Surfactant Engineering and Its Role in Determining the Performance of Nanoparticulate Organic Photovoltaic Devices

[Image: see text] The fabrication of organic photovoltaics (OPVs) from non-hazardous nanoparticulate (NP) inks offers considerable promise for the development of eco-friendly large-scale printed solar modules. However, the typical NP core–shell morphology (driven by the different donor/acceptor affinities for the surfactant used in NP synthesis) currently hinders the photovoltaic performance. As such, surfactant engineering offers an elegant approach to synthesizing a more optimal intermixed NP morphology and hence an improved photovoltaic performance. In this work, the morphology of conventional sodium dodecyl sulfate (SDS) and 2-(3-thienyl) ethyloxybutylsulfonate (TEBS)-stabilized poly(3-hexylthiophene) (P3HT) donor:phenyl-C(61)-butyric acid methyl ester (PC(61)BM) acceptor NPs is probed using scanning transmission X-ray microscopy, UV–vis spectroscopy, grazing-incidence X-ray diffraction, and scanning electron microscopy. While the SDS-stabilized NPs exhibit a size-independent core–shell morphology, this work reveals that TEBS-stabilized NPs deliver an intermixed morphology, the extent of which depends on the particle size. Consequently, by optimizing the TEBS-stabilized NP size and distribution, NP-OPV devices with a power conversion efficiency that is ∼50% higher on average than that of the corresponding SDS-based NP-OPV devices are produced.