Large pi-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(II) bipyridyl complexes have proven to be the most efficient TiO(2) sensitizers in dye-sensitized solar cells. However, a gradual increment in the highest power conversion efficiency has been recognized in the past decade. More importantly, considering that ruthenium is a rare metal, novel dyes without metal or using inexpensive metal are desirable for highly efficient dye-sensitized solar cells. Large pi-aromatic molecules, such as porphyrins, phthalocyanines, and perylenes, are important classes of potential sensitizers for highly efficient dye-sensitized solar cells, owing to their photostability and high light-harvesting capabilities that can 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 TiO(2) cells. Elongation of the pi 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 close 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 TiO(2) surface, tune the level of the excited state, and strengthen the electronic coupling between the phthalocyanine core and the TiO(2) 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 TiO(2) electrode efficiently. Strongly electron-donating perylene carboxylic acid derivatives with amine substituents at their perylene core have allowed us to increase the power conversion efficiency of up to approximately 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.