Low temperature pH dependent synthesis of flower-like ZnO nanostructures with enhanced photocatalytic activity

In the present study we have synthesized flower-like ZnO nanostructures comprising of nanobelts of 20 nm width by template and surfactant free low-temperature (4 °C) aqueous solution route. The ZnO nanostructures exhibit flower-like morphology, having crystalline hexagonal wurtzite structure with (0 0 1) orientation. The flowers with size between 600 and 700 nm consist of ZnO units having crystallite size of ∼40 nm. Chemical and structural characterization reveals a significant role of precursor:ligand molar ratio, pH, and temperature in the formation of single-step flower-like ZnO at low temperature. Plausible growth mechanism for the formation of flower-like structure has been discussed in detail. Photoluminescence studies confirm formation of ZnO with the defects in crystal structure. The flower-like ZnO nanostructures exhibit enhanced photochemical degradation of methylene blue (MB) with the increased concentration of ligand, indicating attribution of structural features in the photocatalytic properties.     

Hybrid nanostructures of Au nanocrystals and ZnO nanorods: Layer-by-layer assembly and tunable blue-shift band gap emission

A layer-by-layer assembly technique was developed to synthesize the hybrid nanostructures of Au nanocrystals with diameter of about 5 nm and ZnO nanorods via the electrostatic interaction. In comparison with ZnO nanorods, the Au-ZnO hybrid nanostructures exhibited the broadened and red-shifted surface plasmon band, enhanced band gap emission, and suppressed defect emission due to the strong interfacial coupling between Au and ZnO. Moreover, the band gap emission of the Au-ZnO hybrid nanostructures is controllably blue-shifted with decreasing distance between the Au nanocrystals and ZnO nanorods tuned by the amount of the polyelectrolyte layers due to the exciton and plasmon interactions.     

Structural properties and growth mechanism of flower-like ZnO structures obtained by simple solution method

Flower-shaped zinc oxide (ZnO) structures have been synthesized in the reaction of aqueous solution of zinc nitrate and NaOH at 90 °C. To examine the morphology of ZnO nanostructures, time-dependent experiments were carried out. Detailed structural observation showed that the flower-like structures consist of triangular-shaped leaves, having sharpened tips with wider bases. Photoluminescence spectrum measured at room temperature show a sharp UV emission at 381 nm and a strong and broad green emission at 480-750 nm attributed to structural defects. A possible growth mechanism for the formation of flower-shaped ZnO structures is discussed in detail.     

Facile synthesis, optical and photoconductive properties of novel ZnO nanocones

Large-scale, uniform ZnO nanocones with tips about 200 nm and length about 50 μm have been synthesized by a facile hydrothermal method. The morphology and structures were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and high-resolution transmission electron microscope (HR-TEM). The effects of reaction time and PEG-400 on the morphology of ZnO nanostructures were investigated, also an oriented attachment mechanism has been briefly proposed. The optical properties were investigated by lasing confocal microscope and photoluminescence spectrum, a strong near band edge emission peak centered at 387 nm from the ZnO nanocones was observed in photoluminescence spectrum. Finally, we have fabricated UV photodetector based on single ZnO nanocone, which present good switching properties by turning the UV light on and off.     

ZnO and ZnS composited tri-crystal nanoribbons

ZnO and ZnS composited tri-crystal nanoribbons were fabricated by one-step thermal evaporation of ZnS and CuO powders. The tri-crystal nanoribbons have typical length of about 10 μm and width of 100-300 nm. The tri-crystal nanoribbon was composed of three intersected nanoribbons by 120°, which had a thickness of 50 nm with a growth direction along [10-10]. The rough nanoribbon contained several grains and the averaged elemental enrichment of Zn:O:S was 1:0.72:0.28. The tri-crystal nanoribbons exhibited three emission peaks at room temperature, which are associated to band gap and defect emissions of ZnO and ZnS. This 3D composited nanocrystal has potential applications in optoelectronics and energy-harvesting devices.     

Plasmon assisted intense blue-green emission from ZnO/ZnS nanocrystallites

Excellent luminescence properties of ZnO/ZnS nanocrystallites prepared using simple wet chemical approach at room temperature have been reported. ZnS coating on the surface of ZnO nanocrystallites enhanced the green emission (around 500 nm) by a factor of 2. The intensity of the blue emission around 450 nm of ZnO/ZnS nanocrystallites is observed to be as high as three times the emission intensity of pure ZnO nanocrystallites. A further overall increase by a factor of ∼2.5 has also been observed in the intensity of wide blue-green emission when the sample was prepared onto grating compared to that of the samples prepared onto uncoated as well as gold coated quartz. The enhanced emission is thought to be due to plasmon assisted electromagnetic field enhancement near nanocrystallites-metal interface. This is supported by power dependent photoluminescence measurements. The strong enhanced blue-green emission covering a wide spectral range of ∼375-650 nm signifies potential optoelectronic applications in near UV and VIS wavelength regimes.     

Optical and structural characteristics of ZnO thin films grown by rf magnetron sputtering

Nanostructured ZnO thin films on Pyrex glass substrates were deposited by rf magnetron sputtering at different substrate temperatures. Structural features and surface morphology were studied by X-ray diffraction and atomic force microscopy analyses. Films were found to be transparent in the visible range above 400 nm, having transparency above 90%. Sharp ultraviolet absorption edges around 370 nm were used to extract the optical band gap for samples of different particle sizes. Optical band gap energy for the films varied from 3.24 to 3.32 eV and the electronic transition was of the direct in nature. A correlation of the band gap of nanocrystalline ZnO films with particle size and strain was discussed. Photoluminescence emission in UV range, which is due to near band edge emission is more intense in comparison with the green band emission (due to defect state) was observed in all samples, indicating a good optical quality of the deposited films.     

Self-catalytic growth and photoluminescence properties of ZnS nanostructures

Mass production of uniform wurtzite ZnS nanostructures has been achieved by a H₂-assisted thermal evaporation technique. X-ray diffraction (XRD) analyses, scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) observations show that the ZnS nanostructures consist of nanobelts, nanosheets with a hexagonal wurtzite structure. The as-synthesized nanobelts have a length of several tens of micrometers and a width of several hundreds of nanometers. Self-catalytic vapor-liquid-solid (VLS) growth and vapor-solid (VS) growth are proposed for the formation of the ZnS nanostructures because neither a metal catalyst nor a template was introduced in the synthesis process. Room-temperature photoluminescence measurement indicates that the synthesized ZnS nanostructures have a strong emission band at a wavelength of 443 nm, which may be attributed to the presence of various surface states.     

Self-assembly of ZnO nanosheets into nanoflowers at room temperature

A singularity flower-like ZnO nanostructure was prepared on a large scale through a very simple solution method at room temperature and under ambient pressure in a very short time. The flower-like ZnO nanostructures were self-assembled by thin and uniform nanosheets, with a thickness of around 5 nm. X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) were used to characterize the structure and morphology. The possible growth mechanism was discussed based on the reaction process. The blue shift in the UV-vis spectra of the ZnO nanostructures was also observed.     

Rapid synthesis of ZnO ellipsoidal nanostructures in large scale and their photoluminescence properties

ZnO ellipsoidal nanostructures with uniform ellipsoidal morphologies have been synthesized using different hydroxide anion precursors by an ultra-fast, facile (90 °C) solution-phase method without the assistance of sonication or any surfactants. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) measurements. Based on the experimental results, a growth mechanism of ZnO nanostructures was proposed. The obtained ZnO nanostructures exhibit a weak UV emission band at ~ 385 nm and a relatively stronger orange emission band at ~ 615 nm. The solution-phase method is simple, convenient for large-scale fabrication of ZnO ellipsoidal nanostructures.     

Microscale sphere assembly of ZnO nanotubes

In this paper, we report a facile method to perform microsphere organization of ZnO nanotubes. Study shows ZnO nanotubes with diameters of 80-150 nm and lengths of 1.2-2 μm were assembled into 3-4.5 μm microsphere superstructures, the significance of these assembled ZnO nanotubes is that one-dimensional anisotropic ZnO building blocks are selectively aligned into highly symmetrical three-dimensional isotropic conformations, which may promise us new types of ZnO applications. These microsphere assemblies of ZnO nanotubes have a wide visible yellow emission at 600 cm⁻¹. The assembly mechanism was also proposed, the addition of metallic zinc species into linear poly ethylene glycol (PEG) containing ethanol and water mixed solution led to aggregation of PEG polymer coils to Zn(II)/PEG globules with a diameter of ∼500 nm, the globule turned into tube-like-structured ZnO-PEG microsphere assemblies (∼2 μm) after ultrasonic pretreatment, ZnO nanotubes were formed by the oriented attachment and Ostwald ripening of ZnO growth units onto the tube-like structures during the following hydrothermal process.     

Synthesis, characterization and optical properties of sheet-like ZnO

Sheet-like ZnO with regular hexagon shape and uniform diameter has been successfully synthesized through a two-step method without any metal catalyst. First, the sheet-like ZnO precursor was synthesized in a weak alkaline carbamide environment with stirring in a constant temperature water-bath by the homogeneous precipitation method, then sheet-like ZnO was obtained by calcining at 600 °C for 2 h. The structures and optical properties of sheet-like ZnO have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL) and UV-vis-NIR spectrophotometer. The results reveal that the product is highly crystalline with hexagonal wurtzite phase and has appearance of hexagon at (0 0 0 1) plane. The HRTEM images confirm that the individual sheet-like ZnO is single crystal. The PL spectrum exhibits a narrow ultraviolet emission at 397 nm and a broad visible emission centering at 502 nm. The band gap of sheet-like ZnO is about 3.15 eV.     

Synthesis of ZnO flowers and their photoluminescence properties

Flower-like ZnO nano/microstructures have been synthesized by thermal treatment of Zn(NH₃)₄²⁺ precursor in aqueous solvent, using ammonia as the structure directing agent. A number of techniques, including X-ray diffraction (XRD), field emission scan electron microscopy (FESEM), transmission electron microscopy (TEM), thermal analysis, and photoluminescence (PL) were used to characterize the obtained ZnO structures. The photoluminescence (PL) measurements indicated that the as-synthesized ZnO structures showed UV (∼375 nm), blue (∼465 nm), and yellow (∼585 nm) emission bands when they were excited by a He-Gd laser using 320 nm as the excitation source. Furthermore, it has been interestingly found that the intensity of light emission at ∼585 nm remarkably decreased when the obtained ZnO nanocrystals were annealed at 600 °C for 3 h in air. The reason might be the possible oxygen vacancies and interstitials in the sample decreased at high temperature.     

Enhancement of photoluminescence in ZnS/ZnO quantum dots interfacial heterostructures

ZnS/ZnO quantum dots (QDs) were synthesized by controlled oxidation of ZnS nanoparticles. HRTEM image showed small nanocrystals of size 4 nm and the magnified image of single quantum dot shows interfacial heterostructure formation. The optical absorption spectrum shows a blue shift of 0.19 and 0.23 eV for ZnO and ZnS QDs, respectively. This is due to the confinement of charge carries within the nanostructures. Enormous enhancement in UV emission (10 times) is reported which is attributed to interfacial heterostructure formation. Raman spectrum shows phonons of wurtzite ZnS and ZnO. Phonon confinement effect is seen in the Raman spectrum wherein LO phonon peaks of ZnS and ZnO are shifted towards lower wavenumber side and are broadened.     

Low temperature solution synthesis and characterization of ZnO nano-flowers

Synthesis of flower-shaped ZnO nanostructures composed of hexagonal ZnO nanorods was achieved by the solution process using zinc acetate dihydrate and sodium hydroxide at very low temperature of 90 °C in 30 min. The individual nanorods are of hexagonal shape with sharp tip, and base diameter of about 300-350 nm. Detailed structural characterizations demonstrate that the synthesized products are single crystalline with the wurtzite hexagonal phase, grown along the [0 0 0 1] direction. The IR spectrum shows the standard peak of zinc oxide at 523 cm⁻¹. Raman scattering exhibits a sharp and strong E₂ mode at 437 cm⁻¹ which further confirms the good crystallinity and wurtzite hexagonal phase of the grown nanostructures. The photoelectron spectroscopic measurement shows the presence of Zn, O, C, zinc acetate and Na. The binding energy ca. 1021.2 eV (Zn 2p_3/2) and 1044.3 eV (Zn 2p_1/2), are found very close to the standard bulk ZnO binding energy values. The O 1s peak is found centered at 531.4 eV with a shoulder at 529.8 eV. Room-temperature photoluminescence (PL) demonstrate a strong and dominated peak at 381 nm with a suppressed and broad green emission at 515 nm, suggests that the flower-shaped ZnO nanostructures have good optical properties with very less structural defects.     

Preparation and characterization of ZnO/ZnS core/shell nanocomposites through a simple chemical method

In this paper, we reported the preparation of ZnO/ZnS core/shell nanocomposites by sulfidation of ZnO nanostructures via a simple hydrothermal method. The precursors of bare ZnO nanoparticles and ZnO nanorods were synthesized by a surfactant-assisted hydrothermal growth. The structural, morphological, and element compositional analysis of bare ZnO nanostructures and ZnO/ZnS core/shell nanocomposites were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy techniques. The XRD results indicated that the phase of bare ZnO nanoparticles and ZnO nanorods was wurtzite structure, and the phase of coated ZnS nanoparticles on the surface of bare ZnO nanostructures was sphalerite structure with the size of about 8 nm. Photoluminescence measurement was carried out, and the PL spectra of ZnO/ZnS core/shell nanocomposites revealed an enhanced UV emission and a passivated orange emission compared to that of bare ZnO nanostructures. In addition, the growth mechanism of ZnO/ZnS core/shell nanostructures through hydrothermal method was preliminarily discussed.     

A template-free alcoholthermal route to Ti(Sn)-doped ZnO nanorods

Ti(Sn)-doped single-crystalline ZnO nanorods with an average diameter of 20 nm and length up to nearly 1 μm were synthesized by a facile ultrasonic irradiation-assisted alcoholthermal method without involving any templates. Photoluminescence spectra of the Ti-doped ZnO nanorods were measured at room temperature and three emitting bands, being a violet emission at 400-415 nm, a blue band at 450-470 nm and a green band at around 550 nm, were detected. The emission intensities of the Ti-doped ZnO nanorods enhance gradually with increasing the doping concentrations. As to the Sn-doped ZnO nanorods, the green emission shifts to 540 nm and the emission intensities increase first but decrease later with increasing the doping concentrations.     

Transparent conductive ZnO:B films deposited by magnetron sputtering

This paper focuses on the preparation of boron doped ZnO (ZnO:B) films prepared by nonreactive mid-frequency magnetron sputtering from ceramic target with 2 wt.% doping source. Adjusting power density, ZnO:B film with low resistivity (1.54 × 10^− 3 Ω cm) and high transparency (average transparency from 400 to 1100 nm over 85%) was obtained. Different deposition conditions were introduced as substrate fixed in the target center and hydrogen mediation. Hall mobility increased from 11 to above 26 cm²/V·s, while carrier concentration maintained almost the same, leading to low resistivity of 6.45 × 10^− 4 Ω cm. Transmission spectra of ZnO:B films grown at various growth conditions were determined using a UV-visible-NIR spectrophotometer. An obvious blue-shift of absorption edge was obtained while transmittances between 600 nm and 1100 nm remained almost the same. Optical band baps extracted from transmission spectra showed irregular enhancement due to the Burstein-Moss effect and band gap renormalization. Photoluminescence spectra also showed a gradual increase at UV emission peak due to free exciton transition near band gap. We contributed this enhancement in both optical band gap and UV photoluminescence emission to the lattice structure quality melioration.     

Catalyst-free growth of pyramidal zinc sulfide nanostructure arrays on single walled carbon nanotubes

Uniform and ordered pyramidal zinc sulfide (ZnS) nanostructure arrays have been fabricated on the single walled carbon nanotube (SWNT) films by chemical vapor deposition without using any metal catalyst. Each ZnS pyramid has a 100 nm-sized base, a uniform length of 600 nm, and a sharp tip of 10 nm. The control of interspatial distance between ZnS nanostructures was achieved by creation of selective growth on the SWNTs in voids with the assistance of a close-packed silica particle monolayer as a template. Furthermore, this kind of morphology control of nanostructure arrays can play an important role for potential applications, such as high efficiency of field emission because of the strong correlation between shapes and functionalities of nanostructures.     

Surface plasmon enhanced bandgap emission of electrochemically grown ZnO nanorods using Au nanoparticles

Electrochemical deposition of ZnO nanorods having a diameter of 80-150 nm and length ~ 2 μm has been carried out. Au particles were sputtered on the ZnO nanorods for different sputtering times (from 0 to 100 s). The Photoluminescence spectra of bare ZnO nanorods showed a weak bandgap emission at around 375 nm and a broad defect-related emission band centered at ~ 596 nm. After the Au sputtering, the defect-related emission disappeared for all the samples. Moreover, the band edge emission intensity was enhanced with Au sputtering time 50 s. The enhancement factor reached a maximum value for the Au sputtering time of 50 s The enhancement in band edge emission is due to the transfer of electrons from defect states to the Au nanoparticles that cause not only an increase of resonant electron density, but also creates energetic electrons in the higher energy states. These resonant electrons can escape from the surface of the Au nanoparticles to conduction band of ZnO nanorods leading to the suppression of defect related emission intensity.