Unveiling the critical role of ammonium bromide in blue emissive perovskite films

Implementation of ammonium halides to trigger low-dimensional perovskite formation has been intensively investigated to achieve blue perovskite light-emitting diodes (PeLEDs). However, the general roles of the incorporated ammonium cations on the quality of the perovskite films, as well as device performance, are still unclear. It is indispensable to build a guideline to rationalize ammonium halides for decent blue emissive films. Here, by thoroughly investigating a series of ammonium cations containing the different number of ammonium groups and ionic radius, we reveal that the mechanism beyond the tunable emission wavelength, crystallization kinetics, and spectral stability of the obtained blue perovskite films is highly relevant to the molecular structure of the ammonium cations. In parallel with reducing the dimensionality to form normal Ruddlesden–Popper phases, the incorporated ammonium cations also likely modulate the Pb–Br orbit coupling through A-site engineering and generate either Dion–Jacobson or “hollow” perovskites, providing alternative routes to achieve efficient and stable blue emissive films. Our work paves a way to rationalize ammonium halides to develop prevailing active layers for further improving the performance of blue PeLEDs.