Domains rich in different blend components phase-separate during deposition, creating a film morphology that determines the performance of active layers in organic electronics. However, morphological control either relies on additional fabrication steps or is limited to a small region where an external interaction is applied. Here, we show that different semiconductor-insulator polymer composites can be rapidly dip-coated with the film structure electrically switched between distinct morphologies during deposition guided by the meniscus formed between the stationary barrier and horizontally drawn solid substrate. Reversible and repeatable changes between the morphologies used in devices, e.g., lateral morphologies and stratified layers of semiconductors and insulators, or between phase-inverted droplet-like structures are manifested only for one polarity of the voltage applied across the meniscus as a rectangular pulse. This phenomenon points to a novel mechanism, related to voltage-induced doping and the doping-dependent solubility of the conjugated polymer, equivalent to an increased semiconductor content that controls the composite morphologies. This is effective only for the positively polarized substrate rather than the barrier, as the former entrains the nearby lower part of the coating solution that forms the final composite film. The mechanism, applied to the pristine semiconductor solution, results in an increased semiconductor deposition and 40-times higher film conductance.
Keywords: conjugated polymers; electric field; phase separation; poly(3-hexylthiophene); voltage-induced doping.