Panchromatic Sensitizer for Dye-Sensitized Solar Cells: Unsymmetrical Squaraine Dyes Incorporating Benzodithiophene π-Spacer with Alkyl Chains to Extend Conjugation, Control the Dye Assembly on TiO2, and Retard Charge Recombination

Metal-free near-infrared (NIR) active unsymmetrical squaraine dyes, RSQ1 and RSQ2, with benzodithiophene (BDT) pi-spacer and cyanoacrylic acid acceptor were synthesized by utilizing palladium catalyzed direct (hetero)arylation reaction. Methyl and 2-ethylhexyl groups were strategically placed at the BDT unit for RSQ1 and RSQ2, respectively, to investigate the effect of alkylated pi-spacer on dye aggregation on the TiO2 surface and recombination reactions at TiO2/dye/electrolyte interface. These dyes have strong absorption (epsilon > 10(5) M-1 cm(-1)) in near-infrared (NIR) region and exhibit similar optical and electrochemical properties as they have same conjugated framework. RSQ2 performed better than RSQ1 owing to its higher open-circuit voltage (V-oc) and fill factor (ff) in spite of having comparable short-circuit current density (J(SC)). The panchromatic incident photon-to-current conversion efficiency (IPCE) response was also observed for both the dyes. RSQ2 showed power conversion efficiency (PCE) of 6.72% with short-circuit current density (J(SC)) of 18.53 mA/cm(2), open circuit voltage (V-oc) of 0.538 V, and fill factor (ff) of 67.4%, without any coadsorbent. Attenuation of the charge recombination for RSQ2 was revealed by electrochemical impedance analysis (EIS) and open-circuit potential decay transients (OCVD), which attributes to its higher V-OC and ff in comparison to RSQ1.