AbstractThis work describes the effect of a rubidium chloride (RbCl) interlayer in CsPbBr3 perovskite light-emitting diode (LED) structures. RbCl crystallites exhibited polyhedral structures and lattice parameters similar to those of CsPbBr3 perovskite crystallites. The lattice mismatch between the RbCl interlayer and CsPbBr3 active layer was only approximately 2%. The devices exhibited the best quality and performance when RbCl was used as the nucleation and carrier confinement layer. The crystallite sizes of CsPbBr3 with 0.2-, 0.5-, and 1-nm-thick RbCl bottom layers were 55.1, 65.4, and 55.1 nm, respectively. The full width at half maximum (FWHM) of the photoluminescence (PL) emission peak for CsPbBr3 with the RbCl bottom layer was 0.096 eV.