Templating Effect of Diammonium Cations on Structural and Optical Properties of Lead Bromide Perovskites

The role of templating the formation of 2D metal halide perovskites has been investigated by considering the 1,3-phenylenediammonium (1,3-PDA), 1,3-xylylenediamimonium (1,3-XDA), 1,4-phenylenediammonium (1,4-PDA), and 1,4-xylylenediamimonium (1,4-XDA) cations in lead bromide systems. Single-crystal x-ray diffraction confirms the formation 2D Dion-Jacobons (DJ) perovskites for all the cations except for the 1,3-XDA cation leading to a so-called 0D perovskitoid. Analysis of the structural data showed a higher distortion degree for the systems containing the shorter cation, namely 1,4-PDA. A detailed spectroscopic investigation, with both static and time resolved photoluminescence spectroscopy, revealed a broadband emissive component at room temperature with hundreds of nanometers of bandwidth when 1,3-PDA and 1,4-PDA cations are present, while a narrow peak is found for the longer cation, i.e. 1,4-XDA. A broadband emission arises in this last sample as well by decreasing temperature. Such broad emission, as indicated by the analysis of the power and temperature dependence of the PL, can be attributed to trap-mediated excitonic recombination or STEs, and the trend in emissive properties can be correlated to the different level of octahedral distortions. The novel systems reported in this work enlarge the family of broadband emitters and add further clues to develop efficient perovskite-based broadband and white light emitters.