Spray pyrolysis deposition of ZnO thin films on FTO coated substrates from zinc acetate and zinc chloride precursor solution at different growth temperatures

ZnO thin films were fabricated using zinc chloride and zinc acetate precursors by the spray pyrolysis technique on FTO coated glass substrates. The ZnO films were grown in different deposition temperature ranges varying from 400 to 550 °C. Influences of substrate temperature and zinc precursors on crystal structure, morphology and optical property of the ZnO thin films were investigated. XRD patterns of the films deposited using chloride precursor indicate that (1 0 1) is dominant at low temperatures, while those deposited using acetate precursor show that (1 0 1) is dominant at high temperatures. SEM images show that deposition temperature and type of precursor have a strong effect on the surface morphology. Optical measurements show that ZnO films are obviously influenced by the substrate temperatures and different types of precursor solutions. It is observed that as temperature increases, transmittance decreases for ZnO films obtained using zinc chloride precursor, but the optical transmittance of ZnO films obtained using zinc acetate precursor increases as temperature increases.     

Iron oxide thin film growth on Al2O3/NiAl(1 1 0)

The electronic structure and the growth morphology of iron oxide thin films were studied by means of Synchrotron Radiation Photoelectron Spectroscopy (SRPES) and Low Energy Electron Diffraction (LEED). A thin well-ordered alumina film on a NiAl(1 1 0) single crystal surface as a template for iron oxide growth was employed. Two different methods of iron oxide film preparation were applied. In the first attempt, iron deposited at room temperature was subsequently annealed in oxygen. Even though a whole layer of iron was oxidized, an expected long-range order was not achieved. The second attempt was to perform reactive deposition. For this reason iron was evaporated in oxygen ambient at elevated substrate temperature. This method turned out to be more efficient. Diffused but clear LEED patterns of six-fold symmetry indicating hexagonal surface atoms arrangement were observed. From the PES measurements, binding energies for Fe2p for grown iron oxide film were established as well as energy distribution curves for the valence band. Growth curves based on Fe3p core-level peak intensities for iron and iron oxide were plotted identifying type of film growth for both deposition methods. Based upon these results we have found evidence for interdiffusion in the interface between alumina and iron oxide at the early stages of growth. Further deposition led to formation of Fe₃O₄(1 1 1) (magnetite) overlayer. Moreover, the quality of the film could also be improved by long-time annealing at temperatures not exceeding 575 K. Higher annealing temperature caused disappearance of LEED pattern indicating loss of long-range ordering.     

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.     

Effects of deposition temperature and thickness on the structural properties of thermal evaporated bismuth thin films

Bismuth (Bi) thin films of different thicknesses were deposited onto Si(1 0 0) substrate at various substrate temperatures by thermal evaporation technique. Influences of thickness and deposition temperature on the film morphologies, microstructure, and topographies were investigated. A columnar growth of hexahedron-like grains with bimodal particle size distribution was observed at high deposition temperature. The columnar growth and the presence of large grains induce the Bi films to have large surface roughness as evidenced by atomic force microscopy (AFM). The dependence of the crystalline orientation on the substrate temperature was analyzed by X-ray diffraction (XRD), which shows that the Bi films have completely randomly oriented polycrystalline structure with a rhombohedral phase at high deposition temperature (200 °C) and were strongly textured with preferred orientation at low deposition temperatures (30 and 100 °C).     

Self-limiting growth of ZnO films on (0 0 0 1) sapphire substrates by atomic layer deposition at low temperatures using diethyl-zinc and nitrous oxide

Atomic layer deposition (ALD) of zinc oxide (ZnO) films on (0 0 0 1) sapphire substrates was conducted at low temperatures by using diethyl-zinc (DEZn) and nitrous oxide (N₂O) as precursors. It was found that a monolayer-by-monolayer growth regime occurred at 300 °C in a range of DEZn flow rates from 5.7 to 8.7 μmol/min. Furthermore, the temperature self-limiting process window for the ALD-grown ZnO films was also observed ranging from 290 to 310 °C. A deposition mechanism is proposed to explain how saturated growth of ZnO is achieved by using DEZn and N₂O. Transmission spectroscopic studies of the ZnO films prepared in the self-limiting regime show that the transmittances of ZnO films are as high as 80% in visible and near infrared spectra. Experimental results indicate that ZnO films with high optical quality can be achieved by ALD at low temperatures using DEZn and N₂O precursors.     

Effect of temperature on pulsed laser deposition of ZnO films

ZnO thin films have been deposited on Si(1 1 1) substrates at different substrate temperature by pulsed laser deposition (PLD) of ZnO target in oxygen atmosphere. An Nd:YAG pulsed laser with a wavelength of 1064 nm was used as laser source. The influences of the deposition temperature on the thickness, crystallinity, surface morphology and optical properties of ZnO films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), selected area electron diffraction (SAED), photoluminescence (PL) spectrum and infrared spectrum. The results show that in our experimental conditions, the ZnO thin films deposited at 400 °C have the best surface morphology and crystalline quality. And the PL spectrum with the strongest ultraviolet (UV) peak and blue peak is observed in this condition.     

Lead-free ferroelectric thin films obtained by pulsed laser deposition

Na_0.5Bi_0.5TiO₃-BaTiO₃ (NBT-BT) thin films grown by pulsed laser deposition have been investigated by X-ray diffraction, scanning electron microscopy, and dielectric spectroscopy in order to clarify the role of substrate temperature on crystalline structure, grain morphology, and dielectric properties. We have shown that the structural and dielectric properties of NBT-BT thin films with composition at morphotropic phase boundary (6% BT) critically depend on the substrate temperature: small variations of this parameter induce structural changes, shifting the morphotropic phase boundary toward tetragonal or rhombohedral side. Higher deposition temperature (1000 K) favor the formation of rhombohedral phase, films deposited at 923 K and 973 K have tetragonal symmetry at room temperature. Grains morphology depends also on the deposition temperature. Atomic force micrographs show grains with square or rectangular shape in a compact structure for films grown at lower temperatures, while grains with triangular shape in a porous structure are observed for films grown at 1000 K. Dielectric spectroscopy measurements evidenced the phase transition between ferroelectric and antiferroelectric phase at 370 K. Films grown at 1000 K shown low electrical resistivity due to their porous structure. High dielectric constant values (about 800 at room temperature and 2700 at 570 K) have been obtained for films grown at temperatures up to 973 K.     

Deposition of aluminum nitride thin film on Si(1 1 1) by KrF excimer laser and its characterizations

We present the deposition of aluminum nitride (AlN) thin film by KrF excimer laser sputtering and the study of the effects of substrate temperature and laser fluences. Deposition rate of AlN thin film at 0.3 Å/pulse has been achieved with laser fluence of 1500 mJ/cm² and at substrate temperature of 250 K, and this shows the enhancement of the deposition rate at low substrate temperature. Surface morphology of the deposited films is characterized by atomic force microscopy (AFM). In addition, the electrical performance of the MIS devices with AlN thin films prepared in this experiment has been characterized.     

Formation of Al-N co-doped p-ZnO/n-Si (1 0 0) heterojunction structure by RF co-sputtering technique

Al-N co-doped ZnO (ZnO:Al-N) thin films were grown on n-Si (1 0 0) substrate by RF co-sputtering technique. As-grown ZnO:Al-N film exhibited n-type conductivity whereas on annealing in Ar ambient the conduction of ZnO:Al-N film changes to p-type, typically at 600 °C the high hole concentration of ZnO:Al-N co-doped film was found to be 2.86 × 10¹⁹ cm⁻³ and a low resistivity of 1.85 × 10⁻² Ω-cm. The current-voltage characteristics of the obtained p-ZnO:Al-N/n-Si heterojunction showed good diode like rectifying behavior. Room temperature photoluminescence spectra of annealed co-doped films revealed a dominant peak at 3.24 eV.     

Misfit driven azimuthal orientation of NaCl domains on Ag(1 0 0)

We investigated the growth of thin NaCl films on Ag(1 0 0) by spot-profile-analysis low energy electron diffraction (SPA-LEED), varying extensively the growth temperature (200–500 K) and the film thickness (0.5–14 ML). The incommensurate growth of NaCl on Ag(1 0 0) yields (1 0 0)-terminated epitaxial NaCl domains, which are preferentially oriented with their [0 1 0] axis parallel to that of the substrate. At 300 K, the NaCl domains exhibit an azimuthal mosaicity by 14° around this orientation and the NaCl unit cell is laterally contracted in the first layers by 0.9% with respect to the bulk. At higher growth temperatures, the azimuthal mosaic distribution sharpens and additional distinct orientations appear, presumably due to a higher-order commensurability. The evolution of the azimuthal mosaic distribution with increasing temperature can be ascribed to both the NaCl thermal expansion and higher diffusion rates of NaCl on Ag(1 0 0). The best epitaxy, i.e. that with the highest selectivity of a specific azimuthal domain orientation, is achieved by growing NaCl films at low deposition rate (0.1 ML min⁻¹) on the Ag(1 0 0) substrate at constant high temperature (450–500 K). The observations made here can probably be applied more generally to other heterogeneous interfaces and, in particular, be used to improve the quality of thin insulating films.     

First-principles calculation of Mg(0 0 0 1) thin films: Quantum size effect and adsorption of atomic hydrogen

We have carried out first-principles calculation of Mg(0 0 0 1) free-standing thin films to study the oscillatory quantum size effect exhibited in the surface energy, work function, interlayer relaxation, and adsorption energy of the atomic hydrogen adsorbate. The quantum well states have been shown. The calculated energetics and interlayer relaxation of clean and H-adsorbed Mg films are clearly featured by quantum oscillations as a function of the thickness of the film, with oscillation period of about eight monolayers, consistent with recent experiments. The calculated quantum size effect in H adsorption can be verified by observing the dependence of H coverage on the thickness of Mg(0 0 0 1) thin films gown on Si(1 1 1) or W(1 1 0) substrate which has been experimentally accessible.     

Characteristics of Ni films deposited on SiO2/Si(1 0 0) and MgO(0 0 1) by direct current magnetron sputtering system with the oblique target

280 nm-thick Ni films were deposited on SiO₂/Si(1 0 0) and MgO(0 0 1) substrates at 300 K, 513 K and 663 K by a direct current magnetron sputtering system with the oblique target. The films deposited at 300 K mainly have a [1 1 0] crystalline orientation in the film growth direction. The [1 1 0]-orientation weakens and the [1 1 1]- and [1 0 0]-orientations enhance with increasing deposition temperature. The lattice constant of the Ni films is smaller than that of the Ni bulk, except for the film grown on MgO(0 0 1) at 663 K. Furthermore, as the deposition temperature increases, the lattice constant of the films grown on the SiO₂/Si(1 0 0) decreases whereas that of the films grown on the MgO(0 0 1) increases. The films deposited at 300 K and 513 K grow with columnar grains perpendicular to the substrate. For the films deposited at 663 K, however, the columnar grain structure is destroyed, i.e., an about 50 nm-thick layer consisting of granular grains is formed at the interface between the film and the substrate and then large grains grow on the layer. The Ni films deposited at 300 K consist of thin columnar grains and have many voids at the grain boundaries. The grains become thick and the voids decrease with increasing deposition temperature. The resistivity of the film decreases and the saturation magnetization increases with increasing deposition temperature.     

Si(001)基片上反应射频磁控溅射ZnO薄膜的两步生长方法

利用反应射频磁控溅射技术，采用两步生长方法制备了ZnO薄膜，探讨了基片刻蚀时间和低温过渡层沉积时间对ZnO薄膜生长行为的影响.研究结果表明，低温ZnO过渡层的沉积时间所导致的薄膜表面形貌的变化与过渡层在Si(001)表面的覆盖度有关.当低温过渡层尚未完全覆盖基片表面时，ZnO薄膜的表面岛尺度较小、表面粗糙度较大，薄膜应力较大；当低温过渡层完全覆盖Si(001)基片后，ZnO薄膜的表面岛尺度较大、表面粗糙度较小，薄膜应力较小.基片刻蚀时间对薄膜表面形貌的影响与低温过渡层的成核密度有关.随着刻蚀时间的增加，ZnO薄膜的表面粗糙度逐渐下降，表面形貌自仿射结构的关联长度逐渐减小. 关键词： ZnO薄膜 反应射频磁控溅射 两步生长 形貌分析     

Second harmonic generation of fluorine-doped zinc oxide thin films grown on soda-lime glass substrates by a chemical spray technique

Second harmonic generation (SHG) studies of fluorine-doped zinc oxide (ZnO:F) thin films deposited on soda-lime glass substrates from an aged solution in conjunction with zinc pentanedionate, using the chemical spray deposition technique were carried out. The and independent tensorial components of the quadratic nonlinear optical susceptibility of the ZnO:F thin films were evaluated. Scanning electron microscopy and X-ray diffraction investigations revealed a homogeneous distribution of nanoparticles of similar size and morphology for various samples deposited at different substrate temperatures (ranging from 400 to 525 °C). The SHG-technique revealed a clear dependence of the nonlinear optical response with the deposition temperature. Typical optical transmittance and photoluminescence (PL) studies were also performed, from which a bandgap (E_g) of 3.3 eV was evaluated in films deposited under optimal conditions of conductivity and transmittance.     

Direct current magnetron sputter-deposited ZnO thin films

Zinc oxide (ZnO) is a very promising electronic material for emerging transparent large-area electronic applications including thin-film sensors, transistors and solar cells. We fabricated ZnO thin films by employing direct current (DC) magnetron sputtering deposition technique. ZnO films with different thicknesses ranging from 150 nm to 750 nm were deposited on glass substrates. The deposition pressure and the substrate temperature were varied from 12 mTorr to 25 mTorr, and from room temperature to 450 °C, respectively. The influence of the film thickness, deposition pressure and the substrate temperature on structural and optical properties of the ZnO films was investigated using atomic force microscopy (AFM) and ultraviolet-visible (UV-Vis) spectrometer. The experimental results reveal that the film thickness, deposition pressure and the substrate temperature play significant role in the structural formation and the optical properties of the deposited ZnO thin films.     

Effect of temperature on pulsed laser deposition of HgCdTe films

HgCdTe thin films have been deposited on Si(1 1 1) substrates at different substrate temperatures by pulsed laser deposition (PLD). An Nd:YAG pulsed laser with a wavelength of 1064 nm was used as laser source. The influences of the substrate temperature on the crystalline quality, surface morphology and composition of HgCdTe thin films were characterized by X-ray diffraction (XRD), selected area electron diffraction (SAED), atomic force microscopy (AFM) and energy dispersive X-ray spectroscopy (EDS). The results show that in our experimental conditions, the HgCdTe thin films deposited at 200 °C have the best quality. When the substrate temperature is over 250 °C, the HgCdTe film becomes thermodynamically unstable and the quality of the film is degraded.     

Morphological,optical, and nonlinear optical properties of fluorine-indium-doped zinc oxide thin films

Chemically sprayed fluorine-indium-doped zinc oxide thin films (ZnO:F:In) were deposited on glass substrates. A mixture of zinc pentanedionate, indium sulfate, and fluoride acid was used in the starting solution. The influence of both the dopant concentration in the starting solution and the substrate temperature on the transport, morphological, linear, and nonlinear optical (NLO) properties were fully characterized with atomic force microscopy (AFM), scanning-electron microscopy (SEM), UV-VIS, and photoluminescence (PL) spectroscopies, and the second-harmonic generation (SHG) technique, respectively. A decrease in the resistivity was observed for increasing substrate temperatures, reaching a minimum value of 1.2 × 10^?2 Ω cm for samples deposited at 500°C. The surface morphology was also dependent on the dopant concentration in the starting solution and on the substrate temperature. The X-ray diffraction (XRD) patterns revealed that the ZnO:F:In thin solid films are polycrystalline in nature fitting with a hexagonal wurtize type and showing (002) preferential growth for all of the studied samples. The optical transmittance of these films was found to be higher than 80%, from which the optical band gap of these samples was determined. Finally, a clear dependence on the quadratic NLO properties of the developed semiconducting ZnO:F:In thin films with the substrate temperatures was established, where huge x ⁽²⁾-NLO coefficients on the order of x ₃₃ ⁽²⁾ = 37 pm V^?1 were measured for high substrate temperatures.     

Regrowth of ZnO thin film with high surface flatness and enhanced optical properties on annealed buffer layers by rf sputtering deposition

We report a study on improving the surface flatness, optical properties, and crystallinity of ZnO thin films by rf sputtering deposition. ZnO thin films grown on sapphire substrate were first exposed to post-growth annealing, and then used to regrow high-quality ZnO thin films on top. Under the same deposition conditions, the regrown ZnO layers showed much improved crystallinity, surface flatness and enhanced optical properties. The effect of the annealed layer in improving the quality of the ZnO thin film is discussed in terms of characterization results from crystal orientation, surface morphology, and photoluminescence. It was clearly observed that, during the annealing process, the ZnO grains coalesced to form larger grains and smoother surfaces, with better crystallinity and fewer defects, which resulted in the much improved quality of the regrown ZnO thin films.     

A route to continuous ultra-thin cerium oxide films on Cu(1 1 1)

The growth and morphology of ultra-thin CeO₂(1 1 1) films on a Cu(1 1 1) substrate were investigated by means of low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). The films were grown by physical vapor deposition of cerium in an oxygen atmosphere at different sample temperatures. The preparation procedure is based on a modification of a previous method suggested by Matolin and co-workers [1], involving growth at elevated temperature (520 K). Here, LEED shows good long range ordering with a “(1.5 × 1.5)” superstructure, but STM reveals a three-dimensional growth mode (Vollmer-Weber) with formation of a closed film only at larger thickness. Using a kinetically limited growth process by reactive deposition at low sample temperatures (100 K) and subsequent annealing, we show that closed layers of ceria with atomically flat terraces can be prepared even in the regime of ultra-thin films (1.5 ML). Closed and atomically flat ceria films of larger thickness (3 ML) are obtained by applying a multistep preparation procedure, in which successive ceria layers are homoepitaxially grown on this initial film. The resulting overlayers show strong similarities with the morphology of CeO₂(1 1 1) single crystal surfaces, suggesting the possibility to model bulk ceria by thin film systems.     

Effects of post-annealing on the structural and nanomechanical properties of Ga-doped ZnO thin films deposited on glass substrate by rf-magnetron sputtering

In this study, the effects of post-annealing on the structure, surface morphology and nanomechanical properties of ZnO thin films doped with a nominal concentration of 3 at.% Ga (ZnO:Ga) are investigated using X-ray diffraction (XRD), atomic force microscopy (AFM) and scanning electron microscopy (SEM) and nanoindentation techniques. The ZnO:Ga thin films were deposited on the glass substrates at room temperature by radio frequency magnetron sputtering. Results revealed that the as-deposited ZnO:Ga thin films were polycrystalline albeit the low deposition temperature. Post-annealing carried out at 300, 400 and 500 °C, respectively, has resulted in progressive increase in both the average grain size and the surface roughness of the ZnO:Ga thin film, in addition to the improved thin films crystallinity. Moreover, the hardness and Young's modulus of ZnO:Ga thin films are measured by a Berkovich nanoindenter operated with the continuous contact stiffness measurements (CSM) option. The hardness and Young's modulus of ZnO:Ga thin films increased as the annealing temperature increased from 300 to 500 °C, with the best results being obtained at 500 °C.