SURFACE MODIFICATION OF HYDROTHERMALLY GROWN ZnO NANOSTRUCTURES WITH PROCESS PARAMETERS

ZnO nanorods (NRs) were hydrothermally synthesized by using equimolar zinc nitrate hydrate (Zn(NO₃)₂ [sdot] 6H₂O) and hexamethylenetetramine (C₆H₁₂N₄) solutions. The shape of the nanostructures, obtained by aqueous method, was greatly influenced by the growth temperature and the molar concentrations. NRs grown at higher temperature (90°C) have rounded tips, whereas nanostructures of hexagonal flat-end shape were obtained at 75°C. Hardly any nanostructures were observed by further reducing the temperature to 60°C. In addition, solutions with higher molarity favored the appearance of nanoflowers. Scattered ZnO NRs were observed on silicon substrate, whereas aligned ZnO nanowires (NWs) 50–70 nm in diameter were obtained at 75°C by introducing sputtered ZnO film as a seed layer. High-resolution transmission electron microscopy (HRTEM) confirmed the growth of ZnO nanowires along [001] direction. A band-edge luminescence along with a broad visible spectrum was observed for the ZnO nanowires.     

The O2-dependent growth of ZnO nanowires and their photoluminescence properties

ZnO nanowires were massively synthesized on a Ni(NO₃)₂-coated silicon substrate under oxygen-containing argon atmosphere by a simple chemical vapor deposition method. The average diameter of the ZnO nanowires was about 50 nm and the average length was about 20 μm. The morphologies of the ZnO nanowires strongly depended on oxygen content in the growth atmosphere. At low oxygen concentration (about 5–10 ppm), ZnO nanocones and nanoneedles were obtained, while at high oxygen concentration (about ∼250 ppm), ZnO nanoparticles deposited on the substrate. The room temperature photoluminescence (PL) spectrum of the ZnO nanowires revealed that a strong UV band at 384 nm dominated the whole spectrum. These results indicate that the ZnO nanowires grown under oxygen-containing atmosphere possess better crystalline quality and UV luminescence properties than those grown in reducing hydrogen atmosphere. Based on the analysis of oxygen effect on the ZnO nanostructures, a vapor–liquid–solid mechanism assisted by the redox growth mode was proposed to understand the growth of the ZnO nanowires.     

Seedless Pattern Growth of Quasi-Aligned ZnO Nanorod Arrays on Cover Glass Substrates in Solution

A hybrid technique for the selective growth of ZnO nanorod arrays on wanted areas of thin cover glass substrates was developed without the use of seed layer of ZnO. This method utilizes electron-beam lithography for pattern transfer on seedless substrate, followed by solution method for the bottom-up growth of ZnO nanorod arrays on the patterned substrates. The arrays of highly crystalline ZnO nanorods having diameter of 60 ± 10 nm and length of 750 ± 50 nm were selectively grown on different shape patterns and exhibited a remarkable uniformity in terms of diameter, length, and density. The room temperature cathodluminescence measurements showed a strong ultraviolet emission at 381 nm and broad visible emission at 585–610 nm were observed in the spectrum.     

One-step synthesis of high purity ZnO micro/nanostructures from pure Zn and pre-alloyed brass powders by vapor phase transport

In this research, vapor phase transport (VPT) was introduced as a facile, inexpensive method to produce ZnO micro/nanostructures from various Zn sources such as pure Zn and alpha brass pre-alloyed powders (Cu–20Zn and Cu–28Zn) at different processing temperatures of 930 °C–1050 °C. Simultaneous thermal analysis (STA) was carried out to investigate Zn evaporation and ZnO micro/nanostructure formation. STA results showed an exothermic peck at 711 °C and 728 °C for Cu–20Zn and Cu–28Zn, respectively, due to oxidation of the evaporated Zn element and formation of ZnO micro/nanostructures. X-ray diffraction results showed that high purity ZnO micro/nanostructures were successfully synthesized via VPT process and the crystallite size was increased from ~60 nm to ~100 nm with increasing processing temperature. Field emission scanning electron microscopy observations showed morphology (e.g. rods, column, tetrapods, and combs) and size of the synthesized micro/nanostructures were dependent on the Zn sources and processing temperature, in which average diameter of the synthesized ZnO structures was increased with increasing the processing temperature. The smallest (98 nm) and largest (603 nm) average diameters of synthesized ZnO micro/nanostructures were attained from the pure Zn and Cu–28Zn brass powders at 930 °C and 1050 °C, respectively.     

Two-step growth of ZnO films on silicon by atomic layer deposition

Two-step growth of ZnO by atomic layer deposition at low temperatures was performed to grow quality ZnO films on silicon substrates: first, the growth of a buffer layer at 130 ?C and second, the growth of the main layer at 210 ?C. Structural and optical properties of the ZnO films deposited on ZnO-buffer/Si(111) were investigated as a function of buffer layer thickness. The films showed a strong UV emission at 380 nm and a weak green emission at 520–570 nm. The ZnO films deposited on a 327 å buffer layer showed overall the best surface morphology and structural and optical properties.     

One-dimensional ZnO nanostructure growth prepared by thermal evaporation on different substrates: Ultraviolet emission as a function of size and dimensionality

Large-scale uniform one-dimensional ZnO nanostructures were fabricated through thermal evaporation via the vapor solid mechanism on different substrates. The effects of Si (100), Si (111), SiO₂ and sapphire substrates with constant oxygen treatment on the morphology and diameter of ZnO nanostructures were investigated. It is found that the type of substrate has a great effect on the shape and diameter of the synthesized nanowires, nanorods, and nanotubes. It is noticed that the size and dimensionality were the most influential parameters on both structural and optical properties of the grown ZnO nanostructures. X-ray diffraction analysis confirms the stability of the wurtzite crystal structure for all grown ZnO nanostructures and the preferred orientation is substrate dependent. The crystallinity as well as the defects within the crystal lattice of the grown ZnO nanostructures was studied through Raman spectroscopy. The photoluminescence spectra of ZnO nanostructures grown on Si (100), Si (111), SiO₂ and sapphire substrates showed two peaks at a near-band-edge (NBE) emission in the ultraviolet region and a broad deep-level emission (DLE) around the green emission.     

Synthesis of ZnO nanowires on Si substrate by thermal evaporation method without catalyst: Structural and optical properties

Synthesis of ZnO nanowires was achieved on Si(100) substrate by the thermal evaporation of high purity metallic zinc powder without the use of any metal catalyst or additives. The diameter and length of the as-grown nanowires were in the range of 20–35 nm and few micrometers, respectively. The shapes and sizes of ZnO nanowires were dependent on the growth time. The high resolution transmission electron microscopy and selected area electron diffraction patterns indicated that the as-grown products are single crystalline with wurtzite hexagonal phase. Room temperature photoluminescence studies exhibited a strong UV emission and a suppressed green emission, confirming the good optical properties for the deposited nanowires.     

A catalyst-free growth of aluminum-doped ZnO nanorods by thermal evaporation

The growth of Al:ZnO nanorods on a silicon substrate using a low-temperature thermal evaporation method is reported. The samples were fabricated within a horizontal quartz tube under controlled supply of O₂ gas where Zn and Al powders were previously mixed and heated at 700°C. This allows the reactant vapors to deposit onto the substrate placed vertically above the source materials. Both the undoped and doped samples were characterized using scanning electron microscopy (SEM), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), high-resolution transmission electron microscopy (HRTEM) and photoluminescence (PL) measurements. It was observed that randomly oriented nanowires were formed with varying nanostructures as the dopant concentrations were increased from 0.6 at.% to 11.3 at.% with the appearance of ‘pencil-like’ shape at 2.4 at.%, measuring between 260 to 350 nm and 720 nm in diameter and length, respectively. The HRTEM images revealed nanorods fringes of 0.46 nm wide, an equivalent to the lattice constant of ZnO and correspond to the (0001) fringes with regard to the growth direction. The as-prepared Al:ZnO samples exhibited a strong UV emission band located at approximately 389 nm (E _g  = 3.19 eV) with multiple other low intensity peaks appeared at wavelengths greater than 400 nm contributed by oxygen vacancies. The results showed the importance of Al doping that played an important role on the morphology and optical properties of ZnO nanostructures. This may led to potential nanodevices in sensor and biological applications.     

Growth and optical properties of ZnO–In2O3 heterostructure nanowires

ZnO–In₂O₃ heterostructure nanowires were grown on a Si (111) substrate using the thermal evaporation method. Scanning electron microscopy results showed that the ZnO nanowires had spherical caps. The X-ray diffraction (XRD) pattern and energy-dispersive X-ray (EDX) spectrum indicated that these caps were In₂O₃. An analysis of the early growth process revealed that indium oxide might have played a self-catalytic role. Therefore, it was plausible that the vapor–liquid–solid mechanism (VLS) was responsible for the growth of the ZnO–In₂O₃ heterostructure nanowires. The optical properties of the products were characterized using a photoluminescence (PL) technique. The PL results for the ZnO–In₂O₃ heterostructure nanowires showed a strong peak in the ultraviolet region as a result of the near band emission and a negligible peak for the visible emissions that occurred as a result of the defects. Based on these PL results, it was found that the In₂O₃ nanostructures not only introduced the caps at the tips of the ZnO nanowires but also partially passivated the nanowire surfaces, leading to an improved near band edge emission and the suppression of the defect luminescence.     

Synthesis of ZnO nanowires on steel alloy substrate by thermal evaporation: Growth mechanism and structural and optical properties

ZnO nanowires having a diameter in the range of 15–40 nm and several tens of micrometers in length were grown on steel alloy substrates by the thermal evaporation technique without the use of any catalyst or additives. A detailed structural analysis revealed that the as-grown ZnO nanowires are single crystalline with wurtzite hexagonal structures and preferentially oriented in the c-axis direction. Origination of a strong and sharp Raman-active E₂ mode at 436.6 cm^-1 indicated that the grown ZnO nanowires have good crystal quality with the hexagonal wurtzite phase. Photoluminescence spectra also exhibited a sharp and strong peak in UV and a suppressed and weak band in the visible region, confirming the good optical properties and less structural defects for the deposited products. Additionally, a systematic growth mechanism is also proposed in detail to acquire a better understanding for the growth of nanowires on steel alloy substrate.     

Parametric Study on Dimensional Control of ZnO Nanowalls and Nanowires by Electrochemical Deposition

A simple electrochemical deposition technique is used to synthesize both two-dimensional (nanowall) and one-dimensional (nanowire) ZnO nanostructures on indium-tin-oxide-coated glass substrates at 70°C. By fine-tuning the deposition conditions, particularly the initial Zn(NO₃)₂·6H₂O electrolyte concentration, the mean ledge thickness of the nanowalls (50–100 nm) and the average diameter of the nanowires (50–120 nm) can be easily varied. The KCl supporting electrolyte used in the electrodeposition also has a pronounced effect on the formation of the nanowalls, due to the adsorption of Cl⁻ ions on the preferred (0001) growth plane of ZnO and thereby redirecting growth on the (10[`1] \bar{1} 0) and (2[`1] \bar{1} [`1] \bar{1} 0) planes. Furthermore, evolution from the formation of ZnO nanowalls to formation of nanowires is observed as the KCl concentration is reduced in the electrolyte. The crystalline properties and growth directions of the as-synthesized ZnO nanostructures are studied in details by glancing-incidence X-ray diffraction and transmission electron microscopy.     

High-yield synthesis of ZnO nanowire arrays and their opto-electrical properties

In this article, ZnO nanostructures were synthesized via the hydrothermal method which used ZnCl(2) and HMTA mixed solution as the precursor. A multistep growth was adopted to improve the growth restriction of a closed system, not only the length but also the aspect ratio were increased with steps of growth, and the shape of nanorods maintained integrity. Furthermore, photoluminescence spectra which have the near-band-edge-emission (～3.37 eV) and defect-related emission show the optical properties of ZnO nanostructures. The defect-related emission intensity was greatly enhanced with the increasing surface area of ZnO nanowires. The level of the OH group was attributed to the yellow-light emission (～580 nm) and the red-shift phenomenon. In addition, we fabricated two types of ultraviolet photodetectors: a single nanowire device and a nanowire-array device, operating at a low bias (less than 5 mV). With the lower energy consumption and the weaker persistent photoconductive effect, our ultraviolet photodetectors have better performance, exhibiting a short response time and higher sensitivity.     

Rapidly synthesized ZnO nanowires by ultraviolet decomposition process in ambient air for flexible photodetector

We are the first group to use a simple direct ultraviolet light (UV, λ=365 nm, I=76 mW cm(-2)) in a decomposition process to fabricate ZnO nanowires on a flexible substrate using a zinc acetylacetonate hydrate precursor in ambient air. ZnO nanocrystal (or nanowire) production only requires three to ten minutes. A field emission scanning electron microscopy (FESEM) image reveals a high aspect ratio of the ZnO nanowires, which are grown on a substrate with a diameter of ～50-100 nm, and a length of up to several hundred microns. High resolution transmission electron microscopy (HRTEM) images reveal that the nanowires consist of many single crystalline ZnO nanoparticles that grow along the c axis, which suggests an oriented attachment process. A potential application for flexible UV photodetectors was investigated using a UV lamp (λ=365 nm, I=2.34 mW cm(-2)). A significant ratio of photocurrent to dark current--around 11,300%--was achieved.     

Synthesis of Na-doped ZnO nanowires and their antibacterial properties

Na-doped ZnO nanowires with an average diameter of ~ 40 nm have been fabricated by a thermal decomposition route at temperatures around 400 °C. Their properties have been investigated using X-ray diffraction, field emission scanning electron microscope, Raman spectra, photoluminescence spectra and X-ray photoelectron spectra. Photoluminescence spectra showed that the as-synthesized ZnO samples exhibited strong visible emission with a major peak at 420 nm. Furthermore, intensity of the visible emission at 420 nm enhanced as the increase of Na concentration. The improvement of visible emission in the Na-doped ZnO samples should be a result of the surface defects increased by doping of Na in ZnO. Their antibacterial activities were also evaluated by determination of minimum inhibitory concentration (MIC) against Escherichia coli 25922 in vitro. Antibacterial tests indicated these nanomaterials showed good antibacterial properties after UV illumination for a short time.     

Preparation of ZnO nanoparticles localized on SiC@SiO2 nanocables by a physical templating method

Impregnation of interlaced SiC@SiO₂ nanocables (SiC NWs sheathed by SiO₂ coatings) into a ZnO sol at 0 °C yielded, after thermal treatment up to 600 °C under argon, SiC@SiO₂@ZnO nanostructures. These novel nanostructures consist in SiC@SiO₂ nanocables covered by numerous agglomerated ZnO nanoparticles. The latter are less than 5 nm in diameter. This result is to our knowledge the first example of a physical templating technique involving SiC-based nanowires. Moreover, we have obtained localized ZnO nanoparticles. This localization can be of interests for a further study of their physical properties. When a similar experiment was conducted with pure SiC nanowires, there was no interaction between the nanowires (NWs) and the solution, resulting in the formation of agglomerated ZnO NPs embedded into the 3D NWs network.     

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.     

Synthesis and Optical Properties of Mullite Nanowires

Single-crystalline mullite (3Al₂O₃·2SiO₂) nanowires have been synthesized on silicon substrates by forcing aluminum and chromium chloride powders to react under an ammonia gas flow. The diameter and length of the nanowires have uniform diameters of <100 nm and several micrometers, respectively. High-resolution transmission electron microscope and selected-area electron diffraction analyses indicated that the nanowires were almost structural defect free and had a single-crystalline phase with a 〈0001〉 growth direction. The photoluminescence spectra showed that the mullite nanowires reached an emission peak at the center wavelength of 442 nm originating from the Al–O bonds in preference to the Al–O and Si–O bonds in the mullite bonding structure. Comparison of the photoluminescence between as-synthesized, oxygen–annealed, and plasma-etched nanowires indicates that the nanowires have few defects (i.e., oxygen vacancies).     

Structural and photoluminescence studies on catalytic growth of silicon/zinc oxide heterostructure nanowires

Silicon/zinc oxide (Si/ZnO) core-shell nanowires (NWs) were prepared on a p-type Si(111) substrate using a two-step growth process. First, indium seed-coated Si NWs (In/Si NWs) were synthesized using a plasma-assisted hot-wire chemical vapor deposition technique. This was then followed by the growth of a ZnO nanostructure shell layer using a vapor transport and condensation method. By varying the ZnO growth time from 0.5 to 2 h, different morphologies of ZnO nanostructures, such as ZnO nanoparticles, ZnO shell layer, and ZnO nanorods were grown on the In/Si NWs. The In seeds were believed to act as centers to attract the ZnO molecule vapors, further inducing the lateral growth of ZnO nanorods from the Si/ZnO core-shell NWs via a vapor-liquid-solid mechanism. The ZnO nanorods had a tendency to grow in the direction of [0001] as indicated by X-ray diffraction and high resolution transmission electron microscopy analyses. We showed that the Si/ZnO core-shell NWs exhibit a broad visible emission ranging from 400 to 750 nm due to the combination of emissions from oxygen vacancies in ZnO and In₂O₃ structures and nanocrystallite Si on the Si NWs. The hierarchical growth of straight ZnO nanorods on the core-shell NWs eventually reduced the defect (green) emission and enhanced the near band edge (ultraviolet) emission of the ZnO.     

Novel ozone gas sensor based on ZnO nanostructures grown by the microwave-assisted hydrothermal route

Good quality ZnO nanostructures were obtained by the microwave-assisted hydrothermal synthesis, at low reaction temperatures, using zinc acetate as the starting precursor. X-ray diffraction confirmed the crystallinity of the ZnO nanostructures, which resulted free of impurities. Field emission gun scanning electron microscopy analysis revealed that the ZnO nanostructures crystallized at 120 °C were more homogeneous and had a constant diameter along the entire wire length, exhibiting an ideal defect density that favors the gas sensing response. A new ozone gas sensor based on these nanostructures was evaluated at low exposure times (15 s) by recording the change in the film resistance. The ZnO nanostructures showed good sensitivity even at low ozone concentration (100 ppb), and fast response and short recovery time at 200 °C, demonstrating great potential for a variety of applications. Two main effects were observed: the first one is intrinsic to that of the sample, while the second is a consequence of the surface and interface complex cluster defects, which produce extrinsic defects.     

Growth of In2O3 Nanowires Catalyzed by Cu via a Solid–Liquid–Solid Mechanism

In₂O₃ nanowires that are 10–50 nm in diameter and several hundred nanometers to micrometers in length have been synthesized by simply annealing Cu–In compound at a relatively low temperature of 550°C. The catalysis of Cu on the growth of In₂O₃ nanowires is investigated. It is believed that the growth of In₂O₃ nanowires is via a solid–liquid–solid (SLS) mechanism. Moreover, photoluminescence (PL) peaks of In₂O₃ nanowires at 412 and 523 nm were observed at room temperature, and their mechanism is also discussed.