Solution Processing Dependent Bulk Heterojunction Nanomorphology of P3HT/PCBM Thin Films

Mixtures of poly(3-hexyl-thiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) have been widely employed as donor and acceptor materials, respectively, for the active layer of the bulk heterojunction (BHJ) organic solar cells. Experiments are able to provide only limited insights on the dynamics of blend morphology of these organic materials because of the challenges in extracting microstructural characterization amidst the poor contrast in electron microscopy. We present results from coarse-grained molecular dynamics simulations (CGMD) describing the morphological evolution of P3HT/PCBM active layer under solution processing in chlorobenzene (CB). We examine the impact of various processing parameters such as weight ratio, degree of polymerization (DOP), thermal annealing, and preheating on the BHJ active layers using morphological characterizations from atomic trajectories. Simulated diffraction patterns are compared with experimental results of X-ray diffraction and Small Angle X-ray Scattering (SAXS). Both simulated scattering and experimental X-ray diffraction and X-ray scattering measurements reveal increase in crystallinity for P3HT upon annealing until PCBM weight fraction ∼50%. The solubility of PCBM being greater in CB than that of P3HT facilitates the phase separation of the polymer during early stages of solvent evaporation. An increase in the average size of the P3HT domain relative to the preannealed morphology, is due to phase segregation and crystallization of the polymer upon annealing. Percolation for PCBM remains unchanged until PCBM constitutes at least one-half of the composition. Although 1.0:2.0 weight ratio is predicted to be ideal for balanced charge transport, 1.0:1.0 weight ratio is the most beneficial of overall power conversion based on exciton generation and charge separation at the interface. DOP of P3HT molecules is another important design variable as larger P3HT molecules tend to entangle more often deteriorating molecular order of P3HT phase in the active layer. Preheating the ternary mixture of P3HT, PCBM, and CB modifies the structural order and morphology of the BHJ due to changes in PCBM diffusion into the P3HT phase.