Application of the Tris(acetylacetonato)iron(III)/(II) Redox Couple in p‐Type Dye‐Sensitized Solar Cells

An electrolyte based on the tris(acetylacetonato)iron(III)/(II) redox couple ([Fe(acac)₃]^0/1?) was developed for p‐type dye‐sensitized solar cells (DSSCs). Introduction of a NiO blocking layer on the working electrode and the use of chenodeoxycholic acid in the electrolyte enhanced device performance by improving the photocurrent. Devices containing [Fe(acac)₃]^0/1? and a perylene–thiophene–triphenylamine sensitizer (PMI–6T–TPA) have the highest reported short‐circuit current (J_SC=7.65 mA cm^?2), and energy conversion efficiency (2.51 %) for p‐type DSSCs coupled with a fill factor of 0.51 and an open‐circuit voltage V_OC=645 mV. Measurement of the kinetics of dye regeneration by the redox mediator revealed that the process is diffusion limited as the dye‐regeneration rate constant (1.7×10⁸ M ^?1 s^?1) is very close to the maximum theoretical rate constant of 3.3×10⁸ M ^?1 s^?1. Consequently, a very high dye‐regeneration yield (>99 %) could be calculated for these devices.     

Platinum‐Free Binary Co‐Ni Alloy Counter Electrodes for Efficient Dye‐Sensitized Solar Cells

Dye‐sensitized solar cells (DSSCs) have attracted growing interest because of their application in renewable energy technologies in developing modern low‐carbon economies. However, the commercial application of DSSCs has been hindered by the high expenses of platinum (Pt) counter electrodes (CEs). Here we use Pt‐free binary Co‐Ni alloys synthesized by a mild hydrothermal strategy as CE materials in efficient DSSCs. As a result of the rapid charge transfer, good electrical conduction, and reasonable electrocatalysis, the power conversion efficiencies of Co‐Ni‐based DSSCs are higher than those of Pt‐only CEs, and the fabrication expense is markedly reduced. The DSSCs based on a CoNi_0.25 alloy CE displays an impressive power conversion efficiency of 8.39 %, fast start‐up, multiple start/stop cycling, and good stability under extended irradiation.     

Metal‐Free Organic Dyes for Dye‐Sensitized Solar Cells: From Structure: Property Relationships to Design Rules

Works without ruthenium as well : Dye‐sensitized solar cells (DSSCs) incorporating metal‐free organic dyes have been considerably improved in recent years. Various design strategies have been established and are employed successfully in the synthesis of novel sensitizers. In this Review, structure–property–efficiency correlations are deduced from a vast number of dyes, which should help to design new and highly efficient sensitizers.

     

Photophysical and Electrochemical Properties,and Molecular Structures of Organic Dyes for Dye‐Sensitized Solar Cells

Dye‐sensitized solar cells (DSSCs) based on organic dyes adsorbed on oxide semiconductor electrodes, such as TiO₂, ZnO, or NiO, which have emerged as a new generation of sustainable photovoltaic devices, have attracted much attention from chemists, physicists, and engineers because of enormous scientific interest in not only their construction and operational principles, but also in their high incident‐solar‐light‐to‐electricity conversion efficiency and low cost of production. To develop high‐performance DSSCs, it is important to create efficient organic dye sensitizers, which should be optimized for the photophysical and electrochemical properties of the dyes themselves, with molecular structures that provide good light‐harvesting features, good electron communication between the dye and semiconductor electrode and between the dye and electrolyte, and to control the molecular orientation and arrangement of the dyes on a semiconductor surface. The aim of this Review is not to make a list of a number of organic dye sensitizers developed so far, but to provide a new direction in the epoch‐making molecular design of organic dyes for high photovoltaic performance and long‐term stability of DSSCs, based on the accumulated knowledge of their photophysical and electrochemical properties, and molecular structures of the organic dye sensitizers developed so far.     

Molecular Design Principle of All‐organic Dyes for Dye‐Sensitized Solar Cells

All‐organic dyes have shown promising potential as an effective sensitizer in dye‐sensitized solar cells (DSSCs). The design concept of all‐organic dyes to improve light‐to‐electric‐energy conversion is discussed based on the absorption, electron injection, dye regeneration, and recombination. How the electron‐donor–acceptor‐type framework can provide better light harvesting through bandgap‐tuning and why proper arrangement of acceptor/anchoring groups within a conjugated dye frame is important in suppressing improper charge recombination in DSSCs are discussed. Separating the electron acceptor from the anchoring unit in the donor–acceptor‐type organic dye would be a promising strategy to reduce recombination and improve photocurrent generation.     

Peripherally and Axially Carboxylic Acid Substituted Subphthalocyanines for Dye‐Sensitized Solar Cells

A series of subphthalocyanines (SubPcs) bearing a carboxylic acid group either at the peripheral or axial position have been designed and synthesized to investigate the influence of the COOH group positions on the dye‐sensitized solar cell (DSSC) performance. The DSSC devices based on SubPcs with axially substituted carboxylic acid groups showed low photovoltaic performance, whereas peripherally substituted one exhibited higher power conversion efficiency owing to improved injection from LUMO of SubPcs to the TiO₂ conduction band.     

Sonochemical Preparation of Hierarchical ZnO Hollow Spheres for Efficient Dye‐Sensitized Solar Cells

Hierarchical ZnO hollow spheres (400–500 nm in diameter) consisting of ZnO nanoparticles with a diameter of approximately 15 nm have been successfully prepared by a facile and rapid sonochemical process. The formation of hierarchical ZnO hollow spheres is attributed to the oriented attachment and subsequent Ostwald ripening process according to time‐dependent experiments. The as‐prepared ZnO hollow spheres are used as a photoanode in dye‐sensitized solar cells and exhibit a highly efficient power conversion efficiency of 4.33 %, with a short‐circuit current density of 9.56 mA cm^?2, an open‐circuit voltage of 730 mV, and a fill factor of 0.62 under AM 1.5 G one sun (100 mW cm^?2) illumination. Moreover, the photovoltaic performance (4.33 %) using the hierarchical ZnO hollow spheres is 38.8 % better than that of a ZnO nanoparticle photoelectrode (3.12 %), which is mainly attributed to the efficient light scattering for the former.     

Opp‐Dibenzoporphyrins as a Light‐Harvester for Dye‐Sensitized Solar Cells

New opp‐dibenzoporphyrins were prepared in a concise method that was based on a Pd⁰‐catalyzed cascade reaction. These porphyrins, which contained carboxylic‐acid linker groups on benzene rings that were fused to the porphyrin at their β,β′‐positions, were examined as sensitizers for dye‐sensitized solar cells for the first time. Whereas all of the porphyrins showed solar‐energy‐to‐electricity conversion, an opp‐dibenzoporphyrin with conjugated carboxylic‐acid linkers displayed the highest conversion efficiency and an exceptionally high J_sc value. Cyclic voltammetry of these porphyrins suggested that the fusion of two aromatic benzene rings onto the periphery of the porphyrin lowered the HOMO–LUMO energy gap; the incorporation of a conjugated carboxylic‐acid linker group decreased the HOMO–LUMO gap even further. These CV data are consistent with DFT calculations for these porphyrins and agree well with the UV/Vis absorption‐ and fluorescence spectra of these porphyrins.     

Structural Control of Hierarchically‐Ordered TiO2 Films by Water for Dye‐Sensitized Solar Cells

A facile way of controlling the structure of TiO₂ by changing the amount of water to improve the efficiency of dye‐sensitized solar cells (DSSCs) is reported. Hierarchically ordered TiO₂ films with high porosity and good interconnectivity are synthesized in a well‐defined morphological confinement arising from a one‐step self‐assembly of preformed TiO₂ (pre‐TiO₂) nanocrystals and a graft copolymer, namely poly(vinyl chloride)‐g‐poly(oxyethylene methacrylate). The polymer–solvent interactions in solution, which are tuned by the amount of water, are shown to be a decisive factor in determining TiO₂ morphology and device performance. Systematic control of wall and pore size is achieved and enables the bifunctionality of excellent light scattering properties and easy electron transport through the film. These properties are characterized by reflectance spectroscopy, incident photon‐to‐electron conversion efficiency, and electrochemical impedance spectroscopy analyses. The TiO₂ photoanode that is prepared with a higher water ratio, [pre‐TiO₂]:[H₂O]=1:0.3, shows a larger surface area, greater light scattering, and better electron transport, which result in a high efficiency (7.7 %) DSSC with a solid polymerized ionic liquid. This efficiency is much greater than that of commercially available TiO₂ paste (4.0 %).