Influence of Donor Groups of Organic D−π–A Dyes on Open-Circuit Voltage in Solid-State Dye-Sensitized Solar Cells

In solid-state dye-sensitized solar cells (ssDSCs), the poor pore filling of the mesoporous semiconductor and the short diffusion length of charge carriers in the hole-transport material (HTM) have limited the mesoscopic titania layer to a thickness of 2–3 μm. To increase the amount of light harvested by ssDSCs, organic dyes with high molar extinction coefficients are of great importance and have been the focus of intensive research. Here we investigate ssDSCs using an organic D−π–A dye, coded Y123, and 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene as a hole-transport material, exhibiting 934 mV open-circuit potential and 6.9% efficiency at standard solar conditions (AM1.5G, 100 mW cm^–2), which is a significant improvement compared to the analogue dyes C218, C220, and JK2 (V_oc values of 795, 781, and 914 mV, respectively). An upward shift in the conduction band edge was observed from photovoltage transient decay and impedance spectroscopy measurements for devices sensitized with Y123 and JK2 dyes compared to the device using C220 as sensitizer, in agreement with the high photovoltage response of the corresponding ssDSCs. This work highlights the importance of the interaction between the HTM and the dye-sensitized TiO₂ surface for the design of ssDSCs.