Untying the Cesium "not": Cesium-Iodoplumbate Complexation in Perovskite Solution-Processing Inks Has Implications for Crystallization

Yannick Eatmon, Oluwaseun Romiluyi, Connor Ganley, Ruihao Ni, István Pelczer, Paulette Clancy, Barry P. Rand, Jeffrey Schwartz

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

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.

Original languageEnglish (US)
Pages (from-to)6130-6137
Number of pages8
JournalJournal of Physical Chemistry Letters
Volume13
Issue number26
DOIs
StatePublished - Jul 7 2022
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Materials Science
  • Physical and Theoretical Chemistry

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