One-step solution synthesis and formation mechanism of flower-like ZnO and its structural and optical characterization

The regular hierarchical flower-like ZnO nanostructures assembled by nanosheets were successfully synthesized by one-step solution route with citrate assistance at room temperature. It was demonstrated that the concentration of citrate and the molar ratio of Zn²⁺/OH⁻ had strong effect on the formation of nanosheets and self-assembly flower-like nanostructures. A reasonable formation mechanism of the flower-like nanostructures was proposed. According to UV–vis spectrum, the flower-like ZnO nanostructures exhibited strong light absorption, and the value of band gap of the obtained ZnO was estimated to be 3.26 eV. Moreover, the room-temperature photoluminescence (PL) spectrum of the sample presented only a near-band edge emission at 382 nm.     

Controllable electrochemical synthesis of La/ZnO hierarchical nanostructures and their optical and magnetic properties

Here we presented a facile electrochemical deposition route for the controllable preparation of La³⁺/ZnO hierarchical nanostructures, such as flower-like nanostructures consisted of nanorods, flower bundles, and hexagonal nanorods with nests at the top. These prepared La³⁺/ZnO deposits were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV-vis spectrophotometer, and photoluminescence spectroscopy. The formation process of La³⁺-doped ZnO and the growth mechanisms of La³⁺/ZnO hierarchical nanostructures were discussed. The UV and PL spectra measurements show that the surface morphologies of La³⁺/ZnO deposits have an obvious effect on their optical properties and we can easily adjust their optical properties as well as La³⁺/ZnO nanostructures by changing electrochemical deposition parameters. In addition, the magnetic properties of La³⁺/ZnO deposits were also investigated.     

Controllable ZnO nanostructures evolution via synergistic pulsed laser ablation and hydrothermal methods

We report the morphology-controlled ZnO nanostructures (ZNSs) evolution synthesized via a novel and facile technique at different growth times, where the pulse laser ablation in liquid (PLAL) is creatively combined with hydrothermal (H) method (hereafter called PLAL-H technique). Four types of ZNSs with varying sizes and shapes such as tapers, multipods, flowers, and hollow flowers are produced on Si substrate via PLAL-H technique. Furthermore, multipod- and flower-like ZNSs are grown using direct hydrothermal method to compare them with the one obtained via synergistic effects of PLAL-H method. This catalyst-free fabrication method is not only cost-effective but greatly useful for the rapid production of different quality of ZNSs at low temperature. ZNSs synthesized under prolonged growth time (60 min) exhibited structural deformation. Growth technique and time dependent morphology, structure, composition, and optical properties of these as-grown ZNSs are characterized using FESEM, X-ray diffraction, FTIR, photoluminescence, and UV–vis measurements. Synthesized ZNSs revealed excellent crystallinity and growth process dependent variation in the physical and optical features. The ZNSs growth mechanism is understood. Excellent features of the results demonstrate that this synergized new growth technique may constitute a basis for modifying the morphology, sizes, and optical properties of ZNSs in a controllable manner useful for diverse applications.     

Growth and formation mechanism of sea urchin-like ZnO nanostructures on Si

Sea urchin-like nanostructures of ZnO consisting of ZnO nanowires with blunt faceted ends were grown on Si (100) substrates by oxidation of metallic Zn at 600 °C. ZnO nanowires having a diameter of 30–60 nm and length of 2–4 Μm were in similar shape with uniform diameter along its entire length with well faceted blunt ends. X-ray diffraction and transmission electron microscope analysis showed that the as-grown nanostructures were highly crystalline with wurtzite hexagonal structure having lattice constants of a=b=3.25 å and c=5.21 å. Room temperature photoluminescence (PL) measurements showed a weak near band-edge emission at 380 nm, but a strong green emission at 500–530 nm. A model for vapor-solid (VS) growth mechanism of ZnO nanowires was presented, in which nucleation of ZnO is crucial for the growth of the nanostructures.     

Effect of indium concentration on morphology and optical properties of In-doped ZnO nanostructures

In-doped ZnO nanostructures with different indium concentrations were grown using a thermal evaporation method. The In-doped ZnO nanostructures with a low concentration of indium exhibited a javelin shape, while the In-doped ZnO nanostructures with a high concentration of indium showed a flake shape. In addition, undoped ZnO nanojavelins were grown under the same conditions, but the sizes of these undoped ZnO nanojavelins were larger than the In-doped ZnO nanojavelins. It was shown that the In³⁺ cations played a crucial role in controlling the size. X-ray diffraction and Raman spectroscopy clearly showed hexagonal structures for all of the products. However, the Raman results demonstrated that the In-doped ZnO nanoflakes had a lower crystalline quality than the In-doped ZnO nanojavelins. Furthermore, photoluminescence (PL) measurements confirmed the Raman results. Moreover, the PL results demonstrated a larger band-gap for the In-doped ZnO nanostructures in comparison to the undoped ZnO.     

Electronic structures and optical properties for Ag-N-codoped ZnO nanotubes

The structural and electronic/optical properties of pure and Ag-N-codoped (8,0) ZnO nanotubes have been studied using first-principles calculations in the framework of the local spin density approximation. The configurations for Zn atoms replaced by Ag atoms are p-type semiconductor materials, and the bandgap increases when N atoms are doped into ZnO nanotube configurations. The optical studies based on dielectric function and reflectivity indicate that new transition peaks in the visible light range are observed, which can be ascribed to the Ag and N doping. Furthermore, there is a red shift observed with the increase of N concentration.     

Controllable preparation of ZnO porous flower through a membrane dispersion reactor and their photocatalytic properties

Three dimensional (3D) flower-like basic zinc carbonate constructed by multilayered nanoplates were rapidly prepared at room temperature through the direct precipitation method coupled with membrane dispersion technology, and porous ZnO with similar structures could be obtained after calcining the precursor. The structural properties of the products before and after the calcining process were characterized by SEM, TEM and XRD. The supersaturation of the reaction system due to the membrane dispersion played an important role in the formation of uniform Zn₅(CO₃)₂(OH)₆ precursors. A plausible mechanism was proposed for the formation of the flower-like ZnO assembled by nanoplates composed of nanoparticles. The obtained ZnO microspheres showed excellent photocatalytic properties, which could be attributed to the open structure and remarkable amount of porous nanoplates.     

Tuning electronic structure and optical properties of ZnO monolayer by Cd doping

Structural, electronic and optical properties of Cd-doped ZnO monolayer have been investigated using first-principles density-functional theory based on the local density approximation plus Hubbard U approach, which precisely predicts the band gap. The formation energy of doped system is negative, implying a stable incorporation of Cd. The band gaps of Cd-doped ZnO monolayer decrease with increasing Cd concentration. Furthermore, Cd doping is found to result in a red-shift of the absorption peaks, enhancing the visible light absorption. These findings demonstrate that Cd-doped ZnO monolayer could display potential application in optoelectronic and photocatalytic fields.     

Growth and optical properties of ZnO nanorod arrays on Al-doped ZnO transparent conductive film

ZnO nanorod arrays (NRAs) on transparent conductive oxide (TCO) films have been grown by a solution-free, catalyst-free, vapor-phase synthesis method at 600°C. TCO films, Al-doped ZnO films, were deposited on quartz substrates by magnetron sputtering. In order to study the effect of the growth duration on the morphological and optical properties of NRAs, the growth duration was changed from 3 to 12 min. The results show that the electrical performance of the TCO films does not degrade after the growth of NRAs and the nanorods are highly crystalline. As the growth duration increases from 3 to 8 min, the diffuse transmittance of the samples decreases, while the total transmittance and UV emission enhance. Two possible nanorod self-attraction models were proposed to interpret the phenomena in the sample with 9-min growth duration. The sample with 8-min growth duration has the highest total transmittance of 87.0%, proper density about 75 μm⁻², diameter about 26 nm, and length about 500 nm, indicating that it can be used in hybrid solar cells.     

Low-temperature precipitation synthesis of flower-like ZnO with lignin amine and its optical properties

A facile precipitation method has been developed to synthesize ZnO with [bis(2-aminoethyl)amino]methyl lignin (lignin amine) that is chemically modified from low-cost pulp industrial lignin. The obtained ZnO crystallites have been characterized to exhibit a hexagonal wurtzite structure, and their sizes have been determined at ca. 24 nm (mean value). These ZnO nanocrystallites are of high purity and well crystallized. Our present synthetic approach apparently exempts the commonly used calcining purification procedure. It is found that the morphology of ZnO and its specific surface area are capable of being tuned by varying the added lignin amine amount. Using the optimal 10 mL lignin amine, the synthesized ZnO exhibits flower-like morphology with proper specific surface area. Additionally, photoluminescence property of the obtainable ZnO displays two emissive bands at 383 nm (sharp) and in the range of 480 to 600 nm (broad) at room temperature. Their intensities were revealed to depend on the added lignin amine amount as well as on the molar ratio of Zn²⁺/OH^-. The present investigation demonstrates that our method is simple, eco-friendly, and cost-effective for the synthesis of small-size ZnO materials.     

Facile synthesis of different morphologies of Te-doped ZnO nanostructures

Te-doped ZnO nanostructures were synthesized by an annealing (vapor–solid) process under ambient conditions, and characterized in terms of their morphological, structural, compositional and optical properties. The structural and morphological characterizations revealed that the synthesized nanostructures were well-defined multipods, needles and spherical particles, and possessed well-crystalline ZnO wurtzite hexagonal phase. Also, in the X-ray diffraction studies, the presence of a shift in the peak positions towards a lower angle, and a decrease in the intensity, with an increase in the Te concentration, as compared to the undoped ZnO, were observed. The chemical composition confirmed the presence of Te, in the case of multipod and needle morphologies. The effect of doping on the crystalline quality and optical properties was also investigated, by using photoluminescence (PL) and Raman spectrometers. The Raman results demonstrated that the doped ZnO nanostructures had a lower crystalline quality than the undoped ZnO. Moreover, the PL results showed a decrease in the band gap for the doped ZnO nanostructures, in comparison to the undoped ZnO. A possible growth mechanism was also proposed.     

Preparation and electrochemical performance of flower-like hematite for lithium-ion batteries

Flower-like hematite (α-Fe₂O₃) has been successfully prepared by heat-treatment from the iron(III)-oxyhydroxide precursor, which is obtained by the hydrolysis of FeCl₃ solution in the presence of NaClO. In this process, no templates or catalysts are required. SEM and TEM characterizations confirm that micro-flowers are composed of several dozen self-assembled nanopetals with the thickness of about 20 nm. On the basis of the morphology investigations in time-dependent experiments, the possible growth mechanism of the flower-like α-Fe₂O₃ is proposed, which is similar to a two-stage growth process. Furthermore, as an anode electrode material for rechargeable lithium-ion batteries, the flower-like α-Fe₂O₃ exhibits excellent electrochemical performance, which can be attributed to the high surface area induced by the flower-like structure, the short lithium diffusion length and the restriction of volume change of the Li⁺ insertion/extraction.     

Growth mechanism of needle-shaped ZnO nanostructures over NiO-coated Si substrates

ZnO nanostructures were synthesized over NiO-coated Si substrate by a thermal evaporation of Zn powders in a vertical chemical vapor deposition reactor. The ZnO nanostructures had a needle-like morphology and the diameter of the structures decreased linearly from the bottom to the top. The bottom diameters of the ZnO nano-needles normally ranged from 20–100 nm and the lengths were in the range of 2–3 Μm. The clear lattice fringes in HRTEM image indicated the growth of good quality hexagonal single-crystal ZnO. Field emission characteristics of the ZnO nano-needles showed that the turn-on field was about 8.87 V/Μm with a field enhancement factor of about 1099. The growth mechanism of the ZnO nano-needles was proposed on the basis of experimental data.     

Highly stable field emission properties from well-crystalline 6-Fold symmetrical hierarchical ZnO nanostructures

Herein, we report the growth, characterization and field emission application of well-crystalline 6-fold symmetrical hierarchical ZnO nanostructures grown on silicon substrate by thermal evaporation process. The detailed morphological characterizations revealed that the prepared material possess six-fold structures in which ZnO nanoneedles are symmetrically grown on each facets of core hexagonal ZnO nanorods in such a manner that they made beautiful 6-fold symmetrical hierarchical structure. The detailed structural studies confirmed that the grown hierarchical structures possess well-crystallinity with wurtzite hexagonal phase. The room-temperature photoluminescence (PL) spectrum exhibited a strong UV emission confirming good optical properties. The Raman-scattering revealed the wurtzite hexagonal phase for as-grown hierarchical structures. The field emission properties of the 6-fold symmetrical hierarchical ZnO nanostructures were tested and a turn-on voltage equal to 2.8 kV, corresponds to emission current of 65 nA, was observed. A threshold voltage of 4.6 kV with a maximum emission current of about 9.36 µA was also recorded. A high emission current stability profile over a period of ~7000 s was noted for the fabricated FE device.     

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.     

Morphology and composition controlled synthesis of flower-like silver nanostructures

Flower-like silver nanostructures with controlled morphology and composition were prepared through wet-chemical synthesis. The reaction rate is simply manipulated by the amount of catalyzing agent ammonia added which is the key point to determine the ratio of hexagonal close-packed (HCP) to face-centered cubic (FCC) phase in silver nanostructures. The existence of formic acid that is the oxidation product of aldehyde group is demonstrated to play a crucial role in achieving the metastable HCP crystal structures by replacing ionic surfactants with polyvinylpyrrolidone (PVP). Utilizing flower-like silver nanostructures as surface-enhanced Raman scattering (SERS) substrates, Raman signal of Rhodamine 6G, or 4-aminothiophenol with concentration as low as 10⁻⁷ M was detected. Moreover, it is demonstrated that phase composition has no direct relation to the SERS enhancing factor which is mainly determined by the amount of hot spots.     

Flower-shaped ZnO nanomaterials for low-temperature operations in NOX gas sensors

In this study, we synthesized nanostructured zinc oxide (ZnO) by using various concentrations (0–0.05 M) of cetyltrimethylammonium bromide (CTAB) as a surfactant to optimize its morphology for gas sensor applications. The optimization process was used to elucidate the morphology effects (rod-shaped and flower-shaped morphologies). The morphologies were investigated through scanning electron microscopy, in which the assembly of nanorods leading to a spherical microstructure with a CTAB concentration of 0.005 M was observed. Brunauer–Emmett–Teller isotherm measurements revealed a surface area of 7.928 g/m² for the flower-like morphology, which was relatively higher than those of other CTAB-assisted morphologies. Such morphological features were expected to contribute toward high-performance gas-sensing. The effect of morphology variation on the resistance of ZnO microstructures was used for gas measurements. Among the varied morphologies, a sample with a spherical flower-shaped morphology exhibited a very high response at low temperatures (~29 at 25 °C) toward NO_X gas (0.75 ppm) and a high selectivity toward NO_x among ammonia (NH₃), toluene (C₆H₅CH₃), carbon monoxide (CO), acetone (CH₃COCH₃), and ethanol (C₂H₅OH). Raman and photoluminescence spectroscopy analyses unraveled the presence of a high density of oxygen vacancies in the sample, thereby suggesting a close link between the defective nature of the sample and the high response of the flower-like ZnO at low temperatures.     

Growth of ZnO nanoneedles on silicon substrate by cyclic feeding chemical vapor deposition: Structural and optical properties

Well-crystallized ZnO nanoneedles were grown on Au-coated Si(100) substrate by cyclic feeding chemical vapor deposition (CFCVD) process using diethyl zinc and oxygen as precursors for zinc and oxygen, respectively. Morphological investigations revealed that the as-grown nanoneedles exhibited sharpened tips and wider bases, having the typical diameters at their bases and tips, 60±10 nm and 20±10 nm, respectively. Detailed structural characterizations confirmed that the as-grown products were single crystalline with a wurtzite hexagonal phase and were grown preferentially along the [0001] direction. The room-temperature photoluminescence (PL) spectrum showed a strong and sharp UV emission at 378 nm with a very weak, suppressed and broad green emission at 520 nm, substantiating good optical properties for the as-grown ZnO nanoneedles.     

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.     

Microstructure and optical properties of electrodeposited Al-doped ZnO nanosheets

This study grew A1-doped ZnO nanosheets on polycrystalline zinc foils using cathodic electrodeposition in an aqueous solution consisting of 0.02 M Zn(NO₃)₂ and 0.001 M Al(NO₃)₃ at 90 °C. The effects of the electrodepositing potential and thermal annealing on the physical properties of the Al-doped ZnO sheets were investigated. This study observed a high quality sheet-like structure of the electrodeposited Al-doped ZnO for the applied potential larger than −1.1 V, and the sheets were interconnected over the area of interest. The X-ray diffraction patterns showed that the intensity of the Bragg reflections of the electrodeposited Al-doped ZnO sheets increases with the electrodepositing potential because a larger applied potential results in the Al-doped ZnO sheets having a larger lateral dimension and thickness. However, the appearance of the Al-doped ZnO sheets becomes coarse and rough after thermal annealing at 400 °C in ambient air for 4 h. The intensity of the Bragg reflections of the Al-doped ZnO sheets was markedly increased through the thermal annealing due to the improvement of the crystalline quality of the annealed Al-doped ZnO sheets. Annealing caused a large decrease in structural defects of the Al-doped ZnO sheets electrodeposited at −1.3 V causing the sheets to exhibit a sharp photoluminescence peak at ∼380 nm.