A new metric to control nucleation and grain size distribution in hybrid organic–inorganic perovskites by tuning the dielectric constant of the antisolvent
Abstract
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 antisolventmore »
- Authors:
-
[1];
[2];
[1]
- Johns Hopkins Univ., Baltimore, MD (United States)
- Univ. of Virginia, Charlottesville, VA (United States)
- Publication Date:
- Research Org.:
- Univ. of Virginia, Charlottesville, VA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1852102
- Alternate Identifier(s):
- OSTI ID: 1761258
- Grant/Contract Number:
- SC0016144
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Materials Chemistry. A
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 6; Journal ID: ISSN 2050-7488
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Sorenson, Blaire A., Yoon, Lucy U., Holmgren, Eric, Choi, Joshua J., and Clancy, Paulette. A new metric to control nucleation and grain size distribution in hybrid organic–inorganic perovskites by tuning the dielectric constant of the antisolvent. United States: N. p., 2021.
Web. doi:10.1039/d0ta12364a.
Sorenson, Blaire A., Yoon, Lucy U., Holmgren, Eric, Choi, Joshua J., & Clancy, Paulette. A new metric to control nucleation and grain size distribution in hybrid organic–inorganic perovskites by tuning the dielectric constant of the antisolvent. United States. https://doi.org/10.1039/d0ta12364a
Sorenson, Blaire A., Yoon, Lucy U., Holmgren, Eric, Choi, Joshua J., and Clancy, Paulette. Sat .
"A new metric to control nucleation and grain size distribution in hybrid organic–inorganic perovskites by tuning the dielectric constant of the antisolvent". United States. https://doi.org/10.1039/d0ta12364a. https://www.osti.gov/servlets/purl/1852102.
@article{osti_1852102,
title = {A new metric to control nucleation and grain size distribution in hybrid organic–inorganic perovskites by tuning the dielectric constant of the antisolvent},
author = {Sorenson, Blaire A. and Yoon, Lucy U. and Holmgren, Eric and Choi, Joshua J. and Clancy, Paulette},
abstractNote = {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.},
doi = {10.1039/d0ta12364a},
journal = {Journal of Materials Chemistry. A},
number = 6,
volume = 9,
place = {United States},
year = {Sat Jan 16 00:00:00 EST 2021},
month = {Sat Jan 16 00:00:00 EST 2021}
}
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