Alkyl-Group-Wrapped Unsymmetrical Squaraine Dyes for Dye-Sensitized Solar Cells: Branched Alkyl Chains Modulate the Aggregation of Dyes and Charge Recombination Processes

Abstract

Electron transfer processes at the interfaces dictate the factors that improve the photovoltaic parameters, such as open-circuit voltage (<i>V</i>_oc) and short-circuit current (<i>J</i>_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 <i>J</i>_sc and <i>V</i>_oc. Hence, tailoring the factors that govern the improvement of <i>J</i>_sc and <i>V</i>_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 sp³-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 <i>V</i>_oc from 672 (SQS1) to 718 mV (SQS6) and <i>J</i>_sc from 7.95 (SQS1) to 12.22 mA/cm² (SQS6), with the device efficiency ranging from 3.82% to 6.23% without any coadsorbent. Dye SQS4 achieves the highest efficiency of 7.1% (<i>V</i>_oc = 715 mV, <i>J</i>_sc = 13.05 mA/cm²) with coadsorbent chenodeoxycholic acid (CDCA) using an iodine (<i>I</i>^-/<i>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.