Designing Efficient Metal-Free Dye-Sensitized Solar Cells: A Detailed Computational Study.

The modulation of molecular characteristics in metal-free organic dyes holds significant importance in dye-sensitized solar cells (DSSCs). The D-π-A molecular design, based on the furan moiety (π) in the conjugated spacer between the arylamine (D) and the 2-cyanoacrylic acid (A), was developed and theoretically evaluated for its potential application in DSSCs. Utilizing linear response time-dependent density functional theory (TDDFT) with the CAM-B3LYP functional, different donor and acceptor groups were characterized in terms of the electronic absorption properties of these dyes. All the studied dye sensitizers demonstrate the ability to inject electrons into the semiconductor's conduction band (TiO2) and undergo regeneration through the redox potential triiodide/iodide (I3-/I-) electrode. TDDFT results indicate that the dyes with CSSH anchoring groups exhibit improved optoelectronic properties compared to other dyes. Further, the photophysical properties of all dyes absorbed on a Ti(OH)4 model were explored and reported. The observed results indicate that bidentate chemisorption occurs between dyes and TiO4H5. Furthermore, the HOMO-LUMO energy gaps for almost all dye complexes are significantly smaller than those of the free dyes. This decrease of the HOMO-LUMO energy gaps in the dye complexes facilitates electron excitation, and thus more photons can be adsorbed, guaranteeing larger values of efficiency and short-circuit current density.

Efficient D-π-π-A-Type Dye Sensitizer Based on a Benzothiadiazole Moiety: A Computational Study.

The design of highly efficient sensitizers is one of the most significant areas in dye-sensitized solar cell (DSSC) research. We studied a series of benzothiadiazole-based D-π-π-A organic dyes, putting emphasis on the influence of the donor moiety on the DSSC's efficiency. Using (linear-response time-dependent) density functional theory ((TD)DFT)) with the CAM-B3LYP functional, different donor groups were characterized in terms of electronic absorption spectra and key photovoltaic parameters. As a reference, a dye was considered that had a benzothiadiazole fragment linked via thiophene rings to a diphenylamine donor and a cyanoacrylic-acid acceptor. The different systems were first studied in terms of individual performance parameters, which eventually aggregated into power conversion efficiency. Only the amino-substituted species showed a modest increase, whereas the dimethylamino case showed a decrease.