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 - 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 -