Atomic layer deposition of ZnO electron transporting layers directly onto the active layer of organic solar cells

Abstract Interlayers in organic solar cells (OSCs) are used to reduce energy barriers for charge injection/extraction, act as optical spacers, introduce carrier selectivity and increase organic/contact compatibility. To date, the most widely used inorganic interlayers are metal oxides such as TiO 2 and ZnO. However, these materials require harsh deposition conditions that could damage the organic active layers, and hence are generally used in inverted devices. Here we show, for the first time, that judicious selection of materials and processing conditions allow the use of an atomic layer deposition (ALD) system to deposit thin conformal ZnO interlayers on bulk heterojunctions (BHJs). ALD-ZnO interlayers were utilized as electron transporting layers (ETLs) in OSCs and compared to similar devices with solution deposited ZnO nanoparticle (np) ETLs. OSCs with ALD-ZnO ETLs exhibited higher photocurrent densities, J sc , but lower open circuit voltages, V oc . The low V oc is associated with the presence of pinholes and an offset between the ALD-ZnO and PC 70 BM electron conducting states. This offset results from traps and acceptor sites generated during the low temperature ALD process. To recover the V oc we introduced a fluorinated phosphonic acid (PA) additive to the blend. We suggest that the additive migrates to the film surface, interacts with the ZnO to produce a denser layer and to passivate traps, effectively improving the device shunt resistance and energy level alignment and increasing V oc . Overall, the devices with PA and ALD-ZnO ETLs possess significantly higher power conversion efficiencies (PCEs) than those with np-ZnO ETLs. For example, the champion ALD-ZnO device PCE is 3.5%, while that with np-ZnO is 2.75%.