Theoretical study of nitrogen cation modified aromatics containing thiophene as π-linker for p -type photosensitizers

On the basis of triphenylamine as an electron donor with attachment of two –COOH anchoring groups and dicyanovinyl as acceptor, ten dyes with D-π-A structures were designed to investigate the effects of different π-linker groups on the properties of the sensitizers, especially the influence of the π-linkers containing nitrogen cation (N + ). The optimized structures and electronic and optical properties were investigated by the density functional theory (DFT) and time-dependent DFT (TD-DFT). The results show that all the investigated dyes can be used as dye sensitizers for the p -type dye-sensitized solar cells (DSSCs) except one dye which contains two N + . The N + modified dye (named S3-PZL1C) has narrow energy gap (2.02 eV), the best light-harvesting efficiency (LHE, 0.9974), and the smallest internal reorganization energy ( λ int = 7.00 kcal/mol). Importantly, S3-PZL1C displays the largest red shift of the UV-vis absorption, the maximum integral values of the adsorption-wavelength curves over the visible light (400~800 nm), and the strongest adsorption energy (− 66.84 kcal/mol) on NiO surface. In addition, S3-PZL1C not only enhances the electronic excitation but also improves the reorganization energy and charge separation. The intramolecular charge transfer towards the acceptor is sensitive to the N + position in π-linkers. Therefore, the suitable introduction of N + in dyes can improve the performance of the dyes, and the PZL1C moiety may be a promising π-linker for p -type DSSCs. Graphical abstract