Synthesis and characterization of 3D ZnO superstructures via a template-free hydrothermal method

The ZnO microrods and flower-like 3D superstructures have been synthesized via a template-free hydrothermal method. The prepared ZnO samples are characterized by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). It is found that the flower-like 3D ZnO superstructures can be obtained simply by tuning the volume ratio of Zn(OH)₂⁴⁻ precursor solution to water, or the volume ratio of ethylene glycol to water. When the volume ratio of Zn(OH)₄²⁻ precursor solution to water is 1:7, the flower-like 3D ZnO superstructures are obtained, in which the diameter of an individual pencil-like rod is about 1.0 μm, and the tip size is several nanometers. While when the volume ratio of Zn(OH)₄²⁻ precursor solution to ethylene glycol (EG) is 1:1, the flower-like 3D ZnO superstructure consists of hexagonal rods with about 500 nm in diameter. A plausible formation mechanism of flower-like 3D ZnO superstructures is discussed in detail.     

ZnO Nanorods via Spray Deposition of Solutions Containing Zinc Chloride and Thiocarbamide

In this work we present the results on formation of ZnO nanorods prepared by spray of aqueous solutions containing ZnCl₂ and thiocarbamide (tu) at different molar ratios. It has been observed that addition of thiocarbamide into the spray solution has great impact on the size, shape and phase composition of the ZnO crystals. Obtained layers were characterized by scanning electron microscopy (SEM) equipped with energy selected backscattered electron detection system (ESB), X-ray diffraction (XRD) and photoluminescence spectroscopy (PL). Small addition of thiocarbamide into ZnCl₂ solution (ZnCl₂:tu = 1:0.25) supports development of significantly thinner ZnO nanorods with higher aspect ratio compared to those obtained from ZnCl₂ solution. Diameter of ZnO rods decreases from 270 to 100 nm and aspect ratio increases from ∼2.5 to 12 spraying ZnCl₂ and ZnCl₂:tu solutions, respectively. According to XRD, well crystallized (002) orientated pure wurtzite ZnO crystals have been formed. However, tiny ‘spot’—like formations of ZnS were detected on the side planes of hexagonal rods prepared from the thiocarbamide containing solutions. Being adsorbed on the side facets of the crystals ZnS inhibits width growth and promotes longitudinal c-axis growth.     

Preparation and antibacterial properties of titanium-doped ZnO from different zinc salts

To research the relationship of micro-structures and antibacterial properties of the titanium-doped ZnO powders and probe their antibacterial mechanism, titanium-doped ZnO powders with different shapes and sizes were prepared from different zinc salts by alcohothermal method. The ZnO powders were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-vis), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED), and the antibacterial activities of titanium-doped ZnO powders on Escherichia coli and Staphylococcus aureus were evaluated. Furthermore, the tested strains were characterized by SEM, and the electrical conductance variation trend of the bacterial suspension was characterized. The results indicate that the morphologies of the powders are different due to preparation from different zinc salts. The XRD results manifest that the samples synthesized from zinc acetate, zinc nitrate, and zinc chloride are zincite ZnO, and the sample synthesized from zinc sulfate is the mixture of ZnO, ZnTiO₃, and ZnSO₄ · 3Zn (OH)₂ crystal. UV-vis spectra show that the absorption edges of the titanium-doped ZnO powders are red shifted to more than 400 nm which are prepared from zinc acetate, zinc nitrate, and zinc chloride. The antibacterial activity of titanium-doped ZnO powders synthesized from zinc chloride is optimal, and its minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) are lower than 0.25 g L⁻¹. Likewise, when the bacteria are treated by ZnO powders synthesized from zinc chloride, the bacterial cells are damaged most seriously, and the electrical conductance increment of bacterial suspension is slightly high. It can be inferred that the antibacterial properties of the titanium-doped ZnO powders are relevant to the microstructure, particle size, and the crystal. The powders can damage the cell walls; thus, the electrolyte is leaked from cells.     

Synthesis and magnetic properties of Cu-doped ZnO nanowire arrays

Arrays of Cu-doped ZnO nanowires were successfully fabricated by electrodeposition of Zn²⁺ and Cu²⁺ into anodic aluminum oxide template and post-oxidation annealing in air atmosphere. The transmission electron microscopy result shows that the nanowires are uniform, about 100 nm in diameter and with the aspect ratio of up to 40. Selected area electron diffraction and X-ray diffraction results indicate that the nanowires are in hexagonal wurtzite structure. Magnetization measurements show that the Zn_1−xCu_xO (x = 0.07 and 0.11) nanowires exhibit room-temperature ferromagnetism and the enhancement of the ferromagnetism is revealed for the Zn_0.93Cu_0.07O nanowires annealed in vacuum.     

XPS and optical studies of different morphologies of ZnO nanostructures prepared by microwave methods

Zinc oxide (ZnO) nanostructures of various morphologies were prepared using a microwave-assisted aqueous solution method. Herein, a comparative study between three different morphologies of ZnO nanostructures, namely nanoparticles (NPs), nanoflowers (NFs) and nanorods (NRs) has been reviewed and presented. The morphologies of the prepared powders have been studied using field effect scanning electron microscopy (FESEM). X-ray diffraction (XRD) results prove that ZnO nanorods have biggest crystallite size compared with nanoflowers and nanoparticles. The texture coefficient (T_c) of three morphologies has been calculated. The T_c changed with varying morphology. A comparative study of surfaces of NPs, NFs and NRs were investigated using X-ray photoelectron spectroscopy (XPS). The possible growth mechanisms of ZnO NPs, NFs and NRs have been described. The optical properties of the ZnO nanostructures of various morphologies have been investigated and showed that the biggest crystallite size of ZnO nanostructures has lowest band gap energy. The obtained results are in agreement with experimental and theoretical data of other researchers.     

Optical and electrical properties of p-type Ag-doped ZnO nanostructures

Zn_1−xAg_xO nanoparticles (NPs) (x=0, 0.02, 0.04, and 0.06) were synthesized by a sol–gel method. The synthesized undoped ZnO and Zn_1−xAg_xO-NPs were characterized by X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and UV–visible spectroscopy. The XRD patterns indicated that undoped and Ag-doped ZnO crystallize in a hexagonal wurtzite structure. The TEM images showed ZnO NPs with nearly spherical shapes, with particle size distributed over the nanometer range. Evidence of dopant incorporation is demonstrated in the XPS measurements of the Ag-doped ZnO NPs. The Raman measurements indicated that the undoped and Ag-doped ZnO-NPs had a high crystalline quality. From the result of UV–vis, the band-gap values of prepared undoped and Ag-doped ZnO were found to decrease with an increase in Ag concentration. The obtained undoped and Ag-doped ZnO nanoparticles were used as a source material to grow undoped and Ag-doped ZnO nanowires on n-type Si substrates, using a thermal evaporation set-up. Two probe method results indicated that the Ag-doped ZnO nanowires exhibit p-type properties.     

Cu-doped ZnO nanorod arrays: the effects of copper precursor and concentration

Cu-doped ZnO nanorods have been grown at 90°C for 90 min onto a quartz substrate pre-coated with a ZnO seed layer using a hydrothermal method. The influence of copper (Cu) precursor and concentration on the structural, morphological, and optical properties of ZnO nanorods was investigated. X-ray diffraction analysis revealed that the nanorods grown are highly crystalline with a hexagonal wurtzite crystal structure grown along the c-axis. The lattice strain is found to be compressive for all samples, where a minimum compressive strain of −0.114% was obtained when 1 at.% Cu was added from Cu(NO₃)₂. Scanning electron microscopy was used to investigate morphologies and the diameters of the grown nanorods. The morphological properties of the Cu-doped ZnO nanorods were influenced significantly by the presence of Cu impurities. Near-band edge (NBE) and a broad blue-green emission bands at around 378 and 545 nm, respectively, were observed in the photoluminescence spectra for all samples. The transmittance characteristics showed a slight increase in the visible range, where the total transmittance increased from approximately 80% for the nanorods doped with Cu(CH₃COO)₂ to approximately 90% for the nanorods that were doped with Cu(NO₃)₂.     

Morphological exploration of chemical vapor–deposited P-doped ZnO nanorods for efficient photoelectrochemical water splitting

Photoelectrochemical (PEC) water splitting is beneficial and has received attractive attention due to a greater potential to generate hydrogen and oxygen from water by using plentiful solar light to solve the problem of energy crisis. Various active semiconductor materials are used in PEC water splitting applications. Nevertheless, in past decades, most of the researchers suggested that titanium oxide (TiO₂) is the best photoanode for this type of applications. Now, Zinc oxide (ZnO) is considered a perfect substitution to TiO₂ due to its comparable energy band structure and superior photogenerated electron transfer rate. In this study, bare and phosphorous-doped ZnO nanorods were successfully developed on fluorine-doped tin oxide-coated glass (FTO) substrate by chemical vapor deposition. X-ray diffraction (XRD) pattern authenticated hexagonal structure formation with strong diffraction peak of (101), which showed that ZnO nanorods were perfectly developed along c axis. The optical and morphological properties were analyzed by UV–Vis and scanning electron microscopy images. The energy-dispersive X-ray spectra demonstrated that doping agent phosphorous was present in ZnO nanorods. The PEC properties of the developed ZnO nanorods were further investigated and obtained results suggested that a small amount of phosphorous-doped ZnO nanorods enhances their PEC performance.     

Microwave hydrothermal synthesis of Sr doped ZnO crystallites with enhanced photocatalytic properties

Pure and Sr²⁺ doped ZnO crystallites were successfully synthesized via a microwave hydrothermal method using Zn(NO₃)₂·6H₂O and Sr(NO₃)₂·6H₂O as source materials. The phase and microstructure of the as-prepared Zn_1−xSr_xO crystallites were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Ultraviolet–visible spectrum (UV–vis) and photochemical reaction instrument were used to analyze the photocatalytic properties of the particles. XRD results show that the diffraction peaks of the as-prepared Zn_1−xSr_xO crystallites shifted slightly toward lower 2θ angle with the increasing of Sr²⁺ doping concentration from 0% to 0.3%. The pure ZnO crystallites with lamellar structure are found transforming to a hexagonal columnar morphology with the increase of Sr²⁺ doping concentration. UV–vis analysis shows that the particles have a higher absorption in UV region with a slightly decreased of optical band (E_g) gap. The photocatalytic activity of Sr²⁺ doped ZnO crystallites was evaluated by the Rhodamine B (RhB) degradation in aqueous solution under visible-light irradiation. Compared with the pure ZnO particles, the photocatalytic properties of the Sr²⁺ doped ZnO crystallites are obviously improved. The photocatalysis experiment results demonstrate that the 0.1% Sr²⁺ doped ZnO exhibits the best photocatalytic activity for the degradation of Rhodamine B.     

Structure and optical properties of ZnO nanowires coated with silica

Abstract

Abstract

It is essential to passivate one-dimensional nanostructures with insulating materials to protect them from contamination and oxidation as well as to avoid cross-talking between the building blocks of complex nanoscale circuits. The ZnO nanowires synthesised by the thermal evaporation of ZnO powders were coated with SiO₂ by the sputtering technique. Transmission electron microscopy and X-ray diffraction analyses revealed that the cores and shells of the ZnO core–SiO₂ shell nanowires were single crystal wurtzite type ZnO and amorphous SiO₂ respectively. Photoluminescence measurements at room temperature showed that the passivation of the ZnO nanowires was successfully achieved with SiO₂ without nearly degrading the near band edge emission from the wires. However, subsequent thermal annealing treatment was found to be undesirable owing to the degradation of the near band edge emission in intensity.     

Optical and structural properties of ZnO NPs and ZnO–Bi2O3 nanocomposites

Pure ZnO and ZnO–Bi₂O₃ nanocomposites with 5 wt% and 10 wt% of Bi₂O₃ content were synthesized using the co-precipitation method. Optical properties such as refractive index (n), extinction coefficient (k), bandgap (E_g), and Urbach energies, as well as the band structure, were determined by modeling the experimental transmittance and reflectance UV–Vis spectra. The deduced bandgap and Urbach energies for pure ZnO (3.758 eV) increase with the increase of the doping degree of Bi₂O₃ in ZnO–Bi₂O₃ nanocomposite films. X-ray diffraction and scanning electron microscopy (SEM) was used to study the structural and morphological properties of these nanocomposite films. Pure ZnO and nanocomposites with Bi₂O₃ exhibit crystalline domains with wurtzite hexagonal structures, and as the doping degree of Bi₂O₃ increases, the crystallite size decreases. Based on SEM micrographs, the ZnO nanoparticles (NPs) structure shows the presence of aggregation. Moreover, Bi₂O₃ NPs in the nanocomposite film led to the further aggregation in the form of large rods. The elemental and chemical properties of the nanocomposites were investigated using infrared and energy-dispersive X-ray spectroscopy. The charge transfer process in the studied system is between ZnO and Bi₂O₃ conduction bands. Density-functional theory (DFT) calculations were performed for ZnO, Bi₂O₃, and ZnO-Bi₂O₃ compounds to investigate structural, optical, and electronic properties, being in agreement with the experimental results.     

Novel synthesis of ZnO nanoparticles and their enhanced anticancer activity: Role of ZnO as a drug carrier

In this work, a simple and versatile technique was developed to prepare highly crystalline ZnO nanoparticles (ZnO NPs) by organic precursor method using 5, 6 dimethyl benzimidazole and Zn(CH₃COO)₂·2H₂O followed by calcination. These synthesized ZnO NPs were used as a drug carrier to form 5-Fluorouracil (5 Fu) encapsulated ZnO NPs by varying the molar ratio (100–300:1) of ZnO NPs to 5-Fu. X-ray diffraction (XRD) results indicated that the ZnO NPs had single phase nature with the wurtzite structure. Field emission scanning electron microscopy (FESEM) and Transmission electron microscopy (TEM) results showed nanometer dimension of the NPs. FTIR analysis further reaffirmed the formation/encapsulation of ZnO NPs. UV–vis spectroscopy determined the encapsulation efficiency (EE) and loading capacity (LC) of 5-Fu drug on ZnO NPs. HPLC analysis of encapsulated NPs indicated release of 5-Fu was higher at tumor cell pH (pH 6.0) than physiological pH. Moreover, the anti-tumor activity of ZnO NPs and 5-Fu-encapsulated ZnO NPs investigated using flow cytometry demonstrated that 5-Fu encapsulated ZnO NPs have more anti-tumor activities than 5-Fu itself toward MCF-7 (Breast cancer) cell line. Also, cytotoxicity of MCF-7 increased with the increase of ZnO NPs: 5-Fu ratio. This research will introduce a new concept to synthesize 5-fluorouracil encapsulated ZnO NPs and its application towards the cancer cell line. Thus, the ZnO NPs could not only apply as the drug carrier to deliver 5-Fluorouracil into the cancer cells, but also enhances anti-tumor activity.     

Farming of ZnO nanorod-arrays via aqueous chemical route for photoelectrochemical solar cell application

A low temperature aqueous chemical route is employed for the synthesis of zinc oxide (ZnO) nanorod arrays onto the soda lime and fluorine-doped tin oxide (FTO) coated glass substrates at various deposition times. Synthesis/farming of ZnO nanorod arrays (ZNRs) consists of the three-step as-ZnO seed forming, ZnO seed sowing followed by ZnO nanorod arrays growing. The length and diameter of ZnO nanorods increased with the reaction time prolonging. The physical, chemical and morphological properties were analyzed by means of X-ray diffraction (XRD), UV–visible spectroscopy (UV–vis), photoluminescence (PL), energy dispersive spectroscopy (EDS) and scanning electron microscopy (SEM) respectively. The XRD pattern revealed wurtzite crystal structures of ZNRs, preferentially orienting in the (002) direction. SEM micrographs show that the ZnO nanorods grew up perpendicular to the substrate and their length increases with increase in deposition time. Finally, the photoelectrochemical (PEC) performance of ZNRs thin films were studied. The junction quality factor upon illumination (n_l), series and shunt resistance (R_s and R_sh), flat-band-potential (V_FB), fill factor (FF) and efficiency (η) have been estimated.     

Synthesis of large-scale uniform mulberry-like ZnO particles with microwave hydrothermal method and its antibacterial property

Large-scale uniform mulberry-like ZnO particles were successfully synthesized via a fast and simple microwave hydrothermal method. The formation mechanism of mulberry-like ZnO particles was investigated by adding different types of alkalis and different amounts of triethanolamine (TEA). Transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray diffraction (XRD) were used to observe the morphology and crystal structure of the obtained ZnO. The results revealed that the as-prepared ZnO products had an average diameter of about 150 nm and polycrystalline wurtzite structure. The existence of TEA was vital for the formation of nanoparticle-assembled mulberry-like ZnO particles. These mulberry-like ZnO particles exhibited stronger antibacterial effects on Candida albicans than did sheet-like and flower-like ZnO.     

C2H2 gas sensor based on Ni-doped ZnO electrospun nanofibers

Pure and Ni-doped ZnO nanofibers were synthesized using the electrospinning method. The morphology, crystal structure and optical properties of the nanofibers were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy, respectively. It is found that Ni doping does not change the morphology and crystal structures of the nanofibers, and the ultraviolet emissions of ZnO nanofibers present red shift with increasing Ni doping concentration. C₂H₂ sensing properties of the sensors based on the nanofibers were investigated. The results show that the C₂H₂ sensing properties of ZnO nanofibers are effectively improved by Ni doping, and 5 at% Ni-doped ZnO nanofibers exhibit a maximum sensitivity to C₂H₂ gas.     

Indirect charge transfer of holes via surface states in ZnO nanowires for photoelectrocatalytic applications

In this work, ZnO nanowires with high aspect ratio were obtained by fast and simple electrochemical anodization. Morphological, structural and photoelectrochemical characteristics of the synthesized ZnO nanowires were evaluated by using different techniques: field emission scanning electron microscopy, atomic force microscopy, high resolution transmission electron microscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV–VIS spectroscopy, Mott-Schottky analysis and photoelectrochemical impedance spectroscopy. The synthesized ZnO nanowires presented high roughness and high crystallinity. Besides, surface defects were identified in the sample. The value of the donor density (N_D) was in the order of 10¹⁹ cm^?3 in the dark and 10²⁰ cm^?3 under illumination. In addition, the ZnO nanowires presented good photosensibility, with a photocurrent density response 85 times higher than a ZnO compact layer, and lower resistance to charge transfer. The charge transfer processes taking place at the ZnO/electrolyte interface were studied, since these processes strongly influence the photoelectrocatalytic efficiency of the material. According to the results, the charge transfer of holes in the synthesized ZnO nanowires occurs indirectly via surface states. In this regard, surface states may be an important feature for photoelectrocatalytic applications since they could provide lower onset voltages and higher anodic current densities.     

Hydrothermal synthesis of dumbbell-shaped ZnO microstructures

Dumbbell-shaped ZnO microstructures have been successfully synthesized by a facile hydrothermal method using only Zn(NO₃)₂·6H₂O and NH₃·H₂O as raw materials at 150 °C for 10 h. The results from X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) show that the prepared ZnO samples exhibit dumbbell-shaped morphology and hexagonal wurtzite structure. The length of ZnO dumbbells is about 5–20 μm, the diameters of the two ends and the middle part are about 1–5 μm and 0.5–3 μm, respectively. The dumbbell-shaped ZnO microstructures may be formed by self-assembly of ZnO nanorods with 1–5 μm in length and 100–200 nm in diameter. The photoluminescence (PL) spectrum of dumbbell-shaped ZnO microstructures at room temperature shows three emission peaks at about 362, 384 and 485 nm.     

Synthesis of flower-like 3D ZnO microstructures and their size-dependent ethanol sensing properties

Flower-like 3D ZnO microstructures constructed from nanorods of different sizes were prepared by a microwave hydrothermal (MH) process in the presence of o-, m- and p-nitrobenzoic acid, respectively. Well-crystallized flower-like ZnO microstructures were obtained after 10 min MH treatment. The X-ray powder diffraction (XRD) test indicated that all the products were consistent with the hexagonal ZnO phase, and scanning electron microscopy (SEM) investigation revealed that the flower-like 3D ZnO microstructures were built with sword-like nanorods 60-100 nm in width and several micrometers in length. The formation mechanism of these flower-like 3D ZnO microstructures is discussed briefly. The gas sensitivity of the as-prepared ZnO microstructures to ethanol at different operation temperatures and concentrations was also studied. The results indicated that the gas sensitivity of the ZnO microstructures was influenced by the particle size and microcosmic configuration, the larger particles with crowded nanorods having higher gas sensitivity.     

Structural,optical, cytotoxicity,and antimicrobial properties of MgO,ZnO and MgO/ZnO nanocomposite for biomedical applications

In this study, MgO nanoparticles were successfully fabricated and incubated inside ZnO NPs to form MgO/ZnO nanocomposite for biomedical applications. The x-ray diffraction analysis of MgO, ZnO, and MgO/ZnO has shown the single-phase x-ray diffraction patterns through X'pert High score. The crystallite sizes were calculated as 18 nm, 42 nm, and 53 nm, respectively. The average particle size of MgO, ZnO, and MgO/ZnO nanopowders depicted from secondary electron images of field emission electron microscopy were 56 nm, 400 nm, and 450 nm, respectively. The presence of MgO NPs inside ZnO NPs was confirmed by transmission electron microscopy. The elemental dispersive spectroscopy of MgO, given the peaks of oxygen and magnesium, also showed only zinc and oxygen peaks in ZnO, which confirms no other impurities in MgO and ZnO powders. The elemental analysis of MgO/ZnO nanocomposite showed the peaks of Zinc and Oxygen, along with a tiny peak of Mg. The photoluminescence and UV–vis spectroscopy revealed the absorbance fluorescence limit of the nanomaterials. Fourier transform infrared spectroscopy confirmed the several groups present in the nanocomposite. The biocompatibility of MgO, ZnO, and MgO/ZnO was observed with human peripheral blood mononuclear cells. The cytotoxicity studies were also performed against human cancer (liver and breast) cell lines. The MgO, ZnO, and MgO/ZnO exhibited the antimicrobial properties against Escherichia coli and Staphylococcus aureus.     

Superhydrophobic ZnO networks with high water adhesion

ZnO structures were deposited using a simple chemical bath deposition technique onto interdigitated electrodes fabricated by a conventional photolithography method on SiO₂/Si substrates. The X-ray diffraction studies show that the ZnO samples have a hexagonal wurtzite crystalline structure. The scanning electron microscopy observations prove that the substrates are uniformly covered by ZnO networks formed by monodisperse rods. The ZnO rod average diameter and length were tuned by controlling reactants'' concentration and reaction time. Optical spectroscopy measurements demonstrate that all the samples display bandgap values and emission bands typical for ZnO. The electrical measurements reveal percolating networks which are highly sensitive when the samples are exposed to ammonia vapors, a variation in their resistance with the exposure time being evidenced. Other important characteristics are that the ZnO rod networks exhibit superhydrophobicity, with water contact angles exceeding 150° and a high water droplet adhesion. Reproducible, easily scalable, and low-cost chemical bath deposition and photolithography techniques could provide a facile approach to fabricate such ZnO networks and devices based on them for a wide range of applications where multifunctionality, i.e., sensing and superhydrophobicity, properties are required.

PACS

81.07.-b; 81.05.Dz; 68.08.Bc