Sulfur-Doped ZnO as Cathode Interlayer for Efficient Inverted Organic Solar Cells

Bulk heterojunction (BHJ) organic solar cells (OSCs) represent a promising technology due to their cost-effectiveness, lightweight design and potential for flexible manufacturing. However, achieving a high power conversion efficiency (PCE) and long-term stability necessitates optimizing the interfacial layers. Zinc oxide (ZnO), commonly used as an electron extraction layer (EEL) in inverted OSCs, suffers from surface defects that hinder device performance. Furthermore, the active control of its optoelectronic properties is highly desirable as the interfacial electron transport and extraction, exciton dissociation and non-radiative recombination are crucial for optimum solar cell operation. In this regard, this study investigates the sulfur doping of ZnO as a facile method to effectively increase ZnO conductivity, improve the interfacial electron transfer and, overall, enhance solar cell performance. ZnO films were sulfur-treated under various annealing temperatures, with the optimal condition found at 250 °C. Devices incorporating sulfur-doped ZnO (S-ZnO) exhibited a significant PCE improvement from 2.11% for the device with the pristine ZnO to 3.14% for the OSC based on the S-ZnO annealed at 250 °C, attributed to an enhanced short-circuit current density (J_sc) and fill factor (FF). Optical and structural analyses revealed that the sulfur treatment led to a small enhancement of the ZnO film crystallite size and an increased n-type transport capability. Additionally, the sulfurization of ZnO enhanced its electron extraction efficiency, exciton dissociation at the ZnO/photoactive layer interface and exciton/charge generation rate without altering the film morphology. These findings highlight the potential of sulfur doping as an easily implemented, straightforward approach to improving the performance of inverted OSCs.