A new metric to control nucleation and grain size distribution in hybrid organic–inorganic perovskites by tuning the dielectric constant of the antisolvent

Sorenson, Blaire A.; Yoon, Lucy U.; Holmgren, Eric; Choi, Joshua J.; Clancy, Paulette

doi:10.1039/d0ta12364a

A new metric to control nucleation and grain size distribution in hybrid organic–inorganic perovskites by tuning the dielectric constant of the antisolvent

Journal Article · Sat Jan 16 00:00:00 EST 2021 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d0ta12364a· OSTI ID:1852102

^[1]; Yoon, Lucy U. ^[2]; Holmgren, Eric ^[2]; ^[2]; ^[3]

Johns Hopkins Univ., Baltimore, MD (United States); OSTI
Univ. of Virginia, Charlottesville, VA (United States)
Johns Hopkins Univ., Baltimore, MD (United States)

In perovskite research, there is a widely exploited but poorly explained phenomenon in which the addition of “antisolvents (ATS)” to precursor solutions results in higher-quality films. We explain the mechanism and driving force underlying an antisolvent-driven solvent extraction process. Density functional theory calculations uncover the defining effects of antisolvent choice on the extent of complexation between a lead salt and a methylammonium cation in solution. We experimentally validate the computational results using ultraviolet-visible spectroscopy and ²⁰⁷Pb nuclear magnetic spectroscopy of methylammonium lead iodide solutions, containing both a processing solvent and an antisolvent. Furthermore, we uncover, and subsequently identify, the appearance of new species in solution as a result of the addition of the antisolvent. Furthermore, we observe that the choice of antisolvent has a substantial effect on the nature of the complexation of the methylammonium lead iodide (MAPbI₃) precursor species, whose origin we explain at an atomic level; specifically, the lower the dielectric of the antisolvent, the stronger the intermolecular binding energy between methylammonium cation (MA⁺) cation and PbI₃^- plumbate, independent of the solvent or antisolvent interaction with the lead salt. Thin films were characterized using scanning electron microscopy; images of the films show how the addition of an antisolvent influences and, importantly, can be used to alter thin-film grain size. Grain size and distribution in thin films is reflected by the choice of antisolvent, promoting slower nucleation rates, a lower nucleation density, and hence larger final grain size.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Virginia, Charlottesville, VA (United States)

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

Grant/Contract Number:: SC0016144

OSTI ID:: 1852102

Alternate ID(s):: OSTI ID: 1761258

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 6 Vol. 9; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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