Simple diphenylamine based D–π–A type sensitizers/co-sensitizers for DSSCs: a comprehensive study on the impact of anchoring groups

Abstract

Herein, we report the design, synthesis and characterization of a new series of simple donor–π spacer–acceptor/anchor (D–π–A) type diphenylamine based metal-free organic dyes possessing three different anchoring groups, viz. 4-aminobenzoic acid (DTP), 2-(4-nitrophenyl)acetonitrile (DTN), and barbituric acid (DTB), connected with 2-(thiophene-2-yl)-acetonitrile, as effective sensitizers and co-sensitizers in Dye Sensitized Solar Cells (DSSCs). They were subjected to photophysical, electrochemical and theoretical studies. The dyes exhibited characteristic λ_abs and λ_emi in the range of 445–485 and 545–570 nm, respectively. Both optical and electrochemical band gaps were found to be in the range of 2.2 to 2.35 eV. The driving forces for injection (ΔG_inj), recombination (ΔG_rec) and regeneration (ΔG_reg) processes were evaluated to understand their feasibility. Finally, the DSSC devices were fabricated employing the new dyes as sensitizers as well as co-sensitizers along with the Ru(II) based N3 dye. Interestingly, DTP carrying 4-aminobenzoic acid as the anchoring group shows the best photoelectrochemical performance, viz. photovoltaic conversion efficiency (PCE) = 4.4%, open circuit potential (V_OC) = 0.577 V, and short-circuit current density (J_SC) = 9.06 mA cm⁻² with a broad incident photon conversion efficiency (IPCE) spectrum. Co-sensitization of the dyes brought about enhanced V_OC values, compared to the N3 dye alone. Finally, different interface resistance values obtained from the electrochemical impedance spectroscopy (EIS) circuit fitting were used to study the fundamental processes of energy conversion.