Chemical Behavior and Local Structure of the Ruddlesden-Popper and Dion-Jacobson Alloyed Pb/Sn Bromide 2D Perovskites

Ping Fu, Michael A. Quintero, Eugenia S. Vasileiadou, Parth Raval, Claire Welton, Mikaël Kepenekian, George Volonakis, Jacky Even, Yukun Liu, Christos Malliakas, Yi Yang, Craig Laing, Vinayak P. Dravid, G. N.Manjunatha Reddy, Can Li, Edward H. Sargent, Mercouri G. Kanatzidis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

The alloyed lead/tin (Pb/Sn) halide perovskites have gained significant attention in the development of tandem solar cells and other optoelectronic devices due to their widely tunable absorption edge. To gain a better understanding of the intriguing properties of Pb/Sn perovskites, such as their anomalous bandgap’s dependence on stoichiometry, it is important to deepen the understanding of their chemical behavior and local structure. Herein, we investigate a series of two-dimensional Ruddlesden-Popper (RP) and Dion-Jacobson (DJ) phase alloyed Pb/Sn bromide perovskites using butylammonium (BA) and 3-(aminomethyl)pyridinium (3AMPY) as the spacer cations: (BA)2(MA)n−1PbxSnn-xBr3n+1 (n = 1-3) and (3AMPY)(MA)n−1PbxSnn-xBr3n+1 (n = 1-3) through a solution-based approach. Our results show that the ratio and site preference of Pb/Sn atoms are influenced by the layer thickness (n) and spacer cations (A′), as determined by single-crystal X-ray diffraction. Solid-state 1H, 119Sn, and 207Pb NMR spectroscopy analysis shows that the Pb atoms prefer the outer layers in n = 3 members: (BA)2(MA)PbxSnn-xBr10 and (3AMPY)(MA)PbxSnn-xBr10. Layered 2D DJ alloyed Pb/Sn bromide perovskites (3AMPY)(MA)n−1PbxSnn-xBr3n+1 (n = 1-3) demonstrate much narrower optical band gaps, lower energy PL emission peaks, and longer carrier lifetimes compared to those of RP analogs. Density functional theory calculations suggest that Pb-rich alloys (Pb:Sn ∼4:1) for n = 1 compounds are thermodynamically favored over 50:50 (Pb:Sn ∼1:1) compositions. From grazing-incidence wide-angle X-ray scattering (GIWAXS), we see that films in the RP phase orient parallel to the substrate, whereas for DJ cases, random orientations are observed relative to the substrate.

Original languageEnglish (US)
Pages (from-to)15997-16014
Number of pages18
JournalJournal of the American Chemical Society
Volume145
Issue number29
DOIs
StatePublished - Jul 26 2023

ASJC Scopus subject areas

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry

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