Chemical Dopant Engineering in Hole Transport Layers for Efficient Perovskite Solar Cells: Insight into the Interfacial Recombination

Chemical doping of organic semiconductors has been recognized as an effective way to enhance the electrical conductivity. In perovskite solar cells (PSCs), various types of dopants have been developed for organic hole transport materials (HTMs); however, the knowledge of the basic requirements for being efficient dopants as well as the comprehensive roles of the dopants in PSCs has not been clearly revealed. Here, three copper-based complexes with controlled redox activities are applied as dopants in PSCs, and it is found that the oxidative reactivity of dopants presents substantial impacts on conductivity, charge dynamics, and solar cell performance. A significant improvement of open- circuit voltage (V-oc) by more than 100 mV and an increase of power conversion efficiency from 13.2 to 19.3% have been achieved by tuning the doping level of the HTM. The observed large variation of V-oc for three dopants reveals their different recombination kinetics at the perovskite/HTM interfaces and suggests a model of an interfacial recombination mechanism. We also suggest that the dopants in HTMs can also affect the charge recombination kinetics as well as the solar cell performance. Based on these findings, a strategy is proposed to physically passivate the electron- hole recombination by inserting an ultrathin Al2O3 insulating layer between the perovskite and the HTM. This strategy contributes a significant enhancement of the power conversion efficiency and environmental stability, indicating that dopant engineering is one crucial way to further improve the performance of PSCs.