“Solvent Annealing” Effect in Polymer Solar Cells Based on Poly(3‐hexylthiophene) and Methanofullerenes

The self‐organization of the polymer in solar cells based on regioregular poly(3‐hexylthiophene) (RR‐P3HT):6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) is studied systematically as a function of the spin‐coating time t_s (varied from 20–80 s), which controls the solvent annealing time t_a, the time taken by the solvent to dry after the spin‐coating process. These blend films are characterized by photoluminescence spectroscopy, UV‐vis absorption spectroscopy, atomic force microscopy, and grazing incidence X‐ray diffraction (GIXRD) measurements. The results indicate that the π‐conjugated structure of RR‐P3HT in the films is optimally developed when t_a is greater than 1 min (t_s ～ 50 s). For t _s < 50 s, both the short‐circuit current (J_SC) and the power conversion efficiency (PCE) of the corresponding polymer solar cells show a plateau region, whereas for 50 < t_s < 55 s, the J_SC and PCE values are significantly decreased, suggesting that there is a major change in the ordering of the polymer in this time window. The PCE decreases from 3.6 % for a film with a highly ordered π‐conjugated structure of RR‐P3HT to 1.2 % for a less‐ordered film. GIXRD results confirm the change in the ordering of the polymer. In particular, the incident photon‐to‐electron conversion efficiency spectrum of the less‐ordered solar cell shows a clear loss in both the overall magnitude and the long‐wavelength response. The solvent annealing effect is also studied for devices with different concentrations of PCBM (PCBM concentrations ranging from 25 to 67 wt %). Under “solvent annealing” conditions, the polymer is seen to be ordered even at 67 wt % PCBM loading. The open‐circuit voltage (V_OC) is also affected by the ordering of the polymer and the PCBM loading in the active layer.