with enhanced stability compared to organic–inorganic lead halide species. However, small-bandgap cubic CsPbI3 has been difficult to study due to challenges forming CsPbI₃ in the cubic phase. Here, a low-temperature procedure to form cubic CsPbI₃ has been developed through a halide exchange reaction using films of sintered CsPbBr₃ nanocrystals. The reaction was found to be strongly dependent upon temperature, featuring an Arrhenius relationship. Additionally, film thickness played a significant role in determining internal film structure at intermediate reaction times. Thin films (50 nm) showed only a small distribution of CsPbBr_xI_3–x species, while thicker films (350 nm) exhibited much broader distributions. Furthermore, internal film structure was ordered, featuring a compositional gradient within film. Transient absorption spectroscopy showed the influence of halide exchange on the excited state of the material. In thicker films, charge carriers were rapidly transferred to iodide-rich regions near the film surface within the first several picoseconds after excitation. Furthermore, this ultrafast vectorial charge-transfer process illustrates the potential of utilizing compositional gradients to direct charge flow in perovskite-based photovoltaics.

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Research Organization:: University of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FC02-04ER15533

OSTI ID:: 1259934

Alternate ID(s):: OSTI ID: 1267221

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 138 Journal Issue: 27; ISSN 0002-7863

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 295 works

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Title: Transformation of Sintered CsPbBr ₃ Nanocrystals to Cubic CsPbI ₃ and Gradient CsPbBr _x I _{3– x} through Halide Exchange