The role of the donor group and electron-accepting substitutions inserted in π-linkers in tuning the optoelectronic properties of D–π–A dye-sensitized solar cells: a DFT/TDDFT study

Abstract

The design of low-cost and high-efficiency sensitizers is one of the most important factors in the expansion of dye-sensitized solar cells (DSSCs). To obtain effective sensitizer dyes for applications in dye-sensitized solar cells, a series of metal-free organic dyes with the D–π–A–A arrangement and with different donor and acceptor groups have been designed by using computational methodologies based on density functional theory (DFT) and time-dependent density functional theory (TD-DFT). We have designed JK-POZ(1–3) and JK-PTZ(1–3) D–π–A–A organic dyes by modifying the donor and π-linker units of the JK-201 reference dye. Computational calculations of the structural, photochemical properties and electrochemical properties, as well as the key parameters related to the short-circuit current density and open-circuit voltage, including light-harvesting efficiency (LHE), singlet excited state lifetime (τ), reorganization energies (λ_total), electronic injection-free energy (ΔG^inject) and regeneration driving forces (ΔG^reg) of dyes were calculated and analyzed. Moreover, charge transfer parameters, such as the amount of charge transfer (q^CT), the charge transfer distance (D^CT), and dipole moment changes (μ^CT), were investigated. The results show that ΔG^reg, λ_max, λ_total and τ of JK-POZ-3 and JK-PTZ-3 dyes are superior to those of JK-201, indicating that novel JK-POZ-3 and JK-PTZ-3 dyes could be promising candidates for improving the efficiency of the DSSCs devices.