Influence of solvents and substrates on the morphology and the performance of low-bandgap polyfluorene: PCBM photovoltaic devices

Spin-coated thin films of poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-5,5-(4\u27,7\u27-di-2-thienyl-2\u27,1\u27,3\u27-benzothiadiazole)] (APFO-3) blended with [6,6]-phenyl-C61-butyric acid Me ester (PCBM) are used as the active material in polymer photovoltaic cells. Such blends are known for their tendency to phase sep. during film formation. Tuning the morphol. of the blend in a controlled way is one possible road towards higher efficiency. We studied the effect of adding chlorobenzene to chloroform-based blend solns. before spin-coating on the conversion efficiency of APFO-3:PCBM photodiodes, and related that to the lateral and vertical morphol. of thin films of the blend. The lateral morphol. is imaged by at. force microscopy (AFM) and the vertical compositional profile is obtained by dynamic secondary ion mass spectrometry (SIMS). The profiles reveal compositional variations consisting of multilayers of alternating polymer-rich and PCBM-rich domains in the blend film spin-coated from chloroform. The vertical compositional variations are caused by surface-directed spinodal waves and are frozen in during the rapid evapn. of a highly volatile solvent. With addn. of the low-vapor pressure solvent chlorobenzene, a more homogeneous vertical compn. is found. The conversion efficiency for solar cells of this blend was found to be optimal for chloroform:chlorobenzene mixts. with a vol.-ratio of 80:1. We have also investigated the role of the substrate on the morphol. We found that blend films spin-coated from chloroform solns. on PEDOT:PSS-coated ITO show a similar compositional structure as the films on silicon, and that changing the substrate from silicon to gold only affects the vertical phase sepn. in a region close to the substrate interface. [on SciFinder (R)