Effect of ZnO seed layers on the solution chemical growth of ZnO nanorod arrays

High density ZnO nanorod arrays were grown on Si substrates coated with ZnO seed layers via aqueous solution route. The ZnO seed layers were deposited on the substrate using DC reactive sputtering and RF magnetron sputtering. It was found that ZnO seed layer with (1 0 3) preferred orientation, prepared using DC reactive sputtering, did not facilitate the formation of ZnO nanorods in the solution grown process. Prior seeding of the surface by ZnO layer with (0 0 2) preferred orientation, deposited using RF magnetron sputtering, leads to nucleation sites on which ZnO nanorod arrays can grow in a highly aligned fashion. ZnO nanorods with well-defined hexagonal facets (0 0 2) were grown almost vertically over the entire substrate. The uniformity and alignment of the nanorod arrays are strongly related to the properties of underneath ZnO seed layers.     

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.     

Synthesis of mono- and diglycerides in water-in-oil microemulsions

Enzyme-catalyzed esterification was carried out in single-phase, oil-continuous microemulsions. The lipozyme was solubilized, along with glycerol and water, in the aqueous core of water/diethylhexyl sodium sulfosuccinate/hydrocarbon microemulsion system. Upon addition of fatty acid, mono- and diglycerides were formed, due to the esterification reaction taking place at the interface of the droplets in the microemulsion. The initial rate of conversion of oleic acid increases with oil chainlength of the continuous phase whereas final conversion is maximum for hexane. The conversion of stearic acid is 30% whereas conversion of oleic acid is 70%. The percent conversion of various fatty acids in the same continuous medium increases with fatty acid chainlength. The oleic acid/glycerol ratio is an important parameter for optimum conversion of oleic acid into glycerides. The yield can be increased by subsequent addition of glycerol after equilibrium is reached. High-performance liquid chromatography analysis of samples from microemulsions shows the presence of mono- and diglycerides. Possible mechanisms for the abovementioned effects are discussed.     

Photocurrent detection of chemically tuned hierarchical ZnO nanostructures grown on seed layers formed by atomic layer deposition

We demonstrate the morphological control method of ZnO nanostructures by atomic layer deposition (ALD) on an Al₂O₃/ZnO seed layer surface and the application of a hierarchical ZnO nanostructure for a photodetector. Two layers of ZnO and Al₂O₃ prepared using ALD with different pH values in solution coexisted on the alloy film surface, leading to deactivation of the surface hydroxyl groups. This surface complex decreased the ZnO nucleation on the seed layer surface, and thereby effectively screened the inherent surface polarity of ZnO. As a result, a 2-D zinc hydroxyl compound nanosheet was produced. With increasing ALD cycles of ZnO in the seed layer, the nanostructure morphology changes from 2-D nanosheet to 1-D nanorod due to the recovery of the natural crystallinity and polarity of ZnO. The thin ALD ZnO seed layer conformally covers the complex nanosheet structure to produce a nanorod, then a 3-D, hierarchical ZnO nanostructure was synthesized using a combined hydrothermal and ALD method. During the deposition of the ALD ZnO seed layer, the zinc hydroxyl compound nanosheets underwent a self-annealing process at 150 °C, resulting in structural transformation to pure ZnO 3-D nanosheets without collapse of the intrinsic morphology. The investigation on band electronic properties of ZnO 2-D nanosheet and 3-D hierarchical structure revealed noticeable variations depending on the richness of Zn-OH in each morphology. The improved visible and ultraviolet photocurrent characteristics of a photodetector with the active region using 3-D hierarchical structure against those of 2-D nanosheet structure were achieved.     

A new single step process for synthesis and growth of ZnGeP2 crystal

A new one-step process for synthesis and growth of zinc-germanium-phosphide, ZnGeP₂ (ZGP), is reported for the first time herein using a three-zone resistance furnace by the horizontal gradient freeze technique. A safe and proper temperature scheme has been obtained for both synthesis and growth of ZGP crystals via the melt growth route from Zn, Ge and P powder. The prepared material has been investigated using powder X-ray diffraction which shows the correct ZGP tetragonal phase. EPMA results are also obtained to estimate the compositional homogeneity of the grown crystal.     

Preparation and characterization of monoclinic sulfur nanoparticles by water-in-oil microemulsions technique

Nanosized monoclinic sulfur particles have been successfully prepared via the chemical reaction between sodium polysulfide and hydrochloric acid in a reverse microemulsions system, with theolin, butanol, and a mixture of Span80 and Tween80 (weight ratio 8 : 1) as the oil phase, co-surfactant and surfactant, respectively. Transparent microemulsions were obtained by mixing the oil phase, surfactant, co-surfactant, and the aqueous phase in appropriate proportion using an emulsification machine at the room temperature. The resulting sulfur nanoparticles were characterized by dynamic light scattering (DLS), X-ray diffraction (XRD), infrared spectroscopy (IR) and transmission electron microscopy (TEM).     

针状氧化锌晶须的银纳米颗粒修饰及其表征

以硝酸锌和氢氧化钠为主要原料,借助表面活性剂十二烷基苯磺酸钠,在低温水热条件下制备了氧化锌.以该氧化锌为基体,葡萄糖为还原剂,通过磁力搅拌的方式,将溶液中的银离子还原为银颗粒修饰氧化锌.所得氧化锌和修饰后的氧化锌经X射线衍射(XRD)、扫描电镜(SEM)和透射电镜(TEM)表征,结果表明:氧化锌是一种针状的纳米晶须;修饰后的氧化锌银颗粒很好地附着在其表面,为纳米尺寸.讨论了银纳米颗粒修饰针状氧化锌晶须的可能机制.     

One-step solution synthesis of urchin-like ZnO superstructures from ZnO rods

The urchin-like ZnO superstructures have been directly prepared by the assistance of poly (acrylic acid) (PAA, M_w 5000) under a one-step solution-based process. X-ray diffraction (XRD) patterns indicate that the crystal structure of the special ZnO urchins is hexagonal. The results of Field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) tests show that the urchins are composed of rods and the average aspect ratio of them is about 10 with a length of about 1.5 μm. Selected area electron diffraction (SAED) pattern reveals that the rods are single crystal in nature, which preferentially grow up along the 〈0001〉 direction. Furthermore, the sizes and aspect ratios of the rods can be easily controlled by regulating the concentration of ZnSO₄ solution. It is believed that the process of crystallization, including nucleation and crystal growth, happens along PAA chains resulting in the production of rods and assembly of them into superstructures.     

Large-scale and uniform preparation of pure-phase wurtzite GaAs NWs on non-crystalline substrates

One of the challenges to prepare high-performance and uniform III-V semiconductor nanowires (NWs) is to control the crystal structure in large-scale. A mixed crystal phase is usually observed due to the small surface energy difference between the cubic zincblende (ZB) and hexagonal wurtzite (WZ) structures, especially on non-crystalline substrates. Here, utilizing Au film as thin as 0.1 nm as the catalyst, we successfully demonstrate the large-scale synthesis of pure-phase WZ GaAs NWs on amorphous SiO₂/Si substrates. The obtained NWs are smooth, uniform with a high aspect ratio, and have a narrow diameter distribution of 9.5 ± 1.4 nm. The WZ structure is verified by crystallographic investigations, and the corresponding electronic bandgap is also determined to be approximately 1.62 eV by the reflectance measurement. The formation mechanism of WZ NWs is mainly attributed to the ultra-small NW diameter and the very narrow diameter distribution associated, where the WZ phase is more thermodynamically stable compared to the ZB structure. After configured as NW field-effect-transistors, a high I_ON/I_OFF ratio of 10⁴ − 10⁵ is obtained, operating in the enhancement device mode. The preparation technology and good uniform performance here have illustrated a great promise for the large-scale synthesis of pure phase NWs for electronic and optical applications.     

表面活性剂在纳米材料制备领域的研究概况

表面活性剂是用途非常广泛的一类两亲分子,现如今已运用在纳米粒子模板,有机化学制备等诸多领域。而纳米材料的微乳液合成方法是一项日趋完善的技术,它可以用于控制许多有机和无机材料的粒子尺寸。本文将对表面活性剂,以及表面活性剂在溶液中形成的微乳液制备纳米材料的应用趋势做详细的介绍。     

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.     

Raman study on zinc-blende single InAs nanowire grown on Si (111) substrate

We report polarized Raman scattering studies on single InAs nanowires (NWs). The NWs were grown by metalorganic chemical vapor deposition on Si (111) substrates without external catalyst and showed a zinc-blende crystal structure. The single NWs were studied for different polarization excitation of the incident laser beam relative to the NW axis. The transverse optical (TO) mode exhibits maximum intensity when both the incident and analyzed light polarizations are parallel to the NW axis. The TO mode of InAs NWs is found to act like a nearly perfect dipole antenna, which can be attributed to the one-dimensional NW geometry and Raman selection rules.     

Solvothermal synthesis of microsphere ZnO nanostructures in DEA media

Microsphere ZnO nanostructures (ZnO-MNs) were synthesized via solvothermal method in diethanolamine (DEA) media. DEA was utilized to terminate the growth of ZnO nanoparticles which forms the ZnO-MNs. The ZnO-MNs were characterized by a number of techniques, including X-ray diffraction analysis (XRD) and field emission scanning electron microscopy (SEM). The ZnO-MNs prepared by solvothermal process at the temperature of 150 °C for 6, 12, 18, and 24 h exhibited a hexagonal (wurtzite) structure with sizes ranging from 2 to 4 μm. The growth mechanism and morphology of the ZnO-MNs were also investigated, and it was found that the ZnO-MNs were formed by ZnO nanoparticles with average particle size of 25 ± 5 nm. To show role of DEA in the formation of Zn-MNs, effect of MEA (monoethanolamine) and TEA (triethanolamine) on morphology of the final product are also investigated. The results showed that DEA is a good polymerization agent that can be used as a stabilizer in the solvothermal technique for preparing fine ZnO powder.     

Partition of bromophenol blue in toluene/water/sodium bis(2-ethylhexyl)-sulfosuccinate water-in-oil microemulsions

The partition of bromophenol blue between oil-water interfaces and water droplets in water-in-oil microemulsions of toluene/water/sodium bis(2-ethylhexyl)sulfosuccinate was studied by a spectroscopic method at different water fractions and pH. The partition equilibrium constant, K _p , between the two domains decreased considerably with an increase in the water fraction and pH. The decrease in K _p with an increase in the water fraction suggests the retention of more dye molecules in water. The decrease in K _p with an increase in pH has been attributed to a lower tendency of the base form to associate with the anionic oil-water interface compared with that of the acid form and to an increase in the negative charge density at the oil-water interface at a higher pH.     

The effect ofn-decanol on solubilization of water-in-oil microemulsions and stability of lamellar liquid crystals of alkylphenol ethoxylates

Addition of n-decanol at appropriate concentrations is beneficial to increasing the solubilization amount of water in a water-in-oil microemulsion in the system of nonylphenol ethoxylate/olive oil/water, but it destabilized the lamellar liquid crystal and reduced the solubilization of olive oil in the lamellar liquid crystal.     

Tuning the dimensionality of ZnO nanowires through thermal treatment: an investigation of growth mechanism

ABSTRACT: In this study we synthesized various dimensionalities of ZnO nanowires using the Ti-grid assisted chemical vapor deposition process. Energy dispersive x-ray spectroscopic mapping technique accompanied with a lattice diffusion model was used to characterize the growth mechanism. A diffusion ratio was obtained to describe the mechanism based on short-circuit- and lattice- diffusion of Zn ions from the Zn base film is then proposed for the growth of ZnO nanowires. The tunable dimensionalities of ZnO nanowires allow us to modify the morphology of ZnO nanocrystals by developing well controlled potential applications.     

Polymer-assisted freeze-drying synthesis of Ag-doped ZnO nanoparticles with enhanced photocatalytic activity

Ag-doped ZnO nanoparticles with high and stable photocatalytic activity were prepared by polymer-assisted freeze-drying method with simple process and without organic solvents used. The structural morphology and optical properties of Ag-doped ZnO nanoparticles were characterized by X-ray Diffraction (XRD), Inductive Coupled Plasma Optical Emission Spectrometry (ICP-OES), Field Emission Scanning Electron Microscopy (FESEM), Transmission Electron Microscopy (TEM) and high resolution TEM (HRTEM) with energy dispersive X-ray spectroscopy, Ultraviolet-visible Diffuse Reflectance Spectroscopy (UV–vis DRS), X-ray Photoelectron Spectroscopy (XPS) and Fourier Transmission Infrared Spectroscopy (FTIR). Moreover, the thermoanalytical measurements (TGA–DTG) analysis is carried out for proper calcination temperature. XRD results show that Ag nanoparticles were successfully doped into ZnO lattice, and UV–vis DRS results indicate that the doped Ag nanoparticles result in ZnO exhibiting enhanced light trapping capability in the 400?nm and 600?nm range. The photocatalytic activity of Ag-doped ZnO was examined by analyzing the degradation of methyl orange (MO) and methylene blue (MB) dyes under UV light and solar light irradiation, and the results show that all Ag-doped ZnO nanoparticles exhibit better photocatalytic activity than those of pure ZnO nanoparticles at the same degradation conditions; especially the synthesized Ag-ZnO nanoparticles are easy to be recycled and have high photocatalytic stability. Based on the experimental results, the photocatalytic electron transfer path and the photocatalytic mechanism of Ag-ZnO nanoparticles under UV and solar irradiation conditions are explained and clarified.     

Morphology-controlled synthesis of quasi-aligned AlN nanowhiskers by combustion method: Effect of NH4Cl additive

Uniform quasi-aligned AlN nanowhiskers grown in the reacting Al particles have been successfully prepared in high content by combustion synthesis using NH₄Cl as a morphology-controlled promoting additive. FE-SEM and TEM images show that the nanowhiskers, which are single-crystalline hexagonal wurtzite AlN growing along [0 0 1] direction, have diameters in the range of 80–170 nm and a length of several to several tens of micrometers. The effect of NH₄Cl on the growth of nanowhiskers was discussed. It was found that NH₄Cl not only controlled the products’ morphology, but also changed the combustion behavior and nitridation mechanism in the combustion synthesis process.     

Template free synthesis of highly ordered mullite nanowhiskers with exceptional photoluminescence

An efficient method to produce highly ordered mullite nanowhiskers using B₂O₃-doped molten salt synthesis was reported in this work. The morphology and optical properties of the obtained nanowhiskers were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and photoluminescence (PL) spectroscopy. The results show that highly ordered mullite nanowhiskers with uniform morphology in large scale are obtained at 1000 °C for 3 h in air. The structure of mullite is Al-rich and single crystalline. The diameter is in the range of 90–110 nm and length up to 20–30 μm. The reaction mechanism of the highly ordered mullite nanowhiskers is attributed to local concentration gradient. Due to the Al-rich structure, mullite nanowhiskers demonstrate strong photoluminescence (PL) emission at 399 nm, 452 nm and 468 nm, implying mullite nanowhiskers can be applied as a promising candidate in optical and electronic fields.