Preparation and properties of ZnO nanostructures by electrochemical anodization method

ZnO thin films with diverse nanostructures, including nanodot, nanowire and nanoflower, have been fabricated on zinc foils by a simple and rapid electrochemical anodization method. The ZnO thin films reveal very strong visible emission that is ascribed to the transition between V_OZn_i and valence band. Under the dc or ac electric field, the electroinduced surface wettability conversion from the superhydrophobic to hydrophilic state was observed and the generation of surface defective sites on ZnO films under electric field was used to explain the transition mechanism. This work provides a simple and rapid method for synthesizing different ZnO nanostructures in large scale, and electric field can be used to modulate the wettability of ZnO nanostructures.     

A twice liquid arc discharge approach for synthesis of visible-light-active nanocrystalline Ag:ZnO photocatalyst

Ag:ZnO hybrid nanostructures were successfully prepared by a twice arc discharge method in liquid. The visible light photocatalytic activities were successfully demonstrated for the degradation of Rhodamine B (Rh. B), Methyl orange (MO), and Methylene blue (MB) as standard organic compounds under the irradiation of 90 W halogen light for 2 h. The Ag:ZnO nanostructures were characterized by X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and ultraviolet-visible absorption spectroscopy (UV-Vis). The results revealed that the Ag:ZnO nanostructures extended the light absorption spectrum toward the visible region and significantly enhanced the Rh. B photodegradation under visible light irradiation. 3 mM Ag:ZnO nanostructures exhibited highest photocatalytic efficiency. It has been confirmed that the Ag:ZnO nanostructures could be excited by visible light (E<3.3 eV). The significant enhancement in the Ag:ZnO nanostructures photocatalytic activity under visible light irradiation can be ascribed to the effect of physisorbed noble metal Ag by acting as electron traps in ZnO band gap. A mechanism for photocatalytic degradation of organic pollutant over Ag:ZnO photocatalyst was proposed based on our observations.     

Photoluminescence and Raman analysis of novel ZnO tetrapod and multipod nanostructures

Novel ZnO tetrapod and multipod nanostructures were successfully synthesized in bulk quantity through thermal evaporation method. The morphologies and structures of the ZnO nanostructures were characterized by scanning electron microscopy, X-ray diffraction and transmission electron microscopy. The results revealed that the ZnO nanostructures consisted of tetrapods and multipods with tower-like legs. The ZnO nanostructures were of high purity and were well crystallized with wurtzite structure. The preferred growth direction of legs was found to be the [0 0 0 1] direction. Possible growth mechanisms were proposed for the formation of the ZnO nanostructures. Room temperature photoluminescence (PL) spectra showed that the as-synthesized ZnO nanostructures had a strong green emission centered at 495 nm and a weak ultraviolet emission at 383 nm. Raman spectroscopy was also adopted to explore the structural quality of the ZnO nanostructures.     

Zinc oxide nanostructures for applications as ethanol sensors and dye-sensitized solar cells

ZnO nanostructures were prepared by thermal oxidation technique for applying as ethanol sensors and dye-sensitized solar cells. To improve sensitivity of the sensor based on ZnO nanostructures, gold doping was performed in ZnO nanostructures. Gold-doped with 0%, 5%, and 10% by weight were investigated. The improvement of sensor sensitivity toward ethanol due to gold doping was observed at entire operating temperature and ethanol concentration. The sensitivity up to 145 was obtained for 10% Au-doped ZnO sensor. This can be explained by an increase of the quantity of oxygen ion due to catalytic effect of gold. Also, it was found that oxygen ion species at the surface of the Au-doped ZnO sensor remained O²⁻ as pure ZnO sensor. For dye-sensitized solar cell application, the dye-sensitized solar cell structure based on ZnO as a photoelectrode was FTO/ZnO/Eosin-Y/electrolyte/Pt counter electrode. ZnO with different morphologies of nanobelt, nano-tetrapod, and powder were investigated. It was found that DSSCs with ZnO powder showed higher photocurrent, photovoltage and overall energy conversion efficiencies than that of ZnO nanobelt and ZnO nano-tetrapod. The best results of DSSCs were the short circuit current (J_sc) of 1.25 mA/cm², the open circuit voltage (V_oc) of 0.45 V, the fill factor (FF) of 0.65 and the overall energy conversion efficiency (η) of 0.68%.     

One-dimensional and quasi-one-dimensional ZnO nanostructures prepared by spray-pyrolysis-assisted thermal evaporation

One-dimensional (1D) and quasi-1D ZnO nanostructures have been fabricated by a kind of new spray-pyrolysis-assisted thermal evaporation method. Pure ZnO powder serves as an evaporation source. Thus-obtained products have been characterized by X-ray diffraction (XRD) analysis, scanning electron microscope (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), transmission electron microscope (TEM). The room temperature photoluminescence spectrum of these ZnO nanostructures is presented. The results show that as-grown ZnO nanomaterials have a hexagonal wurtzite crystalline structure. Besides nanosaws, nanobelts and nanowires, complex ZnO nanotrees have also been observed in synthesized products. The study provides a new simple route to construct 1D and quasi-1D ZnO nanomaterials, which can probably be extended to fabricate other oxide nanomaterials with high melting point and doped oxide nanomaterials.     

The effect of morphology and doping on photoluminescence of ZnO nanostructures

In this work, optical properties of ZnO nanostructures prepared by chemical vapor deposition under different conditions were investigated. ZnO nanostructures were characterized by electron microscopy and photoluminescence. A high intensity green emission and a narrow UV emission band are observed in photoluminescence spectra of ZnO nanostructures related to the below-band-gap and band-edge that their intensities depend on the morphology of the nanostructures. It is considered that the green emission is originated from structural defects. In addition, the influence of thermal treatment and dopants such as iron and copper, on the photoluminescence (PL) properties of the ZnO nanostructures was investigated.     

Fabrication of ZnO nanostructures of various dimensions using patterned substrates

ZnO nanostructures were grown on silicon, porous silicon, ZnO/Si and AlN/Si substrates by low-temperature aqueous synthesis method. The shape of nanostructures greatly depends on the underlying surface. Scattered ZnO nanorods were observed on silicon substrate, whereas aligned ZnO nanowires were obtained by introducing sputtered ZnO film as a seed layer. Furthermore, both the combination of nanorods and the bunch of nanowires were found on porous silicon substrates, whereas platelet-like morphology was observed on AlN/Si substrates. XRD patterns suggest the crystalline nature of aqueous-grown ZnO nanostructures and high-resolution transmission electron microscopy images confirm the single-crystalline growth of the ZnO nanorods along [0 0 1] direction. Room-temperature photoluminescence characterization clearly shows a band-edge luminescence along with a visible luminescence in the yellow spectral range.     

Comparative study of ethanol sensor based on gold nanoparticles: ZnO nanostructure and gold: ZnO nanostructure

Gold colloid:ZnO nanostructures were prepared from Zn powder by using thermal oxidation technique on alumina substrates, then it was impregnated by gold colloid for comparative study. The gold colloid is the solution prepared by chemical reduction technique; it appeared red color for gold nanoparticle solution and yellow color for gold solution. The heating temperature and sintering time of thermal oxidation were 700 °C and 24 h, respectively under oxygen atmosphere. The structural characteristics of gold colloid:ZnO nanostructures and pure ZnO nanostructures were studied using filed emission scanning electron microscope (FE-SEM). From FE-SEM images, the diameter and length of gold colloid:ZnO nanostructures and ZnO nanostructures were in the ranges of 100-500 nm and 2.0-7.0 μm, respectively. The ethanol sensing characteristics of gold colloid:ZnO nanostructures and ZnO nanostructures were observed from the resistance alteration under ethanol vapor atmosphere at concentrations of 50, 100, 200, 500, and 1000 ppm with the operating temperature of 260-360 °C. It was found that the sensitivity of sensor depends on the operating temperature and ethanol vapor concentrations. The sensitivity of gold colloid:ZnO nanostructures were improved with comparative pure ZnO nanostructures, while the optimum operating temperature was 300 °C. The mechanism analysis of sensor revealed that the oxygen species on the surface was O²⁻.     

Aqueous chemical growth of free standing vertical ZnO nanoprisms,nanorods and nanodiskettes with improved texture co-efficient and tunable size uniformity

Tuning the morphology, size and aspect ratio of free standing ZnO nanostructured arrays by a simple hydrothermal method is reported. Pre-coated ZnO seed layers of two different thicknesses (≈350 nm or 550 nm) were used as substrates to grow ZnO nanostructures for the study. Various parameters such as chemical ambience, pH of the solution, strength of the Zn²⁺ atoms and thickness of seed bed are varied to analyze their effects on the resultant ZnO nanostructures. Vertically oriented hexagonal nanorods, multi-angular nanorods, hexagonal diskette and popcorn-like nanostructures are obtained by altering the experimental parameters. All the produced nanostructures were analysed by X-ray powder diffraction analysis and found to be grown in the (002) orientation of wurtzite ZnO. The texture co-efficient of ZnO layer was improved by combining a thick seed layer with higher cationic strength. Surface morphological studies reveal various nanostructures such as nanorods, diskettes and popcorn-like structures based on various preparation conditions. The optical property of the closest packed nanorods array was recorded by UV-VIS spectrometry, and the band gap value simulated from the results reflect the near characteristic band gap of ZnO. The surface roughness profile taken from the Atomic Force Microscopy reveals a roughness of less than 320 nm.     

Effect of substrate temperature on the growth and luminescence properties of ZnO nanostructures

ZnO nanowires, nanorods and nanoribbons have been prepared 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 nanostructures are grown as a function of substrate temperature ranging from 900 to 1300 K. These nanostructures are of the size 100–300 nm in diameter or width and several tens of micrometers in length. We studied the influence of the substrate temperature on the luminescent properties of these nanostructures. We observed a strong relationship between the substrate temperature and the green emission band in ZnO, i.e., the photoluminescence study revealed that the green emission peak of the ZnO nanostructures is suppressed relative to the band edge emission when the substrate temperature is decreased from 1300 to 900 K.     

Effect of sputtered films on morphology of vertical aligned ZnO nanowires

Vertical aligned ZnO nanowires were grown by MOCVD technique on silicon substrate using ZnO and AlN thin films as seed layers. The shape of nanostructures was greatly influenced by the under laying surface. Vertical nanopencils were observed on ZnO/Si, whereas the nanowires on both sapphire and AlN/Si substrate have the similar aspect ratio. XRD patterns suggest that the nanostructures have good crystallinity. High-resolution transmission electron microscopy (HRTEM) confirmed the single crystalline growth of the ZnO nanowires along [0 0 1] direction. Room-temperature photoluminescence (PL) spectra of ZnO nanowires on AlN/Si clearly show a band-edge luminescence accompanied with a visible emission. More interestingly, no visible emission for the nanopencils on ZnO/Si substrates, were observed.     

Growth mechanism and photoluminescence property of flower-like ZnO nanostructures synthesized by starch-assisted sonochemical method

Flower-like ZnO nanostructures have been synthesized by starch-assisted sonochemical method and the effect of starch and ultrasound on the formation of ZnO nanostructure has been investigated. It is observed that starch and ultrasonic wave both plays a vital role on the growth of ZnO nanostructure. X-ray diffraction (XRD) pattern indicated that the synthesized flower-like ZnO nanostructures were hexagonal. FTIR spectrum confirms the presence of starch on the surface of flower-like ZnO nanostructure. The photoluminescence spectrum of flower-like ZnO nanostructure consists of band-edge emission at 393 nm as well as emission peaks due to defects. On the basis of structural information provided by X-ray diffraction (XRD) and morphological information by Scanning Electron Microscopy (SEM), a growth mechanism is proposed for formation of flower-like ZnO nanostructures. Differential Scanning Calorimetry (DSC) of starch in liquid medium confirms that gelatinization is a two step process involving two phases.     

Effect of annealing temperature on optical and electrochemical properties of chitosan–ZnO nanostructure

Chitosan–ZnO nanostructures were prepared by chemical precipitation method using different concentration of zinc chloride and sodium hydroxide solutions. Nanorod-shaped grains with hexagonal structure for samples annealed at 300 °C and porous structure with amorphous morphology for samples annealed at 600 °C were revealed in SEM analysis. X-ray diffraction patterns confirmed the hexagonal phase ZnO with crystallite size found to be in the range of ~24.15–34.83 nm. Blue shift of UV–Vis absorption shows formation of nanocrystals/nanorods of ZnO with marginal increase in band gap. Photoluminescence spectra show that blue–green emission band at 380–580 nm. The chitosan–ZnO nanostructures used on surface of a glassy carbon electrode gives the oxidation peak potential at ~0.6 V. The electrical conductivity of chitosan–ZnO composites were observed at 2.1?×?10^?5 to 2.85?×?10^?5?S/m. The nanorods with high surface area and nontoxicity nature of chitosan–ZnO nanostructures observed in samples annealed at 300 °C were suitable as a potential material for biosensing.     

Synthesis of ZnO nanoplates decorated rhombus-shaped ZnO nanorods and their application in solar cells

Novel nanostructures of ZnF(OH) nanoplates decorated rhombus-shaped ZnF(OH) nanorods were fabricated. The obtained precursors were transformed by calcination to porous hierarchical ZnO nanostructures with the original morphologies retained. Field emission scanning electron microscope images exhibit that the nanoplates are grown in the interstices between the nanorods and on the top of the nanorods. The structure and composition of the obtained products have been confirmed by transmission electron microscope and X-ray diffraction measurements. The obtained ZnO nanostructures have been successfully used in solar cells. The light-to-electricity conversion results show that the complex nanostructures exhibit a power conversion efficiency of 1.36% with a photoelectrode thickness of 4.2 µm, which is comparable to those based on 40 µm vertically aligned hexagonal-shaped ZnO nanowire array photoelectrodes. These results indicate that the synthesized ZnO nanoplate decorated rhombus-shaped ZnO nanorod nanostructures are more suitable for application as a photoelectrode in solar cells.     

40% Efficiency enhancement in solar cells using ZnO nanorods as shell prepared via novel hydrothermal synthesis

Herein, rod-like ZnO nanostructures were synthesized via a novel hydrothermal route using Zn(OAc)₂, ethylenediamine and hydrazine as a new set of starting reagents. The as-synthesized products were characterized by techniques including XRD, EDS, SEM, XPS, Pl and FTIR. The prepared ZnO nanostructures were utilized as shell on TiO₂ film in DSSCs. Effect of precursor type, morphology and thickness of ZnO shell (number of electrophoresis cycle) on solar cells efficiency were well studied. Our results showed that ethylenediamine has crucial effect on morphology of synthesized ZnO nanostructures and using ZnO nanostructures leads to an increase in DSSCs efficiency compared to bare TiO₂ from 4.66 to 7.13% (~40% improvement). Moreover, highest amount of solar cell efficiency (7.13%) was obtained by using ZnO nanorods with two cycle of electrophoresis for deposition.     

Growth of nanostructures of Zn/ZnO by thermal evaporation and their application for room-temperature sensing of H<Subscript><Emphasis Type="Bold">2</Emphasis></Subscript>S gas

ZnO micro- and nanostructures were prepared by thermal evaporation of Zn and a mixture of ZnO with graphite. On heating Zn powder in a quartz tube at temperatures between 600 °C to 800 °C, radial growth of nanowires was observed on the source. On increasing the temperature to 900 °C, various interesting micro- and nanostructures of Zn and ZnO were observed to have deposited all over the quartz tube. On the other hand, when ZnO was heated in the presence of graphite, predominant growth of ZnO nanotetrapods was observed. Nanowires and tetrapods of ZnO were characterized by photoluminescence measurements and were found to show significantly improved response for detection of H₂S gas at room temperature when compared with earlier studies. The response was seen to improve with increase in oxygen vacancies in the material. PACS 78.55.Et; 07.07.Df     

Growth of ZnO nanostructures by vapor–liquid–solid method

Zinc oxide nanorods have been grown by vapor–liquid–solid (VLS) catalytic growth. The optical properties and structures properties of the grown ZnO nanostructures have been studied by photoluminescence, high resolution X-ray diffraction and scanning electron microscopy. The results show that the formation of ZnO nanostructures is strongly influenced by the growth conditions and used substrates. It was found that oriented ZnO nanorods are grown more easily on a substrate with a similar crystalline structure as ZnO. By optimizing growth conditions, oriented-ZnO nanorods grown on Si(001) substrate with a diameter of around 300 nm and lengths of 20 to 35 μm have been achieved, and they show excellent optical properties. Laser action has been observed at room temperature by using optical pumping. PACS 81.05.Dz; 81.10.Bk; 81.16.Hc     

Surface-enhanced Raman spectroscopy of semiconductor nanostructures

We review our recent results concerning surface-enhanced Raman scattering (SERS) by confined optical and surface optical phonons in semiconductor nanostructures including CdS, CuS, GaN, and ZnO nanocrystals, GaN and ZnO nanorods, and AlN nanowires. Enhancement of Raman scattering by confined optical phonons as well as appearance of new Raman modes with the frequencies different from those in ZnO bulk attributed to surface optical modes is observed in a series of nanostructures having different morphology located in the vicinity of metal nanoclusters (Ag, Au, and Pt). Assignment of surface optical modes is based on calculations performed in the frame of the dielectric continuum model. It is established that SERS by phonons has a resonant character. A maximal enhancement by optical phonons as high as 730 is achieved for CdS nanocrystals in double resonant conditions at the coincidence of laser energy with that of electronic transitions in semiconductor nanocrystals and localized surface plasmon resonance in metal nanoclusters. Even a higher enhancement is observed for SERS by surface optical modes in ZnO nanocrystals (above 10⁴). Surface enhanced Raman scattering is used for studying phonon spectrum in nanocrystal ensembles with an ultra-low areal density on metal plasmonic nanostructures.     

Enhancement of the light extraction of GaN-based green light emitting diodes via nanohybrid structures

Improvement in the light extraction efficiency (LEE) of GaN-based green light emitting diodes (LEDs) with ZnO nanostructures synthesized by a hydrothermal method is reported. Formation of ZnO nanorods, hemispheres, and cones was controlled by varying the pH of the aqueous synthesis solution. The shape of the ZnO nanostructures integrated onto the LEDs shows a strong relationship with the LEE characteristics of GaN-based green LEDs. The electroluminescence (EL) intensity of LEDs covered by ZnO nanostructures increased compared to conventional LEDs. In terms of LEE, LEDs with surface-textured ZnO hemispheres showed the highest EL intensity, which can be attributed to an increase in the effective critical angle, the escape cone, and multiple scattering. Finite difference time domain (FDTD) simulation was conducted to theoretically confirm the experimental results.     

Enhanced acetone sensing characteristics by decorating Au nanoparticles on ZnO flower-like structures

A well-organized hierarchical structure of ZnO was developed by chemical bath deposition and used as templates for making gold-coated ZnO (Au/ZnO) hybrid nanostructures. The coverage of Au nanoparticles (Au NPs) on ZnO was controlled by changing the amount of the Au precursor. The Au/ZnO hybrids were applied as gas sensing materials to detect acetone. The improved sensor response, selectivity and short response, and recovery time to acetone vapor due to Au NPs on ZnO nanostructures has been observed and explained by considering the formation of Au/ZnO heterostructures, which are favorable for the diffusion of gas molecules. In addition, the dependence of Au amount on gas sensor properties was systematically investigated. ZnO decorated by 6 wt% Au NPs displayed a 9.05-fold enhancement in gas response to 100 ppm of acetone at 280 °C compared to pristine ZnO.