Improved Interfacial Crystallization by Synergic Effects of Precursor Solution Stoichiometry and Conjugated Polyelectrolyte Interlayer for High Open-Circuit Voltage of Perovskite Photovoltaic Diodes

The open-circuit voltage (V_oc) of perovskite photovoltaic diodes depends largely on the selection of charge transport layers (CTLs) and surface passivation, which makes it important to understand the physical processes occurring at the interface between the perovskite and a CTL. We provide a direct correlation between V_oc and the interfacial characteristics of perovskites tuned through stoichiometry engineering of precursor solutions and surface modification of the underlying poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) layer. Poor quality interfacial perovskite crystals were observed on top of the PEDOT:PSS layer, resulting in strong interfacial recombination and a low V_oc. In contrast, the growth of the interfacial perovskite crystals was significantly improved by the synergic effects of varying the precursor solution composition and covering the surface with a pH-neutral conjugated polyelectrolyte, poly[2,6-(4,4-bis(potassium butanylsulfonate)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (CPE-K), which possesses potassium ions as counter ions. The influence of the energy-level alignment at the interface on V_oc was also discussed. Our findings highlight that improved perovskite crystallization at the interface can facilitate bulk growth of perovskite grains in the vertical direction and effectively suppress nonradiative surface charge recombination, thus enhancing the short-circuit current and V_oc