Effects of morphology on photocatalytic performance of Zinc oxide nanostructures synthesized by rapid microwave irradiation methods

In this study, two different chemical solution methods were used to synthesize Zinc oxide nanostructures via a simple and fast microwave assisted method. Afterwards, the photocatalytic performances of the produced ZnO powders were investigated using methylene blue (MB) photodegradation with UV lamp irradiation. The obtained ZnO nanostructures showed spherical and flower-like morphologies. The average crystallite size of the flower-like and spherical nanostructures were determined to be about 55 nm and 28 nm, respectively. X-ray diffraction (XRD), scanning electronic microscopy (SEM), Brunauer–Emmett–Teller (BET), room temperature photoluminescence (RT-PL) and UV–vis analysis were used for characterization of the synthesized ZnO powders. Using BET N₂-adsorption technique, the specific surface area of the flower-like and spherical ZnO nanostructures were found to be 22.9 m²/gr and 98 m²/gr, respectively. Both morphologies show similar band gap values. Finally, our results depict that the efficiency of photocatalytic performance in the Zinc oxide nanostructures with spherical morphology is greater than that found in the flower-like Zinc oxide nanostructures as well as bulk ZnO.     

Synthesis of ZnO nanostructures with controlled morphology and size in ionic liquids

Nanostructured ZnO has been synthesized by a hydrothermal route, using different ionic liquids (ILs) as the morphology templates. The morphology of ZnO changes from rod-like to star-like and flower-like in different ILs. A 3D nano/micro structure ZnO with unique flower-like morphology has been synthesized via the assembly of dicationic IL and [Zn(OH)₄]²⁻. The flower-like pattern was obtained in the presence of IL 1. The flower-like ZnO structure has a hexagonal prism, with a hexagonal pyramid on the tip, and diameter of ~444 nm. While the ZnO prepared in IL 2, shows uniform rod-like shape with a diameter of 91 nm, star-like morphology consisting of nanorods with diameter of ~109 nm was formed in IL 3. The XRD, SEM, and PL spectra have been employed for characterization of the synthesized ZnO nano structures.     

Direct assembly of ZnO nanostructures on glass substrates by chemical bath deposition through precipitation method

In this work, spindle/flower-like zinc oxide (ZnO) nanostructured arrays have been directly grown on glass substrates using triethanolamine (TEA) as a complexing agent by chemical bath deposition (CBD). Control over the morphology of ZnO nanocrystallites was achieved by varying the concentration of the complexing agent in the bath solution. ZnO crystallites exhibited a hexagonal wurtzite structure with preferential orientation along the c-axis. The morphology of the ZnO crystallites with star or needle-like spindles was altered to flower like nanostructures by adjusting the complexing agent concentration. Compared to as-deposited films, films sintered at 300 ^°C exhibited a sharp UV emission due to a decrease in the defect density. A possible growth mechanism for obtaining ZnO nanoflower arrays without a seed layer on glass substrates has been discussed.     

Facile Preparation and characterization of zinc phosphate with self-assembled flower-like micro-nanostructures

The three-dimensional flower-like zinc phosphate [Zn₃(PO₄)₂·4H₂O] micro-nanostructures was synthesized by a microwave-assisted sonochemical method in the absence of template under ambient conditions. The effects of reaction temperature of water bath and reactant concentrations on the particle size and morphology of flower-like zinc phosphate were studied. The scanning electron microscopy, transmission electron microscopy, X-ray diffraction and infrared spectroscopy were used to characterize the samples. The results showed that the three-dimensional flower-like zinc phosphate is composed of self-assembled two-dimensional nanosheets. The average thickness of two-dimensional nanosheet was 35–40 nm, and 5–12 layers of nanosheets formed a layered flower with an average thickness of 220–540 nm. The reaction temperatures of water bath and reactant concentrations are the key factors to synthesize perfect three-dimensional flower-like zinc phosphate. The self-assembly is main growth mechanism to form the flower-like zinc phosphate.     

Synthesis of morphology-controlled ZnO microstructures via a microwave-assisted hydrothermal method and their gas-sensing property

Controllable ZnO architectures with flower-like and rod-like morphologies were synthesized via a microwave-assisted hydrothermal method. By adjusting the concentration of Zn²⁺ in the aqueous precursors, different morphologies of ZnO microstructures were obtained. The size of ZnO was uniform after ultrasonic treatment. The growth process of ZnO in solution was studied by monitoring the intermediate products, which were extracted at different stages of the reactions: (i) precursor preparation, (ii) microwave irradiation heating, (iii) natural cooling. Studies of the SEM images and XRD data revealed that the formation of ZnO occurred via in situ assembly or dissolution–reprecipitation of zinc hydroxide complexes. The morphology-dependent ethanol sensing performance was observed; the seven-spine ZnO structures exhibit the highest activity.     

Synthesis and photocatalysis properties of ZnO structures with different morphologies via hydrothermal method

The special flower-like and sheet-like ZnO structures were successfully synthesized by hydrothermal method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS). The photocatalytic activity of different morphologies of ZnO structures was evaluated by degradating of methyl orange (MO). The photocatalytic degradation process was monitored in terms of decolorization and total organic carbon (TOC) removals. The results indicated that the flower-like ZnO structures were consisted of numerous flower-like aggregates with the size of 2 μm. The sheet-like ZnO nanostructures were obtained by increasing the reaction time. They exhibited higher photodegradation efficiencies under UV light irradiation than flower-like ZnO structures due to the blue shift of the band gap. The photodegradation could be described as the pseudo-first-order kinetics with apparent rate constants ranging from 1.17 × 10⁻² to 3.42 × 10⁻² min⁻¹, which were based on the morphology of the structures. The photodegradation was faster than the mineralization, indicating that the accumulation of by-products were resistant to photocatalytic degradation.     

Nanostructured ZnO thin films by chemical bath deposition in basic aqueous ammonia solutions for photovoltaic applications

This paper presents further insights and observations of the chemical bath deposition (CBD) of ZnS thin films using an aqueous medium involving Zn-salt, ammonium sulfate, aqueous ammonia, and thioure. Results on physical and chemical properties of the grown layers as a function of ammonia concentration are reported. Physical and chemical properties were analyzed using scanning electron microscopy (SEM), X-ray energy dispersive (EDX), and X-ray diffraction (XRD). Rapid growth of nanostructured ZnO films on fluorine-doped SnO₂ (FTO) glass substrates was developed. ZnO films crystallized in a wurtzite hexagonal structure and with a very small quantity of Zn(OH)₂ and ZnS phases were obtained for the ammonia concentration ranging from 0.75 to 2.0 M. Flower-like and columnar nanostrucured ZnO films were deposited in two ammonia concentration ranges, respectively: one between 0.75 and 1.0 M and the other between 1.4 and 2.0 M. ZnS films were formed with a high ammonia concentration of 3.0 M. The formation mechanisms of ZnO, Zn(OH)₂, and ZnS phases were discussed in the CBD process. The developed technique can be used to directly and rapidly grow nanostructured ZnO film photoanodes. Annealed ZnO nanoflower and columnar nanoparticle films on FTO substrates were used as electrodes to fabricate the dye sensitized solar cells (DSSCs). The DSSC based on ZnO-nanoflower film showed an energy conversion efficiency of 0.84%, which is higher compared to that (0.45%) of the cell being constructed using a photoanode of columnar nanoparticle ZnO film. The results have demonstrated the potential applications of CBD nanostructured ZnO films for photovoltaic cells.     

Formation of CuS with flower-like,hollow spherical,and tubular structures using the solvothermal-microwave process

CuCl₂ · 2H₂O and CH₃CSNH₂ were dissolved in ethylene glycol, and followed by the addition of NaOH to form solutions with different pH values. Reactions proceeded in surfactant-free solutions contained in an acid digestion bomb using a microwave irradiation at different conditions. Pure CuS (hcp) with flower-like, hollow spherical, and tubular structures were detected, and had the same vibration wavenumber at 474 cm⁻¹. They displayed two emission peaks at 411, and 432 nm. The formation of CuS with different morphologies was proposed according to the analytical results.     

Growth and interconversion of ZnO nanostructure films on different substrates

Hexagonal c-axis oriented ZnO nanorod (NR) arrays were grown on ZnO-coated glass substrates by chemical bath deposition (CBD). By varying the concentration of the precursor solutions, NRs’ mean diameter was controlled from about 100-400 nm. With increasing the growing time, the morphology of as-synthesized ZnO NRs evolved: the top center of the ZnO NRs was eroded into volcano-like structures which developed into ZnO nanotubes (NT) and finally the ZnO NTs split to form ZnO nanosheets (NS). We have also introduced Al to the fabrication of some different ZnO nanostructures: on Al substrate, freestanding ZnO NSs formed a flower-like structure at the early growing period and these ZnO NSs reassembled into ZnO NTs as growing time increased; while on ZnO-coated glass substrate with an Al foil dipped in the growing precursor solution ZnO NR-NS composited arrays were synthesized.     

The role of pH variation on the growth of zinc oxide nanostructures

In this paper we present a systematic study on the morphological variation of ZnO nanostructure by varying the pH of precursor solution via solution method. Zinc acetate dihydrate and sodium hydroxide were used as a precursor, which was refluxed at 90 °C for an hour. The pH of the precursor solution (zinc acetate di hydrate) was increased from 6 to 12 by the controlled addition of sodium hydroxide (NaOH). Morphology of ZnO nanorods markedly varies from sheet-like (at pH 6) to rod-like structure of zinc oxide (pH 10-12). Diffraction patterns match well with standard ZnO at all pH values. Crystallinity and nanostructures were confirmed by high-resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) pattern, which indicates structure grew along [0 0 0 1] direction with an ideal lattice fringes distance 0.52 nm. FTIR spectroscopic measurement showed a standard peak of zinc oxide at 464 cm⁻¹. Amount of H⁺ and OH⁻ ions are found key to the structure control of studied material, as discussed in the growth mechanism.     

Influence of bases on hydrothermal synthesis of titanate nanostructures

A hydrothermal treatment of titanium dioxide (TiO₂) with various bases (i.e., LiOH, NaOH, KOH, and NH₄OH) was used to prepare materials with unique morphologies, relatively small crystallite sizes, and large specific surface areas. The experimental results show that the formation of TiO₂ is largely dependent on the type, strength and concentration of a base. The effect of the nature of the base used and the concentration of the base on the formation of nanostructures were investigated using X-ray diffraction, Raman spectroscopy, transmission and scanning electron microscopy, as well as surface area measurements. Sodium hydroxide (NaOH) and potassium hydroxide (KOH) were both used to transform the morphology of starting TiO₂ material.     

镉掺杂氧化锌纳米花的制备及其光催化活性

以氯化锌、氯化镉、氢氧化钠为原料,采用水热法合成Cd掺杂纳米花状ZnO光催化剂,并通过该样品对罗丹明B水溶液的降解来研究其光催化活性。利用X射线衍射（XRD）、扫描电子显微镜（SEM）、X射线能量色散谱（EDS）、光致发光谱（PL）及紫外-可见分光光度计（UV-Vis）等测试手段对材料物性进行表征。实验结果表明：当掺杂Cd²⁺时,样品形貌发生变化、粒径减小;掺杂Cd²⁺后的ZnO的吸收边和紫外峰对比于纯ZnO均发生红移,禁带宽度由3.24 eV 减小到3.16 eV。通过光催化实验分析可知,掺杂后纳米ZnO光催化剂对罗丹明B 水溶液的降解率有所提高,光照3 h其降解率高达98%,说明与纯ZnO相比,Cd掺杂ZnO纳米花具有更高的光催化活性。     

Morphology–luminescence correlations in europium-doped ZnO nanomaterials

In order to investigate the correlations of morphologies and optical properties, different morphologies of Eu-doped ZnO were synthesized by different methods. Specifically, the structure of SiO₂/ZnO:Eu nanoflower was synthesized for the first time and has not been reported previously. One percent was chosen as the Eu doping concentration. The relations of the morphology, diameter, and uniformity with the PL intensity were examined. The PL intensity of ZOE samples has a close relationship with the morphology. The PL intensity order of the different morphologies of ZnO:Eu is as follows: nanorod arrays > thin film > nanospheres > nanoparticles > nanoflowers > nanorods. The PL intensity of nanomaterials is larger, if the diameter of the nanomaterials is larger. However, the size of diameter is not the most important reason. It was found that the sample uniformity plays a key role on ZnO:Eu PL intensity. ZnO:Eu with small particle diameters may have strong photoluminescence intensity, if the nanoparticles are uniform.     

Optimisation of the CBD CdS deposition parameters for ZnO/CdS/CuGaSe2/Mo solar cells

We present an optimisation of our recipe for the CdS chemical bath deposition process as applied to solar cells based on polycrystalline CuGaSe₂ (CGSe) absorber layers prepared in two stages by physical vapour deposition. We investigate the influence of the ammonia (NH₃) and the thiourea (H₂NCSNH₂) concentration, both being constituents of the chemical bath deposition (CBD) solution, at a deposition temperature of 80 °C on the microstructural and optical properties of CdS layers and on ZnO/CdS/CuGaSe₂/Mo device parameters. The composition of the CdS layers and their thickness were determined using X-ray Fluorescence Analysis. Transmission and reflection measurements performed at 300 K were used for the calculation of absorption and optical band gap energy (E_g). The E_g values of the films varied from 2.41 to 2.46 eV depending on deposition conditions. Cubic phase of the as-grown layers was identified by X-ray diffraction analysis. An improvement in the investigated solar cells efficiency was achieved when the ammonia concentration was increased and the thiourea concentration was reduced, compared to the previously used standard HMI recipe. The influence of the CBD CdS preparation recipe on the ZnO/CdS/CuGaSe₂/Mo electrical and photoelectrical properties is discussed.     

Switching of hydrophilic to ultra hydrophilic properties of flower-like gold nanostructures

Flower-like morphologies of gold nanostructures were obtained via chemical method by controlling molar concentration ratio of reducing agent and precursor. Chloroauric acid was used as a metal precursor while tri-sodium citrate as the reducing agent. These flower-like structures were characterized by UV-vis spectroscopy, Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD) techniques. The basic crystallite size calculated via XRD measurement was found to be ∼10 nm and remain unaffected by the different concentration ratios. The coating of these structures was made over clean glass substrate and analyzed for wettability by measuring their water contact angles. Our analysis indicates that the coatings of hierarchical flower-like structures of gold are able to provide ultra hydrophilic properties to glass substrate.     

Influence of Sb on a controlled-growth of aligned ZnO nanowires in nanoparticle-assisted pulsed-laser deposition

Single-crystalline ZnO nanowires on a sapphire substrate have been synthesized by a nanoparticle-assisted pulsed-laser deposition (NAPLD) using a pure and Sb₂O₃ doped ZnO target. Low density and vertically well-aligned ZnO nanowires were grown on hexagonal cone-shape ZnO cores by introduction of a ZnO buffer layer. More than 90% of the ZnO cores of the Sb-induced ZnO nanowires are formed in the same size of 400 nm. The ZnO nanowires consist of single-crystalline wurtzite ZnO crystal and grow along [0001] direction. The room-temperature photoluminescence spectrum exhibited a strong ultraviolet emission at around 380 nm and a relatively low broad band emission in the visible region, indicating a low concentration of structural defect in the nanowires. Sb can be used as one of the effective additives to control the morphology and alignment of ZnO nanowires synthesized by NAPLD.     

Annealing effects on electrical and optical properties of ZnO thin films synthesized by the electrochemical method

Microstructural and electrical properties of potentiostatically electrodeposited ZnO thin films from an aqueous bath were investigated after annealing at different temperatures in Ar and 5% H₂/Ar atmospheres. It is confirmed that the bandgap energy of ZnO thin films decreased with annealing from 3.42 to 3.27-3.29 eV by calculating the wavelength of the absorption region. The annealing at temperatures as low as 200 °C decreased the sheet resistance of ZnO thin films because of the extinction of Zn(OH)₂ in the atmosphere. In addition, the sheet resistance of ZnO thin films decreased by annealing in a 5% H₂ atmosphere, which caused an increase of carrier concentration by hydrogen reduction.     

Synthesis and optical properties of flower-like ZnO nanorods by thermal evaporation method

Flower-like ZnO nanorods have been synthesized by heating a mixture of ZnO/graphite powders using the thermal evaporation and vapor transport on Si (1 0 0) substrates without any catalyst. The structures, morphologies and optical properties of the products were characterized in detail by using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and Raman spectroscopy. The synthesized products consisted of large quantities of flower-like ZnO nanostructures in the form of uniform nanorods. The flower-like ZnO nanorods had high purity and well crystallized wurtzite structure, whose high crystalline quality was proved by Raman spectroscopy. The as-synthesized flower-like ZnO nanorods showed a strong ultraviolet emission at 386 nm and a weak and broad yellow-green emission in visible spectrum in its room temperature photoluminescence (PL) spectrum. In addition, the growth mechanism of the flower-like ZnO nanorods was discussed based on the reaction conditions.     

ZnO nanorod arrays fabrication via chemical bath deposition: Ligand concentration effect study

A new ligand, N,N,N′,N′-tetramethylethylenediamine, has been used to grow ZnO nanorods on silicon substrates via a two steps approach. A preliminary seeding on silicon substrates has been combined with chemical bath deposition using a Zinc acetate–N,N,N′,N′-tetramethylethylenediamine aqueous solution. The used diamino ligand has been selected as Zn²⁺ complexing agent and the related hydrolysis generates the reacting ions (Zn²⁺ and OH⁻) responsible for the ZnO growth. The seed layer has been annealed at low temperature (<200 °C) and the ZnO nanorods have been grown on this ZnO amorphous layer. There is experimental evidence that the ligand concentration (ranging from 5 to 50 mM) strongly affects the alignment of ZnO nanorods on the substrate, their lateral dimension and the related surface density. Length and diameter of ZnO nanorods increase upon increasing the ligand concentration, while the nanorod density decreases. Even more important, it has been demonstrated, as proof of concept, that chemical bath deposition can be usefully combined with colloidal lithography for selective ZnO nanorod deposition. Thus, by patterning the ZnO seeded substrate with polystyrene microsphere colloidal lithography, regular Si hole arrays, spatially defined by hexagonal ZnO nanorods, have been successfully obtained.     

Effect of the reaction conditions on the formation of the ZnO nanostructures

ZnO nanorods were synthesized through a simple chemical method by reacting Zn(C₂H₃O₂)₂·2H₂O and NaOH at low temperature and the effects of changing the order of addition of reactants on the morphological evolution of ZnO nanorods were investigated. The samples were characterized by using XRD, SEM, EDX, TEM, BET and Raman techniques. Optical properties of the ZnO nanostructures were too investigated by UV–Vis spectroscopy at room temperature.The hexagonal wurtzite phase of ZnO was confirmed by X-ray diffraction (XRD) for all the samples. SEM and TEM analysis indicated that different morphologies were obtained by changing the order of addition of reactants.