02883nas a2200241   4500008004100000022001400041245023400055210006900289260000800358300001600366490000600382520186700388653002502255653003002280653003002310653002402340653003002364653002802394100002802422700003902450700002702489856012502516       2017                        eng d  a1944-824400aInterplay between pi-bridges and positions of branched alkyl groups of unsymmetrical D-A-D-pi-A squaraines in dye-sensitized solar cells: mode of dye anchoring and the charge transfer process at the TiO2/Dye/electrolyte interface0 aInterplay between pibridges and positions of branched alkyl grou  cSEP  a32698-327120 v93 a<p>Far-red-absorbing squaraines possessing high molar absorptivity (&gt;10(5) M-1 cm(-1)) are being attracted as high-efficiency chromophores in dye-sensitized solar cells (DSSCs). A series of donor acceptor -donor-pi spacer-acceptor (D-A-D-pi-A) unsymmetrical squaraines, PSQ1-5, with indoline donor and squaric/cyanoacetic acid acceptor units, were designed for sensitized solar cells. For extending the absorption toward the near-infrared region (NIR) and controlling the orientation on the TiO2 surface, benzene (PSQ1 and PSQ2) and thiophene (PSQ3-5) 7r-spacers and out-of-plane branched alkyl groups at the indoline that are away (PSQ1, PSQ3, and PSQS) or near (PSQ2 and PSQ4) the anchoring group, respectively, were introduced. Dynamic aggregation tendency of PSQ1 and PSQ3 than that of their isomers systematically modulates the orientation on the TiO2 surface, which in turn enhances photovoltaic performance. Absorptance on a thin transparent TiO2 film shows a visible-to-NIR response with an onset around 800 nm for PSQ3-5. Although there is resemblance in electrochemical redox levels, their high injection efficiency and recombination resistance differentiated impact on the way of anchoring and the dihedral angle between D-A-D units and g-spacers. DSSCs sensitized with PSQS achieved a PCE of 8.15% under simulated AM 1.5G illumination (100 mW cm(-2)), with the current density (j) and open-circuit voltage (Voc) of 19.73 mA cm(-2) and 630 mV, respectively. A clear comparison of the incident-photon-to-current conversion efficiency versus the light-harvesting efficiency correlates the structure-property relationship with J obtained for PSQ dyes. Electrochemical impedance spectroscopy was carried out to examine the TiO2/dye/electrolyte interface for further confirmation of the enhanced PCE of top-se-alkylated PSQS over that of other dyes.</p>10aD-A-D-pi-A framework10adye-sensitized solar cell10aH- and J-type aggregation10aorientation of dyes10astatic/dynamic aggregates10aunsymmetrical squaraine1 aPunitharasu, Vellimalai1 aKavungathodi, Munavvar, Fairoos Me1 aNithyanandhan, Jayaraj  uhttps://library.ncl.res.in/content/interplay-between-pi-bridges-and-positions-branched-alkyl-groups-unsymmetrical-d-d-pi02581nas a2200265   4500008004100000022001400041245010200055210006900157260000800226300001600234490000700250520165100257653003101908653002401939653003001963653001901993653003002012653001902042100001802061700002402079700003902103700001902142700002702161856012702188       2018                        eng d  a1944-824400aFused fluorenylindolenine-donor-based unsymmetrical squaraine dyes for dye-sensitized solar cells0 aFused fluorenylindoleninedonorbased unsymmetrical squaraine dyes  cAUG  a26335-263470 v103 a<p>A series of four unsymmetrical squaraine dyes, XSQ1-4, were synthesized using a fused fluorenylindolenine-based donor unit for dye-sensitized solar cells (DSSCs). The fused structure of fluorenylindolenine helped in moving the absorption toward the near-infrared (NIR) region, and the two sp(3)-C centers available on this donor were utilized to incorporate out-of-plane alkyl chains in opposite directions to control the dye-dye interactions on the TiO2 surface. High extinction coefficient (epsilon &gt;= 10(5) M-1 cm(-1)) for absorbing NIR photons and suitable highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels with respect to the conduction band of TiO2 and electrolyte for charge injection and dye regeneration processes, respectively, make these dyes potential sensitizers for DSSCs. Introduction of branched alkyl groups in the pi-framework helped in controlling dye aggregation to reduce exciton quenching and assisted in TiO2 surface passivation to avoid the charge recombination process. Furthermore, having a naphthyl group on the indole part of the anchoring group containing segment helped to red-shift the absorption spectrum of dyes 15 nm toward the NIR region (XSQ3-4). Among all of the dyes under investigation, XSQ2 gave the best photovoltaic performance, having a short-circuit current density (J(SC)) of 13.99 mA cm(-2), open -circuit voltage (V-OC) of 0.66 V, and a fill factor (ff) of 0.71, with a device performance (eta) of 6.57%. Electrochemical impedance spectroscopy revealed higher electron lifetime on TiO2 for XSQ2, which helps to avoid the charge recombination process.</p>10aDye-sensitized solar cells10afluorenylindolenine10aH- and J-type aggregation10aNIR absorption10aout-of-plane alkyl groups10asquaraine dyes1 aBisht, Rajesh1 aSudhakar, Vediappan1 aKavungathodi, Munavvar, Fairoos Me1 aKarjule, Neeta1 aNithyanandhan, Jayaraj  uhttps://library.ncl.res.in/content/fused-fluorenylindolenine-donor-based-unsymmetrical-squaraine-dyes-dye-sensitized-solar