A stable quasi-solid-state dye-sensitized solar cell with an amphiphilic ruthenium sensitizer and polymer gel electrolyte

Dye-sensitized nanocrystalline solar cells (DSC) have received considerable attention as a cost-effective alternative to conventional solar cells. One of the main factors that has hampered widespread practical use of DSC is the poor thermostability encountered so far with these devices. Here we show a DSC with unprecedented stable performance under both thermal stress and soaking with light, matching the durability criteria applied to silicon solar cells for outdoor applications. The cell uses the amphiphilic ruthenium sensitizer cis-RuLL'(SCN)(2) (L = 4,4'-dicarboxylic acid-2,2'-bipyridine, L' = 4,4'-dinonyl-2,2'-bipyridine) in conjunction with a quasi-solid-state polymer gel electrolyte, reaching an efficiency of >6% in full sunlight (air mass 1.5, 100 mW cm(-2)). A convenient and versatile new route is reported for the synthesis of the heteroleptic ruthenium complex, which plays a key role in achieving the high-temperature stability. Ultramicroelectrode voltammetric measurements show that the triiodide/iodide couple can perform charge transport freely in the polymer gel. The cell sustained heating for 1,000 h at 80 degrees C, maintaining 94% of its initial performance. The device also showed excellent stability under light soaking at 55 degrees C for 1,000 h in a solar simulator (100 mW cm(-2)) equipped with a ultraviolet filter. The present findings should foster widespread practical application of dye-sensitized solar cells.     

Theoretical study of indoline dyes for dye-sensitized solar cells

Indoline dye sensitizers were designed and studied theoretically to increase molar extinction coefficients in the visible to near infrared region for solar-cell devices. To gain insight into dye sensitizers' structural, electronic, and optical properties, DFT/TDDFT calculations were performed on a series of dye sensitizers derived from the D149. The good agreement between the experimental and TDDFT calculated absorption spectra of the D149 sensitizer allowed us to provide a detailed assessment of the main spectral features of a series of dye sensitizers. Increase in the conjugation length resulted in a more red-shifted spectral response and less positive oxidation potential than that of the D149. The dye with the dimethylfluorene group showed stronger absorption bands due to a large dipole moment. The calculated dipoles for the dye series correlate well with the observed strong absorption bands of the electronic spectra. These results provided useful clues for the molecular engineering of efficient organic dye sensitizers.     

Effect of highly ordered single-crystalline TiO2 nanowire length on the photovoltaic performance of dye-sensitized solar cells

One-dimensional semiconductor nanostructures grown directly onto transparent conducting oxide substrates with a high internal surface area are most desirable for high-efficiency dye-sensitized solar cells (DSSCs). Herein, we present a multicycle hydrothermal synthesis process to produce vertically aligned, single crystal rutile TiO(2) nanowires with different lengths between 1 and 8 μm for application as the working electrode in DSSCs. Optimum performance was obtained with a TiO(2) nanowire length of 2.0 μm, which may be ascribed to a smaller nanowire diameter with a high internal surface area and better optical transmittance with an increase in the incident light intensity on the N719 dye; as well as a firm connection at the FTO/TiO(2) nanowire interface.     

Influence of donor moiety in ruthenium sensitizers on the properties of dye-sensitized solar cells

Heteroleptic ruthenium complexes cis-[Ru(H2dcbpy)(L)(NCS)2], where H2dcbpy is 4,4'-dicarboxylic acid-2,2'-bipyridine and L is 4-(4-(N,N-di-(p-hexyloxyphenyl)-amino)styryl)-4'-methyl-2,2'-bipyridine (Rut-A) or 4-(4'-(3,6-dihexyloxycarbazole-9-yl)-styryl)-4'-methyl-2,2'-bipyridine (Rut-B), have been synthesized and characterized by NMR, UV-Vis spectroscopy, and cyclic voltammogram. The effect of different electron donors on the properties of dye-sensitized solar cells has been studied. The power conversion efficiency of DSSC based on Rut-B is 6.1% while Rut-A delivered a lower efficiency of 4.52% under the same device fabrication and measuring conditions. The better photovoltaic performance of Rut-B is mainly associated with enhanced dye absorptivity and charge recombination suppression.     

Surfactant chain length effects on the light emission of tris(2,2'-bipyridyl)ruthenium(II)/ tripropylamine electrogenerated chemiluminescence

The effects of nonionic surfactant chain length on the properties of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)3(2+) where bpy = 2,2'-bipyridine) electrochemiluminescence (ECL) have been investigated. The electrochemistry, photophysics, and ECL of Ru(bpy)3(2+) in the presence of a series of nonionic surfactants are reported (Triton X-100, 114, 165, 405, 305, and 705-70). These surfactants differ in the number of poly(ethylene oxide) units incorporated into the surfactant molecule. The anodic oxidation of Ru(bpy)3(2+) produces ECL in the presence of tri-n-propylamine (TPrA) in aqueous surfactant solution. Increases in ECL efficiency (> or = 5-fold) and TPrA oxidation current (> or = 2-fold) have been observed in surfactant media. Slight decreases in ECL intensity are observed as the chain length of the nonionic surfactant increases. The data supports adsorption of surfactant on the electrode surface, thus facilitating TPrA and Ru(bpy)3(2+) oxidation and leading to higher ECL efficiencies.     

Effects of chain length on oligopeptide hydrogelation

The co-assembly of mutually complementary, but self-repulsive oligopeptide pairs into viscoelastic hydrogels has been studied. Oligopeptides of 6, 10, and 14 amino acid residues were used to investigate the effects of peptide chain length on the structural and mechanical properties of the resulting hydrogels. Biophysical characterizations, including dynamic rheometry, small-angle X-ray scattering (SAXS) and fluorescence spectroscopy, were used to investigate hydrogelation at the bulk, fiber, and molecular levels, respectively. Upon mixing, the 10-mer peptides and the 14-mer peptides both form hydrogels while the 6-mer peptides do not. SAXS studies point to morphological similarity of the cross-sections of fibers underlying the 10:10 and 14:14 gels. However, fluorescence spectroscopy data suggest tighter packing of the amino acid side chains in the 10:10 fibers. Consistent with this tighter packing, dynamic rheometry data show that the 10:10 gel has much higher elastic modulus than the 14:14 mer (18 kPa vs. 0.1 kPa). Therefore, from the standpoint of mechanical strength, the optimum peptide chain length for this class of oligopeptide-based hydrogels is around 10 amino acid residues.     

Control of ruthenium oxide nanorod length in reactive sputtering

Ruthenium oxide nanorods have been grown on Si wafer substrates under a variety of pre-existing surface conditions by reactive radio frequency sputtering in an electron cyclotron resonant plasma process. Nanorod formation by this method is fast relative to that observed in other processes reported in the literature, with nucleation being the rate determining step. Growth in the axial direction is limited by the availability of ruthenium precursors which competes with their consumption in the lateral growth of the nanorods. The availability of Ru precursors at the top of the nanorods can be controlled by surface diffusion and therefore substrate temperature. The ultimate length of the nanorods is determined by the mole fraction of oxygen used in the reactor ambient through the production of mobile Ru hyperoxide precursors. The results of this investigation show the way to develop a process for producing a high density field of nanorods with a specified length.     

Layer-by-layer formation of block-copolymer-derived TiO(2) for solid-state dye-sensitized solar cells

Morphology control on the 10 nm length scale in mesoporous TiO(2) films is crucial for the manufacture of high-performance dye-sensitized solar cells. While the combination of block-copolymer self-assembly with sol-gel chemistry yields good results for very thin films, the shrinkage during the film manufacture typically prevents the build-up of sufficiently thick layers to enable optimum solar cell operation. Here, a study on the temporal evolution of block-copolymer-directed mesoporous TiO(2) films during annealing and calcination is presented. The in-situ investigation of the shrinkage process enables the establishment of a simple and fast protocol for the fabrication of thicker films. When used as photoanodes in solid-state dye-sensitized solar cells, the mesoporous networks exhibit significantly enhanced transport and collection rates compared to the state-of-the-art nanoparticle-based devices. As a consequence of the increased film thickness, power conversion efficiencies above 4% are reached.     

High-efficiency solid-state dye-sensitized solar cells based on TiO(2)-coated ZnO nanowire arrays

Replacing the liquid electrolytes in dye-sensitized solar cells (DSCs) with solid-state hole-transporting materials (HTMs) may solve the packaging challenge and improve the long-term stability of DSCs. The efficiencies of such solid-state DSCs (ss-DSCs), however, have been far below the efficiencies of their counterparts that use liquid electrolytes, primarily due to the challenges in filling HTMs into thick enough sensitized films based on sintered TiO(2) nanoparticles. Here we report fabrication of high-efficiency ss-DSCs using multilayer TiO(2)-coated ZnO nanowire arrays as the photoanodes. The straight channel between the vertically aligned nanostructures combined with a newly developed multistep HTM filling process allows us to effectively fill sensitized films as thick as 50 μm with the HTMs. The resulting ss-DSCs yield an average power conversion efficiency of 5.65%.     

Development of a new solid-state absorber material for dye-sensitized solar cell (DSSC)

In contrast to the conventional DSSC systems, where the dye molecules are used as light harvesting material, here a solid-state absorber was used as a sensitizer in conjunction with the dye. The materials like ZnO and Al₂O₃ : C, which will show optically stimulated luminescence (OSL) upon irradiation were used as extremely thin absorber layers. This novel architecture allows broader spectral absorption, an increase in photocurrent, and hence, an improved efficiency because of the mobility of the trapped electrons in the absorber material after irradiation, to the TiO₂ conduction band. Nanocrystalline mesoporous TiO₂ photoanodes were fabricated using these solid-state absorber materials and after irradiation, a few number of samples were co-sensitized with N719 dye. On comparing both the dye loaded photoanodes (ZnO/TiO₂ and Al₂O₃ : C/TiO₂), it can be concluded from the present studies that, the Al₂O₃ : C is superior to ZnO under photon irradiation. Al₂O₃ : C is more sensitive to photon irradiation than ZnO and hence there can be more trap centres produced in Al₂O₃ : C.     

Effect of polymer modifier chain length on thermal conductive property of polyamide 6/graphene nanocomposites

The influence of polymer modifier chain length on the thermal conductivity of polyamide 6/graphene (GA) nanocomposites, including through-plane (λ_z) and in-plane (λ_x) directions were investigated. Here, three chain lengths of double amino-terminated polyethylene glycol (NH₂–PEG–NH₂) were used to covalently functionalize graphene with graphene content of 5.0 wt%. Results showed that λ_z was enhanced with the chain length of NH₂–PEG–NH₂ increased, but λ_x reached a maximum value at a certain chain length of NH₂–PEG–NH₂. The maximum λ_z and λ_x of GA are 0.406 W m⁻¹ K⁻¹ and 9.710 W m⁻¹ K⁻¹, respectively. This study serves as a foundation for further research on the thermal conductive property of graphene nanocomposites using different chain lengths of polymer modifier to improve the λ_z and λ_x of the thermal conductive materials.     

Effect of the side chain length on the optical and electrical properties of soluble PPV derivatives

2-Alkoxy-5-methoxy poly(1,4-phenylenevinylene) derivatives with different lengths of the alkoxy side chain have been synthesized via a modified Gilch polymerization. Their number-average molecular weights are in the range of 10,000–14,000. ¹H NMR, ¹³C NMR, FT-IR spectroscopies have shown that the polymer structures are the expected ones and were free from defects. The polymers are amorphous and show good thermal stability up to 300 °C. The optical absorption band of MB-PPV, MH-PPV, MO-PPV and MDD-PPV thin films are at 496 nm, 496 nm, 494 nm and 507 nm, respectively. Photoluminescence emission maxima of the above polymers appear at 624 nm, 582 nm, 629 nm and 578 nm, respectively. A composite photoluminescence response is observed at the exception of MO-PPV showing a single PL maximum. Light-emitting diodes (LEDs) based on these polymers were fabricated and characterized by current–voltage measurements. The comparison of the optical and electrical properties of these different polymers showed a small influence of the length of the side alkoxy chain and/or to the length of the main polymeric chain.     

TiO2 pore-filling and its effect on the efficiency of solid-state dye-sensitized solar cells

Solid-state dye-sensitized solar cells have been the focus of much attention over the past few years. We have recently been able to demonstrate efficiencies in excess of 4% and further improvements are expected. Here we compare a range of different hole conductor materials and investigate a number of key parameters which affect their performance. Wetting and pore-filling of the nanoporous TiO₂ layer by the hole transporter appears to play a critical role in determining the final efficiency of the cell. A comparison of our results shows the importance of complete filling in contrast to just wetting of the nanoporous TiO₂ layer, which is generally underestimated.     

Improving conversion efficiency of dye-sensitized solar cells by metal plasma ion implantation of ruthenium ions

Dye-sensitized solar cells (DSSC) are based on the concept of photosensitization of wide-band-gap mesoporous oxide semiconductors. At present, DSSC have ventured into advanced development and pilot production. Our current research emphasizes on improvements on titanium dioxide (TiO₂) photosensitivity under visible light irradiation by using metal plasma ion implantation (MPII). The anatase TiO₂ electrode was prepared via a sol-gel process and deposited onto indium-tin oxide glass substrates. Subsequently, the as-deposited TiO₂ films were subjected to MPII at 20 keV in order to incorporate ruthenium (Ru) atoms onto the TiO₂ surface layer. The Ru-implanted TiO₂ thin film possessed nanocrystalline Ru clusters of 20 nm in diameter and distributed in near surface layer of TiO₂ films. The Ru clusters showed effective in both prohibiting electron-hole recombination and generating additional Ru-O impurity levels for the TiO₂ band gap structure. A significant reduction of TiO₂ band gap energy from 3.22 to 3.11 eV was achieved, which resulted in the extension of photocatalysis of TiO₂ from UV to Vis regime. A small drop of photoelectric performance of 8% was obtained due to the incorporation of Ru atoms in the surface layer of TiO₂, a similar side effect as observed in the Fe-implanted TiO₂. However, the overall retention of the photocatalysis capability is as high as 92% when switch from UV to Vis irradiation. The improvement of the photosensitivity of TiO₂ DSSC by means of metal plasma ion implantation is promising.     

A solid-state dye-sensitized solar cell based on a novel ionic liquid gel and ZnO nanoparticles on a flexible polymer substrate

This paper describes a new strategy to make a full solid-state, flexible, dye-sensitized solar cell (DSSC) based on novel ionic liquid gel, organic dye, ZnO nanoparticles and carbon nanotube (CNT) thin film stamped onto a polyethylene terephthalate (PET) substrate. The CNTs serve both as the charge collector and as scaffolds for the growth of ZnO nanoparticles, where the black dye molecules are anchored. It opens up the possibility of developing a continuous roll to roll processing for THE mass production of DSSCs.     

Performance evaluation of dye-sensitized solar cells (DSSCs) based on metal-free thieno[3,2-b]indole dyes

Journal of Materials Science: Materials in Electronics - A series of thieno[3,2-b]indole-based dyes (IS 1–10) was readily synthesized in three steps from 2-(thien-2-yl)thieno[3,2-b]indole as...     

Effect of electric fields on solid-state reactions between oxides

Interdiffusion in sintered polycrystalline pellets of CaO and SiO₂ occurs predominantly by migration of Ca into SiO₂ and is influenced by the application of d.c, electric fields which increase the penetration distance when the silica is negatively charged, and markedly decrease the diffusion when the polarity is reversed. Pseudowollastonite (-CaSiO₃) is formed in the interfacial region of the silica pellets under all conditions, with-Ca₂SiO₄ also appearing in the SiO₂ (–ve) electrolysed samples, possibly as a result of stabilization by the excess Ca present which also occurs as CaO interpenetrating the silica pellet. Diffusion coefficients estimated for both the unelectrolysed and field-assisted (SiO₂–ve) samples are similar to those for Ca diffusion in-CaSiO₃, but samples electrolysed under reverse polarity conditions (SiO₂ + ve) have a much larger diffusion activation energy. The effective electrical mobilities of Ca in the CaO-SiO₂ system derived from these results are discussed.     

Effect of electric fields on solid-state reactions between oxides

Interdiffusion in sintered polycrystalline pellets of MgO and Al₂O₃ at temperatures in the range 1300 to 1450° C was shown by scanning electron microscope energy dispersive X-ray probe (EDAX) and X-ray diffraction techniques to be enhanced by the application of direct current electric fields, particularly when the alumina pellet is of negative polarity, under which conditions the diffusion activation energy of Mg in Al₂O₃ is significantly increased. The diffusion process involved, principally, the transport of Mg by grain-boundary diffusion and possibly vapour-phase transport into the interstices of the comparatively porous alumina pellets; only minimal counter-migration of aluminium was observed in these experiments. The Mg-content of the discrete spinel grains within the reaction interface region is increased by electrolysis above the values calculated from solid solubility data, particularly where the alumina pellet is of positive polarity. The excess Mg is most apparent at the side of the spinel grains nearest the reaction interface, and precipitates as a surface MgO layer on the grains. The effective electrical mobility of the migrating species was calculated from the down-field shift of the diffusion profile and compared with values calculated from the electrical conductivity of the system.