Computational study of diketopyrrolopyrrole-based organic dyes for dye sensitized solar cell applications

•We studied four organic dyes incorporating DPPs moieties.•Electron-deficient DPPs show great effect on spectra and electrochemical properties.•Newly designed DPP-I show desirable energetic and spectroscopic parameters.•We provide theoretical guidance for design of DPP dyes for DSSC optimizations. Four diketopyrrolopyrrole (DPP)-based organic dyes utilizing the donor–π-acceptor motif were investigated by density functional theory (DFT) and time-dependent DFT (TDDFT) approaches. The four dyes were composed of different donor groups, i.e. indoline, carbazole, triphenylamine, and coumarin. We investigated the effects of the DPP unit and different donors on the spectra and electrochemical properties of the dyes, respectively. In comparison with the model dye which adopts a phenylene unit as the π-spacer, the DPP dyes all display remarkably enhanced spectral responses in the visible region of the solar spectrum. The key to this increase was the incorporation of electron-deficient DPP moieties to the molecular core, which significantly lowers LUMO levels and therefore reduces the band gap. The dye/(TiO2)46 anatase nanoparticle systems were also simulated to show the electronic structures at the interface. We studied some key properties including absorption spectra, light-harvesting efficiency, molecular orbital distributions, and injection time of electrons from the excited state of dye to the conduction band of TiO2. The dye DPP-I with indoline moiety as the electron donor demonstrates desirable energetic, electronic, and spectroscopic parameters for dye sensitized solar cells (DSSCs) applications. Our theoretical study is expected to provide valuable insights into the molecular design of novel DPP-based organic dyes for the optimizations of DSSCs.