Mechanical properties optimization of tungsten nitride thin films grown by reactive sputtering and laser ablation

Transition metal nitrides coatings are used as protective coatings against wear and corrosion. Their mechanical properties can be tailored by tuning the nitrogen content during film synthesis. The relationship between thin film preparation conditions and mechanical properties for tungsten nitride films is not as well understood as other transition metal nitrides, like titanium nitride. We report the synthesis of tungsten nitride films grown by reactive sputtering and laser ablation in the ambient of N₂ or N₂/Ar mixture at various pressures on stainless steel substrates at 400  C. The composition of the films was determined by XPS. The optimal mechanical properties were found by nanoindentation based on the determination of the proper deposition conditions. As nitrogen pressure was increased during processing, the stoichiometry and hardness changed from W₉N to W₄N and 30.8-38.7 GPa, respectively, for films deposited by reactive sputtering, and from W₆N to W₂N and 19.5-27.7 GPa, respectively, for those deposited by laser ablation.     

Structural, morphological, and mechanical properties of amorphous carbon and carbon nitride thin films deposited by reactive and ion beam assisted laser ablation

Amorphous carbon nitride thin films have been prepared on Si (100) wafers by nitrogen ion beam assisted Nd:YAG laser ablation techniques. Amorphous carbon and carbon nitride films have also been prepared by the conventional laser ablation techniques for comparison. Raman spectroscopy and spectroscopic ellipsometry have been performed for the films to analyze structural properties, atomic force microscopy to observe surface morphologies, and scratch, acoustic emission, and Vicker hardness test to examine mechanical properties. The amorphous carbon nitride films deposited by the ion beam assisted laser ablation techniques had generally better mechanical properties compared to the amorphous carbon films and amorphous carbon nitride films deposited in N₂ atmosphere. The amorphous carbon nitride films deposited at optimum ion beam current of 10 mA and laser power density of 1.7 × 10⁹ W/cm² showed excellent mechanical properties: root mean square surface roughness of 0.33 nm, friction coefficient of 0.02–0.08, the first crack and critical load of 11.5 and 19.3 N respectively, and Vicker hardness of 2300 [Hv]. It is considered that the films have high potential for protective coatings for microelectronic devices such as magnetic data storage media and heads.     

R.F. reactive sputter deposition of hydrogenated amorphous silicon carbide films

The preparation of hydrogenated amorphous silicon carbide films by r.f. reactive sputtering of a silicon target in Ar-CH₄ gas mixtures with and without an r.f. bias on the substrates was studied. Starting with a pure silicon target and increasing monotonically the CH₄ percentage from 0% to about 10%, films with 1 ⩾ x ⩾ 0 were obtained at decreasing deposition rates. After sputtering for some hours in methane-rich gas mixtures, carbon atoms were incorporated into the silicon target surface, probably as a result of atomic peening, and nearly stoichiometric SiC films were prepared by sputtering of such a target in pure argon. The different mechanisms of film formation, deposition rate, composition, hardness, friction coefficient and stresses in the films as functions of the partial pressure of methane and the value of the r.f. bias were investigated. The IR spectra offilms with different carbon contents were analysed. The greatest hardness was found for nearly stoichiometric SiC films deposited with a bias.     

Effects of sputtering power on mechanical properties of Cr films deposited by magnetron sputtering

Abstract

Chromium (Cr) films were deposited on plain carbon steel sheets by dc and rf magnetron sputtering as well as by electroplating. Effects of dc or rf sputtering power on the deposition rate and properties such as, hardness, adhesion strength, surface roughness and corrosion resistance of the Cr films were investigated. X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microcopy (SEM) analyses were performed to investigate the crystal structure, surface roughness, thickness of the Cr films. Salt fog tests were used to evaluate the corrosion resistance of the samples. The deposition rate, hardness and surface roughness of the Cr film deposited by either dc or rf sputtering increase with the increase in sputtering power but the adhesion strength is nearly independent of the sputtering power. The deposition rate, hardness and adhesion strength of the Cr film deposited by dc sputtering are higher than those of the Cr film deposited by rf sputtering, but rf sputtering offers smoother surface and higher corrosion resistance. The sputter deposited Cr film is harder and has a smoother surface than the electroplated one. The sputter deposited Cr film also has higher corrosion resistance than the electroplated one, which may be attributed to the smoother surface of the sputter deposited film.     

Effect of bias voltage on growth property of Cr-DLC film prepared by linear ion beam deposition technique

Cr-containing diamond-like carbon films were deposited on silicon wafers by a combined linear ion beam and DC magnetron sputtering. The influence of the bias voltage on the growth rate, atomic bond structure, surface topography and mechanical properties of the films were investigated by SEM, XPS, Raman spectroscopy, AFM, and nano-indentation. It was shown that the chromium concentration of the films increased with negative bias voltage and that a carbide phase was detected in the as-deposited films. The surface topography of the films evolved from a rough surface with larger hillocks reducing to form a smoother flat surface as the bias voltage increased from 0 to −200 V. The highest hardness and elastic modulus were obtained at a bias voltage of about −50 V, while the maximum sp³ bonding fraction was acquired at −100 V. It was suggested that the mechanical properties of the films not only depended on the sp³ bonding fraction in the films but also correlated with the influence of Cr doping and ion bombardment.     

Hard amorphous Ti–Al–N coatings deposited by sputtering

Ti–Al–N coatings were deposited by direct current reactive magnetron sputtering using two titanium and two aluminum targets. Two series of films with Al/(Al + Ti) atomic ratios of ≈ 23.5 and ≈ 34.5% were studied. The amount of nitrogen in the films was varied from 0 to 44at.%. The incorporation of N atoms led to a change of the -Ti lattice preferential orientation from <100> to <001>, a decrease in the degree of crystallinity, and subsequently to the collapse of the crystalline structure. Annealing at 975K promotes the formation of the Ti₃Al compound. The hardness increases smoothly with the nitrogen content. The high hardness values (31 and 41GPa) measured for the films with the highest N contents may be explained by the deposition of a nanocomposite phase. For the Ti–Al–N film deposited with Al/(Al + Ti) atomic ratio of 34.5% the -Ti structure was completely transformed to TiO₂ upon oxidation. The high oxidation resistance of the film deposited with 44at.% N at 1075K is characteristic of Ti–Al–N films.     

Reactive pulsed laser deposition of thin molybdenum- and tungsten-nitride films

In this work reactive pulsed laser deposition of molybdenum- and tungsten-nitride thin films is investigated. Metallic targets were ablated in low-pressure (1, 10 and 100 Pa) nitrogen atmosphere by KrF excimer laser pulses (fluence ∼6.5 J/cm²). Films were deposited on silicon wafers heated to ∼25, 250 and 500 °C. The characteristics of the films strongly depend on the N₂ pressure. By increasing N₂ pressure, the nitrogen content increases in the films, which leads to a monotonous increase of the electrical resistivity. Deposition rate decreases at 100 Pa as indicated by Rutherford backscattering spectrometry. At this pressure, hardness of the films significantly decreases also, as shown by microhardness measurements. X-ray diffractometry shows that films crystallinity is improved by increasing the substrate temperature. In addition, atomic force microscopy (AFM) and scanning electron microscopy (SEM) were applied for visualising the film surface.     

Effect of pressure and substrate temperature on the deposition of nano-structured silicon-carbon-nitride superhard coatings by magnetron sputtering

A systematic investigation on the deposition of silicon-carbon-nitride (Si-C-N) films under varying deposition conditions such as pressure, substrate temperature and nitrogen content was carried out by radio frequency and direct current magnetron sputtering techniques. Significant role of the different deposition parameters on hardness and structure in the film was observed. It was observed that there was a certain range of nitrogen to argon partial pressure ratio (90:10 to 98:2) for which the particle size was reduced and the films were smooth with fine particle growth, beyond this limit the films had larger particle growth and roughness. The hardness of the deposited film varied between 4400 Hv and 473 Hv depending on deposition condition. Si-C-N film with hardness above 4400 Hv by reactive RF magnetron sputtering from SiC-C composite target in nitrogen-argon was obtained. X-ray diffraction studies revealed the amorphous nature of the deposited films, whereas nano-crystallinity of the particles was noticed during atomic forced microscopy observations. X-ray photoelectron spectroscopy analysis showed the presence of C-N and Si-N bonds in the harder films. It was found that the presence of β-C₃N₄, Si₃N₄ and graphite phases and the particle growth in the deposited films control the hardness of the film.     

Studies on the target conditioning for deposition of LiCoO2 films

Deposition of good quality thin films of Lithium Cobalt Oxide (LiCoO₂), by sputtering is preceded by target conditioning, which dictates the surface composition, morphology and electrochemical performance of the deposited film. Sputtering from a virgin target surface, results in films with excess of the more reactive elements. The concentration of these reactive elements in the films decreases until the system reaches a steady state after sufficient sputtering from the target. This paper discusses the deposition kinetics in terms of target conditioning of LiCoO_2. The composition, morphology and texturing of deposited film during various hours of sputtering were analyzed using X-ray photoelectron spectroscopy (XPS) and Field Emission Scanning electron microscopy (FESEM). The compositional stability is not observed in the films formed during the initial hours of sputtering from the fresh target, which becomes stable after several hours of sputtering. The Li and Co concentration in the films deposited subsequently is found to be varying and possible causes are discussed. After the compositional stability is reached, electrochemical analysis of LiCoO₂ thin films was performed, which shows a discharge capacity of 129 μAh/cm².     

Substrate and Fe-doping effects on the hydrophilic properties of TiO2 thin films

Titanium dioxide films are known for their hydrophilic and photocatalytic characteristics. Increasing specific surface area and doping can enhance their photocatalytic activity and hydrophilicity. We report here results regarding the enhancement of the photocatalytic properties of titania by both controlling surface morphology and the anatase/rutile ratio. The samples were deposited on glass, indium tin oxide covered glass, and SrTiO₃ by sputtering and laser ablation techniques. Film structure and surface morphology were investigated by X-ray diffraction and atomic force microscopy. Film hydrophilicity was assessed from contact angle measurements during- and post-irradiation with UV light. The contact angle data are discussed in terms of the synergic effects of surface morphology, structure and composition of the films.     

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.     

Characterization on pulsed laser deposited nanocrystalline ZnO thin films

Nanocrystalline zinc oxide thin films were deposited on glass and silicon substrates by using pulsed laser deposition at different laser energy densities (1.5, 2, and 3 J/cm²). The film thickness, surface roughness, composition, optical and structural properties of the deposited films were studied using an α-step surface profilometer, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), optical transmittance, and X-ray diffraction (XRD), respectively. The film thickness was calculated as 244 nm. AFM analysis shows that the root-mean-square roughness increases with increasing laser energy density. XPS analysis shows that the interaction of zinc with oxygen atoms is greatly increased at high laser energy density. In the optical transmittance spectra, a shift of the absorption edge towards higher wavelength region confirms that the optical band gap increases with an increase in laser energy density. The particle size of the deposited films was measured by XRD, it is found to be in the range from 7.87 to 11.81 nm. It reveals that the particle size increases with an increase in laser energy density.     

Influence of thickness on the crystallography and surface topography of TiN nano-films deposited by reactive DC and pulsed magnetron sputtering

TiN films of 50 nm and 500 nm thickness were deposited on M2 tool steel substrates by reactive closed field unbalanced magnetron sputtering operating in direct current (DC) and pulsed magnetron sputtering (PMS) modes. Parameters of the crystallographic structure and surface roughness and their evolution during the films growth were analyzed via X-ray diffraction and atomic force microscopy. The obtained results show that all the analyzed films have polycrystalline and mono-phase (TiN) structures. In the 50 nm films, the in plane crystallographic texture that formed was 100% {111}. During film growth a weakening of the preferred crystallographic orientation and a decrease of the concentration of lattice imperfections occurred. Both processes are more pronounced in the film deposited by PMS compared to that deposited by DC sputtering. Film growth is accompanied by increasing of surface smoothness. Pulsing the target power led to a decrease of the mean surface roughness of both the 50 nm and 500 nm films.     

等离子体基离子注入制备TiN膜的成分结构

采用Ti、N等离子体基离子注入和先在基体表面沉积纯钛层然后离子注氮混合两种方法在铝合金基体上制备了TiN膜.利用XPS分析了两种方法制备TiN薄膜的成分深度分布和元素化学价态,并用力学性能显微探针测试对比了TiN膜的纳米硬度.研究表明:两种方法制备的薄膜均由TiN组成,Ti、N等离子体基离子注入薄膜中Ti/N≈1.1,而离子注入混合薄膜中Ti/N≈1.3,Ti、N等离子体基离子注入薄膜表面区域为TiN和TiO2的混合组织,TiN含量多于TiO2,离子注入混合薄膜表面主要是TiO2;Ti、N等离子体基离子注入所制备的薄膜的纳米硬度峰值为12.26 GPa,高于离子注入混合的7.98 GPa.     

Structural and mechanical properties of multi-element (AlCrMoTaTiZr)Nx coatings by reactive magnetron sputtering

(AlCrMoTaTiZr)N_x high-entropy films were deposited on silicon wafer and cemented carbide substrates from a single alloy target by reactive RF magnetron sputtering under a mixed atmosphere of Ar and N₂. The effect of nitrogen flow ratio R_N on chemical composition, morphology, microstructure, and mechanical properties of the (AlCrMoTaTiZr)N_x films was investigated. Nitrogen-free alloy film had an amorphous structure, while nitride films with at least 37 at.% N exhibited a simple NaCl-type FCC (face-centered cubic) structure. Mixed structures occurred in films with lower nitrogen contents. Films with the FCC structure were thermally stable without phase decomposition at 1000 °C after 10 h. The (AlCrMoTaTiZr)N film deposited at R_N = 40% exhibited the highest hardness of 40.2 GPa which attains the superhard grade. The main strengthening mechanisms for this film were grain-size and solid-solution strengthening. A residual compressive stress of 1.04 GPa was small to account for the observed hardness. The nitride film was wear resistant, with a wear rate of 2.8 × 10^− 6 mm³/N m against a loaded 100Cr6 steel ball in the sliding wear test. These high-entropy films have potential in hard coating applications.     

Ion bombardment-induced enhancement of the properties of indium tin oxide films prepared by plasma-assisted reactive magnetron sputtering

Research on tin doped indium oxide (ITO) has for many years been stimulated by the need to simultaneously optimize the electrical, optical and mechanical properties, and by new challenges related to the deposition of transparent conducting oxides on flexible plastic substrates. In the present work, we investigate the growth and optical, electrical, and mechanical (hardness, elastic modulus and stress) properties of ITO films deposited by plasma assisted reactive magnetron sputtering (PARMS) from an indium-tin alloy target. PARMS achieves an effective control of bombardment by reactive species (e.g., O₂⁺, O⁺) on the surface of the growing film by varying the bias voltage, V_B, induced by a radiofrequency power applied to the substrate. Stress-free films possessing high transparency (> 80% — film on glass) and low resistivity (4 × 10^− 4 Ω cm) can be deposited by PARMS under conditions of intense ion bombardment (≤ 600 eV).     

Pulsed Laser Processing of Carbon and Silicon Clusters and Thin Films

Abstract

Several new processes have been developed for the preparation of fullerenes and thin films by using a pulsed excimer laser. The irradiation of a pulsed KrF excimer laser beam onto a C₆₀ powder target produced single phase C₆₀ thin films when the laser energy fluence was in the range between 40 and 50mJ/cm². By atomic force microscopy, the laser-deposited C₆₀ thin film was verified to have a surface far smoother that the surfaces of films produced by the conventional evaporation method. The stainless steel rods coated with this film exhibited an excellent tribological property. Cluster formation from SiC and other carbides MC_n(M=Ti,W,B) was investigated by laser desorption time-of-flight mass spectrometry. No clear indication was observed for the production of such clusters as (SiC)₆₀ and (M_xC_60-x) from the sintered targets directly as well as from the films laser deposited from the targets. However, C₆₀ and C₇₀ were found to exists in the laser-deposited films, indicating a new applicability of pulsed laser processing for segregative cluster synthesis from solid solution. Preliminiary results on thin film deposition via pulsed ablation of (Ba,Na)_xSi₄₆ clathrate were also presented.     

Improving hardness of biomedical Co-Cr by deposition of dense and uniform TiN films using negative substrate bias during reactive sputtering

This paper reports the deposition of a fully dense and uniform TiN film to improve the surface hardness of Co-Cr, particularly, by applying a negative substrate bias during reactive direct current (DC) sputtering. As the TiN film was deposited with a negative substrate bias voltage of 150 V, the microstructure of the films was shifted from a columnar to non-columnar one that was observed to have a dense, uniform and smooth surface. In addition, the preferred orientation was the (111) plane when the films were deposited with a negative substrate bias; however, the (200) plane when they were deposited without a substrate bias. The deposition of the dense and uniform TiN film resulted in a significant increase of the hardness of the Co-Cr. The TiN-deposited Co-Cr with a negative substrate bias showed a very high hardness of 44.7 ± 1.7 GPa, which was much higher than those of the bare Co-Cr (4.2 ± 0.3 GPa) and TiN-deposited Co-Cr without a negative substrate bias (23.6 ± 2.8 GPa).     

Preparation of the hard CNx thin films using NO ambient gas by pulsed laser deposition

Pulsed laser deposition (PLD) technique has been widely used in thin film preparation because of its wonderful and excellent properties and amorphous carbon nitride (CN_x) thin films are recognized to have potential for applications like hard coating and electron field emission device. We have deposited CN_x thin films by KrF excimer laser – (λ= 248 nm) ablation of pure graphite target in pure NO gas ambient condition. In this paper, we have prepared the CN_x thin films at various ambient NO gas pressure of 1.3–26 Pa and laser fluence of 2– 5J cm^?2 on Si (100) substrate. We consider that the hardness of CN_x thin films improves due to the increase the nitrogen/carbon (N/C) ratio. The N/C ratio depended on the ambient NO gas pressure and laser fluence. We obtainedthe maximum N/C ratio of 1.0 at NO 3.3 Pa. The typical absorption of CN bonds such as sp² C–N, sp³ C–N, G band and D band were detected from the infrared absorption measurement by FTIR in the deposited CN_x thin films.     

Photoluminescence of nc-Si:Er thin films obtained by physical and chemical vapour deposition techniques: The effects of microstructure and chemical composition

Erbium doped nanocrystalline silicon (nc-Si:Er) thin films were produced by reactive magnetron rf sputtering and by Er ion implantation into chemical vapor deposited Si films. The structure and chemical composition of films obtained by the two approaches were studied by micro-Raman scattering, spectroscopic ellipsometry and Rutherford backscattering techniques. Variation of deposition parameters was used to deposit films with different crystalline fraction and crystallite size. Photoluminescence measurements revealed a correlation between film microstructure and the Er³⁺ photoluminescence efficiency.