We report the synthesis, characterization, and solar cell properties of new donor−acceptor-type low band gap polymers (POBDTPD and PEBDTPD) that incorporate dialkoxybenzodithiophene (BDT) as the donor and N-octyl-2,7-dithia-5-azacyclopenta[a]pentalene-4,6-dione (DTPD) as the acceptor. The newly developed DTPD moiety was carefully designed to lower a band gap via strong interaction between donor−acceptor moieties and keep polymer energy levels deep. Remarkably, the DTPD acceptor moiety effectively widens the light absorption range of the polymers up to ∼900 nm while positioning their HOMO and LUMO levels in the optimal range, i.e., −5.3 and −4.0 eV, respectively, for high power conversion efficiencies (PCEs) as we intended. Solar cell devices were fabricated according to the structure ITO/ PEDOT:PSS/photoactive (polymer:PC 70 BM)/TiO 2 /Al. The POBDTPD devices exhibited a PCE of 4.7% with a V oc of 0.70 V, a J sc of 10.6 mA/cm 2 , and a FF of 0.64. The PEBDTPD devices yielded a higher PCE of 5.3% with a V oc of 0.72 V, a J sc of 13.5 mA/cm 2 , and a FF of 0.54. AFM, TEM, and PL quenching measurements revealed that the high J sc s are a result of the appropriate morphology and efficient charge separation. In comparing the performances of the two polymer devices, the higher J sc for the PEBDTPD device was attributed to its better nanoscale phase separation, smoother surface, and higher carrier mobility in the polymer:PC 70 BM blend films. The higher FF for the POBDTPD device was ascribed to a good balance between the hole and electron mobilities. Overall, we demonstrate that the DTPD unit is a promising electron-accepting moiety to develop high performance low band gap polymers.

We synthesized four polymers (pT3DPP-HD, pT3DPP-OD, pT2TTDPP-HD, and pT2TTDPP-OD) and characterized their photovoltaic properties as a function of the backbone planarity, alkyl side chain length, and film morphology. The polymers were donor–acceptor type low-band-gap (1.2–1.3 eV) polymers employing terthiophene (T3) or thiophene–thieno[3,2-b]thiophene–thiophene (T2TT) as the donor and 2,5-bis(2-hexyldecyl)pyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione (DPP-HD) or 2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione (DPP-OD) as the acceptor. The T2TT moiety in the polymer backbone is more planar than the T3; the OD moiety as the alkyl side chain ensured a higher solubility than the HD moiety. Polymer solar cells (PSCs) were fabricated, and their properties were characterized. The photoactive layer consisted of one of the four polymers and one of the fullerene derivatives (PC70BM or PC60BM). For a given fullerene derivative, the PCEs prepared with each of the four polymers were ordered according to pT3DPP-OD, pT2TTDPP-HD, pT3DPP-HD, and pT2TTDPP-OD. Studies on the morphologies of the polymer:fullerene layers revealed that the pT3DPP-OD:PC70BM blend exhibited an optimal degree of phase separation between the polymer and the fullerene, while retaining a high degree of interconnectivity, thereby yielding the highest PCE measured in this series. By contrast, the pT2TTDPP-OD:fullerene yielded the lowest PCE because of too high crystalline fibrous polymer domains. In conclusion, we demonstrate that minute variations in the polymer chemical structure strongly affects both (i) the nanoscale miscibility between the polymers and fullerenes and (ii) the interconnectivity of the polymer chains, and these properties are tightly correlated with the solar cell performance.

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We fabricated solution-processed organic photovoltaic cells (OPVs) using substituted two sexithiophenes, a,w-bis(dimethyl-n-octylsilyl)sexithiophene (DSi-6T) and a,w-dihexylsexithiophene (DH-6T), as electron donors, and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as an electron acceptor. Solution-processed OPVs usingDH-6TandDSi-6Tshowed good photovoltaic properties in spite of their poor solubility. The best performance was observed onDSi-6T : PCBM 1 : 5 (w/w) blend cell with an open circuit voltage (Voc) of 0.63 V, short circuit current density (Jsc) of 1.34 mA/cm2, fill factor (FF) of 55%, and power conversion efficiency of 0.44% under AM 1.5 G illumination. AlthoughDH-6Thas higher hole mobility thanDSi-6T, theDSi-6T : PCBM blend cell showed higher hole mobility thanDH-6T : PCBM cell. Therefore,DSi-6Tcell showed higher device performance thanDH-6Tcell due to its silyl substitutions, which lead to the increase of the solubility. The incorporation of solution-processed TiO2interfacial layer in theDSi-6T : PCBM devices significantly enhances FF due to the reduced charge recombination near active layer/Al interface.