TY - JOUR
T1 - Untying the Cesium "not"
T2 - Cesium-Iodoplumbate Complexation in Perovskite Solution-Processing Inks Has Implications for Crystallization
AU - Eatmon, Yannick
AU - Romiluyi, Oluwaseun
AU - Ganley, Connor
AU - Ni, Ruihao
AU - Pelczer, István
AU - Clancy, Paulette
AU - Rand, Barry P.
AU - Schwartz, Jeffrey
N1 - Funding Information:
Yannick Eatmon, István Pelczer, Barry Rand, and Jeffrey Schwartz acknowledge support from the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE) under the Solar EnergyTechnologies Office, Award Number DE-EE0008560. Oluwaseun Romiluyi and Paulette Clancy acknowledge support from the U.S. Department of Energy’s Basic Energy Sciences (BES) Award Number DE-SC0022305. The views expressed herein do not necessarily represent the views of the U.S. Department of Energy or the United States Government. Oluwaseun Romiluyi, Connor Ganley, Ruihao Ni, and Paulette Clancy acknowledge support afforded by access to the computing facilities at the petascale Advanced Research Computing at Hopkins (ARCH) facility, supported by the National Science Foundation (NSF), Grant Number OAC 1920103, for providing the extensive computational resources needed here. Partial funding for the infrastructure for ARCH was originally provided by the State of Maryland.
Publisher Copyright:
© 2022 American Chemical Society.
PY - 2022/7/7
Y1 - 2022/7/7
N2 - We illustrate the critical importance of the energetics of cation-solvent versus cation-iodoplumbate interactions in determining the stability of ABX3 perovskite precursors in a dimethylformamide (DMF) solvent medium. We have shown, through a complementary suite of nuclear magnetic resonance (NMR) and computational studies, that Cs+ exhibits significantly different solvent vs iodoplumbate interactions compared to organic A+-site cations such as CH3NH3+ (MA+). Two NMR studies were conducted: 133Cs NMR analysis shows that Cs+ and MA+ compete for coordination with PbI3- in DMF. 207Pb NMR studies of PbI2 with cationic iodides show that perovskite-forming Cs+ (and, somewhat, Rb+) do not comport with the 207Pb chemical shift trend found for Li+, Na+, and K+. Three independent computational approaches (density functional theory (DFT), ab initio Molecular Dynamics (AIMD), and a polarizable force field within Molecular Dynamics) yielded strikingly similar results: Cs+ interacts more strongly with the PbI3- iodoplumbate than does MA+ in a polar solvent environment like DMF. The stronger energy preference for PbI3- coordination of Cs+ vs MA+ in DMF demonstrates that Cs+ is not simply a postcrystallization cation "fit"for the perovskite A+-site. Instead, it may facilitate preorganization of the framework precursor that eventually transforms into the crystalline perovskite structure.
AB - We illustrate the critical importance of the energetics of cation-solvent versus cation-iodoplumbate interactions in determining the stability of ABX3 perovskite precursors in a dimethylformamide (DMF) solvent medium. We have shown, through a complementary suite of nuclear magnetic resonance (NMR) and computational studies, that Cs+ exhibits significantly different solvent vs iodoplumbate interactions compared to organic A+-site cations such as CH3NH3+ (MA+). Two NMR studies were conducted: 133Cs NMR analysis shows that Cs+ and MA+ compete for coordination with PbI3- in DMF. 207Pb NMR studies of PbI2 with cationic iodides show that perovskite-forming Cs+ (and, somewhat, Rb+) do not comport with the 207Pb chemical shift trend found for Li+, Na+, and K+. Three independent computational approaches (density functional theory (DFT), ab initio Molecular Dynamics (AIMD), and a polarizable force field within Molecular Dynamics) yielded strikingly similar results: Cs+ interacts more strongly with the PbI3- iodoplumbate than does MA+ in a polar solvent environment like DMF. The stronger energy preference for PbI3- coordination of Cs+ vs MA+ in DMF demonstrates that Cs+ is not simply a postcrystallization cation "fit"for the perovskite A+-site. Instead, it may facilitate preorganization of the framework precursor that eventually transforms into the crystalline perovskite structure.
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U2 - 10.1021/acs.jpclett.2c01344
DO - 10.1021/acs.jpclett.2c01344
M3 - Article
C2 - 35759533
AN - SCOPUS:85134360939
SN - 1948-7185
VL - 13
SP - 6130
EP - 6137
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 26
ER -