Spark Discharge Doping—Achieving Unprecedented Control over Aggregate Fraction and Backbone Ordering in Poly(3‐hexylthiophene) Solutions

Abstract The properties of semiconducting polymers are strongly influenced by their aggregation behavior, that is, their aggregate fraction and backbone planarity. However, tuning these properties, particularly the backbone planarity, is challenging. This work introduces a novel solution treatment to precisely control the aggregation of semiconducting polymers, namely current‐induced doping (CID). It utilizes spark discharges between two electrodes immersed in a polymer solution to create strong electrical currents resulting in temporary doping of the polymer. Rapid doping‐induced aggregation occurs upon every treatment step for the semiconducting model‐polymer poly(3‐hexylthiophene). Therefore, the aggregate fraction in solution can be precisely tuned up to a maximum value determined by the solubility of the doped state. A qualitative model for the dependences of the achievable aggregate fraction on the CID treatment strength and various solution parameters is presented. Moreover, the CID treatment can yield an extraordinarily high quality of backbone order and planarization, expressed in UV–vis absorption spectroscopy and differential scanning calorimetry measurements. Depending on the selected parameters, an arbitrarily lower backbone order can be chosen using the CID treatment, allowing for maximum control of aggregation. This method may become an elegant pathway to finely tune aggregation and solid‐state morphology for thin‐films of semiconducting polymers.