Boosting ZnO nanowire dye-sensitized solar cell efficiency by coating a porous ZnO layer on the nanowires

Novel ZnO core/shell nanostructures were constructed by depositing a porous ZnO layer directly on the surfaces of pre-fabricated ZnO nanowires through a facile chemical method. The morphology and structure of the obtained products have been investigated by field-emission scanning electron microscopy, high-resolution transmission electron microscopy and X-ray diffraction analysis. In these unique nanostructures, the porous overlayer exhibits a large surface area for sufficient dye loading to enhance light harvesting and the ZnO nanowire cores provide direct conduction pathways for the photogenerated electron transport to diminish the chance of electron recombination. The obtained ZnO nanostructures were used as photoanode material in dye-sensitized solar cell which showed an increase in performance of 141 % compared with an equivalent solar cell employing ZnO nanowire arrays as photoanode. This result was achieved mainly due to an increase in photogenerated current density directly resulting from improved light harvesting of the porous layer.     

Photoresponse of hydrothermally grown lateral ZnO nanowires

In this paper, a simple self-assembled lateral growth of ZnO nanowires (NWs) photodetector has been synthesized by a hydrothermal method at a temperature as low as 85 °C. The ZnO NWs exhibit single-crystalline wurtzite with elongated c-axis and can be selectively lateral self-assembled around the edges of ZnO seeding layer. The current of ZnO NWs is sensitive to the variation of ambient pressures, i.e. 4.47 μA was decreased to 1.48 μA with 5 V-bias as 1.1 × 10^− 6 Torr changed to 760 Torr, accordingly. Moreover, the current-voltage characteristics of ZnO NWs photodetectors can be evidently distinguished by UV illumination (i.e. λ = 325 nm). The photocurrent of ZnO NWs with UV illumination is twice larger than dark current while the voltage biased at 5 V. Consequently, this faster photoresponse convinces that the hydrothermally grown lateral ZnO NWs devices have a fairly good for the fabrication of UV photodetectors.     

ZnO nanosheet-based hierarchical microarchitectures for enhanced conversion efficiency in dye-sensitized solar cells

Hierarchical ZnO microarchitectures have been fabricated on a large scale by a simple and economical citrate-mediated hydrothermal route for application in dye-sensitized solar cells (DSSCs). These flowerlike architectures are constructed by many interleaving nanosheets which have ultrathin thickness of about 5 nm. Compared with the DSSCs based on other forms of nanostructures, such as ZnO nanorods and nanoparticles, the DSSCs constructed by these hierarchical ZnO microarchitectures demonstrate a remarkable enhancement in photoelectric conversion efficiency. This enhanced performance is mainly due to the large surface area of the hierarchical microarchitectures for dye loading, and their special structural feature to ensure rapid transportation of electrons. Our results suggest that this new type of ZnO nanosheet-based microarchitectures is a promising material for application in DSSCs.     

ZnO nanowires hydrothermally grown on PET polymer substrates and their characteristics

Zinc oxide nanowires (ZnO NWs) were successfully synthesized on the ITO/PET polymer substrates by a hydrothermal method. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy investigations were carried out to characterize the crystallinity, surface morphologies, and orientations of these NWs, respectively. The influence of NW surface morphologies on the optical and electrical properties of ZnO NWs was studied. The hydrothermally grown ZnO NWs with direct band gap of 3.21 eV emitted ultraviolet photoluminescence of 406 nm at room temperature. Field emission measurements revealed that the threshold electric fields (Eth, current density of 1 mA/cm2) of ZnO NWs/ITO/PET and ZnO NWs/ZnO/ITO/PET are 1.6 and 2.2 V/microm with the enhancement factors, beta values, of 3275 and 4502, respectively. Furthermore, the field emission performance of ZnO NWs deposited on the ITO/PET substrate can be enhanced by illumination with Eth of 1.3 V/microm and displays a maximum emission current density of 18 mA/cm2. The ZnO NWs successfully grown on polymer substrate with high transmittance, low threshold electric field, and high emission current density may be applied to a flexible field emission display in the future.     

Ultra-fast microwave-assisted hydrothermal synthesis of long vertically aligned ZnO nanowires for dye-sensitized solar cell application

Long vertically aligned ZnO nanowire arrays were synthesized using an ultra-fast microwave-assisted hydrothermal process. Using this method, we were able to grow ZnO nanowire arrays at an average growth rate as high as 200?nm?min(-1) for maximum microwave power level. This method does not suffer from the growth stoppage problem at long growth times that, according to our investigations, a normal microwave-assisted hydrothermal method suffers from. Longitudinal growth of the nanowire arrays was investigated as a function of microwave power level and growth time using cross-sectional FESEM images of the grown arrays. Effect of seed layer on the alignment of nanowires was also studied. X-ray diffraction analysis confirmed c-axis orientation and single-phase wurtzite structure of the nanowires. J-V curves of the fabricated ZnO nanowire-based mercurochrome-sensitized solar cells indicated that the short-circuit current density is increased with increasing the length of the nanowire array. According to the UV-vis spectra of the dyes detached from the cells, these increments were mainly attributed to the enlarged internal surface area and therefore dye loading enhancement in the lengthened nanowire arrays.     

ZnO hierarchical nanostructures and application on high-efficiency dye-sensitized solar cells

Uniform hierarchical ZnO nanostructures are synthesized on a large scale based on a solution approach at low temperature. The primary ZnO hexagonal prisms are firstly produced by the reaction of Zn(NO₃)₂ with hexamethylenetetramine, and then ZnO branches grow on the primary prisms by using ethylenediamine molecules as an evocator. The morphology of the hierarchical nanostructure can be controlled conveniently by adjusting the molar ratio of [EDA]/[Zn²⁺]. The hierarchical structure provides an effective pathway for carrier transport as well as larger surface area for dye adsorption, when ZnO hierarchical nanostructures serve as photoanode materials, the solar cells show higher conversion efficiency than that of primary ZnO nanowires.     

Achievement of 4.7% conversion efficiency in ZnO dye-sensitized solar cells fabricated by spray deposition using hydrothermally synthesized nanoparticles

ZnO-based dye-sensitized solar cells (DSSCs) have been fabricated using hydrothermally synthesized ZnO nanoparticles by spray deposition. The effect of self-assembled nanostructures in ZnO photoelectrodes, due to the electric field during spray deposition, has been studied. Thickness of the photoelectrode is found to play a role on the cell performance, the cell with nanocrystalline film thickness of ～4.3?μm yielding an efficiency of ～2.8% for a cell area of ～3.2?cm(2). On the other hand, the cell with ZnO nanostructures is found to yield an efficiency of 4.7% (enhancement of ～60%) which is highest for the cell with area>1?cm(2) having a photoelectrode thickness of ～4.5?μm. Increased surface area due to the presence of ZnO nanostructures in the photoelectrode film helps in the adsorption of more dye molecules to the ZnO surface, which contributes to the better cell performance. The improved dye-sensitized solar cell performance is also explained with the help of light scattering by the ZnO nanostructures through extending the distance traveled by light so as to increase the light-harvesting efficiency of the photoelectrode film.     

ZnO hierarchical aggregates: Solvothermal synthesis and application in dye-sensitized solar cells

ZnO hierarchical aggregates have been successfully synthesized by solvothermal methods through reaction of zinc acetate and potassium hydroxide in methanol solution. The shapes of the aggregates were controlled by varying the ratio of Zn²⁺ and OH^? ions in the reaction system, while the size can be tuned from 2 μm to 100 nm. Oriented attachment was found to be the main mechanism of the three-dimensional assembly of small ZnO nanocrystallites into large aggregates. The performance of these aggregates in dye-sensitized solar cells (DSCs) indicated that hierarchical structured photoelectrodes can increase energy conversion efficiency of DSCs effectively when the sizes of aggregates match the wavelengths of visible light.      

Nanoforest Nb2O5 photoanodes for dye-sensitized solar cells by pulsed laser deposition

Vertically aligned bundles of Nb(2)O(5) nanocrystals were fabricated by pulsed laser deposition (PLD) and tested as a photoanode material in dye-sensitized solar cells (DSSC). They were characterized using scanning and transmission electron microscopies, optical absorption spectroscopy (UV-vis), and incident-photon-to-current efficiency (IPCE) experiments. The background gas composition and the thickness of the films were varied to determine the influence of those parameters in the photoanode behavior. An optimal background pressure of oxygen during deposition was found to produce a photoanode structure that both achieves high dye loading and enhanced photoelectrochemical performance. For optimal structures, IPCE values up to 40% and APCE values around 90% were obtained with the N(3) dye and I(3)(-)/I(-) couple in acetonitrile with open circuit voltage of 0.71 V and 2.41% power conversion efficiency.     

Electrodeposition of hierarchical ZnO nanorod-nanosheet structures and their applications in dye-sensitized solar cells

We present a two-step electrochemical deposition process to synthesize hierarchical zinc oxide (ZnO) nanorod-nanosheet structures on indium tin oxide (ITO) substrate, which involves electrodeposition of ZnO nanosheet arrays on the conductive glass substrate, followed by electrochemical growth of secondary ZnO nanorods on the backbone of the primary ZnO nanosheets. The formation mechanism of the hierarchical nanostructure is discussed. It is demonstrated that annealing treatment of the primary nanosheets synthesized by the first-step deposition process plays a key role in synthesizing the hierarchical nanostructure. Photovoltaic properties of dye-sensitized solar cells (DSSCs) based on hierarchical ZnO nanostructures are investigated. The hierarchical ZnO nanorod-nanosheet DSSC exhibits improved device performance compared to the DSSC constructed using photoelectrode of bare ZnO nanosheet arrays. The improvement can be attributed to the enhanced dye loading, which is caused by the enlargement of internal surface area within the nanostructure photoelectrode. Furthermore, we perform a parametric study to determine the optimum geometric dimensions of the hierarchical ZnO nanorod-nanosheet photoelectrode through adjusting the preparation conditions of the first- and second-step deposition process. By utilizing a hierarchical nanostructure photoelectrode with film thickness of about 7 μm, the DSSC with an open-circuit voltage of 0.74 V and an overall power conversion efficiency of 3.12% is successfully obtained.     

Growth mechanism of titanium dioxide nanowires for dye-sensitized solar cells

Mesoporous films made of titanium dioxide nanowires are desirable for dye-sensitized solar cells because nanowires provide direct conduction pathways for photogenerated electrons. Anatase titanium dioxide nanowires with polycrystalline microstructure were synthesized on titanium foil using a three-step process. First, the top surface of the titanium foil was transformed to Na(2)Ti(2)O(4)(OH)(2) nanotubes through hydrothermal oxidation in NaOH. Next, the Na(2)Ti(2)O(4)(OH)(2) nanotubes were converted to H(2)Ti(2)O(4)(OH)(2) nanotubes by ion exchange. Finally, the H(2)Ti(2)O(4)(OH)(2) nanotubes were converted to polycrystalline anatase nanowires through a topotactic transformation. The film morphology evolution, crystal structure transformations and growth mechanism are described in detail. Titanium foil reacts with NaOH to form Na(2)Ti(2)O(4)(OH)(2) sheets, which exfoliate and spiral into nanotubes. The Na(2)Ti(2)O(4)(OH)(2) nanotubes are immersed in HCl solution to replace the Na(+) ions with H(+) ions. During the topotactic transformation of H(2)Ti(2)O(4)(OH)(2) nanotubes to anatase TiO(2) nanowires, the sheets made of edge bonded TiO(6) octahedra in the H(2)Ti(2)O(4)(OH)(2) nanotubes dehydrate and move towards each other to form anatase crystals oriented along the nanotube axis which creates a polycrystalline nanowire. These mesoporous TiO(2) nanowire films were suitable for use as dye-sensitized solar cell photoanodes.     

ZnO nanoparticles and porous coatings for dye-sensitized solar cell application: Photoelectrochemical characterization

Nanoscale zinc oxide (ZnO) powder with Brunauer-Emmelt-Teller surface area of 43 m² g^− 1 has been synthesized by soft chemistry at low temperature via reaction of zinc acetate dehydrate (Zn(CH₃COO)₂.2H₂O) and sodium hydroxide (NaOH). The influence of the pH value of the sol on the structure and morphology of ZnO powder have been investigated by X-Ray Diffraction, Scanning Electron Microscopy and High Resolution Transmission Electron Microcopy. Their thermal properties have been determined by simultaneous Differential Thermal Analysis and Thermogravimetry coupled to Mass Spectroscopy analysis. The nanoparticles are single crystals with (101) preferred orientation but agglomerated. Their crystallite size can be adjusted from 15 nm to 35 nm by controlling the pH value between 7 and 13. Thick porous crystalline coatings have been obtained by doctor blade coating on conducting SnO₂:F glass substrates using pastes prepared by wetting the crystalline powders with polyethylene glycol and water. After sintering at 400 °C and Ruthenium 535 dye sensitization, the coatings have been tested in a three electrode electrochemical cell containing an appropriate electrolyte in the dark and under 450 W Xenon lamp illumination. The influence of the electrolyte iodine concentration, the film thickness and the light intensity on the current density are presented and discussed. Such coatings appeared promising for the realization of dye sensitized solar cells.     

Facile synthesis of ZnO nanocrystals via a solid state reaction for high performance plastic dye-sensitized solar cells

We report the facile synthesis of ZnO nanocrystals via a one-step solid state reaction at room temperature and their application as the photoanode in plastic dye-sensitized solar cells (DSCs). ZnO nanoparticles were prepared utilizing zinc acetate dihydrate and sodium hydroxide with a short grinding time and without a sintering process. The as-prepared samples with the polycrystalline hexagonal wurtzite structure were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The obtained ZnO nanoparticles exhibited high crystallinity even without a high temperature sintering treatment during the preparation process. The effects of compression post-treatment on the photovoltaic performance of DSCs were also investigated using intensity modulated photocurrent spectroscopy (IMPS), incident photo-to-current conversion efficiency (IPCE), and electrochemical impedance spectroscopy (EIS). The results indicate that the improvement of power conversion efficiency after compression post-treatment of ZnO photoelectrode can be attributed to its high photoelectron collection efficiency and effective electron transport. Under the optimized conditions, a full plastic D149-sensitized ZnO solar cell measured under illumination of 100 mW·cm⁻² (AM 1.5G) presents an energy conversion efficiency of 3.76% with open-circuit voltage of 0.688 V, short-circuit current density of 8.55 mA·cm⁻², and fill factor of 0.64. These results demonstrate that the one-step solid state reaction is a convenient and effective method for the synthesis of ZnO nanocrystals for use in plastic DSCs.      

Synthesis of hierarchical nanoparticles-based ZnO spheres for their application as the light blocking layers in dye-sensitized solar cells

Three-dimensional nanoparticles-based ZnO hierarchical spheres (ZnO-HS) with strong light harvesting and dye loading abilities have been fabricated by a simple hydrothermal method in this paper. These ZnO-HS were designed as the overlayer for light blocking and applied to the dye-sensitized solar cells (DSSCs) based on bare ZnO nanoparticles (ZnO-NP) or TiO₂ nanoparticles (TiO₂-NP). The results show that the values of the short-circuit current density (J _sc) and the power conversion efficiency (η) have been heightened up to 12.6 mA cm^?2 and 3.40 % for the ZnO-NP/ZnO-HS double-layered DSSC, far higher than the bare ZnO-NP DSSC. However, another DSSC assembled by the TiO₂-NP/ZnO-HS double-layered film displays an adverse result for the decreasing of J _sc and η even though the ZnO-HS light blocking layer has been established on the TiO₂-NP film. According to the electrochemical impedance data compared between the ZnO-NP/ZnO-HS double-layered and TiO₂-NP/ZnO-HS double-layered DSSC, it is found that the former possesses less possibility for the occurrence of charge recombination and electronic loss, which is responsible for its better photovoltaic response.     

Electrodeposited nanoporous versus nanoparticulate ZnO films of similar roughness for dye-sensitized solar cell applications

We present a comparative study of two different ZnO porous film morphologies for dye-sensitized solar cell (DSSC) fabrications. Nanoparticulate ZnO was prepared by the doctor-blade technique starting from a paste containing ZnO nanoparticles. Nanoporous ZnO films were grown by a soft template-assisted electrochemical growth technique. The film thicknesses were adjusted at similar roughness of about 300 in order to permit a worthy comparison. The effects on the cell performances of sensitization by dyes belonging to three different families, namely, xanthene (eosin Y) and indoline (D102, D131, D149 and D205) organic dyes as well as a ruthenium polypyridine complex (N719), have been investigated. The mesoporous electrodeposited matrix exhibits significant morphological changes upon the photoanode preparation, especially upon the dye sensitization, that yield to a dramatic change of the inner layer morphology and increase in the layer internal specific surface area. In the case of indoline dyes, better efficiencies were found with the electrodeposited ZnO porous matrixes compared to the nanoparticulate ones, in spite of significantly shorter electron lifetimes measured by impedance spectroscopy. The observation is interpreted in terms of much shorter transfer time in the oxide in the case of the electrodeposited ZnO films. Among the tested dyes, the D149 and D205 indoline organic dyes with a strong acceptor group were found the most efficient with the best cell over 4.6% of overall conversion efficiency.     

Ag nanoparticle-decorated SiO2@TiO2 hierarchical microspheres improve the efficiency of dye-sensitized solar cells

SiO₂@TiO₂-Ag (STA) microspheres decorated with Ag nanoparticles (Ag NPs) were prepared and assembled into the photoanode. The photoanode composed of STA microspheres and TiO₂ nanoparticles (P25) was prepared by doctor blade method. UV–vis measurement indicates that the introduction of a few STA microspheres observably enhances the light scattering and capturing ability of the photoanode. The photoelectric conversion efficiency of the DSSCs with 2wt% STA photoanode increased to 7.4% from 4.3% comparing with pure P25 TiO₂ nanoparticles. The configuration DSSCs have the maximum short circuit current density (J_sc) of 16.0 mA cm^?2 and open-circuit voltage (V_oc) of 0.780 V, which are significantly higher than the pure TiO₂ DSSCs. The significant improvement of the DSSCs performance can be due to the synergistic effect of the superior light scattering of STA and the localized surface plasma resonance (LSPR) effect of Ag NPs modified on the microspheres surface.

     

TiO2 nanotube membranes on transparent conducting glass for high efficiency dye-sensitized solar cells

Crack-free TiO(2) nanotube (NT) membranes were obtained by short time re-anodization of a sintered TiO(2) NT array on Ti foil, followed by dilute HF etching at room temperature. The resulting freestanding TiO(2) membranes were opaque with a slight yellow color having one end open and another end closed. The membranes were then fixed on transparent fluorine-tin-oxide glass using a thin layer of screen-printed TiO(2) nanoparticles (NPs) as a binding medium. It was found that low temperature treatment of the resulting NT/NP film under appropriate pressure before sintering at 450?°C was critical for successful fixation of the NT membrane on the NP layer. The resulting films with open-ends of NT membranes facing the NP layer (open-ends down, OED, configuration) exhibited better interfacial contact between NTs and NPs than those with closed-ends facing the NP layer (closed-ends down, CED, configuration). The cells with an OED configuration exhibit higher external quantum efficiency, greater charge transfer resistance from FTO/TiO(2) to electrolyte, and better dye loading compared to CED configurations. The solar cells with the OED configuration gave 6.1% energy conversion efficiency under AM1.5G condition when the commercial N719 was used as a dye and I(-)/I(3)(-) as a redox couple, showing the promise of this method for high efficiency solar cells.     

Single-crystalline zinc oxide nanowires as photoanode material for dye-sensitized solar cells

This study reports the use of single-crystalline and well-aligned ZnO nanowires as photoanode material for dye-sensitized solar cells. The ZnO nanowires are grown on fluorine-doped tin oxide coated glass substrates without catalysts by thermal evaporation. In spite of low roughness factors of around 25 for the nanowire photoanodes, the fabricated solar cells yield power conversion efficiencies of around 1.3% under AM 1.5G (100 mW cm-2) illumination. Moreover, fill factors of around 0.5 have been achieved and are relatively high when compared with reported values from ZnO nanowire photoanodes. The results reveal the advantage of using single-crystalline nanowires as photoanode material and provide clues for the advancement of nanowire based dye-sensitized solar cells.