(Ti,Al,Si,C)N nanocomposite coatings synthesized by plasma-enhanced magnetron sputtering

Materials’ surface service property could be enhanced by transition metal nitride hard coatings due to their high hardness, wear and high temperature oxidation resistance, but the higher friction coefficient (0.4-0.9) of which aroused terrible abrasion. In this work, quinternary (Ti,Al,Si,C)N hard coating 3-4 μm was synthesized at 300 °C using plasma enhanced magnetron sputtering system. It was found that the coating's columnar crystals structure was restrained obviously with the increase of C content and a non-columnar crystals growth mode was indicated at the C content of 33.5 at.%. Both the XRD and TEM showed that the (Ti,Al,Si,C)N hard coatings had unique nanocomposite structures composed of nanocrystalline and amorphous nc-(Ti,Al)(C,N)/nc-AlN/a-Si₃N₄/a-Si/a-C. However, the coatings were still super hard with the highest hardness of 41 GPa in spite of the carbon incorporation. That a-C could facilitate the graphitization process during the friction process which could improve the coating's tribological performance. Therefore, that nanocomposite (Ti,Al,Si,C)N coatings with higher hardness (>36 GPa) and a lower friction coefficient (<0.2) could be synthesized and enhance the tribological performance and surface properties profoundly.     

Structural and tribological properties of CrTiAlN coatings on Mg alloy by closed-field unbalanced magnetron sputtering ion plating

In this paper, a series of multi-layer hard coating system of CrTiAlN has been prepared by closed-field unbalanced magnetron sputtering ion plating (CFUBMSIP) technique in a gas mixture of Ar + N₂. The coatings were deposited onto AZ31 Mg alloy substrates. During deposition step, technological temperature and metallic atom concentration of coatings were controlled by adjusting the currents of different metal magnetron targets. The nitrogen level was varied by using the feedback control of plasma optical emission monitor (OEM). The structural, mechanical and tribological properties of coatings were characterized by means of X-ray photoelectron spectrometry, high-resolution transmission electron microscope, field emission scanning electron microscope (FESEM), micro-hardness tester, and scratch and ball-on-disc tester. The experimental results show that the N atomic concentration increases and the oxide on the top of coatings decreases; furthermore the modulation period and the friction coefficient decrease with the N₂ level increasing. The outstanding mechanical property can be acquired at medium N₂ level, and the CrTiAlN coatings on AZ31 Mg alloy substrates outperform the uncoated M42 high speed steel (HSS) and the uncoated 316 stainless steel (SS).     

Influence of negative ion resputtering on Al-doped ZnO thin films prepared by mid-frequency magnetron sputtering

Al-doped ZnO (AZO) films were deposited on glass substrates by mid-frequency magnetron sputtering with a ceramic ZnO:Al₂O₃ (98 wt%:2 wt%) target. The origin of the high resistivity of the films at the substrate position facing the erosion area of the target was investigated. The results indicate a preferential resputtering of Zn atoms caused by the negative ions, which leads to an increase of the oxygen/metal ratio in the films. Then more Al oxides form and result in the decrease of Al_Zn (the main donor in the films) concentration in the films. Thus the free carrier concentration decreases badly. This is the main mechanism responsible for the high resistivity.     

Crystal structure and tribological properties of molybdenum disulfide films prepared by magnetron sputtering technology

Molybdenum disulfide (MoS₂) is widely used in practice due to its excellent lubricating properties. However, research on the tribological properties of magnetron sputtering for depositing MoS₂ films remains limited. Herein, the tribological properties of MoS₂ films were investigated in detail through a series of characterization and friction coefficient tests. MoS₂ films were deposited onto silicon substrates by magnetron sputtering under different radio-frequency powers (P_rf). With increased P_rf, the crystallinity of the films gradually increases, whereas the friction coefficient initially decreases and then increases. P_rf also affects the chemical composition, surface morphology, and grain size of MoS₂ films. At P_rf = 300 W, the film surface is dense and smooth, the grain distribution is uniform. Moreover, the films have superior tribological properties and low friction coefficient, which can be attributed to the weak van der Waals force among MoS₂ layers and the microscopic morphology of the films. All these results indicate that by reasonably controlling the preparation parameters, MoS₂ films with excellent tribological properties can be prepared by magnetron sputtering.     

A magnetron sputtering technique to prepare a-C:H films: Effect of substrate bias

Amorphous hydrogenated carbon (a-C:H) films were deposited by magnetron sputtering with a mixture gas of Ar and CH₄. The a-C:H films deposited by this method have relatively low internal stress (<1 GPa) compared to some films deposited by conventional deposition process. The effects of substrate bias voltage on microstructure, surface morphology and mechanical properties of the films were investigated by various techniques. It has been found that the polymer-like structure is dominated at low bias voltage (−100 V), while the diamond-like structure with the highest hardness and internal stress is the main feature of the a-C:H films deposited under high bias voltage (−300 V). With increasing the bias voltage further, the feature of diamond-like structure decreases associating with the increase of graphitization. The frictional test shows that the friction coefficient and wear rate of the a-C:H films are depended strongly on structure and mechanical properties, which were ultimately influenced by the deposition method and bias voltage.     

Growth, structural, and magnetic properties of iron nitride thin films deposited by dc magnetron sputtering

FeN thin films were deposited on glass substrates by dc magnetron sputtering at different Ar/N₂ discharges. The composition, structure and the surface morphology of the films were characterized using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and atomic force microscopy (AFM). Films deposited at different nitrogen pressures exhibited different structures with different nitrogen contents, and the surface roughness depended on the mechanism of the film growth. Saturation magnetization and coercivity of all films were determined using superconducting quantum interference device, which showed that if N₂/(Ar+N₂) flow ratio was equal to or larger than 30% the nonmagnetic single-phase γ″-FeN appeared. If N₂/(Ar+N₂) flow ratio was less than 10%, the films consisted of the mixed phases of FeN_0.056 and γ′-Fe₁₆N₂, whose saturation magnetizations were larger than that of -Fe. If N₂/(Ar+N₂) flow ratio was 10%, the phases of γ′-Fe₄N and -Fe₃N appeared, whose saturation magnetizations were lower than that of -Fe.     

磁控溅射(Ti,N)/Al纳米复合薄膜的微结构和力学性能

采用Al和TiN靶通过磁控共溅射方法, 制备了一系列Ti:N≈1的不同(Ti, N) 含量的铝基纳米复合薄膜, 利用X射线能量分散谱仪、X射线衍射仪、透射电子显微镜和纳米力学探针表征了薄膜的成分、 微结构和力学性能, 研究了(Ti, N)含量对复合薄膜微结构和力学性能的影响. 结果表明: Ti, N原子的共同加入使复合薄膜形成了同时具有置换固溶和间隙固溶特征的"双超过饱和固溶体", 薄膜的晶粒随着溶质含量的增加逐步纳米化, 并进一步形成非晶结构, 晶界区域形成溶质原子的富集区. 相应地, 复合薄膜的硬度在含1.8 at.%(Ti, N) 时就可迅速提高到3.9 GPa; 随着TiN含量的增加, 薄膜的硬度进一步提高到含17.1 at.%(Ti, N)时的8.8 GPa. 以上结果显示出Ti和N"双超过饱和固溶"对Al薄膜极其显著的强化效果.     

Microstructure, optical and electrical properties of nitrogen doped sp-rich a-C thin films grown by facing-target magnetron sputtering

N atoms were incorporated into sp²-rich a-C networks using DC facing-target reactive sputtering at various N₂ fraction (P_N2) and their structure and opto-electrical properties were investigated systematically. As P_N2 increases, the fraction of CN bonded carbons (or the N content) increases primarily at the expense of the CC bonded carbons and then reaches its saturated value at P_N2 > 40%. The incorporated N preferentially forms different kinds of non-aromatic CN phase, leading to more localization of π electrons and the loss of the connectivity of nanographite fragments in the films, which is different from the case in N-doped sp³-rich a-CN_x films. Hence, with increasing P_N2, the a-C(:N) film converts from a semiconductor with a narrower optical band gap to an insulator-like material with a wider gap. Additionally, the variation of optical constants (n and k) and spin defects are related to the enhancement of the non-aromatic CN phase.     

Structural and tribological properties of nitrogen doped amorphous carbon thin films synthesized by CFUBM sputtering method for protective coatings

Nitrogen doped amorphous carbon (a-C:N) films are a material that may successfully compete with DLC coatings, which have high hardness, high wear resistance, and a low friction coefficient. The a-C:N films were prepared on silicon substrate by a closed-field unbalanced magnetron sputtering method with a graphite target and using the Ar/N₂ mixture gases. And, we investigated the effects of various DC bias voltages from 0 to −300 V on the structural and tribological properties of the a-C:N films. This study was focused on improving physical properties of the a-C:N film by controlling process parameters like negative substrate DC bias voltage. The maximum hardness of the a-C:N film was 23 GPa, the friction coefficient was 0.08, and the critical load was 25 N on a Si wafer. Consequently, the structural and tribological properties of the a-C:N film showed a clear dependence on the energy of ions bombardment and the density of the sputtering and the reaction gases during film growth.     

溅射功率对直流磁控溅射Ti膜结构的影响

 采用直流磁控溅射方法制备了纯Ti膜,研究了不同功率下Ti膜的沉积速率、表面形貌及晶型结构,并对其应力进行了研究。研究表明：薄膜的沉积速率随溅射功率的增加而增加,当溅射功率为20 W时,原子力显微镜(AFM)图像显示Ti膜光洁、致密,均方根粗糙度最小可达0.9 nm。X射线衍射(XRD)分析表明薄膜的晶体结构为六方晶型,Ti膜应力先随溅射功率增大而增大,在60 W时达到最大值（为945.1 MPa）,之后随溅射功率的增大有所减小。     

The influence of residual gas on boron carbide thin films prepared by magnetron sputtering

Boron carbide (B₄C) thin films were prepared by magnetron sputtering and residual gas impurities in the films were analyzed by X-ray photoelectron spectroscopy. The impurities, mainly oxygen, decrease with improving vacuum. By using argon ion beam etching of the films, the atomic concentration was measured as a function of etching depth. The binding energy spectra were analyzed using wavelet transform and curve fitting, showing that most of the oxygen impurity is in the form of boron oxides, and that the impurities are physically trapped among columnar structures in the film. In order to improve the base vacuum before coating the film, a range of methods were used, including argon gas filling on the target surface and titanium pre-sputtering. The experimental results show that the latter is an efficient and feasible method. Based on the titanium pre-sputtering technology, the optical performance of W/B₄C multilayer was improved so much.     

Optical and electrical properties of nanocrystal zinc oxide films prepared by dc magnetron sputtering at different sputtering pressures

The nanocrystal thin films of zinc oxide doped by Al (ZnO:Al) were deposited by dc reactive magnetron sputtering on the glass substrates, in the pressure range of 33-51 Pa. From the X-ray diffraction patterns, the nanocrystalline structure of ZnO:Al films and the grain size were determined. The optical transmission spectra depend from the sputtering pressure, but their average value was 90% in the range from 33 Pa to 47 Pa. Also, the sputtering pressure changes the optical band gap of ZnO:Al films, which is highest for films deposited at 37 Pa, 40 Pa and 47 Pa. The obtained films at room temperature have a sheet resistance of 190 Ω/cm² which increases with time, but the films annealed at temperature of 400 °C have constant resistance. The surface morphology of the films was studied by Scanning electron microscopy. XPS spectra showed that the peak of O1s of the as-deposited films is smaller than the peak of the annealed ZnO:Al films.     

非平衡磁控溅射制备类石墨碳膜及性能研究

利用中频非平衡磁控溅射技术在单晶硅基底上沉积了类石墨碳膜, 采用Raman光谱、高分辨透射电子显微镜、原子力显微镜分析了薄膜微观结构和表面形貌; 采用纳米压痕仪和CSM摩擦磨损试验机测试了碳膜力学性能和摩擦学性能. 结果表明: 利用中频非平衡磁控溅射技术沉积的碳膜是一种以sp²键合碳为主、结构非晶、硬度适中、应力较低、表面粗糙度较大、摩擦性能优异的薄膜. 脉冲占空比对薄膜微观结构和性能有显著影响, 随着脉冲占空比的增大, Raman光谱D峰和G峰的强度比I_D/I_G先减小后增大, 而硬度随脉冲占空比的增大却呈现出相反的变化趋势, 即先增大后减小; 大气氛围中的摩擦性能测试表明, 本实验制备的薄膜具有优异的抗磨性能(～10^-11 cm³/N^-1. m^-1)和承载能力(～2.5 GPa). 随脉冲占空比的增大, 薄膜摩擦系数变化甚微而磨损率却呈现先显著减小后轻微增大的变化趋势. 类石墨碳膜优异的摩擦学性能主要归因于其独特的结构、较低的内应力及良好的结构稳定性.     

Structural and electrical properties of fluorine-doped zinc tin oxide thin films prepared by radio-frequency magnetron sputtering

Transparent and conductive thin films of fluorine doped zinc tin oxide (FZTO) were deposited on glass substrates by radio-frequency (RF) magnetron sputtering using a 30 wt% ZnO with 70 wt% SnO₂ ceramic targets. The F-doping was carried out by introducing a mixed gas of pure Ar, CF₄, and O₂ forming gas into the sputtering chamber while sputtering ZTO target. The effect of annealing temperature on the structural, electrical and optical performances of FZTO thin films has been studied. FZTO thin film annealed at 600 °C shows the decrease in resistivity 5.47 × 10⁻³ Ω cm, carrier concentration ∼10¹⁹ cm⁻³, mobility ∼20 cm² V⁻¹ s⁻¹ and an increase in optical band gap from 3.41 to 3.60 eV with increasing the annealing temperatures which is well explained by Burstein–Moss effect. The optical transmittance of FZTO films was higher than 80% in all specimens. Work function (ϕ) of the FZTO films increase from 3.80 eV to 4.10 eV through annealing and are largely dependent on the amounts of incorporated F. FZTO is a possible potential transparent conducting oxide (TCO) alternative for application in optoelectronics.     

Study of nanocrystalline V02 thin films prepared by magnetron sputtering and post-oxidation

Nanocrystalline VO2 thin films were deposited onto glass slides by direct current magnetron sputtering and postoxidation. These films undergo semiconductor-metal transition at 70 ℃, accompanied by a resistance drop of two magnitude orders. The crystal structures and surface morphologies of the VO2 films were characterized by x-ray diffraction （XRD） and atomic force microscope （AFM）, respectively. Results reveal that the average grain size of VO2 nanograins measured by XRD is smaller than those measured by AFM. In addition, Raman characterization indicates that stoichiometric VO2 and oxygen-rich VO2 phases coexist in the films, which is supported by x-ray photoelectron spectroscopy （XPS） results. Finally, the optical properties of the VO2 films in UV-visible range were also evaluated. The optical band gap corresponding to 2p-3d inter-band transition was deduced according to the transmission and reflection spectra. And the deduced value, Eopt2p-3d ： 1.81 eV, is in good agreement with that previously obtained by theoretical calculation.     

X-ray determination of the thickness of thin films of TiC,TiN, Ti(N,C)

The paper deals with a possible application of X-ray diffraction methods in studying thin wear-resistant films of titanium carbides, nitrides and carbonitrides, deposited on hard metal substrates. Special emphasis is laid on the texture elimination when measuring the layer thickness. The results are compared with those of the metallographical method.     

溅射功率对直流磁控溅射Ti膜结构的影响

采用直流磁控溅射方法制备了纯Ti膜,研究了不同功率下Ti膜的沉积速率、表面形貌及晶型结构,并对其应力进行了研究。研究表明：薄膜的沉积速率随溅射功率的增加而增加,当溅射功率为20 W时,原子力显微镜(AFM)图像显示Ti膜光洁、致密,均方根粗糙度最小可达0.9 nm。X射线衍射(XRD)分析表明薄膜的晶体结构为六方晶型,Ti膜应力先随溅射功率增大而增大,在60 W时达到最大值（为945.1 MPa）,之后随溅射功率的增大有所减小。     

Effect of balanced and unbalanced magnetron sputtering processes on the properties of SnO2 thin films

A comparative study has been carried on the role of balanced magnetron (BM) and unbalanced magnetron (UBM) sputtering processes on the properties of SnO₂ thin films. The oxygen partial pressure, substrate temperature and deposition pressure were kept 20%, 700 °C and 30 mTorr, respectively and the applied RF power varied in the range of 150–250 W. It is observed that the UBM deposition causes significant effect on the structural, electrical and optical properties of SnO₂ thin films than BM as evidenced by X-ray diffraction, C-V, Spectroscopic Ellipsometer and Photoluminescence measurements. The value of band gap (E_g) of the films deposited at 150 W in UBM is found as E_g = 3.83 eV which is much higher than the value of E_g = 3.69 eV as observed in BM sputtering indicating that UBM sputtering results in good crystalline quality. Further, the C-V measurements of SnO₂ thin films deposited using UBM at high power 250 W show hysteresis with large flat band shift indicating that these thin films can be used for the fabrication of memory device. The observed results have been attributed to different mechanisms which exist simultaneously under unbalanced magnetron sputtering due to ion bombardment of growing SnO₂ thin film by energetic Ar+ ions.     

Magnetic properties and magnetoresistance of Co_xC_(1-x) granular films prepared by magnetron sputtering

Amorphous CoxC1-x granular films were prepared on n-Si(100) substrate by dc magnetron sputtering.The effects of Co concentration,film thickness and annealing temperature on the magnetic properties and magnetoresistance(MR) were investigated.After annealing at 500°C for 0.5 hour,the Co(002) peak of the CoxC1-x(x>2.5 at.%) films was observed,but cracks appeared in the films.Saturation magnetization Ms increased steadily with the increase of Co concentration from 2.5 at.% to 50 at.% and also increased with ann...     

Structural and optical properties of ZnO thin films on (111) CaF2 substrates grown by magnetron sputtering

ZnO thin films were grown on (111) CaF₂ substrates by magnetron sputtering at room temperature. Structural and optical properties of the ZnO thin films were studied. XRD analysis showed that the ZnO thin films had the (002) preferential orientation. The transmittance of ZnO thin films was over 80% in the visible range. The optical band gap of the ZnO thin films was 3.26 eV. The optical constants (n,k)$(n,k)$ of the ZnO thin films in the wavelength range 300–1000 nm were obtained by infrared spectroscopic ellipsometry measurement. PL spectra of ZnO thin films showed strong UV near-band-edge emission peak at 376.5 nm and weak visible red emission at 643.49 nm using He–Cd laser as the light source, using a synchrotron radiation light source PL spectra showed three emission peak at 320 nm, 410 nm and 542 nm respectively.