Porphyrin sensitizers with π-extended pull units for dye-sensitized solar cells.

New π-extended porphyrin dyes YD26-YD29 with long alkoxyl chains at the ortho positions of the meso-phenyls, and meta di-tert-butylphenyl-substituted porphyrins YD12-CN, and YD13-CN were synthesized for dye-sensitized solar cells, and their optical, electrochemical and photovoltaic properties were investigated and compared with those of YD12 and YD13. The absorption spectra of YD26-YD29 showed a slight red shift of Soret bands and blue shift of Q bands as compared to the meta-substituted porphyrins due to the electron-donating effects of dioctyloxy substituents at the ortho-positions of the meso-phenyl rings. Replacement of the carboxyl with a cyanoacrylic acid as the anchoring group results in significant broadening and red shifts of the absorptions, which is due to the strong electronic coupling between the pull unit and the porphyrin ring facilitated by the C≡C triple bond. The electrochemical studies and quantum-chemical calculations (DFT) indicated that the ortho alkoxy-substituted sensitizers exhibit lower oxidation potential, i.e. a higher HOMO energy level, and their HOMO-LUMO gaps are comparable to the meta-substituted analogues. The photovoltaic measurements confirmed that the ortho-octyloxy groups in the two meso-phenyls of YD26 and YD27 play a significant role in preventing dye aggregation thereby enhancing the corresponding short-circuit current density and open-circuit voltage. The power conversion efficiency (η) of YD26 is 8.04%, which is 11% higher than that of YD12, whereas the efficiency of YD27 is 6.03%, which is 135% higher than that of YD13. On the other hand, the poor performance of YD28 and YD29 is due to the floppy structural nature and limited molecular rigidity of the cyanoacrylic acid anchor.

Novel zinc porphyrin sensitizers for dye-sensitized solar cells: synthesis and spectral, electrochemical, and photovoltaic properties.

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.

Hybrid Titania Photoanodes with a Nanostructured Multi-Layer Configuration for Highly Efficient Dye-Sensitized Solar Cells.

To construct a hybrid titania photoanode containing nanoparticles and nanorods of varied size in a multilayer (ML) configuration for dye-sensitized solar cells, the essence of our ML design is a bilayer system with additional layers of nanorods of well-controlled size inserted between the transparent and the scattering layers to enhance the light-harvesting capability for photosensitizers with small absorptivity, such as Z907. We measured charge-extraction and intensity-modulated photoelectric spectra to show the advantages of one-dimensional nanorods with an improved electron-transport property and an upward shift of the potential band edge; a favorable ML configuration was constructed to have a cascade potential feature for feasible electron transport from long nanorods, to normal nanorods, to small nanoparticles. On the basis of the ML system reported herein, we demonstrate how the performance of a Z907 device is improved to attain η ∼10%, which is a milestone for its future commercialization.

Size-controlled anatase titania single crystals with octahedron-like morphology for dye-sensitized solar cells.

A simple hydrothermal method with titanium tetraisopropoxide (TTIP) as a precursor and triethanolamine (TEOA) as a chelating agent enabled growth in the presence of a base (diethylamine, DEA) of anatase titania nanocrystals (HD1-HD5) of controlled size. DEA played a key role to expedite this growth, for which a biphasic crystal growth mechanism is proposed. The produced single crystals of titania show octahedron-like morphology with sizes in a broad range of 30-400 nm; a typical, extra large, octahedral single crystal (HD5) of length 410 nm and width 260 nm was obtained after repeating a sequential hydrothermal treatment using HD3 and then HD4 as a seed crystal. The nanocrystals of size ~30 nm (HD1) and ~300 nm (HD5) served as active layer and scattering layer, respectively, to fabricate N719-sensitized solar cells. These HD devices showed greater V(OC) than devices of conventional nanoparticle (NP) type; the overall device performance of HD attained an efficiency of 10.2% power conversion at a total film thickness of 28 µm, which is superior to that of a NP-based reference device (η = 9.6%) optimized at a total film thickness of 18-20 µm. According to results obtained from transient photoelectric and charge extraction measurements, this superior performance of HD devices relative to their NP counterparts is due to the more rapid electron transport and greater TiO(2) potential.

Spirally configured cis-stilbene/fluorene hybrids as bipolar, organic sensitizers for solar cell applications.

Hybrids based on a dibenzosuberene core bearing a spiro-fluorene junction at the C-5 position and with amino donor and ß-thiophenyl-α-cyanoacrylic acid acceptor groups at C-3 and C-7, respectively, serve as new organic sensitizer materials for solar cell applications. Solar cell devices based on these materials show a conversion efficiency (η) of up to 6.1% (V(oc) = 697 mV, J(sc) = 12.2 mA cm(-2), FF = 0.72) under AM 1.5 G conditions. The best IPCE values exceed 75% within the 450-550 nm absorption range.

A strategy to design highly efficient porphyrin sensitizers for dye-sensitized solar cells.

We designed highly efficient porphyrin sensitizers with two phenyl groups at meso-positions of the macrocycle bearing two ortho-substituted long alkoxyl chains for dye-sensitized solar cells; the ortho-substituted devices exhibit significantly enhanced photovoltaic performances with the best porphyrin, LD14, showing J(SC) = 19.167 mA cm(-2), V(OC) = 0.736 V, FF = 0.711, and overall power conversion efficiency η = 10.17%.