Effect of the second chromophore energy gap on photo-induced electron injection in di-chromophoric porphyrin-sensitized solar cells

This work investigates the effect of the second chromophore energy gap on charge generation in porphyrin-based di-chromophoric dye-sensitized solar cells (DSSCs). Three di-chromophoric porphyrin dyes (PorY, PorO and PorR) containing three organic chromophores with decreasing frontier orbital energy offsets, including a carbazole-triphenylamine chromophore (yellow, Y), a carbazole fused-thiophene chromophore (orange, O) or a carbazole-thiophene benzothiadiazole thiophene chromophore (red, R), were investigated using optical and electrochemical methods, steady-state photoluminescence and photovoltaic device characterization. Energy transfer from the organic chromophore to the porphyrin was suggested in PorY and PorO as the main charge generation mechanism in DSSCs using these di-chromophoric dyes. On the other hand, electron transfer from the photo-excited porphyrin to the organic chromophore as a competing pathway leading to the loss of photocurrent is suggested for PorR-sensitized solar cells. The latter pathway leading to a loss of photocurrent is due to the lower lying lowest unoccupied molecular orbital of the additional organic chromophore (R) and suggests the limitation of the current di-chromophoric approach to increase the overall efficiency of DSSCs.