Chloride-Passivated Mg-Doped ZnO Nanoparticles for Improving Performance of Cadmium-Free, Quantum-Dot Light-Emitting Diodes

Colloidal ZnO nanoparticles (NPs) are widely used as an electron-transporting layer (ETL) in the solution-processed quantum-dot light-emitting diodes (QD-LEDs). However, the inherent drawbacks including surface defect sites and unbalanced charge injection prevent the device from realizing their further performance enhancement. In this work, a series of Mg doped ZnO (ZnO:Mg) and chloride-passivated ZnO (Cl@ZnO) NPs were synthesized by using a solution-precipitation strategy, and they exhibited tunable optical bandgaps and upward-shift of conduction-band maximum (CBM). Solution-processed QD-LEDs based on cadmium-free Cu-In-Zn-S/ZnS (CIZS/ZnS) nanocrystals (NCs) were fabricated by using ZnO:Mg and Cl@ZnO NPs as the ETLs, whose maximum peak external quantum efficiency (EQE) was nearly twice as high as that of QD-LEDs using ZnO NPs as the ETL (EQE = 1.54%). To take advantage of the benefits of ZnO:Mg and Cl@ZnO NPs, Cl@ZnO:Mg NPs were developed through the integration of Mg doping and Cl-passivation. Surprisingly, the cadmium-free QD-LEDs with the Cl@ZnO:Mg NPs as the ETL exhibited a maximum peak EQE of 3.72% and current efficiency of 11.08 cd A(-1), which could be enhanced to be 4.05% and 12.17 cd A(-1) by optimizing the Cl amount, respectively. The positive effects of the Mg doping and Cl-passivation on the cadmium-free QD-LEDs are primarily ascribed to the reduced electron injection barrier of ETL/the emitting layer interface and slower electron mobility, which can be verified by the ultraviolet photoelectron spectroscopy (UPS) measurements and current density voltage characteristics of electron-only devices.