Synthesis of bamboo-leaf-shaped ZnO nanostructures by oxidation of Zn/SiO2 composite films deposited with radio frequency magnetron co-sputtering

Bamboo-leaf-shaped ZnO nanostructures were synthesized by oxidation of metal Zn/SiO₂ matrix composite thin films deposited on Si(1 1 1) substrates with radio frequency magnetron co-sputtering. The synthesized bamboo-leaf-shaped ZnO are single crystalline in nature with widths ranging from 30 to 60 nm and lengths of up to 5-10 μm, room temperature photoluminescence spectrum of the nanostructures shows a strong and sharp UV emission band at 372 nm and a weak and broad green emission band at about 520 nm which indicates relatively excellent crystallization and optical quality of the ZnO nanostructures synthesized by this novel method.     

Synthesis and characterization of ZnO nano/microfibers thin films by catalyst free solution route

Zinc oxide (ZnO) nano/microfibrous thin films were successfully synthesized by a catalyst free solution route on glass and Si substrates. X-ray diffraction study revealed the formation of ZnO nanofibers of hexagonal crystalline structure. The texture coefficient of different planes varied with annealing temperature and that of the (0 0 2) plane was the highest for films annealed at temperature 873 K. Scanning electron micrograph showed the well formation of ZnO nano/microfibers with an average diameter 500 nm and having an average aspect ratio 150. UV–Vis–NIR spectroscopic study for the films deposited on glass substrates showed the high transmittance in the visible and near-infrared region. It was also observed that the band gap energy decreased as the films were annealed at higher temperature. The band gap energies of nanostructured ZnO thin films were determined to be in the range 3.03–3.61 eV. The photoluminescence study showed an UV emission peak at 397 nm, a visible blue–green emission peak at 468 nm and a green emission peak at 495 nm. Field emission properties of nanofiber ZnO thin film showed considerably low turn-on field around 1.4 V/μm. The emission current was as high as 70 μA at the field of 3.6 V/μm.     

Modulation of field emission properties of vertically aligned ZnO nanorods with aspect ratio and number density

Vertically aligned ZnO nanorod arrays with different aspect ratios were synthesized by hybrid wet chemical route. Modulation of the field emission properties (FE) with aspect ratio of ZnO nanorods was examined. With the increase in the aspect ratio, the emission current density increases from 0.02 to 8 μA/cm² at 7.0 V/μm. Turn-on voltage was seen to decrease from 9.6 to 7 V/μm at a current density of 10 μA/cm² with the increase in aspect ratio in the ZnO films. The interrelation between the FE characteristics (emission thresholds, current density, surface uniformity, etc.) and microstructure of the ZnO nanostructure obtained from scanning electron microscopy (SEM) and atomic force microscopy (AFM) was discussed. Quality of the ZnO nanorods was also examined by using Raman spectroscopy and Fourier transformed infrared spectroscopy (FTIR). It was found that the observed enhancements of FE characteristics could mainly be attributed to the increase in aspect ratio and associated number density of ZnO nanorods.     

The structural and optical properties of ZnO/Si thin films by RTA treatments

ZnO/Si thin films were prepared by rf magnetron sputtering method and some of the samples were treated by rapid thermal annealing (RTA) process at different temperatures ranging from 400 to 800 °C. The effects of RTA treatment on the structural properties were studied by using X-ray diffraction and atomic force microscopy while optical properties were studied by the photoluminescence measurements. It is observed that the ZnO film annealed at 600 °C reveals the strongest UV emission intensity and narrowest full width at half maximum among the temperature ranges studied. The enhanced UV emission from the film annealed at 600 °C is attributed to the improved crystalline quality of ZnO film due to the effective relaxation of residual compressive stress and achieving maximum grain size.     

The effect of heat treatment on the physical properties of sol-gel derived ZnO thin films

Zinc oxide (ZnO) thin films were deposited on microscope glass substrates by sol-gel spin coating method. Zinc acetate (ZnAc) dehydrate was used as the starting salt material source. A homogeneous and stable solution was prepared by dissolving ZnAc in the solution of monoethanolamine (MEA). ZnO thin films were obtained after preheating the spin coated thin films at 250 °C for 5 min after each coating. The films, after the deposition of the eighth layer, were annealed in air at temperatures of 300 °C, 400 °C and 500 °C for 1 h. The effect of thermal annealing in air on the physical properties of the sol-gel derived ZnO thin films are studied. The powder and its thin film were characterized by X-ray diffractometer (XRD) method. XRD analysis revealed that the annealed ZnO thin films consist of single phase ZnO with wurtzite structure (JCPDS 36-1451) and show the c-axis grain orientation. Increasing annealing temperature increased the c-axis orientation and the crystallite size of the film. The annealed films are highly transparent with average transmission exceeding 80% in the visible range (400-700 nm). The measured optical band gap values of the ZnO thin films were between 3.26 eV and 3.28 eV, which were in the range of band gap values of intrinsic ZnO (3.2-3.3 eV). SEM analysis of annealed thin films has shown a completely different surface morphology behavior.     

The Al-doping and post-annealing treatment effects on the structural and optical properties of ZnO:Al thin films deposited on Si substrate

Al-doped ZnO (ZnO:Al) thin films with different Al contents were deposited on Si substrates using the radio frequency reactive magnetron sputtering technique. X-ray diffraction (XRD) measurements showed that the crystallinity of the films was promoted by appropriate Al content (0.75 wt.%). Then the ZnO:Al film with Al content of 0.75 wt.% was annealed in vacuum at different temperatures. XRD patterns revealed that the residual compressive stress decreased at higher annealing temperatures. While the surface roughness of the ZnO:Al film annealed at 300 °C became smoother, those of the ZnO:Al films annealed at 600 and 750 °C became rougher. The photoluminescence (PL) measurements at room temperature revealed a violet, two blue and a green emission. The origin of these emissions was discussed and the mechanism of violet and blue emission of ZnO:Al thin films were suggested. We concluded that the defect centers are mainly ascribed to antisite oxygen and interstitial Zn in annealed (in vacuum) ZnO:Al films.     

Synthesis of Cu-ZnO and C-ZnO nanoneedle arrays on zinc foil by low temperature oxidation route: Effect of buffer layers on growth, optical and field emission properties

Different densities of ZnO nanoneedle films have been prepared by pre-coated zinc foils with thin layer of copper and carbon followed by thermal oxidation at 400 °C in air. The X-ray diffraction patterns show well defined peaks, which could be indexed to the wurtzite hexagonal phase of ZnO. The scanning electron microscope images clearly reveal formation of ZnO needles on the entire substrate surface. The X-ray photoelectron spectroscopy studies indicate that Cu and C ions are incorporated into the ZnO lattice. Photoluminescence studies evaluate different emission bands originated from different defect mechanism. From the field emission studies, the threshold field, required to draw emission current density of ∼100 μA/cm², is observed to be 2.25 V/μm and 1.57 V/μm for annealed zinc foil pre-coated with copper and carbon, respectively. The annealed film with copper layer exhibits good emission current stability at the pre-set value of ∼100 μA over a duration of 4 h. The results show that buffer layer is an important factor to control the growth rate, resulting in different density of ZnO needles, which leads to field emission properties. This method may have potential in fabrication of electron sources for high current density applications.     

Microstructural and surface property variations due to the amorphous region formed by thermal annealing in Al-doped ZnO thin films grown on n-Si (1 0 0) substrates

X-ray diffraction (XRD) patterns revealed that the as-grown and annealed Al-doped ZnO (AZO) films grown on the n-Si (1 0 0) substrates were polycrystalline. Transmission electron microscopy (TEM) images showed that bright-contrast regions existed in the grain boundary, and high-resolution TEM (HRTEM) images showed that the bright-contrast regions with an amorphous phase were embedded in the ZnO grains. While the surface roughness of the AZO film annealed at 800 °C became smoother, those of the AZO films annealed at 900 and 1000 °C became rougher. XRD patterns, TEM images, selected-area electron diffraction patterns, HRTEM images, and atomic force microscopy (AFM) images showed that the crystallinity in the AZO thin films grown on the n-Si (1 0 0) substrates was enhanced resulting from the release in the strain energy for the AZO thin films due to thermal annealing at 800 °C. XRD patterns and AFM images show that the crystallinity of the AZO thin films annealed at 1000 °C deteriorated due to the formation of the amorphous phase in the ZnO thin films.     

Influence of annealing temperature on the properties of ZnO thin films deposited by thermal evaporation

ZnO thin films were deposited by thermal evaporation of a ZnO powder. The as-deposited films are dark brown, rich zinc and present a low transmittance. Then, these films were annealed in air atmosphere at different temperatures between 100 and 400 °C. Their microstructure and composition were studied using XRD and RBS measurements respectively. By increasing the temperature, it was found that film oxidation starts at 250 °C. XRD peaks related to ZnO appear and peaks related to Zn decrease. At 300 °C, zinc was totally oxidised and the films became totally transparent. The electrical conductivity measurement that were carried out in function of the annealing temperature showed the transition from highly conductive Zn thin film to a lower conductive ZnO thin film. The optical gap (E_g) was deduced from the UV-vis transmittance, and its variation was linked to the formation of ZnO.     

Effect of growth time on the structure, Raman shift and photoluminescence of Al and Sb codoped ZnO nanorod ordered array thin films

Al and Sb codoped ZnO nanorod ordered array thin films have been deposited on glass substrate with a ZnO seed layer by hydrothermal method at different growth time. The effect of growth time on structure, Raman shift, and photoluminescence (PL) was studied. The thin films at growth time of 5 h consist of nanorods growth vertically oriented with ZnO seed layer, and the nanorods with an average diameter of 27.8 nm and a length of 1.02 μm consist of single crystalline wurtzite ZnO crystal and grow along [0 0 1] direction. Raman scattering analysis demonstrates that the thin films at the growth time of 5 h have great Raman shift of 15 cm⁻¹ to lower wavenumber and have low asymmetrical factor Г_a/Г_b of 1.17. Room temperature photoluminescence reveals that there is more donor-related PL in films with growth time of 5 h.     

Epitaxial growth of Sc-doped ZnO films on Si by sol-gel route

The epitaxial growth of doped ZnO films is of great technological importance. Present paper reports a detailed investigation of Sc-doped ZnO films grown on (1 0 0) silicon p-type substrates. The films were deposited by sol-gel technique using zinc acetate dihydrate as precursor, 2-methoxyethanol as solvent and monoethanolamine (MEA) as a stabilizer. Scandium was introduced as dopant in the solution by taking 0.5 wt%¹ of scandium nitrate hexahydrate. The effect of annealing on structural and photoluminescence properties of nano-textured Sc-doped films was investigated in the temperature range of 300-550 °C. Structural investigations were carried out using X-ray diffraction, scanning electron microscopy and atomic force microscopy. X-ray diffraction study revealed that highly c-axis oriented films with full-width half maximum of 0.21° are obtained at an annealing temperature of 400 °C. The SEM images of ZnO:Sc films have revealed that coalescence of ZnO grains occurs due to annealing. Ostwald ripening was found to be the dominant mass transport mechanism in the coalescence process. A surface roughness of 4.7 nm and packing density of 0.93 were observed for the films annealed at 400 °C. Room temperature photoluminescence (PL) measurements of ZnO:Sc films annealed at 400 °C showed ultraviolet peak at about (382 nm) with FWHM of 141 meV, which are comparable to those found in high-quality ZnO films. The films annealed below or above 400 °C exhibited green emission as well. The presence of green emission has been correlated with the structural changes due to annealing. Reflection high energy electron diffraction pattern confirmed the nearly epitaxial growth of the films.     

Photoluminescence study of pure and Li-doped ZnO thin films grown by sol-gel technique

The effect of annealing atmosphere, temperature and aging on the photoluminescence of pure and Li-doped ZnO thin films has been investigated. Annealing the pure ZnO in N₂ and He above 800 °C results in green emission centered at ca. 500 nm; however annealing in air red-shifts the green emission to 527 nm. The visible emission of the Li-doped ZnO is found to be largely dependent on the annealing atmosphere. Warm-white photoluminescence with a broad emission band covering nearly the whole visible spectrum is obtained for the Li-doped ZnO films annealed in helium. The substitutional and interstitial extrinsic point defects created by lithium doping may mediate the relative concentration of the intrinsic defects and thereby tune the intrinsic-defect-related visible emission. The enhanced intensity ratio of near-band-edge ultraviolet emission to deep-level visible emission with aging time may be ascribed to both in-diffusion of oxygen from air and self-diffusion of oxygen interstitials to heal the oxygen vacancies during the aging process.     

Enhanced field emission from Si doped nanocrystalline AlN thin films

Si doped and undoped nanocrystalline aluminum nitride thin films were deposited on various substrates by direct current sputtering technique. X-ray diffraction analysis confirmed the formation of phase pure hexagonal aluminum nitride with a single peak corresponding to (1 0 0) reflection of AlN with lattice constants, a = 0.3114 nm and c = 0.4986 nm. Energy dispersive analysis of X-rays confirmed the presence of Si in the doped AlN films. Atomic force microscopic studies showed that the average particle size of the film prepared at substrate temperature 200 °C was 9.5 nm, but when 5 at.% Si was incorporated the average particle size increased to ∼21 nm. Field emission study indicated that, with increasing Si doping concentration, the emission characteristics have been improved. The turn-on field (E_to) was 15.0 (±0.7) V/μm, 8.0 (±0.4) V/μm and 7.8 (±0.5) V/μm for undoped, 3 at.% and 5 at.% Si doped AlN films respectively and the maximum current density of 0.27 μA/cm² has been observed for 5 at.% Si doped nanocrystalline AlN film. It was also found that the dielectric properties were highly dependent on Si doping.     

Initial study on the structure and photoluminescence properties of SiC films doped with Al

SiC films doped with aluminum (Al) were prepared by the rf-magnetron sputtering technique on p-Si substrates with a composite target of a single crystalline SiC containing several Al pieces on the surface. The as-deposited films were annealed in the temperature range of 400-800 °C under nitrogen ambient. The thin films have been characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The results show that the introduction of Al into films hinders crystalline formation process. And with the increase of annealing temperature, more Si particles are formed in the films, which strongly affect the optical absorption properties. The photoluminescence (PL) spectra of the samples show two peaks at 370 nm and 412 nm. The intensities of the PL peaks are evidently improved after Al doped. We attribute the origin of the two PL peaks to a kind of Si-related defect centres. The obtained results are expected to have important applications in modern optoelectronic devices.     

Effect of annealing temperature and annealing atmosphere on the structure and optical properties of ZnO thin films on sapphire (0 0 0 1) substrates by magnetron sputtering

ZnO thin films were epitaxially grown on sapphire (0 0 0 1) substrates by radio frequency magnetron sputtering. ZnO thin films were then annealed at different temperatures in air and in various atmospheres at 800 °C, respectively. The effect of the annealing temperature and annealing atmosphere on the structure and optical properties of ZnO thin films are investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), photoluminescence (PL). A strong (0 0 2) diffraction peak of all ZnO thin films shows a polycrystalline hexagonal wurtzite structure and high preferential c-axis orientation. XRD and AFM results reveal that the better structural quality, relatively smaller tensile stress, smooth, uniform of ZnO thin films were obtained when annealed at 800 °C in N₂. Room temperature PL spectrum can be divided into the UV emission and the Visible broad band emission. The UV emission can be attributed to the near band edge emission (NBE) and the Visible broad band emission can be ascribed to the deep level emissions (DLE). By analyzing our experimental results, we recommend that the deep-level emission correspond to oxygen vacancy (V_O) and interstitial oxygen (O_i). The biggest ratio of the PL intensity of UV emission to that of visible emission (I_NBE/I_DLE) is observed from ZnO thin films annealed at 800 °C in N₂. Therefore, we suggest that annealing temperature of 800 °C and annealing atmosphere of N₂ are the most suitable annealing conditions for obtaining high quality ZnO thin films with good luminescence performance.     

Effects of different annealing atmospheres on the surface and microstructural properties of ZnO thin films grown on p-Si (1 0 0) substrates

Effects of different annealing atmospheres on the surface and microstructural properties of ZnO thin films grown on Si (1 0 0) substrates were investigated. X-ray diffraction results showed that the crystallinity of the ZnO thin film annealed in an oxygen atmosphere was better than that annealed in a nitrogen atmosphere. Atomic force microscopy and transmission electron microscopy (TEM) images showed that the surfaces of the ZnO thin films annealed in a nitrogen atmosphere became very rough in contrast to those annealed in an oxygen atmosphere. High-resolution TEM images showed that many stacking faults and tilted grains could be observed in the ZnO thin films annealed in a nitrogen atmosphere in contrast to those annealed in an oxygen atmosphere. Surface morphology and microstructural property variations due to different annealing atmospheres in ZnO thin films are also described on the basis of the experimental results.     

Transitions of microstructure and photoluminescence properties of the Ge/ZnO multilayer films in certain annealing temperature region

The Ge/ZnO multilayer films have been prepared by rf magnetron sputtering. The effects of annealing on the microstructure and photoluminescence properties of the multilayers have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) spectrometry and photoluminescence (PL) spectrometry. The investigation of structural properties indicates that Zn₂GeO₄ has been formed with (2 2 0) texture and Zn deficiency from Ge/ZnO multilayer films in the process of annealing. However, lower Zn/Ge ratio can be improved by annealing. The annealed multilayers show three main emission bands at 532, 700, and 761 nm, which originate from the transition between oxygen vacancy () and Zn vacancies (V_Zn), the radiative recombination of quantum-confined excitons (QCE) in Ge nanocrystals, and the optical transition in the GeO color centers, respectively. Finally, the fabrication of thin film Zn₂GeO₄ from Ge/ZnO multilayer films by annealing at low temperature provides another approach to prepare the green-emitting oxide phosphor film:Zn₂GeO₄:Mn.     

Sol-gel synthesis of sub-50 nm ZnO nanowires on pulse laser deposited ZnO thin films

A simple synthesis route to high-quality sub-50 nm ZnO nanowires is reported, utilizing ZnO thin films grown by pulse laser deposition (PLD) as seed layers. Depending upon the PLD growth conditions, the surface morphology of the ZnO nanowires on ZnO film was distinctively different whereas the diameters were almost the same. With the increase of the concentration of zinc nitrate/methenamine solution from 0.002 to 0.02 M, the average diameter of the ZnO nanowire increased but remained sub-50 nm. The grown ZnO nanowires showed a high crystallinity with a low defect density confirmed by a sharp photoluminescence spectrum.     

Structure and properties of ZnO films grown on Si substrates with low temperature buffer layers

Zinc oxide (ZnO) thin films were grown on Si (1 0 0) substrates by pulsed laser deposition (PLD) using two-step epitaxial growth method. Low temperature buffer layer (LTBL) was initially deposited in order to obtain high quality ZnO thin film; the as-deposited films were then annealed in air at 700 °C. The effects of LTBL and annealing treatment on the structural and luminescent properties of ZnO thin film were investigated. It was found that tensile strain was remarkably relaxed by employing LTBL and the band-gap redshifted, correspondingly. The shift value was larger than that calculated from band-gap theories. After annealing treatment, it was found that the annealing temperature with 700 °C has little influence on strains of ZnO films with LTBLs other than directly deposited film in our experiments. Interestingly, the different behaviors in terms of the shift of ultraviolet (UV) emission after annealing between films with and without buffer were observed, and a tentative explanation was given in this paper.     

The structural and optical properties of ZnO nanorod arrays

High quality vertical-aligned ZnO nanorod arrays were synthesized by a simple vapor transport process on Si (111) substrate at a low temperature of 520 °C. Field-emission scanning electron microscopy (FESEM) showed the nanorods have a uniform length of about 1 μm with diameters of 40-120 nm. X-ray diffraction (XRD) analysis confirmed that the nanorods are c-axis orientated. Selected area electron diffraction (SAED) analysis demonstrated the individual nanorod is single crystal. Photoluminescence (PL) measurements were adopted to analyze the optical properties of the nanorods both a strong UV emission and a weak deep-level emission were observed. The optical properties of the samples were also tested after annealing in oxygen atmosphere under different temperatures, deep-level related emission was found disappeared at 600 °C. The dependence of the optical properties on the annealing temperatures was also discussed.