Optimizing Carrier Balance in CsPbBr₃ Nanocrystal LEDs: The Role of Alkyl Ligands and Polar Electron Transport Layers

Abstract The study of lead halide perovskite nanocrystal based light‐emitting diodes (LEDs) has advanced significantly, with notable improvements in stability and optical properties. However, optimizing charge carrier injection and transport remains a challenge. Efficient electroluminescence requires a balanced transport of both holes and electrons within the emitting material. Here, cubic CsPbBr 3 nanocrystals passivated with oleylamine and oleic acid are investigated, comparing them to ligand‐exchanged nanocrystals with didodecyldimethylammonium bromide (DDABr). Nuclear magnetic resonance spectroscopy and transmission electron microscopy confirm successful ligand exchange, revealing reduced ligand coverage in DDABr‐treated nanocrystals. Photoelectron spectroscopy, spectroelectrochemistry, and single‐carrier devices indicate improved hole injection in DDABr‐capped nanocrystals. Density functional theory calculations further reveal the influence of ligand type and coverage on energy levels, with oleic acid introducing localized states in native nanocrystals. Additionally, incorporation of a polar electron transport layer enhances LED performance by over an order of magnitude in DDABr‐capped nanocrystals, driven by improved charge balance arising from the spontaneous orientation polarization of the electron transport layer. These findings highlight the critical role of ligand selection, passivation degree, and charge transport control by the adjacent organic transport layers in optimizing LED efficiency.