Chemical and Structural Diversity of Hybrid Layered Double Perovskite Halides

TitleChemical and Structural Diversity of Hybrid Layered Double Perovskite Halides
Publication TypeJournal Article
Year of Publication2019
AuthorsMao, Lingling, Samuel M. L. Teicher, Constantinos C. Stoumpos, Rhys M. Kennard, Ryan A. DeCrescent, Guang Wu, Jon A. Schuller, Michael L. Chabinyc, Anthony K. Cheetham, and Ram Seshadri
JournalJournal of the American Chemical Society
Date Published11/2019

Hybrid halide double perovskites are a class of compounds attracting growing interest because of their richness of structure and property. Two-dimensional (2D) derivatives of hybrid double perovskites are formed by the incorporation of organic spacer cations into three-dimensional (3D) double perovskites. Here, we report a series of seven new layered double perovskite halides with propylammonium (PA), octylammonium (OCA), and 1,4-butydiammonium (BDA) cations. The general formulae of the compounds are AmMIMIIIX8 (single-layered Ruddlesden-Popper with m = 4 and A = PA or OCA, and single-layered Dion-Jacobson with m = 2 and A = BDA, MI = Ag, MIII = In or Bi, X = Cl or Br) and PA2CsMIMIIIBr7 (bi-layered, with MI = Ag, MIII = In or Bi). These families of compounds demonstrate great versatility, with tunable layer thickness, the ability to vary the interlayer spacing, and the ability to selectively tune the band gap by varying the MI and MIII cations along with the halide anions. The band gap of the single-layered materials varies from 2.41 eV for PA4AgBiBr8 to 3.96 eV for PA4AgInCl8. Photoluminescent emission spectra of the layered double perovskites at low-temperature (100 K) are reported, and density functional theory electronic structure calculations are presented to understand the nature of the band gap evolution. The development of new structural and compositions in layered double perovskite halides enhances the understanding of structure-property relations in this important family.