title: Novel zinc porphyrin sensitizers for dye-sensitized solar cells: synthesis and spectral, electrochemical, and photovoltaic properties.
abstract: Novel meso- or beta-derivatized porphyrins with a carboxyl group have been designed and synthesized for use as sensitizers in dye-sensitized solar cells (DSSCs). The position and nature of a bridge connecting the porphyrin ring and carboxylic acid group show significant influences on the spectral, electrochemical, and photovoltaic properties of these sensitizers. Absorption spectra of porphyrins with a phenylethynyl bridge show that both Soret and Q bands are red-shifted with respect to those of porphyrin 6. This phenomenon is more pronounced for porphyrins 3 and 4, which have a pi-conjugated electron-donating group at the meso position opposite the anchoring group. Upon introduction of an ethynylene group at the meso position, the potential at the first oxidation alters only slightly whereas that for the first reduction is significantly shifted to the positive, thus indicating a decreased HOMO-LUMO gap. Quantum-chemical (DFT) results support the spectroelectrochemical data for a delocalization of charge between the porphyrin ring and the amino group in the first oxidative state of diarylamino-substituted porphyrin 5, which exhibits the best photovoltaic performance among all the porphyrins under investigation. From a comparison of the cell performance based on the same TiO(2) films, the devices made of porphyrin 5 coadsorbed with chenodeoxycholic acid (CDCA) on TiO(2) in ratios [5]/[CDCA] = 1:1 and 1:2 have efficiencies of power conversion similar to that of an N3-based DSSC, which makes this green dye a promising candidate for colorful DSSC applications.
authors.affiliation: Department of Chemistry, National Chung Hsing University, Taichung 402, Taiwan.
authors.forename: Cheng-Wei
authors.initials: CW
authors.lastname: Lee
authors.forename: Hsueh-Pei
authors.initials: HP
authors.lastname: Lu
authors.forename: Chi-Ming
authors.initials: CM
authors.lastname: Lan
authors.forename: Yi-Lin
authors.initials: YL
authors.lastname: Huang
authors.forename: You-Ren
authors.initials: YR
authors.lastname: Liang
authors.forename: Wei-Nan
authors.initials: WN
authors.lastname: Yen
authors.forename: Yen-Chun
authors.initials: YC
authors.lastname: Liu
authors.forename: You-Shiang
authors.initials: YS
authors.lastname: Lin
authors.forename: Eric Wei-Guang
authors.initials: EW
authors.lastname: Diau
authors.forename: Chen-Yu
authors.initials: CY
authors.lastname: Yeh