Effect of growth time on Ti-doped ZnO nanorods prepared by low-temperature chemical bath deposition

Ti-doped ZnO nanorod arrays were grown onto Si substrate using chemical bath deposition (CBD) method at 93 °C. To investigate the effect of time deposition on the morphological, and structural properties, four Ti-doped ZnO samples were prepared at various deposition periods of time (2, 3.5, 5, and 6.5 h). FESEM images displayed high-quality and uniform nanorods with a mean length strongly dependent upon deposition time; i.e. it increases for prolonged growth time. Additionally, EFTEM images reveal a strong erosion on the lateral side for the sample prepared for 6.5 h as compared to 5 h. This might be attributed to the dissolution reaction of ZnO with for prolonged growth time. XRD analysis confirms the formation of a hexagonal wurtzite-type structure for all samples with a preferred growth orientation along the c-axis direction. The (100) peak intensity was enhanced and then quenched, which might be the result of an erosion on the lateral side of nanorods as seen in EFTEM. This study confirms the important role of growth time on the morphological features of Ti-doped ZnO nanorods prepared using CBD.     

Control of diameter of ZnO nanorods grown by chemical vapor deposition with laser ablation of ZnO

We made a study of controlling diameters of well-aligned ZnO nanorods grown by low-pressure thermal chemical vapor deposition combined with laser ablation of a sintered ZnO target, which was developed by us. Until now, it has been impossible to control diameters of ZnO nanorods, while the growth orientation was maintained well-aligned. In this study we developed a multi-step growth method to fabricate well-aligned nanorods whose diameters could be controlled. Metal Zn vapor and O₂ are used as precursors to grow ZnO nanorods. N₂ is used as a carrier gas for the precursors. A substrate is an n-Si (111) wafer. A sintered ZnO target is placed near the substrate and ablated by a Nd–YAG pulsed laser during ZnO nanorod growth. The growth temperature is 530 C and the pressure is 66.5 Pa. A vertical growth orientation of ZnO nanorods to the substrate is realized in the first-step growth although the diameter cannot be controlled in this step. When an O₂ flow rate is 1.5 sccm, well-aligned nanorods with 100 nm diameter are grown. Next, the second-step nanorods are grown on only the flat tip of the first-step nanorods. The diameters of the second-step nanorods can be controlled by adjusting the O₂ flow rate, and the growth direction is kept the same as that of the first-step nanorods. When the O₂ flow rate in second-step growth is smaller than 0.6 sccm, the diameter of the second-step nanorods is 30–50 nm. When the O₂ flow rate is between 0.75 and 3.0 sccm, the diameter is almost same as that of the first-step nanorods. When the O₂ flow rate is larger than 4.5 sccm, the diameter is increased with increasing O₂ flow rate. Further, the third-step ZnO nanorods with gradually increased diameters can be grown on the second-step nanorods with 1.5 sccm O₂ flow rate and without laser ablation.     

Patterned growth of ZnO nanorods and their field emission properties

Patterned zinc oxide (ZnO) nanorods were fabricated on the different patterned silicon nanocrystallite (SiNC) substrates via a simple thermal evaporation method without any catalyst. The as-synthesized products were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), respectively. The efficient field emission with low turn-on and threshold field, 3.5 V/μm and 8.1 V/μm, was obtained. The experimental results demonstrate that these products could be one of the promising candidates for field emission displays.     

Low-temperature growth of ZnO nanorods on PET fabrics with two-step hydrothermal method

An effective low-temperature growth method to fabricate hexagonally oriented ZnO nanorod arrays onto PET fabrics is reported. The effect of substrate pre-treatment and C₆H₁₂N₄ concentration on the structure of ZnO nanorod arrays were investigated in details by X-ray diffraction (XRD), FE-SEM and ultraviolet protection factor (UPF). The results show that substrate pre-treatment, C₆H₁₂N₄ concentration indeed have great influence on the growth of ZnO nanorod arrays. It is indispensable to introduce a ZnO seed layer on the substrate and under growth condition of n(C₆H₁₂N₄):n[Zn(NO₃)₂] = 1:1, T = 90 °C, t = 3 h, the well-aligned ZnO nanorod arrays with 40-50 nm in diameter and 300-400 nm in length were achieved on the pre-treated PET fabrics. The ZnO nanorods grown on PET fabrics possessed an ultrahigh ultraviolet protection factor of 480.52 in this study, indicating an excellent protection against ultraviolet radiation in comparison with the untreated PET fabrics.     

Zn-catalyzed growth processes and ferromagnetism of Mn-doped ZnO nanorods on Si substrate

Well-aligned ZnO nanorods and Mn-doped ZnO nanorods are fabricated on Si (1 0 0) substrate according to the contribution of Zn metal catalysts. Scanning electron microscopy and high-resolution transmission electron microscopy images indicate that the influence of Zn catalyst on the properties of ZnO can be excluded and the growth of ZnO nanorods follows a vapor-liquid-solid and self-catalyzed model. Mn-doped ZnO nanorods show a typical room temperature ferromagnetic characteristic with a saturation magnetization (M_S) of 0.273μ_B/Mn. Cathodoluminescence suggests that the ferromagnetism of Mn-doped ZnO nanorods originates from the Mn²⁺-Mn²⁺ ferromagnetic coupling mediated by oxygen vacancies. This technique provides exciting prospect for the integration of next generation Si-technology-based ZnO spintronic devices.     

Surface morphology and growth mechanism of catalyst‐free ZnO and Mgx Zn1–x O nanorods

High‐resolution transmission electron microscopy was employed to investigate morphologies and catalyst‐free growth mechanism of ZnO/Mg_x Zn_1–x O ‘multi‐quantum well’ and ‘core‐shell’ nanorod heterostructures as well as ZnO nanorods. The one‐dimensional growth mechanism and the hexagonal faceting of ZnO nanorod were explained by the surface energy anisotropy. The morphology change by alloying with Mg was successfully explained by investigating the energy gain by adatom adsorption and the reduction in the surface energy anisotropy. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Particulate assisted growth of ZnO nanorods and microrods by pulsed laser deposition

Zinc oxide (ZnO) thin films were deposited on the gallium nitride (GaN) and sapphire (Al₂O₃) substrates by pulsed laser deposition (PLD) without using any metal catalyst. The experiment was carried out at three different laser wavelengths of Nd:YAG laser (λ = 1064 nm, λ = 532 nm) and KrF excimer laser (λ = 248 nm). The ZnO films grown at λ = 532 nm revealed the presence of ZnO nanorods and microrods. The diameter of the rods varies from 250 nm to 2 μm and the length varies between 9 and 22 μm. The scanning electron microscopy (SEM) images of the rods revealed the absence of frozen balls at the tip of the ZnO rods. The growth of ZnO rods has been explained by vapor-solid (V-S) mechanism. The origin of growth of ZnO rods has been attributed to the ejection of micrometric and sub-micrometric sized particulates from the ZnO target. The ZnO films grown at λ = 1064 nm and λ = 248 nm do not show the rod like morphology. X-ray photoelectron spectroscopy (XPS) has not shown the presence of any impurity except zinc and oxygen.     

Use of various growth catalysts for laser sputtering of ZnO micro- and nanorods

Pulsed laser deposition and various catalysts are used to fabricate ZnO micro- and nanorods at temperatures close to the optimum temperature for each catalyst. A comparative analysis of the optical and structural properties of the rods shows that, as the temperature of growth on Al₂O₃(11–20) substrates decreases, the internal stresses in the rods decrease, which improves their structure and optical properties. This effect is not observed for GaN/Si substrates because of the high stresses induced by the difference in the lattice parameters. An increase in the synthesis temperature leads to an increase in the lattice strains and the concentration of point defects, the relaxation of selection rules, and the appearance of numerous phonon A ₁(LO) overtones. The lattice strains calculated from unit cell parameter a and the shift in the phonon A ₁(LO) frequency agree qualitatively. The study of the photoluminescence of the rods shows that a decrease in the synthesis temperature decreases the imperfection of the ZnO rods and improves their optical properties for UV applications.     

Hierarchical evolution of arrayed nanowires, nanorods, and nanosheets in ZnO

Various intriguing arrayed nanostructures of ZnO, i.e., arrayed nanowires, arrayed nanorods, arrayed nanosheets, were fabricated in series by controlling the processing temperature and oxygen contents systematically based on a simple thermal evaporation process. These structures are monolithically single crystalline and the examples of spontaneous organization of vapor molecular species into nanoscale structures and their microscale assemblies or superlattices in one step. These kinds of arrayed structures might be useful in arrayed nanoscale optoelectronic and electrochemical applications. PACS 81.10; 81.05.Y; 85.60; 52.75.R; 81.15.G     

ZnO nanorod arrays with tunable size and field emission properties on an ITO substrate achieved by an electrodeposition method

In the present work,vertically aligned ZnO nanorod arrays with tunable size are successfully synthesized on nonseeded ITO glass substrates by a simple electrodeposition method.The effect of growth conditions on the phase,morphology,and orientation of the products are studied in detail by X-ray diffraction(XRD),scanning electron microscopy(SEM),and transmission electron microscopy(TEM).It is observed that the as-prepared nanostructures exhibit a preferred orientation along c axis,and the size and density of the ZnO nanorod can be controlled by changing the concentration of ZnCl2.Field emission properties of the as-synthesized samples with different diameters are also studied,and the results show that the nanorod arrays with a smaller diameter and appropriate rod density exhibit better emission properties.The ZnO nanorod arrays show a potential application in field emitters.     

A comparative study of the electrodeposition and the aqueous chemical growth techniques for the utilization of ZnO nanorods on p-GaN for white light emitting diodes

Vertically well aligned zinc oxide nanorods (ZnO NRs) were grown on p-GaN by electrodeposition (ED) and aqueous chemical growth (ACG) techniques and the structures were employed to fabricate white light emitting diodes (LEDs). Room temperature current voltage (I–V$I–V$), photoluminescence (PL), and electroluminescence (EL) measurements were performed to investigate and compare both LEDs. In general, the I–V$I–V$ characteristics and the PL spectra of both LEDs were rather similar. Nevertheless, the EL of the ED samples showed an extra emission peak shoulder at 730 nm. Moreover, at the same injection current, the EL spectrum of the ED light emitting diode showed a small UV shift of 12 nm and its white peak was found to be broader when compared to the ACG grown LED. The broadening of the EL spectrum of the LED grown by ED is due to the introduction of more radiative deep level defects. The presented LEDs have shown excellent color rendering indexes reaching a value as high as 95. These results indicate that the ZnO nanorods grown by both techniques possess very interesting electrical and optical properties but the ED is found to be faster and more suitable for the fabrication of white LEDs.     

金纳米棒核/贵金属壳杂化纳米结构的可控制备和性质调控

贵金属纳米颗粒由于其独特的光学及催化性能引起了人们的广泛关注,而这些性能与纳米颗粒的尺寸、形貌、结构组成等密切相关.目前如何有意识地控制晶体生长过程,以得到人们需要的纳米结构和组成,仍具有相当大的挑战性.文章重点介绍了利用具有特定形貌和晶面组成的金纳米棒(Au nanorods)作为种子,借助形成核/壳结构,诱导了Ag, Pd, Pt棒状纳米结构的形成,并实现了对杂化纳米结构光学和催化性能的调控,进一步扩展了贵金属纳米结构的应用范围.作者的研究结果表明,形成杂化纳米结构是性能调控的一种有效方式.     

金纳米棒核/贵金属壳杂化纳米结构的可控制备和性质调控

贵金属纳米颗粒由于其独特的光学及催化性能引起了人们的广泛关注,而这些性能与纳米颗粒的尺寸、形貌、结构组成等密切相关.目前如何有意识地控制晶体生长过程,以得到人们需要的纳米结构和组成,仍具有相当大的挑战性.文章重点介绍了利用具有特定形貌和晶面组成的金纳米棒（Au nanorods）作为种子,借助形成核/壳结构,诱导了Ag...     

Morphology, photocatalytic and antibacterial activities of radial spherical ZnO nanorods controlled with a diblock copolymer

Radial spherical ZnO nanorods were synthesized directly from an aqueous zinc acetate dihydrate solution in the presence of the poly(ethylene oxide)-b-poly(propylene oxide) copolymer at a mole ratio of Zn²⁺:OH⁻ = 1:10. The diameter of the hexagonal facet and the length of each rod decreased with an increase of the copolymer concentrations. The blue-shift in the optical band gap was caused by an increase of the compressed lattice. The efficiency of photocatalytic degradation of methylene blue in aqueous solution increased with an increase of their surface areas. However, the decrease of their sizes did not improve their antibacterial activities.     

Preparation and characterization of ZnO nanorods from NaOH solutions with assisted electrical field

ZnO naorods on ZnO-coated seed substrates were fabricated by solution chemical method from Zn(NO₃)₂/NaOH under assisted electrical field. The working mechanism of electrical field was analyzed and the factors affecting the rod growth such as potential, precursor concentration and growth temperature were elucidated. The structural and optical properties are characterized by SEM, TEM, XRD, HRTEM and UV-vis. The results indicated that the nanorods have wurtzite structure without electrical field and are primarily of zincite structure under electrical field; when the electrical field is 1.1-1.3 V, not only the elevation of ion diffusion and adsorption lower the crystallite/solution interfacial energy and then the crystal nucleation barrier by increasing charge intensity, but also the production of H⁺ through oxidation of OH⁻ increases properly the degree of solution supersaturation near the substrate, and thus lowers the activation energy. Both the two processes do favor to rod growth. With increasing precursor concentration in this system, the average diameter and length of ZnO nanorods increase, leading to decreasing of optical transmittance. The maximum rod growth rate at given concentration of Zn²⁺ occurs at a specific temperature.     

Synthesis of ZnO films with a special texture and enhanced field emission properties

ZnO films with special textures are fabricated on Mo-coated Al₂O₃ ceramic substrates by the catalyst-free electron beam evaporation method, and the as-deposited films are treated by hydrogen plasma. It is found that the surface morphologies of the films are changed significantly after hydrogen plasma treatment and that the films consist of vertically standing and intersecting nanosheets. A lower turn-on field of 1.2 V/μm and an enhanced current density ～0.11 mA/cm² at 2.47 V/μm are achieved. The low threshold field and the high emission current density are attributed primarily to the unique shape and smaller resistivity of the ZnO nanosheet films.     

The study of low temperature hydrothermal growth of ZnO nanorods on stents and its applications of cell adhesion and viability

The hydrothermal growths of the ZnO nanorods with the densities ranging from 157 to 73 nanorods/μm² were achieved by diluting the ZnO seed solution. However, the ZnO seed nanocrystals started to agglomerate for the seed solution diluted below 1% of the original nano-crystalline solutions and resulted in the formation of clustered nanorods. With the assistance of a surfactant, Triton X-100, the nanorod density can be further reduced to 4 nanorods/μm². The diameters of the nanorods depended on the concentration of the seed solution and agitation speed of the nanorod growth solution. More diluted seed solution used and less agitation of the growth solution, the larger diameter of the nanorods was obtained. This indicated that the nanorod growth mechanism was controlled by the diffusion of reactants. With sufficient agitation of the growth solution, the nanorod can be uniformly grown with subjects on any arbitrary geometry. We have demonstrated ZnO nanorods growth on both inside and outside of biliary stents as well as on nitinol wires used as metal stents. The effect of nanorod density on the NIH 3T3 and HUVEC cells growth was also investigated in this study and the results suggested nanorod-coating to be a suitable method for controlling cell adhesion and viability on implantable devices.     

Effects of surface adsorbed oxygen,applied voltage,and temperature on UV photoresponse of ZnO nanorods

The ultraviolet(UV) photoresponses of ZnO nanorods directly grown on and between two micro Au-electrodes by using electric-field-assisted wet chemical method are measured comprehensively under different conditions, including ambient environment, applied bias voltage, gate voltage and temperature. Experimental results indicate that the photoresponses of the ZnO nanorods can be modulated by surface oxygen adsorptions, applied voltages, as well as temperatures. A model taking into account both surface adsorbed oxygen and electron-hole activities inside ZnO nanorods is proposed. The enhancement effect of the bias voltage on photoresponse is also analyzed. Experimental results shows that the UV response time(to 63%) of ZnO nanorods in air and at 59°C could be shortened from 34.8 s to 0.24 s with a bias of 4 V applied between anode and cathode.     

Ethylene glycol-assisted solvothermal fabrication of ZnWO4 nanostructures with tunable size,optical properties,and photocatalytic activities

Large scale of uniform small ZnWO₄ nanocrystals and ZnWO₄ nanorods with tunable size have been fabricated in ethylene glycol (EG)-assisted solvothermal process, ZnWO₄ samples ranging in shape from tiny nanocrystals to nanorods were dependent on the volume ratio of EG and water (H₂O). The optical properties of ZnWO₄ nanocrystals and nanorods were investigated by photoluminescence (PL) spectroscopy, showing longer ZnWO₄ nanorods own the increased PL intensity in comparison with that of shorter ones and small ZnWO₄ nanocrystals. The photocatalytic performance of ZnWO₄ nanostructures was studied also, which indicated that the increased size of ZnWO₄ nanorods resulted the degradation of photocatalytic performance in aqueous solution.     

Shape and size transformation of gold nanorods (GNRs) via oxidation process: A reverse growth mechanism

The anisotropic shape transformation of gold nanorods (GNRs) with H₂O₂ was observed in the presence of “cethyl trimethylammonium bromide” (CTAB). The adequate oxidative dissolution of GNR is provided by the following autocatalytic scheme with H₂O₂: Au⁰ → Au⁺, Au⁰ + Auⁿ⁺ → 2Au³⁺, n = 1 and 3. The shape transformation of the GNRs was investigated by UV-vis spectroscopy and transmission electron microscopy (TEM). As-synthesised GNRs exhibit transverse plasmon band (TPB) at 523 nm and longitudinal plasmon band (LPB) at 731 nm. Upon H₂O₂ oxidation, the LPB showed a systematic hypsochromic (blue) shift, while TPB stays at ca. 523 nm. In addition, a new emerging peak observed at ca. 390 nm due to Au(III)-CTAB complex formation during the oxidation. TEM analysis of as-synthesised GNRs with H₂O₂ confirmed the shape transformation to spherical particles with 10 nm size in 2 h, whereas centrifuged nanorod solution showed no changes in the aspect ratio under the same condition. Au³⁺ ions produced from oxidation, complex with excess free CTAB and approach the nanorods preferentially at the end, leading to spatially directed oxidation. This work provides some information to the crystal stability and the growth mechanism of GNRs, as both growth and shortening reactions occur preferentially at the edge of single-crystalline GNRs, all directed by Br⁻ ions.