Microstructure of ZnO thin films produced by magnetron sputter oblique deposition

ZnO films deposited at different oblique angles of 40, 60 and 80°, under different Ar pressures 0.27, 0.67, 1.33 and 2.67 Pa, DC currents of 0.15 and 0.25 A, and distances of 10-15 cm from the target were studied. It was found that the film grains grow at an angle to the substrate when deposition angle is above 40°. It was shown that the grains consisted of a number of small crystals growing one on top of the other and shifted towards the target with the crystal orientation not along the grain growth but perpendicular to the substrate. Crystal size decreased with the deposition angle and internal stress disappeared when α = 80°. It was found that 1.33 Pa pressure provided the best balance between the deposition parameters. Growth rate reached maximum, samples had the biggest crystal size and high crystal density. However, crystal spatial alignment changed gradually with pressure and distance.     

Optical thin-film linear polarization selector fabricated by oblique angle deposition

A linear polarization selector was made from a three-section sculptured thin film deposited using an oblique angle deposition technique. In this device, the circular Bragg reflector with a left-handed helical structure was sandwiched in between two quarter-wave plates with opposite in-plane birefringence. Within the Bragg regime, the normal incident S-polarized light on this device was reflected, whereas the incident P-polarized light was transmitted through it. The microstructure of the linear polarization selector was also examined by scanning electron microscopy.     

Low temperature synthesis of single crystalline ZnO nanorods by oblique angle deposition

The authors report the growth of single crystalline ZnO nanorods by direct current magnetron sputtering in the oblique angle deposition configuration near room temperature. These isolated nanorods have a diameter of  40 nm, an inter-rod spacing of  20 nm, and a height of  100 nm. The nanorods show a (002) orientation along the rod-axis which is normal to the substrate. The low temperature fabrication of single crystal ZnO nanorods may find potential applications in optoelectronics and energy conversion devices.     

Effect of deposition angle on the structure and properties of pulsed-DC magnetron sputtered TiAlN thin films

This article reports the comparison of structure and properties of titanium aluminum nitride (TiAlN) films deposited onto Si(100) substrates under normal and oblique angle depositions using pulsed-DC magnetron sputtering. The substrate temperature was set at room temperature, 400 °C and 650 °C, and the bias was kept at 0, − 25, − 50, and − 80 V for both deposition angles. The surface and cross-section of the films were observed by scanning electron microscopy. It was found that as the deposition temperature increases, films deposited under normal incidence exhibit distinct faceted crystallites, whereas oblique angle deposited (OAD) films develop a kind of “tiles of a roof” or “stepwise structure”, with no facetted crystallites. The OAD films showed an inclined columnar structure, with columns tilting in the direction of the incident flux. As the substrate temperature was increased, the tilting of columns nearly approached the substrate normal. Both hardness and Young's modulus decreases when the flux angle was changed from α = 0° to 45° as measured by nanoindentation. This was attributed to the voids formed due to the shadowing effect. The crystallographic properties of these coatings were studied by θ-2θ scan and pole figure X-ray diffraction. Films deposited at α = 0° showed a mixed (111) and (200) out-of-plane orientation with random in-plane alignment. On the other hand, films deposited at α = 45° revealed an inclined texture with (111) orientation moving towards the incident flux direction and the (200) orientation approaching the substrate normal, showing substantial in-plane alignment.     

Temperature dependent biaxial texture evolution in Ge films under oblique angle vapor deposition

The morphology and texture of Ge films grown under oblique angle vapor deposition on native oxide covered Si(001) substrates at temperatures ranging from 230 °C to 400 °C were studied using scanning electron microscopy, X-ray diffraction and X-ray pole figure techniques. A transition from polycrystalline to {001}<110> biaxial texture was observed within this temperature range. The Ge films grown at substrate temperatures < 375 °C were polycrystalline. At substrate temperatures of 375 °C and 400 °C, a mixture of polycrystalline and biaxial texture was observed. The 230 °C sample consisted of isolated nanorods, while all other films were continuous. The observed biaxial texture is proposed to be a result of the loss of the interface oxide layer, resulting in epitaxial deposition of Ge on the Si and a texture following that of the Si(001) substrates used. The rate of oxide loss was found to increase under oblique angle vapor deposition.     

Ordered arrays of nanocolumns grown by the oblique angle deposition technique on a self-assembled layer of polystyrene spheres

Ordered arrays of upright nanocolumns of chalcogenide glass were fabricated by combining the oblique angle deposition technique with substrate rotation. Self-assembled close-packed arrays of polystyrene spheres of 200 nm and 500 nm in diameter were used as templates. Our method allows the fabrication of GeSbSe nanocolumns of controlled height, cross-sectional diameter and two-dimensional distribution. Finally, preliminary optical characterization suggests the possible use of the ordered arrays of GeSbSe nanocolumns in optical devices, in particular photonic crystals.     

Nanostructures and sensing properties of ZnO prepared using normal and oblique angle deposition techniques

Nanostructured zinc oxide (ZnO) for gas sensing application has been prepared by using normal and oblique angle sputtering deposition techniques under different substrate temperatures. Oblique angle plasma beam deposition is demonstrated effectively growing large-area uniformly aligned and inclined ZnO nanorod arrays on catalyst-free silicon substrate due to a self-shadowing mechanism, whereas normal radio frequency sputtering deposition yields nanoparticles as island growth mode. Furthermore, the density of the nanorod arrays is dependent on the incident angle of ZnO plasma beam. With an increase of the incident flux angle, large inter spacing was induced, resulting in sparser nanorod arrays. The nanorod arrays grown with an incident angle of 70° have an average diameter of ∼ 150-300 nm and length of ∼ 700-750 nm. The experimental data from characterization of the samples indicates that the obtained samples at different substrate temperatures and incident angles have wurtzite structure with a c-axis orientation.Sensing characterization reveals that the nanorod-based sensor shows higher sensitivity, faster response and recovery time, as well as better reproducibility than that of nanoparticle-based gas sensor to 100 ppm hydrogen and methane at low operating temperature below 150 °C due to the porosity and large grain boundaries of the nanorod arrays. It demonstrates that oblique angle of sputtering deposition is a simple, inexpensive synthesis process to get high-porosity nanostructures and as a result, improves the sensing properties of fabricated ZnO sensors, which permits us to obtain sensors with high sensitivity, low operating temperature and stability.     

Characterization of TiO2 thin films prepared by electrolytic deposition for lithium ion battery anodes

The electrolytic deposition of TiO₂ thin films on platinum for lithium batteries is carried out in TiCl₄ alcoholic solution and the films are subsequently annealed. The as-prepared films are amorphous TiO(OH)₂·H₂O, transformed into anatase TiO₂ at 350 °C, and then gradually into rutile TiO₂ at 500 °C. Cyclic voltammograms show oxidation and reduction peaks at 2.20 and 1.61 V, respectively, corresponding to charge and discharge plateaus at 1.98 and 1.75 V vs. Li⁺/Li. The specific capacity decreases with increasing current density for film of 128-nm thickness in the initial discharge. It is observed that the diffusion flux of Li⁺ insertion/extraction into/from TiO₂ controls the reaction rate at higher current densities. Consequently, at low film thickness, high discharge capacity (per weight) is found for the initial cycle at a current density of 10 μA cm^− 2. However, the capacity of prepared films in various thicknesses approach 103 ± 5 mAh g^− 1 after 50 cycles, since the formation of cracks for thicker films offers shorter diffusion paths for Li⁺. In addition, TiO₂ films show electrochromic properties during lithiation and delithiation.     

In-situ reflection high-energy electron diffraction study of epitaxial growth of Cu on NaCl (100) under oblique angle vapor deposition

Epitaxial growth of copper on annealed NaCl(100) surface was carried out using thermal evaporation at an oblique angle of incidence (75 ± 5)° with respect to the substrate normal. The substrate was kept at a temperature of (150 ± 5)°C. The crystalline structure of the Cu film was studied in situ by reflection high energy electron diffraction at various deposition times. We observed that the film grows through nucleation of epitaxial islands followed by coalescence and then flattening of the film. The chevron shaped diffraction patterns formed by the refraction effect of electrons were used to identify the crystal facets. With longer deposition times, instead of columnar structures, a continuous epitaxial film was formed despite the oblique angle incidence of the vapor. The morphology of the final film was characterized ex situ by atomic force microscopy and shows L-shaped pores asymmetric with respect to the vapor incident direction.     

Retardance of chalcogenide thin films grown by the oblique-angle-deposition technique

Columnar and chevronic thin films of GeSbSe chalcogenide glasses were grown by the oblique-angle-deposition technique. These thin films were found to exhibit dielectric anisotropy in the near-infrared regime. The retardance of any of the fabricated thin films was found to increase linearly with the thickness. Columnar thin films exhibited significantly lower retardance per unit thickness than chevronic thin films. The experimental results indicate the potential of these thin films for near-infrared polarizers.     

蓝宝石衬底的斜切角对GaN薄膜特性的影响

利用金属有机物化学气相沉积技术在具有斜切角度的蓝宝石衬底(0～0.3°)上生长了非故意掺杂GaN薄膜,并采用显微镜、X射线双晶衍射、光荧光及霍尔技术对外延薄膜的表面形貌、晶体质量、光学及电学特性进行了分析.结果表明,采用具有斜切角度的衬底,可以有效改善GaN外延薄膜的表面形貌、降低位错密度、提高GaN的晶体质量及其光电特性,并且存在一个衬底最优斜切角度0.2°,此时外延生长出的GaN薄膜的表面形貌和晶体质量最好.     

Phase formation and morphology control of niobium oxide nanopillars

Nanopillar metal oxide thin films offer versatility as ultra high surface area supports and conductors. Metal oxide properties (e.g. stability, conductivity) can be tuned via phase and composition control to achieve desired application-specific functionality. Here we demonstrate phase control of high surface area thin films grown by glancing angle deposition and transformed to desired phases through high temperature annealing in a reducing environment. The post-annealed properties such as stoichiometry, phase, and morphology are shown to be largely dependent on initial film structure and hydrogen forming gas flow rate. Initially amorphous films of approximate stoichiometry Nb₂O₅ are transformed to NbO₂ or NbN_xO_1−x through annealing. Transformation to oxygen-deficient phases is more easily achieved for films of higher initial porosity. Higher forming gas flow rates result in both increased oxygen removal and significantly less physical degradation of nanostructures. A phase map is included as a guide to phase formation and morphology control in annealed nanopillar niobium oxide films.     

Nanostructured tungsten and tungsten trioxide films prepared by glancing angle deposition

Nanostructured tungsten (W) and tungsten trioxide (WO₃) films were prepared by glancing angle deposition using pulsed direct current magnetron sputtering at room temperature with continuous substrate rotation. The chemical compositions of the nanostructured films were characterized by X-ray photoelectron spectroscopy, and the film structures and morphologies were investigated using X-ray diffraction and high resolution scanning electron microscopy. Both as-deposited and air annealed tungsten trioxide films exhibit nanostructured morphologies with an extremely high surface area, which may potentially increase the sensitivity of chemiresistive WO₃ gas sensors. Metallic W nanorods formed by sputtering in a pure Ar plasma at room temperature crystallized into a predominantly simple cubic β-phase with <100> texture although evidence was found for other random grain orientations near the film/substrate interface. Subsequent annealing at 500 °C in air transformed the nanorods into polycrystalline triclinic/monoclinic WO₃ structure and the nanorod morphology was retained. Substoichiometric WO₃ films grown in an Ar/O₂ plasma at room temperature had an amorphous structure and also exhibited nanorod morphology. Post-deposition annealing at 500 °C in air induced crystallization to a polycrystalline triclinic/monoclinic WO₃ phase and also caused a morphological change from nanorods into a nanoporous network.     

Atomic layer deposition of palladium films on Al2O3 surfaces

We examined the atomic layer deposition (ALD) of Pd films using sequential exposures of Pd(II) hexafluoroacetylacetonate (Pd(hfac)₂) and formalin and discovered that formalin enables the efficient nucleation of Pd ALD on Al₂O₃. In situ quartz crystal microbalance measurements revealed that the Pd nucleation is hampered by the relatively slow reaction of the adsorbed Pd(hfac)₂ species, but is accelerated using larger initial Pd(hfac)₂ and formalin exposures. Pd nucleation proceeds via coalescence of islands and leaves hfac contamination at the Al₂O₃ interface. Pd films were deposited on the thermal oxide of silicon, glass and mesoporous anodic alumina following the ALD of a thin Al₂O₃ seed layer and analyzed using a variety of techniques. We measured a Pd ALD growth rate of 0.2 Å/cycle following a nucleation period of slower growth. The deposited films are cubic Pd with a roughness of 4.2 nm and a resistivity of 11 μΩ cm at 42 nm thickness. Using this method, Pd deposits conformally on the inside of mesoporous anodic alumina membranes with aspect ratio ∼1500 yielding promising hydrogen sensors.     

Synthesis of SrSnO3 thin films by pulsed laser deposition: Influence of substrate and deposition temperature

SrSnO₃ thin films were prepared by pulsed laser deposition on amorphous silica and single crystal substrates of R-sapphire, (100)LaAlO₃ and (100)SrTiO₃. High quality epitaxial (100) oriented films were obtained on LaAlO₃ and SrTiO₃ while a texture was revealed for films on sapphire deposited at the same deposition temperature of 700 °C. Amorphous films were obtained on silica but a post annealing at 800 °C induced crystallization with a random orientation. The screening of deposition temperature showed epitaxial features on SrTiO₃ from 650 °C while no crystallization was observed at 600 °C. The influence of substrate and deposition temperature was confirmed by Scanning Electron Microscopy and Atomic Force Microscopy observations.     

Growth and properties of the CuInS2 thin films produced by glancing angle deposition

We use the glancing angle deposition technique (GLAD) to grow CuInS₂ thin films by a vacuum thermal method onto glass substrates. During deposition, the substrate temperature was maintained at 200 °C. Due to shadowing effect the oblique angle deposition technique can produce nanorods tilted toward the incident deposition flux. The evaporated atoms arrive at the growing interface at a fixed angle θ measured from the substrate normal. The substrate is rotated with rotational speed ω fixed at 0.033 rev s^− 1. We show that the use of this growth technique leads to an improvement in the optical properties of the films. Indeed high absorption coefficients (10⁵–3.10⁵ cm^− 1) in the visible range and near-IR spectral range are reached. In the case of the absence of the substrate rotation, scanning electron microscopy pictures show that the structure of the resulting film consists of nanocolumns that are progressively inclined towards the evaporation source as the incident angle was increased. If a rapid azimuthal rotation accompanies the substrate tilt, the resulting nanostructure is composed of an array of pillars normal to the substrate. The surface morphology show an improvement without presence of secondary phases for higher incident angles (θ > 60°).     

基片温度对磁控溅射沉积二氧化硅的影响

本文详细地研究了基片温度对磁控溅射沉积二氧化硅的影响,随着基片温度的增加,溅射沉积速率下降明显,薄膜的折射率也出现上升趋势,薄膜也由低温时的疏松粗糙发展为致密光滑.250℃时的溅射沉积速率仅为室温时的1/3,由此,针对间歇式在大面积玻璃上沉积二氧化硅薄膜,我们采取了沉积完ITO薄膜后,先快速降温,再沉积二氧化硅的工艺.     

Interface strength of structured nanocolumns grown by glancing angle deposition

In order to investigate the mechanics of interfacial fracture in structured nano-elements grown by glancing angle deposition (GLAD), fracture experiments were conducted on oblique Ti nanocolumns grown on a Si substrate using a micro-brick specimen. Two types of specimens, a Forward specimen (loading with the column tilt direction) and a Reverse specimen (loading against the column tilt), were prepared to clarify the effect of an asymmetric nanostructure on the interface strength. The specimens fractured at the interface or near the interface between the Ti nanocolumns and the Si substrate for both specimens. The critical force and displacement at fracture in the Forward specimens were about 2.0 times and 1.6 times as large as those in the Reverse specimens, respectively, showing clear anisotropy in the interface strength. The local stress distribution along the interface in the single nanocolumn at fracture was analyzed by finite element analysis. While the stress singularity in the Reverse specimen was greater than that in the Forward specimen, the normal stresses in a region 1–3 nm near the interface edge were almost identical regardless of the loading direction, suggesting that intensified stress in the nanoscale region dominated fracture.     

The structure of Ta nanopillars grown by glancing angle deposition

Regular arrays of Ta nanopillars, 200 nm wide and 500 nm tall, were grown on SiO₂ nanosphere patterns by glancing angle sputter deposition (GLAD). Plan-view and cross-sectional scanning electron microscopy analyses show dramatic changes in the structure and morphology of individual nanopillars as a function of growth temperature T_s ranging from 200 to 700 °C. At low temperatures, T_s ≤ 300 °C, single nanopillars develop on each sphere and branch into subpillars near the pillar top. In contrast, T_s ≥ 500 °C leads to branching during the nucleation stage at the pillar bottom. The top branching at low T_s is associated with surface mounds on a growing pillar that, due to atomic shadowing, develop into separated subpillars. At high T_s, the branching occurs during the nucleation stage where multiple nuclei on a single SiO₂ sphere develop into subpillars during a competitive growth mode which, in turn, leads to intercolumnar competition and the extinction of some nanopillars.