Large π-Aromatic Molecules as Potential Sensitizers for Highly Efficient Dye-Sensitized Solar Cells

Recently, dye-sensitized solar cells have attracted much attention relevant to global environmental issues. Thus far, ruthenium(11) bipyridyl complexes have proven be the most efficient TiO2 sensitizers in dye-sensitized solar cells. However, a gradual increment in the highest power conversion efficiency has been recognized in the decade. More importantly, considering that ruthenium is a rare metal, novel dyes metal or using inexpensive metal are desirable for highly efficient dye-sensitized solar cells. Large pi-aromatic molecules, such as porphydris, phthalocyanines, and are important classes of potential sensitizers for highly efficient dye-sensitized-solar cells, owing to their photostability and high light-harvesting capabilities that allow applications in thinner, low-cost dye-sensitized solar cells. Porphyrins possess an intense Soret band at 400 nm and moderate Q bands at 600 nm. Nevertheless, the poor light-harvesting properties relative to the ruthenium complexes have limited the cell performance of porphyrin-sensitized TiO2 cells. Elongation of the T conjugation and loss of symmetry in porphyrins cause broadening and a red shift of the absorption bands together with an increasing intensity of the Q bands relative to that of the Soret band. On the basis of the strategy, the cell performance of porphyrin-sensitized solar cells has been improved intensively by the enhanced light absorption. Actually, some push-pull-type porphyrins have disclosed a remarkably high power conversion efficiency (6-7%) that was dose to that of the ruthenium complexes. Phthalocyanines exhibit strong absorption around 300 and 700 nm and redox features that are similar to porphyrins. Moreover, phthalocyanines are transparent over a large region of the visible spectrum, thereby enabling the possibility of using them as photovoltaic windows. However, the cell performance was poor, owing to strong aggregation and lack of directionality in the excited state. Novel unsymmetrical zinc phthalocyanine sensitizers with push and 'pull groups have made it possible to reduce the aggregation on a TiO2 surface, tune the level of the excited state, and strengthen the electronic coupling between the phthalocyanine core and the TiO2 surface. As a result, the power conversion efficiency of up to 3.5% has been achieved. Perylenes are well-known as chemically, thermally, and photophysically stable dyes and have been used in various optical devices and applications. Nevertheless, the power conversion efficiency remained low compared to other organic dyes. The origin of such limited cell performance is the poor electron-donating abilities of the perylenes, which makes it difficult to inject electrons from the excited singlet state of the perylenes to the conduction band of the TiO2 electrode efficiently. Strongly electron-donating perylene carboxylic add derivatives with amine substituents at their perylene core have allowed us to increase the power conversion efficiency of up to similar to 7% in perylene-sensitized solar cells. The efficiency of large pi-aromatic molecule-sensitized solar cells could be improved significantly if the dyes with larger red and near-infrared absorption could be developed.