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 Képénékian, George Volonakis, Jacky Even, Yukun Liu, Christos D. Malliakas, Yi Yang, Craig C. Laing, Vinayak P. Dravid, G. N. Manjunatha Reddy, Can Li, Edward H. Sargent, Mercouri G. Kanatzidis
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 −1 Pb x Sn n – x Br 3 n +1 ( n = 1–3) and (3AMPY)(MA) n −1 Pb x Sn n – x Br 3 n +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 1 H, 119 Sn, and 207 Pb NMR spectroscopy analysis shows that the Pb atoms prefer the outer layers in n = 3 members: (BA) 2 (MA)Pb x Sn n – x Br 10 and (3AMPY)(MA)Pb x Sn n – x Br 10 . Layered 2D DJ alloyed Pb/Sn bromide perovskites (3AMPY)(MA) n −1 Pb x Sn n – x Br 3 n +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.