02322nas a2200229 4500008004100000022001400041245013200055210006900187260000800256300001200264490000800276520148200284653000901766653002101775653002001796653003001816653002501846100002401871700003901895700002701934856013101961 2019 eng d a0143-720800aEffect and position of spiro-bipropylenedioxythiophene pi-spacer in donor-pi-spacer-acceptor dyes for dye-sensitized solar cell0 aEffect and position of spirobipropylenedioxythiophene pispacer i cFEB a313-3230 v1613 a

Improper orientation and self-assembly of dyes on TiO2 surface are the main disadvantages at the dye-TiO2 interface that governs both charge injection and dye regeneration processes. In this report, a series of homo spiro-dimeric donor-pi-spacer-acceptor (D-pi-A) dyes based on bithiophene and terthiophene spacers with two-anchoring group containing dyes, TT1, T1T, TT1T were designed and synthesized by Pd-catalyzed successive Suzuki coupling followed by direct arylation reactions. The position of branching centre in TT1 and T1T was systematically varied, where the spiro unit was placed near and away from the anchoring carboxylic acid unit, respectively. The dimeric spiro-dye T1T showed device performance, which is 1.6 fold higher than its structural isomeric analogue TT1, of 3.9% with a V-oc and J(sc) of 0.593 V and 9.09 mA/cm2, respectively, whereas for the isomeric analogue TT1 a device performance of 2.45% (V-oc of 0.568 V and J(sc) of 6.25 mA/cm2) under simulated 1 Sun (100 mW/cm2) condition. The improved Voc for the dye T1T compared to TT1 dye was ascribed to the dipole moment exerted by the dyes on TiO2 surface. Further the PCE of 4.16% (V-oc 0.589 V, J(sc) 9.79 mA/cm2 respectively) maximum was observed, when an extra thiophene unit was inserted in between the donor and pi-spacer in dye TT1T. The shifting the position of branching spiroBiProDOT pi-spacer makes an impact on the device performance by synergistically enhancing both Voc and Jsc.

10aCDCA10aD-pi-A Spiro dye10aDye aggregation10adye-sensitized solar cell10aspiroBiProDOT spacer1 aSil, Manik, Chandra1 aKavungathodi, Munavvar, Fairoos Me1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/effect-and-position-spiro-bipropylenedioxythiophene-pi-spacer-donor-pi-spacer-acceptor-dyes02335nas 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-cells03762nas a2200265 4500008004100000022001400041245015300055210007000208260000800278300001600286490000600302520279600308653002003104653002003124653003103144653003003175653002803205100002403233700001603257700001703273700001703290700003003307700002703337856013203364 2025 eng d a2574-096200aVisible-light active π-extended unsymmetrical squaraine dyes for dye-sensitized solar cells: steric effects for controlling the aggregation of dyes0 aVisiblelight active πextended unsymmetrical squaraine dyes for d cOCT a15459-154700 v83 a

The dye-anchored TiO2 photoanode plays a vital role in the light harvesting and charge separation processes in dye-sensitized solar cells. Aggregation of dyes (H- and J-type) on the TiO2 surface is a facile process due to the presence of a periodical dye anchoring sites on the exposed facet of titania, and such self-assembled dye structures help broadening the absorption profile. However, photocurrent generation from such aggregated structure is a challenging task in dye-sensitized solar cell devices. Hence, controlling the dye aggregation on the TiO2 surface is an important aspect. Controlling the aggregation of dyes by which (i) an enhanced photocurrent generation (J SC) and (ii) enhanced V OC can be achieved by including the steric factors to the dye design principles, the steric factor in the sensitizer may help passivate the TiO2 surface to avoid the charge recombination process between electrons present in TiO2 and the oxidized electrolyte. On the other hand, extension of pi-conjugation in a sensitizer helps enhance the light absorption in the visible region besides modulating the HOMO and LUMO energy levels. Hence, synergizing both pi-extensions along with features that control the dye aggregation has been considered in designing visible active squaraine dyes. A thiophene pi-spacer was inserted in between a visible-light active unsymmetrical squaraine unit and a cyanoacetic acid acceptor unit to provide the AJ1 and AJ2 dyes. Though both the dye molecules possess a similar pi-framework, the AJ2 dye was functionalized with both in-plane and out-of-plane alkyl groups to decrease the aggregation of dyes on the TiO2 surface compared to AJ1. The AJ1 and AJ2 dyes absorbed at 560 nm with shoulder peaks appeared at 528 nm, which can be assigned to vibronic progression (1082 cm-1), and additional characteristic peaks of thiophene appeared at 392 nm with the molar extinction coefficient of 1.16-1.19 x 105 M-1 cm-1 in CH3CN. The LUMO and HOMO energy levels are well aligned with the conduction band of TiO2 and the redox potential of iodolyte (I-/I3 -) electrolyte with sufficient overpotentials for charge injection and dye regeneration processes, respectively. The highest DSSC device efficiency of 7.37% (J SC 14.44 mA/cm2, V OC 0.771 V, ff 67.1%) was achieved for the AJ2 dye with iodolyte (I-/I3 -) electrolyte in the presence of 2 equiv of optically transparent coadsorbent chenodeoxycholic acid (CDCA), which showed a good IPCE response in between 400 and 700 nm. Further, cosensitization of visible-light active AJ1, AJ2, and SQA10 dyes with a complementary far-red active SQS4 dyes showed the device efficiencies of 5.53% (AJ1:SQS4:CDCA), 7.14% (AJ2:SQS4:CDCA), and 7.18% (SQA10:SQS4:CDCA) with a good IPCE response in the 400-720 nm region.

10acosensitization10aDye aggregation10aDye-sensitized solar cells10api-extended squaraine dye10avisible-lightactivedyes1 aJadhav, Avinash, P.1 aSiby, Jesna1 aPandya, Rinu1 aVanka, Kumar1 aKrishnamoorthy, Kothandam1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/visible-light-active-%CF%80-extended-unsymmetrical-squaraine-dyes-dye-sensitized-solar-cells02133nas a2200229 4500008004100000022001400041245012400055210006900179260000900248300001100257490000800268520131200276653002501588653002001613653003101633653002301664653001901687653002401706100001601730700002701746856013001773 2026 eng d a1010-603000aD-A-D based NIR and visible homodimeric squaraine dyes for dye-sensitized solar cells: Modulation of excitonic coupling0 aDAD based NIR and visible homodimeric squaraine dyes for dyesens cAPR  a1168740 v4733 a

Dye-TiO2 interface plays a crucial role in the overall performance of dye-sensitized solar cells. Anchoring groups help to bind the dye on TiO2 and inject the electrons to the conduction band of TiO2. In this work, a series of homodimeric NIR squaraine dyes C6NIR, C10NIR, and visible squaraine dyes C6VIS, C10VIS are designed and synthesised. These dimeric dyes are covalently connected by decyl or hexyl units between the nonanchoring side of their monomeric unit. Optical spectroscopy in solution and on TiO2 surface indicates that the excitonic coupling between the dyes can be modulated. All the dimeric dyes showed better photovoltaic performance than their corresponding monomeric dyes. The dyes showed device performance SQ1 (1.28%) < C6NIR (2.26%) < C10NIR (2.79%) and AK2 (3.59%) < C6VIS (4.34%) < C10VIS (5.28%) respectively. The dimeric dyes showed better light harvesting efficiency and better passivation of the TiO2 surface. It helps to enhance the device's overall performance by improving the photocurrent and open circuit voltage. The decyl-linked dimeric dyes showed better performance among this set of dyes and C10NIR dyes showed V-oc of 614 mV, J(sc) of 7.08 mA/cm(2), and ff of 64.2%. and C10VIS showed V-oc of 724 mV, J(sc) of 10.74 mA/cm(2), and ff of 67.9%.

10acharge recombination10aDye aggregation10aDye-sensitized solar cells10aDye-TiO2 interface10asquaraine dyes10asurface passivation1 aSiby, Jesna1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/d-d-based-nir-and-visible-homodimeric-squaraine-dyes-dye-sensitized-solar-cells-modulation