Yamato Fujimori

Highly Asymmetrical Porphyrins with Enhanced Push–Pull Character for Dye‐Sensitized Solar Cells

A porphyrin π-system has been modulated by enhancing the push-pull character with highly asymmetrical substitution for dye-sensitized solar cells for the first time. Namely, both two diarylamino moieties as a strong electron-donating group and one carboxyphenylethynyl moiety as a strong electron-withdrawing, anchoring group were introduced into the meso-positions of the porphyrin core in a lower symmetrical manner. As a result of the improved light-harvesting property as well as high electron distribution in the anchoring group of LUMO, a push-pull-enhanced, porphyrin-sensitized solar cell exhibited more than 10% power conversion efficiency, which exceeded that of a representative highly efficient porphyrin (i.e., YD2)-sensitized solar cell under optimized conditions. The rational molecular design concept based on highly asymmetric, push-pull substitution will open the possibilities of further improving cell performance in organic solar cells.

Tropolone as a High-Performance Robust Anchoring Group for Dye-Sensitized Solar Cells

A tropolone group has been employed for the first time as an anchoring group for dye-sensitized solar cells (DSSCs). The DSSC based on a porphyrin, YD2-o-C8T, with a tropolone moiety exhibited a power-conversion efficiency of 7.7 %, which is only slightly lower than that observed for a reference porphyrin, YD2-o-C8, with a conventional carboxylic group. More importantly, YD2-o-C8T was found to be superior to YD2-o-C8 with respect to DSSC durability and binding ability to TiO2 . These results unambiguously demonstrate that tropolone is a highly promising dye-anchoring group for DSSCs in terms of device durability as well as photovoltaic performance.

Effects of Bulky Substituents of Push-Pull Porphyrins on Photovoltaic Properties of Dye-Sensitized Solar Cells.

To evaluate the effects of substituent bulkiness around a porphyrin core on the photovoltaic properties of porphyrin-sensitized solar cells, long alkoxy groups were introduced at the meso-phenyl group (ZnPBAT-o-C8) and the anchoring group (ZnPBAT-o-C8Cn, n = 4, 8) of an asymmetrically substituted push-pull porphyrin with double electron-donating diarylamino groups and a single electron-withdrawing carboxyphenylethynyl anchoring group. The spectroscopic and electrochemical properties of ZnPBAT-o-C8 and ZnPBAT-o-C8Cn were found to be superior to those of a push-pull porphyrin reference (YD2-o-C8), demonstrating their excellent light-harvesting and redox properties for dye-sensitized solar cells. A power conversion efficiency (η) of the ZnPBAT-o-C8-sensitized solar cell (η = 9.1%) is higher than that of the YD2-o-C8-sensitized solar cell (η = 8.6%) using iodine-based electrolyte due to the enhanced light-harvesting ability of ZnPBAT-o-C8. In contrast, the solar cells based on ZnPBAT-o-C8Cn, possessing the additional alkoxy chains in the anchoring group, revealed the lower η values of 7.3% (n = 4) and 7.0% (n = 8). Although ZnPBAT-o-C8Cn exhibited higher resistance at the TiO2-dye-electrolyte interface by virtue of the extra alkoxy chains, the reduced amount of the porphyrins on TiO2 by excessive addition of coadsorbent chenodeoxycholic acid (CDCA) for mitigating the aggregation on TiO2 resulted in the low η values. Meanwhile, the ZnPBAT-o-C8-sensitized solar cell showed the lower η value of 8.1% than the YD2-o-C8-sensitized solar cell (η = 9.8%) using cobalt-based electrolyte. The smaller η value of the ZnPBAT-o-C8-sensitized solar cell may be attributed to the insufficient blocking effect of the bulky substituents of ZnPBAT-o-C8 under the cobalt-based electrolyte conditions. Overall, the alkoxy chain length and substitution position around the porphyrin core are important factors to affect the cell performance.

A new class of epitaxial porphyrin metal–organic framework thin films with extremely high photocarrier generation efficiency: promising materials for all-solid-state solar cells

We demonstrate the fabrication of a new class of epitaxial porphyrin metal–organic framework thin films whose photophysical properties can be tuned by the introduction of electron-donating diphenylamine (DPA) groups into the porphyrin skeleton. The attachment of DPA groups results in strongly improved absorption characteristics, yielding the highest photocarrier generation efficiency reported so far. DFT calculations identify a shift of the charge localization pattern in the VBM (lowest unoccupied molecular orbital), confirming that the introduction of the DPA groups is the main reason for the shift of the optical absorption spectrum and the improved photocurrent generation.

Effects of Immersion Solvent on Photovoltaic and Photophysical Properties of Porphyrin-Sensitized Solar Cells.

Memory effects in self-assembled monolayers (SAMs) of zinc porphyrin carboxylic acid on TiO2 electrodes have been demonstrated for the first time by evaluating the photovoltaic and electron transfer properties of porphyrin-sensitized solar cells prepared by using different immersion solvents sequentially. The structure of the SAM of the porphyrin on the TiO2 was maintained even after treating the porphyrin monolayer with different neat immersion solvents (memory effect), whereas it was altered by treatment with solutions containing different porphyrins (inverse memory effect). Infrared spectroscopy shows that the porphyrins in the SAM on the TiO2 could be exchanged with the same or analogous porphyrin, leading to a change in the structure of the porphyrin SAM. The memory and inverse memory effects are well correlated with a change in porphyrin geometry, mainly the tilt angle of the porphyrin along the long molecular axis from the surface normal on the TiO2, as well as with kinetics of electron transfer between the porphyrin and TiO2. Such a new structure-function relationship for DSSCs will be very useful for the rational design and optimization of photoelectrochemical and photovoltaic properties of molecular assemblies on semiconductor surfaces.

Synthesis of push–pull porphyrin with two electron-donating and two electron-withdrawing groups and its application to dye-sensitized solar cell

We synthesized for the first time a push–pull porphyrin dye bearing two diarylamino groups and two carboxyphenylethynyl groups as electron-donating and electron-withdrawing anchoring groups, respectively. The absorption spectrum displayed broad and red-shifted absorption, achieving panchromic light-harvesting in visible and NIR regions. Introduction of multiple push–pull groups into meso-positions is a promising strategy for the rational design of porphyrin sensitizers for light-harvesting applications. The preliminary photovoltaic performance is moderate (3.0%), but the extensive photocurrent generation matches with the excellent light-harvesting ability. Further modulation of the photovoltaic properties of porphyrin DSSCs will be possible by suitable selection of electron-donating and electron-withdrawing groups as well as introduction of the substituents into the porphyrin core.

A Hydroxamic Acid Anchoring Group for Durable Dye-Sensitized Solar Cells Incorporating a Cobalt Redox Shuttle

A hydroxamic acid group has been employed for the first time as an anchoring group for cobalt-based dye-sensitized solar cells (DSSCs). The porphyrin dye YD2-o-C8HA including a hydroxamic acid anchoring group exhibited a power conversion efficiency (η) of 6.4 %, which is close to that of YD2-o-C8, a representative porphyrin dye incorporating a conventional carboxylic acid. More importantly, YD2-o-C8HA was found to be superior to YD2-o-C8 in terms of both binding ability to TiO2 and durability of cobalt-based DSSCs. Notably, YD2-o-C8HA photocells revealed a higher η-value (4.1 %) than YD2-o-C8 (2.8 %) after 500 h illumination. These results suggest that the hydroxamic acid can be used for DSSCs with other transition-metal-based redox shuttle to ensure high cell durability as well as excellent photovoltaic performance.

Structural Effects on the Incident Photon-to-Current Conversion Efficiency of Zn Porphyrin Dyes on the Low-Index Planes of TiO2

The structural effects of substrates on the incident photon-to-current conversion efficiency (IPCE) of Zn porphyrin (ZnP) dyes (ZnP-ref, YD2, and ZnPBAT) have been studied on well-defined single-crystal surfaces of rutile TiO2 (TiO2(111), TiO2(100), and TiO2(110)). IPCE of ZnP-ref depends on the structure of the substrates remarkably: TiO2(100) < TiO2(110) < TiO2(111). IPCE of ZnP-ref/TiO2(111) is 13 times as high as that of ZnP-ref/TiO2(100) at 570 nm. YD2 and ZnPBAT also give the highest IPCE on TiO2(111). The relative coverages of the porphyrin dyes give the following order: TiO2(111) < TiO2(110) < TiO2(100). This order is opposite to that of IPCEs. The orientation of the dyes is predicted using density functional theory calculations on simplified models of TiO2 surfaces. The highest IPCE on TiO2(111) is attributed to the high rate of electron transfer through the space due to the fluctuation of the tilt angle of the adsorbed dyes.