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Untying the Cesium "Not": Cesium-Iodoplumbate Complexation in Perovskite Solution-Processing Inks Has Implications for Crystallization.
Eatmon, Yannick; Romiluyi, Oluwaseun; Ganley, Connor; Ni, Ruihao; Pelczer, István; Clancy, Paulette; Rand, Barry P; Schwartz, Jeffrey.
Afiliación
  • Eatmon Y; Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544, United States.
  • Romiluyi O; Department of Chemical and Biomolecular Engineering, Johns Hopkins University, Baltimore, Maryland 21218, United States.
  • Ganley C; Department of Chemical and Biomolecular Engineering, Johns Hopkins University, Baltimore, Maryland 21218, United States.
  • Ni R; Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland 21218, United States.
  • Pelczer I; Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
  • Clancy P; Department of Chemical and Biomolecular Engineering, Johns Hopkins University, Baltimore, Maryland 21218, United States.
  • Rand BP; Department of Electrical Engineering and Andlinger Center for Energy and the Environment, Princeton University, Princeton, New Jersey 08544, United States.
  • Schwartz J; Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
J Phys Chem Lett ; 13(26): 6130-6137, 2022 Jul 07.
Article en En | MEDLINE | ID: mdl-35759533
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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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Tinta / Plomo Idioma: En Revista: J Phys Chem Lett Año: 2022 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos
Texto completo
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Tinta / Plomo Idioma: En Revista: J Phys Chem Lett Año: 2022 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos