Matthew J. Griffith

Porphyrins for dye-sensitised solar cells: new insights into efficiency-determining electron transfer steps

Porphyrin molecules offer immense potential as the light harvesting component of dye-sensitised nanocrystalline TiO(2) solar cells. Synthetic porphyrin dyes were amongst the first dyes trialled for sensitisation of inorganic semiconducting oxides. Today, they exhibit the best performance reported for dye-sensitised solar cells. Accompanying the significant performance improvement over the last two decades is a much improved understanding of efficiency-determining fundamental electron transfer steps, from charge photogeneration to recombination. In this feature article we highlight our recent discoveries of the influence of porphyrin molecule structure on efficiency determining electron transfer kinetics and device performance by systematically changing the molecular structure and observing electron injection and recombination kinetics using time-resolved optical and electrical probes. Despite our observation of ultrafast charge injection for all porphyrin dyes studied by transient absorption spectroscopy, the injection yield estimated using an internal standard remains below 100% and depends strongly on the molecular structure. The observed discrepancy between kinetic competition and the injection yield is attributed to non-injecting dyes, probably arising due to inhomogeneity. A very interesting sub-ns (0.5 ns to 100 ns) charge recombination channel between photo-injected electrons and porphyrin cations is observed, which is found to be more prominent in free-base porphyrin dyes with a conjugated linker. Charge recombination between the acceptor species in the redox containing electrolyte and injected electrons is shown to be an important limitation of most porphyrin-sensitised solar cells, accelerated by the presence of porphyrin molecules at the TiO(2)-electrolyte interface. This recombination reaction is strongly dependent on the porphyrin molecular structure. Bulky substituents, using a porphyrin dimer instead of a porphyrin monomer, a light soaking treatment of freshly prepared films and co-sensitization of TiO(2) with multiple dyes are shown to be successful strategies to improve electron lifetime. Finally, new developments unique to porphyrin dye-sensitised solar cells, including performance enhancements from a light exposure treatment of a zinc porphyrin dye, a significant performance improvement observed after co-sensitisation of TiO(2) with free-base and zinc porphyrin dyes and the use of porphyrin dimers with increased light harvesting in thin-film TiO(2) solar cells are described.

Zn−Zn Porphyrin Dimer-Sensitized Solar Cells: Toward 3-D Light Harvesting

Zn-Zn porphyrin dimers have been incorporated into thin dye-sensitized solar cells (DSSCs) to boost their light harvesting efficiency. The photoexcited dimers show efficient and fast electron injection into TiO(2) indicating that both photoexcited chromophores contribute to current generation. The improved light harvesting ability coupled to enhanced DSSC performance demonstrates the potential of 3-D light harvesting arrays as next generation light harvesters for artificial solar energy conversion systems.

Determining the orientation and molecular packing of organic dyes on a TiO2 surface using X-ray reflectometry.

The determination of the orientation and molecular density for several porphyrin dyes adsorbed on planar TiO(2) surfaces using X-ray reflectometry (XRR) is reported. Adsorption of nanoscale water layers occurred rapidly upon exposure of freshly prepared TiO(2) surfaces to ambient conditions; however, this was successfully eliminated, resulting in clearly discernible adsorbed dye layers for sensitized surfaces. Adsorbed dye orientations, determined from computations constrained by the measured dye layer thickness, were calculated to have a binding tilt angle of 35°-40°. Combining the XXR data with the orientation models indicates that the porphyrins form densely packed surfaces with an intermolecular spacing of 3-4 Å, consistent with π-π stacking interactions. Changes in the molecular size of probe dyes were reflected in corresponding changes in the measured dye layer thickness, confirming the ability of this technique to resolve small variations in dye layer thickness and consequently adsorption orientation. Application of these results to understanding the behavior of dye-sensitized devices is discussed.

Remarkable synergistic effects in a mixed porphyrin dye-sensitized TiO2 film

A remarkable 300% efficiency enhancement driven by a matching increase in the short circuit current was observed in a mixed porphyrin dye-sensitized solar cell constructed from two dyes in a 3:1 ratio. Absorbed photon-to-current conversion efficiency measurements indicate an improved charge injection yield for both dyes in the mixture. Several possible origins for the observed performance enhancement are discussed.

Enhanced performance of dye-sensitized solar cells using carbazole-substituted di-chromophoric porphyrin dyes

The purpose of this work is to investigate the origin of improved photovoltaic performance of a series of di-chromophoric carbazole-substituted porphyrin dyes employed as sensitizers in dye-sensitized solar cells. Five di-chromophoric zinc porphyrin dyes with the same porphyrin core, a carbazole unit attached in the meso-position through a phenylethenyl linkage, and substituents spanning a range of electron affinities, in an attempt to tune the electronic level of the carbazole unit, have been synthesized (CZPs). Density functional theory (DFT) calculations predicted the nature of the electronic transitions observed in the CZP systems, showing a large degree of orbital mixing. In contrast, UV-vis absorption, resonance Raman spectroscopy and differential pulse voltammetry investigations suggested negligible interaction between the porphyrin and carbazole chromophores. Carbazole substitution led to a moderate increase in photon absorption intensity within the ∼300 nm to 400 nm wavelength region, a smaller but broader Soret band absorption and slightly increased photon absorption intensity in the 550 nm to 650 nm Q band region. Despite the rather small changes in light harvesting and negligible changes in the HOMO/LUMO electronic levels, the photovoltaic performance of the new dyes is increased by as much as 30% compared to the single chromophore Zn porphyrin dye 5-(4-(2-cyano-2-carboxyethenyl)phenyl-15-phenyl-10,20-bis(2,4,6-trimethylphenyl)porphyrinato zinc(II) (ZP1), leading to over 6% power conversion efficiencies (PCEs). Both open circuit voltage (VOC) and short circuit current (JSC) have increased. The increased VOC is attributed to increased electron lifetimes due to a steric blocking effect. Analysis of the increased short circuit current (ΔJSC) showed that only less than 10% of ΔJSC originates from increased light absorption under simulated air mass 1.5 illumination, while the rest of the improvements are attributed to a steric effect enhancing the electron injection efficiency. These results suggest that developing non-conjugated multichromophoric dyes can lead to simultaneous increases in both the photocurrent and the photovoltage of dye-sensitized solar cells.

Combining Printing, Coating, and Vacuum Deposition on the Roll-to-Roll Scale: A Hybrid Organic Photovoltaics Fabrication

The potential for organic electronic technologies to produce low-cost energy at large scales is often cited as the most attractive feature of these materials. Such aspirations depend on the ability of materials to be printed from solution at high speeds across large areas using roll-to-roll (R2R) processing. However, progressing the technology from the laboratory environment into the industrial manufacturing arena is highly challenging. Closing the gap between exciting laboratory scale insights and the industrial scale potential requires a new focus on upscaling existing technology. Some recent progress in this area is discussed, concentrating on the need to pursue research across several different scales simultaneously in order to most effectively optimize large-scale fabrication efforts. These discussions are placed in the context of a design philosophy that combines printing, coating, and vacuum-based procedures. The challenges associated with selecting, and subsequently synthesizing, the optimal materials for device construction at large scales are considered. Case histories that highlight the unique challenges encountered during printing, coating, and sputtering at the R2R scale are presented. Developing testing and characterization procedures that can interrogate organic photovoltaic device (OPV) structures in real time is also discussed, and the opportunity for new tools to probe device photophysics is highlighted. The collection of innovative approaches to R2R fabrication challenges discussed here highlights the exciting progress toward efficient OPV modules becoming a commercial reality.

A low-cost mixed fullerene acceptor blend for printed electronics

The synthesis and performance of a cost-effective mixed fullerene at the 100+ g scale with a reaction yield of 85% is demonstrated. The cost to convert a fullerene such as C60 into the mixed acceptor blend is less than

A nonconjugated bridge in dimer-sensitized solar cells retards charge recombination without decreasing charge injection efficiency

1 g−1. The photovoltaic performance of the mixed acceptor is demonstrated in both small scale and roll-to-roll printed devices.

Solution processable interface materials for nanoparticulate organic photovoltaic devices

Dye sensitized solar cells (DSSCs) employing a dimer porphyrin, which was synthesised with two porphyrin units connected without conjugation, have shown that both porphyrin components can contribute to photocurrent generation, that is, more than 50 % internal quantum efficiency. In addition, the open-circuit voltage (Voc) of the DSSCs was higher than that of DSSCs using monomer porphyrins. In this paper, we first optimized cell structure and fabrication conditions. We obtained more than 80% incident photon to current conversion efficiency from the dimer porphyrin sensitized DSSCs and higher Voc and energy conversion efficiency than monomer porphyrin sensitized solar cells. To examine the origin of the higher Voc, we measured electron lifetime in the DSSCs with various conditions, and found that the dimer system increased the electron lifetime by improving the steric blocking effect of the dye layer, whilst the lack of a conjugated linker prevents an increase in the attractive force between conjugated sensitizers and the acceptor species in the electrolyte. The results support a hypothesis; dispersion force is one of the factors influencing the electron lifetime in DSSCs.

Activation of Organic Photovoltaic Light Detectors Using Bend Leakage from Optical Fibers

Nanoparticulate zinc oxide can be prepared at low temperatures from solution processable zinc acetylacetonate. The use of this material as a cathode interfacial layer in nanoparticulate organic photovoltaic devices results in comparable performances to those based on reactive calcium layers. Importantly, the enhanced degradation stability and full solution processability make zinc oxide a more desirable material for the fabrication of large area printed devices.