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.     

Post-annealing influence on properties of N-In codoped ZnO thin films prepared by ion beam enhanced deposition method

N-In codoped ZnO thin films were prepared by ion beam enhanced deposition method (IBED) and were annealed in nitrogen and oxygen ambient after deposition. The influence of post-annealing on structure, electrical and optical properties of thin films were investigated. As-deposited and all post-annealed samples showed preferential orientation along (0 0 2) plane. Electrical property studies indicated that the as-deposited ZnO film showed p-type with a sheet resistance of 67.5 kΩ. For ZnO films annealed in nitrogen with the annealing temperature increasing from 400 to 800 °C, the conduction type of the ZnO film changed from p-type to n-type. However, for samples annealed in oxygen the resistance increased sharply even at a low annealing temperature of 400 °C and the conduction type did not change. Room temperature PL spectra of samples annealed in N₂ and in O₂ showed UV peak located at 381 and 356 nm, respectively.     

Effects of rapid thermal annealing on structural, magnetic and optical properties of Ni-doped ZnO thin films

XPS depth profiles were used to investigate the effects of rapid thermal annealing under varying conditions on the structural, magnetic and optical properties of Ni-doped ZnO thin films. Oxidization of metallic Ni from its metallic state to two-valence oxidation state occurred in the film annealed in air at 600 °C, while reduction of Ni²⁺ from its two-valence oxidation state to metallic state occurred in the film annealed in Ar at 600 and 800 °C. In addition, there appeared to be significant diffusion of Ni from the bottom to the top surface of the film during annealing in Ar at 800 °C. Both as-deposited and annealed thin films displayed obvious room temperature ferromagnetism (RTFM) which was from metallic Ni, Ni²⁺ or both with two distinct mechanisms. Furthermore, a significant improvement in saturation magnetization (M_s) in the films was observed after annealing in air (M_s = 0.036 μ_B/Ni) or Ar (M_s = 0.033 μ_B/Ni) at 600 °C compared to that in as-deposited film (M_s = 0.017 μ_B/Ni). An even higher M_s value was observed in the film annealed in Ar at 800 °C (M_s = 0.055 μ_B/Ni) compared to that at 600 °C mainly due to the diffusion of Ni. The ultraviolet emission of the Ni-doped ZnO thin film was restored during annealing in Ar at 800 °C, which was also attributed to the diffusion of Ni.     

Structural and photoluminescence characteristics of ZnO films by room temperature sputtering and rapid thermal annealing process

ZnO thin films deposited on SiO₂/Si substrates at room temperature by sputtering technology were annealed with a rapid thermal annealing process at various temperatures from 200 °C to 900 °C. The physical and optical properties of the ZnO films were investigated by X-ray diffraction, scanning electron microscopy and room-temperature photoluminescence (PL). The surface structures of the thin films showed great variations with increased annealing temperature. The PL spectrum illustrated that a stronger UV emission intensity appeared at an annealing temperature of 500 °C. On the other hand, visible-light emission could be obtained when the ZnO films were annealed above 500 °C and reached a maximum intensity at 900 °C. The possible mechanisms for visible-light emission are discussed. PACS 81.15.Cd; 81.40.Ef; 78.55.-m; 78.55.Et     

ZnO thin films on Si(1 1 1) grown by pulsed laser deposition from metallic Zn target

ZnO thin films with highly c-axis orientation have been fabricated on p-type Si(1 1 1) substrates at 400 °C by pulsed laser deposition (PLD) from a metallic Zn target with oxygen pressures between 0.1 and 0.7 mbar. Experimental results indicate that the films deposited at 0.3 and 0.5 mbar have better crystalline and optical quality and flatter surfaces than the films prepared at other pressures. The full width at half maximum (FWHM) of (0 0 0 2) diffraction peak decreases remarkably from 0.46 to 0.19° with increasing annealing temperature for the film prepared at 0.3 mbar. In photoluminescence (PL) spectra at room temperature, the annealed film at 700 °C exhibits a smaller ultraviolet (UV) peak FWHM of 108 meV than the as-grown film (119 meV). However, an enhanced deep-level emission is observed. Possible origins to above results are discussed.     

Effect of different annealing temperature on Sb-doped ZnO thin films prepared by pulsed laser deposition on sapphire substrates

Influence of annealing temperature on the properties of Sb-doped ZnO thin films were studied. Hall measurement results indicated that the Sb-doped ZnO annealed at 950 °C was p-type conductivity. X-ray diffraction (XRD) results indicated that the Sb-doped ZnO thin films prepared at the experiments are high c-axis oriented. It was worth noting that p-type sample had the worst crystallinity. The measurements of low-temperature photoluminescence (PL) spectra indicate that the sample annealed at the temperatures of 950 °C showed strong acceptor-bound exciton (A⁰X) emission, and confirmed that it is related to Sb-doping by comparing with the undoped ZnO low-temperature PL spectrum.     

Influence of annealing temperature on the structural, optical and mechanical properties of ALD-derived ZnO thin films

ZnO thin films grown on Si(1 1 1) substrates by using atomic layer deposition (ALD) were annealed at the temperatures ranging from 300 to 500 °C. The X-ray diffraction (XRD) results show that the annealed ZnO thin films are highly (0 0 2)-oriented, indicating a well ordered microstructure. The film surface examined by the atomic force microscopy (AFM), however, indicated that the roughness increases with increasing annealing temperature. The photoluminescence (PL) spectrum showed that the intensity of UV emission was strongest for films annealed at 500 °C. The mechanical properties of the resultant ZnO thin films investigated by nanoindentation reveal that the hardness decreases from 9.2 GPa to 7.2 GPa for films annealed at 300 °C and 500 °C, respectively. On the other hand, the Young's modulus for the former is 168.6 GPa as compared to a value of 139.5 GPa for the latter. Moreover, the relationship between the hardness and film grain size appear to follow closely with the Hall-Petch equation.     

Influence of annealing temperature on structural and optical properties of ZnO: In thin films prepared by ultrasonic spray technique

Transparent conducting indium doped zinc oxide was deposited on glass substrate by ultrasonic spray method. The In doped ZnO samples with indium concentration of 3 wt.% were deposited at 300, 350 and 400 °C with 2 min of deposition time. The effects of substrate temperature and annealing temperature on the structural, electrical and optical properties were examined. The DRX analyses indicated that In doped ZnO films have polycrystalline nature and hexagonal wurtzite structure with (0 0 2) preferential orientation and the maximum average crystallite size of ZnO: In before and annealed at 500 °C were 45.78 and 55.47 nm at a substrate temperature of 350 °C. The crystallinity of the thin films increased by increasing the substrate temperature up 350 °C, the crystallinity improved after annealing temperature at 500 °C. The film annealed at 500 °C and deposited at 350 °C show lower absorption within the visible wavelength region. The band gap energy increased from E_g = 3.25 to 3.36 eV for without annealing and annealed films at 500 °C, respectively, indicating that the increase in the transition tail width. This is due to the increase in the electrical conductivity of the films after annealing temperature.     

Effect of annealing on the properties of N-doped ZnO films deposited by RF magnetron sputtering

N-doped ZnO films were deposited by RF magnetron sputtering in N₂/Ar gas mixture and were post-annealed at different temperatures (T_a) ranging from 400 to 800 °C in O₂ gas at atmospheric pressure. The as-deposited and post-annealed films were characterized by their structural (XRD), compositional (SIMS, XPS), optical (UV-vis-NIR spectrometry), electrical (Hall measurements), and optoelectronic properties (PL spectra). The XRD results authenticate the improvement of crystallinity following post-annealing. The weak intensity of the (0 0 2) reflection obtained for the as-deposited N-doped ZnO films was increased with the increasing T_a to become the preferred orientation at higher T_a (800 °C). The amount of N-concentration and the chemical states of N element in ZnO films were changed with the T_a, especially above 400 °C. The average visible transmittance (400-800 nm) of the as-deposited films (26%) was increased with the increasing T_a to reach a maximum of 75% at 600 °C but then decreased. In the PL spectra, A⁰X emission at 3.321 eV was observed for T_a = 400 °C besides the main D⁰X emission. The intensity of the A⁰X emission was decreased with the increasing T_a whereas D⁰X emission became sharper and more optical emission centers were observed when T_a is increased above 400 °C.     

Effect of the annealing environment on the optical properties of ZnO/GaAs grown by MOCVD

The optical properties of ZnO grown on (1 0 0) GaAs substrate using metalorganic chemical vapor deposition are investigated by photoluminescence (PL) spectroscopy. Postgrowth annealing in nitrogen and oxygen was performed for different times and temperatures in order to incorporate As from the substrate into the ZnO thin films. The PL spectra of the samples annealed in different ambients reveal that the effect of As diffusion into the ZnO thin films is more pronounced when the annealing is performed in oxygen at 550 °C. The 11 K PL spectra show the appearance of a transition at ∼3.35 eV after annealing in oxygen at 550 °C for 1 h. A further increase in the annealing temperature leads to the disappearance of this line, while for annealing times longer than 2 h at 550 °C, it is no longer prominent. The increase in intensity of this new transition is also accompanied by the enhancement of radiative centers related to structural defects, such as the stacking fault-related transition at 3.31 eV and the Y-line. Temperature dependent PL illustrates the excitonic nature of the new transition at ∼3.35 eV, which is therefore assigned to (A⁰, X) transition, where the acceptor is possibly the 2V_Zn-As_Zn complex, with an activation energy E_A in the range of 160-240 meV. Furthermore, the enhancement of the radiative centers related to structural defects is regarded as evidence that As atoms tend to segregate in the vicinity of structural defects to relieve local strain.     

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.     

High efficiency white luminescence of alumina doped ZnO

The application of alumina-doped ZnO (AZO) films as luminescent material for large area lighting sources has been evaluated. Thin films were grown on quartz using magnetron sputtering and subsequently annealed under argon atmosphere in a rapid thermal annealing experiment. Below 550 °C, red-shift of the optical band gap and increase of the visible emission are observed in agreement with Al diffusion and formation of interstitial oxygen atoms. At temperatures higher than 800 °C, diffusion is activated and Ostwald ripening leads to the formation of larger grains and an increase of the crystalline phase. The photoluminescence (PL) intensity is enhanced, specifically in the UV range. As a result the emission spectrum of AZO thin films can be adjusted by the annealing conditions, with equal contributions from the UV and orange parts of the PL spectrum resulting in an efficient white emission as quantified using the color space map of the Commission Internationale de l'Éclairage.     

Effects of magnesium film thickness and annealing temperature on formation of Mg2Si films on silicon (1 1 1) substrate deposited by magnetron sputtering

Magnesium films of various thicknesses were first deposited on silicon (1 1 1) substrates by magnetron sputtering method and then annealed in annealing furnace filled with argon gas. The effects of the magnesium film thickness and the annealing temperature on the formation of Mg₂Si films were investigated by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). The Mg₂Si thin films thus obtained were found to be polycrystalline and the Mg₂Si (2 2 0) orientation is preferred regardless of the magnesium film thickness and annealing temperature. XRD results indicate that high quality magnesium silicide films are produced if the magnesium/silicon samples are annealed at 400 °C for 5 h. Otherwise, the synthesized films annealed at annealing temperatures lower than 350 °C or higher than 450 °C contain magnesium crystallites or magnesium oxide. SEM images have revealed that microstructure grains in the polycrystalline films are about 1-5 μm in dimensions, and the texture of the Mg₂Si films becomes denser and more homogeneous as the thickness of the magnesium film increases.     

Pure UV photoluminescence from ZnO thin film by thermal retardation and using an amorphous SiO2 buffer layer

ZnO/SiO₂ thin films were fabricated on Si substrates by E-beam evaporation with thermal retardation. The as-prepared films were annealed for 2 h every 100 °C in the temperature range 400-800 °C under ambient air. The structural and optical properties were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL). The XRD analysis indicated that all ZnO thin films had a highly preferred orientation with the c-axis perpendicular to the substrate. From AFM images (AFM scan size is 1 μm×1 μm), the RMS roughnesses of the films were 3.82, 5.18, 3.65, 3.40 and 13.2 nm, respectively. PL measurements indicated that UV luminescence at only 374 nm was observed for all samples. The optical quality of the ZnO film was increased by thermal retardation and by using an amorphous SiO₂ buffer layer.     

Unidirectional variation of lattice constants of Al-N-codoped ZnO films by RF magnetron sputtering

Al-N-codoped ZnO films were fabricated by RF magnetron sputtering in the ambient of N₂ and O₂ on silicon (1 0 0) and homo-buffer layer, subsequently, annealed in O₂ at low pressure. X-ray diffraction (XRD) spectra show that as-grown and 600 °C annealed films grown by codoping method are prolonged along crystal c-axis. However, they are not prolonged in (0 0 1) plane vertical to c-axis. The films annealed at 800 °C are not prolonged in any directions. Codoping makes ZnO films unidirectional variation. X-ray photoelectron spectroscopy (XPS) shows that Al content hardly varies and N escapes with increasing annealing temperature from 600 °C to 800 °C.     

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.     

Effect of annealing temperature on photocatalytic activity of ZnO thin films prepared by sol-gel method

Zinc oxide thin films are deposited on Si and quartz substrates using the sol-gel method. The thin films, annealed at 400, 600 and 800 °C respectively, are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), ultraviolet-visible spectrophotometer (UV-Vis), fluorescence spectrometer (FL) and the photocatalytic activity is tested by the decomposition of methyl orange dye under UV illumination. The results show that the mean grain size, surface-to-volume ratio, rms roughness and degradation efficiency of the thin films increases with increasing annealing temperature. In particular, ZnO thin film annealed at 800 °C exhibits the highest photocatalytic activity, degrading methyl orange by almost 88% in 180 min. Photocatalytic reaction mechanism of the ZnO thin films is discussed in detail, and the oxygen defects are proposed to be the active sites of the ZnO photocatalyst.     

Effects of annealing temperature and method on structural and optical properties of TiO2 films prepared by RF magnetron sputtering at room temperature

TiO₂ thin film was deposited on non-heated Si(1 0 0) substrate by RF magnetron sputtering. The as-deposited films were annealed by a conventional thermal annealing (CTA) and rapid thermal annealing (RTA) at 700 and 800 °C, and the effects of annealing temperature and method on optical properties of studied films were investigated by measuring the optical band gaps and FT-IR spectra. And we also compared the XRD patterns of the studied samples. The as-deposited film showed a mixed structure of anatase and brookite. Only rutile structures were found in samples annealed above 800 °C by CTA, while there are no special peaks except the weak brookite B(2 3 2) peak for the sample annealed at (or above) 800 °C by RTA. FT-IR spectra show the broad peaks due to Ti-O vibration mode in the range of 590-620 cm⁻¹ for the as-deposited film as well as samples annealed by both annealing methods at 700 °C. The studied samples all had the peaks from Si-O vibration mode, which seemed to be due to the reaction between TiO₂ and Si substrate, and the intensities of these peaks increased with increasing of annealing temperature. The optical band gap of the as-deposited film was 3.29 eV but it varied from 3.39 to 3.43 eV as the annealing temperature increased from 700 to 800 °C in the samples annealed by CTA. However, it varied from 3.38 to 3.32 eV as the annealing temperature increased from 700 to 800 °C by RTA.     

Structural and optical properties of Au-implanted ZnO films

The structural and luminescence related optical behaviours of Au ion implanted ZnO films grown by magnetic sputtering and their post implantation annealing behaviours in the temperature range of 100-700 °C have been investigated. Optical absorption and transmittance spectra of the films indicate that band edge of Au-implanted ZnO has shifted to high energy range and optical band gap has increased, because the sharp difference of thermal expansion induces the lattice mismatch between ZnO and SiO₂. PL spectra reveal that UV and visible luminescence bands of ZnO films can be improved after thermal annealing due to recovery of defects and Au ions incorporation. Importantly, green luminescence band of 530 nm has been only observed in the Au-implanted and subsequently annealed ZnO films and it enhances with the increasing annealing temperature, which can be related to Au atoms or clusters in ZnO films. Furthermore, X-ray photoelectron spectroscopy measurements reveal that the Au⁰ is dominant state in Au implanted and annealed ZnO films. Possible mechanisms, such as optical transitions of Au atoms or clusters and deep level luminescence of ZnO, have been proposed for green emission.     

Epitaxially grown ZnO thin films on 6H-SiC(0 0 0 1) substrates prepared by spin coating-pyrolysis

Epitaxially grown ZnO thin film on 6H-SiC(0 0 0 1) substrate was prepared by using a spin coating-pyrolysis with a zinc naphthenate precursor. As-deposited film was pyrolyzed at 500 °C for 10 min in air and finally annealed at 800 °C for 30 min in air. In-plane alignment of the film was investigated by X-ray pole-figure analysis. Field emission-scanning electron microscope, scanning probe microscope, and He-Cd laser (325 nm) was used to analyze the surface morphology, the surface roughness and photoluminescence of the films. In the photoluminescence spectra, near-band-edge emission with a broad deep-level emission was observed. The position of the near-band-edge peak was around 3.27 eV.