Controllable synthesis of hexagonal ZnO–carbon core–shell microrods and the removal of ZnO to form hexagonal carbon microtubes

A simple and efficient approach was developed to produce regular and uniform shaped hexagonal ZnO–C core–shell micro-rods and carbon micro-tubes. A single-source raw material, zinc acetate dihydrate, has been used for the in situ generation of the hexagonal ZnO–C micro-rods in a sealed autoclave system at 500 °C for 12 h without a catalyst. The resulting products were characterized by X-ray powder diffraction, scanning and transmission electron microscopy, energy-dispersive X-ray analysis and room-temperature photoluminescence spectroscopy (PL). The partial or complete carbon coating on the ZnO surfaces plays an important role in modifying the PL properties. Impacting factors including thermolysis temperature, time and dose of the reactant on the evolution of the hexagonal shape were investigated. A possible formation diagram for the materials has been proposed and discussed based on the features of the reaction system.     

Solvothermal synthesis of hexagonal ZnO nanorods and their photoluminescence properties

Pure hexagonal ZnO nanorods were synthesized by low-temperature (90 °C) solvothermal treatment of zinc acetate in 40-80 wt.% hydrazine hydrate aqueous solutions. The products were characterized by means of powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electronic microscopy (TEM), selected area electron diffraction (SAED), and room temperature photoluminescence (RTPL) spectra. They show a strong UV emission at around 380 nm upon excitation at 360 nm using a Xe lamp at room temperature. The influence on the quality of the nanorods was investigated while the content of the solvent changed. The as-synthesized ZnO nanorods are promising materials for nanoscale optoelectronic devices due to their excellent UV emission properties.     

Synthesis,characterization and photoresponse study of undoped and transition metal (Co,Ni, Mn) doped ZnO thin films

The synthesis, characterization and photoresponse studies of undoped and transition metal doped zinc oxide thin films are carried out in this work, in prospect of visible light photo detection and sensor applications. The undoped and transition metal ions such as, Co, Ni and Mn doped ZnO films in this study were synthesized by chemical solution deposition, involving spin-coating. We have characterized the deposited films using X-ray diffraction, scanning electron microscopy, photoluminescence and UV–vis spectroscopy studies. The devices of the films for photoresponse study were fabricated by top Ag contacts on the film surface in metal–semiconductor–metal configuration. The current–voltage characteristics and switching measurements of these devices were studied under the illumination of an incandescent lamp. We found a high ON/OFF ratio of 8 and highest photocurrent density of 0.7 mA/cm² for Ni doped ZnO film.     

Effect of α-Fe2O3 addition on the morphological,optical and decolorization properties of ZnO nanostructures

Visible light sensitive photocatalysts of Fe₂O₃/ZnO nanocomposites were prepared by a simple solid-state reaction method, using zinc acetate, α-Fe₂O₃ and sodium hydroxide at room temperature. The products were characterized by scanning electron microscopy, powder X-ray diffraction, N₂ adsorption–desorption measurement, UV–vis absorption, and photoluminescence spectroscopy and used for photodecolorization of Congo red. The characterization results showed that the morphology, crystallite size, BET surface area and optical absorption of the samples varied significantly with the Fe³⁺ to Zn²⁺ ratios. The nanocomposites show two absorption edges at ultraviolet and visible region. The optical band gap values of these nanocomposites were calculated to be about 3.98–3.81 eV and 2.88–2.98 eV, which show a red shift from that of pure ZnO. These red shifts are related to the formation of Fe s-levels below the conductive band edge of ZnO and effectively extend the absorption edge into the visible region. The growth mechanisms of the samples are proposed. These nanocomposites showed high decolorization ability in visible light with wavelength up to about 400 nm. Among the samples, Fe₂O₃/ZnO nanoflower (molar ratio of Fe³⁺ to Zn²⁺ is 1:100) exhibited higher decolorization efficiency than the other nanocomposites. It could be considered as a promising photocatalyst for dyes treatment.     

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.     

Triangle-shape ZnO prepared by thermal decomposition

Using oleic acid as surfactant, triangle-shape ZnO with an average diameter of 250 nm can be synthesized by thermal decomposition of precursor zinc acetate (Zn(CH₃CH₂COO)₂) in the high boil-point solvent trioctylamine (TOA). Fundamental characterizations including transmission electron microscopy, X-ray diffraction, high-resolution transmission electron microscopy, scanning electron microscopy and photoluminescence were conducted for the as-synthesized ZnO particles. The effects of refluxing time and the content of surfactant on size and morphology of ZnO particles were studied. It is found that the shape of ZnO particles changes from round-shape, disk-shape to triangle-shape. Based on experimental observations and surface and attachment energies simulation for various crystallographic planes, a possible growth mechanism was put forward to explain the formation of triangle-shape ZnO particles.     

Effect of solvents on the synthesis of nano-size zinc oxide and its properties

The effect of the solvents on particle size and morphology of ZnO is investigated. The optical properties of nano ZnO were studied extensively. During this study, zinc oxalate was prepared in aqueous and organic solvents using zinc acetate and oxalic acid as precursors. The thermo-gravimetric analysis (TGA/DTA) showed formation of ZnO at 400 °C. Nano-size zinc oxide was obtained by thermal decomposition of aqueous and organic mediated zinc oxalate at 450 °C. The phase purity was confirmed by XRD and crystal size determined from transmission electron microscopy (TEM) was found to be 22–25 nm for the aqueous and 14 –17 nm in organic mediated ZnO. Scanning electron microscope (SEM) also revealed different nature of surfaces and microstructures for zinc oxide obtained in aqueous and organic solvents. The UV absorption spectra showed sharp absorption peaks with a blue shift for organic mediated ZnO, due to monodispersity and lower particle size. Sharp peaks and absence of any impurity peaks in photoluminescence spectra (PLS) complement the above observations.     

Effect of Al dopants on the structural,optical and gas sensing properties of spray-deposited ZnO thin films

Undoped and Al-doped ZnO thin films were deposited on glass substrates by the spray pyrolysis method. The structural, morphological and optical properties of these films were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV–Vis spectroscopy, photoluminescence (PL) and photoconductivity (PC) measurements, respectively. XRD analyses confirm that the films are polycrystalline zinc oxide with the hexagonal wurtzite structure, and the crystallite size has been found to be in the range 20–40 nm. SEM and AFM analyses reveal that the films have continuous surface without visible holes or faulty zones, and the surface roughness decreases on Al doping. The Al-doped films have been found to be highly transparent (>85%) and show normal dispersion behavior in the wavelength range 450–700 nm. The doped films show only ultraviolet emission and are found to be highly photosensitive. Among all the films examined, at 300 °C the 1.0 at% Al-doped film shows the selective high response (98.2%) to 100 ppm acetone concentration over to methanol, ethanol, propan-2-ol, formaldehyde and hydrogen.     

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.     

Control of ZnO thin film surface by ZnS passivation to enhance photoluminescence

To enhance the optical property of zinc oxide (ZnO) thin film, zinc sulfide (ZnS) thin films were formed on the interfaces of ZnO thin film as a passivation and a substrate layer. ZnO and ZnS thin films were deposited by atomic layer deposition (ALD) using diethyl zinc, H₂O, and H₂S as precursors. Investigations by X-ray diffraction and transmission electron microscopy showed that ZnS/ZnO/ZnS multi-layer thin films with clear boundaries were achieved by ALD and that each film layer had its own polycrystalline phase. The intensity of the photoluminescence of the ZnO thin film was enhanced as the thickness of the ZnO thin film increased and as ZnS passivation was applied onto the ZnO thin film interfaces.     

Synthesis of Er-doped ZnO nanoparticle/organic hybrid from metal-organics

An Er-doped ZnO nanoparticle/organic hybrid was synthesized in situ from zinc acrylate (ZA) and erbium acetate (EA) using methylhydrazine. Nano-sized Er-doped ZnO particles were formed in an organic matrix by hydrolysis and polymerization of ZA–EA at 80 °C. The crystallinity of the Er-doped ZnO particles in the hybrid was dependent upon the hydrolysis temperature and water amount. Analysis by transmission electron microscopy and energy dispersive X-ray analyzer revealed that crystalline ZnO nanoparticles doped with Er were dispersed in the organic matrix. The hybrid film sandwiched between fused silica plates was highly transparent. The Er-doped ZnO particle/organic hybrid showed a photoluminescence peak at 0.81 eV (1.54 μm) attributed to the transition of Er³⁺ ions.     

ZnO micro and nanocrystals with enhanced visible light absorption

In this paper, we investigate the effect of the particle size and morphology on the optical properties of ZnO. A series of ZnO micro and nanocrystals were synthesized by the hydrothermal processing of zinc acetate dihydrate and sodium hydroxide as the starting materials, and polyvinylpyrrolidone (PVP) as the polymer surfactant. The particle size and morphology were tailored by adjusting the reactant molar ratios [Zn²⁺]/[OH⁻], while the reaction temperature and the time remained unchanged. X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and high-resolution TEM (HRTEM) have shown that the micro and nanocrystals have a high crystalline pure wurtzite-type hexagonal structure with nanosized crystallites. The size and morphology of the ZnO micro and nanocrystals were investigated by field emission scanning electron microscopy (FE-SEM), which showed a modification from micro-rods via hexagonal-faceted prismatic morphology to nanospheres, caused by simple adjustment of the reactant molar ratio [Zn²⁺]/[OH⁻] from 1:1 to 1:5. The optical properties of the ZnO micro and nanocrystals, as well as their dependence on the particle size and morphology were investigated by Raman and ultraviolet–visible (UV–vis) diffuse reflectance spectroscopy (DRS). The UV–vis spectra showed that the modification of the particle size and morphology from nanospheres to micro-rods resulted in increased absorption, and a slight red-shift of the absorption edge (0.06 eV). Besides, the band gap energy of the synthesized ZnO micro and nanocrystals showed the red shift (∼0.20 eV) compared to bulk ZnO. According to the results of a Raman spectroscopy, the enhanced visible light absorption of the ZnO micro and nanocrystals is related to two phenomena: (1) the existence of lattice defects (oxygen vacancies and zinc interstitials), and (2) the particle surface sensitization by PVP.     

Synthesis, microstructure and photoluminescence of well-aligned ZnO nanorods on Si substrate

Well-aligned zinc oxide (ZnO) nanorods were densely grown on Si substrate using ZnO thin-film seed layer without any catalysts and/or additives by a simple solid–vapour phase thermal sublimation technique. The growth mechanism can be interpreted as self-catalyst of zinc particles based on vapour–solid (VS) mechanism. High-resolution transmission electron microscopy (HRTEM) image and selected area electron diffraction (SAED) pattern confirmed that the single-crystalline growth of the nanorods were preferentially along c-axis of hexagonal crystal system. High-crystal quality ZnO nanorods with strong near band edge emission centred at 380 nm can be achieved on Si substrate by the introduction of sufficient oxygen during the nanorod growth processing.     

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。     

Growth and optical and field emission properties of flower-like ZnO nanostructures with hexagonal crown

Flower-like zinc oxide (ZnO) nanostructures with hexagonal crown were synthesized on a Si substrate by direct thermal evaporation of zinc power at a low temperature of 600 °C and atmospheric pressure. Field emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectroscopy and photoluminescence were applied to study the structural characteristics and optical properties of the product. The result indicated that the flower-like product with many slender branches and hexagonal crowns at the ends were single-crystalline wurtzite structures and were preferentially oriented in the <001> direction. The photoluminescence spectrum demonstrated a strong UV emission band at about 386 nm and a green emission band at 516 nm. The field emission of the product showed a turn-on field of 3.0 V/µm at a current density of 0.1 μA/cm², while the emission current density reached about 1 mA/cm² at an applied field of 5.9 V/μm.     

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.     

The photo-electrochemical studies of Eu doped yttrium orthovanadate–zinc oxide–reduced graphene oxide nanohybrid

A new class of nanostructured photo-electrocatalyst Eu³⁺ doped yttrium orthovanadate–zinc oxide–reduced graphene oxide (YVO₄:Eu³⁺–ZnO–RGO) nanohybrid was developed by a simple electrostatic self-assembly at room temperature, using ZnO, YVO₄:Eu³⁺ and RGO as building blocks. Interaction among YVO₄:Eu³⁺, ZnO and RGO is indicated by variation in hydrodynamic diameter (H_D) and zeta potentials of the products as compared to their individual components, thus suggesting that YVO₄:Eu³⁺–ZnO–RGO is a nanohybrid and not a physical mixture. Electrochemical response of this nanohybrid towards the redox couple of Fe(CN)₆^3−/4− was investigated before and after UV irradiation. Apart from quenching of the green emission of ZnO in photoluminescence spectrum, which serves as a probe to monitor the interfacial electron transfer from excited ZnO to RGO, degradation in electrochemical redox process provides an additional path to monitor interfacial electron transfer.     

Brush-shaped ZnO heteronanorods synthesized using thermal-assisted pulsed laser deposition

Brush-shaped ZnO heteronanostructures were synthesized using a newly designed thermal-assisted pulsed laser deposition (T-PLD) system that combines the advantages of pulsed laser deposition (PLD) and a hot furnace system. Branched ZnO nanostructures were successfully grown onto CVD-grown backbone nanowires by T-PLD. Although ZnO growth at 300 °C resulted in core-shell structures, brush-shaped hierarchical nanostructures were formed at 500-600 °C. Materials properties were studied via photoluminescence (PL), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) characterizations. The enhanced photocurrent of a SnO(2)-ZnO heterostructures device by irradiation with 365 nm wavelength ultraviolet (UV) light was also investigated by the current-voltage characteristics.     

Efficient field emission properties of ZnO (core)/graphite (shell) nanowires

In this work the field emission studies of a new type of field emitter, zinc oxide (ZnO) core/graphitic (g-C) shell nanowires are presented. The nanowires are synthesized by chemical vapor deposition of zinc acetate at 1300 °C Scanning and transmission electron microscopy characterization confirm high aspect ratio and novel core–shell morphology of the nanowires. Raman spectrum of the nanowires mat represents the characteristic Raman modes from g-C shell as well as from the ZnO core. A low turn on field of 2.75 V/μm and a high current density of 1.0 mA/cm² at 4.5 V/μm for ZnO/g-C nanowires ensure the superior field emission behavior compared to the bare ZnO nanowires.     

Formation and characterization of zinc oxide nanowires grown on hexagonal-prism microstructures

In this paper, zinc oxide (ZnO) micro- and nano-structures were synthesized through a chemical vapor deposition route. X-ray diffraction (XRD), energy dispersive X-ray analysis (EDX), and scanning electron microscopy (SEM) were used to study the samples’ phase, composition, purity, and structure. XRD analysis confirmed the formation of the wurtzite phase in all samples. SEM images revealed the formation of hexagonal-prism microstructures of ZnO. After we changed the conditions, nano-wires 40–50 nm in diameter appeared on these hexagonal-prism microstructures. Further, we investigated the photoluminescence properties of these structures at room temperature. The modified structures showed UV emission and strong blue-green photoluminescence line due to near-band emission and oxygen vacancies respectively.