Preparation and photoluminescence of ZnO with nanostructure by hollow-cathode discharge

Without the use of a metal catalyst in the process, ZnO with nanostructures was successfully prepared on Si (100) substrate by simple chemical vapor-deposition method. In our work, Ar was used as the plasma forming gas, O₂ was the reactive gas and metal zinc powder (99.99% purity) vaporized by cylinder hollow-cathode discharge (HCD) acted as the zinc source. The crystal structures of the as-synthesized ZnO nanostructures were characterized by X-ray diffraction (XRD); the ZnO sample growing on the wall of the crucible showed a ‘comb-like’ nanostructure, while the other one at the bottom of the crucible showed a ‘rod-like’ structure, which can be attributed to the difference of the oxygen content. The measurement on the photoluminescence (PL) performance of the ZnO nanostructures was carried out at room temperature. The results indicated that the ‘comb-shape’ ZnO nanomaterial possessed a remarkably strong ultraviolet emission peak centered at 388 nm, while ZnO nanorods, except better ultraviolet emission, also had relatively strong blue-green emission ranging from 470 to 600 nm due to the existence of oxygen vacancies. The growth mechanism of ZnO with nanostructures is also discussed in this paper.     

Facile preparation of Ag/ZnO nanoparticles via photoreduction

Ag/ZnO nanoparticles can be obtained via photocatalytic reduction of silver nitrate at ZnO nanorods when a solution of AgNO₃ and nanorods ZnO suspended in ethyleneglycol is exposed to daylight. The mean size of the deposited sphere like Ag particles is about 5 nm. However, some of the particles can be as large as 20 nm. The ZnO nanorods were pre-prepared by basic precipitation from zinc acetate di-hydrate in the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide. They are about 50–300 nm in length and 10–50 nm in width. Transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDS), X-ray powder diffraction (XRD), UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) were used to characterize the resulting Ag/ZnO nanocomposites.     

Rapid growth of nanotubes and nanorods of würtzite ZnO through microwave-irradiation of a metalorganic complex of zinc and a surfactant in solution

Large quantities of single-crystalline ZnO nanorods and nanotubes have been prepared by the microwave irradiation of a metalorganic complex of zinc, in the presence of a surfactant. The method is simple, fast, and inexpensive (as it uses a domestic microwave oven), and yields pure nanostructures of the hexagonal würtzite phase of ZnO in min, and requires no conventional templating. The ZnO nanotubes formed have a hollow core with inner diameter varying from 140–160 nm and a wall of thickness, 40–50 nm. The length of nanorods and nanotubes varies in the narrow range of 500–600 nm. These nanostructures have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED). The ZnO nanorods and nanotubes are found by SAED to be single-crystalline. The growth process of ZnO nanorods and nanotubes has been investigated by varying the surfactant concentration and microwave irradiation time. Based on the various results obtained, a tentative and plausible mechanism for the formation of ZnO nanostructures is proposed.     

A comparative study on the NO2 gas sensing properties of ZnO thin films, nanowires and nanorods

ZnO thin films were fabricated using the spin coating method, ZnO nanowires by cathodically induced sol-gel deposition by the means of an anodic aluminum oxide (AAO) template, and ZnO nanorods with the hydrothermal technique. For thin film preparation, a clear, homogeneous and stable ZnO solution was prepared by the sol-gel method using zinc acetate (ZnAc) precursor which was then coated on a glass substrate with a spin coater. Vertically aligned ZnO nanowires which were approximately 65 nm in diameter and 10 μm in length were grown in an AAO template by applying a cathodic voltage in aqueous zinc nitrate solution at room temperature. For fabrication of the ZnO nanorods, the sol-gel ZnO solution was coated on glass substrate by spin coating as a seed layer. Then ZnO nanorods were grown in zinc nitrate and hexamthylenetetramine aqueous solution. The ZnO nanorods are approximately 30 nm in diameter and 500 nm in length. The ZnO thin film, ZnO nanowires and nanorods were characterized by X-ray diffraction (XRD) analysis and scanning electron microscope (SEM). The NO₂ gas sensing properties of ZnO thin films, nanowires and nanorods were investigated in a dark chamber at 200 °C in the concentration range of 100 ppb-10 ppm. It was found that the response times of both ZnO thin films and ZnO nanorods were approximately 30 s, and the sensor response was depended on shape and size of ZnO nanostructures and electrode configurations.     

Nanostructured ZnO hexagons and optical properties

We report the solvothermal synthesis of nanostructured ZnO hexagons by hydrothermal method via intermediate zinc adipate. The intermediate zinc adipate was obtained using precursors zinc acetate and adipic acid in aqueous and organic medium. Detailed XRD analysis of the zinc adipate was studied for the first time. Thermal study of intermediate showed the formation of ZnO at 400 °C. XRD study demonstrated the existence of wrutzite ZnO of high degree of crystallinity with crystallite size in the range of 20–25 nm. Scanning Electron Microscopy (SEM) showed distinguished morphology in different medium. Transmission Electron Microscopy (TEM) demonstrated nanostructured ZnO hexagons with average size 25–50 nm. The band gap for aqueous and organic mediated ZnO was found to be 3.24 and 3.26 eV, respectively. The band gap obtained is higher than the bulk ZnO, which implies nanocrystalline nature of the material.     

ZnO nanocrystalline thin films: a correlation of microstructural,optoelectronic properties

The compositional, structural, microstructural, dc electrical conductivity and optical properties of undoped zinc oxide films prepared by the sol–gel process using a spin-coating technique were investigated. The ZnO films were obtained by 5 cycle spin-coated and dried zinc oxide films followed by annealing in air at 600 °C. The films deposited on the platinum coated silicon substrate were crystallized in a hexagonal wurtzite form. The energy-dispersive X-ray (EDX) spectrometry shows Zn and O elements in the products with an approximate molar ratio. TEM image of ZnO thin film shows that a grain of about 60–80 nm in size is really an aggregate of many small crystallites of around 10–20 nm. Electron diffraction pattern shows that the ZnO films exhibited hexagonal structure. The SEM micrograph showed that the films consist in nanocrystalline grains randomly distributed with voids in different regions. The dc conductivity found in the range of 10⁻⁵–10⁻⁶ (Ω cm)⁻¹. The optical study showed that the spectra for all samples give the transparency in the visible range.     

The features of the synthesis of ZnO nanostructures by laser ablation of zinc in water-surfactant solutions

The data of experimental investigation of optical properties of colloidal solution, its composition and morphology of the dispersed phase, resulting from laser ablation of zinc in aqueous solutions of surfactants—sodium dodecyl sulfate (SDS) and dioctil sodium sulfosuccinate (AOT) are presented. It is shown that an optical absorption spectra of the colloids, X-ray spectra and AFM (atomic force microscopy) images solid phase of colloids can trace the dynamics of synthesis ZnO nanostructures from zinc nanoclusters in the size of nanometers to fractal aggregates (FA) up to hundreds of nanometers. Determinants of this process are the average power and duration of irradiation, the frequency of the laser pulses, the colloid aging time, the type and concentration of surfactant in the solution. At the selecting of appropriate regimes of the process, along with zinc oxide other nanoproducts-hydrozincite and organic-inorganic layered composite [(β)-Zn(OH)₂ + SDS] are obtained.     

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.     

ZnO ultra-fine powders and films: hydrothermal synthesis,luminescence and UV lasing at room temperature

Zinc oxide ultra-fine crystalline powders and polycrystalline films of high optical quality were synthesized under soft hydrothermal conditions. The phase composition, crystal morphology, and luminescent properties of submicron ZnO powders and films were studied depending on synthesis conditions (system composition, precursor kind, solvent type and concentration, temperature). For the systems containing metallic zinc, the ZnO growth mechanism was suggested. The most intensive UV luminescence and the highest values of I_UV/I_VIS were observed for polycrystalline films grown on Zn substrates. Low-threshold UV lasing at room temperature was found for ZnO-films, grown in hydrothermal systems with hydroxide or halide solutions as solvents, E _th = 1–5 MW/cm². The lowest threshold was observed on the ZnO films grown using LiOH as a solvent and zinc nitrate as ZnO-precursor. Clear mode structures with line-width 0.3 nm are characteristic of the lasing spectra.     

Synthesis and optical characteristics of ZnO nanocrystals

Zinc oxide nanomaterials with an average particle size of 20–30 nm are readily synthesized by the reaction of zinc acetate and oxalic acid under hydrothermal conditions. The samples are characterized by XRD, SEM, TEM, UV and photoluminescence (PL) studies. The average crystal size of the as prepared ZnO nanopowder is determined by XRD and the values are in good agreement with the TEM analysis. UV absorption spectra revealed the absorption at wavelength < 370 nm indicating the smaller size of ZnO nanoparticles. The quality and purity of ZnO nanomaterial crystalline samples are confirmed by photoluminescence spectra.     

Morphology, structures and properties of ZnO nanobelts fabricated by Zn-powder evaporation without catalyst at lower temperature

Uniform ZnO normal nanobelts and toothed-nanobelts have been successfully synthesized respectively through pure zinc powder evaporation without catalyst at 600°C. Experimental results indicate that the key to the fabricating method is to control the gas flow rates and the partial pressures of argon, oxygen and zinc vapor. Scanning electron microscopy and high-resolution transmission electron microscopy observations show that the ZnO nanobelts have several types of single crystalline morphology. HRTEM images reveal that there are numerous screw dislocations and the growth is around the dislocations in the toothed-nanobelts. The growth of ZnO nanobelts is controlled by vapor-solid and screw dislocation mechanisms. Room temperature photoluminescence spectra of the toothed-nanobelts showed a UV emission at ∼390 nm and a broad green emission with 4 subordinate peaks at 455–495 nm.     

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.     

Fabrication of hybrid solar cells using poly(2,5-dimethoxyaniline) hexagonal structures and zinc oxide nanorods

Flower-shaped zinc oxide (ZnO) structures have been synthesized in a microwave at 180 °C for 20 min using zinc nitrate and KOH. Detailed structural and morphology observation showed that the micron-sized ZnO nano-pencils grow out of the base of the flower-shaped ZnO structures. Photoluminescence spectrum measured at room temperature showed a sharp UV emission band around 390 nm which is attributed to the radiative annihilation of excitons. The synthesized PDMA and ZnO nanopencils are highly crystalline materials with one-dimensional morphology which improves the electron charge transport in the device. A distinctive photoluminescence quenching effect was observed indicating a photo-induced electron transfer. The solar cell devices fabricated from these materials demonstrated a short circuit current density of about 0.93 μA/cm², open-circuit voltage 0.58 V, and efficiency of 0.16 %.     

Low-temperature synthesis of ZnO nanorods using organic-inorganic composite as a seed layer

Well-aligned zinc oxide (ZnO) nanorods were synthesized using a low-temperature hydrothermal method employing a zinc/sodium dodecyl sulfate (Zn/SDS) composite as a seed layer. The results of X-ray diffraction measurements indicate that the Zn/SDS composite has a lamellar structure with an interlayer distance of 3.12 nm, which is shorter than that of the lamellar structure of SDS (3.82 nm) due to ion exchange between Zn and Na. The results of X-ray absorption fine structure analyses suggest that ZnO crystals start to grow after an induction period of 20-30 min. The length of nanorods and the aspect ratio of ZnO nanorods could be controlled by altering the molarity of ammonium and zinc nitrate in the growth solutions.     

On the Optical,Thermal, and Vibrational Properties of Nano-ZnO:Mn,A Diluted Magnetic Semiconductor

Nano-zinc oxide and Mn-doped zinc oxide were synthesized by a chemical process, and the average size of the particles observed was 35 nm for nano-ZnO. Optical and thermal characterizations were carried out by means of photoluminescence and photoacoustic spectroscopy. It was found that nano-ZnO has a thermal diffusivity one order of magnitude larger than bulk ZnO. Similarly, a less explored localized defect mode in ZnO:Mn was studied theoretically and experimentally using FTIR spectroscopy. The localized mode was experimentally found to be 514cm⁻¹, compared to its theoretical value of 502cm⁻¹. These values suggest that the current theory of bulk materials can also be extended to nanosystems and they are consistent with our hypothesis that Mn goes substitutionally as an impurity displacing Zn in nano-ZnO.      

A facile and green approach for the fabrication of ZnO nanorods using bamboo charcoal as the template

A green synthetic approach was presented for the fabrication of ZnO nanorods via the bamboo charcoal-assisted impregnation route with ZnC₂O₄ colloid in ethanol as the inorganic precursor, followed by calcination at 800 °C for 7 h in air. These ZnO samples were characterized by means of X-ray diffraction (XRD) and transmission electron microscopy (TEM). It is shown that wurtzite hexagonal structured ZnO nanorods were fabricated, with an average diameter of about 300 nm and a length up to several micrometers. Bamboo charcoal played a key role in the formation of ZnO nanorods. The possible formation mechanism for ZnO nanorods was proposed.     

Synthesis of ZnO nanowhiskers by a simple method

By means of a novel and simple method, zinc oxide (ZnO) nanowhiskers, which the diameters are about 15–30 nm and the lengths are up to 100 nm, are synthesized in the presence of a nonionic surfactant (Polyethylene glycol 400). The products are investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM). These nanowhiskers have fine crystal structure. The surfactant is used to control the sizes of ZnO particles in precursor.     

Preparation and properties of ZnO thin films deposited by sol-gel technique

Zinc oxide (ZnO) thin films were deposited on (100) Si substrates by sol-gel technique. Zinc acetate was used as the precursor material. The effect of different annealing atmospheres and annealing temperatures on composition, structural and optical properties of ZnO thin films was investigated by using Fourier transform infrared spectroscopy, X-ray diffraction, atomic force microscopy and photoluminescence (PL), respectively. At an annealing temperature of 400°C in N₂ for 2 h, dried gel films were propitious to undergo structural relaxation and grow ZnO grains. ZnO thin film annealed at 400°C in N₂ for 2 h exhibited the optimal structure and PL property, and the grain size and the lattice constants of the film were calculated (41.6 nm, a = 3.253 ? and c = 5.210 ?). Moreover, a green emission around 495 nm was observed in the PL spectra owing to the oxygen vacancies located at the surface of ZnO grains. With increasing annealing temperature, both the amount of the grown ZnO and the specific surface area of the grains decrease, which jointly weaken the green emission. Translated from Journal of Lanzhou University (Natural Science), 2006, 42(1): 67–71 [译自: 兰州大学学报 (自然科学版)]     

Analysis of growth parameters for hydrothermal synthesis of ZnO nanoparticles through a statistical experimental design method

Nanocrystalline ZnO particles were synthesized from an aqueous solution composed of zinc acetate dihydrate (Zn(CH₃COO)₂·2H₂O) and urea (H₂NCONH₂). A precipitating precursor, basic zinc carbonate (Zn₅(CO₃)₂(OH)₆), was first formed by hydrothermally treating the solution at 120 °C for 2–4 h. Nanocrystalline ZnO particles were then obtained by calcining the precursors at 350–650 °C for 0.5–2 h. The synthesis products were characterized using thermogravimetry–differential scanning calorimetry–mass spectrometry, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and photoluminescence techniques. Based on the experimental results, a possible reaction mechanism for the ZnO formation was proposed. The effects of experimental parameters (namely, the hydrothermal treatment time, the calcination time, and the calcination temperature) on the characteristics of the resulting ZnO products (i.e., the crystalline size and the photoluminescence properties) were analyzed by the Taguchi method to attain the optimum synthesis conditions. By using the appropriate parameters derived from this method, we verified that the optimized synthesis provided a yield of ~70% and that the resulting ZnO particles possessed the characteristics of a ~25 nm crystalline size and a satisfactory photoluminescence property.     

Preparation and properties of composite particles made by nano zinc oxide coated with titanium dioxide

In this paper, composite particles of nano zinc oxide coated with titanium dioxide were prepared and characterized by TEM, XRD, XPS and FT-IR, and the properties of the composite particles for photo catalysis and light absorption were studied. Tetrabutyl titanate (TBT) was hydrolyzed in an alcoholic suspension of nano zinc oxide with diethanolamine (DEA) as an additive, resulting in a film with a thickness of 20–30 nm being coated on the surface of nano zinc oxide, and the composite particles contained ZnTiO₃ after drying and calcination. Photocatalysis capabilities of the composite particles for the degradation of phenol in an aqueous solution were greatly improved as compared with nano zinc oxide particles before coating, with pure nano ZnO and nano TiO₂ with similar average sizes, or with the mixture of nano ZnO and TiO₂ with the similar composition as the composite particles. The light absorption scope of the composite particles was enlarged when compared to nano titanium dioxide with same average size.