The effect of ZnO photoanode morphology on the performance of solid-state dye-sensitized solar cells (DSSCs) is reported. Four different structures of dye-loaded ZnO layers have been fabricated in conjunction with poly(3-hexylthiophene). A significant improvement in device efficiency with ZnO nanorod arrays as photoanodes has been achieved by filling the interstitial voids of the nanorod arrays with ZnO nanoparticles. The overall power conversion efficiency increases from 0.13% for a nanorod-only device to 0.34% for a device with combined nanoparticles and nanorod arrays. The higher device efficiency in solid-state DSSCs with hybrid nanorod/nanoparticle photoanodes is originated from both large surface area provided by nanoparticles for dye adsorption and efficient charge transport provided by the nanorod arrays to reduce the recombinations of photogenerated carriers.
A simple method for the synthesis of ZnO nanofilms composed of vertical array of quasi-1D ZnO nanostructures (quasi-NRs) on the surface was demonstrated via a 1D crystal growth of the attached nanoseeds under a rapid hydrolysis process of zinc salts in the presence of ammonia at room temperature. In a typical procedure, by simply controlling the concentration of zinc acetate and ammonia in the reaction, a high density of vertically oriented nanorod-like morphology could be successfully obtained in a relatively short growth period (approximately 4 to 5 min) and at a room-temperature process. The average diameter and the length of the nanostructures are approximately 30 and 110 nm, respectively. The as-prepared quasi-NRs products were pure ZnO phase in nature without the presence of any zinc complexes as confirmed by the XRD characterisation. Room-temperature optical absorption spectroscopy exhibits the presence of two separate excitonic characters inferring that the as-prepared ZnO quasi-NRs are high-crystallinity properties in nature. The mechanism of growth for the ZnO quasi-NRs will be proposed. Due to their simplicity, the method should become a potential alternative for a rapid and cost-effective preparation of high-quality ZnO quasi-NRs nanofilms for use in photovoltaic or photocatalytics applications.
By thermal evaporation of pure ZnO powders, high-density vertical-aligned ZnO nanorod arrays with diameter ranged in 80–250 nm were successfully synthesized on Si substrates covered with ZnO seed layers. It was revealed that the morphology, orientation, crystal, and optical quality of the ZnO nanorod arrays highly depend on the crystal quality of ZnO seed layers, which was confirmed by the characterizations of field-emission scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and photoluminescence measurements. For ZnO seed layer with wurtzite structure, the ZnO nanorods grew exactly normal to the substrate with perfect wurtzite structure, strong near-band-edge emission, and neglectable deep-level emission. The nanorods synthesized on the polycrystalline ZnO seed layer presented random orientation, wide diameter, and weak deep-level emission. This article provides a C-free and Au-free method for large-scale synthesis of vertical-aligned ZnO nanorod arrays by controlling the crystal quality of the seed layer.
We demonstrate the morphological control method of ZnO nanostructures by atomic layer deposition (ALD) on an Al2O3/ZnO seed layer surface and the application of a hierarchical ZnO nanostructure for a photodetector. Two layers of ZnO and Al2O3 prepared using ALD with different pH values in solution coexisted on the alloy film surface, leading to deactivation of the surface hydroxyl groups. This surface complex decreased the ZnO nucleation on the seed layer surface, and thereby effectively screened the inherent surface polarity of ZnO. As a result, a 2-D zinc hydroxyl compound nanosheet was produced. With increasing ALD cycles of ZnO in the seed layer, the nanostructure morphology changes from 2-D nanosheet to 1-D nanorod due to the recovery of the natural crystallinity and polarity of ZnO. The thin ALD ZnO seed layer conformally covers the complex nanosheet structure to produce a nanorod, then a 3-D, hierarchical ZnO nanostructure was synthesized using a combined hydrothermal and ALD method. During the deposition of the ALD ZnO seed layer, the zinc hydroxyl compound nanosheets underwent a self-annealing process at 150 °C, resulting in structural transformation to pure ZnO 3-D nanosheets without collapse of the intrinsic morphology. The investigation on band electronic properties of ZnO 2-D nanosheet and 3-D hierarchical structure revealed noticeable variations depending on the richness of Zn-OH in each morphology. The improved visible and ultraviolet photocurrent characteristics of a photodetector with the active region using 3-D hierarchical structure against those of 2-D nanosheet structure were achieved.
In this study, zinc oxide (ZnO) nanorod arrays were synthesized using a simple hydrothermal reaction on ZnO seeds/n-silicon substrate. Several parameters were studied, including the heat-treatment temperature to produce ZnO seeds, zinc nitrate concentration, pH of hydrothermal reaction solution, and hydrothermal reaction time. The optimum heat-treatment temperature to produce uniform nanosized ZnO seeds was 400°C. The nanorod dimensions depended on the hydrothermal reaction parameters. The optimum hydrothermal reaction parameters to produce blunt tip-like nanorods (770 nm long and 80 nm in top diameter) were 0.1 M zinc nitrate, pH 7, and 4 h of growth duration. Phase analysis studies showed that all ZnO nanorods exhibited a strong (002) peak. Thus, the ZnO nanorods grew in a c-axis preferred orientation. A strong ultraviolet (UV) emission peak was observed for ZnO nanorods grown under optimized parameters with a low, deep-level emission peak, which indicated high optical property and crystallinity of the nanorods. The produced ZnO nanorods were also tested for their UV-sensing properties. All samples responded to UV light but with different sensing characteristics. Such different responses could be attributed to the high surface-to-volume ratio of the nanorods that correlated with the final ZnO nanorods morphology formed at different synthesis parameters. The sample grown using optimum synthesis parameters showed the highest responsivity of 0.024 A/W for UV light at 375 nm under a 3 V bias.
We report a simple catalyst-free vapor-phase method to fabricate Zn1−xCuxO micro-cross structures. Through a series of controlled experiments by changing the location of the substrate and reaction time, we have realized the continuous evolution of product morphology from nanorods into brush-like structures and micro-cross structures at different positions, together with the epitaxial growth of branched nanorods from the central stem with the time extended. The growth mechanism of the Zn1−xCuxO micro-cross structures has been proposed to involve the synthesis of Cu/Zn square-like core, surface oxidation, and the secondary growth of nanorod arrays. By the detailed structural analysis of the yielded Zn1−xCuxO samples at different locations, we have shown that the CuO phases were gradually formed in Zn1−xCuxO, which is significant to induce the usual ZnO hexagonal structures changing into four-folded symmetrical hierarchical micro-cross structures. Furthermore, the visible luminescence can be greatly enhanced by the introduction of Cu, and the observed inhomogeneous cathode luminescence in an individual micro-cross structure is caused by the different distributions of Cu.
Large-scale CdSe nanotube arrays on indium tin oxide (ITO) glass have been synthesized using ZnO nanorod template. The strong visible light absorption in CdSe, its excellent photoresponse, and the large surface area associated with the tubular morphology lead to good visible light-driven photocatalytic capability of these nanotube arrays. Compared to freestanding nanoparticles, such one-piece nanotube arrays on ITO make it very convenient for catalyst recycling after their usage
ZnO nanorod arrays were synthesized by chemical bath deposition. After heat treatment in hydrogen or air, Ag nanoparticles were deposited on ZnO nanorod arrays by photo-reduction method. The size of Ag nanoparticles as well as the surface morphology, structure, composition, and optical property of ZnO nanorod arrays before and after the deposition of Ag nanoparticles were characterized by SEM, XRD, EDS, and UV/VIS/NIR spectrophotometer. As compared to the samples with heat treatment in air or without heat treatment, the ZnO nanorod arrays after heat treatment in hydrogen allowed Ag nanoparticles to be deposited more uniformly, densely, and numerously. Also, they exhibited higher efficiency for the visible light-driven photocatalytic degradation of Rhodamine 6G (R6G) dye. The effects of the amount of Ag nanoparticles, initial dye concentration, and temperature on the photocatalytic degradation efficiency were investigated. Furthermore, they also exhibited better surface-enhanced Raman scattering property for the detection of R6G dyes.
In this study, a non-selenized CuInGaSe2 (CIGS) solar device with textured zinc oxide (ZnO) antireflection coatings was studied. The ZnO nanostructure was fabricated by a low-temperature aqueous solution deposition method. With controlling the morphology of the solution-grown tapered ZnO nanorod coatings, the average reflectance of the CIGS solar device decreased from 8.6% to 2.1%, and the energy conversion efficiency increased from 9.1% to 11.1%. The performance improvement in the CuInGaSe2 thin-film solar cell was well explained due to the gradual increase of the refractive index between air and the top electrode of solar cell device by the insertion of the ZnO nanostructure. The results demonstrate a potential application of the ZnO nanostructure array for efficient solar device technology.
Undoped ZnO, Ce-doped ZnO, and (Li, Ce)-codoped ZnO nanophosphors were prepared by a sol-gel process. The effects of the additional doping with Li ions on the crystal structure, particle morphology, and luminescence properties of Ce-doped ZnO were investigated by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy and photoluminescence spectroscopy. The results indicate that the obtained samples are single phase, and a nanorod shaped morphology is observed for (Li, Ce)-codoping. Under excitation with 325 nm light, Ce-doped ZnO phosphors show an ultraviolet emission, a green emission, and a blue emission caused by Zn interstitials. The spectrum of the sample codoped with a proper Li concentration features two additional emissions that can be attributed to the Ce3+ ions. With the increase of the Li doping concentration, the Ce3+ blue luminescence of (Li, Ce)-codoped ZnO is obviously enhanced, which results not only from the increase of the Ce3+ ion concentration itself but also from the energy transfer from the ZnO host material to the Ce3+ ions. This enhancement reaches a maximum at a Li content of 0.02, and then decreases sharply due to the concentration quench. These nanophosphors may promise for application to the visible-light-emitting devices.
TeO2-nanostructured sensors are seldom reported compared to other metal oxide semiconductor materials such as ZnO, In2O3, TiO2, Ga2O3, etc. TeO2/CuO core-shell nanorods were fabricated by thermal evaporation of Te powder followed by sputter deposition of CuO. Scanning electron microscopy and X-ray diffraction showed that each nanorod consisted of a single crystal TeO2 core and a polycrystalline CuO shell with a thickness of approximately 7 nm. The TeO2/CuO core-shell one-dimensional (1D) nanostructures exhibited a bamboo leaf-like morphology. The core-shell nanorods were 100 to 300 nm in diameter and up to 30 μm in length. The multiple networked TeO2/CuO core-shell nanorod sensor showed responses of 142% to 425% to 0.5- to 10-ppm NO2 at 150°C. These responses were stronger than or comparable to those of many other metal oxide nanostructures, suggesting that TeO2 is also a promising sensor material. The responses of the core-shell nanorods were 1.2 to 2.1 times higher than those of pristine TeO2 nanorods over the same NO2 concentration range. The underlying mechanism for the enhanced NO2 sensing properties of the core-shell nanorod sensor can be explained by the potential barrier-controlled carrier transport mechanism.
High-density and well-aligned ZnO–ZnS core–shell nanocone arrays were synthesized on fluorine-doped tin oxide glass substrate using a facile and cost-effective two-step approach. In this synthetic process, the ZnO nanocones act as the template and provide Zn2+ ions for the ZnS shell formation. The photoluminescence spectrum indicates remarkably enhanced luminescence intensity and a small redshift in the UV region, which can be associated with the strain caused by the lattice mismatch between ZnO and ZnS. The obtained diffuse reflectance spectra show that the nanocone-based heterostructure reduces the light reflection in a broad spectral range and is much more effective than the bare ZnO nanocone and nanorod structures. Dye-sensitized solar cells based on the heterostructure ZnO–ZnS nanocones are assembled, and high conversion efficiency (η) of approximately 4.07% is obtained. The η improvement can be attributed primarily to the morphology effect of ZnO nanocones on light-trapping and effectively passivating the interface surface recombination sites of ZnO nanocones by coating with a ZnS shell layer.
Uniformly distributed ZnO nanorods with diameter 70-100 nm and 1-2μm long have been successfully grown at low temperatures on GaN by using the inexpensive aqueous solution method. The formation of the ZnO nanorods and the growth parameters are controlled by reactant concentration, temperature and pH. No catalyst is required. The XRD studies show that the ZnO nanorods are single crystals and that they grow along the c axis of the crystal plane. The room temperature photoluminescence measurements have shown ultraviolet peaks at 388nm with high intensity, which are comparable to those found in high quality ZnO films. The mechanism of the nanorod growth in the aqueous solution is proposed. The dependence of the ZnO nanorods on the growth parameters was also investigated. While changing the growth temperature from 60°C to 150°C, the morphology of the ZnO nanorods changed from sharp tip (needle shape) to flat tip (rod shape). These kinds of structure are useful in laser and field emission application.; Singapore-MIT Alliance (SMA)
Uniformly distributed ZnO nanorods with
diameter 80-120 nm and 1-2µm long have been
successfully grown at low temperatures on GaN by using the inexpensive aqueous solution method. The formation of the ZnO nanorods and the growth parameters are controlled by reactant concentration, temperature and pH. No catalyst is required. The XRD studies show that the ZnO nanorods are single crystals and that they grow
along the c axis of the crystal plane. The room
temperature photoluminescence measurements have
shown ultraviolet peaks at 388nm with high intensity, which are comparable to those found in high quality ZnO films. The mechanism of the nanorod growth in the aqueous solution is proposed. The dependence of the ZnO
nanorods on the growth parameters was also investigated. While changing the growth temperature from 60°C to
150°C, the morphology of the ZnO nanorods changed from sharp tip with high aspect ratio to flat tip with smaller aspect ratio. These kinds of structure are useful in laser and field emission application.; Singapore-MIT Alliance (SMA)
This paper reports combined hydrophobicity and mechanical durability through the nanoscale engineering of surfaces in the form of nanorod-polymer composites. Specifically, the hydrophobicity derives from nanoscale features of mechanically hard ZnO nanorods and the mechanical durability derives from the composite structure of a hard ZnO nanorod core and soft polymer shell. Experimental characterization correlates the morphology of the nanoengineered surfaces with the combined hydrophobicity and mechanical durability, and reveals the responsible mechanisms. Such surfaces may find use in applications, such as boat hulls, that benefit from hydrophobicity and require mechanical durability.
We study in this paper the atomic mechanisms of nanorod growth and propose
the way of diameter selection of nanorod. A characteristic radius is
demonstrated to be crucial in nanorod growth, which increases proportional to
one fifth power of the ratio of the interlayer hopping rate of adatoms across
the monolayer steps to the deposition rate. When the radius of the initial
island is larger than this characteristic radius, the growth morphology evolves
from a taper-like structure to a nanorod with radius equal to the
characteristic radius after some transient layers. Otherwise the nanorod
morphology can be maintained during the growth, with stable radius being
limited by both the radius of the initial island and the three-dimensional
Ehrlich-Schwoebel barrier. Therefore different growth modes and diameter of
nanorod can be selected by tuning the characteristic radius. The theoretical
predictions are in good agreement with experimental observations of ZnO growth.; Comment: 7 pages, 4 figures, submitted to APS
Three-dimensional hierarchical ZnO films with lotus-leaf-like micro/nano
structures were successfully fabricated via a biomimetic route combining
sol-gel technique, soft lithography and hydrothermal treatments. PDMS mold
replicated from a fresh lotus leaf was used to imprint microscale pillar
structures directly into a ZnO sol film. Hierarchical ZnO micro/nano structures
were subsequently fabricated by a low-temperature hydrothermal growth of
secondary ZnO nanorod arrays on the micro-structured ZnO film. The morphology
and size of ZnO hierarchical micro/nano structures can be easily controlled by
adjusting the hydrothermal reaction time. Wettability of hierarchical ZnO thin
films was found to convert from superhydrophilicity to hydrophobicity after a
low-surface-energy fluoroalkylsilane modification. Improved wetting properties
from hydrophobic to superhydrophobic can be tuned by increasing the growth of
ZnO nanorods structures.; Comment: Accepted Manuscript,7 pages, 8 figures