Agrivoltaics is an encouraging application area for organic photovoltaics (OPVs) that merges solar power generation with the energy demands of crop growth, thus providing dual functionality to dedicated farmland. When integrated on greenhouses, semitransparent OPV technologies are expected to improve the sustainability of crop growth and turn net zero energy greenhouses a reality. In this work, we screen all-polymer and polymer:small-molecule, donor:acceptor blends for their use in organic agrivoltaics. The optical requirements of the blends are benchmarked according to a novel greenhouse figure-of-merit (gh-FoM) to account for the -simultaneous- transparency requirements of crops and humans. Modeling of the gh-FoM reveals that photoactive layer thicknesses between 25-125 nm and acceptor-enriched ratios (such as 1:4, w:w, with the acceptor being the lower band gap material) are more suitable for the optical constraints imposed by most types of crops. Nevertheless, such ratios are found to be less thermally stable, thus imposing an undesirable trade-off between the required device semitransparency and its long-term stability.

The optimized blends are then upscaled to form 25 cm² active area laminated modules processed entirely from solution, on flexible substrates, via roll-to-roll compatible methods (slot-die and blade coating) and in ambient conditions. These modules are installed on a domestic greenhouse in Sweden, where their outdoor stability is tracked 24 hours per day over the spring and summer periods while in compliance with the ISOS-O-2 protocol. We accordingly design an autonomous, Arduino-based IV-tracing setup that automatically collects, analyses and uploads relevant device data to the cloud for remote tracking worldwide, at very low cost. Our outdoor stability study shows degradation modes undetectable under laboratory conditions such as decreased ideality factors and detrimental module delamination, which accounts for 10-20% loss in active area as per photocurrent imaging. Harsh thermal and humidity cycling conditions are correspondingly tracked during the day-night cycles, which are found to contribute to the amplified degradation pace of the agrivoltaic modules. Among the active layers tested in this work in the form of air-processed laminated modular architectures, polymer:small-molecule blends are the most stable and position as prominent photoactive layers toward sustainable organic agrivoltaic technologies.