Two Origins of Broadband Emission in Multilayered 2D Lead Iodide Perovskites.

Broadband emission in lead iodide 2D perovskites has been alternately attributed to self-trapped excitons (STEs) or permanent structural defects and/or impurities. Here, we investigate six different multilayered (n > 1) 2D lead iodide perovskites as a function of sample temperature from 5 to 300 K. We distinguish shallow defect-associated emission from a broad near-infrared (NIR) spectral feature, which we assign to an STE through subgap photoexcitation experiments. When we varied the thickness (n = 2, 3, 4), A-site cation (methylammonium vs formamidinium), and organic spacer (butylammonium vs hexylammonium vs phenylethylammonium), we found that the temperature dependence of broad NIR emission was strongly correlated with both the strength of electron-phonon coupling and the extent of structural deformation of the ground-state lattice, strongly supporting the assignment of this spectral feature to an STE. However, the extent to which formation of these STEs is intrinsic versus defect-assisted remains open to debate.