Influence of S incorporation on the luminescence property of ZnO nanowires by electrochemical deposition

Sulfur-doped zinc oxide (ZnO) nanowires have been successfully synthesized by an electric field-assisted electrochemical deposition in porous anodized aluminum oxide template at room temperature. X-ray diffraction and the selected area electron diffraction results show that the as-synthesized nanowires are single crystalline and have a highly preferential orientation. Transmission electron microscopy observations indicate that the nanowires are uniform with an average diameter of 120 nm and length up to several tens of micrometers. Room-temperature photoluminescence is observed in the doped ZnO nanowires, which exhibits a violet emission and blue emissions besides the typical photoluminescence spectrum of a single crystal ZnO.     

Na mole concentration dependence on optical p-type behaviors of Na-doped ZnO nanowires

We report the structural and optical features of Na-doped ZnO nanowires as a function of Na mole concentration to demonstrate the p-type conduction of Na-doped ZnO nanowires. The samples are prepared on RF-sputtered ZnO seed layers by using a simple hydrothermal method with sodium nitrate, zinc nitrate, and hexamethylenetetramine (HMTA) in an aqueous solution at low temperature (<90 °C). At first, the crystal structure of the c-axis orientation was analyzed using X-ray diffraction patterns. These exhibited a slight shift to lower values of the diffraction angle with decreasing Na mole concentration. To further verify the p-type behaviors of Na-doped ZnO nanowires, cryo-photoluminescence was employed at temperatures ranging from 10 to 300 K, corresponding to the clear appearance of excitons bound to a deeper acceptor (A_D⁰X) and its LO phonon replicas.     

Sol-gel synthesis of sub-50 nm ZnO nanowires on pulse laser deposited ZnO thin films

A simple synthesis route to high-quality sub-50 nm ZnO nanowires is reported, utilizing ZnO thin films grown by pulse laser deposition (PLD) as seed layers. Depending upon the PLD growth conditions, the surface morphology of the ZnO nanowires on ZnO film was distinctively different whereas the diameters were almost the same. With the increase of the concentration of zinc nitrate/methenamine solution from 0.002 to 0.02 M, the average diameter of the ZnO nanowire increased but remained sub-50 nm. The grown ZnO nanowires showed a high crystallinity with a low defect density confirmed by a sharp photoluminescence spectrum.     

紫外吸收光谱法研究ZnO/碳纳米管复合材料催化降解偶氮染料

以Zn(NO₃)₂和酸化多壁碳纳米管为原料采用水热法合成了ZnO/碳纳米管复合材料,产物经X射线粉末衍射(XRD)和透射电子显微镜(TEM)表征,表明六方晶相的ZnO颗粒大小约为28 nm。紫外吸收光谱研究表明, 该复合材料在太阳光照下具有较高的光催化降解偶氮染料的活性。探究了光照时间﹑催化剂用量﹑染料浓度以及不同的染料结构等因素对催化效率的影响,结果表明随光照时间的延长,偶氮染料位于400 nm的特征峰强度逐渐减弱,且偶氮染料的降解呈准一级的反应。该复合材料对三种染料：酸性橙﹑酸性大红﹑酸性嫩黄的溶液都具有较好的降解能力,反应速率分别为0.09,0.28,0.22 mg· L-1·min-1,此光催化降解速率的差异是由于偶氮染料分子中有机官能团的不同所造成。当选用最优条件时,该复合材料可以迅速降解染料,且经过五次循环后,其催化效率仍高于50％。     

Effect of Mn doping on the microstructures and photoluminescence properties of CBD derived ZnO nanorods

Mn-doped ZnO nanorods were synthesized from aqueous solutions of zinc nitrate hexahydrate, manganese nitrate and methenamine by the chemical solution deposition method (CBD). Their microstructures, morphologies and optical properties were studied in detail. X-ray diffraction (XRD) results illustrated that all the diffraction peaks can be indexed to ZnO with the hexagonal wurtzite structure. Scanning electron microscope (SEM) results showed that the average diameter of Mn-doped ZnO nanorods was larger than that of the undoped one. Photoluminescence (PL) spectra indicated that manganese doping suppressed the emission intensity and caused the blue shift of UV emission position compared with the undoped ZnO nanorods. In the Raman spectrum of Mn-doped ZnO nanorods, an additional mode at about 525 cm⁻¹ appeared which was significantly enhanced and broadened with the increase of Mn doping concentration.     

Ni-doped zinc oxide nanocombs and phonon spectra properties

Ni-doped comb-like zinc oxide (ZnO) semiconductor nanostructures have been synthesized by a simple chemical vapor-deposition method (CVD) at relatively low temperature. The as-synthesized ZnO nanocombs consist of an array of very uniform, perfectly aligned, evenly spaced and long single-crystalline nanobelts (nanowires) with periods of about several tens of nanometers. X-ray diffraction and Raman spectra results provide the evidence that Ni is incorporated into the ZnO lattice at Zn site. Photoluminescence spectra of the as-obtained samples have been detected, in which the incorporation of donor Ni leads to the increases of the ultraviolet emission intensity and a blueshift of emission peak. This technique can be used to prepare other semiconductors and morphology-controlled doping nanocombs.     

球形ZnO的微波辅助合成及光谱研究

以Zn(NO₃)₂为原料,CO(NH₂)2为沉淀剂,加入表面活性剂甲基丙烯酸甲酯,经微波加热制备获得颗粒尺度为亚微米级的ZnO.采用X射线衍射(XRD)、扫描电镜(SEM)研究了制备条件对样品结构、形貌的作用;PL方法讨论了其荧光发光光谱.发现采用微波加热法获得的ZnO呈球形,尺度在100nm左右,相比较,传统高温加热获得的样品呈c轴优先取向的短棒状.讨论认为,由于微波辅助方法能够使前驱物温度梯度变化小,表面Zn²⁺,O²⁺析出均匀,因此有助于获得球形的粉末粒子.     

A study on morphology control and optical properties of ZnO nanorods synthesized by microwave heating

In this study, we present morphology control investigations on zinc oxide (ZnO) nanorods synthesized by microwave heating of a mixture of zinc nitrate hexahydrate and hexamethylenetetramine (HMTA) precursors in deionized water (DI water). To study the morphology and structural variations of the obtained ZnO nanorods in different molar ratio of zinc nitrate hexahydrate to HMTA, X-ray diffraction (XRD), scanning electron microscopy (SEM) images, Raman scattering, and photoluminescence (PL) spectroscopy were measured. XRD and SEM images are utilized to examine the crystalline quality as well as the morphological properties of the ZnO nanorods. It is found that morphology control can be achieved by simply adjusting the reactant concentrations and the molar ratio of zinc nitrate hexahydrate to HMTA. Raman scattering and PL spectroscopy measurements were demonstrated to study the size- and shape-dependent optical response of the ZnO nanorods. The Raman scattering result shows that the intensity of LO mode at around 576 cm^?1 decreases with the increase in the molar ratio of zinc nitrate hexahydrate to HMTA, indicating the reduction of defect concentrations in the synthesized ZnO nanorods. Room temperature PL spectrum of the synthesized ZnO nanorods reveals an ultraviolet (UV) emission peak and a broad visible emission. An enhancement of UV emission appears in the PL spectra as the molar ratio of zinc nitrate hexahydrate to HMTA increases, indicating that the defect concentration of the synthesized ZnO nanorods can be reduced by increasing the molar ratio.     

Synthesis,characterization, and effect of concentration variation on metal oxide nanostructures

Zinc oxide (ZnO) has been successfully synthesized by an anodization method, and it has been fabricated through anodization method with different concentration of zinc nitrate. The element composition, surface inspection, structural, and morphological features of the products are depend on the concentration of zinc nitrate. At lower concentration (0.01M), SEM image shows ZnO nanowires with average width of about 30 and 50 nm. With increase in the concentration of zinc nitrate from 0.01 to 0.05 M, the nanowires change into the nanosheets with average width of about 0.5 and 1.5 μm. For samples (0.1 M) exhibits nanodots, morphology was composed of hundreds of nanosheets with thickness is about 90 nm on average. When the concentration increases to 0.2 M, the nanodots trench became bigger with diameter about 1.2–2.0 μm. When the concentration of zinc nitrate is 0.3 M, the average diameter of nanodots is about 2–2.5 μm. The trench of nanosheets becomes thinner and shorter, but the number of nanosheets increases with diameter 20–50 nm. The formation of nanowires, nanodots, and nanosheets nanostructures is also believed to result from actions on concentration of zinc nitrate as an aquas medium. The EDX result shows the atomic percentage (at.%) of the oxygen increased when the concentration of zinc nitrate increased. The pattern of EDX indicates that the ZnO nanostructures are composed of Zn, O, and Al. They represent Al composition in the sample because the anode using the aluminum rod during experiment.     

Structures of nanowires with Zn-ZnO:CuO junctions for detecting ethanol vapors

The synthesis of ZnO-ZnO:CuO structures in the form of overlapping layers of nanowires of pure and copper oxide-doped zinc oxide is described. These structures are tested as ethanol vapor sensors. The following two-stage method is used to form ZnO:CuO nanowires. At the first stage, ZnO nanowires are formed by chemical deposition from a solution. At the second stage, arrays of ZnO nanowires are coated with a copper-containing layer. The CuO content on the surface of ZnO nanowires is changed by varying the number of immersions in a Cu(NO₃)₂ solution. The formed structures are studied by scanning electron microscopy, X-ray diffraction, and energy dispersive X-ray analysis. The interaction of the grown sensor structures with ethanol vapors is analyzed by measuring the potential difference between the layers of pure zinc oxide and copper oxide-modified zinc oxide in the temperature range 190–300°C. The response of the sensor is investigated at various ethanol vapor concentrations and detection temperatures.     

Evidences dominating the formation of ZnO nanostructures via in-situ study in an environmental scanning electron microscope

In order to well understand the growth mechanism of the diverse morphology of the ZnO nanostructures, in situ analysis of the formation of different ZnO nanostructures, such as nanowires, nanocombs, and nanosheets, has been conducted in an environmental scanning electron microscope (ESEM). It is found that both nanocombs and nanosheets grew in two-stage heating processes on parent nanowires. The difference is that the nanocombs were synthesized in extremely high pressure of zinc vapor via a self-catalyzed vapor-liquid-solid process, while the ZnO nanosheets were grown in relatively low pressure of zinc vapor. All the growth processes were revealed in real time imaging. It is demonstrated that the change in the growth environments can influence the thickness of the ZnO polycrystalline surface of the zinc powder, which alters the pressure of the zinc vapor and in turn determines the morphology of the final nanostructures.     

Large-scale and catalyst-free synthesis of zinc nanotubes and nanowires

Metallic zinc one-dimensional materials including nanotubes and nanowires were synthesized on a large scale by a simple method. The process was both catalyst and template free. The resulting Zn nanotubes and Zn nanowires were characterized and confirmed by means of X-ray diffraction, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, and transmission electron microscopy. The growth of Zn nanotubes was reported for the first time.     

ZnO nanostructures with different morphologies and their field emission properties

Zinc oxide (ZnO) products with the morphologies of balls, nunchakus and belts have been synthesized from aqueous solutions by adjusting the reagent concentration and reaction time. The X-ray diffraction (XRD) peaks of the products were indexed to ZnO materials, but exhibited different relative intensities for the (0 0 2) diffraction peak. Field emission (FE) measurements showed that the turn-on and threshold field for the ZnO nanonunchakus were 3.01 ± 0.005 and 5.47 ± 0.005, 3.71 ± 0.005 and 6.43 ± 0.005 V/μm, respectively, for the ZnO nanobelts, revealing that the products have comparable FE properties with those of the reported ZnO nanowires and carbon nanotubes (CNTs).     

硫掺杂ZnO纳米线的电化学制备及发光特性

"采用电场辅助电化学沉积法,利用阳极氧化铝模板模板制备了高度择优取向的硫掺杂ZnO单晶纳米线．X射线衍射仪、隧道电子显微镜、选取电子衍射对所得样品的结构、形貌分析表明,所得纳米线是沿(101)择优取向的六方纤锌矿结构单晶纳米线,长约几十微米、平均直径约70 nm. X射线光电子能谱对化学组成的分析进一步证实掺杂硫原子的存在．用荧光光谱仪(PL)对S掺杂前后的ZnO纳米线进行光学特性测量发现,S掺杂较大地改变了ZnO纳米线的发光性质．在PL谱中,除了有典型的ZnO纳米线在378、392 nm处的强紫外发光峰     

Catalyst-free MOCVD growth of aligned ZnO nanotip arrays on silicon substrate with controlled tip shape

Quasi-aligned zinc oxide nanotip arrays have been grown by MOCVD without using catalyst. The tip shape was controlled systematically by varying the gas flow rate, demonstrating a technique for growing tip arrays of ZnO on silicon. This technology can be large-scale on the wafer level and it has the potential to be directly integrated with clean room silicon technology. The diameter of these ZnO nanowires or nanotips could be controlled by the varying of source flow rate, providing a simple but unique way of fabricating ZnO nanotip arrays for application in field emission and nanogenerators.     

六角锥状ZnO纳米结构的生长机理、结构及光学性能(英文)

利用醋酸锌[Zn(CH3COO)2·2H2O]和六次甲基四胺(C6H12N4)以一定比例配置成反应溶液,通过水热合成法制备了六角锥状ZnO纳米结构。同时,使用了扫描电子显微镜(SEM)、X射线衍射和选区电子衍射(SAED),对样品的形貌与结构进行了分析。结果表明,样品形貌成六角锥状结构,并且在[002]方向择优生长。通过对样品的光学性能测试,由PL光谱分析可知,样品在379nm处有一个较强的紫外发光峰,并且在可见光区域产生了一些较弱的可见光发射峰,表明制备的六角锥状ZnO纳米结构的晶体质量不是很好。除此之外,对六角锥状ZnO的生长机理也进行了讨论。     

One step solution synthesis towards ultra-thin and uniform single-crystalline ZnO nanowires

Bundles of high-aspect-ratio single-crystalline ZnO nanowires were fabricated by a single-step mild hydrothermal condition without the use of a seeding layer, thus eliminating an annealing step. The growth yields nanowires of high aspect ratio (>200). No significant lateral growth takes place with prolonged reaction time. The morphology and aspect ratio of the final products depend on the concentration of the precursors; a highly water-soluble tetradentate cyclic tertiary amine and zinc nitrate system. The nanowires grow along the [0001] direction and have an average width of <10 nm and a narrow distribution of ±5 nm. Photoluminescence measurements of the ultra-thin nanowires exhibit a strong band-edge emission at room temperature. The highly crystalline sub tens of nanometer scale diameter nanowires can, in combination, be a good one-dimensional candidate to study optical and electronic properties. PACS 81.16.Be; 81.07.Bc     

Effect of substrates and anions of zinc salts on the morphology of ZnO nanostructures

The ZnO nanostructures were hydrothermally synthesized on glass and Al substrates, respectively, using zinc chloride, zinc nitrate, and zinc acetate as precursor. The as-prepared products were characterized by scanning electron microscopy (SEM) and X-ray powder diffraction (XRD). Different ZnO nanostructures were obtained, such as nanorods, nanosheets, flower-like nanostructures and so on. The effects of the substrates and anions of zinc salts on the morphologies of the resulting products have been investigated.     

Non-catalytic growth of high aspect-ratio ZnO nanowires by thermal evaporation

High-density and high aspect-ratio ZnO nanowires were grown on Si(100) substrates by the thermal evaporation of metallic zinc powder without the use of metal catalysts or additives. The as-grown nanowires had diameters in the range of 60-100 nm with lengths 5-15 μm. Detailed structural characterization indicated that the obtained nanowires are single-crystalline with a perfect hexagonal facet and surfaces. The room temperature PL spectrum exhibited strong UV emission, affirming that the as-grown products have good optical properties. The possible growth mechanism for the formation of hexagonal-faceted and perfect surface ZnO nanowires is also discussed.     

In situ study of epitaxial growth of ZnO nanowires at the junctions of nanowall networks on zinc particles

The authors show the real-time growth of ZnO nanowalls and nanowires on zinc particles via in situ observation in an environmental scanning electron microscopy. It was observed that a ZnO polycrystalline film is first deposited on zinc particles. The nanowires started to grow when the nanowalls had just formed and they grew epitaxially on the junctions of the nanowalls. The nanowalls and the nanowires grew together until the source of zinc was exhausted. The vapor–solid mechanism is deemed to be the growth mechanism as it quantitatively accounts for the growth speed of the nanowalls and nanowires observed in the experiment. Cathodoluminescence reveals that the growth at low zinc concentration leads to blue emission from defects, which may be zinc vacancies.