Morphology investigation of hydrothermally prepared ZnO micro-crystals influenced by Cu ions

Micrometer-sized ZnO with various shapes have been synthesized by a hydrothermal route with Zn(Ac)₂/NH₃·H₂O in the presence of copper ions. Powder X-ray diffraction and scanning electron microscopy were utilized to characterize the composition and structure of the samples, respectively. As-synthesized, the ultrasonic pretreatment, pH value, reaction time and hydrothermal temperature played important roles in crystal structure tailoring. Novel nut-like ZnO crystal with improved crystal quality was obtained with initial Zn²⁺/Cu²⁺ ratio of 10, at reaction temperature of 100 °C, with initial pH of 7.0 and in a reaction time of 4 h, with ultrasonic pretreatment. Time-dependent experiments show that transfer of the Cu ions plays a crucial role as it causes the difference in crystal growth velocity.     

Fabrication and growth mechanism of hexagonal zinc oxide nanorods via solution process

This article presents, the fabrication of perfectly hexagonal zinc oxide nanorods performed via solution process using zinc nitrate hexahydrate (Zn(NO₃)₂·6H₂O) and hexamethylenetetramine (HMT) at various concentrations of i.e. 1 × 10⁻³ to 10 × 10⁻² M in 50 mL distilled water and refluxed at 100 °C for 1 h. We used HMT because it acts as a template for the nucleation and growth of zinc oxide nanorods, and it also works as a surfactant for the zinc oxide structures. The X-ray diffraction patterns clearly reveal that the grown product is pure zinc oxide. The diameters and lengths of the synthesized nanorods lie in the range of 200–800 nm and 2–4 μm, respectively as observed from the field emission scanning electron microscopy (FESEM). The morphological observation was also confirmed by the transmission electron microscopy (TEM) and clearly consistent with the FESEM observations. The chemical composition was analyzed by the FTIR spectroscopy, and it shows the ZnO band at 405 cm⁻¹. On the basis of these observations, the growth mechanism of ZnO nanostructures was also proposed.     

Facile synthesis of ZnO nanostructures and investigation of structural and optical properties

ZnO nanostructures were synthesized by chemical bath deposition method, using zinc nitrate [Zn(NO₃)₂] and hexa-methylene-tetra-amine [(HMT),C(H₂)₆N₄] as precursors. Controlled size and shape evolution of ZnO nanostructures were achieved by changing the HMT concentration from 0.025 M to 0.1 M, whereas Zn(NO₃)₂ concentration kept constant. X-ray diffraction (XRD) and Raman study confirmed the formation of single crystalline, hexagonal wurtzite ZnO structure. Sharp peaks in Raman spectra, corresponding to E₂(low) and E₂(high) referred to wurtzite structure with higher order of crystallinity. Transmission electron microscopy (TEM) revealed that the shape and size of the nanostructures reduced, with increasing concentration of HMT. Further, effect of structure's size was observed in the band gap (shift). Photoluminescence study showed two peaks at ~ 380 nm and ~ 540 nm corresponding to the band to band transition and defect transitions. Modifications of properties are explained in detail on the basis of shape and size change of the structures and possible mechanism is discussed.     

低温化学法合成单晶氧化锌纳米带

用低温化学溶液法在100℃制备了非层状结构的单晶ZnO纳米带。在反应初期先形成层状结构的碱式醋酸锌(Zn(OH)_(2-x)(CH_3COO)_x nH_2O)前驱体,然后在水热条件下使其转化成单晶ZnO纳米带。用透射电子显微镜(TEM)、场发射扫描电子显微镜(FESEM)、X射线衍射(XRD)、高分辨透射电子显微镜(HRTEM)和荧光光谱(PL)对ZnO纳米带的形态、结构和光学性质进行了表征.结果表明,在上述反应中醋酸根阴离子和弱有机碱六次甲基四胺(HMT)对前驱体和ZnO纳米带的形成起了关键作用。     

Effects of ZnO nanowire synthesis parameters on the photovoltaic performance of dye-sensitized solar cells

Determination of the effects of ZnO nanowires on the efficiency of ZnO nanowire-based dye-sensitized solar cells (DSSCs) is important. In this study, we determined the effects of different OH^- precursors, concentrations, the ratio of zinc nitrate to hexamethylene tetramine (HMT), and the hydrothermal synthesis temperature on the physical, crystal, and optical properties of ZnO nanowires and investigated the performance of the resulting DSSCs. We observed that ZnO nanowires synthesized using an equimolar ratio of HMT to zinc nitrate yielded a DSSC with high incident photon-to-current efficiency (IPCE), cell efficiency, short circuit current density (J_sc), and fill factor (FF), and low ZnO-dye-electrolyte interface resistance due to an increased amount of dye and a decreased density of defects. Furthermore, ZnO nanowires made using optimal concentrations and ratios of zinc nitrate to HMT had a high surface area and low defect density. All the photovoltaic performance parameters of DSSCs assessed such as IPCE, cell efficiency, J_sc, open circuit potential (V_oc), and FF increased with synthesis temperature, which was related to a decrease in the resistance at the ZnO-dye-electrolyte interface. We attributed these results to an increased amount of dye facilitated by a large nanowire surface area and fast electron transfer because of the improved crystalline structure of the ZnO nanowires and their low defect density. By optimizing the ZnO nanowires, we increased DSSC efficiency to 0.26% using ZnO nanowires synthesized with 25 mM of both zinc nitrate and HMT at 90 °C, while only a 0.02% increase in efficiency was obtained when NH₄OH was used as OH⁻ precursor.     

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.     

Photo-initiated growth of zinc oxide (ZnO) nanorods

A photo-initiated process via femtosecond pulse-induced heterogeneous nucleation in zinc ammine complex (Zn(NH₃)₄²⁺)-based aqueous solution without catalyst and surfactant, followed by hydrothermal treatments for crystal growth into zinc oxide (ZnO) nanorods, was investigated. Flat-top hexagonal ZnO nanorods with smooth planes of diameter ≥ 100 nm and length ≤ 1 μm were grown with laser irradiation, compared to porous rod-like structures without irradiation. The flat-top planes indicate slow growth rate, due to the intermediate step of Zn(NH₃)₄²⁺ decomposition to Zn(OH)₄²⁻, before dehydration to ZnO. Prolonged hydrothermal treatment produced nanotubes and lateral splits due to OH⁻ erosion of the crystal faces. XRD analysis showed a hexagonal crystal structure while photoluminescence study indicated a peak at about 380 nm.     

Transparent conducting properties of Ni doped zinc oxide thin films prepared by a facile spray pyrolysis technique using perfume atomizer

Undoped and Ni doped zinc oxide (Ni–ZnO) thin films were prepared by a facile spray pyrolysis technique using perfume atomizer from aqueous solution of anhydrous zinc acetate (Zn(CH₃COOH)₂ and hexahydrated nickel chloride (NiCl₂·6H₂O) as sources of zinc and nickel, respectively. The films were deposited onto the amorphous glass substrates kept at (450 °C). The effect of the [Ni]/[Zn] ratio on the structural, morphological, optical and electrical properties of Ni doped ZnO thin film was studied. It was found from X-ray diffraction (XRD) analysis that both the undoped and Ni doped ZnO films were crystallized in the hexagonal structure with a preferred orientation of the crystallites along the [002] direction perpendicular to the substrate. The scanning electron microscopy (SEM) images showed a relatively dense surface structure composed of crystallites in the spherical form whose average size decreases when the [Ni]/[Zn] ratio increases. The optical study showed that all the films were highly transparent. The optical transmittance in the visible region varied between 75 and 85%, depending on the dopant concentrations. The variation of the band gap versus the [Ni]/[Zn] ratio showed that the energy gap decreases from 2.95 to 2.72 eV as the [Ni]/[Zn] ratio increases from 0 to 0.02 and then increases to reach 3.22 eV for [Ni]/[Zn] = 0.04. The films obtained with the [Ni]/[Zn] ratio = 0.02 showed minimum resistivity of 2 × 10⁻³ Ω cm at room temperature.     

Characterization of ZnO-In2O3 transparent conducting films by pulsed laser deposition

Transparent conducting oxide (TCO) films in the ZnO-In₂O₃ system were prepared by a pulsed laser deposition method. A target that consists of the mixture of ZnO and In₂O₃ powders was used. Influences of the target composition x (x = [Zn]/([Zn] + [In])) and heater temperature on structural, electrical and optical properties of the TCO films were examined. Introduction of oxygen gas into the chamber during the deposition was necessary for improvement in the transparency of the deposited films. The amorphous phase was observed for a wide range of x = 0.20-0.60 at 110 °C. Minimum resistivity was 2.65 × 10⁻⁴ Ω cm at x = 0.20. The films that showed the minimum resistivity had an amorphous structure and the composition shifted toward larger x, as the substrate temperature increased. The films were enriched in indium compared to the target composition and the cationic In/Zn ratio increased as the substrate temperature was increased.     

Oriented growth of urchin-like zinc oxide micro/nano-scale structures in aqueous solution

The urchin-like ZnO microcrystals with high crystallinity decomposed from [Zn(OH)₄]^2? directly were obtained via a hydrothermal method. The morphology, particle size, crystalline structure and fluorescence of the as-prepared ZnO were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and photoluminescence (PL) analyses. The results demonstrated that the urchin-like ZnO crystals with wurtzite structure had a narrow distribution in size, which could be adjusted in the range of 30–80 μm by varying reaction time. Broad visible light emission peak was also observed in the PL spectra of the synthesized ZnO products. A multistep growth process about how to form such a structure was proposed.     

Properties of cu-doped low resistive ZnSe films deposited by two-sourced evaporation

Two-sourced evaporation technique is used to prepare hard ZnSe films by controlling the evaporation rates of both Zn and Se at substrate temperature of 400 °C. The films are doped with Cu by immersion in the Cu(NO₃)₂-H₂O solution for different periods of time. The XRD has not shown a drastic change in the film structure while the electrical resistivity of the deposited film dropped from 10⁹ Ω-cm to about 1.6 Ω-cm for solution immersed films after heat treatment. Optical properties of deposited and doped films, such as film thickness, absorption coefficient and optical band gap have been calculated from the normal transmission spectra in the range of 300-2200 nm.The optical results show a decrease of the transmission and an increase of the refractive index and a slight shift in the optical band gap. Chemical composition of the Cu is determined by using absorption of immersed films. The composition of Cu is also compared with the composition detected by electron microprobe analyzer (EMPA).     

Flower-like zinc oxide deposited on the film of graphene oxide and its photoluminescence

The graphene oxide films have been fabricated by simply filtering the graphene oxide solution through the micropore filter. Then the flower-like ZnO grows on the graphene layer by immersing the seed-coated graphene oxide films in the dilute growing solution containing NH₃·H₂O and Zn(NO₃)₂·6H₂O. The morphologies of the as-obtained ZnO deposited on the graphene oxide layer are characterized by using scanning electron microscope (SEM), X-ray powder diffraction (XRD) and photoluminescence (PL). The formation mechanism of the flower-like ZnO has also been investigated. The results show that the morphology of the finally-obtained ZnO is tunable by seeds, the concentration of growing solution and the reaction time.     

Metal-free indoline dye sensitized zinc oxide nanowires solar cell

Dye sensitized solar cell (DSSC) based on metal-free indoline dye D102 sensitized zinc oxide (ZnO) nanowires (NWs) derived from aqueous solution on seeded substrate was investigated. The morphology, composition and crystalline structure of the highly oriented ZnO NWs were characterized by field-emission scanning electron microscope, energy dispersive X-ray spectrum spectroscopy and X-ray diffraction, respectively. The chemical bond between D102 and ZnO NWs was confirmed by Fourier transfer infrared spectra. The photovoltaic property of DSSC was characterized at full sun intensity of 100 mW/cm² (AM 1.5) with short circuit current J_sc = 14.06 mA/cm² and energy conversion efficiency η = 2.6%.     

Reaction processes in a ZnO + 1%Gd2O3 powder mixture during mechanical and laser processing

X-ray diffraction, electron paramagnetic resonance, Fourier transform infrared spectroscopy and scanning electron microscopy were used to study the defect formation and reaction processes in a ZnO + 1%Gd₂O₃ powder mixture during its mechanical and laser processing. Mechanical treatment of the ZnO + 1%Gd₂O₃ powder mixture leads to a grinding of initial ZnO particles and formation of three types of superficial paramagnetic donor defect centers. The rise of the sample temperature with increasing processing time promotes a successive annealing of ZnO defects with small activation energies and of superficial defects in Gd₂O₃. The formation of a ZnO:Gd³⁺ solid solution in the used mechanical processing regimes has not been observed. Laser surface melting of the ZnO + 1%Gd₂O₃ pellets provokes formation of a surface layer exhibiting a texture. The crystallization directions in the superficial layers of different specimens have a random character. In the superficial layers and deep sub-surface layers, processes of solid-state interactions (formation of an inhomogeneous ZnO:Gd³⁺ solid solution) take place. The surplus charges of the Gd³⁺ ions are compensated by the formation of Zn vacancies or interstitial oxygen ions which in the laser-surface-melted layers are located closer to the Gd³⁺ ions than in the case of single-crystalline samples.     

Reactivity of molten aluminium with polycrystalline ZnO substrate

The microstructure studies of the reaction product region (RPR) obtained due to the interaction between the liquid aluminium and polycrystalline zinc oxide substrate at 1273 K has been studied. The RPR extended over the oxide substrate and showed a typical C4 (co-continuous-ceramic-composites) structure composed of two interpenetrating phases. The scanning electron microscopy studies revealed that the large crystals of alumina were surrounded by an Al(Zn) metallic phase. Moreover, the transmission electron microscopy investigation showed the presence of a thin (~250 nm) layer next to the ZnO. The chemical analysis accompanied by the selected area electron diffraction patterns indicated in both cases the same stoichiometric aluminium oxide but of different crystallographic structure, i.e., large crystals had α-Al₂O₃ structure while the layer was identified as metastable δ-Al₂O₃. The results were compared to those reported for interaction between liquid aluminium and monocrystalline ZnO.     

Fabrication of ZnO nanoneedle arrays by direct microwave irradiation

We report a method for the fabrication of ZnO nanoneedle arrays by direct microwave irradiation on the Zn sheet under O₂ and Ar atmosphere (the total pressure: 1 atm). Pure hexagonal-phase ZnO structures were grown on the Zn substrate through this synthetic method. Dimensions of synthesized needle-like ZnO structures are ~ 500 nm in length and ~ 50 and ~ 100 nm in diameter at the tip and the pillar, respectively. This method needs relatively low microwave irradiation power (300 W) and a short reaction time (3 min). Also, it does not require any template or catalyst. The results of this research allow us to propose the growth mechanism of ZnO nanoneedles on the Zn substrate by direct microwave irradiation.     

Synthesis of size-tunable ZnO nanorod arrays from NH3·H2O/ZnNO3 solutions

Well-aligned crystalline ZnO nanorod arrays were fabricated via an aqueous solution route with zinc nitrate and ammonia as precursors. Dip-coating was firstly utilized to form a ZnO film on ITO substrate as a seed layer for subsequent growth of ZnO nanorods. The effects of NH₃·H₂O/ZnNO₃ molar ratio, ZnNO₃ concentration, growth temperature and time on nanorod morphology were respectively investigated. It was found that the size of nanorod is mainly determined by the molar ratio and concentration. XRD demonstrates that ZnO nanorods are wurtzite crystal structures preferentially orienting in the direction of the c-axis. SEM confirms that ZnO nanorods grew up perpendicular to the substrate. The diameter and length were tunable in a broad range from 80 nm to 500 nm and 250 nm up to 8 μm, respectively. The aspect ratio changed from 3 to 17 mainly dependent on composition of the aqueous solution.     

Rapid synthesis of pure and narrowly distributed Eu doped ZnO nanoparticles by solution combustion method

Pure ZnO:Eu³⁺ nanoparticles (~ 50 nm) were prepared by a solution combustion method. ZnO and Eu₂O₃ were used as starting materials and dissolved in nitric acid. Citric acid was used as a fuel. The reaction mixture was heated at 350 °C resulting into a rapid exothermic reaction yielding pure nanopowders. The atomic weight concentration of Eu³⁺ doped in ZnO was 20%. Transmission electron microscopy (TEM) was used to study the particle size and morphology. The nanopowders were characterized for phase composition using X-ray diffractrometry (XRD). Particle size distribution (PSD) analysis of ZnO: Eu³⁺ showed particle sizes ranging from 30 to 80 nm.The photoluminescence emission spectra of ZnO:Eu³⁺ nanostructures showed a strong band emission around 618 nm when excited with 515 nm wavelength.     

Study of relationships among synthesis, microstructure and mechanical properties of lithium aluminosilicate glass-ceramics containing ZnO and MgF2 by synchrotron XRD and XANES

The effect of MgF₂ and ZnO as additives on the microstructure evolution of a lithium aluminosilicate glass-ceramic is studied by X-ray powder diffraction and X-ray absorption near edge structure. The changes of main, secondary phase development and morphology under different additive concentrations are responsible for the variation in flexural strength. The decreased flexural strength (>50 %) of MgF₂-bearing samples can be attributed to the non-uniform microstructure, while the increased flexural strength of the ZnO-doped samples might be due to the decreased residual stress resulting from a reduction of viscosity. In addition, the structural role of Zn ions is changed under different phase evolutions. For highly crystalline samples with commercial-like composition, Zn ions tend to have spinel-like local environments; while in a simplified composition, Zn ions favor hexagonal ZnO-like surroundings. The appearance of significant multiple scattering peaks in the near edge structure indicates Zn ions usually presented in an ordered local environment in high doping level samples (>1 % ZnO or MgF₂).     

Characterization of mechanical properties of epoxy resin reinforced with submicron-sized ZnO prepared via in situ synthesis method

In this paper, ZnO/epoxy composites with homogeneous dispersion were prepared via two simple steps: firstly, in situ preparation of zinc hydroxide (Zn(OH)₂)/epoxy from the reaction of aqueous zinc acetate (Zn(Ac)₂·2H₂O) and sodium hydroxide (NaOH) at 30 °C in the presence of high viscosity epoxy resin; secondly, thermal treatment of the as-prepared Zn(OH)₂/epoxy hybrid into ZnO/epoxy composites. Meanwhile, the structure, composition and mechanical properties of the resultant products were successfully investigated. From the result of characterization we found that the composite had the optimal mechanical property at ZnO fraction of 5 wt.%. Compared to pure epoxy resin, the improvement of ultimate tensile stress, elongation at break, tensile modulus and flexural strength achieved about 40.84%, 24.35%, 27.27% and 51.43%, respectively. The crack arresting mechanisms included particle matrix debonding, plastic void growth, in the composites with a stronger interface, significant plastic deformation of the matrix around the well bonded particles. At the same time, the possible reactive mechanism of the preparation of ZnO/epoxy composite was discussed in this paper.