Electrochemical synthesis of Sn doped ZnO nanowires on zinc foil and their field emission studies

Sn doped ZnO films were obtained by cathodic electrodeposition on Zn foil. The X-ray diffraction analysis revealed formation of the wurtzite phase of ZnO only. The scanning electron microscopic images showed formation of randomly oriented ZnO nanowires having diameter less than 150 nm and lengths of several micrometers. The relative atomic percentage of Sn, estimated from the energy-dispersive spectra, was found to be 0.5 and 2.0 in the post-annealed ZnO films deposited for 10 and 40 min durations, respectively. The field emission characteristics of the Sn doped ZnO nanowires are found to be appreciable in terms of the threshold field and emission current stability.     

An alternative approach to <Emphasis Type="Italic">in situ</Emphasis> synthesize single crystalline ZnO nanowires by oxidizing granular zinc film

ZnO nanowires were synthesized by a relatively simple process—oxidizing granular Zn films at a relatively low temperature (450–600 °C) without catalyst. The zinc film was initially fabricated by sputter deposition in an argon atmosphere at ambient temperature using Zn metal as the sputter target. After subsequent annealing in an air or oxygen atmosphere, ZnO nanowires were found to grow from individual Zn nanograins. The investigation has also showed that the nanowires preferably grow from relatively porous Zn film and a small amount of oxygen flow is beneficial to the growth of nanowires. The resultant single crystal ZnO nanowires obtained from annealing at 600 °C in an oxygen atmosphere had a mean diameter less than 50 nm and had a very good structural quality. This process provides an alternative method to produce ultra-fine ZnO nanowires standing on the substrate.     

Sputter deposition of ZnO thin films at high substrate temperatures

ZnO thin films have been deposited on GaN and ZnO substrates at substrate temperatures up to 750 °C by radio-frequency sputtering using ZnO ceramic targets in pure argon or in a mixture of argon and oxygen. By optimizing the sputter parameters, such as sputtering power, Ar/O₂ sputtering gas ratio and temperature of the substrates high quality films were obtained as judged from the X-ray rocking curve half width and luminescence line width. The crystallinity of the ZnO films increases with increasing substrate temperature. Yet there are distinct differences between films grown on GaN templates and on O- and Zn-polar ZnO substrates.     

Single-crystalline ZnO nanowires on zinc substrate by a simple hydrothermal synthesis method

A simple synthesis route to long ZnO nanowires with high aspect ratio of up to ∼ 1000 on zinc substrate in the NaOH aqueous solution was reported, without the assistance of any catalyst, templates or high temperature. We studied the key influencing factors including the reaction time and the solution concentration. With the increase of reaction time from 12 h to 24 h, the average length of ZnO nanowires would increase correspondingly. Through this synthesis route, we can obtain a mass of products and the method is both convenient and reproducible. The as-grown ZnO nanowires are single crystalline with a wurtzite structure.     

ZnO sputter coating on SnO2 nanowires: Effects of thin coating and subsequent thermal annealing

The structural and optical properties of SnO₂–ZnO core–shell nanowires were studied and the effects of thermal annealing were investigated. As-prepared SnO₂–ZnO core–shell nanowires exhibited a smooth and continuous shell layer along the nanowire, with a thickness in the range of 5–10 nm. While the thin ZnO shell layer disappeared after annealing at 800 °C, this did not occur after annealing at 600 °C. The as-fabricated SnO₂–ZnO core–shell nanowires exhibited yellow emission, presumably from the core SnO₂ nanowires. The UV emission from ZnO shell layer was obtained by annealing at 600 °C, whereas it was removed by annealing at 800 °C.     

The incorporation of preformed metal nanoparticles in zinc oxide thin films using aerosol assisted chemical vapour deposition

The feasibility of Aerosol Assisted Chemical Vapour Deposition (AA-CVD) has been investigated for the growth of zinc oxide (ZnO) films containing preformed metal nanoparticles. The deposition parameters were first established for ZnO thin films, by varying the heating configuration, substrate temperature and deposition time. Films were characterised using Scanning Electron Microscopy and X-Ray Diffraction. As-deposited films, grown at 250 °C, were mostly amorphous and transformed to highly crystalline Wurtzite ZnO at higher substrate temperatures (400-450 °C). A change in the preferential orientation of the films was observed upon changing (i), the substrate temperature or (ii), the heating configuration. Following this, the applicability of the AA-CVD process for the incorporation of preformed nanoparticles (platinum and gold) in ZnO thin films was investigated. It was found that surface agglomeration occurred, such that the ZnO films were capped with an inhomogeneous coverage of the metal. These layers were characterised using Transmission Electron Microscopy and Electron Diffraction. A possible mechanism for the formation of these metal surface clusters is presented.     

Analysis of single junction a-Si:H solar cells grown on different TCO’s

In consequence of previous investigation of individual transparent conductive oxide (TCO) and absorber layers a study was carried out on hydrogenated amorphous silicon (a-Si:H) solar cells with diluted intrinsic a-Si:H absorber layers deposited on glass substrates covered with different TCO films. The TCO film forms the front contact of the super-strata solar cell and has to exhibit good electrical (high conductivity) and optical (high transmittance) properties. In this paper we focused our attention on the influence of using different TCO’s as a front contact in solar cells with structure as follows: Corning glass substrate/TCO (800, 950 nm)/p-type μc-Si:H (∼5 nm)/p-type a-Si:H (10 nm)/a-SiC:H buffer layer (∼5 nm)/intrinsic a-Si:H absorber layer with dilution R = [H₂]/[SiH₄] = 20 (300 nm)/n-type a-Si:H layer (20 nm)/Ag + Al back contact (100 + 200 nm). Diode sputtered ZnO:Ga, textured and non-textured ZnO:Al [3] and commercially fabricated ASAHI (SnO₂:F) U-type TCO’s have been used. The morphology and structure of ZnO films were altered by reactive ion etching (RIE) and post-deposition annealing.It can be concluded that the single junction a-Si:H solar cells with ZnO:Al films achieved comparable parameters as those prepared with commercially fabricated ASAHI U-type TCO’s.     

Influence of secondary phases during annealing on re-crystallization of CuInSe2 electrodeposited films

Electrodeposited CuInSe₂ thin films are of potential importance, as light absorber material, in the next generation of photovoltaic cells as long as we can optimize their annealing process to obtain dense and highly crystalline films. The intent of this study was to gain a basic understanding of the key experimental parameters governing the structural-textural-composition evolution of thin films as function of the annealing temperature via X-ray diffraction, scanning/transmission electron microscopy and thermal analysis measurements. The crystallization of the electrodeposited CuInSe₂ films, with the presence of Se and orthorhombic Cu_2 − xSe (o-Cu_2 − xSe) phases, occurs over two distinct temperature ranges, between 220 °C and 250 °C and beyond 520 °C. Such domains of temperature are consistent with the melting of elemental Se and the binary CuSe phase, respectively. The CuSe phase forming during annealing results from the reaction between the two secondary species o-Cu_2 − xSe and Se (o-Cu_2 − xSe + Se → 2 CuSe) but can be decomposed into the cubic β-Cu_2 − xSe phase by slowing down the heating rate. Formation of liquid CuSe beyond 520°C seems to govern both the grain size of the films and the porosity of the substrate-CuInSe₂ film interface. A simple model explaining the competitive interplay between the film crystallinity and the interface porosity is proposed, aiming at an improved protocol based on temperature range, which will enable to enhance the film crystalline nature while limiting the interface porosity.     

Direct evidence for electron beam irradiation-induced phenomena in nanowired ZnO thin films

In-situ electron beam induced microstructural transformation experiments, leading to porosity in nanowires of ZnO, have been performed under a TEM operated at an electron accelerating voltage of 200 kV. For this purpose, nanowired (diameter: 20 to 80 nm) films of ZnO with thickness ~ 100 to 120 nm, were grown via metal-catalyst free-vapor phase mechanism. The evolved porosity (pore size about 2 to 20 nm) in nanowires, under electron beam irradiation, has been attributed to different bond-breaking phenomena at molecular Zn-O. Such nanoporous objects of ZnO are beneficial for various optical and sensing devices.     

Effect of annealing temperature on the tribological behavior of ZnO films prepared by sol-gel method

The tribological behavior of zinc oxide (ZnO) films grown on glass and silicon (100) substrates by sol-gel method was investigated. Particularly, the as-coated films were post-annealed at different temperatures in air to investigate the effect of annealing temperature. Crystal structural and surface morphology of the films were measured by X-ray diffraction (XRD) and Atomic Force Microscopy (AFM). XRD patterns and AFM images indicated that the crystallinity and grain size of the films were enhanced and increased, respectively, with temperature. The tribological behavior of films was evaluated by sliding the ZnO films against a Si₃N₄ ball under 0.5 gf normal load using a reciprocating pin-on-plate tribo-tester. The wear tracks of the films were measured by AFM to quantify the wear resistance of the films. The results showed that the wear resistance of the films could be improved by the annealing process. The wear resistance of the films generally increased with annealing temperature. Specifically, the wear resistance of the films was significantly improved when the annealing temperature was higher than 550° C. The increase in the wear resistance is attributed to the increase in hardness and modulus of the film with annealing temperature.     

A study on the origin of emission of the annealed n-ZnO/p-GaN heterostructure LED

We report the effects of thermal annealing in air and N₂ ambient on the structural, optical, and electrical properties of zinc oxide (ZnO) films deposited on a p-GaN substrate. Also, we report on the fabrication and device characterization of heterojunction light-emitting diodes based on the n-ZnO/p-GaN systems. In the case of N₂ ambient, room-temperature electroluminescence (EL) in the violet region with peak wavelength 400 nm was observed under forward bias. In air ambient, EL spectrum consisted of a broad band from 400 nm to 700 nm due to the Ga-O mixed region formed interface between the ZnO and GaN layer.     

High-temperature-dependent optical properties of ZnO film on sapphire substrate

In order to fabricate fiber-optic temperature sensors based on ZnO film, it is important to study the temperature-dependent optical properties of this material. In this work, we deposited ZnO films on c-plane (0001) sapphire substrate at 250 °C. Atomic force microscope and X-ray diffraction measurements show the smooth surface and high orientation along [0001] of ZnO film, respectively. The high-temperature-dependent optical properties of ZnO film were measured by ultraviolet-visible transmission with temperatures ranging from room-temperature to 300 °C and analyzed by theoretically fitting the optical absorption edge curve. It is observed that the band gap energy red shifts nonlinearly from 3.345 to 3.153 eV with increasing temperature. The sharp absorption edge of ZnO films after annealing at 300 °C is almost consistent with that of the as-deposited sample, indicating an excellent thermal stability and the potential application in fiber-optic temperature sensors.     

Influence of seed layers on the vertical growth of ZnO nanowires

We synthesized vertically aligned ZnO nanowires on SiO₂ wafer <100> using the Au, ZnO and Au/ZnO seed layers through the physical vapor deposition process. The growth direction of ZnO nanowire was controlled by using the three different seed layers. From the XRD results, we observed the highest intensity of the (002) peak on the Au/ZnO seed layer among the three seed layers. The SEM images show that all of the ZnO nanowires have an average diameter of about 100 ~ 200 nm and a length of about 5 μm, and the nanowires grown on the Au/ZnO seed layer are oriented the most perpendicularly to the substrate surface. From the PL analysis, we observed that the intensity of broad emissions at 400-600 nm relating the green emission for the ZnO nanowires on the Au/ZnO seed layer was much weaker than that for the ZnO nanowires on the ZnO seed layer. The experiment results indicate that the selection of seed layers is important to grow nanowires vertically for the application of nanoscale devices.     

Thickness of ITO thin film influences on fabricating ZnO nanorods applying for dye-sensitized solar cell

Background and purposeIn order to compare the substrates influence on the properties of ZnO films and nanostructures, in this paper, the ITO substrates with different thicknesses were investigated.MethodITO thin films of different thickness (200 nme500 nm) were deposited on glass substrates by DC sputtering, on which ZnO nanorods were fabricated from as-deposited ZnO films by reducing annealing method.ResultsIt was found that the structural and electrical properties of ITO films were significantly influenced by the ITO film thickness. The roughness of ITO films was increased with increase in thickness. The Hall mobility of ITO films was also increased with the increase of film thickness; in contrast, the resistivity was decreased. The highest Hall mobility of 29.2 cm²/V s and the lowest resistivity of 1.303 × 10⁻⁴ Ω cm were obtained from 500 nm-thick ITO film. The structural properties of ZnO nanorods were significantly influenced by the ITO film thickness. The density of ZnO nanorods gradually decreased with the increase in thickness of ITO film.ConclusionThe overall conversion efficiency of demonstrated dye-sensitized solar cell was 2.11% with a fill factor 0.526, indicating high potential to be used as photoanodes in dye-sensitized solar cell applications.     

Characterizations of gallium-doped ZnO films on glass substrate prepared by atmospheric pressure metal-organic chemical vapor deposition

Ga-doped zinc oxide (ZnO:Ga) films were grown on glass substrate by atmospheric pressure metal-organic chemical vapor deposition (AP-MOCVD) using diethylzinc and water as reactant gases and triethyl gallium (TEG) as an n-type dopant gas. The structural, electrical and optical properties of ZnO:Ga films obtained at various flow rates of TEG ranging from 1.5 to 10 sccm were investigated. X-ray diffraction patterns and scanning electron microscopy images indicated that Ga-doping plays an important role in forming microstructures in ZnO films. A smooth surface with a predominant orientation of (101) was obtained for the ZnO:Ga film grown at a flow rate of TEG = 7.5 sccm. Moreover, a lowest resistivity of 3.6 × 10^− 4 Ω cm and a highest mobility of 30.4 cm² V^− 1 s^− 1 were presented by the same sample, as evaluated by Hall measurement. Otherwise, as the flow rate of TEG was increased, the average transmittance of ZnO:Ga films increased from 75% to more than 85% in the wavelength range of 400-800 nm, simultaneously with a blue-shift in the absorption edge. The results obtained suggest that low-resistivity and high-transparency ZnO films can be obtained by AP-MOCVD using Ga-doping sufficiently to make the films grow degenerate and effect the Burstein-Moss shift to raise the band-gap energy from 3.26 to 3.71 eV.     

Efficient field emission properties of ZnO (core)/graphite (shell) nanowires

In this work the field emission studies of a new type of field emitter, zinc oxide (ZnO) core/graphitic (g-C) shell nanowires are presented. The nanowires are synthesized by chemical vapor deposition of zinc acetate at 1300 °C Scanning and transmission electron microscopy characterization confirm high aspect ratio and novel core–shell morphology of the nanowires. Raman spectrum of the nanowires mat represents the characteristic Raman modes from g-C shell as well as from the ZnO core. A low turn on field of 2.75 V/μm and a high current density of 1.0 mA/cm² at 4.5 V/μm for ZnO/g-C nanowires ensure the superior field emission behavior compared to the bare ZnO nanowires.     

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.     

Investigation of the growth of In2O3 on Y-stabilized ZrO2(100) by oxygen plasma assisted molecular beam epitaxy

Thin films of In₂O₃ have been grown on Y-stabilised ZrO₂(100) substrates by oxygen plasma assisted molecular beam epitaxy over a range of substrate temperatures between 650 °C and 900 °C. Growth at 650 °C leads to continuous but granular films and complete extinction of substrate core level structure in X-ray photoelectron spectroscopy. However with increasing substrate temperature the films break up into a series of discrete micrometer sized islands. Both the continuous and the island films have excellent epitaxial relationship with the substrate as gauged by X-ray diffraction and selected area electron diffraction and lattice imaging in high resolution transmission electron microscopy.     

Effect of heat treatment on characteristics of nanocrystalline ZnO films by electron beam evaporation

Zinc oxide thin films have been grown on glass substrate at room temperature by electron beam evaporation and then were annealed in annealing pressure 600 mbar at different temperatures ranging from 250 to 550 °C for 30 min. Electrical, optical and structural properties of thin films such as electrical resistivity, optical transmittance, band gap and grain size have been obtained as a function of annealing temperature. X-ray diffraction has shown that the maximum intensity peak corresponds to the (002) predominant orientation for ZnO films annealed at various temperatures. The full width at half maximum, decreases after annealing treatment which proves the crystal quality improvement. Scanning electron microscopy images show that the grain size becomes larger by increasing annealing temperature and this result agrees with the X-ray diffraction analysis.     

Structure and stimulated emission of a high-quality zinc oxide epilayer grown by atomic layer deposition on the sapphire substrate

A high-quality ZnO epilayer was grown on the (0001) sapphire substrate by atomic layer deposition (ALD) and followed by high-temperature rapid thermal annealing (RTA). The layer-by-layer growth and low deposition temperature of ALD, as well as the RTA treatment, prevent the formation of columnar structures in the ZnO epilayer. A distorted ZnO layer at the ZnO/sapphire interface, which relaxes the misfit in ZnO leads to a low threading dislocation density in the ZnO epilayer. Optically-pumped stimulated emission was achieved with a low-threshold intensity of 153 kW/cm² at room temperature. The good crystalline quality and low-threshold stimulated emission indicate that the ALD approach is appropriate for preparing high-quality ZnO epilayers.