Influence of the target composition on reactively sputtered titanium oxide films

Titanium dioxide thin films have many interesting properties and are used in various applications. High refractive index of titania makes it attractive for the glass coating industry, where it is used in low-emissivity and antireflective coatings. Magnetron sputtering is the most common deposition technique for large area coatings and a high deposition rate is therefore of obvious interest. It has been shown previously that high rate can be achieved using substoichiometric targets. This work deals with reactive magnetron sputtering of titanium oxide films from TiO_x targets with different oxygen contents.The deposition rate and hysteresis behaviour are disclosed. Films were prepared at various oxygen flows and all films were deposited onto glass and silicon substrates with no external heating. The elemental compositions and structures of deposited films were evaluated by means of X-ray photoelectron spectroscopy, elastic recoil detection analysis and X-ray diffraction. All deposited films were X-ray amorphous. No significant effect of the target composition on the optical properties of coatings was observed. However, the residual atmosphere is shown to contribute to the oxidation of growing films.     

Physical properties of high pressure reactively sputtered hafnium oxide

Hafnium oxide films were deposited on silicon by High Pressure Reactive Sputtering (HPRS) at pressures between 0.8 and 1.6 mbar. Growth, composition and morphology were investigated using Transmission Electron Microscopy (TEM), Heavy Ion Elastic Recoil Detection Analysis (HI-ERDA), Fourier Transform Infrared spectroscopy (FTIR) and X-Ray Diffraction (XRD). The growth rate was found to decrease exponentially with deposition pressure. The films showed a monoclinic polycrystalline structure, with higher grain size for intermediate pressures. All the films were slightly oxygen rich with respect to stoichiometric HfO₂, which is attributed to the oxygen plasma. Additionally, it was observed the formation of an interfacial silicon oxide layer, with a minimum thickness for deposition pressures around 1.2 mbar. These results are explained by the oxidation action of the oxygen plasma and the diffusion of oxygen through the grain boundaries of the HfO₂ film.     

Some properties of reactively sputtered tin lead oxide films

Reactive d.c. sputtering was used to produce thin oxide films of Pb_xSn_1?xO₂, where x was in the range from 0 to 0.6. The optical transmission and reflection spectra were measured at wavenumbers between 1.3 × 10⁴ and 3.5 × 10⁴cm^-1. From these data the optical constants, surface roughness and thicknesses of films were derived. The results show that the optical constants depend on the composition of the source material used in sputtering. Measurements of the electron energy losses show that, in addition to the basic phase of Pb_xSn_1?xO₂, the films contain other phases of lead oxides as well as pure lead (for x different from zero).     

Mechanical, microstructural and oxidation properties of reactively sputtered thin CrN coatings on steel

Thin (40 nm and 160 nm) CrN coatings were deposited on steel by reactive magnetron sputtering deposition, varying the N₂ flow. The coatings were characterized in the as-deposited condition and after annealing in air at 500 °C for 1 h, by X-Ray Diffraction, Transmission Electron Microscopy, Raman and Fourier Transform Infrared spectroscopies. Hardness was measured by nanoindentation. Coatings have a nanocrystalline microstructure with the phase shifting from Cr₂N to CrN, increasing grain size, thermal stability and resistance to oxidation with increasing N₂. Also intrinsic coating hardness is influenced by both N₂ flow during deposition and film thickness, as a result of changes in phase composition and microstructural properties.     

Photocatalytic activity of reactively sputtered and directly sputtered titania coatings

It is well known that, depending on deposition conditions, the structure of titania coatings may be amorphous, anatase or rutile, or a mixture of phases, and that the anatase phase is the most promising photocatalyst for the degradation of organic pollutants. The formation of anatase depends on the energy delivered to the growing film, which in turn depends on the operating parameters chosen. In this study, titania coatings have been deposited onto glass substrates by pulsed magnetron sputtering both from metallic targets in reactive mode and directly from oxide powder targets. The as-deposited coatings were analysed by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and micro-Raman spectroscopy. Selected coatings were then annealed at temperatures in the range of 400–700 °C and re-analysed. The photocatalytic activity of the coatings has been investigated through measurements of the degradation of organic dyes, such as methyl orange, under the influence of UV and fluorescent light sources. Further sets of coatings have been produced both from metallic and powder targets in which the titania is doped with tungsten. These coatings have also been analysed and the influence of the dopant element on photocatalytic activity has been investigated. It has been found that, after annealing, both sputtering processes produced photo-active surfaces and that activity increased with increasing tungsten content over the range tested. Furthermore, the activity of these coatings under exposure to fluorescent lamps was some 50–60% of that observed under exposure to UV lamps.     

Effects of substrate temperature and substrate material on the structure of reactively sputtered TiN films

Stoichiometric TiN films were reactively magnetron sputtered in an Ar-N₂ atmosphere. The films were deposited at various substrate temperatures in the range 200–650°C onto two types of substrate material, high speed steel and stainless steel. The microstructure of the films obtained was investigated by the use of a transmission electron microscope and the morphology was studied in a scanning electron microscope. Measurements of the hardness were also performed. The analysis of the microstructure shows that the growth of the film is markedly influenced by the substrate material. In particular, the high speed steel substrates were found to have a considerable influence on the microstructure. The vanadium carbide particles in these steels, which have a good lattice match to TiN, stimulate a localized epitaxial growth to occur on these carbide particles. This results in a microstructure consisting of large grains surrounded by small grains. The shape of the large grains is influenced by the temperature. In the development of these large grains cracks and/or voids occur in and around the grains at substrate temperatures above 400°C and the hardness drops by about 20%. No large grains were found on films deposited onto stainless steel and their hardness increases slightly with temperature. High hardness for films deposited onto the high speed steel substrate at temperatures above 400°C can also be obtained if a substrate bias is used. Ion bombardment during film growth suppresses the formation of the large grains with voided or cracked boundaries because of a continuous renucleation process. The formation of the different microstructures is discussed in terms of surface energy minimization and thermally activated processes as surface and grain boundary migration.     

沉积条件对RF反应溅射多晶ZnO薄膜结构的影响

采用ＲＦ反应溅射法在Ｓｉ（１１１）、玻璃衬底上制备了具有良好Ｃ轴承向的多晶ＺｎＯ薄膜。用ＸＲＤ分析了沉积条件（衬底温度、工作气体中的氧与氩气压比和衬底种类）对样品结构的影响,发现（１）薄膜的取向性随着衬底温或高而增强,超过４００℃后薄膜质量开始变差;（２）工作气体中氧与氩气压比（Ｐｏ２／ＰＡｒ）为２：３时,薄膜取向性最好;（３）薄膜晶粒尺寸１１－３４ｎｍ,相同沉积条件下,单晶硅衬底样品（００２）衍     

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。     

The structure of reactively sputtered metal carbide and metal silicide solar selective absorbers

Transition metal carbide and metal silicide films have recently been reported to produce excellent solar selective absorbers when deposited as interference layers onto metal substrates by d.c. reactive sputtering. These films, with a graded or multilayered profile, typically have solar absorptances greater than 0.90 and thermal emittances less than 0.05. In this paper we report the results of electron diffraction and electron microprobe studies on uniform titanium carbide and titanium silicide films produced by d.c. magnetron sputtering titanium in an atmosphere of argon plus methane or silane.The films were found to be rich in the non-metallic component and to consist of small particles of a metallic titanium carbide or silicide embedded in a porous matrix of carbon or silicon. The ratio of non-metal to metal increases with the reactive gas pressure in the sputter discharge, as does the film resistivity.Films which had been annealed in vacuum for sufficient time to change their optical properties showed no observable structural changes but it is inferred that the changes in optical properties are caused by a precipitation of carbon or silicon from the metallic particles into the matrix, causing the deposits to become more dielectric.     

Phase structure characteristics of r.f. reactively sputtered zirconia thin film

Zirconia thin films were deposited by an r.f. magnetron reactive sputtering method. Three kinds of target (pure Zr metal and compounds of Y-ZrO₂ and Mg-ZrO₂) were employed. The phase characteristics of the three series of films deposited with various oxygen partial pressures and substrate temperatures were investigated. It is found that only monoclonic phase was formed in the sputtered thin films when using Zr target, and both tetragonal and monoclinic phases were formed when using the compound targets.     

Structure and tribological properties of reactively sputtered Zr-Si-N films

Zr-Si-N films were deposited on silicon and steel substrates by magnetron sputtering of a Zr-Si composite target in Ar-N₂ reactive mixtures. The silicon concentration in the films was adjusted in the 0-7.6 at.% range by varying the surface of Si chips located on the erosion zone of the target. The films were characterised by X-ray diffraction, electron probe microanalysis, atomic force microscopy and wear tests. The structure and the tribological properties of Zr-Si-N films were compared to those of ZrN coatings. Depending on the silicon concentration, the films were either nanocomposites (nc-ZrN/a-SiN_x) or amorphous. Introduction of silicon into the zirconium nitride coatings induced a change in the preferential orientation of the ZrN grains: [111] for ZrN films and [100] for Zr-Si-N ones. This texture modification was also observed for a ZrN film deposited on an amorphous SiN_x layer. Thus, within our deposition conditions, the occurrence of a-SiN_x enhanced the [100] preferred orientation. Friction and wear behaviour of the films were carried out against spheres of alumina or 100 Cr6 steel by using a ball-on-disc tribometer. The results showed that addition of silicon into ZrN-based coating induced a strong decrease in the friction coefficient and in the wear rate compared to those of ZrN films. These results were discussed as a function of the films structure and composition.     

Chemical-state information obtained by AES and XPS from thin oxide layers on duplex stainless steel surfaces

Thin oxide films were produced by the exposure of polished, sputter-cleaned metallic surfaces kept in UHV to several thousands of Langmuirs at 10⁻⁵ mbar oxygen yielding oxide layers of several nanometers. Metallic substrates used were iron, chromium and duplex stainless steel (DSS 2205). AES and XPS profiling analyses were performed. An attempt was made to use certain features observed in the AES spectra, i.e. to correlate Fe and Cr MNN peak shapes with the chemical state of the corresponding element. A similar approach has been tried before and may, when combined with high-lateral-resolution AES, provide small-area chemical-state information. Localized chemical-state information derived from the MNN peak shapes by a Linear Least Squares Fit (LLSF) procedure appeared to match reasonably well with that provided by XPS, which is averaged over approximately 2 mm². This is a plausible result for a thin homogeneous layer on a polished substrate.     

Chemical-state information obtained by AES and XPS from thin oxide layers on duplex stainless steel surfaces

Thin oxide films were produced by the exposure of polished, sputter-cleaned metallic surfaces kept in UHV to several thousands of Langmuirs at 10⁻⁵ mbar oxygen yielding oxide layers of several nanometers. Metallic substrates used were iron, chromium and duplex stainless steel (DSS 2205). AES and XPS profiling analyses were performed. An attempt was made to use certain features observed in the AES spectra, i.e. to correlate Fe and Cr MNN peak shapes with the chemical state of the corresponding element. A similar approach has been tried before and may, when combined with high-lateral-resolution AES, provide small-area chemical-state information. Localized chemical-state information derived from the MNN peak shapes by a Linear Least Squares Fit (LLSF) procedure appeared to match reasonably well with that provided by XPS, which is averaged over approximately 2 mm². This is a plausible result for a thin homogeneous layer on a polished substrate.     

The influence of target oxidation and growth-related effects on the electrical properties of reactively sputtered films of tin-doped indium oxide

The electrical properties of tin-doped indium oxide films prepared by reactive r.f. magnetron sputtering were studied. The properties vary markedly with the added oxygen pressure and also with the film thickness owing to growth effects and target oxidation. The growth effects were analysed in terms of the grain size effects and of the target oxidation by a simple kinetic model. We show that films exhibiting a wide range of electrical properties can be prepared if the deposition conditions are carefully controlled. Films with conductivities as high as 2.5 × 10³ ohms⁻¹ cm⁻¹ and with optical transmission greater than 85% averaged over the visible spectrum were deposited.     

The influence of substrate temperature and sputtering gas atmosphere on the electrical properties of reactively sputtered indium tin oxide films

Tin-doped indium oxide (ITO) films were prepared by d.c. magnetron sputtering of an In-Sn alloy target, and the influence of the sputtering gas atmosphere and substrate temperature on their electrical properties was studied.The conditions for the deposition of the transparent ITO films were divided into three regions by varying the sputtering gas pressure. The first region was characterized by a high efficiency of oxygen gas consumption for film formation and a high deposition rate. In the second region the as-deposited films contained slightly less than the stoichiometric amount of oxygen. The third region was characterized by a low efficiency of oxygen consumption and a low deposition rate. The ratio of the amount of oxygen consumed to the amount of oxygen admitted to the sputtering chamber was about 15% when films with resistivities as low as 6 × 10^-4Ω cm were prepared at the optimum oxygen partial pressure.In the case of metallic deposited in an oxygen-poor atmosphere the carrier mobility, which mainly depends on the crystal structure, increased and the carrier concentration, which depends on the number of oxygen vacancies and donor centres, decreased with increasing substrate temperature. The opposite results were obtained for films deposited in an oxygen-rich atmosphere. Well-defined grain growth was observed, particularly for metallic films deposited at high substrate temperatures, and this caused the low carrier mobility.Subsequent heat treatment improved the resistivity of films deposited at substrate temperatures below 100°C, mainly because of the increase in carrier mobility, but it had little effect on the resistivity of films deposited at substrate temperatures above 150 °C because the increase in carrier mobility was cancelled by the decrease in carrier concentration.     

Nanoindentation and atomic force microscopy measurements on reactively sputtered TiN coatings

Titanium nitride (TiN) coatings were deposited by d.c. reactive magnetron sputtering process. The films were deposited on silicon (111) substrates at various process conditions, e.g. substrate bias voltage (V_B) and nitrogen partial pressure. Mechanical properties of the coatings were investigated by a nanoindentation technique. Force vs displacement curves generated during loading and unloading of a Berkovich diamond indenter were used to determine the hardness (H) and Young’s modulus (Y) of the films. Detailed investigations on the role of substrate bias and nitrogen partial pressure on the mechanical properties of the coatings are presented in this paper. Considerable improvement in the hardness was observed when negative bias voltage was increased from 100–250 V. Films deposited at |V _B| = 250 V exhibited hardness as high as 3300 kg/mm². This increase in hardness has been attributed to ion bombardment during the deposition. The ion bombardment considerably affects the microstructure of the coatings. Atomic force microscopy (AFM) of the coatings revealed fine-grained morphology for the films prepared at higher substrate bias voltage. The hardness of the coatings was found to increase with a decrease in nitrogen partial pressure.     

Stress stability and thermo-mechanical properties of reactively sputtered alumina films

The stability of residual stress inherent on deposition in reactively sputtered alumina films is studied during thermal cycling and annealing, simulating temperature excursions experienced by the films during device fabrication and subsequent operation. Increasing the magnitude of substrate bias applied during deposition acts to reduce the amount of argon incorporated in the films; more incorporated argon corresponds to smaller values of modulus and hardness and a larger coefficient of thermal expansion (CTE). Large, irreversible changes in film stress develop on heating, acting to decrease the compressive residual stress of films deposited on silicon substrates to a smaller, equilibrium value, whereas films deposited on Al₂O₃-TiC substrates behave differently. Thermal cycling and annealing have little effect on the modulus and CTE, but the hardness increases significantly and the threshold load for indentation crack initiation decreases precipitously during heat treatment. Possible mechanisms of irreversible stress development and mechanical property modifications are discussed.     

Influence of carbon diffusion on microstructure and wear behaviour of duplex stainless steel surface layers on lamellar grey cast iron

Surface welding with duplex stainless steel was performed to enhance the wear and corrosion properties of grey cast iron, which is used as material for applications as pump components in maritime and chemical environments. The method used for surface welding and the corresponding process parameters determine the chemical composition and microstructure, which both determine the corrosion and wear properties of the surface layer. High heat input leads to high chemical dilution and thus, reduced corrosion resistance. Slow cooling rates, which are recommended for welding of grey cast iron components, facilitate the formation of carbides in the fusion zone of the chromium‐rich duplex stainless steel surface layer. On the one hand, carbides lead to increased hardness and thus, improved wear resistance of the surface layers. On the other hand, carbides and high chemical dilution rates reduce the corrosion resistance and therefore should be avoided. Under high cooling rates, the risk of cracking in the heat affected zone of the grey cast iron increases due to martensitic phase transformations. The paper describes the correlation of process parameters, microstructure and chemical composition with a focus on carbon diffusion and carbide formation, ever considering the effect on the wear behaviour in an oscillation tribometer and under erosion‐corrosion conditions.     

Influence of substrate temperature on the growth and properties of reactively sputtered In-rich InAlN films

Indium-rich InAlN films were prepared on Si (111) substrates by using reactive co-sputtering in a mixed Ar-N₂ atmosphere. The substrate temperature was varied from room temperature to 300 °C to investigate the film’s growth and properties at different temperatures. Structural and optical properties of the films were evaluated through high resolution XRD and Raman spectroscopy respectively, surface morphology and roughness analysis was performed by using FE-SEM and AFM respectively, whereas the electrical characterizations were made through resistivity and current–voltage (I–V) measurements respectively. Highly c-axis oriented nanocrystalline InAlN films with wurtzite structure were obtained at a substrate temperature of 100 °C and above. Structural quality of the films was improved with increase of the substrate temperature. The Raman spectroscopy revealed A₁ (LO) modes which became more intense by the increasing the substrate temperature. The electrical studies indicated n-type nature of InAlN film having electron concentration in the range 3 × 10¹⁹–20 × 10¹⁹ cm^?3. The electrical resistivity exhibited a decreasing trend with increase of the deposition temperature. The I–V measurements showed a noticeable increase in the value of current by increasing the substrate temperature to 300 °C.