Dithieno[3,2-b:2',3'-d]pyrrole-benzo[c][1,2,5]thiadiazole conjugate small molecule donors: effect of fluorine content on their photovoltaic properties.

Two new small molecule donors, namely ICT4 and ICT6 with D1-A-D2-A-D1 architecture having 2,4-bis(2-ethylhexyl)-4H-dithieno[3,2-b:2',3'-d]pyrrole (EHDTP, D1) and 4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b']dithiophene (OBDT, D2) as the terminal and central donor, and benzo[c][1,2,5]thiadiazole (BT for ICT4) and 5,6-difluorobenzo[c][1,2,5]thiadiazole (F2BT for ICT6) as the acceptor (A) moieties, are synthesized and their optical, electronic and photovoltaic properties are investigated. Both ICT4 and ICT6 have considerable solubility in various solvents and possess efficient light absorption ability [ε (×105 mol-1 cm-1) is 0.99 and 1.06, respectively for ICT4 and ICT6] and appropriate frontier molecular orbital energy offsets with [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM). Bulk heterojunction solar cells (BHJSCs) are fabricated using ICT4/ICT6 and PC71BM as donors and acceptors, respectively and BHJSCs with two-step annealed (thermal followed by solvent vapor annealing) active layers of ICT4 and ICT6 show overall power conversion efficiencies (PCEs) of 5.46% and 7.91%, respectively. The superior photovoltaic performance of the ICT6 based BHJSCs is due to the favourable morphology with a nanoscale interpenetrating network in the ICT6:PC71BM active layer induced by the fluorine atoms on the BT acceptor, which significantly enhances the dissociation of excitons, charge transport and the charge collection efficiency, and suppresses bimolecular recombination in the BHJ. The observed higher PCE of 7.91% indicates that ICT6 is one of the best BT based donor material for small molecular BHJSCs.

A dithieno[3,2-b:2',3'-d]pyrrole based, NIR absorbing, solution processable, small molecule donor for efficient bulk heterojunction solar cells.

A novel, NIR absorbing organic small molecular donor material denoted as ICT3 with an A-D-D-D-A architecture having dithieno[3,2-b:2',3'-d]pyrrole (DTP) and butylrhodanine as donor and acceptor moieties, respectively, is synthesized and its thermal, photophysical, electrochemical and photovoltaic properties are explored. ICT3 has excellent stability over a broad range of temperatures with a decomposition temperature (Td corresponds to 5% weight loss) of 372 °C, soluble in most common organic solvents (solubility up to 30 mg mL-1) and suitable for solution processing during device fabrication. ICT3 has broad (520-820 nm) and intense visible region absorption (molar excitation coefficient is 1.69 × 105 mol-1 cm-1) and has suitable HOMO and LUMO energy levels with the [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) acceptor for efficient exciton dissociation and charge transfer. Bulk heterojunction solar cells (BHJSCs) with an indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS)/ICT3:PC71BM/poly(9,9-bis(3'-(N,N-dimethylamino)propyl)fluorene-2,7-diyl)-alt-(9,9-dioctylfluorene-2,7-diyl) (PFN)/aluminium (Al) structure are fabricated and the BHJSCs with the active layer as cast from chloroform solution displayed a power conversion efficiency (PCE) of 3.04% (JSC = 8.22 mA cm-2, VOC = 0.86 V and FF = 0.43). Annealing the active layer significantly improved the PCE of these BHJSCs. While thermal annealing of the active layer improved the PCE of the BHJSCs to 4.94%, thermal followed by solvent vapour annealing enhanced the PCE to 6.53%. X-ray diffraction and atomic force microscopy analyses are carried out on the active layer and these results revealed that annealing treatment improves the crystallinity and nanoscale morphology of the active layer, enriches the device exciton generation and dissociation efficiency, charge transport and collection efficiency and reduces carrier recombination. The observed higher PCE (6.53%) of the BHJSCs having ICT3 with a DTP donor moiety broadens the scope to develop new, efficient DTP based small molecular donor materials for BHJSCs.

Novel 4'-functionalized 4,4''-dicarboxyterpyridine ligands for ruthenium complexes: near-IR sensitization in dye sensitized solar cells.

Novel ruthenium complexes (MC113-MC117), obtained by modifying the terpyridine ligand of the black dye (N749), have been evaluated as sensitizers for dye sensitized solar cells (DSSCs). The modification is carried out by attaching selected chromophores, with varying electron donating strength, covalently to the central ring of the ligand. The complexes, compared to the parent dye, show red shifted absorption covering visible and near IR regions and higher molar extinction coefficients. We report in this work synthesis of a series of these ruthenium complexes with chromophores such as tert-butyl phenyl, triphenylamine, bithiophene, phenoxazine and phenothiazine. Detailed experimental characterization using optical, electrochemical and photovoltaic techniques has been carried out and complemented by density functional theory studies. The fill factors (ff) obtained for these dyes are larger than those of the parent black dye. In spite of these superior properties, the dyes show only moderate to good power conversion efficiencies. The possible reasons for this have been investigated and discussed.

Thiocyanate-free cyclometalated ruthenium(II) sensitizers for DSSC: a combined experimental and theoretical investigation.

In an effort to bring out efficient thiocyanate-free dyes for dye sensitized solar cells (DSSC) we have designed, synthesized and characterized four novel cyclometalated ruthenium(II) dyes (M1 to M4) with superior photochemical properties. All dyes contain terpyridyl ligands (TPY) with carboxylic acids as anchoring groups and cyclometalated ligand (TPY-C) with substituents for fine tuning the electronic properties. We obtain a broad absorption band which extends up to 725 nm due to metal to ligand charge transfer (MLCT) when donating groups are used, which slightly blue-shifts when a withdrawing group is used. In addition to the CT, small HOMO-LUMO gaps are obtained from electrochemical measurements which indicate characteristics of an ideal sensitizer. All four dyes were used as sensitizers for DSSC and photoelectrochemical measurements were carried out. Reasonably good efficiency (7.1%) has been achieved for . We have carried out periodic-DFT studies of these dyes adsorbed on the (TiO2)38 cluster. They revealed that, in bidentate bridging mode the dyes preferably bind with the help of two carboxylic groups onto the TiO2. To the best of our knowledge we are the first to do DFT studies of thiocyanate free cyclometalated ruthenium(ii) dyes tethered to TiO2.