Catalyst-free ZnO nanowires grown on a-plane GaN

ZnO nanowires were grown on a-plane GaN templates by chemical vapor deposition (CVD) without employing a catalyst. The a-plane GaN templates were pre-deposited on an r-plane sapphire substrate by metal-organic CVD. The resulting ZnO nanowires grow in angles off- related to the GaN basal plane. X-ray diffraction (XRD) spectra showed that the ZnO layer was grown with a heteroepitaxial relationship of (110)_ZnO||(110)_GaN. Photoluminescence spectra measured at 17 K exhibited near-band-edge emission at 372 nm with a full width at half maximum of 10 nm. The growth mechanism on a-GaN was the Volmer-Weber (VW) mode and differed from the Stranski-Krastanow (SK) mode observed for growth on c-GaN. This difference results from the higher interfacial free-energy on the a-plane between ZnO and GaN than that on the c-plane orientation.     

Enhancement of green emission from Sn-doped ZnO nanowires

Oxygen vacancies play a crucial role in the emission characteristics of oxide nanomaterials. In this study, we found that the green emission intensity of ZnO nanowires can be enhanced through a Sn-doping concentration which increases the number of oxygen vacancies. Undoped ZnO nanowires showed blue emission at 380 nm, but as the concentration of Sn was increased, the green emission peak at around 500 nm, which is attributed to oxygen vacancies, showed drastic enhancement. On the basis of XPS compositional analysis, it was confirmed that the green luminescence intensity was closely related to the number of oxygen vacancies in Sn-doped ZnO nanowires. These results pave the way to a greater understanding of tunable light emission from nanowires, which could be a key technology for next-generation display devices, including flexible and transparent displays.     

Growth and characterization of non-polar ZnO thin films by pulsed laser deposition

Non-polar ZnO thin films were fabricated on r-plane sapphire substrates by pulsed laser deposition at various temperatures from 100 to 500 °C. The effects of the substrate temperature on structural, morphological and optical properties of the films were investigated. Based on the X-ray diffraction analysis, the ZnO thin films grown at 300, 400 and 500 °C exhibited the non-polar (a-plane) orientation and those deposited below 300 °C exhibited polar (c-plane) orientation. In the optical properties of non-polar ZnO films, there were two photoluminescence peaks detected. The peaks (near-band edge emission, blue emission) are due to electron transitions from band-to-band and shallow donor level to valence band, respectively.     

Defect induced room temperature ferromagnetism in well-aligned ZnO nanorods grown on Si (100) substrate

In this work, we report the fabrication of high quality single-crystalline ZnO nanorod arrays which were grown on the silicon (Si) substrate using a microwave assisted solution method. The as grown nanorods were characterized using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), photo-luminescence (PL) and magnetization measurements. The XRD results indicated that the ZnO nanorods are well oriented with the c-axis perpendicular to the substrate and have single phase nature with the wurtzite structure. FE-SEM results showed that the length and diameter of the well aligned rods is about ~ 1 μm and ~ 100 nm respectively, having aspect ratio of 20-30. Room-temperature PL spectrum of the as-grown ZnO nanorods reveals a near-band-edge (NBE) emission peak and defect induced green light emission. The green light emission band at ~ 583 nm might be attributed to surface oxygen vacancies or defects. Magnetization measurements show that the ZnO nanorods exhibit room temperature ferromagnetism which may result due to the presence of defects in the ZnO nanorods.     

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.     

Optical and structural properties of Mg-ion implanted GaN nanowires

Mg⁺ ions (60 keV) were implanted into GaN nanowires (NWs) with total fluxes of 5 × 10¹²-5 × 10¹⁴ cm⁻² followed by thermal annealing at 700 °C in N₂ ambient. Transmission electron microscopic images showed amorphous layer formation and defect accumulation in the higher dose Mg-implanted GaN NWs after annealing. Photoluminescence spectra (300 K) of the annealed Mg-implanted GaN NWs exhibited near-band-edge (NBE) emission, donor-acceptor pair (DAP) emission, and defect-related yellow luminescence. With increasing dose, the NBE and DAP emissions are red shifted. Similar phenomena were observed in samples implanted with Ar to produce similar amounts of lattice disorder. The NWs show a much higher sensitivity to defect accumulation than GaN thin films.     

Influence of Sb as a catalyst in the growth of ZnO nano wires and nano sheets using Nanoparticle Assisted Pulsed Laser Deposition (NAPLD)

The methodology on the synthesis of Sb-doped ZnO nanostructures by considering dopant as a catalyst is proposed and demonstrated. The nanostructures were synthesized using intrinsic ZnO as target and Sb-coated Si as substrate, where Sb simultaneously acts as dopant and the catalyst. The catalyst Sb is highly sensitive to temperature conditions resulted in two different nanostructures, the nanowires and the nanosheets. The surface, structural and optical characteristics of the nanowires and the nanosheets are comparatively investigated through SEM, EDX, XRD, Raman spectroscopy and photo luminescence (PL) spectroscopy. The nanowires showed a strong green emission in the PL spectrum and the presence of oxygen vacancies is confirmed thorough Raman peak shift at 556 cm⁻¹. In the case of nanosheets, the defect in oxygen vacancies is completely reduced, and improved UV emission is observed, which confirms the diffusion of Sb in the ZnO lattice.     

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.     

Photoluminescence and field-emission characteristics of ZnO nanowires synthesized by two-step method

ZnO nanowires with excellent photoluminescence (PL) and field-emission properties were synthesized by a two-step method, and the ZnO nanowires grew along (0 0 2) direction. PL measurements showed that the ZnO nanowires have stronger ultraviolet emission properties at 376 nm and there is 3 nm blue shift after the nanowires were immersed in thiourea (TU) solution compared with those of without immersion. The immersed-ZnO nanowires show a turn-on field of 2.3 V/μm at a current density of 0.1 μA/cm and emission current density up to 1 mA/cm² at an applied field of 6.8 V/μm, which demonstrate that the immersed-ZnO nanowires posses efficient field-emission properties in contrast with those not immersed. The ZnO nanowires may be ideal candidates for making luminescent devices and field-emission displays.     

Investigation of indium oxide as a self-catalyst in ZnO/ZnInO heterostructure nanowires growth

We investigated the self-catalytic role of indium oxide in the growth process of ZnO/ZnInO heterostructure nanowires on Si(111). The prepared nanowires had hexagonal cross sections and were tapered with tip diameters of 90 ± 5 nm and base diameters of 230 ± 5 nm. Energy dispersive X-ray and field emission Auger spectroscopies indicated that the grown nanowires were heterostructures of ZnO and ZnInO. Analysis of the early growth process revealed that indium may play a self-catalytic role. Therefore, the vapor-liquid-solid mechanism is likely to be responsible for growth of ZnO/ZnInO nanowires. X-ray diffraction and room temperature photoluminescence (PL) data demonstrated that the presence of indium results in a decrease in nanowires' crystallinity. These wires produced a large PL emission peak in the ultraviolet (UV) region and a smaller peak in the green region of the electromagnetic spectrum. The UV peak of the ZnO/ZnInO nanowires is blue-shifted with respect to that of pure ZnO nanowires.     

Plasmon assisted intense blue-green emission from ZnO/ZnS nanocrystallites

Excellent luminescence properties of ZnO/ZnS nanocrystallites prepared using simple wet chemical approach at room temperature have been reported. ZnS coating on the surface of ZnO nanocrystallites enhanced the green emission (around 500 nm) by a factor of 2. The intensity of the blue emission around 450 nm of ZnO/ZnS nanocrystallites is observed to be as high as three times the emission intensity of pure ZnO nanocrystallites. A further overall increase by a factor of ∼2.5 has also been observed in the intensity of wide blue-green emission when the sample was prepared onto grating compared to that of the samples prepared onto uncoated as well as gold coated quartz. The enhanced emission is thought to be due to plasmon assisted electromagnetic field enhancement near nanocrystallites-metal interface. This is supported by power dependent photoluminescence measurements. The strong enhanced blue-green emission covering a wide spectral range of ∼375-650 nm signifies potential optoelectronic applications in near UV and VIS wavelength regimes.     

Fabrication and optical emission of TiO2-sheathed ZnO nanowires

The ZnO nanowires were synthesized by using vapor-liquid-solid mechanism and then the ZnO nanowires were sheathed with TiO2 by metal organic chemical vapor deposition. The coaxial nanowires were 30-200 nm in diameter and up to 0.2 microm in length. Transmission electron microscopy and X-ray diffraction analysis results showed that the ZnO cores and TiO2 shells of the core-shell nanowires had wurtzite and amorphous structures, respectively. Photoluminescence measurement showed that TiO2 coating increased and decreased the near-band edge (NBE) and deep-level emissions of the ZnO nanowires in intensity, respectively. However, it appeared that subsequent annealing was undesirable since it decreased the NBE emission in intensity.     

Field emission from zinc oxide nanostructures and its degradation

Arrays of zinc oxide (ZnO) nanowires and nanobelts were synthesized by the thermal evaporation of mixed powders of ZnO and graphite. Neither catalyst nor vacuum environment was involved in the fabrication. For comparison, the ZnO nanowires were grown on a pre-deposited transitional ZnO film on a brass substrate and the ZnO nanobelts were grown directly on a Si substrate. Their field emission properties were systematically measured. Current density of 10 μA/cm² was achieved at the fields of 5.7 and 6.2 V/μm from the nanowires and nanobelts, respectively. Also, the emission sites were found to distribute uniformly on the whole cathode. In the preliminary test on the stability, the ZnO nanobelts, which were sharp at the tip but wide at the root, exhibited better robustness than the ZnO nanowires. The post-test scanning electron microscopy (SEM) observation showed that the degradation of their field emission capability resulted from the breaking of the nanowires, which was tentatively attributed to the resistive heating during the field emission. In contrast, the shedding of the ZnO from the substrate was not so serious as imagined.     

Highly luminescent columnar ZnO films grown directly on n-Si and p-Si substrates by low-temperature electrochemical deposition

In this study, nanocolumnar zinc oxide thin films were catalyst-free electrodeposited directly on n-Si and p-Si substrates, what makes an important junction for optoelectronic devices. We demonstrate that ZnO thin films can be grown on Si at low cathodic potential by electrochemical synthesis. The scanning electron microscopy SEM showed that the ZnO thin films consist of nanocolumns with radius of about 150 nm on n-Si and 200 nm on p-Si substrates, possess uniform size distribution and fully covers surfaces. X-ray diffraction (XRD) measurements show that the films are crystalline material and are preferably grown along (0 0 2) direction. The impact of thermal annealing in the temperature range of 150-800 °C on ZnO film properties has been carried out. Low-temperature photoluminescence (PL) spectra of the as-prepared ZnO/Si samples show the extremely high intensity of the near bandgap luminescence along with the absence of visible emission. The optical quality of ZnO thin films was improved after post-deposition thermal treatment at 150 °C and 400 °C in our experiments, however, the luminescence intensity was found to decrease at higher annealing temperatures (800 °C). The obtained results indicate that electrodeposition is an efficient low-temperature technique for the growth of high-quality and crystallographically oriented ZnO thin films on n-Si and p-Si substrates for device applications.     

Effects of growth atmosphere and homo-buffer layer on properties of ZnO films prepared on Si(1 1 1) by PLD

ZnO films were synthesized on Si(1 1 1) substrates by pulsed laser deposition (PLD) under four different growth conditions. The structural and optical properties of the samples were characterized by reflection high-energy electron diffraction (RHEED), X-ray diffraction (XRD), and photoluminescence (PL) measurement. It is found that when ZnO film is directly prepared on Si, oxygen atmosphere can significantly enhance the near-band-edge (NBE) emission and decrease the deep-level (DL) emission, but cause a polycrystalline film. By introducing a homo-buffer layer fabricated at 500 °C in vacuum, epitaxial ZnO film with three-dimensional (3D) growth mode is achieved instead of the polycrystalline film. In particular, the epitaxial film with the buffer layer shows more intensive NBE emission and narrower full-width at half maximum (FWHM) of 98 meV than the film without the buffer layer. The experimental results suggest that both oxygen atmosphere and buffer layer are quite efficient during PLD to grow high-quality ZnO/Si heteroepitaxial films suitable for applications in optoelectronic devices.     

Enhanced H2 sensing properties of a-plane ZnO prepared on c-cut sapphire substrate by sputtering

Zinc oxide (ZnO) thin films have been prepared on c-plane sapphire substrate by magnetron sputtering technique. The influence of deposition time on the structural, optical and photoluminescence properties of the films have been investigated. XRD patterns reveal the growth of preferentially oriented (101) non-polar a-plane ZnO film with hexagonal wurtzite structure. The PL peak shifts towards lower wavelength for deposition time up to 20 min, which is in consistent with the results obtained from UV absorption studies. The blue shift in the PL peak confirms the possibility for quantum confinement effect. The band gap energy of the film increases from 3.33 to 3.38 eV, indicating enhanced quantum confinement effects. FESEM micrographs showed that the films have a smooth and dense morphology with uniform grain growth. Hydrogen sensing measurements indicated that a-plane ZnO film on c-sapphire showed higher response than c-plane ZnO film reported earlier. The sensor response of 44 nm thick ZnO film exhibit highest response of 145 towards 500 ppm H₂ gas at the operating temperature of 200 °C.     

Synthesis and characterization of ZnO nanowires for nanosensor applications

In this paper we report the synthesis of ZnO nanowires via chemical vapor deposition (CVD) at 650 °C. It will be shown that these nanowires are suitable for sensing applications. ZnO nanowires were grown with diameters ranging from 50 to 200 nm depending on the substrate position in a CVD synthesis reactor and the growth regimes. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), and Raman spectroscopy (RS) have been used to characterize the ZnO nanowires. To investigate the suitability of the CVD synthesized ZnO nanowires for gas sensing applications, a single ZnO nanowire device (50 nm in diameter) was fabricated using a focused ion beam (FIB). The response to H₂ of a gas nanosensor based on an individual ZnO nanowire is also reported.     

Synthesis and cathode luminescence properties of ZnO multipod nanoneedles

Zinc oxide (ZnO) multipod nanoneedles over a large area have been synthesized on silicon substrate by thermally oxidizing zinc foil at 650 °C. These nanoneedles have sharp tails with diameter down to less than 100 nm, with length of 10 μm, growing from the surface of the silicon substrate and legs connected at a common base. X-ray diffraction (XRD) confirmed the sample as pure ZnO nanostructures with growth direction of [002]. The cathode luminescence behaviors at different regions of an individual nanoneedle of these multipod ZnO nanostructures were characterized. It is shown the whole nanostructures are luminescent, while the tips have relative higher visible emission than the bottom. The cathode luminescence mechanisms were also discussed.     

Structure, luminescence and electrical properties of ZnO thin films annealed in H2 and H2O ambient: A comparative study

Undoped ZnO films were grown on a c-plane sapphire by plasma-assisted molecular-beam epitaxy technique, and subsequently annealed at 200-500 °C with steps of 100 °C in water vapour and hydrogen ambient, respectively. It is found that the c-axis lattice constant of the ZnO films annealed in hydrogen or water vapour at 200 °C increases sharply, thereafter decreases slowly with increasing annealing temperature ranging from 300 °C to 500 °C. The stress in the as-grown ZnO films was more easily relaxed in water vapour than in hydrogen ambient. Interestingly, the controversial luminescence band at 3.310 eV, which is often observed in photoluminescence (PL) spectra of the ZnO films doped by p-type dopants, was observed in the PL spectra of the annealed undoped ZnO films and the PL intensity increases with increasing annealing temperature, indicating that the 3.310 eV band is not related to p-type doping of ZnO films. The electron concentration of the ZnO films increases sharply with increasing annealing temperature when annealed in hydrogen ambient but decreases slowly when annealed in water vapour. The mechanisms of the effects of annealing ambient on the properties of the ZnO films are discussed.     

Tunable electronic transport characteristics of surface-architecture-controlled ZnO nanowire field effect transistors

Surface-architecture-controlled ZnO nanowires were grown using a vapor transport method on various ZnO buffer film coated c-plane sapphire substrates with or without Au catalysts. The ZnO nanowires that were grown showed two different types of geometric properties: corrugated ZnO nanowires having a relatively smaller diameter and a strong deep-level emission photoluminescence (PL) peak and smooth ZnO nanowires having a relatively larger diameter and a weak deep-level emission PL peak. The surface morphology and size-dependent tunable electronic transport properties of the ZnO nanowires were characterized using a nanowire field effect transistor (FET) device structure. The FETs made from smooth ZnO nanowires with a larger diameter exhibited negative threshold voltages, indicating n-channel depletion-mode behavior, whereas those made from corrugated ZnO nanowires with a smaller diameter had positive threshold voltages, indicating n-channel enhancement-mode behavior.