Effects of Porphyrin Substituents and Adsorption Conditions on Photovoltaic Properties of Porphyrin-Sensitized TiO₂ Cells

A series of meso-tetraphenylzincporphyrins have been prepared to examine the effects of the porphyrin substituents and adsorption conditions on photovoltaic properties of the porphyrin-sensitized TiO2 cells. The cell performance strongly depended on the linking bridge between the porphyrin core and the TiO2 surface, the bulkiness around the porphyrin core, and the immersing solvents and times for the porphyrin adsorption. In particular, the high cell performance of the porphyrin-sensitized TiO2 cells was achieved when protic solvent (i.e., methanol) and short immersing time (0.5−1 h) were used for the conditions of the dye adsorption on TiO2, which is in sharp contrast with Ru dye-sensitized TiO2 cells. The highest cell performance was obtained with 5-(4-carboxyphenyl)-10,15,20-tris(2,4,6-trimethylphenyl)porphyrinatozinc(II) as a sensitizer and methanol as an immersing solvent with an immersing time of 1 h: a maximal incident photon-to-current efficiency of 76%, a short circuit photocurrent density of 9.4 mA cm−2, an open-circuit voltage of 0.76 V, a fill factor of 0.64, and a power conversion efficiency of 4.6% under standard AM 1.5 sunlight. These results will provide basic and valuable information on the development of dye-sensitized solar cells exhibiting a high performance

An Unsymmetrical 5,15-Disubstituted Tetrabenzoporphyrin: Effect of Molecular Symmetry on the Packing Structure and Charge Transporting Property

Molecular design strategy to control the crystal structure of two-dimensional (2D) π-extended organic semiconductors has not been intensively explored. We synthesized an unsymmetric tetrabenzoporphyrin derivative (TIPS-Ph-BP) to demonstrate the effect of molecular symmetry on crystal packing. TIPS-Ph-BP formed an antiparallel slipped π-stacking and 2D herringbone-like structure. An unsymmetric structure would make 2D π-stacking more stable than a one-dimensional (1D) columnar structure to counteract steric and electronic imbalance in the crystal. As a result, TIPS-Ph-BP achieved the high hole mobility of 0.71 cm2 V–1 s–1

Naphthyl-Fused π-Elongated Porphyrins for Dye-Sensitized TiO₂ Cells

Novel unsymmetrically π-elongated porphyrins, in which the naphthyl moiety is fused to the porphyrin core at the naphthyl bridge with a carboxyl group (fused-Zn-1) or at the opposite side of the phenyl bridge with a carboxyl group (fused-Zn-2), have been synthesized to improve the light-harvesting abilities in porphyrin-sensitized solar cells. As the results of π-elongation with low symmetry, Soret and Q bands of fused-Zn-1 and fused-Zn-2 were red-shifted and broadened, and the intensity of Q-band relative to that of Soret band was enhanced. The fused-Zn-1 and fused-Zn-2-sensitized TiO2 solar cells showed the power conversion efficiencies (η) of 4.1% and 1.1%, respectively, under standard AM 1.5 conditions. The η value of the fused-Zn-1 cell was improved by 50% compared to the reference cell using unfused porphyrin (Zn-1). The fused-Zn-1-sensitized cell revealed high IPCE (incident photon-to-current efficiency) values of up to 55%, extending the response of photocurrent generation close to 800 nm. Thus, the improved photocurrent generation of the fused-Zn-1-sensitized cell relative to the Zn-1-sensitized reference cell is responsible for the remarkable difference in the η values. The η value of the fused-Zn-2 cell was much lower than that of the fused-Zn-1 cell. DFT calculations disclosed that there are significant electron densities on the carboxyl group in the LUMO of fused-Zn-1, whereas there are little electron densities on the carboxyl group in the LUMO of fused-Zn-2. Accordingly, the larger electronic coupling between the porphyrin and the TiO2 surface in the fused-Zn-1-sensitized cell may be responsible for the high cell performance, due to the efficient electron injection from the porphyrin excited singlet state to the conduction band of the TiO2 electrodes. To further improve the cell performance, 5-(4-carboxylphenyl)-10,15,20-tetrakis-(2,4,6-trimethylphenyl)porphyrinatozinc(II) (Zn-3), possessing different light-harvesting properties, was coadsorbed with fused-Zn-1 onto an TiO2 electrode. Under the optimized conditions, the cosensitized cell yielded maximal IPCE value of 86%, short circuit photocurrent density of 11.7 mA cm−2, open-circuit voltage of 0.67 V, fill factor of 0.64, and η of 5.0% under standard AM 1.5 conditions

Segregated Donor–Acceptor Columns in Liquid Crystals That Exhibit Highly Efficient Ambipolar Charge Transport

Liquid crystalline donor (i.e., phthalocyanine) was covalently linked to acceptor (i.e, fullerene) to achieve efficient charge-transport properties in a liquid crystalline phase. The columnar structure exhibited highly efficient ambipolar charge-transport character, demonstrating the potential utility of the strategy in organic electronics

Electron Transfer Cascade by Organic/Inorganic Ternary Composites of Porphyrin, Zinc Oxide Nanoparticles, and Reduced Graphene Oxide on a Tin Oxide Electrode that Exhibits Efficient Photocurrent Generation

A bottom-up strategy has been developed to construct a multiple electron transfer system composed of organic/inorganic ternary composites (porphyrin, zinc oxide nanoparticles, reduced graphene oxide) on a semiconducting electrode without impairing the respective donor–acceptor components. The hierarchical electron transfer cascade system exhibited remarkably high photocurrent generation with an incident-photon-to-current efficiency of up to ca. 70%

Quantitative Analysis of Photochemical Reactions in Pentacene Precursor Films

On-surface reactions are rapidly gaining attention as a chemical technique for synthesizing organic functional materials, such as graphene nanoribbons and molecular semiconductors. Quantitative analysis of such reactions is essential for fabricating high-quality film structures, but until our recent work using p-polarized multiple-angle incidence resolution spectrometry (pMAIRS), no analytical technique is available to quantify the reaction rate. In the present study, the pMAIRS technique is employed to analyze the photochemical reaction from 6,13-dihydro-6,13-ethanopentacene-15,16-dione to pentacene in thin films. The spectral analysis on a pMAIRS principle readily reveals the photoconversion rate accurately without other complicated calculations. Thus, this study underlines that the pMAIRS technique is a powerful tool for quantitative analysis of on-surface reactions, as well as molecular orientation

Exploration of Alkyl Group Effects on the Molecular Packing of 5,15-Disubstituted Tetrabenzoporphyrins toward Efficient Charge-Carrier Transport

The high design flexibility of organic semiconductors should lead to diverse and complex electronic functions. However, currently available high-performance organic semiconductors are limited in variety; most of p-type materials are based on thienoacenes or related one-dimensionally (1D) extended π-conjugated systems. In an effort to expand the diversity of organic semiconductors, we are working on the development of tetrabenzoporphyrin (BP) derivatives as active-layer components of organic electronic devices. BP is characterized by its large, rigid two-dimensionally (2D) extended π-framework with high light absorptivity and therefore is promising as a core building unit of organic semiconductors for optoelectronic applications. Herein, we demonstrate that BP derivatives can afford field-effect hole mobilities of >4 cm2 V–1 s–1 upon careful tuning of substituents. Comparative analysis of a series of 5,15-bis­(n-alkyldimethylsilylethynyl)­tetrabenzoporphyrins reveals that linear alkyl substituents disrupt the π–π stacking of BP cores, unlike the widely observed “fastener effect” for 1D extended π-systems. The n-octyl and n-dodecyl groups have the best balance between high solution processability and minimal π–π stacking disruption, leading to superior hole mobilities in solution-processed thin films. The resulting thin films show high thermal stability wherein the field-effect hole mobility stays above 1 cm2 V–1 s–1 even after heating at 160 °C in air, reflecting the tight packing of large BP units. These findings will serve as a good basis for extracting the full potential of 2D extended π-frameworks and thus for increasing the structural or functional diversities of high-performance organic semiconductors

Exploration of Alkyl Group Effects on the Molecular Packing of 5,15-Disubstituted Tetrabenzoporphyrins toward Efficient Charge-Carrier Transport

The high design flexibility of organic semiconductors should lead to diverse and complex electronic functions. However, currently available high-performance organic semiconductors are limited in variety; most of p-type materials are based on thienoacenes or related one-dimensionally (1D) extended π-conjugated systems. In an effort to expand the diversity of organic semiconductors, we are working on the development of tetrabenzoporphyrin (BP) derivatives as active-layer components of organic electronic devices. BP is characterized by its large, rigid two-dimensionally (2D) extended π-framework with high light absorptivity and therefore is promising as a core building unit of organic semiconductors for optoelectronic applications. Herein, we demonstrate that BP derivatives can afford field-effect hole mobilities of >4 cm2 V–1 s–1 upon careful tuning of substituents. Comparative analysis of a series of 5,15-bis­(n-alkyldimethylsilylethynyl)­tetrabenzoporphyrins reveals that linear alkyl substituents disrupt the π–π stacking of BP cores, unlike the widely observed “fastener effect” for 1D extended π-systems. The n-octyl and n-dodecyl groups have the best balance between high solution processability and minimal π–π stacking disruption, leading to superior hole mobilities in solution-processed thin films. The resulting thin films show high thermal stability wherein the field-effect hole mobility stays above 1 cm2 V–1 s–1 even after heating at 160 °C in air, reflecting the tight packing of large BP units. These findings will serve as a good basis for extracting the full potential of 2D extended π-frameworks and thus for increasing the structural or functional diversities of high-performance organic semiconductors

Exploration of Alkyl Group Effects on the Molecular Packing of 5,15-Disubstituted Tetrabenzoporphyrins toward Efficient Charge-Carrier Transport

The high design flexibility of organic semiconductors should lead to diverse and complex electronic functions. However, currently available high-performance organic semiconductors are limited in variety; most of p-type materials are based on thienoacenes or related one-dimensionally (1D) extended π-conjugated systems. In an effort to expand the diversity of organic semiconductors, we are working on the development of tetrabenzoporphyrin (BP) derivatives as active-layer components of organic electronic devices. BP is characterized by its large, rigid two-dimensionally (2D) extended π-framework with high light absorptivity and therefore is promising as a core building unit of organic semiconductors for optoelectronic applications. Herein, we demonstrate that BP derivatives can afford field-effect hole mobilities of >4 cm2 V–1 s–1 upon careful tuning of substituents. Comparative analysis of a series of 5,15-bis­(n-alkyldimethylsilylethynyl)­tetrabenzoporphyrins reveals that linear alkyl substituents disrupt the π–π stacking of BP cores, unlike the widely observed “fastener effect” for 1D extended π-systems. The n-octyl and n-dodecyl groups have the best balance between high solution processability and minimal π–π stacking disruption, leading to superior hole mobilities in solution-processed thin films. The resulting thin films show high thermal stability wherein the field-effect hole mobility stays above 1 cm2 V–1 s–1 even after heating at 160 °C in air, reflecting the tight packing of large BP units. These findings will serve as a good basis for extracting the full potential of 2D extended π-frameworks and thus for increasing the structural or functional diversities of high-performance organic semiconductors