The Effect of UV-Irradiation (under Short-Circuit Condition) on Dye-Sensitized Solar Cells Sensitized with a Ru-Complex Dye Functionalized with a (diphenylamino)Styryl-Thiophen Group

A new ruthenium complex, cis-di(thiocyanato)(2,2′-bipyridine-4,4′-dicarboxylic acid)(4,4′-bis(2-(5-(2-(4-diphenylaminophenyl)ethenyl)-thiophen-2-yl)ethenyl)-2,2′-bipyridine)ruthenium(II) (named E322) has been synthesized for use in dye-sensitized solar cells (DSCs). Higher extinction coefficient and a broader absorption compared to the standard Ru-dye, N719, were aimed. DSCs were fabricated with E322, and the efficiency was 0.12% initially. (4.06% for N719, as reference). The efficiency was enhanced to 1.83% by exposing the cell under simulated sunlight containing UV-irradiation at short-circuit condition. The reasons of this enhancement are (1) enhanceing electron injection from sensitizer to TiO2 following a shift toward positive potentials of the conduction band of TiO2 by the adsorption of protons or cations from the sensitizer, or from the redox electrolyte and (2) improving the regeneration reaction of the oxidized dye by the redox electrolyte by the dissolution of aggregated dye from the surface of TiO2 following the treatment

Nanoparticulate dye-semiconductor hybrid materials formed by electrochemical self-assembly as electrodes in photoelectrochemical cells

Dye-sensitized zinc oxide thin films were prepared, characterized and optimized for applications as photoelectrochemically active electrodes. Conditions were established under which crystalline thin films of ZnO with a porous texture were formed by electrochemically induced crystallization controlled by structure-directing agents (SDA). Dye molecules were adsorbed either directly as SDA during this preparation step or, preferably, following desorption of a SDA. The external quantum efficiency (IPCE) could thereby be increased significantly. Particular emphasis was laid on dye molecules that absorb in the red part of the visible spectrum. Model experiments under ultrahigh vacuum (UHV) conditions with dye molecules adsorbed on defined crystal planes of single crystals aimed at a deeper understanding of the coupling of the chromophore electronic π-system within molecular aggregates and to the semiconductor surface. Detailed photoelectrochemical kinetic measurements were used to characterize and optimize the electrochemically prepared dye-sensitized ZnO films. Parallel electrical characterization in vacuum served to distinguish between contributions of charge transport within the ZnO semiconductor matrix and the ions of the electrolyte in the pore system of the electrode

Novel Blue Organic Dye for Dye-Sensitized Solar Cells Achieving High Efficiency in Cobalt-Based Electrolytes and by Co-Sensitization

Blue and green dyes as well as NIR-absorbing dyes have attracted great interest because of their excellent ability of absorbing the incident photons in the red and near-infrared range region. A novel blue D-pi-A dye (Dyenamo Blue), based on the diketopyrrolopyrrole (DPP)-core, has been designed and synthesized. Assembled with the cobalt bipyridine-based electrolytes, the device with Dyenamo Blue achieved a satisfying efficiency of 7.3% under one sun (AM1.5 G). The co-sensitization strategy was further applied on this blue organic dye together with a red D-pi-A dye (D35). The successful co-sensitization outperformed a panchromatic light absorption and improved the photocurrent density; this in addition to the open-circuit potential result in an efficiency of 8.7%. The extended absorption of the sensitization and the slower recombination reaction between the blue dye and TiO2 surface inhibited by the additional red sensitizer could be the two main reasons for the higher performance. In conclusion, from the results, the highly efficient cobalt-based DSSCs could be achieved with the co-sensitization between red and blue D-pi-A organic dyes with a proper design, which showed us the possibility of applying this strategy for future high-performance solar cells

Trends in patent applications for dye-sensitized solar cells

Dye-sensitized solar cell (DSC) technol. has grown into a massive field of research and development with a fast increasing no. of scientific publications and patent applications. We have created a database for patents and patent applications that deal with dye-sensitized solar cell technol. In this paper the database has been used to analyze the no. of patent applications over time, as well as tech., organizational, and geog. trends in patent applications for dye-sensitized solar cells. Activity in relation to DSC patents seriously took off after the millennium, with the majority of DSC patent applications coming from Asia. Almost 90% of the documents in the database derive from Japan, China, and Korea. From a tech. perspective, approx. 75% of the DSC patent applications deal with DSC materials, mainly semiconductor materials, dyes, electrolytes, and device substrates. The DSC patent situation is complex and we recommend any potential manufacturer of DSC devices and/or DSC components to carefully analyze their freedom-to-operate

Organic chromophore-sensitized ZnO solar cells: Electrolyte-dependent dye desorption and band-edge shifts

An org. chromophore D5 (3-(5-(4-(diphenylamino)styryl)thiophene-2-yl)-2-cyanoacrylic acid) was tested as a sensitizer in photoelectrochem. mesoporous ZnO solar cells. Using thin (∼3 μm) mesoporous ZnO electrodes, high incident photon-to-current conversion efficiencies of up to 70% were obtained, while power conversion efficiencies up to 2.4% were found in simulated sunlight (100 mW cm-2). Long dye adsorption times (16 h) could be used without aggregation or pptn. of the dye. The compn. of the iodide/triiodide-based electrolyte was found to be crucial in optimization of the ZnO-based dye-sensitized solar cell. A high concn. of Li+ ions was found to be shift the ZnO conduction band edge to more neg. potential, whereas opposite behavior is found for mesoporous TiO2 cells. It was also found to be detrimental for solar cell performance and stability. Electrolyte-dependent and photoinduced dye desorption from the ZnO electrode was identified as a major stability problem in D5-sensitized ZnO solar cells

Effect of TiO2 Photoanodes Morphology and Dye Structure on Dye-Regeneration Kinetics Investigated by Scanning Electrochemical Microscopy

The dye regeneration in dye-sensitized solar cells (DSSCs) is improved by optimizing the charge separation at the level of the sensitized semiconductor treatment of the mesoporous electrode by TiCl4 that passivates the surface for back electron transfer reactions. The dye-regeneration kinetics is analyzed for DN216- and D358-sensitized porous TiO2 electrodes with and without a TiCl4 treatment by means of scanning electrochemical microscopy (SECM). Different mass transport limitation of the [Co(bpy)3]3+ mediator through the porous electrode is found for the comparison of the structurally similar dyes but cannot be detected for the thin layer introduced by the TiCl4 treatment. Phototransient measurements are conducted directly in the SECM cell without any intermediated sample manipulation. The results from those measurements corroborate the findings from steady state SECM measurement

Blocking the Charge Recombination with Diiodide Radicals by TiO2 Compact Layer in Dye-Sensitized Solar Cells

The addition of a compact titanium dioxide (TiO2) layer between the fluorine-doped tin oxide (FTO) coated glass substrate and the mesoporous TiO2 layer in the dye-sensitized solar cell (DSC) based on the iodide/triiodide redox couple (I-/I-3(-)) is known to improve its current-voltage characteristics. The compact layer decreases the recombination of electrons extracted through the FTO layer with I-3(-) around the maximum power point. Furthermore, the short-circuit photocurrent was improved, which previously has been attributed to the improved light transmittance and/or better contact between TiO2 and FTO. Here, we demonstrate that the compact TiO2 layer has another beneficial effect: it blocks the reaction between charge carriers in the FTO and photogenerated diiodide radical species (I-2(-center dot)). Using photomodulated voltammetry, it is demonstrated that the cathodic photocurrent found at bare FTO electrodes is blocked by the addition of a compact TiO2 layer, while the anodic photocurrent due to reaction with I-2(-center dot) is maintained

Triarylamine-based hydrido-carboxylate rhenium(i) complexes as photosensitizers for dye-sensitized solar cells

Two new dyes based on a dinuclear rhenium complex and (E)-3-(5-(4-(bis(2,4-dibutoxy-[1,1-biphenyl]-4-yl)amino)phenyl)thiophen-2-yl)-2-cyanoacrylic acid (namely D35) have been investigated as sensitizers for dye sensitized solar cells (DSSCs). Two different pyridazine ligands have been used, namely 4-pyridazine-carboxylic acid for dye 2 ([Re-2(-H)(-D35)(CO)(6)(-pyridazine-4-COOH)]) and 4-pyridazinyl-butanoic acid for dye 3 ([Re-2(-H)(-D35)(CO)(6)(-pyridazine-4-C3H6-COOH)]). The performances of these new dyes have been compared with those of the dye containing the bare 4-diphenylaminobenzoic acid, namely TPA, as the ancillary ligand (dye 1). Compared to dye 1, dyes 2 and 3 show an impressive tenfold increase in the absorption intensity in the range of 487-493 nm on TiO2 films, with great improvement of the light harvesting. Cyclic voltammetry experiments, performed on derivatives containing the methyl ester of the pyridazine ligands, show narrow electrochemical band gaps in the range of 1.36-1.84 eV. Solar cells with each dye have been prepared, using both iodide/triiodide and cobalt redox couples as the electrolytes, platinum or carbon as the counter electrodes, and TiO2 or SnO2 as the metal oxide photoelectrodes, respectively. The best DSSC results have been obtained using dye 3, with an overall solar-to-electric conversion efficiency of 3.5%, which greatly overcomes the previous result of 1.0% obtained for dye 1 in a not-optimized setup of the device. The performances of dye 3 are due to the presence of D35 ligand, which further suppresses the recombination of the injected electron with the electrolyte and with the oxidized state of the dye

Defect minimization and morphology optimization in TiO2 nanotube thin films, grown on transparent conducting substrate, for dye synthesized solar cell application

TiO2 nanotube (TNT) arrays have proven to be a perspective material for dye- or semiconductor sensitized solar cells. Although their preparation by anodic oxidation method is well elaborated for Ti foil substrate, the synthesis of high quality, homogeneous TNT arrays on a transparent conductive oxide (TCO) is still associated with some experimental challenges. In this paper we present a way of preparation of defect-free, homogenous TNT film on a TCO substrate by a combination of high temperature Ti sputtering and controlled “interrupted” anodization in viscous electrolyte. High temperature of the substrate during Ti sputter coating was found crucial for good adhesion between the Ti thin film and TCO, which seems to be the most important condition for synthesis of TNTs from a Ti thin film. The reason of poor adhesion of the Ti layer sputtered at room temperature is discussed in terms of internal stress forces. An Ar-ion sputtering was proposed as a method for removal of the non-organized top porous layer to reveal a well organized tubular geometry of TNTs and control their final lengths. Such control of morphology of the top layer is important for preparation of solid state solar cells

Defect minimization and morphology optimization in TiO2 nanotube thin films, grown on transparent conducting substrate, for dye synthesized solar cell application

TiO2 nanotube (TNT) arrays have proven to be a perspective material for dye- or semiconductor sensitized solar cells. Although their prepn. by anodic oxidn. method is well elaborated for Ti foil substrate, the synthesis of high quality, homogeneous TNT arrays on a transparent conductive oxide (TCO) is still assocd. with some exptl. challenges. In this paper a way is presented of prepn. of defect-free, homogeneous TNT film on a TCO substrate by a combination of high temp. Ti sputtering and controlled interrupted anodization in viscous electrolyte. High temp. of the substrate during Ti sputter coating was found crucial for good adhesion between the Ti thin film and TCO, which seems to be the most important condition for synthesis of TNTs from a Ti thin film. The reason of poor adhesion of the Ti layer sputtered at room temp. is discussed in terms of internal stress forces. An Ar-ion sputtering was proposed as a method for removal of the non-organized top porous layer to reveal a well organized tubular geometry of TNTs and control their final lengths. Such control of morphol. of the top layer is important for prepn. of solid state solar cells