Improving Microstructured TiO2 Photoanodes for Dye Sensitized Solar Cells by Simple Surface Treatment

TiCl₄ surface treatment studies of porous electrode structure of TiO₂ aggregates synthesized using an acidic precursor and CTAB as a templating agent are carried out in order to understand and improve upon recombination kinetics in the photonanode film matrix, together with enhancing the intrinsic light scattering. The key beneficial features of the photoanode included high surface roughness, necessary for superior dye adsorption, nanocrystallite aggregates leading to diffuse light scattering within the film matrix, and a hierarchical macro‐ and mesopore structure allowing good access of electrolyte to the dye, thereby assisting in dye regeneration (enhanced charge transfer). Pre‐treatment of the TiO₂ electrodes reduced recombination at the fluorine‐doped tin oxide (FTO)/electrolyte interface. The post‐treatment study showed enhanced surface roughness through the deposition of a thin overlayer of amorphous TiO₂ on the film structure. This led to a notable improvement in both dye adsorption and inherent light scattering effects by the TiO₂ aggregates, resulting in enhanced energy harvesting. The thin TiO₂ overlayer also acted as a barrier in a core‐shell configuration within the porous TiO₂ matrix, and thereby reduced recombination. This allowed the hierarchical macro‐ and mesoporosity of the film matrix to be utilized more effectively for enhanced charge transfer during dye regeneration. Post‐treatment of the aggregated TiO₂ matrix resulted in a 36% enhancement in power conversion efficiency from 4.41% of untreated cells to 6.01%.     

TiO2 Nanocrystals Synthesized by Laser Pyrolysis for the Up‐Scaling of Efficient Solid‐State Dye‐Sensitized Solar Cells

A crucial issue regarding emerging nanotechnologies remains the up‐scaling of new functional nanostructured materials towards their implementation in high performance applications on a large scale. In this context, we demonstrate high efficiency solid‐state dye‐sensitized solar cells prepared from new porous TiO₂ photoanodes based on laser pyrolysis nanocrystals. This strategy exploits a reduced number of processing steps as well as non‐toxic chemical compounds to demonstrate highly porous TiO₂ films. The possibility to easily tune the TiO₂ nanocrystal physical properties allows us to demonstrate all solid‐state dye‐sensitized devices based on a commercial benchmark materials (organic indoline dye and molecular hole transporter) presenting state‐of‐the‐art performance comparable with reference devices based on a commercial TiO₂ paste. In particular, a drastic improvement in pore infiltration, which is found to balance a relatively lower surface area compared to the reference electrode, is evidenced using laser‐synthesized nanocrystals resulting in an improved short‐circuit current density under full sunlight. Transient photovoltage decay measurements suggest that charge recombination kinetics still limit device performance. However, the proposed strategy emphasizes the potentialities of the laser pyrolysis technique for up‐scaling nanoporous TiO₂ electrodes for various applications, especially for solar energy conversion.     

Recent Progress in Dye‐Sensitized Solar Cells Using Nanocrystallite Aggregates

Nanocrystallite aggregates are spherical assemblies of nanometer‐sized crystallites and feature a size on the order of sub‐micrometers. This paper reports and summarizes recent progress in nanocrystallite aggregates for applications in dye‐sensitized solar cells. It emphasizes that nanocrystallite aggregates are a promising class of materials with the capability to generate light scattering, enhance electron transport, retain high specific surface area for dye adsorption, and facilitate electrolyte diffusion while serving as the photoelectrode film of a dye‐sensitized solar cell. In the Perspectives section, it is suggested that optimization of the porosity of the aggregates, the facets of nanocrystallites forming the aggregates, and the structure of photoelectrode film could possibly lead to breakthroughs in improving the power conversion efficiency of the current state‐of‐the‐art dye‐sensitized solar cells.     

Determination of amlodipine using terbium‐sensitized luminescence in the presence of europium(III) as a co‐luminescence reagent

A sensitive time‐resolved luminescence method for the determination of amlodipine (AM) in methanol and in aqueous solution is described. The method is based on the luminescence sensitization of terbium (Tb³⁺) by formation of a ternary complex with AM in the presence of tri‐n‐octylphosphine oxide (TOPO) as co‐ligand, dodecylbenzenesulfate as surfactant and europium ion as a co‐luminescence reagent. The signal for Tb–AM–TOPO is monitored at λ_ex = 242 nm and λ_em = 550 nm. Optimum conditions for the formation of the complex in aqueous system were 0.015 m Tris (hydroxylmethyl) amino methane buffer, pH 9.0, TOPO (1.0 × 10^–4 m ), Eu³⁺ (2.0 × 10^–7 m ), dodecylbenzenesulfate (0.14%) and 6.0 × 10^–5 m of Tb³⁺, which allows the determination of 10–50 ppb of AM with a limit of detection of 1.2 ppb. The relative standard deviations of the method range between 0.1 and 0.2% indicated excellent reproducibility of the method. The proposed method was successfully applied for the assay of AM in pharmaceutical formulations and in plasma samples. Average recoveries of 98.5 ± 0.2% and 95.2 ± 0.2% were obtained for AM in tablet and plasma samples respectively. Copyright © 2013 John Wiley & Sons, Ltd.     

Minimizing Energy Losses in Dye‐Sensitized Solar Cells Using Coordination Compounds as Alternative Redox Mediators Coupled with Appropriate Organic Dyes

To further boost the efficiency of dye‐sensitized solar cells, a correct evaluation of the real limitations of this type of solar cell should be conducted. From a simple analysis of the photovoltaic data found in the literature, it is evident that the V_oc decrease, through energy losses, seems to be the most crucial factor diminishing the overall system efficiency. In particular, losses arising from the regeneration of the dye by the iodide/triiodide redox mediator are huge. The most convenient manner to recuperate these losses is the use of alternative redox mediators with more positive redox potentials than that of the iodide‐based shuttle. Among various types of redox active compounds, ferrocene/ferrocenium, Cu^+/2+, and Co^2+/3+ complexes are found to be the most effective in solar cells and the obtained efficiencies of more than 12% clearly show that a breakthrough is close, paving revolutionary roads towards making new records.     

Structural parameters controlling the performance of organized mesoporous TiO2 films in dye sensitized solar cells

Titanium dioxide films with organized mesoporous structure were investigated as photoanodes in dye sensitized solar cells. High-quality films were grown on FTO supports by implementing the protocol of supramolecular templating with an amphiphilic triblock copolymer, Pluronic P123. Thicker films were obtained by repeated dip-coating and calcination cycles of up to 10 layers. The TiO₂ films were crack-free, optically transparent, and had thicknesses exceeding 2 μm, while still preserving the organized mesoporous morphology. Their roughness factors, determined from Kr-adsorption isotherms, exceeded 500. The sorption of N-3 and N-719 dyes was fitted to a surface coverage of 0.31 molecules/nm², which is about one third of the ideal dye loading assumed for the (1 0 1) anatase face. The solar performance of multilayer films sensitized with N-945 dye scaled linearly for 1-3 layer films, but approached a plateau for thicker films.     

Molecular identification, heterologous expression and properties of light-insensitive plant catalases

Most catalases are inactivated by light in a heme-sensitized and O2-dependent reaction. In leaves of the alpine plant Homogyne alpina and in the peroxisomal cores of Helianthus annuus, light-insensitive catalases were observed. For the catalases Hacat1 of H. alpina and HnncatA3 of H. annuus, cDNA clones were obtained. Expression of recombinant active enzymes in insect cells confirmed that they coded for light-insensitive catalases. Kinetic and catalytic properties of light-sensitive or light-insensitive catalases did not differ substantially. However, the specific activity of the latter was markedly lower. The light-insensitive catalase HaCAT-1 was not resistant against inactivation by superoxide. Amino acid sequences of the light-insensitive catalases HaCAT-1 and HNNCATA3 were highly identical. They showed only a few exceptional amino acid substitutions at positions that are highly conserved in other catalases. These appeared to be localized mainly in a surface cavity at the entrance of a minor channel leading to the central heme, suggesting that this region played some, though yet undefined, role for light sensitivity. While the replacement of a highly conserved His by Thr225 was the most unique substitution, a single exchange of His225 by Thr in the light-sensitive catalase SaCAT-1 by mutagenesis was not sufficient to reduce its sensitivity to photoinactivation.     

Engineering Processes at the Interface of p‐Semiconductor for Enhancing the Open Circuit Voltage in p‐Type Dye‐Sensitized Solar Cells

To prevent the interfacial charge recombination between injected holes in the valence band and the redox mediator in the electrolyte in p‐type dye sensitized solar cells (p‐DSSC) the passivation of the recombination sites by organic insulator chenodeoxycholic acid (CDCA) layer is critically investigated in this study. Rather than classical coating of the semiconductor's surface by simultaneous co‐adsorption of CDCA during the dyeing step, two other methods are investigated. The first consists in dissolving CDCA in the electrolyte, while the second consists in spin coating an ethanol solution of CDCA onto the already dyed photocathode. In this study, different sensitizers, electrolytes, and p‐SCs, (NiO, CuGaO₂) are explored. Analysis of the current/voltage curves and electrochemical impedance spectroscopy provides evidence that the role of the CDCA layer is to create a physical barrier to prevent the approach of the redox mediator from the NiO surface and consequently raise the open circuit voltage (V_oc). The important finding of this study is the demonstration that the V_oc in p‐DSSC is heavily limited by interfacial charge recombination and that higher V_oc values much above 100 mV and as high as 500 mV can be attained with conventional materials (NiO) if this deleterious side reaction can be suppressed or diminished.