Vertically aligned growth of ZnO nanonails by nanoparticle-assisted pulsed-laser ablation deposition

Vertically aligned ZnO nanonails have been successfully grown on annealed sapphire substrates at comparatively high gas pressure using catalyst-free nanoparticle-assisted pulsed-laser ablation deposition (NAPLD). The growth behavior of the ZnO nanonails has been investigated by variation of the ablation time, which we name ‘isolated particle initiated growth’ and a three-step growth mechanism for ZnO nanonails is proposed. SEM analysis reveals that each of the uniquely shaped ZnO nanonails consists of a so-called hexagonal rod-shaped ‘root’ and a slightly tapered ‘stem’. The well-aligned ZnO nanonails exhibit a strong ultraviolet (UV) emission at around 390 nm under room temperature and only negligible visible emission, which indicates that there is a very low concentration of oxygen vacancies in the highly oriented ZnO nanonails. The as-synthesized nanonail arrays on sapphire substrate could offer novel opportunities for both fundamental research and technological applications. PACS 81.07.Bc; 78.66.Hf; 78.67.Bf; 81.16.Mk     

Substrate effects on ZnO nanostructure growth via nanoparticle-assisted pulsed-laser deposition

The effects of various substrate conditions on the morphology, crystal structure and photoluminescence of ZnO nanostructures synthesized by nanoparticle-assisted pulsed-laser ablation deposition were investigated. It is concluded that the sapphire substrate with a 1 h anneal at 1000 °C is the most favorable to the vertical growth of ZnO nanostructures. SEM analysis indicates that the well-aligned diameter-modulated ZnO nanonails with unique shape were successfully synthesized on the annealed sapphire substrate. The as-synthesized ZnO nanostructures exhibit an ultraviolet emission at around 390 nm and the absent green emission under room temperature, indicating that there is a very low concentration of deep-level defects inside ZnO lattices. The novel ZnO nanostructures could offer novel opportunities for both fundamental research and technological applications.     

ZnO nano-rods synthesized by nano-particle-assisted pulsed-laser deposition

We succeeded in synthesizing ZnO nanorods by nanoparticle assisted pulsed-laser deposition (PLD) without using any catalyst where nanoparticles formed by condensation of ablated particles play an important role. The nanorods have an average size of about 120 nm. Stimulated emission was observed from ZnO nanorods at 388 nm by optical pumping. The size-controlling of nanorods can be achieved by controlling the size and the density of these nanoparticles. PACS 61.46.+w; 81.07.Bc; 78.66.Hf; 78.67.Bf; 81.16.Mk.     

Inclined ZnO thin films produced by pulsed-laser deposition

ZnO thin films with a uniformly inclined structure are grown by pulsed-laser deposition on SrTiO₃. The c-axis of ZnO films is inclined by an angle =20±0.5° and =42±0.5° against the surface normal of 25° miscut (100) SrTiO₃ and (110) SrTiO₃ single crystal substrates, respectively. The inclined structure is due to epitaxial growth of hexagonal ZnO on cubic SrTiO₃ as evidenced by X-ray diffraction and high-resolution transmission electron microscopy investigations. The range of deposition parameters (substrate temperature, oxygen background pressure) to achieve epitaxial growth is determined. The inclined films are smooth with an rms surface roughness of 1.5 nm for layer thicknesses up to 700 nm. PACS 61.10.-i; 68.37.-d; 81.15.Fg     

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.     

Position-controlled and catalyst-free growth of ZnO nanocrystals by nanoparticle-assisted pulsed laser deposition

We have synthesized ZnO nanocrystals, such as nanowires, nanorods, and nanosheets, using a nanoparticle-assisted pulsed laser deposition (NAPLD) method. Recently, we achieved position-controlled growth of the ZnO nanocrystals by means of a ZnO buffer layer and laser irradiation without any catalyst. The periodic structure was formed on the ZnO buffer layer by multi-beam interference patterning, and then vertically aligned ZnO nanowalls, corresponding to the patterning, were grown on the buffer layer. It was found that the periodic ZnO nanowalls grew along the c-axis direction by X-ray diffraction measurement. The well-aligned ZnO nanowalls are expected to be utilized as building blocks for field emitters and UV LEDs. The proposed technique can be used as one of the effective methods to control the growth position of the ZnO nanocrystals because various structures can be easily fabricated by a laser writing and a spatial light modulator.     

XPS investigation of vacuum annealed vertically aligned ultralong ZnO nanowires

The surface properties of vertically aligned ZnO nanowires grown by chemical vapour deposition on GaN using a gold layer as a catalyst are investigated by X-ray Photoelectron Spectroscopy as a function of annealing temperature in ultra high vacuum (UHV). The nanowires are 8.5 μm long and 60 nm wide. 87% of the surface carbon content was removed after annealing at 500 °C in UHV. Analysis of the gold intensity suggests diffusion into the nanowires after annealing at 600 °C. Annealing at 300 °C removes surface water contamination and induces a 0.2 eV upward band bending, indicating that adsorbed water molecules act as surface electron donors. The contaminants re-adsorbed after 10 days in UHV and the surface band bending caused by the water removal was reversed. The UHV experiment also affected the nanowires arrangement causing them to bunch together. These results have clear implications for gas sensing applications with ZnO NWs.     

Enhanced hardness in B-doped ZnO thin films on fused quartz substrates by pulsed-laser deposition

B-doped ZnO thin films have been fabricated on fused quartz substrates using boron-ZnO mosaic target by pulsed-laser deposition technique, and the mechanical properties have been studied by nanoindentation continuous stiffness measurement technique and transmission electron microscope (TEM). Nanoindentation measurement revealed that the hardness of B-doped ZnO films, 9.32 ± 0.90 to 12.10 ± 1.00 GPa, is much greater than that of undoped ZnO films and very close to that of traditional semiconductor Si. The mean transmittance (%) is larger than 81% in the visible range (380-780 nm) for all the films, and the Hall effect measurement showed that the carrier density is around 2 × 10²⁰ cm⁻³ and the resistivity lower than 3 × 10⁻³ Ω cm. TEM characteristics show undoped thin films have more amorphous area between grains while the B-doped ZnO films have thin grain boundaries. We suggest that the grain boundaries act as the strain compensation sites and the decrease in thickness of grain boundaries enhances the hardness of the B-doped ZnO films.     

Growth, modulation and photoresponse characteristics of vertically aligned ZnO nanowires

Vertically aligned, c-axis oriented zinc oxide (ZnO) nanowires were grown on Si substrate by metal organic chemical vapor deposition (MOCVD) technique, where sputtered aluminum nitride (AlN) film was used as an intermediate layer and thermally evaporated barium fluoride (BaF₂) film as a sacrificial layer. The aspect ratio and density of the nanowires were also varied using only Si microcavity without any interfacial or sacrificial layer. The UV detectors inside the microcavity have shown the higher on-off current ratio and fast photoresponse characteristics. The photoresponse characteristics were significantly varied with the aspect ratio and the density of nanowires.     

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.     

Synthesis of ZnO nanowires by pulsed laser deposition in furnace

ZnO nanowires were fabricated on Au coated (0 0 0 1) sapphire substrates by using a pulsed Nd:YAG laser with a ZnO target in furnace. ZnO nanowires have various sizes and shapes with a different substrate position inside a furnace. The length and the diameter of these ZnO nanowires were around 3-4 μm and 120-200 nm, respectively, confirmed by scanning electron microscopy (SEM). The diameter control of the nanowires was achieved by varying the position of substrates. The ultraviolet emission of nanowires from the near band-edge emission (NBE) was observed at room temperature. The formation mechanism and the effect of different position of substrates on the structural and optical properties of ZnO nanowires are discussed.     

Self-catalyst synthesis of aligned ZnO nanorods by pulsed laser deposition

High-density well-aligned ZnO nanorods were successfully synthesized on ZnO-buffer-layer coated indium phosphide (InP) (100) substrates by a pulsed laser deposition (PLD) method. Scanning electron microscopy images show that the ZnO buffer layer formed uniform drip-like structure and ZnO nanorods were well-oriented perpendicular to the substrate surface. The sharp diffraction peak observed at 34.46° in X-ray diffraction scanning pattern suggests that the ZnO nanorods exhibit a (002)-preferred orientation. The PL spectra of ZnO samples shows a strong near band edge emission centered at about 380 nm and a weak deep level emission centered at around 495 nm, and it demonstrates that the ZnO nanorods produced in this work have high optical quality, which sheds light on further applications for nanodevices. Supported by the National Natural Science Foundation of China (Grant No. 50532080), the Science & Technology Foundation for Key Laboratory of Liaoning Province (Grant No. 20060131), and the Doctoral Project by China Ministry of Education (Grant No. 20070141038)     

Fill factor controlled nanoimprinted ZnO nanowires based on atomic layer deposition

Enhanced diffraction by sub-wavelength nanostructures to convert incident electromagnetic radiation into waveguide modes has applications in anti-reflective coatings for optoelectronic devices. We propose a metal oxide (ZnO) nanowire grid polarizer as such a nanostructure, fabricated by ultraviolet nanoimprint lithography and whose fill factor (FF) is controlled by atomic layer deposition. Using finite difference time domain simulations, we investigated the polarization-dependent optical transmittance of the structures and calculated the polarizing efficiency. Optical profiles such as electric and magnetic field intensity and current density distributions of specific FF nanopatterns were determined for the transverse magnetic and transverse electric modes. The effects of geometrical parameters including the wire-grid period, fill ratio, and spacing between the wire-grid layers on diffraction wavelength were characterized. Respective FF-controlled ZnO nanowire structures were fabricated and their experimental optical transmittances were measured for nanowire grid polarizer applications.     

Photoluminescence study of aligned ZnO nanorods grown using chemical bath deposition

The photoluminescence study of self-assembled ZnO nanorods grown on a pre-treated Si substrate by a simple chemical bath deposition method at a temperature of 80 °C is hereby reported. By annealing in O₂ environment the UV emission is enhanced with diminishing deep level emission suggesting that most of the deep level emission is due to oxygen vacancies. The photoluminescence was investigated from 10 K to room temperature. The low temperature photoluminescence spectrum is dominated by donor-bound exciton. The activation energy and binding energy of shallow donors giving rise to bound exciton emission were calculated to be around 13.2 meV, 46 meV, respectively. Depending on these energy values and nature of growth environment, hydrogen is suggested to be the possible contaminating element acting as a donor.     

Pulsed-laser deposition and characterization of ZnO nanowires with regular lateral arrangement

We report on the high-pressure pulsed-laser deposition growth of periodic arrays of free-standing single zinc oxide nanowires with uniform hexagonal arrangement and cross-section with thickness of less than 100 nm. In order to achieve the wire alignment, we prepared an ordered array of catalytic gold seed particles by a nanosphere lithography mask transfer technique using monodisperse spherical polystyrol nanoparticles. These templates were investigated by scanning electron microscopy and atomic force microscopy prior to nanowire growth. X-ray diffraction revealed the epitaxial relationships between the nanostructures and the a-plane sapphire substrate and excellent crystal quality. The optical properties of the ZnO nanowire arrays were measured by cathodoluminescence. PACS 61.82.Rx; 81.05.-t; 81.05.Dz; 81.10.-h     

Electrowetting on ZnO nanowires

In this paper, we study the electrowetting character on ZnO nanowires. We grow the ZnO nanowires on indium tin oxide (ITO) by a hydrothermal method, and the ZnO nanowires surface is further hydrophobized by spin-coating Teflon. Such a prepared surface shows superhydrophobic properties with an initial contact angle 165°. When the applied external voltage between the ITO and the sessile droplet is less than 50 V, the contact angle continuously changed from 165° to 120°, and exhibits instant reversibility. For a slightly higher voltage, a mutation of the contact angle changing to 100° was observed and the contact angle was not reversible after removing the applied voltage, which indicates a transition from non-wetting state to wetting state. Further increasing of the applied voltage, the apparent contact angle decreased to an invariable value 70°, and electrical breakdown emerged synchronously.     

Ultraviolet lasing and field emission characteristics of ZnO nano-rods synthesized by nano-particle-assisted pulsed-laser ablation deposition

We describe the lasing and the field emission characteristics of ZnO nano-rod crystals synthesized by nano-particle-assisted pulsed-laser ablation deposition, where nano-particles formed in the gas phase by the condensation of the laser-ablated species are transported on to the substrate to form nanorods. The nano-rod crystals having a hexagonal shape with a pyramidal top were synthesized on a sapphire substrate by a single-step process. The nano-rod crystals act as an efficient ultraviolet emitter showing the stimulated emission under an optical excitation and also act as field emitters with a current density of 1 mA/cm² at an electric field strength of 16 V/μm. PACS 42.70.Hj; 85.45.Db; 81.05.Ea; 81.15.Fy     

Influence of metallic coatings on the photoluminescence properties of ZnO nanowires

We report on low‐temperature photoluminescence studies of ZnO nanowires coated with thin metallic films. For all analyzed metals (Al, In, Au, Ni, Cu), we find an increased relative intensity of the green deep‐level emission. This is accompanied by a significant reduction of the relative intensity of the surface exciton band. The observed effects are most likely related to the formation of metal induced gap states in the surface region of the ZnO nanowires. A model for the band structure in the surface region of the metal‐coated nanowires is proposed that successfully explains the changes in the photoluminescence spectra after the coating process. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Catalyst-free growth of well-aligned arsenic-doped ZnO nanowires by chemical vapor deposition method

ZnO nanowires with different arsenic concentration were grown on Si (1 0 0) substrates by chemical vapor deposition method without using catalyst. Zn/GaAs mixed powders were used as Zn and As source, respectively. Oxygen was used as oxidant. The images of scanning electron microscope show that the arsenic-doped ZnO nanowires with preferred c-axial orientation were obtained, which is in well accordance with the X-ray diffraction analysis. The arsenic related acceptor emission was observed in the photoluminescence spectra at 11 K for all arsenic-doped ZnO samples. This method for the preparation of arsenic-doped ZnO nanowires may open the way to realize the ZnO nanowires based light-emitting diode and laser diode.