Fabrication of PCDTBT Conductive Network via Phase Separation

Poly[N-9′-hepta-decanyl-2,7-carbazole-alt-5-5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) is a stable semiconducting polymer with high rigidity in its molecular chains, which makes it difficult to organize into an ordered structure and affects the device performance. Here, a PCDTBT network consisting of aggregates and nanofibers in thin films was fabricated through the phase separation of mixed PCDTBT and polyethylene glycol (PEG). Using atomic force microscopy (AFM), the effect of the blending conditions (weight ratio, solution concentration, and molecular weight) and processing conditions (substrate temperature and solvent) on the resulting phase-separated morphologies of the blend films after a selective washing procedure was studied. It was found that the phase-separated structure’s transition from an island to a continuous structure occurred when the weight ratio of PCDTBT/PEG changed from 2:8 to 7:3. Increasing the solution concentration from 0.1 to 3.0 wt% led to an increase in both the height of the PCDTBT aggregate and the width of the nanofiber. When the molecular weight of the PEG was increased, the film exhibited a larger PCDTBT aggregate size. Meanwhile, denser nanofibers were found in films prepared using PCDTBT with higher molecular weight. Furthermore, the electrical characteristics of the PCDTBT network were measured using conductive AFM. Our findings suggest that phase separation plays an important role in improving the molecular chain diffusion rate and fabricating the PCDTBT network.