Solution-free and catalyst-free synthesis of ZnO-based nanostructured TCOs by PED and vapor phase growth techniques

Zinc oxide (ZnO) is one of the most promising materials for realizing three-dimensional (3D) nanostructured transparent conducting oxides (TCOs) on large scale, because it is cheap, it can be modified with large concentrations of trivalent elements (such Al, Ga or In) and it is characterized by good electron mobility, wide bandgap and visible-range transparency. But, above all, it can be easily obtained in the form of different nanostructures with a large number of growth techniques. A solution-free and catalyst-free approach has been explored here by the vapor phase synthesis of vertically aligned ZnO nanorods on ZnO:Al (AZO) films grown by pulsed electron deposition (PED). The obtained nanostructured TCOs resulted to be homogeneous on large areas and easily patternable by means of mechanical masks. The morphology, crystalline structure, electrical and optical properties of the obtained samples have been characterized in depth. The possible use of such a nanostructured TCO in excitonic (e.g.?DSSC) or low-reflectivity traditional solar cells is discussed.     

Thickness optimized nanocrystalline ZnO-coated silicon nanowires for cold cathode application

Silicon nanowire is an important material for the potential use as a cold cathode, but there are some bottlenecks like oxidation of the surface during field emission thereby degradation of its performance. To compete with carbon based nanostructures in this field the performance of Si nanowires as field emitter should be improved. Here, we report a simple technique for the significant improvement of field emission properties of Si nanowires by ZnO nanoparticle coating. Boron-doped p-type Si wafers were chemically etched to synthesize vertically aligned silicon nanowires and they were coated with different thicknesses of ZnO layer by radio frequency magnetron sputtering technique. The nanostructured thin films were studied by X-ray photoelectron spectroscopy for compositional and valence states information while their morphological information was obtained by a field emission scanning electron microscope and a high resolution transmission electron microscope. The field assisted electron emission performance of Si nanowires significantly improved for the thickness optimized ZnO coating. The photoluminescence spectra showed a peak at ~558 nm assigned to surface defect states of ZnO and the field emission from Si nanowires coated with ZnO for different times were correlated with the surface defect structures. The mechanism of such improvement is also discussed.     

Structural and photoluminescence characterization of vertically aligned multiwalled carbon nanotubes coated with ZnO by magnetron sputtering

Zinc oxide (ZnO) nanostructures are very attractive in various optoelectronic applications such as light emitting devices. A fabrication process of these ZnO nanostructures which gives a good crystalline quality and being compatible with that of micro-fabrication has significant importance for practical application. In this work ZnO films with different thicknesses were deposited by RF-sputtering on vertically aligned multiwalled carbon nanotube (MWCNTs) template in order to obtain ZnO nanorods. The obtained hybrid structures (ZnO/MWCNTs) were characterized by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and time resolved photoluminescence spectroscopy (PL). Results show that the ZnO/MWCNTs have a nanorod structure like morphology with a good crystalline quality of the deposited ZnO on the MWCNTs. PL measurements reveal an enhancement of the band edge signal of ZnO/MWCNTs which is three times of magnitude higher compared to the ZnO film deposited on silicon. Moreover, the intensity enhancement varies as function of the ZnO thickness. Such hybrid structures are promising for optoelectronic application, such as blue-violet sources.     

Combination of surface texturing and nanostructure coating for reduction of light reflection in ZnO/Si heterojunction thin film solar cell

In this study, we report a single heterojunction solar cell based on n-type zinc oxide/p-type silicon. Three different solar cells were fabricated based on ZnO thin film on Si substrate, ZnO nanorods on Si substrate, and ZnO nanorods on micro-pyramidal structure of Si substrate. The comparison between these three kinds of solar cells was studied. Pyramidal structure of silicon was fabricated using chemical etching technique of p-type Si (100). The chemical solution consists of NaOH, isopropyl alcohol and hydrazine hydrate. The results showed that Si micro-pyramids can enhance optical absorption of Si substrates by increasing surface area and entrapping of incident light. For fabrication of uniform ZnO nanorods, a seed layer of ZnO was deposited on Si substrates via radio frequency magnetron sputtering technique. This layer can be used as an active n-type material in heterojunction solar cells as well. ZnO nanostructures can increase light absorption due to their high specific surface area. The combination of ZnO nanorods and Si micro-pyramids can enhance light trapping effect and increase the efficiency of solar cells. The structural and morphology of samples were studied using field-emission scanning electron microscopy, atomic force microscopy and X-ray diffractometry while the optical properties were investigated using photoluminescence and reflectance spectrometry. The efficiency and fill factor of solar cells were obtained from current–voltage characteristics using a solar simulator and a source-meter. The results showed that the efficiency of solar cell based on nanostructures of ZnO/micropyramids of Si is highly increased due to high anti-reflective behavior of this sample.     

Fabrication and optical property of vertically-aligned ZnO/Si double nanostructures

We fabricated the vertically-aligned zinc oxide (ZnO)/silicon (Si) double nanostructures by simple processes using the metal-assisted chemical etching and a subsequent hydrothermal synthesis, and their optical property was investigated. For efficient antireflection characteristics, Si nanostructures were optimized by changing the size of the dewetted silver (Ag) at different etching times. The thermally dewetted Ag nanoparticles or semi-island films as metal catalysts were controlled by the Ag film thickness and dewetting temperature. To form the ZnO/Si double nanostructures, ZnO nanorods were synthesized on the chemically etched Si nanostructures using a thin sputtered ZnO seed layer. The grown ZnO nanorod arrays (NRAs) exhibited good crystallinity and further reduced the surface reflection due to their antireflective property. The ZnO/Si double nanostructures showed the increased peak intensity of X-ray diffraction as well as the significantly reduced solar weight reflectance of 6.05% compared to 11.71% in the ZnO NRAs on the flat Si substrate. Also, the enhanced antireflection property of ZnO/Si double nanostructures was theoretically analyzed by performing the rigorous coupled wave analysis simulation.     

Growth of aligned hexagonal ZnO nanorods on FTO substrate for dye-sensitized solar cells (DSSCs) application

This article reports a facile growth of well-crystalline aligned hexagonal ZnO nanorods on fluorine-doped tin-oxide (FTO) substrate via non-catalytic thermal evaporation process. The morphological investigations done by field-emission scanning electron microscope (FESEM) and transmission electron microscopy (TEM) reveal that the grown products are aligned hexagonal ZnO nanorods which are grown in a very high density over the whole substrate surface. The detailed structural properties observed by high-resolution TEM equipped with selected area electron diffraction (SAED) and X-ray diffraction (XRD) pattern confirmed that the synthesized nanorods are well-crystalline possessing wurtzite hexagonal phase and preferentially grown along the c-axis direction. A sharp and strong UV emission at 381 nm in room-temperature photoluminescence (PL) spectrum showed that the as-grown ZnO nanorods possess excellent optical properties. The as-grown nanorods were used as photo-anode for the fabrication of dye-sensitized solar cells (DSSCs) which exhibits an overall light-to-electricity conversion efficiency (ECE) of 0.7% with V(oc) of 0.571 V, J(sc) of 2.02 mA/cm2 and FF of 0.58.     

Stress dependent band gap shift and valence band studies in ZnO nanorods

ZnO nanorods are grown on seedless and ZnO seeded glass substrates using chemical solution method and their structural, morphological, optical and valence band studies have been carried out. On seedless substrate horizontal nanorods are observed whereas for the seeded substrates vertically aligned hollow and solid nanorods grows. X-ray diffraction analysis revealed the presence of tensile stress in the vertical nanorods. Blue shift has been observed in the band gap of the vertical nanorods as compared to the horizontal nanorods which is attributed to the presence of tensile stress in the vertically aligned nanorods. Photoluminescence spectra revealed the dominance of Zinc vacancies (V(Zn)) related defects in the nanorods and oxygen defects are found to be higher in the vertically aligned nanorods as compared to the horizontal nanorods. The difference between the Fermi level and valence band maxima for horizontal, hollow vertical and solid vertical nanorods are found to be approximately 0.56 eV, approximately 0.70 eV and approximately 0.92 eV respectively indicating the possibility of p-type of conduction in the nanorods which has been attributed to presence of V(Zn) defects in the ZnO nanorods.     

Tunable ZnO nanostructures for ethanol sensing

In this study, ZnO nanostructures with different morphologies including nanorods, nanowires, and nanobrushes were synthesized by a simple hydrothermal process without using any structure-directing reagent. The samples were characterized by X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. The influence of the preparation parameters on the morphology of ZnO is discussed. Gas-sensing properties of the materials were investigated. The results reveal that all the prepared nanostructured ZnO powders show high response to ethanol, among which, the three-dimensional nanobrushes show the highest response, demonstrating excellent potentiality for ethanol sensors.     

A comparative study on the NO2 gas sensing properties of ZnO thin films, nanowires and nanorods

ZnO thin films were fabricated using the spin coating method, ZnO nanowires by cathodically induced sol-gel deposition by the means of an anodic aluminum oxide (AAO) template, and ZnO nanorods with the hydrothermal technique. For thin film preparation, a clear, homogeneous and stable ZnO solution was prepared by the sol-gel method using zinc acetate (ZnAc) precursor which was then coated on a glass substrate with a spin coater. Vertically aligned ZnO nanowires which were approximately 65 nm in diameter and 10 μm in length were grown in an AAO template by applying a cathodic voltage in aqueous zinc nitrate solution at room temperature. For fabrication of the ZnO nanorods, the sol-gel ZnO solution was coated on glass substrate by spin coating as a seed layer. Then ZnO nanorods were grown in zinc nitrate and hexamthylenetetramine aqueous solution. The ZnO nanorods are approximately 30 nm in diameter and 500 nm in length. The ZnO thin film, ZnO nanowires and nanorods were characterized by X-ray diffraction (XRD) analysis and scanning electron microscope (SEM). The NO₂ gas sensing properties of ZnO thin films, nanowires and nanorods were investigated in a dark chamber at 200 °C in the concentration range of 100 ppb-10 ppm. It was found that the response times of both ZnO thin films and ZnO nanorods were approximately 30 s, and the sensor response was depended on shape and size of ZnO nanostructures and electrode configurations.     

Controllable synthesis and photoluminescence properties of ZnO nanorod and nanopin arrays

Well-aligned ZnO nanorods and nanopins are synthesized on a silicon substrate using a one-step simple thermal evaporation of a mixture of zinc and zinc acetate powder under controlled conditions. A self-assembled ZnO buffer layer was first obtained on the Si substrate. The structure and morphology of the as-synthesized ZnO nanorod and nanopin arrays are characterized using X-ray diffraction, and scanning and transmission electron microscopies, energy-dispersive X-ray spectroscopy, and photoluminescence spectroscopy. The influence of the background atmosphere on the two ZnO nanostructures has been studied. Two different growth mechanisms are mentioned to interpret the formation of ZnO nanorod and nanopin arrays in our work. The room-temperature PL features the ZnO nanorods exhibit only sharp and strong ultraviolet (UV) emission emissions, which confirms the better crystalline and optical quality than the ZnO nanopins.     

Nanostructural Features and Optical Performance of RF Magnetron Sputtered ZnO Thin Films

Zinc oxide (ZnO) thin films were grown on silicon substrate by RF (radio frequency) magnetron sputtering.Surface topography of these films exhibited a nanostructured granular appearance with the size of individual grains between 50 to 100 nm.Corresponding cross-sectional electron micrographs revealed columnar grains in the form of aggregated nanorods/wires with length of about 500 nm,similar to the thickness of these thin films of ZnO nucleated and grown vertically on the silicon substrate.High resolution l...     

Anions effect on the low temperature growth of ZnO nanostructures

Seed mediated aqueous chemical growth (ACG) route was used for the growth of ZnO nanostructures on Si substrate in four different growth mediums. The growth medium has shown to affect the morphology and the size of the different nanostructures. We observed that the medium containing zinc nitrate anions yields the nanorods, in a medium containing zinc acetate anions nano-candles are obtained. While in a medium containing zinc chloride anions ZnO nano-discs were obtained and in a medium containing zinc sulfate anions nano-flakes are achieved. Growth in these different mediums has also shown effect on the optical emission characteristics of the different ZnO nanostructures.     

Photovoltaic properties of a ZnO nanorod array affected by ethanol and liquid-crystalline porphyrin

A vertically aligned array of ZnO nanorods, fabricated on conductive ITO substrate in aqueous solution, was characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), and UV-visible transmission spectroscopy. Surface photovoltage (SPV) techniques based on a lock-in amplifier and a Kelvin probe were both employed to study the photogenerated charges in the system. The effects of ethanol solvent and a liquid-crystalline porphyrin, [5-(para-dodecyloxy)phenyl-10,15,20-tri-phenyl] porphyrin (DPTPP), on the photovoltage enhancement in the ZnO nanorod array were studied via SPV comparison between different irradiation directions on the system. We demonstrate that the ethanol adsorption could induce the space charge region to expand towards the ZnO/ITO interface. In the absence of ethanol, the ZnO nanorod array with the DPTPP adsorption showed enhanced SPV with reduced attenuation rate of photogenerated charge carriers. We found that the separation of photogenerated charges could be further improved by coating the surface with DPTPP and ethanol together. Furthermore, the SPV spectra patterns of the composite system with opposite incident-light directions reveal that the DPTPP molecules adsorbed just at the surface of ZnO nanorods adopt a more monomeric alignment in contrast to the aggregative state in the DPTPP bulk.     

Growth of aligned ZnO nanorods

Growth of high-density and aligned ZnO nanorods on ZnO film substrate has been demonstrated using vapor-transport of thermally evaporated Zn metal powders followed by condensation. Morphological studies show that the nanorods grow preferentially from a hexagonal ZnO base with a uniform hexagonal structure following three-dimensional island-like growth mechanism. Structural and spectroscopic properties clearly indicate that the nanorods are relatively good and defect-free in quality. These nanorods have potential for technological implications.     

Synthesis of two kinds of ZnO nanostructures by vapor phase method

Radial and quasi-aligned ZnO nanorod arrays were prepared on Si(111) substrates by a simple vapor phase method using Zn and zinc acetate dihydrate (ZA) as the source materials. X-ray diffraction, field emission scanning electron microscopy, Raman scattering and photoluminescence were used to characterize the structural and optical properties of the obtained nanostructures. The growth mechanisms of the two kinds of ZnO nanostructures were discussed based on the growth conditions. The different decomposing rate of the ZA plays an important role in the initial nucleation of ZnO nanorods.     

Synthesis and photoluminescence properties of aligned Zn2GeO4 coated ZnO nanorods and Ge doped ZnO nanocombs

Aligned Zn₂GeO₄ coated ZnO nanorods and Ge doped ZnO nanocombs were synthesized on a silicon substrate by a simple thermal evaporation method. The structure and morphology of the as-synthesized nanostructure were characterized using scanning electron microscopy and transmission electron microscopy. The growth of aligned Zn₂GeO₄ coated ZnO nanorods and Ge doped ZnO nanocombs follows a vapor-solid (VS) process. Photoluminescence properties were also investigated at room temperature. The photoluminescence spectrum reveals the nanostructures have a sharp ultraviolet luminescence peak centered at 382 nm and a broad green luminescence peak centered at about 494 nm.     

两步法实现ZnO纳米结构的集成及光学性质研究

通过简单的两步热蒸发方法成功地实现了ZnO纳米管和纳米棒的集成.SEM结果表明,大量的纳米线以层层生长的机理从约200℃低温Si基片表面生长出来.EDS和XRD结果进一步表明第一步所制备的样品主要是由大量Zn和少量Zn的氧化物组成.第二步所制备样品的SEM和TME图像证实了在高温下以第一步所制备的样品作为第二步的基片,可实现纳米管和纳米棒的集成.TEM图像表明,纳米管的表面所生长的纳米棒是单晶的.通过改变工作气压,可调控纳米管表面纳米棒的尺寸和形貌,实现ZnO纳米结构可控生长.室温光致发光谱表明,样品的光学性质可通过可控的形貌来调制.     

低温水热法生长ZnO纳米棒阵列的电子结构及光学特性(英文)

使用低温水热法在Si衬底上生长ZnO纳米棒阵列.通过X射线衍射和扫描电子显微镜对ZnO纳米棒的结晶性和形貌进行观测.结果表明,六棱柱形ZnO纳米棒沿c轴方向的阵列性良好,且均匀致密的生长在衬底上.室温光致发光谱表明应用低温水热法可以得到光学性质良好的ZnO纳米棒阵列.使用同步辐射对ZnO纳米棒阵列的氧K带边进行X射线吸收近带边谱测量,研究了不同半径ZnO纳米棒阵列的局部电子结构及其半径对电子结构的影响.另外,对ZnO纳米棒及ZnO薄膜的局部电子结构进行了对比研究.     

Biaxially textured Mo films with diverse morphologies by substrate-flipping rotation

A class of nanostructured Mo thin films was grown by DC magnetron sputtering using a robust substrate rotation mode called 'flipping rotation'. In this rotation mode, the substrate is arranged to rotate continuously at a fixed speed around an axis lying within and parallel to the substrate. The incident flux is perpendicular to the rotational axis, and the incident flux angle changes continuously. Mo nanostructured films, grown under different rotation speeds with three orders of magnitude spread (ranging from 0.008 to 24?rotation?min( - 1)), different flipping directions (clockwise and counter-clockwise), and different ending deposition angles, were characterized using scanning electron microscopy (SEM) and reflection high energy electron diffraction (RHEED) surface-pole-figure techniques. Despite their very different morphologies, such as 'C'-shaped, 'S'-shaped, and vertically aligned nanorods, the same [Formula: see text] biaxial texture with an average out-of-plane dispersion of ～ 15° was observed. In contrast, we showed that only a fiber-textured Mo film was obtained by using the conventional rotation mode where the oblique incident flux angle was fixed with the substrate rotating around the surface normal.     

Silver nanoisland induced synthesis of ZnO nanostructures by vapor phase transport

ZnO nanostructures including nanorod and nanotower were synthesized on Ag nanoisland coated Si substrate by thermal evaporation and vapor phase transport at atmospheric pressure. The as-prepared ZnO nanorods and nanotowers were single crystal growing along [0001] direction. The growth of ZnO nanostructures strongly depended on the surface morphology of the nanoisland Ag film deposited by electroless nanoelectrochemistry. The growth mechanism of the ZnO nanostructures was proposed on the basis of experimental data. A strong room-temperature photoluminescence in ZnO nanostructures has been demonstrated. The growth technique would be of particular interest for direct integration in the current silicon-technology-based optoelectronic devices.