Organic photosensitizers with a heteroleptic dual donor for dye-sensitized solar cells

Using DFT and TDDFT calculations, we investigated the substitution effect in the electronic and optical properties of dye sensitizers with a dual donor composed of triphenylamine and/or indoline moieties. Due to replacement with the dual donor moieties, the HOMO levels were split into HOMO and HOMO - 1 levels, and the bandgaps between the HOMO and LUMO levels decreased, leading to the creation of bathochromically extended absorption spectra. Nearly degenerated splitting of the HOMO levels resulted from the similarity of the electronic structure between the HOMO and the HOMO - 1 levels, delocalized over both dual-donor moieties, when replacing the dual donors. It was shown that the additional electron-donating group creates an additional absorption band and causes a cascading two-electron process aiding the charge separation process. Owing to a more panchromatic attribute, easier energy transfer and feasible retardation of the recombination between the injected electrons and the electrolyte, it is expected that dyeTI will show better performance than the other dyes (dyeT dyeTT and dyeIT) as denoted here in terms of the conversion efficiency of dye-sensitized solar cells (DSSCs). This work presents the probable benefits of dye sensitizers with dual-donor moieties and provides insight into the development of more efficient dye sensitizers for DSSCs through modification of the Frontier molecular orbitals.     

New configuration of optical photosensitizers for dye-sensitized solar cells: combination of carbazole and xantone

Novel organic dyes system containing responsible group for using in dye-sensitized solar cells and effective anchoring group for improving interaction between dye (photosensitizers) and nanolayer were designed and prepared. All intermediates and organic dyes were purified and analyzed using analytical techniques. The results confirmed the structure of intermediates and organic dyes. Dye-coated TiO₂ and ZnO semiconductors were used for the preparation of the photoanode. The synthesized dyes were trapped in J-aggregation, reflected J-aggregation, and red shift in UV–Vis spectra of dyes in solution relative to the coated on nanomaterials. Cyclic voltammetry and DFT methods were used to evaluate the energy levels of the synthesized compounds. Dye-sensitized solar cells were also prepared and evaluated under standard conditions, using the synthesized compounds. The efficiency of Dye 8 as photosensitizer on TiO₂ and ZnO was 6.65% and 6.37%, respectively.

     

Nano-TiO2 for dye-sensitized solar cells

Photovoltaics are amongst the most popular renewable energy sources and low-cost solar cell technologies are making progress to the market. Research on dye-sensitized solar cells (DSSCs) usually based on nanocrystalline TiO2 has been extensively pursued, and the number of papers and patents published in this area has grown exponentially over the last ten years. Research efforts have largely focused on the optimization of the dye, but recently the TiO2 nanocrystalline electrode itself has attracted more attention. It has been shown that particle size and shape, crystallinity, surface morphology and chemistry of the TiO2 material are key parameters to be controlled for optimized performance of the solar cell. This article will review the most recent research activities on nanostructured TiO2 for improvement of the DSSC performance.     

Nanowire dye-sensitized solar cells

Excitonic solar cells-including organic, hybrid organic-inorganic and dye-sensitized cells (DSCs)-are promising devices for inexpensive, large-scale solar energy conversion. The DSC is currently the most efficient and stable excitonic photocell. Central to this device is a thick nanoparticle film that provides a large surface area for the adsorption of light-harvesting molecules. However, nanoparticle DSCs rely on trap-limited diffusion for electron transport, a slow mechanism that can limit device efficiency, especially at longer wavelengths. Here we introduce a version of the dye-sensitized cell in which the traditional nanoparticle film is replaced by a dense array of oriented, crystalline ZnO nanowires. The nanowire anode is synthesized by mild aqueous chemistry and features a surface area up to one-fifth as large as a nanoparticle cell. The direct electrical pathways provided by the nanowires ensure the rapid collection of carriers generated throughout the device, and a full Sun efficiency of 1.5% is demonstrated, limited primarily by the surface area of the nanowire array.     

Simple metal-free organic D-pi-A dyes with alkoxy- or fluorine substitutions: application in dye sensitized solar cells

Two new metal-free organic sensitizers with simplest structural variations have been synthesized for application in nanocrystalline TiO2 sensitized solar cells. The donor-pi-bridge-acceptor (D-pi-A) structure dyes, Y2 and Y3 each designed with three parts, an electron donor unit (substituted phenyl), a linker unit (thiophene), and an anchor unit (cyanoacrylic acid) showed maximal monochromatic incident photon to current conversion efficiencies (IPCE) in a device reaching upto 67% and 82% respectively. The organic sensitizers with 3,4,5-trimethoxy phenyl (Y3) as donor moieties obtained better solar light to electrical energy conversion efficiencies of 3.30% where as the organic sensitizer with 2,4-difluoro phenyl as donor (Y2) showed comparatively lower efficiency of 1.02%. The efficiency obtained with the reference sensitizer N719 under similar fabrication and evaluation conditions was 5.84%.     

Surface-oxidized tungsten for energy-storable dye-sensitized solar cells

Tungsten oxide electrodes were investigated as charge-storage materials for energy-storable dye-sensitized solar cells (ES-DSSCs). The electrochemical and structural properties of the surface-oxidized tungsten (so-WO_3 − x) and monoclinic nanocrystalline WO₃ (nc-WO₃) were studied on the difference of the charge-discharge properties. Although, the electromotive force (EMF) curve of the so-WO_3 − x was associated with structural change, the so-WO_3 − x did not show the significant structural change indicated by X-ray diffraction (XRD) patterns. On the other hand, the nc-WO₃ showed crystal transformation from monoclinic phase to tetragonal phase. The Li⁺ diffusion coefficients of the so-WO_3 − x with different Li⁺ content ratios obtained by the galvanostatic intermittent titration technique (GITT) did not fall down up to 0.3 of Li/W ratio, whereas the diffusion coefficients of nc-WO₃ decreased about two orders of magnitude in the vicinity of phase transitions. The different electrochemical properties could be explained by the less structural change of so-WO_3 − x compared with the nc-WO₃. The large-sized ES-DSSCs with the so-WO_3 − x were fabricated for the first time, and their photocharge-discharge performances were studied.     

Efficient dye-sensitized solar cells based on the combination of ZnO nanorods and microflowers

Well-aligned ZnO nanorod films were grown onto transparent conducting substrates by using an aqueous solution route. The presence of some reflections in the X-ray diffraction pattern of the ZnO films indicates the vertical alignment of the nanorods along the c axis of the wurtzite hexagonal structure. Well-aligned ZnO nanorods were observed by scanning electron microscopy. The presence of top ZnO microflower layers over the ZnO nanorod film was observed for all growth times studied. The ZnO nanorods with ZnO microflower top layers were applied as photoelectrodes in dye-sensitized solar cells. Higher photocurrent densities and photovoltages were observed with longer nanorod growth times. The high performance of the dye-sensitized solar cells might be associated to the combination of ZnO nanorods and microflowers in the same photoelectrode.     

An efficient metal-free sensitizer for dye-sensitized solar cells

A novel metal-free organic dye consisting of a phenothiazine donor, a 3,4-ethylenedioxythiophene bridge, and a cyanoacrylate acceptor is synthesized and its optical, electrochemical and photovoltaic properties are characterized. A solar cell employing the metal-free dye exhibits a maximum solar energy to an electricity conversion efficiency of 6.72% under AM 1.5 solar simulator (100 mW cm^− 2). The results suggest that dye based on a phenothiazine donor and 3,4-ethylenedioxythiophene π-spacer is a promising candidate for high performance dye-sensitized solar cells.     

Progress in nanostructured photoanodes for dye-sensitized solar cells

Solar cells represent a principal energy technology to convert light into electricity. Commercial solar cells are at present predominately produced by single- or multi-crystalline silicon wafers. The main drawback to silicon-based solar cells, however, is high material and manufacturing costs. Dye-sensitized solar cells (DSSCs) have attracted much attention during recent years because of the low production cost and other advantages. The photoanode (working electrode) plays a key role in determining the performance of DSSCs. In particular, nanostructured photoanodes with a large surface area, high electron transfer efficiency, and low electron recombination facilitate to prepare DSSCs with high energy conversion efficiency. In this review article, we summarize recent progress in the development of novel photoanodes for DSSCs. Effect of semiconductor material (e.g. TiO₂, ZnO, SnO₂, N₂O₅, and nano carbon), preparation, morphology and structure (e.g. nanoparticles, nanorods, nanofibers, nanotubes, fiber/particle composites, and hierarchical structure) on photovoltaic performance of DSSCs is described. The possibility of replacing silicon-based solar cells with DSSCs is discussed.     

Quasi-gel-state ionic liquid electrolyte with alkyl-pyrazolium iodide for dye-sensitized solar cells

A series of non-volatile viscous ionic liquid, 1-alkyl-2-methylpyrazolium iodides (RPyI: R = C₃-C₇), were synthesized for the electrolyte of dye-sensitized solar cells (DSSC). Most of RPyI revealed extremely viscous quasi-gel-state electrolytes potentially preventing leakage and evaporation of electrolytes of the solar cells. A DSSC using the electrolyte composed of 1-hexyl-2-methylpyrazolium iodide (C₆PyI) with iodine exhibiting higher conversion efficiency of 3.8% (under 1 Sun) for 10% larger short-circuit photocurrent, J_SC, than that with a conventional ionic liquid, 1-hexyl-3-methyllimidazolium iodide (C₆ImI) with iodine, in spite of less favorable viscosity (2013 mPa s (C₆PyI/I₂) vs. 1439 mPa s (C₆ImI/I₂)) for the physical diffusion of charge carriers in the electrolyte. Furthermore, the quasi-gel-state electrolytes composed of a series of RPyI ionic liquids surprisingly exhibiting comparable J_SC to that with much less viscous C₆ImI/I₂. We discuss the results of quasi-gel-state RPyI ionic liquid electrolyte for DSSC based on the Grotthus-like electron exchange mechanism of iodide redox species in the highly viscous RPyI ionic liquid evaluated qualitatively by Raman spectroscopic observation of poly-iodide species.     

ZnO nanotube based dye-sensitized solar cells

We introduce high surface area ZnO nanotube photoanodes templated by anodic aluminum oxide for use in dye-sensitized solar cells (DSSCs). Atomic layer deposition is utilized to coat pores conformally, providing a direct path for charge collection over tens of micrometers thickness. Compared to similar ZnO-based devices, ZnO nanotube cells show exceptional photovoltage and fill factors, in addition to power efficiencies up to 1.6%. The novel fabrication technique provides a facile, metal-oxide general route to well-defined DSSC photoanodes.     

Review on development of electrolytes for dye-sensitized solar cells

Since the prototype of a dye-sensitized solar cell(DSSC)was reported in 1991 by M. Gratzel,it has aroused intensive interest over the past decade due to its low cost and simple preparation procedure.The typical cell consists of a dye-coated mesoporous nanocrystalline TiO_2 film sandwiched between two transparent electroldes.A liquid electrolyte,traditionally containing the trioidide/iodide redox couple,fills the pores of the mesoporous nanocrystalline TiO_2 film and contacts the nanoparticles.Photoexcite...     

Hierarchical structured TiO2 photoanodes for dye-sensitized solar cells

A novel approach has been developed to fabricate hills-like hierarchical structured TiO2 photoanodes for dye-sensitized solar cells (DSSCs). The appropriately aggregated TiO2 clusters in the photoanode layer could cause stronger light scattering and higher dye loading that increases the efficiency of photovoltaic device. For detailed light-harvesting study, different molecular weights of polyvinyl alcohol (PVA) were used as binders for TiO2 nanoparticles (P-25 Degussa) aggregation. A series of TiO2 films with dissimilar morphology, the reflection of TiO2 films, absorbance of attached dye, amount of dye loading, and performance of fabricated DSSC devices, were measured and investigated. An optimized device had energy conversion efficiency of 4.47% having a higher dye loading and good light harvesting, achieving a 23% increase of short-circuit current J(sc) in DSSCs.     

Glancing angle deposited titania films for dye-sensitized solar cells

A series of sculptured porous nano-columnar titanium oxide films were prepared by glancing angle deposition (GLAD) method using an electron-beam evaporation system. The films were deposited on ITO glasses at various incident angles from 53° to 86°and used as photoanode in a dye-sensitized solar cell (DSSC). The as-deposited TiO₂ films are comprised of helical nano-columns and assembled in an orderly manner with gaps or pores in between. The porous nanostructured films provide a synergetic effect of high surface area, effective route for electron transfer, tight interfaces, and enhanced light trapping, which are all beneficial for higher cell efficiency. The DSSCs incorporated with the GLAD films of 4 μm thick exhibited a high fill factor (FF) up to 0.77. The TiO₂ film deposited at an incident angle of 73° provides the largest internal surface area and the largest amount of dye absorption and results in the highest light conversion efficiency of 2.78%.     

Novel ionic iodide-siloxane hybrid electrolyte for dye-sensitized solar cells

A novel ionic siloxane hybrid electrolyte was fabricated by thermal polymerization of iodide-oligosiloxane resin. The nanosized iodide-oligosiloxane was synthesized by a simple sol-gel condensation of 3-iodopropyltrimethoxysilane and diphenylsilanediol. It is found that the composition and concentration of the oligosiloxane used in the electrolyte affect the performance of the dye-sensitized solar cells (DSSCs). An optimized DSSC with the hybrid electrolyte using smaller molecular-sized oligosiloxane with a greater amount of iodide groups presented solar to electricity conversion efficiency of 5.2% at 1 sunlight (100 mW cm(-2)), which is comparable to that afforded by a liquid electrolyte.     

Transparent, conductive graphene electrodes for dye-sensitized solar cells

Transparent, conductive, and ultrathin graphene films, as an alternative to the ubiquitously employed metal oxides window electrodes for solid-state dye-sensitized solar cells, are demonstrated. These graphene films are fabricated from exfoliated graphite oxide, followed by thermal reduction. The obtained films exhibit a high conductivity of 550 S/cm and a transparency of more than 70% over 1000-3000 nm. Furthermore, they show high chemical and thermal stabilities as well as an ultrasmooth surface with tunable wettability.     

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.     

Holographically defined TiO2 electrodes for dye-sensitized solar cells

We describe a multibeam interference lithography for creating 3D polymeric porous structures. The coating of a TiO(2) shell and subsequent removal of the template produce holographically defined TiO(2) (h-TiO(2)) electrodes. We analyze the morphological features of the h-TiO(2) electrodes and consider their applicability to dye-sensitized solar cells (DSSCs). Specifically, the performance of the h-TiO(2) electrode was evaluated by comparison with a macroporous TiO(2) electrode produced from colloidal crystals. The h-TiO(2) structure possesses a larger specific area than the inverted colloidal crystals because of a bicontinuous air network with the TiO(2) shell. Consequently, the h-TiO(2) electrode can produce a 30% higher photogenerated electron current.     

Tunable synthesis of mesoporous titania with different morphologies for dye-sensitized solar cells

Different TiO₂ mesoporous structures, including core-shell spheres (CCSs) and micro-tubes (MTs), are synthesized through adjusting the pH of the solution using TiOSO₄ as titanium source in a hydrothermal route. TiO₂ CSSs with an average diameter of 1.3–3.5 μm exhibit excellent light scattering property and high specific surface area (177.63 m² g^?1). TiO₂ MTs show ultrahigh specific surface area of 276.03 m² g^?1. Dye-sensitized solar cell is fabricated using TiO₂ CSSs as the light scattering layer and TiO₂ nanoparticles (NPs) layer as the bottom layer. The efficiency of Cell-NPs + CSSs is up to 9.24% due to the good light scattering effect and excellent dye loading capacity. Furthermore, TiO₂ MTs are introduced to form the NPs/MTs bottom layer. The Cell-NPs/MTs + CSSs achieves an outstanding efficiency of 9.60% due to the further optimized electron transport path.