Deposition of nano-scaled CrTiAlN multilayer coatings with different negative bias voltage on Mg alloy by unbalanced magnetron sputtering

In a magnetron sputtering system, the negative substrate bias voltage has been used as a basic process parameter to modify the deposition structure and properties of coatings. In this paper we report the effect of bias voltage ranging from −40 V to −90 V on nano-scaled CrN/TiN/CrN/AlN (CrTiAlN) multilayer coatings synthesized on a Mg alloy by a closed-field unbalanced magnetron sputtering ion plating system in a gas mixture of Ar + N₂. The technological temperature and atomic concentration in the multilayer coatings were controlled by adjusting the current density of different metal magnetron targets and the plasma optical emission monitor. The composition, crystallographic structure, deposition model and friction coefficient of multilayer coatings were characterized by X-ray photoelectron spectrometry (XPS), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and ball-on-disc testing. The experimental results show that the deposition model and friction coefficient of nano-scaled CrTiAlN multilayer coatings were significantly affected by the negative bias voltage (V_b). The nitride species in multilayer coatings mainly involve CrN, AlN and TiN, and XRD analysis shows that the crystallographic structure was face-centered cubic. Under different bias voltage conditions, the multilayer coating composition shows a fluctuation, and the Al and Cr concentrations respond in the opposite sense to the bias voltage, attaining their greatest values at V_b = −70 V. The surface and cross-sectional morphology shows deposition model change from a columnar model into non-columnar model with the increase in negative bias voltage. The friction coefficient of the nano-scaled multilayer coatings at V_b = −55 V stabilize after 10 000 cycles.     

Microstructure and wear behaviour of silicon doped Cr–N nanocomposite coatings

Hard Cr–N and silicon doped Cr–Si–N nanocomposite coatings were deposited using closed unbalanced magnetron sputtering ion plating system. Coatings doped with various Si contents were synthesized by changing the power applied on Si targets. Composition of the films was analyzed using glow discharge optical emission spectrometry (GDOES). Microstructure and properties of the coatings were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), and nano-indentation. The harnesses and the elastic modulus of Cr–Si–N coatings gradually increased with rising of silicon content and exhibited a maximum at silicon content of 4.1 at.% and 5.5 at.%. The maximum hardness and elastic modulus of the Cr–Si–N nanocomposite coatings were approximately 30 GPa and 352 GPa, respectively. Further increase in the silicon content resulted in a decrease in the hardness and the elastic modulus of the coatings. Results from XRD analyses of CrN coatings indicated that strongly preferred orientations of (111) were detected. The diffraction patterns of Cr–Si–N coatings showed a clear (220) with weak (200) and (311) preferred orientations, but the peak of CrN (111) was decreased with the increase of Si concentration. The XRD data of single-phase Si₃N₄ was free of peak. The peaks of CrN (111) and (220) were shifted slightly and broadened with the increase of silicon content. SEM observations of the sections of Cr–Si–N coatings with different silicon concentrations showed a typical columnar structure. It was evident from TEM observation that nanocomposite Cr–Si–N coatings exhibited nano-scale grain size. Friction coefficient and specific wear rate (SWR) of silicon doped Cr–N coatings from pin-on-disk test were significantly lower in comparison to that of CrN coatings.     

Regularities of application of glow discharge spectrometry for quantitative layer-by-layer analysis of thin coatings

Regularities of application of glow discharge spectrometry are considered for quantitative layer-by-layer analysis of thin coatings on steels. The known methods of surface analysis used in industry and in research are compared. The main fields of application of glow discharge spectrometry are considered. The key causes for distortion of the analytical signal shape in quantitative layer-by-layer analysis using glow discharge spectrometers are discussed: the effect of the etching pit shape, analytical noise, and regularities of surface geometry of the studied samples. The main limitations of the methods in analysis of thin layers and coatings are shown. Calibration samples are developed for control of the thickness of thin chromium electrochemical coatings on steels. Metrological characteristics are estimated in measurement of the coating thickness. A method of quantitative layer-by-layer analysis on SA-2000 and GDS 850A glow discharge spectrometers (LECO) is proposed.     

Optical and electric properties of strontium bismuth tantalate thin films

High quality SrBi₂Ta₂O₉ ferroelectric thin films were fabricated on platinized silicon using pulsed laser deposition. The optical properties of the thin films were studied by spectroscopic ellipsometry from the ultraviolet to the infrared region. Optical constants, n ∼ 0.25 in the infrared region and n ∼ 2.18 in the visible spectral region, were determined through multilayer analyses on their respective pseudodielectric functions. The band-gap energy is estimated to be 4.14 eV. It was found that the leakage current mechanism of the film was from bulk limited Poole-Frenkle emission to interface-controlled Schottky emission with applied field increasing, and that the breakdown field of the film had a negative linear variation with the logarithm of the electrode area.     

用辉光放电光谱技术分析稀土离子氮化层中的元素

介绍了辉光放电光谱技术的原理及与其它表面分析技术的比较。用此技术成功快速地测得氮化表层的稀土和氮、碳、氧沿氮化层分布，并由此推出经合物层深。     

Surface density of growth defects in different PVD hard coatings prepared by sputtering

Growth defects are present in all PVD hard coatings. They have detrimental influence on their tribological properties (higher sticking of workpiece material, higher friction coefficient, worse corrosion resistance, higher gas permeation). In order to improve the tribological properties of PVD hard coatings it is important to minimize the concentration of growth defects. Conventional TiAlN single layer as well as AlTiN/TiN and TiAlN/CrN nanolayer coatings were deposited on cemented carbide, powder metallurgical high speed steel (ASP30) and cold work tool steel (D2) by magnetron sputtering in the CC800/7 and CC800/9 sinOx ML (CemeCon) deposition systems, respectively. The surface morphology of the coated substrates was examined by scanning electron microscope (FE-SEM) in combination with focused ion beam (FIB), and 3D stylus profilometer. By means of 3D-profilometry we performed several measurements and detailed analysis on a series of samples from the several hundred production batches. The influence of growth defects on GDOES (glow-discharge optical emission spectrometry) depth resolution and pitting corrosion was also studied.     

Advanced key technologies for magnetron sputtering and PECVD of inorganic and hybrid transparent coatings

Besides classical multilayer systems with alternating low and high refractive indices, reactive pulse magnetron sputtering processes offer various possibilities of depositing gradient films with continuously varying refractive index. Using nanoscale film growth control it is possible to achieve optical filter systems with a defined dependency of refractive index on film thickness, e.g. by sputtering a silicon target in a time variant mixture of oxygen and nitrogen. Also reactive co-sputtering of different target materials such as silicon and tantalum in oxygen is suitable as well. Rugate filters made from SiO_xN_y or Si_xTa_yO_z gradient refractive index profiles find their application in spectroscopy, laser optics and solar concentrator systems.Furthermore polymer substrates are increasingly relevant for the application of optical coatings due to their mechanical and economical advantages. Magnetron PECVD (magPECVD) using HMDSO as precursor allows to deposit carbon containing films with polymer-like properties. Results show the suitability of these coatings as hard coatings or matching layers. Multifunctional coatings with antireflective and scratch-resistant properties were deposited on polymer substrates using a combined magPECVD and sputter deposition process.     

Electrical properties of bulk silicon dioxide and SiO2/Si interface formed by tetraethylorthosilicate (TEOS)-oxygen plasma enhanced chemical vapor deposition

The electrical properties of bulk silicon dioxide and the SiO₂/Si interface formed by TEOS/O₂ PECVD were investigated. Additionally, the gas phase in the glow discharge was investigated using OES analysis under various experimental conditions. Changes of TEOS/O₂ ratio and the deposition temperature influenced the electrical properties of silicon oxide films. With decreasing TEOS/O₂, ratio, the electrical properties of bulk silicon dioxide and the SiO₂/Si interface were improved. This is thought to be due to the decrease of carbon impurity in the growing oxide film. At higher deposition temperatures, the oxide films had good electrical properties, which is thought to be due to the change of structure in the oxide film. From C–V analysis for all experimental conditions, the P_b center defects were observed near E_v+0.25eV and E_v+0.73eV in the Si band gap. The magnitude was influenced by process parameters such as the TEOS/O₂ ratio and the deposition temperature. From OES analysis, the main emission peaks observed in the glow discharge were from CO, CO ₂ ⁺ , CH, and C. With decreasing TEOS/O₂ ratio, the emission intensity of CH decreased and that of CO increased.     

Accurate measurement and evaluation of the nitrogen depth profile in plasma nitrided iron

Nitrogen depth profile of plasma nitrided pure iron was measured and evaluated by accurate experimental techniques. Plasma nitriding cycles were carried out on high purity iron substrate in an atmosphere of 75% H₂-25% N₂. Nitrogen concentration depth profiles in the compound layer and the diffusion zone were characterized by glow discharge optical emission spectroscopy (GDOES) and secondary ion mass spectroscopy (SIMS), respectively. Nitrogen diffusion depths were measured accurately by optical and scanning electron microscopy as well as SIMS technique at different nitriding times. Experimental results indicated good agreement between SIMS data and microscopic evaluations for various nitriding cycles. The results of SIMS showed the nitrogen diffusion depth of about 2000 μm in the diffusion zone for 10 h plasma nitriding at 550 °C. Such high depth had not been detected in previous investigations in which the conventional methods such as EDS, GDS, XPS, EPMA or ion probe techniques were used.     

Cutting Performance and Wear Mechanism of Multilayer Diamond-Coated Tools

Monolayer and multilayer diamond films are deposited on WC-Co cemented carbide by hot-filament chemical vapor deposition. The growth characteristics of diamond coatings are analyzed. Cutting performance characteristics such as tool life and the stability of machining process in the machining of presintered ZrO₂ are compared based on the variation of cutting speed and resultant cutting force, and workpiece surface roughness. For the monolayer diamond coatings, as the concentration of CH₄ increases from 1% to 5%, the diamond crystal is transformed from micron columnar crystal to nanocluster crystal. The multilayer diamond coatings combine the advantages of micron- and nanocrystalline structures. The multilayer diamond-coated tool exhibits longer service life and better machining quality. Because of the appearance of the brittle–plastic conversion mechanism, the surface integrity of ZrO₂ processed by multilayer diamond-coated tool is relatively high. As for the uncoated tool, the workpiece is mainly machined by brittle spalling. The interfacial stratified fracture system between the interlayers is proposed to be the toughening mechanism of the multilayer structure.     

Dielectric reference coatings for the evaluation of thin film characterization techniques

Thin film technology has an increasing demand for industrial reliable characterization techniques. A precise absolute determination of layer thickness, interface width and the quantification of depth profiles in dependence on resolution limits of the measurement are required. Certified reference materials, certified reference coatings (CRCs) and non-destructive evaluation techniques can meet these requirements. Dielectric reference coatings (SiO₂, Si₃N₄) were used for metallographic preparation (e.g. bevelled cross-sections), optical characterization techniques (e.g. spectroscopic ellipsometry (SE)), and films of SiO₂, Si₃N₄ and Al₂O₃ were applied to reference measurements in depth profiling of layer stacks (e.g. radio frequency glow discharge optical emission spectroscopy). Thickness and refractive index of these dielectric single-and multilayer coatings on different substrate materials are accurately determined in advance by means of SE. These values are subsequently used for precise angle determination of bevelled cross-sections, for reference and re-calibration purposes in thin film characterization (system reproducibility) and in surface analysis (determination of sputter and erosion rates, depth profiles). Examples are discussed for different applications and the calculated data are compared with experimental results. It is shown that reproducible commercial coatings are also of importance for use as CRCs.     

Diamond-like a-C:H coatings deposited in a non-self-sustained discharge with plasma cathode

Hydrogenated amorphous carbon (a-C:H) coatings have been obtained by means of acetylene decomposition in a non-self-sustained periodic pulse discharge (2A, 50 kHz, 10 μs) with hollow cathode. The discharge operation was maintained by plasma cathode emission with grid stabilization based on dc glow discharge. Using the proposed method, it is possible to control the deposition conditions (total pressure of the Ar + C₂H₂ mixture, partial pressure of C₂H₂, ion current density, carbon ion energy) within broad limits, to apply a-C:H coatings onto large-area articles, and to perform deposition in one technological cycle with ion etching and ion implantation treatments aimed at improving the adhesion of coatings to substrates (Ti, Al, stainless steel, VK8 hard alloy) at temperatures below 150°C. Results of determining the deposition rate (1–8 μm), the nanohardness of coatings (up to 70 GPa), and the fraction of sp ³ bonds (25–70%) in the diamond-like coating material are presented.     

Influence of substrate temperature on the materials properties of reactive DC magnetron sputtered Ti/TiN multilayered thin films

Ti/TiN multilayers were deposited by DC reactive magnetron sputtering method using a titanium target and an Ar-N₂ mixture discharge gas. XRD technique was employed to study the structure of the coatings and to observe the variations of structural parameters with substrate temperatures. An increase in grain size with increase of substrate temperature was observed. The components of Ti 2p doublet, related to TiN, TiON and TiO₂, were observed in the core-level spectra of the deposited multilayer films from XPS analysis. A microhardness value of 25.5 GPa was observed for Ti/TiN multilayers prepared at 400 °C. Electrical properties were found to depend on substrate temperature.     

State-of-the-art in analytical characterization of high purity solid samples by different spectroscopic methods

Facilities and some results of several spectroscopic methods which have potential applications in the field of analysis of solid high purity substances and which have been elaborated in Russia, will be discussed in this paper. Laser nondispersive atomic fluorescence method with glow discharge cathode sputtering atomiser, may be used for trace element determination as well as a tool for the investigation of technological processes, viz. deposition of thin films. Investigations on reduction of a background level in the new hollow cathode ion source for mass-spectrometry have been carried out. Laser mass spectrometry with tandem laser mass reflectron is successfully designed and applied for gaseous impurities determination in high pure silicon with limit of detection of 10⁻³–10⁻⁵ ppm wt. Several results of the layer-by-layer and bulk trace analysis of solids by high resolution mass spectrometry with radio frequency powered glow discharge ion source with the limits of detection at 10⁻¹–10⁻³ ppm wt will be presented here. The traditional arc and spark emission technique still finds considerable use. One of the examples considered in the paper is the analysis of metalfullerenes. To overcome the calibration problem the fluorination process inside the electrode crater using zinc fluoride has been investigated.     

SIMS and GDMS depth profile analysis of hard coatings

Rapid development in hard coating technology calls for simple construction depth profile analysers. Here we present results of depth profile analysis of a set of Ar arc plasma deposited TiN, CrN layers. The results are obtained with the use of recently constructed simple glow discharge mass spectrometer (GDMS) and compared with secondary ion mass spectrometer (SIMS). In SIMS (SAJW-05 model) we apply 5 keV Ar⁺ ion beam of about 100 μm in diameter. Digitally controlled spiral scanning of primary ion beam is performed over 1.6 mm² area. Secondary ions are extracted from the central part due to an “electronic gate” and analysed by quadrupole mass spectrometer QMA-410 Balzers (16 mm rods).GDMS analyses are performed on SMWJ-01 glow discharge prototype spectrometer. To supply discharge in 1 hPa argon we use 1.5 kV DC voltage. The analysed sample works as a cathode in a discharge cell. Area of the analysis is ∼4 mm² due to the use of secondary cathode—high purity tantalum diaphragm. Sputtered atoms are ionised, next extracted into the analytical chamber and finally analysed by the quadrupole mass analyser SRS-200 (6 mm rods).The results show that the use of simple construction GDMS analyser allows obtaining similar or even slightly better depth resolution than it can be obtained in the SIMS spectrometer. Application of glow discharge analysis opens new possibilities in direct quantitative depth profile analysis of hard coatings.     

A wear-resistant coating—Oxidized graded multilayer TiN/W coating

Combining sputtering technology using an industrial-scale four-target DC closed-field unbalanced magnetron sputtering ion plating system (CFUBMSIPS™) with post heat treatment, a graded multilayer TiN/W coating, consisting of five layers, was synthesized and its outmost W layer was transformed to lubricious WO₃ successfully. The coatings were characterized by using GDOES, GXRD, a Rockwell C indentation tester, a nanoindentation tester, and a scratching tester. Wear behavior of coatings was evaluated by using a pin-on-disc tribometer. Through proper post heat treatment, the multilayer TiN/W coating, in spite of having a lower nano-hardness, showed good adhesion, much better wear performance and lower friction coefficient compared with the reference monolayer TiN coating.     

Depth profiling of thin films with pulsed glow discharge atomic emission spectrometry

The application of microsecond pulsed Grimm glow discharge atomic emission spectrometry for depth profiling of thin films is examined. The effects of pulsed conditions including pulse voltage, pulse frequency, pulse width, and Ar pressure on depth profiling performance were characterized for Zn and Cu coatings on steel. Using optimized conditions, linear calibration curves of coating thickness for Zn (6.1-26.9 μm) and Cu (50-500 nm) on steel were achieved. A precision of 2-5% relative standard deviation was determined. An ultrathin coating of Cu (10 nm) on steel was also measured by this technique.     

Thin polymer films from polyimide vacuum thermal degradation with and without a glow discharge

Polyimide-like thin films were deposited by thermal degradation of polyimide with and without simultaneous activation by a glow discharge excited using an r.f. planar magnetron. The films deposited without discharge are similar in composition to conventional polyimide, whereas the deposition with plasma results in cross-linked coatings with composition typical for plasma polymers e.g. prepared by r.f. sputtering of polyimide. AFM reveals rough surface topography for the films evaporated without plasma. The application of plasma leads to very smooth plasma polymer films.     

Electrochemical investigation and characterization of thin-film porosity

In thin-film applications it is necessary to control film properties such as homogeneity and porosity to obtain high-quality coatings. Electrochemistry can be a very helpful tool since it can provide information about processes taking place at the interface between substrate and coating. Different thin carbon-based coatings were deposited via physical vapour deposition methods and vapour phase polymerization on pure iron substrates: fullerene films, which were modified by an ion bombardment and thin films of poly(p-xylylene), which is a very good insulating polymer. The film porosity and stability of the film/substrate system against aqueous corrosion were investigated and compared using cyclic voltammetry. The dependence of porosity and film stability on various deposition process parameters such as film thickness and plasma conditions was measured via the dissolution current density and the open circuit potential shift of the substrate material. It could be shown that the two measurements, current density I_crit. and open circuit potential E_ocp. can provide useful complementary information about film porosity that can lead to a better understanding of the coatings properties and the deposition process as well.     

Growth of n-type and p-type ZnSe thin films using an electrochemical technique for applications in large area optoelectronic devices

ZnSe layers have been grown by a low temperature (65 °C) electrochemical deposition technique in an aqueous medium. The resulting thin films have been characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive analysis by X-rays (EDAX), glow discharge optical emission spectroscopy (GDOES) and X-ray fluorescence (XRF) for bulk material properties. A photo-electrochemical (PEC) cell and an optical absorption method have been used for determination of the electrical and optical properties of the thin films. XRD patterns indicate the growth of ZnSe layers with (1 1 1) as the preferred orientation. The XPS spectra are similar to those of commercially available ZnSe and the EDAX, GDOES and XRF also indicate the presence of Zn and Se in the layers. PEC studies show p-type semiconducting properties for the as deposited layers and n-type ZnSe can be produced by appropriate doping. Optical absorption is maximum around 460 nm indicating a band gap of 2.7 eV. Annealing at 200 °C for 15 mins improves both the crystallinity of the layers and the photoresponse of the electrolyte/ZnSe liquid/solid Schottky junction. © 1998 Chapman & Hall