02335nas a2200241 4500008004100000022001400041245011500055210006900170260000800239300001400247490000600261520145000267653002301717653002001740653003101760653003201791653002601823100002801849700003901877700002701916700002701943856012301970 2019 eng d a2574-096200api-Extended cis-configured unsynimetrical squaraine dyes for dye-sensitized solar cells: panchromatic response0 apiExtended cisconfigured unsynimetrical squaraine dyes for dyese cDEC a8464-84720 v23 a

{Light absorbing sensitizer is the heart of the third generation photovoltaic technologies such as dye sensitized solar cells. Despite possessing large extinction coefficients for the metal-free organic dyes, the light harvesting efficiency is limited with the narrow absorption 20 profile in either visible or NIR regions of the solar spectrum. Though monolayer formation of organic sensitizers on semiconducting metal oxide surface leads to dye-dye interaction that leads to broadening the absorption profile, the contribution of the aggregated state to the power conversion process is found out to be poor. Here, we have engineered far-red active pi-extended cis-configured unsymmetrical squaraine dyes with carboxylic acid and cycnoacetic acid as anchoring groups with controlled aggregation and panchromatic light absorption by including the steric and electronic factors. The presence of sp(3)-C (out-of-plane) and N-alkyl (in-plane) groups played an important role in modulating the assembly of the dyes on the TiO2 electrode; the cis-squaraine unit helps to extend the conjugation in the NIR region besides enhancing the visible transition and the incident photon-to-current conversion efficiency profile that showed the importance of anchoring groups for the panchromatic response. Dye PSQ10 showed solar-to electric conversion with an onset of 850 nm with the device performance of 7.0% (V-oc = 0.581 V, J(sc) = 17.06 mA/cm(2)

10acis-squaraine dyes10aDye aggregation10aDye-sensitized solar cells10aextended far-red absorption10apanchromatic response1 aPunitharasu, Vellimalai1 aKavungathodi, Munavvar, Fairoos Me1 aSingh, Ambarish, Kumar1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/pi-extended-cis-configured-unsynimetrical-squaraine-dyes-dye-sensitized-solar-cells03102nas a2200229 4500008004100000022001400041245017500055210006900230260000800299300001400307490000700321520219200328653002302520653002102543653002502564653003102589653002902620100002702649700003902676700002702715856013002742 2020 eng d a1944-824400aAlkyl-group-wrapped unsymmetrical squaraine dyes for dye-sensitized solar cells: branched alkyl chains modulate the aggregation of dyes and charge recombination processes0 aAlkylgroupwrapped unsymmetrical squaraine dyes for dyesensitized cJAN a2555-25650 v123 a

Electron transfer processes at the interfaces dictate the factors that improve the photovoltaic parameters, such as open-circuit voltage (V-oc) and short-circuit current (J(sc)), of a dye-sensitized solar cell device, besides selection of a set of suitable anode, dye, electrolyte, and cathode materials. An inefficient charge injection process at the dye-TiO2 interface and charge recombination at the TiO2-dye/electrolyte interface have detrimental effects on improving both J(sc) and V-oc. Hence, tailoring the factors that govern the improvement of J(sc) and V-oc will be an ideal approach to get the desired sensitizers with good device efficiencies. Squaraines are far-red-active zwitterionic dyes and have a high molar extinction coefficient along with unique aggregation properties due to the large dipole moment associated with them. Here, we report a series of unsymmetrical squaraine dyes, SQS1 to SQS6, with systematic variation of alkyl groups at the sp(3)-C and N-atoms of the indoline unit that is away from the anchoring group to control the dye-dye interactions on the TiO2 surface. The branched alkyl groups help in modulating the self-assembly of sensitizers on the TiO2 surface, besides passivating the surface that helps avoid the charge recombination processes. Light harvesting efficiency and cyclic voltammetry studies of dye-sensitized TiO2 electrodes indicate that the aggregation and charge hopping process between the dye molecules can be modulated, respectively, by systematically increasing the number of carbon atoms in the alkyl groups. Such a variation in the branched alkyl group helps enhance V-oc from 672 (SQS1) to 718 mV (SQS6) and J(sc) from 7.95 (SQS1) to 12.22 mA/cm(2) (SQS6), with the device efficiency ranging from 3.82% to 6.23% without any coadsorbent. Dye SQS4 achieves the highest efficiency of 7.1% (V-oc = 715 mV, J(sc) = 13.05 mA/cm(2)) with coadsorbent chenodeoxycholic acid (CDCA) using an iodine (I-/I-3(-)) electrolyte compared to its analogues. An analysis of the incident photon-to-current efficiency profiles indicates that the major contribution to photocurrent generation is from the aggregated squaraine dyes on TiO2.

10aaggregation of dye10acharge injection10acharge recombination10aDye-sensitized solar cells10aunsymmetrical squaraines1 aSingh, Ambarish, Kumar1 aKavungathodi, Munavvar, Fairoos Me1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/alkyl-group-wrapped-unsymmetrical-squaraine-dyes-dye-sensitized-solar-cells-branched-alkyl02669nas a2200229 4500008004100000022001400041245017400055210006900229260000800298300001400306490000600320520174000326653003102066653004102097653003502138653002702173653003402200653002002234100002702254700002702281856013102308 2022 eng d a2574-096200aIndoline-based donor-pi-acceptor visible-light responsive organic dyes for dye-sensitized solar cells: co-sensitization with squaraine dye for panchromatic IPCE response0 aIndolinebased donorpiacceptor visiblelight responsive organic dy cFEB a1858-18680 v53 a

A series of metal-free indoline-based donor-pi-acceptor (D-pi-A) visible-light active organic dyes, where an indoline unit wrapped with alkyl or alkyl and glycolic (TEG) groups is used as a donor, a mono- or bi-thiophene unit is used as a pi-spacer, and cyanoacrylic acid acts as an acceptor unit, have been designed and synthesized for dye-sensitized solar cell (DSSC) application. These dyes showed three absorption bands in a dichloromethane solution: the first and second transitions are observed in the UV (337-385 nm) and visible (477-514 nm) regions and correspond to pi-pi* and intramolecular charge transfer (ICT) transition, respectively, whereas the third absorption band obtained in the near-IR (629-758 nm) region has been observed for the first time for a D-pi-A type dye architecture. Furthermore, the ICT transition band for AKT dyes showed negative solvatochromism with increasing polarity of solvents. Photovoltaic characterizations for AKT dyes have been systematically studied with a cobalt electrolyte to evaluate the effect of thiophene incorporation and alkyl group substitution by the TEG group on the DSSC device performance. Here, AKT2 showed the highest DSSC efficiency of 3.16% with V-OC of 0.680 V and J(SC) of 6.24 mA/cm(2) without chenodeoxycholic acid (CDCA) in the AKT dye series, whereas DSSC efficiencies for AKT dyes were not affected much upon further addition of CDCA. Furthermore, AKT dyes were co-sensitized with a complementary optical responsive indoline-based SQS4 dye and showed enhanced efficiency. The combination of AKT2/SQS4 dyes with a ratio of 1:1 showed a maximum of 5.20% co-sensitized solar cell efficiency compared to other dye combinations with the cobalt electrolyte.

10aDye-sensitized solar cells10aindoline-based donor-pi-acceptor dye10aintramolecular charge transfer10ametal-free organic dye10apanchromatic-light absorption10aSolvatochromism1 aSingh, Ambarish, Kumar1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/indoline-based-donor-pi-acceptor-visible-light-responsive-organic-dyes-dye-sensitized-solar02030nas a2200253 4500008004100000022001400041245010900055210006900164260000800233490000600241520111800247653002201365653002701387653003101414653001701445653003201462100002701494700002401521700003401545700001801579700003001597700002701627856012201654 2023 eng d a2367-093200aModular TiO2-squaraine dyes/electrolyte interface for dye-sensitized solar cells with cobalt electrolyte0 aModular TiO2squaraine dyeselectrolyte interface for dyesensitize cAPR0 v73 a

Strategies to diminish both charge recombination and aggregation of dyes on the photoanode by functionalizing the sensitizer with alkyl groups is the best approach to achieve high dyesensitized solar cell (DSSC) efficiency. Development of such a photoanode with NIR-active dyes which is compatible with a cobalt electrolyte is important to enhance the photovoltaic performance. In this report, alkyl-group-wrapped donor-acceptor-donor (D-A-D) based unsymmetrical squaraine dyes have been used for DSSC device characterization with a cobalt electrolyte. Surface passivation of photoanode was varied systematically by the extent of functionalization with alkyl groups to avoid charge recombination. DSSC device performance of 5.92% was achieved for an alkyl-group-wrapped squaraine dye with a cobalt electrolyte. Hence, appending the alkyl groups on the donor unit of squaraine dyes helps passivating the photoanode, whereas introducing hydrophilic groups provides a leaky surface where oxidized electrolyte species reach the titanium-metal-oxide surface which promotes the charge recombination process.

10acounter-electrode10aDSSC device efficiency10aDye-sensitized solar cells10aElectrolytes10aunsymmetrical squaraine dye1 aSingh, Ambarish, Kumar1 aSudhakar, Vediappan1 aJavaregowda, Bharathkumar, H.1 aBisht, Rajesh1 aKrishnamoorthy, Kothandam1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/modular-tio2-squaraine-dyeselectrolyte-interface-dye-sensitized-solar-cells-cobalt03071nas a2200277 4500008004100000022001400041245013500055210006900190260000900259300001400268490000600282520203300288653002402321653002502345653003102370653003502401653005202436100002402488700002702512700002702539700001602566700002602582700003002608700002702638856012802665 2025 eng d a2574-096200aEffect of cyclization and alkyl group wrapping in visible-light-active unsymmetrical squaraine dyes for dye-sensitized solar cells0 aEffect of cyclization and alkyl group wrapping in visiblelightac cAPR  a5017-50300 v83 a

A series of alkyl group-appended indoline- and carboxylic acid-functionalized indolenine-based visible-light-active unsymmetrical squaraine dyes, SQA7-10, were designed, synthesized, and utilized for the dye-sensitized solar cells device fabrication. The number of alkyl group has been increased systematically on the indoline moiety to control the self-assembly of dyes on TiO2 and to passivate the photoanode that helps in improving the open-circuit voltage (V-OC) by avoiding the charge recombination process. SQA7-10 dyes showed an absorption between lambda(max) 536-540 nm, with molar extinction coefficients of 1.62-2.13 x 10(5) M-1 cm(-1) in CH3CN. Further, ultraviolet-visible (UV-vis) studies on TiO2 indicated the formation of H-aggregated dyes (505-510 nm), which can be controlled by appending the alkyl groups. The energy levels of the highest occupied molecular orbital (HOMO) of these dyes are well aligned with the Nernst potentials of I-/I(3)(-)electrolyte and [Cu(tmby)(2)](+/2+) electrolytes with sufficient overpotentials required for the dye regeneration process. DSSC devices made with these dyes showed systematic enhancements of open-circuit voltage (V-OC) and device efficiency with respect to alkyl group incorporation for SQA7-10 with I-/I-3(-) electrolytes. All of the SQA dyes exhibited the device V-OC of more than 805 mV, where the introduction of alkyl groups systematically enhanced the V-OC in the order of SQA7 (805 mV) < SQA8 (829 mV) < SQA9 (843 mV) < SQA10 (862 mV) without any addition of CDCA. Within the SQA dye series, SQA10 dye has achieved the highest DSSC device efficiency of 7.52% (J(sc) of 11.16 mA/cm(2), V-oc of 862 mV, and ff of 78%) with I-/I-3(-) electrolyte, whereas use of [Cu(tmby)(2)](+/2+) redox shuttle with SQA10 showed enhanced V-oc (1080 mV) and device efficiency (8.35%). The IPCE profile for the device fabricated with SQA dyes showed good response at 480 and 560 nm, which indicates the photocurrent generation from the aggregated structures.

10aaggregation of dyes10acharge recombination10aDye-sensitized solar cells10aindoline and indolenine donors10avisible-light-activeunsymmetrical squaraine dye1 aJadhav, Avinash, P.1 aSingh, Ambarish, Kumar1 aShivankar, Bhavana, R.1 aSiby, Jesna1 aKrishnamurty, Sailaja1 aKrishnamoorthy, Kothandam1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/effect-cyclization-and-alkyl-group-wrapping-visible-light-active-unsymmetrical-squaraine