A DFT study to probe homo-conjugated norbornylogous bridged spacers in dye-sensitized solar cells: an approach to suppressing agglomeration of dye molecules

This work reports a sigma-bridged framework as spacers to design new dye-sensitized solar cells. The norbornylogous bridged spacer can avoid π–π aggregation of dye molecules on the semiconductor surface in DSSCs. These sesquinorbornatrienes are known to exhibit electron propagation through the interaction of sigma and π orbitals via through bond (OITB) and through space (OITS) mechanisms. Density functional theory (DFT) calculations performed with these spacers and a modelled simple donor unit like N,N-dimethylamine and cyanoacrylic acid as the anchoring group showed significant results with the requisite optical parameters for DSSCs. The newly designed dyes have shown comparable or better optical properties compared to the reference dye molecule with π-conjugated thiophene spacer units. The ΔG(injection), V(OC) and μ(normal) values calculated for the designed dyes were found to be higher than those of the reference system. The trans-sesquinorbornatriene system spacer (6-D) showed a V(OC) of 3.3 eV, ΔG(injection) of 2.4 eV and oscillatory strength (f) of 0.96. The total and partial density of states indicates a good communication between the valence and conduction band for the designed dyes. Transition density matrix results suggest that the exciton dissociation in the excited state is sufficiently high to overcome the coulombic attraction of the hole. These results are promising for the design of dye molecules with such scaffolds, to achieve better efficiency and to eliminate one of the major issues with π-spacer units in DSSCs.