Density Functional Theory Study of Optical and Electronic Properties of (TiO2)n=5,8,68 Clusters for Application in Solar Cells.

A range of solution-processed organic and hybrid organic-inorganic solar cells, such as dye-sensitized and bulk heterojunction organic solar cells have been intensely developed recently. TiO2 is widely employed as electron transporting material in nanostructured TiO2 perovskite-sensitized solar cells and semiconductor in dye-sensitized solar cells. Understanding the optical and electronic mechanisms that govern charge separation, transport and recombination in these devices will enhance their current conversion efficiencies under illumination to sunlight. In this work, density functional theory with Perdew-Burke Ernzerhof (PBE) functional approach was used to explore the optical and electronic properties of three modeled TiO2 brookite clusters, (TiO2)n=5,8,68. The simulated optical absorption spectra for (TiO2)5 and (TiO2)8 clusters show excitation around 200-400 nm, with (TiO2)8 cluster showing higher absorbance than the corresponding (TiO2)5 cluster. The density of states and the projected density of states of the clusters were computed using Grid-base Projector Augmented Wave (GPAW) and PBE exchange correlation functional in a bid to further understand their electronic structure. The density of states spectra reveal surface valence and conduction bands separated by a band gap of 1.10, 2.31, and 1.37 eV for (TiO2)5, (TiO2)8, and (TiO2)68 clusters, respectively. Adsorption of croconate dyes onto the cluster shifted the absorption peaks to higher wavelengths.