Surface enhanced Raman scattering and photoluminescence properties of catalytic grown ZnO nanostructures

Sword-like (diameter ranging from 40 nm to 300 nm) and needle-like zinc oxide (ZnO) nanostructures (average tip diameter ∼40 nm) were synthesized on annealed silver template over silicon substrate and directly on silicon wafer, respectively via thermal evaporation of metallic zinc followed by a thermal annealing in air. The surface morphology, microstructure, chemical analysis and optical properties of the grown samples were investigated by field emission scanning electron microscopy, X-ray diffraction, energy dispersive X-ray analysis, room temperature photoluminescence and Raman spectroscopy. The sword-like ZnO nanostructures grown on annealed silver template are of high optical quality compared to needle-like ZnO nanorods for UV emission and show enhanced Raman scattering.     

Defect-controlled growth of ZnO nanostructures using its different zinc precursors and their application for effective photodegradation

Various zinc precursors, such as zinc acetate, zinc nitrate, zinc sulfate, and zinc chloride, have been used to control the formation of zinc oxide (ZnO) nanostructures onto aluminum substrate by chemical means. FESEM images of the ZnO nanostructures showed the formation of different morphologies, such as flakes, nanowalls, nanopetals, and nanodisks, when the nanostructures were synthesized using zinc acetate, zinc nitrate, zinc sulfate, and zinc chloride precursors, respectively. The TEM image of disk-like ZnO nanostructures formed using zinc chloride as a precursor revealed hexagonally shaped particles with an average diameter of 0.5 μm. Room-temperature photoluminescence (PL) spectra revealed a large quantity of surface oxygen defects in ZnO nanodisks grown from zinc chloride compared with those using other precursors. Furthermore, the ZnO nanostructures were evaluated for photocatalytic activity under ultraviolet (UV) light illumination. Nanostructures having a disk-like shape exhibited the highest photocatalytic performance (k = 0.027 min⁻¹) for all the ZnO nanostructures studied. Improved photocatalytic activity of ZnO nanodisks was attributed to their large specific surface area (4.83 m² g⁻¹), surface oxygen defects, and super-hydrophilic nature of their surface, which is particularly suitable for dye adsorption.     

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.     

Evolution of ZnO nanostructures by non-catalytic growth process on steel alloy substrate: Structural and optical properties

Various kind of ZnO nanostructures such as nanowires, nanonails and nanocombs were synthesized by the thermal evaporation process onto the steel alloy substrate without the use of metal catalyst or any additives. Detailed structural characterizations indicated that the grown products possess a single crystallinity with the wurtzite hexagonal crystal structure. Presence of strong optical-phonon E₂ mode, in all the cases, presents the good crystallinity with the wurtzite hexagonal phase for the deposited products. Additionally, appearance of dominated, strong and sharp UV emission in the room-temperature photoluminescence spectra confirmed the good optical properties for the grown nanostructures. A vapor–solid growth mechanism has been proposed for the growth of the nanostructures.     

Large-scale synthesis of ZnO microhollowspheres and their optical properties

ZnO microhollowspheres (MHs) were synthesized by evaporation of a mixture of zinc, graphite, and zinc oxide powders. The microstructures of the resultant MHs have been characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED), X-ray diffraction, and photoluminescence (PL). The PL results indicated that the green emission peak at 510 nm of the MHs was higher and broader than that of the nanocombs, which was due to oxygen vacancies formed in the MHs. In addition, the mechanism of ZnO MHs was discussed in detail.     

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.     

Photoluminescence of ZnO nanowires grown on sapphire (1 1 2¯ 0) substrates

ZnO nanowires were fabricated on c-plane (0 0 0 1), a-plane (1 1 2¯ 0) sapphire, and boron doped p-type (1 0 0) Si substrates in vacuum furnace by simple physical vapor deposition. Room temperature photoluminescence spectra of the nanowires show the near band-edge emission and the deep-level green light emission. The ZnO nanowires formed on sapphire (1 1 2¯ 0) substrates exhibited enhancement on optical properties and better crystalline structures than those of nanowires grown on other substrates. The formation mechanism and the effect of substrate direction on structural and optical properties of the nanowires are discussed.     

Effect of substrate temperature on the growth and luminescence properties of ZnO nanostructures

ZnO nanowires, nanorods and nanoribbons have been prepared by heating a mixture of ZnO/graphite powders using the thermal evaporation and vapor transport on Si(1 0 0) substrates without any catalyst. The nanostructures are grown as a function of substrate temperature ranging from 900 to 1300 K. These nanostructures are of the size 100–300 nm in diameter or width and several tens of micrometers in length. We studied the influence of the substrate temperature on the luminescent properties of these nanostructures. We observed a strong relationship between the substrate temperature and the green emission band in ZnO, i.e., the photoluminescence study revealed that the green emission peak of the ZnO nanostructures is suppressed relative to the band edge emission when the substrate temperature is decreased from 1300 to 900 K.     

Enhanced optical and field emission properties of CTAB-assisted hydrothermal grown ZnO nanorods

We have developed a simple N-cetyl-N,N,N-trimethyl ammonium bromide (CTAB)-assisted hydrothermal route for the production of ZnO one-dimensional (1D) nanostructures on zinc foil at reaction temperature of 160 °C. With the increase of CTAB concentration, the one-dimensional structures change from microrod to a mixture of nano- and microrod and finally to nanorods. X-ray diffraction studies confirmed the proper phase formation of the grown nanostructures. The room temperature photoluminescence spectra showed that ZnO nanostructures prepared with increased CTAB concentration exhibited enhanced band edge UV emission and also blue shift of the emission peak. All the samples show no defect related green emission. Field emission property of the 1D structures has been investigated in detail. By tuning the CTAB concentration, the field emission property was optimized. The nanorods synthesized with high CTAB showed turn-on and threshold fields of 3.2 and 5 V/μm, respectively, which are comparable to the values for vapour phase synthesized high field emitting ZnO nanostructures.     

Photoluminescence behavior of ZnO nanorods produced by eclipse PLD from a Zn metal target

In this work, arrays of one-dimensional ZnO nanostructures were deposited on c-axis sapphire by standard and eclipse pulsed laser deposition (EPLD) using a metallic Zn target. One reference sample was grown by standard PLD and nine were grown by EPLD using a 16 by 16 mm² square shadow mask. Three shadow mask positions were used, with three depositions at varying oxygen pressures for each mask position. The oxygen partial pressure was between 100 and 200 mTorr for all growth procedures with a substrate temperature of 600 C.SEM reveals that arrays of nanorods are formed when growing by standard PLD. When grown by EPLD the rods tend to clump together with ordering on the micron scale. Low temperature photoluminescence was carried out as a function of position over several of the samples with 1 or 2 mm spacing. In general, it was found that the luminescence intensity is maximum in the center of the samples and falls off toward the edges while the shape stays roughly the same. Free exciton emission was resolved in most samples along with several other emission peaks from donor-bound excitons. The integrated PL intensity for all the EPLD samples is an order of magnitude higher than for the standard PLD sample. Linewidths are significantly reduced as well. Hence, the EPLD grown samples have superior optical quality and this growth technique shows promise for growth of high quality ZnO nanostructures.     

Structural and catalytic properties of ZnO and Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanostructures loaded with metal nanoparticles

Nanostructured zinc oxide (ZnO) nanobelts and aluminum oxide (Al₂O₃) nanoribbons have been grown successfully from the vapor phase. XRD results confirmed the purity and the high quality of the formed crystalline materials. TEM images showed that ZnO nanostructures grew in the commonly known tetrapod structure with nanobelts separated from the tetrapods with an average width range of 10–30 nm and a length of about 500 nm. Al₂O₃ nanostructures grew in the form of nanoribbons with an average width range of 20–30 nm and a length of up to 1 μm. The catalytic oxidation of CO gas into CO₂ gas over the synthesized nanostructures is also reported. Higher catalytic activity was observed for Pd nanoparticles loaded on the ZnO nanobelts (100% conversion at 270 °C) and Al₂O₃ nanoribbons (100% conversion at 250 °C). The catalytic activity increased in the order Cu < Co < Au < Pd for the metal-loaded nanostructures. The preparation methods could be applied for the synthesis of novel nanostructures of various materials with novel properties resulting from the different shapes and morphologies.     

Effect of sputtered films on morphology of vertical aligned ZnO nanowires

Vertical aligned ZnO nanowires were grown by MOCVD technique on silicon substrate using ZnO and AlN thin films as seed layers. The shape of nanostructures was greatly influenced by the under laying surface. Vertical nanopencils were observed on ZnO/Si, whereas the nanowires on both sapphire and AlN/Si substrate have the similar aspect ratio. XRD patterns suggest that the nanostructures have good crystallinity. High-resolution transmission electron microscopy (HRTEM) confirmed the single crystalline growth of the ZnO nanowires along [0 0 1] direction. Room-temperature photoluminescence (PL) spectra of ZnO nanowires on AlN/Si clearly show a band-edge luminescence accompanied with a visible emission. More interestingly, no visible emission for the nanopencils on ZnO/Si substrates, were observed.     

Spectromicroscopy and photoluminescence analysis of prickly ZnO nanostructures

Prickly nanostructures of ZnO have been obtained by the hydrothermal synthesis technique. Structures are analyzed using X-ray diffraction, electron microscopy as well as photoelectron spectromicroscopy. The analysis revealed that the prickly ZnO nanostructures are highly crystalline with hexagonal wurtzite phase and possess homogeneous compositional structures. They are assembled of nanothread structures with narrow thickness distribution around 30 nm. The valence band analysis revealed that there are peaks due to the bonding, nonbonding, and antibonding of the zinc and oxygen orbitals. These nanostructures exhibit intense near band-edge emission. Photoluminescence analysis showed that the structures also give defect-induced blue emission along with green emission.     

The effect of substrate surface roughness on ZnO nanostructures growth

The ZnO nanowires have been synthesized using vapor-liquid-solid (VLS) process on Au catalyst thin film deposited on different substrates including Si(1 0 0), epi-Si(1 0 0), quartz and alumina. The influence of surface roughness of different substrates and two different environments (Ar + H₂ and N₂) on formation of ZnO nanostructures was investigated. According to AFM observations, the degree of surface roughness of the different substrates is an important factor to form Au islands for growing ZnO nanostructures (nanowires and nanobelts) with different diameters and lengths. Si substrate (without epi-taxy layer) was found that is the best substrate among Si (with epi-taxy layer), alumina and quartz, for the growth of ZnO nanowires with the uniformly small diameter. Scanning electron microscopy (SEM) reveals that different nanostructures including nanobelts, nanowires and microplates have been synthesized depending on types of substrates and gas flow. Observation by transmission electron microscopy (TEM) reveals that the nanostructures are grown by VLS mechanism. The field emission properties of ZnO nanowires grown on the Si(1 0 0) substrate, in various vacuum gaps, were characterized in a UHV chamber at room temperature. Field emission (FE) characterization shows that the turn-on field and the field enhancement factor (β) decrease and increases, respectively, when the vacuum gap (d) increase from 100 to 300 μm. The turn-on emission field and the enhancement factor of ZnO nanowires are found 10 V/μm and 1183 at the vacuum gap of 300 μm.     

Fabrication and characterization of ZnO and ZnMgO nanostructures grown using a ZnO/ZnMgO compound as the source material

ZnO and ZnMgO nanostructures were synthesized on Si (1 0 0) substrates with the assistance of a gold catalyst, using a thermal evaporation method with a ZnO/ZnMgO compound as the source material. The substrates were placed in different temperature zones. ZnO nanostructures with different morphologies and different compounds were obtained at different substrate temperatures. Nanostructures with nanorods and nanosheets morphologies formed in the low and high temperature zones, respectively. The nanorods grown in the low temperature zone had two phases, hexagonal and cubic. Energy dispersive X-ray (EDX) results showed that the nanorods with a cubic shape contained more Mg in comparison to the nanowires with a hexagonal shape. We found that the substrate temperature and the gold catalyst were two key factors for the doping of Mg and the formation of nanostructures with different morphologies. Room temperature photoluminescence spectroscopy showed a blue-shift for the nanostructures with the nanorods morphology. This shift could be attributed to Mg effects that were detected in the nanorods.     

不同条件制备的ZnO纳米梳结构及其性能研究

采用热蒸发法通过改变衬底放置条件在Si(111)衬底上制备出了ZnO纳米梳结构.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、分光光度计、场发射装置对样品的结构、形貌、光致发光光谱及场发射特性进行了分析.XRD结果表明衬底水平放置(A)和衬底竖直放置(B)制备出的样品均属于多晶六角纤锌矿结构.SEM结果表明两种衬底放置条件下的样品均为纳米梳状结构,改变衬底放置条件ZnO纳米梳的尺寸和形貌有明显改变,其中竖直放置衬底的样品B纳米尺寸较小且比较均匀.室温下的光致发光光谱表明样品B的紫外峰较样品A出现了蓝移,此外样品B的紫外峰强和可见光峰强比值较大,说明此样品的结晶质量较好.场发射特性测试结果表明两个样品的场发射都是通过电子隧道效应进行的,且样品B的场发射性能优于样品A.     

Quasi One-dimensional ZnO Nanostructures Fabricated without Catalyst at Lower Temperature

One- or quasi one-dimensional zinc oxide nanostructures possess plenty of morphologies. Only by controlling the gas flow rates, and partial pressures of argon, oxygen and zinc vapor, can various types of high-quality ZnO nanomaterials (such as wires, belts, arrays, saws or combs, tetraleg rods, nails, and pins) be synthesized through pure zinc powder evaporation without a catalyst at the temperature range of 600–700°C. In this study, deposited nanostructures were characterized by means of scanning electron microscopy, X-ray diffraction and high-resolution transmission electron microscopy. The authors propose and discuss the growth mechanisms of various ZnO. In addition, properties of room temperature photoluminescence and field emission of several typical ZnO nanostructures are measured and investigated.     

ZnO双晶纳米梳

以纯锌粉作为原料，用气相输运法在650℃合成了ZnO双晶纳米梳结构，并用高分辨透射电镜 及选区电子衍射等方法对其微观结构进行了研究.结果表明双晶纳米梳两侧的齿针呈一定角 度以孪晶方式对称生长，其孪晶面为(1 1-3)，两侧齿针都垂直于孪晶界，其直径均匀分布 在50—100nm，每一侧梳背和齿针的生长方向均分别为〈0 1-1 0〉和〈0 0 0 1〉.由于孪晶 造成了晶体取向的变化，基于镜像对称的特征，ZnO双晶纳米梳两侧梳背的外缘可以均为Zn 终结的(0 0 0 1)面，因此都可以发生自催化作用并形成分支结构，这种纳米结构的生长过 程与王中林等人提出的极性生长机理相符合. 关键词： 氧化锌 纳米梳 双晶 极性生长     

Field emission and photoluminescence of ZnO nanocombs

Three kinds of new comb-shape nanostructures of ZnO have been grown on single silicon substrates without catalyst-assisted thermal evaporation of Zn and active carbon powders. The morphology and structure of the prepared nanorods are determined on the basis of field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and x-ray diffraction (XRD). The growth mechanism of the ZnO nanocombs can be explained on the basis of the vapor–solid (VS) processes. In nanocombs 1 and nanocombs 2, the comb teeth grow along [0001] and the comb stem grows along [ $01\overline{1}0$ ], while in nanocombs 3, nanoteeth grow along [ $01\overline{1}0$ ] and stem grows along [0001]. The photoluminescence and field-emission properties of ZnO nanocombs 1–3 have been investigated. The turn-on electric field of ZnO nanocombs 1–3, which is defined as the field required to producing a current density of 10 μA/cm², is 9, 7.7 and 7.1 V/μm, respectively. The field-emission performance relies not only on the tip’s radius of curvature and field enhancement factor, but also on the factor evaluating the degree of the screening effect.     

Influence of solution parameters for the fast growth of ZnO nanostructures by laser-induced chemical liquid deposition

ZnO nanorods, nanoneedles, nanoparticles, and nanoballs were synthesized on fused quartz substrates upon irradiation of a droplet of methanolic zinc acetate dihydrate solution by an infrared (IR) continuous wave CO₂ laser for a few seconds. The addition of monoethanolamine and water to the solution improved the alignment of the nanorods and had a significant effect on the volume and morphology of the deposits. An increase of the zinc acetate concentration was found to lead to an increase of the thickness and area covered by the initial ZnO seed layer on which the nanostructures grew. By investigating the crystal structure of the deposits using X-ray and electron diffraction, we were able to show that the nanorods grow along the c axis with a high crystalline quality. Raman and photoluminescence spectroscopy confirmed the high quality of the grown ZnO nanostructures. As a matter of fact, their photoluminescence spectra are dominated by an intense UV emission around 390 nm.