Structure and composition of sputter-deposited nickel-tungsten oxide films

Films of mixed nickel-tungsten oxide, denoted Ni_xW_1−x oxide, were prepared by reactive DC magnetron co-sputtering from metallic targets and were characterized by Rutherford backscattering spectrometry, X-ray photoelectron spectroscopy, X-ray diffractometry and Raman spectroscopy. A consistent picture of the structure and composition emerged, and at x < 0.50 the films comprised a mixture of amorphous WO₃ and nanosized NiWO₄, at x = 0.50 the nanosized NiWO₄ phase was dominating, and at x > 0.50 the films contained nanosized NiO and NiWO₄.     

二极溅射沉积Fe-N-O薄膜的形貌与结构分析

利用二极溅射的方法在不同衬底上沉积了Fe N O薄膜。通过扫描电子显微镜(SEM)、光电子能谱(XPS)和透射电子显微镜(TEM)等先进实验分析手段对二极溅射沉积Fe N O薄膜的形貌与结构进行了分析。XPS和TEM的结果表明,薄膜的主要成分为FeO和少量的Fe16N2多晶体组成,生长上存在择优取向;表面均匀、致密、平整,晶粒大小在50nm左右。     

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.     

Synthesis of type-II textured tungsten disulfide thin films with bismuth interfacial layer as a texture promoter

Highly textured tungsten disulfide (WS₂) thin films have been obtained by sulfurization of tungsten trioxide. The properties of WS₂ thin films prepared with bismuth interfacial layer as texture promoter has been studied. The WS₂ thin films were found to have predominant type-II orientation. The stacking of 2H-WS₂ crystallites observed with scanning electron microscopy was not reported hitherto. The films can be pictured as an assembly of WS₂ hexagonal crystallites. The energy dispersive X-ray analysis and X-ray photoelectron spectroscopy (XPS) studies confirm that the films are stoichiometric. The XPS analysis described the local environment of the tungsten atoms and the formal oxidation states of the tungsten and sulfur atoms were + 4 and − 2. Together with the high degree of crystallinity and excellent texture of the film, a relatively smooth morphology, on submicron scale, is revealed through atomic force microscopy study. The conditions for the desired textured growth with the van der Waals planes parallel to the substrate surface are reported.     

XPS and X-ray diffraction studies of aluminum-doped zinc oxide transparent conducting films

Aluminum-doped zinc oxide transparent conducting films are prepared by spray pyrolysis at different dopant concentrations. These films are subsequently characterized by X-ray diffractometric and X-ray photoelectron spectroscopic (XPS) techniques. The results are compared with those obtained from pure zinc oxide films prepared under identical conditions. X-ray diffraction measurements show an increase in lattice parameters (c and a) for aluminum-doped films while their ratio remains the same. This study also indicates that within the XPS detection limit the films are chemically identical to pure zinc oxide. However, a difference in the core-electron line shape of the Zn 2p_3/2 photoelectron peaks is predicted. An asymmetry in Zn 2p_3/2 photoelectron peaks has been observed for aluminium-doped films. The asymmetry parameters evaluated from core-electron line-shape analysis yield a value of the order of 0.04±0.01. The value is found to lie between those obtained for pure zinc oxide and has been attributed to the presence of excess zinc in the films.     

On the structure and surface chemical composition of indium-tin oxide films prepared by long-throw magnetron sputtering

Structures and surface chemical composition of indium tin oxide (ITO) thin films prepared by long-throw radio-frequency magnetron sputtering technique have been investigated. The ITO films were deposited on glass substrates using a 20 cm target-to-substrate distance in a pure argon sputtering environment. X-ray diffraction results showed that an increase in substrate temperature resulted in ITO structure evolution from amorphous to polycrystalline. Field-emission scanning electron microscopy micrographs suggested that the ITO films were free of bombardment of energetic particles since the microstructures of the films exhibited a smaller grain size and no sub-grain boundary could be observed. The surface composition of the ITO films was characterized by X-ray photoelectron spectroscopy (XPS). Oxygen atoms in both amorphous and crystalline ITO structures were observed from O 1 s XPS spectra. However, the peak of the oxygen atoms in amorphous ITO phase could only be found in samples prepared at low substrate temperatures. Its relative peak area decreased drastically when substrate temperatures were larger than 200 °C. In addition, a composition analysis from the XPS results revealed that the films deposited at low substrate temperatures contained high concentration of oxygen at the film surfaces. The oxygen-rich surfaces can be attributed to hydrolysis reactions of indium oxides, especially when large amount of the amorphous ITO were developed near the film surfaces.     

Optical properties of tungsten oxide thin films by non-reactive sputtering

Tungsten oxide thin films were grown on glass substrates by RF sputtering at room temperature using a tungsten trioxide target for several values of the argon pressure (P_Ar). The structural and morphological properties of these films were studied using X-ray diffraction and atomic force microscopy. The as-deposited films were amorphous irrespective of the argon pressure, and crystallized in a mixture of hexagonal and monoclinic phases after annealing at a temperature of 350 °C in air. Surface-roughness increased by an order of magnitude (from 1 nm to 20 nm) after thermal treatment. The argon pressure, however, had a strong influence on the optical properties of the films. Three different regions are clearly identified: deep blue films for P_Ar ≤ 2.67 Pa with low transmittance values, light blue films for 2.67 Pa < P_Ar < 6 Pa with intermediate transmittance values and transparent films for P_Ar ≥ 6 Pa with high transmittance values. We suggest that the observed changes in optical properties are due to an increasing number of oxygen vacancies as the growth argon pressure decreases.     

Synthesis and structural characterization of mesoporous V2O5 thin films for electrochromic applications

Mesoporous vanadium pentoxide (V₂O₅) films have been synthesized by hydrolysis of vanadium tri-isopropoxide (VO(OC₃H₇)₃) in the presence of polyethylene glycol (PEG) as a structure-directing agent. The structure, the stoichiometry and the morphology of the films have been studied as a function of the thermal annealing by X-ray diffraction (XRD), micro-Raman spectroscopy, optical microscopy, scanning electron microscopy and atomic force microscopy. XRD patterns and Raman spectra show the presence of two previously unreported crystalline phases. The PEG:V₂O₅ molar ratio affects the temperature of phase formation, the amount and even the order in which the phases appear. The morphological characterization underlines the role of the surfactant to promote porous networks, formed by micrometric clusters of controlled shapes and patterns embedded in a homogeneous host matrix.     

Thin film deposition and characterization of pure and iron-doped electron-beam evaporated tungsten oxide for gas sensors

Pure tungsten oxide (WO₃) and iron-doped (10 at.%) tungsten oxide (WO₃:Fe) nanostructured thin films were prepared using a dual crucible Electron Beam Evaporation (EBE) technique. The films were deposited at room temperature under high vacuum onto glass as well as alumina substrates and post-heat treated at 300 °C for 1 h. Using Raman spectroscopy the as-deposited WO₃ and WO₃:Fe films were found to be amorphous, however their crystallinity increased after annealing. The estimated surface roughness of the films was similar (of the order of 3 nm) to that determined using Atomic Force Microscopy (AFM). As observed by AFM, the WO₃:Fe film appeared to have a more compact surface as compared to the more porous WO₃ film. X-ray photoelectron spectroscopy analysis showed that the elemental stoichiometry of the tungsten oxide films was consistent with WO₃. A slight difference in optical band gap energies was found between the as-deposited WO₃ (3.22 eV) and WO₃:Fe (3.12 eV) films. The differences in the band gap energies of the annealed films were significantly higher, having values of 3.12 eV and 2.61 eV for the WO₃ and WO₃:Fe films respectively. The heat treated films were investigated for gas sensing applications using noise spectroscopy. It was found that doping of Fe to WO₃ produced gas selectivity but a reduced gas sensitivity as compared to the WO₃ sensor.     

Characterization of ultrasonic spray pyrolyzed tungsten oxide thin films

The ultrasonic spray pyrolysis (USP) technique has been employed to deposit tungsten oxide (WO₃) thin films. The films were prepared by spraying 0.02 M ammonium metatungstate solution onto amorphous glass substrates kept at 250°C. These films were further annealed at 400°C for different time periods (1–5 h) in air. The films were characterized for structural, electrical and opto-electronic properties. X-ray diffraction technique was used to determine the crystallinity of the WO₃ films and identify the phases that form as a function of annealing time. The as-prepared WO₃ films were amorphous and crystallize when annealed at 400°C in air for 2 or more hours. From TEM, the grain size and lattice plane spacing are estimated. The films were further characterized by using time resolved microwave conductivity (TRMC) technique and decay time of the photogenerated charge carriers is calculated to be about 154 ns. The concentration and mobility of charge carriers are estimated from thermoelectric power (TEP) measurements.     

Electrochromic properties of nanocrystalline tungsten oxide thin films

Tungsten trioxide films formed of aggregates in the nanometric range have been deposited by thermal evaporation and condensation method. From the atomic force microscopy study, the aggregate dimensions were found to be in the range between 350 nm and 450 nm. The optical, structural and electrochromic performance of these films under lithium intercalation is studied in detail and their properties are compared to those of continuous films of tungsten trioxide. The films show a slightly elevated diffuse reflectance in the lower wavelength range and a very high transmission in the solar and visible wavelengths. Under lithium intercalation, the films exhibit a very good degree of electrochromic optical modulation in both these spectral ranges and hence, are very suitable for electrochromic device application. The high degree of change between the clear state and the colored state render such nanocrystalline films more efficient in their electrochromic performance than the conventional continuous films.     

Growth, structure and properties of sputtered niobium oxide thin films

Niobium oxide (NbO_x) films were deposited by pulsed dc magnetron sputtering at different total gas pressures and oxygen flow rates. Various film properties were characterized by X-ray photoelectron spectroscopy, atomic force microscopy, variable angle spectroscopic ellipsometry and four point probe. It was found that oxygen flow rates required for preparing NbO, NbO₂ and Nb₂O₅ at a constant total pressure of 0.93 Pa were approximately 2, 4 and > 6 sccm, respectively. The results showed that the film properties, specifically composition can be significantly changed by the total gas pressure and the oxygen flow rate.     

Carbide and nanocomposite thin films in the Ti-Pt-C system

Thin films in the Ti-Pt-C system were deposited by non-reactive, DC-magnetron sputtering. Samples were characterised using X-ray photoelectron spectroscopy, X-ray diffraction, and transmission electron microscopy. A previously not reported metastable solid solution carbide, (Ti_1 − xPt_x)C_y with a Pt/Ti ratio of up to 0.43 was observed. This solid solution phase was present both as single phase in polycrystalline samples, and together with amorphous carbon (a-C) in nanocomposite samples. Annealing of nanocomposite samples leads to the decomposition of the solid solution phase and the formation of a nc-TiC_x/a-C/nc-Pt nanocomposite. Test sensors for automotive gas exhausts manufactured from such a three-phase material suffer from complete oxidation of the coating at 400 °C with no observed sensor activity.     

The incorporation of preformed metal nanoparticles in zinc oxide thin films using aerosol assisted chemical vapour deposition

The feasibility of Aerosol Assisted Chemical Vapour Deposition (AA-CVD) has been investigated for the growth of zinc oxide (ZnO) films containing preformed metal nanoparticles. The deposition parameters were first established for ZnO thin films, by varying the heating configuration, substrate temperature and deposition time. Films were characterised using Scanning Electron Microscopy and X-Ray Diffraction. As-deposited films, grown at 250 °C, were mostly amorphous and transformed to highly crystalline Wurtzite ZnO at higher substrate temperatures (400-450 °C). A change in the preferential orientation of the films was observed upon changing (i), the substrate temperature or (ii), the heating configuration. Following this, the applicability of the AA-CVD process for the incorporation of preformed nanoparticles (platinum and gold) in ZnO thin films was investigated. It was found that surface agglomeration occurred, such that the ZnO films were capped with an inhomogeneous coverage of the metal. These layers were characterised using Transmission Electron Microscopy and Electron Diffraction. A possible mechanism for the formation of these metal surface clusters is presented.     

TiO2 thin films using organic liquid materials prepared by Hot-Wire CVD method

TiO₂ thin films prepared by Hot-Wire CVD method have been studied as a protecting material of transparent conducting oxide (TCO) against atomic hydrogen exposures for the fabrications of Si thin film solar cells. It was found that electrical conductivity of the films at room temperature reached a value of 0.4 S/cm. This value is 2-3 orders of magnitude higher than that of TiO₂ films prepared by RF magnetron sputtering and electron-beam evaporation methods in our previous works. The conductivity improvement seems to be partly due to the enlargement of TiO₂ crystallites.     

Magnetron sputtering of Zr-Si-C thin films

The phase composition and chemical bonding of ZrC and ZrSiC films deposited by magnetron sputtering has been studied. The results show that the binary Zr-C films at higher carbon contents form nanocrystallites of ZrC in an amorphous carbon matrix. The addition of Si induces a complete amorphization of the films above a critical concentration of about 15 at.%. X-ray diffraction and transmission electron microscopy confirm that the amorphous films contain no nanocrystallites and therefore can be described as truly amorphous carbides. The amorphous films are thermally stable but start to crystallize above 500 °C. Analysis of the chemical bonding with X-ray photoelectron spectroscopy suggests that the amorphous films exhibit a mixture of different chemical bonds such as ZrC, ZrSi and SiC and that the electrical and mechanical properties are dependent on the distribution of these bonds. For higher carbon contents, strong SiC bonds are formed in the amorphous Zr-Si-C films making them harder than the corresponding binary Zr-C films.     

Microstructure-mechanical and chemical behavior relationships in passive thin films

The passive films play an important role in corrosion and stress corrosion cracking of austenitic stainless steels. The current research investigates the relationship between alloy chemistry, microstructure, and mechanical behavior of passive films formed on 316, 304, and 904L stainless steels (SS). X-ray photoelectron spectroscopy and transmission electron microscopy were used to investigate the effect of alloy chemistry and microstructure constituents on the thin film fracture properties determined by nanoindentation tests. The analyses showed that fracture loads are directly related to the crystallography of the thin films. It was found that decreasing the ratio of iron to other metallic elements in the film led to an increase in the load required to fracture the film. It was also found that films grown on 304, 316, and 904L stainless steels were the cubic polymorph of Cr₂O₃, rather than the lower energy rhombohedral form. In the case of 904L SS the film formed as an epitaxial layer. In the other two cases it consisted of small crystalline islands in an amorphous matrix. A dichromate treatment of 316 SS decreased the iron content in the oxide film and increased the hardness. It also resulted in an epitaxial film.     

Electronic structure of amorphous InGaO3(ZnO)0.5 thin films

The electronic structure of amorphous semiconductor InGaO₃(ZnO)_0.5 thin films, which were deposited by radio-frequency magnetron sputtering process, was investigated using X-ray photoelectron spectroscopy and O K-edge X-ray absorption spectroscopy. The overall features of the valence and conduction bands were analyzed by comparing with the spectra of Ga₂O₃, In₂O₃, and ZnO films. The valence and conduction band edges are mainly composed of O 2p and In 5sp states, respectively. The bandgap of the films determined by spectroscopic ellipsometry was approximately 3.2 eV. Further, it is found that the introduction of oxygen gas during the sputter-deposition does not induce significant variations in the chemical states and band structure.     

Surface and electrical studies of CuO:V2O5 thin films

Results from the studies of multicomponent CuO:V₂O₅ bulk material and thermally evaporated thin films of highly conducting bulk composition prepared at different substrate temperatures are thus compared and discussed. The electronic conductivity is enhanced on increase in the substrate temperature T_s and reaches a maximum value of 12.3 × 10⁻⁶Ω⁻¹ cm⁻¹ for T_s = 423 K. X-ray photoelectron spectroscopy studies indicate an increase in the reduced states of vanadium and copper ions in going from the bulk glass to the thin film. Dynamic secondary-ion mass spectroscopy studies on thin films over a depth of 3000 Å show a strong dependence of T_s on the Cu-to-V intensity ratio. Even though stoichiometric values for thin films are achievable by varying the T_s, the oxidation states of Cu in these films are predominantly monovalent. The electrical behaviors of these materials and their thin film counterparts are finally being discussed in relation to the surface analysis data.     

Reactive radio frequency sputtering deposition and characterization of zinc nitride and oxynitride thin films

Zinc nitride films were deposited on glass or silicon substrates by reactive magnetron radio frequency sputtering of zinc in either N₂-Ar or N₂-Ar-O₂ ambient. The effects of varying the nitrogen contents and the substrate temperature were investigated. X-ray diffraction data showed that the as-deposited films contain the zinc nitride cubic crystalline phase with a preferred orientation, and Raman scattering measurements revealed ZnN related modes. According to energy-dispersive X-ray spectroscopy analysis, the as-deposited films were nitrogen-rich and contained only a small fraction of oxygen. Hall-effect measurements showed that p-type zinc nitride with carrier concentration of ~ 10¹⁹ cm⁻³, mobility of ~ 10¹ cm²/Vs, resistivity of ~ 10⁻² Ω ∗ cm, was obtained. The photon energy dependence of optical transmittance suggested that the material has an indirect bandgap.