Enhanced Performance of Polymeric Bulk Heterojunction Solar Cells via Molecular Doping with TFSA

Organic solar cells based on bis(trifluoromethanesulfonyl)amide (TFSA, [CF₃SO₂]₂NH) bulk doped poly[N-9′′-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole) (PCDTBT):C₇₁-butyric acid methyl ester (PC₇₁BM) were fabricated to study the effect of molecular doping. By adding TFSA (0.2-0.8 wt %, TFSA to PCDTBT) in the conventional PCDTBT:PC₇₁BM blends, we found that the hole mobility was increased with the reduced series resistance in photovoltaic devices. The p-doping effect of TFSA was confirmed by photoemission spectroscopy that the Fermi level of doped PCDTBT shifts downward to the HOMO level and it results in a larger internal electrical field at the donor/acceptor interface for more efficient charge transfer. Moreover, the doping effect was also confirmed by charge modulated electroabsorption spectroscopy (CMEAS), showing that there are additional polaron signals in the sub-bandgap region in the doped thin films. With decreased series resistance, the open-circuit voltage (V_oc) was increased from 0.85 to 0.91 V and the fill factor (FF) was improved from 60.7% to 67.3%, resulting in a largely enhanced power conversion efficiency (PCE) from 5.39% to 6.46%. Our finding suggests the molecular doping by TFSA can be a facile approach to improve the electrical properties of organic materials for future development of organic photovoltaic devices (OPVs).