The iodide/triiodide redox shuttle has limited the efficiencies accessible in dye-sensitized solar cells. Here, we report mesoscopic solar cells that incorporate a Co((II/III))tris(bipyridyl)-based redox electrolyte in conjunction with a custom synthesized donor-π-bridge-acceptor zinc porphyrin dye as sensitizer (designated YD2-o-C8). The specific molecular design of YD2-o-C8 greatly retards the rate of interfacial back electron transfer from the conduction band of the nanocrystalline titanium dioxide film to the oxidized cobalt mediator, which enables attainment of strikingly high photovoltages approaching 1 volt. Because the YD2-o-C8 porphyrin harvests sunlight across the visible spectrum, large photocurrents are generated. Cosensitization of YD2-o-C8 with another organic dye further enhances the performance of the device, leading to a measured power conversion efficiency of 12.3% under simulated air mass 1.5 global sunlight.

Dye-sensitized solar cells (DSCs) are currently attracting considerable attention because of their high light-to-electricity conversion efficiencies, ease of fabrication, and low production costs.[1] Many recent efforts have been devoted to the development of new and efficient sensitizers that are suitable for practical use. Among the investigated compounds, ruthenium sensitizers have been distinguished by attaining more than 11 % efficiencies.[2] Organic sensitizers have also attracted great interest because of their modest cost, ease of synthesis and modification, large molar absorption coefficients, and satisfactory stability. Organic dyes with conversion efficiencies in the range of 5-10 % have been reported. [3][4][5][6][7][8][9][10][11] Porphyrins show strong absorption and emission in the visible region as well as tunable redox potentials. These properties lead to promising applications in many areas, such as optoelectronics, chemosensors, and catalysis.[12]Self-assembled porphyrin molecular structures play a key role in solar energy research as the photosynthetic systems of bacteria and plants contain chromophores based on lightharvesting porphyrins, [13] which collect solar energy and convert it efficiently into chemical energy. Various artificial photosynthetic model systems have been designed and synthesized in order to elucidate the factors that control the photoinduced electron-transfer reaction. [14] Inspired by the efficient energy transfer in naturally occurring photosynthetic reaction centers, numerous porphyrins [15] and phthalocyanines [16] have been synthesized and tested in dye-sensitized solar cells. The best-performing porphyrin dyes have been reported to have conversion efficiencies in DSCs in the range of 5-7 %.[17] A recently reported series of porphyrin dyes with donor-acceptor (D-A) substituents exhibit promising photovoltaic properties.[18]Herein we report the achievement of an 11 % solar-toelectric power conversion efficiency under standard (AM 1.5G, 100 mW cm À2 intensity) reporting conditions by using a judiciously tailored porphyrin dye, YD-2. To the best of our knowledge, this is the first time such a high efficiency has been obtained with a ruthenium-free sensitizer.The structure of the YD-2 porphyrin used in this study is shown in Scheme 1. A diarylamino donor group attached to the porphyrin ring acts as an electron donor, and the ethynylbenzoic acid moiety serves as an acceptor. The porphyrin chromophore itself constitutes the p bridge in this particular D-p-A structure.[18] In a first set of experiments, 2.4 mm thick transparent TiO 2 films loaded with a monolayer of YD-2 were employed in order to accurately measure the spectral response and the internal quantum efficiency of the device. Figure 1 shows the incident photon to current conversion efficiency (IPCE) as a function of the light excitation wavelength. The features of the spectral response of the photocurrent closely match the absorption spectrum of the YD-2 dye. At 460 nm, near the Soret band maximum, the IPCE reach...

Porphyrins have drawn much attention as sensitizers owing to the large absorption coefficients of their Soret and Q bands in the visible region. In a donor and acceptor zinc porphyrin we applied a new strategy of introducing 2,1,3-benzothiadiazole (BTD) as a π-conjugated linker between the anchoring group and the porphyrin chromophore to broaden the absorption spectra to fill the valley between the Soret and Q bands. With this novel approach, we observed 12.75% power-conversion efficiency under simulated one-sun illumination (AM1.5G, 100 mW cm(-2)). In this study, we showed the importance of introducing the phenyl group as a spacer between the BTD and the zinc porphyrin in achieving high power-conversion efficiencies. Time-resolved fluorescence, transient-photocurrent-decay, and transient-photovoltage-decay measurements were employed to determine the electron-injection dynamics and the lifetime of the photogenerated charge carriers.

We report the photovoltaic performances and kinetics of femtosecond fluorescence for three zinc-porphyrin sensitizers (YD0-YD2) coadsorbed with chenodeoxycholic acid (CDCA) at three molar ratios on nanocrystalline semiconductor (TiO(2) or Al(2)O(3)) films. The addition of CDCA improved the efficiencies of YD0 and YD1 so that their maximum performance occurred at a dye/CDCA ratio of 1:2, but the presence of CDCA had a negative effect for YD2. Porphyrin aggregation on TiO(2) surfaces not only accelerates the rate of intermolecular energy transfer but also increases the rate of interfacial electron injection, so that the electron injection yields (Phi(inj)) are balanced by these two important factors. As a result, Phi(inj) increased slightly with increasing amount of CDCA for both YD0 and YD1, but decreased for YD2; for this reason, the presence of CDCA failed to improve the photovoltaic performance for YD2, unlike for YD0 and YD1. The cell performances were optimized on TiO(2) films of similar to 10-mu m thickness with a scattering layer of similar to 4-mu m thickness: the efficiencies 4 if power conversion of YD1 and YD2 are slightly smaller than, but near, that of N719, being 6.5% and 6.8%, respectively, compared to 7.3%. Without a scattering layer on the films, the performance of N719 was degraded significantly (6.3%), whereas the efficiencies of YD1 and YD2 decreased only slightly (6.4% and 6.6%), making this series of green sensitizers promising candidates for future light-penetrable photovoltaic applications

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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.

A series of porphyrin dyes with an electron-donating group (EDG) attached at a meso-position (YD1-YD8) have been designed and synthesized for use as sensitizers in dye-sensitized solar cells (DSSC). The nature of the EDG exerts a significant influence on the spectral, electrochemical and photovoltaic properties of these sensitizers. Absorption spectra of porphyrins having an amino group show broadened Soret band and red-shifted Q bands with respect to those of reference porphyrin YD0. This phenomenon is more pronounced for porphyrins YD7 and YD8 that have a pi-conjugated triphenylamine at the meso-position opposite the anchoring group. Upon introduction of an EDG at the meso-position, the potential for the first oxidation alters significantly to the negative whereas that for the first reduction changes inappreciably, indicating a decreased HOMO-LUMO gap. Results of density-functional theory (DFT) calculations 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 porphyrins YD1-YD4, which exhibit superior photovoltaic performance among all porphyrins under investigation. With long-chain alkyl groups on the diarylamino substituent, YD2 shows the best cell performance with J(SC) = 13.4 mA cm(-2), V(OC) = 0.71 V, and FF = 0.69, giving an overall efficiency 6.6% of power conversion under simulated one-sun AM1.5 illumination

Co-sensitization of two or more dyes with complementary absorption spectra on a semiconductor film is an effective approach to enhance the performance of a dye-sensitized solar cell (DSSC). Porphyrin sensitizer YD2-oC8 showed outstanding photovoltaic performance co-sensitized with an organic dye to cover the entire visible spectral region, 400–700 nm. To promote the light-harvesting capability beyond 700 nm, a porphyrin dimer (YDD6) was synthesized for a co-sensitized system. We report a systematic approach for engineering of molecular co-sensitization of TiO2 films in a cocktail solution containing YD2-oC8, an organic dye (CD4) and YDD6 in a specific molar ratio to optimize the photovoltaic performance of the device. The resulting device showed panchromatic spectral features in the IPCE action spectrum in the region 400–700 nm attaining efficiencies of 75–80%; the spectrum is extended to the near-IR region attaining 40–45% in 700–800 nm region, giving JSC/mA cm 2 ¼ 19.28, VOC/mV ¼ 753, FF ¼ 0.719, and h ¼ 10.4% under standard AM 1.5 G one-sun irradiation. This performance is superior to what is obtained from the individual single-dye devices and the two-dye co-sensitized systems. The shifts of TiO2 potential upon dye uptake and the kinetics of charge recombination were examined through measurements of the charge extraction (CE) and intensity-modulated photovoltage spectroscopy (IMVS), respectively. Five co-sensitized systems were investigated to demonstrate that suppression of dye aggregation of YDD6 in the co-sensitized film is a key factor to further improve the device performance