Pulsed laser deposition of tungsten and tungsten oxide thin films with tailored structure at the nano- and mesoscale

Nanostructured thin films synthesized by assembling atoms or clusters present a structure characterized by a modulation at the nanoscale and by a large effective area, which can be exploited for the tailoring of specific structural or electronic properties. These systems are appealing for functional applications, e.g. in sensing and catalysis. We have investigated the deposition of tungsten and tungsten oxide thin films with a wide range of morphologies by exploiting nanosecond pulsed laser deposition (PLD) in an inert background atmosphere (He, Ar and Kr). We show that the non-dimensional ratio of the target-to-substrate distance to the time integrated visible plume length, which depends on the gas mass and pressure and on the substrate position, permits to select morphologies ranging from a compact structure with a density similar to bulk, to a film with an open, low density foam-like mesostructure and a high fraction of voids.     

Highly uniform electrochromic tungsten oxide thin films deposited by e-beam evaporation for energy saving systems

In the last few decades, there has been a surge of interest in using tungsten oxide thin films as an active layer of electrochromic device. These devices have several practical applications such as smart window of buildings and automobile glazing for energy saving. The main objective of this work was to construct highly homogeneous and uniform e-beam evaporated amorphous WO_3-x based films into electrochromic devices, which were fully characterized for switching speed, coloration efficiencies and cycling voltammetry responses. Fabricated devices contain indium doped transparent oxide coated glass as the transparent conductive electrode, ～200?nm thickness of WO_3-x as the cathodically coloring material and a lithium perchlorate based conducting gel electrolyte. X-ray diffraction patterns indicate that all as-deposited films are amorphous. Experimental results showed that both solid and liquid electrolyte electrochromic devices are initially very transparent that exhibit perfect optical modulation and coloration efficiency (up to 68.7?cm²/C and 52.6?cm²/C at 630?nm, respectively) due to easier intercalation of the Li⁺ within their structure. One of the more significant findings to emerge from this study is that e-beam coated electrochromic devices based on tungsten oxide thin films showed superior performance among to other coating methods. Therefore, excellent reversibility of color change behavior is attractive for pertinent use in electrochromic energy storage devices.     

Valence control of cobalt oxide thin films by annealing atmosphere

The cobalt oxide (CoO and Co₃O₄) thin films were successfully prepared using a spin-coating technique by a chemical solution method with CH₃OCH₂CH₂OH and Co(NO₃)₂·6H₂O as starting materials. The grayish cobalt oxide films had uniform crystalline grains with less than 50 nm in diameter. The phase structure is able to tailor by controlling the annealing atmosphere and temperature, in which Co₃O₄ thin film was obtained by annealing in air at 300-600, and N₂ at 300, and transferred to CoO thin film by raising annealing temperature in N₂. The fitted X-ray photoelectron spectroscopy (XPS) spectra of the Co2p electrons are distinguishable from different valence states of cobalt oxide especially for their satellite structure. The valence control of cobalt oxide thin films by annealing atmosphere contributes to the tailored optical absorption property.     

Microstructural and electrochromic properties of tungsten oxide thin films produced by surfactant mediated electrodeposition

By electrochemically controlling the structure of the surface aggregates, the grain microstructure has been optimized to yield mesoporous thin films of tungsten oxide (WO₃) at the electrode-electrolyte interface in a peroxotungstate sol in the presence of a structure-directing agent (Triton) at room temperature. Apart from the dominant ultrafine nanocrystallites and pores (5-10 nm), well-developed abutting grains (25-100 nm) and nanofibrils also constitute an integral part of the film matrix. X-ray photoemission spectra reveal the as-deposited film (WO_3−x) to be constituted by a high proportion of W⁶⁺ states with a low oxygen deficiency (x = 0.02). A relatively high W⁵⁺ content in the film, upon intercalation of 18 mC cm⁻² charge translates into a large coloring efficiency (η_VIS ∼ 70 cm² C⁻¹) and transmission modulation. At a lithium intercalation level of 22 mC cm⁻², in addition to W⁵⁺ and W⁶⁺ states, the film also comprises of W⁴⁺ states. The extremely fast color-bleach kinetics (3 and 2 s, respectively, for a 50% change in transmittance) shown by the as-deposited WO₃ film are repercussions of the mesopore morphology, the multiple nanostructures and the sixfold channels of its hexagonal modification. The film shows a high cycling stability as the switching times do not show any significant decline even after 3500 repetitive cycles. Coloration efficiency over the solar and photopic regions and current density for lithium intercalation for the as-deposited film are superior to that observed for the films annealed at 100, 250 and 500 °C. The abysmal electrochromic response of the annealed films is a consequence of surface defects like cracks and uncontrolled densification and pore shrinkage.     

Omnidirectional antireflective properties of porous tungsten oxide films with in-depth variation of void fraction and stoichiometry

We report on the fabrication of porous hot-wire deposited WO_x (hwWO_x) films with omnidirectional antireflective properties coming from in-depth variation of both (i) void fraction from 0% at the Si substrate/hwWO_x interface to 30% within less than 7 nm and to higher than 50% at the hwWO_x/air interface, and (ii) x, namely hwWO_x stoichiometry, from 2.5 at the Si/hwWO_x to 3 within less than 7 nm. hwWO_x films were deposited by means of hw deposition at rough vacuum and controlled chamber environment. The films were analyzed by Spectroscopic Ellipsometry to extract the graded refractive index profile, which was then used in a rigorous coupled wave analysis (RCWA) model to simulate the antireflective properties. RCWA followed reasonably the experimental reflection measurements. Void fraction and x in-depth variation, controlled by the hw process, greatly affect the antireflective properties, and improve the omnidirectional and broadband characteristics. The reflection suppression below 10% within the range of 500-1000 nm for angles of incidence up to more than 60° is demonstrated.     

Rapid formation of tungsten oxide nanobundles with controllable morphology

Tungsten oxide (W₁₈O₄₉) nanobundles with controllable morphology were fabricated on Si substrates within 5 min by microwave plasma-enhanced chemical vapor deposition (MPECVD). The crystal structure and chemical composition of these nanobundles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDS). The results of these characterizations confirmed the formation of W₁₈O₄₉ nanobundles with [0 1 0] as the major growth direction. SEM images showed that the nanobundles were several micrometers long with diameters of 20-500 nm. The morphology of the nanobundles can be controlled by simply adjusting the reaction times to the desired level; nanowires (diameter: 15-30 nm), nanorods (diameter: 40-60 nm), and nanoslabs (thickness: 30 nm) were formed at 1.5, 3, and 4 min, respectively. With an increase in reaction times, the nanobundles steadily increased in dimensions to form nanoslabs. Thus, our results indicated that MPECVD is highly effective and suitable for fabrication of various tungsten oxide nanobundles.     

Synthesis and field-emission properties of the tungsten oxide nanowire arrays

High-density, uniformly distributed and quasi-aligned tungsten oxide nanowire arrays have been synthesized by a conventional thermal evaporation approach on indium tin oxide (ITO) coated glass substrates without any catalysts. The temperature of the substrate was . The tungsten oxide nanowires are single crystalline with growth direction of [0 1 0]. For commercial applications, field emission properties of tungsten oxide nanowires were studied under a poor vacuum at room temperature. The electron field-emission turn-on field (E_to), defined as the macroscopic field required to produce a current density of , is about . The performance reveals that the tungsten oxide nanowire arrays can be served as a good candidate for commercial application in field-emission displays.     

Assembly of tungsten oxide nanobundles and their electrochromic properties

Lenticular W₁₈O₄₉ nanobundles composed of ultra-thin nanowires with diameters of 5-10 nm have been synthesized through a simple solvothermal method with hexachloride as precursor and mixed cyclohexanol and ethanol as solvent. Electrochromic films were prepared by assembling the W₁₈O₄₉ nanobundle suspension onto tin-doped indium oxide (ITO) coated glass. Results showed that self-assembly of the W₁₈O₄₉ nanobundles was strongly influenced by the solvents employed to disperse the nanobundles. The W₁₈O₄₉ nanobundles coated films exhibited excellent electrochromic stability and reversibility. The W₁₈O₄₉ nanobundle films also showed much higher charge-insertion density compared with the WO₃ nanorod film, which may be due to the ultrathin feature of single nanowires constituting the nanobundles, unique oxygen vacancies of monoclinic W₁₈O₄₉, and the highly ordered assembly of the nanobundles.     

Investigation of electrochromic tungsten trioxide thin films prepared by the ILGAR method

An ion layer gas reaction dip coating process for the deposition of tungsten trioxide has been developed. Thin films of electrochromic tungsten trioxide with thicknesses of up to 150 nm were prepared. The films were found to be microcrystalline by X-ray diffraction analysis. The growth rate of the films was measured by profilometry. The chemical diffusion coefficient of lithium was investigated as a function of the concentration of lithium by the electrochemical galvanostatic intermittent titration technique. The chemical diffusion coefficient was found to increase slightly from 7×10⁻¹² to 3×10⁻¹ cm²/s, with x increasing from 0.2 to 0.8 in Li _x WO₃.     

氧化钒薄膜微观结构的研究

采用直流磁控反应溅射在Si(100)衬底上溅射得到(001)取向的V₂O₅薄膜.x射线衍射(XRD)、扫描电镜(SEM)和傅里叶变换红外光谱(FTIR)的结果表明，氧分压影响薄膜的成分和生长取向，在氧分压0.4Pa时溅射得到(001)取向的纳米V₂O₅薄膜，即沿c轴垂直衬底方向取向生长的薄膜.V₂O₅薄膜经过真空退火得到(001)取向的VO₂薄膜，晶体颗 关键词： 微观结构 氧化钒薄膜 择优取向 直流磁控溅射     

Microstructural, optical and spectroscopic studies of laser ablated nanostructured tantalum oxide thin films

Thin films of tantalum oxide (Ta₂O₅) have been prepared by pulsed laser deposition technique at different substrate temperatures (300-973 K) under vacuum and under oxygen background (pO₂ = 2 × 10⁻³ mbar) conditions. The films are annealed at a temperature of 1173 K. The as-deposited films are amorphous irrespective of the substrate temperature. XRD patterns show that on annealing, the films get crystallized in orthorhombic phase of tantalum pentoxide (β-Ta₂O₅). The annealed films deposited at substrate temperatures 300 K and 673 K have a preferred orientation along (0 0 1) plane, whereas the films deposited at substrate temperatures above 673 K show a preferred orientation along (2 0 0) crystal plane. The deposited films are characterized using techniques such as grazing incidence X-ray diffraction (GIXRD), atomic force microscopy (AFM), micro-Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy and UV-visible spectroscopy. FTIR and micro-Raman measurements confirm the presence of Ta-O, Ta-O-Ta and O-Ta-O bands in the films. Grain size calculations from X-ray diffraction and AFM show a decrease with increase in substrate temperature. The variation of transmittance and band gap with film growth parameters are also discussed.     

Optical constants and thermocoloration of pulsed laser deposited molybdenum oxide thin films

Molybdenum oxide thin films were prepared by pulsed laser deposition. The as-deposited films were dark. Annealing the films in air at 400 °C resulted in transparent films. These films were further annealed in vacuum at 300 and 400 °C to investigate thermocoloration. The structural, chemical, and optical properties of the films were determined. All films were predominantly amorphous. The air-annealed films were nearly stoichiometric. However, after annealing in vacuum at 400 °C, the films became oxygen-deficient. The transmittance of the films progressively decreased as the vacuum-annealing temperature increased, indicating stronger coloration of the films. The optical constants were determined from the transmittance measurements. Both the refractive index and extinction coefficient increased upon vacuum annealing. However, the band gap slightly decreased after vacuum annealing.     

SRPES investigation of tungsten oxide in different oxidation states

The microstructure and morphology of metal oxide films have a large influence on the sensitivity, selectivity and stability of the gas sensors and catalysts. Considering that the sensing properties of thin film sensors are strongly related to their microstructures and to the exact stoichiometry of their surfaces, an accurate control of these parameters is extremely important for the production of sensors with reproducible behavior. In this paper, an influence of preparation and annealing conditions on the physical and chemical properties of tungsten oxide thin film is investigated. Two types of samples having polycrystalline structure were prepared by different methods (deposition under UHV conditions, oxidation of metallic tungsten layer in air). The samples were reduced by heating in UHV at different temperatures and/or by Ar ion bombardment. It was found that the stability of tungsten oxide layer with respect to the treatment procedures depends strongly on the preparation conditions of the sample. The reduction process is discussed in terms of different oxidation states resolved in the W4f photoelectron spectrum. Easy reducibility of the tungsten oxide layer prepared by vacuum deposition was found to be a consequence of its nano-crystalline structure.     

Microstructural parameters and optical constants of ZnTe thin films with various thicknesses

Different thickness of polycrystalline ZnTe films have been deposited onto glass substrates at room temperature by vacuum evaporation technique. The structural characteristics studied by X-ray diffraction (XRD) showed that the films are polycrystalline and have a zinc blende (cubic) structure. The calculated microstructure parameters revealed that the crystallite size increases and microstrain decreases with increasing film thickness. The transmittance and reflectance have been measured at normal and near normal incidence, respectively, in the spectral range 400-2500 nm. For ZnTe films of different thicknesses, the dependence of absorption coefficient, α on the photon energy showed the occurrence of a direct transition with band gap energy (For ZnTe films of different thicknesses) confirming the independency of deduced energy gap on film thickness. The refractive indices have been evaluated in terms of envelope method, which has been suggested by Swanepoul in the transparent region. The refractive index could be extrapolated by Cauchy dispersion relationship over the whole spectra range, which extended from 400 to 2500 nm. It was observed that the refractive index, n increased upon increasing the film thickness up to 508 nm, lying within the experimental error for further increases in film thickness.     

Modification of electrical properties of tungsten oxide nanorods using conductive atomic force microscopy

Electrical conduction of tungsten oxide nanorods has been characterized by conductive atomic force microscopy (C-AFM). The conduction measurements were carried out in air using a conductive P⁺-type diamond-coated tip. This technique allows either the simultaneous measuring of the topography and the special current distribution or the recording of the current voltage distribution in a single point mode. We have proposed an equivalent electrical circuit which allows us to understand the I(V) curves. During C-AFM observations we have observed significant changes in image contrast and hysteresis in the I(V) characteristics which depend on the applied bias voltage. The bias dependence effect is interpreted as being due to a local oxidation-reduction phenomenon induced by the tip in the presence of water.     

Annealing induced microstructural evolution of electrodeposited electrochromic tungsten oxide films

A significant influence of microstructure on the electrochromic and electrochemical performance characteristics of tungsten oxide (WO₃) films potentiostatically electrodeposited from a peroxopolytungstic acid (PPTA) sol has been evaluated as a function of annealing temperature. Powerful probes like X-ray diffractometry (XRD), transmission electron microscopy (TEM), UV-vis spectrophotometry, multiple step chronoamperometry and cyclic voltammetry have been employed for the thin film characterization. The as-deposited and the film annealed at 60 °C are composed of nanosized grains with a dominant amorphous phase, as well as open structure which ensues from a nanoporous matrix. This ensures a greater number of electroactive sites and a higher reaction area thereby manifesting in electrochromic responses superior to that of the films annealed at higher temperatures. The films annealed at temperatures ≥250 °C are characterized by a prominent triclinic crystalline structure and a hexagonal phase co-exists at temperatures ≥400 °C. The deleterious effect on the electrochromic properties of the film with annealing is ascribed to the loss of porosity, densification and the increasing crystallinity and grain size. Amongst all films under investigation, the film annealed at 60 °C exhibits a high transmission modulation (ΔT ∼ 68%) and coloration efficiency (η ∼ 77.6 cm² C⁻¹) at λ = 632.8 nm, charge storage capacity (Q_ins ∼ 21 mC cm⁻²), diffusion coefficient (6.08 × 10⁻¹⁰ cm² s⁻¹), fast color-bleach kinetics (t_c ∼ 275 s and t_b ∼ 12.5 s) and good electrochemical activity, as well as reversibility for the lithium insertion-extraction process upon cycling. The remarkable potential, which the film annealed at 60 °C has, for practical “smart window” applications has been demonstrated.     

Microstructural study of thin films of 5 mol% gadolinia-doped ceria prepared by pulsed laser ablation

Microstructural characterization of thin films of 5 mol% gadolinia-doped ceria films deposited by pulsed laser ablation in the energy range 100–600 mJ/pulse has been investigated. As-deposited films were found to be nanocrystalline with preferred orientation. X-ray diffraction (XRD) analysis revealed that the size of the nanocrystals of doped ceria does not vary significantly with increasing laser energy, while transmission electron microscopy (TEM) study showed a uniform distribution of nanocrystals of 8–10 nm for energies ≤200 mJ/pulse and nanocrystals embedded in a large crystalline matrix of doped ceria for energies in the range 400–600 mJ/pulse. Though, the laser-ablated films were totally free from secondary phases, lattice imaging of the large grained doped ceria showed growth-induced defects such as dislocations and ledges. This artice was accidentally published twice. This is the second publication, please cite only the authoritative first one which is available at . An additional erratum is available at . An erratum to this article can be found at     

Effect of annealing temperature on K-shell X-ray fluorescence parameters of zinc oxide thin films prepared by the sol-gel method

Zinc oxide thin films were grown on a glass substrate by a sol-gel process using a spin-coating technique. The obtained thin films were annealed between 350?°C and 550?°C in 50?°C steps and were then characterized using X-ray diffraction, scanning electron microscopy, and X-ray fluorescence techniques. The samples were stimulated by 59.5?keV gamma rays emitted from an Americium-241 annular radioisotope source. K X-rays emitted by samples were counted using an ultra-low energy germanium detector with a resolution of 150?eV at 5.96?keV. It was found that there was generally a decrease in both the Kβ/Kα X-ray intensity ratios and the K X-ray fluorescence cross sections for zinc oxide between 350?°C and 500?°C, but not at 550?°C. In addition, the X-ray diffraction patterns of the films showed that the transition phase from an amorphous to a polycrystalline hexagonal wurtzite structure was complete at an annealing temperature of 500?°C. The results show that variations in these parameters can be explained by the reorganization of atoms and the charge transfer process due to the effect of the annealing temperature on the elements forming the compounds.     

Investigation of chemical mechanical polishing of zinc oxide thin films

Zinc oxide has become an important material for various applications. Commercially available zinc oxide single crystals and as-grown zinc oxide thin films have high surface roughness which has detrimental effects on the growth of subsequent layers and device performance. A chemical mechanical polishing (CMP) process was developed for the polishing of zinc oxide polycrystalline thin films. Highly smooth surfaces with RMS roughness <6 Å (as compared to the initial roughness of 26 ± 6 Å) were obtained under optimized conditions with removal rates as high as 670 Å/min. Effects of various CMP parameters on removal rate and surface roughness were evaluated. The role of pH on the polishing characteristics was investigated in detail.     

Structure and electrical properties of tungsten oxide nanorods epitaxially organized on a mica substrate

Our objective was to fabricate nanosized tungsten oxide rods and to test their sensing properties. In the present report, we focus on the crystallographical structure and the electrical properties of tungsten nanorods. The tungsten oxide nanorods were grown by vapor transport from a WO₃ layer onto a substrate (Mica). The nanorods growth was controlled by the temperature gradient between the WO₃ layer and the substrate. Their morphology was investigated by AFM and their structure by TED and TEM. We have investigated the conductivity of the WO₃ nanorods with a technique derived from atomic force microscopy operating in contact mode with a conductive tip (C-AFM). Its provides at the same time a classical topographic image of the sample surface and an image representative of the local electrical resistance between the tip and a metallic contact on the substrate. We also investigated the electrical properties of the WO₃ nanorods by the current-voltage responses in a bias range of 0 ± 1 V. We have performed experiments in an environmental chamber and characterized the role of water vapor on the electrical conductivity of WO₃ nanorods.