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.     

Synthesis of two-dimensional ZnO nanosheet-structures for the application in dye-sensitized solar cells

A large amount of nano-ZnO with a thin sheet-like morphology has been manufactured by a simple citric acid assisted hydrothermal route. The influences on the morphologies and structures of ZnO products for the introduction of citric acid in the reaction system have been investigated. A dye-sensitized solar cell assembled by the ZnO nanosheets as photoanode shows an efficiency of 1.82 % with a short-circuit current density of 7.48 mA cm^?2 which is over 1.5 times higher than the one without adding citric acid during the synthetic process. This result is mainly connected to the unique superiority of the two-dimensional sheet-like ZnO nanostructures for light scattering and dye loading.     

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.      

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.     

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.     

Template-free synthesis of hierarchical TiO2 structures and their application in dye-sensitized solar cells

We demonstrate here the synthesis of a hierarchical TiO(2) architecture without any surfactants or templates. Two kinds of structure existed simultaneously, the ordered nanoarrays at bottom provided direct conduction pathway for photo generated electrons, while the upper micro-flowers consisted of nanobelt as building units increased the light harvesting ability as the scattering part. The formation mechanism of the hierarchical architecture has been proposed by studying the morphology evolution processes upon reaction time. The performance of dye-sensitized solar cells based on the obtained hierarchical anatase TiO(2) has been also studied, giving a J(SC) = 12.44 mA cm(-2), V(OC) = 0.64 V, FF = 69.05%, and η = 5.53%, which is superior than commercial TiO(2) (P25). The UV-vis results prove that the obtained morphology is beneficial to light-scattering and thus increases the light harvesting ability. This hierarchical TiO(2) structure offers great potential for the development of high-efficiency DSSCs.     

One-step large-scale synthesis of porous ZnO nanofibers and their application in dye-sensitized solar cells

A one-step thermal evaporation and vapor-phase transport method was utilized to synthesize porous ZnO nanofibers in large scale. The synthesized nanofibers are highly porous, with diameters in the range of 200–700 nm and lengths of several micrometers. The addition of the CuCl₂·2H₂O into the Zn precursor powder was proved to be critical for the formation of the porous structures, which were proposed to be resulted from the decomposition of the unstable Cl-containing intermediate products such as zinc hydroxide chloride or zinc oxide chloride hydrate phases. In addition, a demonstration of applying the porous ZnO nanofibers as the photoanode of dye-sensitized solar cells is provided.     

Controlled synthesis of ZnO branched nanorod arrays by hierarchical solution growth and application in dye-sensitized solar cells

We demonstrate the controlled synthesis of ZnO branched nanorod arrays on fluorine-doped SnO₂-coated glass substrates by the hierarchical solution growth method. In the secondary growth, the concentration of Zn(NO₃)₂/hexamethylenetetramine plays an important role in controlling the morphology of the branched nanorod arrays, besides that of diaminopropane used as a structure-directing agent to induce the growth of branches. The population density and morphology of the branched nanorod arrays depend on those of the nanorod arrays obtained from the primary growth, which can be modulated though the concentration of Zn(NO₃)₂/hexamethylenetetramine in the primary growth solution. The dye-sensitized ZnO branched nanorod arrays exhibit much stronger optical absorption as compared with its corresponding primary nanorod arrays, suggesting that the addition of the branches improves light harvesting. The dye-sensitized solar cell based on the optimized ZnO branched nanorod array reaches a conversion efficiency of 1.66% under the light radiation of 1000 W/m². The branched nanorod arrays can also be applied in other application fields of ZnO.     

Synthesis and characterization of flower like ZnO nanorods for dye-sensitized solar cells

Flower like ZnO nanorods have been prepared by chemical bath deposition method. X-ray diffraction result shows that flower like ZnO nanorods exhibit hexagonal structure. Dye sensitized solar cells have been assembled by using ZnO nanorod film photoelectrode sensitized using natural dye extracted from daucus carota as sensitizer. The flower like ZnO nanorods have been used as photo-anode material to fabricate the dye sensitized solar cell which exhibited an overall light to electricity conversion efficiency of 0.78 % with a fill factor of 0.39, short-circuit current density of 3.70 mA/cm² and open-circuit voltage of 0.26 V.     

Synthesis of ZnO nanopowders by DC thermal plasma for dye-sensitized solar cells

Zinc oxide (ZnO) nanopowders were synthesized from commercially available micro-sized zinc powders (Aldrich Co., 98%, 10 μm) by a DC thermal plasma process at atmospheric pressure. The micro-sized zinc powders were vaporized in the plasma region, after which the plasma processing equipment was rapidly quenched, resulting in the formation of ZnO nanopowders with a size of less than 300 nm. Two different reaction gases of oxygen and carbon dioxide were used as the oxygen source and each gas flow rate was controlled as a process variable. The obtained ZnO nanopowders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). All synthesized ZnO nanopowders showed high crystalline wurtzite structures and the differences in their morphologies were strongly dependent on the operating variables. The photocurrent–voltage (J–V) curve of the ZnO nanopowders with a dye of ruthenium (II) 535 bis-TBA (N719, Solaronix) in redox electrolyte showed an overall energy conversion efficiency (η) of 2.54%, demonstrating that the application of the mass-producible ZnO nanopowders by thermal plasma processing to DSSC was feasible.     

ZnO nanostructures as efficient antireflection layers in solar cells

An efficient antireflection coating (ARC) can enhance solar cell performance through increased light coupling. Here, we investigate solution-grown ZnO nanostructures as ARCs for Si solar cells and compare them to conventional single layer ARCs. We find that nanoscale morphology, controlled through synthetic chemistry, has a great effect on the macroscopic ARC performance. Compared with a silicon nitride (SiN) single layer ARC, ZnO nanorod arrays display a broadband reflection suppression from 400 to 1200 nm. For a tapered nanorod array with average tip diameter of 10 nm, we achieve a weighted global reflectance of 6.6%, which is superior to an optimized SiN single layer ARC. Calculations using rigorous coupled wave analysis suggest that the tapered nanorod arrays behave like modified single layer ARCs, where the tapering leads to impedance matching between Si and air through a gradual reduction of the effective refractive index away from the surface, resulting in low reflection particularly at longer wavelengths and eliminating interference fringes through roughening of the air-ZnO interface. According to the calculations, we may further improve ARC performance by tailoring the thickness of the bottom fused ZnO layer and through better control of tip tapering.     

The application of freestanding titanate nanofiber paper for scattering layers in dye-sensitized solar cells

A titanate nanofiber paper with robust and good flexible property was successfully prepared by alkali hydrothermal synthesis with simple paper-making method. These nanofibers were about 80 nm in diameter and had a typical length in the range of tens of micrometers. Despite the transformation from titanate to TiO₂-B phase was initially started, such nanofiber paper still kept its original shape and good flexibility after calcinations at 450 °C for 30 min. A solar cell with titanate nanofiber paper as scattering layer yielded an overall conversion efficiency of 4.90% under an incident solar energy of 100 mW/cm², about 27.5% higher than that without nanofiber paper.     

TiO2 hollow spheres as effective additives in oligomer electrolytes for dye-sensitized solar cells

TiO₂ hollow spheres are employed as an additive of oligomer electrolytes for dye-sensitized solar cells (DSSCs). The measurement of steady-state currents confirms that introducing TiO₂ hollow spheres can facilitate ionic diffusion in oligomer electrolytes. Even compared with conventional nanoparticle additives, the hollow spheres are more favorable to increase the diffusion coefficients of I^? and I₃^? in oligomer electrolytes. Furthermore, the hollow structure with a submicron size is effective to scatter incident light and thereby enhance the light-harvesting efficiency of DSSCs. The energy-conversion efficiency of the DSSCs with TiO₂ hollow sphere additives significantly improves up to 7.22% due to the facilitated ionic diffusion and the enhanced light-harvesting efficiency.     

Nanoforest of hydrothermally grown hierarchical ZnO nanowires for a high efficiency dye-sensitized solar cell

In this paper, in order to increase the power conversion efficiency we demonstrated the selective growth of "nanoforest" composed of high density, long branched "treelike" multigeneration hierarchical ZnO nanowire photoanodes. The overall light-conversion efficiency of the branched ZnO nanowire DSSCs was almost 5 times higher than the efficiency of DSSCs constructed by upstanding ZnO nanowires. The efficiency increase is due to greatly enhanced surface area for higher dye loading and light harvesting, and also due to reduced charge recombination by providing direct conduction pathways along the crystalline ZnO "nanotree" multi generation branches. We performed a parametric study to determine optimum hierarchical ZnO nanowire photoanodes through the combination of both length-wise growth and branched growth processes. The novel selective hierarchical growth approach represents a low cost, all solution processed hydrothermal method that yields complex hierarchical ZnO nanowire photoanodes by utilizing a simple engineering of seed particles and capping polymer.     

染料敏化太阳能电池阻挡层的制备及其性能研究

采用电子束蒸发法在光阳极导电玻璃基底上制备了一层致密的TiO2薄膜,并在氧氛围下进行不同温度的退火处理。以此TiO2薄膜为阻挡层来阻止电解质溶液中I3-与导电玻璃基底上光生电子的复合。分别利用X射线衍射（XRD）和X射线光电子能谱（XPS）对此薄膜的结构和成分进行表征。制备不同厚度的TiO2阻挡层薄膜并研究其对电池光电性能的影响。实验结果表明,阻挡层的引入有效地抑制了暗反应的发生,提高了染料敏化太阳能电池（DSSC）的开路电压、短路电流和光电转换效率,比未引入阻挡层的DSSC的光电转换效率提高了31.5%。     

Growth of ZnO nanorods on TiO2 nanoparticles films and their application to the electrode of dye-sensitized solar cells

A ZnO nanorods (NRs)/TiO₂ nanoparticles (NPs) film has been prepared by electrochemical deposition of ZnO NRs growth on P25 TiO₂ NPs film surfaces. It was found that ZnO NRs/TiO₂ NPs could significantly improve the efficiency of dye-sensitized solar cells owing to its relatively enhanced light-scattering capability and efficient charge transport efficiency. The overall energy-conversion efficiency (η) of 3.48 % was achieved by the formation of ZnO NRs/TiO₂ NPs film, which is 33 % higher than that formed by TiO₂ NPs alone (η = 2.62 %). The charge recombination behavior of cells was investigated by electrochemical impedance spectra, and the results showed that ZnO NRs/TiO₂ NPs film has the longer electron lifetime than TiO₂ NPs alone, which could facilitate the reduction of recombination processes and thus would promote the photocatalysis and solar cell performance.     

Facile synthesis of highly branched jacks-like ZnO nanorods and their applications in dye-sensitized solar cells

Highly branched, jacks-like ZnO nanorods architecture were explored as a photoanode in dye-sensitized solar cells, and their photovoltaic performance was compared with that of branch-free ZnO nanorods photoanodes. The highly branched network and large pores of the jacks-like ZnO nanorods electrodes enhances the charge transport, and electrolyte penetration. Thus, the jacks-like ZnO nanorods DSSCs render a higher conversion efficiency of η = 1.82% (V_oc = 0.59 V, J_sc = 5.52 mA cm⁻²) than that of the branch-free ZnO nanorods electrodes (η = 1.08%, V_oc = 0.49 V, J_sc = 4.02 mA cm⁻²). The incident photon-to-current conversion efficiency measurements reveal that the jacks-like ZnO nanorods DSSCs exhibit higher internal quantum efficiency (∼59.1%) than do the branch-free ZnO nanorods DSSC (∼52.5%). The charge transfer resistances at the ZnO/dye/electrolyte interfaces investigated using electrochemical impedance spectroscopy showed that the jacks-like ZnO nanorods DSSC had high charge transfer resistance and a slightly longer electron lifetime, thus improving the solar-cell performance.