Deposition of TiN coatings on shape memory NiTi alloy by plasma immersion ion implantation and deposition

An investigation has been carried out to study the effect of pulse negative bias voltage on the morphology, microstructure, mechanical, adhesive and tribological properties of TiN coatings deposited on NiTi substrate by plasma immersion ion implantation and deposition. The surface morphologies were relatively smooth and uniform with lower root mean square values for the samples deposited at 15 kV and 20 kV negative bias voltages. X-ray diffraction results demonstrated that the pulse negative bias voltage can significantly change the microstructure of TiN coatings. The intensity of TiN(220) peak increased with the increase of negative bias voltage in the range of 5-20 kV. When the negative bias voltage increased to 30 kV, the preferred orientation was TiN(200). Nanoindentation test indicates that hardness and elastic modulus increased with the increase of the negative bias voltage (5 kV, 15 kV and 20 kV), and then dropped sharply at 30 kV. The adhesion between the TiN and NiTi alloy and tribological properties of TiN coated NiTi alloy depend strongly on the bias voltage parameter; the sample deposited at 20 kV possesses good adhesion strength and excellent tribological property.     

Amorphous carbon nitrogenated films prepared by plasma immersion ion implantation and deposition

In this work, an investigation was conducted on amorphous hydrogenated-nitrogenated carbon films prepared by plasma immersion ion implantation and deposition. Glow discharge was excited by radiofrequency power (13.56 MHz, 40 W) whereas the substrate-holder was biased with 25 kV negative pulses. The films were deposited from benzene, nitrogen and argon mixtures. The proportion of nitrogen in the chamber feed (R_N) was varied against that of argon, while keeping the total pressure constant (1.3 Pa). From infrared reflectance-absorbance spectroscopy it was observed that the molecular structure of the benzene is not preserved in the film. Nitrogen was incorporated from the plasma while oxygen arose as a contaminant. X-ray photoelectron spectroscopy revealed that N/C and O/C atomic ratios change slightly with R_N. Water wettability decreased as the proportion of N in the gas phase increased while surface roughness underwent just small changes. Nanoindentation measurements showed that film deposition by means of ion bombardment was beneficial to the mechanical properties of the film-substrate interface. The intensity of the modifications correlates well with the degree of ion bombardment.     

Sheath dynamics in a cylindrical PET-film for plasma immersion ion implantation

The characteristics of sheath in a cylindrical Polyethylene terephthalate (PET) film for plasma immersion ion implantation (PIII) have been investigated numerically using a one-dimensional self-consistent fluid model. The time-dependent surface potential and the charge density accumulated on the inner surface of PET-film are obtained. The numerical results demonstrate that the charging effects lead to the reduction of surface potential during pulse on time, the implanted ions thus cannot reach the desirable energy. In order to diminish the influence of charging effects one can shorten the pulse fall time and thin the PET-film.     

等离子体浸没离子注入及表面强化工艺的进展

等离子体浸没离子注入 (PIII)消除了传统束线离子注入 (IBII)固有的视线限制 ,是一种更适合于处理复杂形状工件的手段 .近十年来 ,PIII及其工业应用在国内外得到了迅速发展 .然而 ,随着PIII的研究与开发的深入 ,发现仍有若干重要的物理与技术问题 ,诸如浅的注入层、离子注入不均匀性、气体 (氮 )等离子体的有限应用范围等等 ,阻碍了PIII工业应用的发展 .目前 ,这些问题已成为国内外学者关注的焦点 .我实验室近年来在注入过程鞘层动力学的计算机理论模拟、离子注入剂量不均匀性改善、圆筒内表面注入研究、新型长射程阴极弧金属等离子体源研制、气体及金属等离子体的综合性表面改性工艺研究、以及低能高温PIII新工艺研究等方面进行了研究工作 .     

Semiconductor applications of plasma immersion ion implantation technology

Many semiconductor integrated circuit manufacturing processes require high dose of implantation at very low energies. Conventional beam line ion implantation system suffers from low beam current at low energies, therefore, cannot be used economically for high dose applications. Plasma immersion ion implantation (PIII) is emerging as a potential technique for such implantations. This method offers high dose rate irrespective of implantation energy. In the present study nitrogen ions were implanted using PIII in order to modify the properties of silicon and some refractory metal films. Oxidation behaviour of silicon was observed for different implantation doses. Diffusion barrier properties of refractory barrier metals were studied for copper metallization.     

Thick TiN films prepared by vacuum arc deposition and high energetic nitrogen ion beam dynamic mixing implantation

TiN films have many features, such as high wear resistance, high corrosion resistance and good oxidization resistance. With the technology of vacuum arc deposition and high current density nitrogen ion beam dynamic mixing implantation (DMI), the TiN film with a thickness of 33 μm and adhesion 58 N is synthesized on hard alloy and high-speed steel substrates. X-ray diffraction has been used to examine the crystal structure of the films. The results showed that the main phases presented in DMI films are TiN and Ti₂N and that the films revealed random growth. Cross-sectional scanning electron microscopy revealed the dense morphology and the thickness of the films. Micro-hardness tests showed that the average hardness of the films was about 2500 HK. Electrochemical experimental results indicated that DMI-TiN film had excellent corrosion resistance both in 3% NaCl solution and in 0.5 Mol H₂SO₄ solution.     

Effects of strong magnetic field on plasma immersion ion implantation of dielectric substrates

In this paper the effects of a strong magnetic field on plasma immersion ion implantation (PHI) of dielectric substrates were investigated. A plasma fluid model and finite difference schemes were used to simulate a one-dimensional system of plasma immersion ion implantation. The effect of secondary electron emission from the electrode on PHI was also taken into consideration. It was found that the magnitude and direction of the magnetic field have slight effects on sheath thickness but have considerable effects on current densities in the y and z directions which are perpendicular to the direction of the electric field (the x direction). The simulations showed that the current densities in the y and z directions increased significantly with increasing magnitude of the magnetic field at a given fixed angle, the reason being attributed to the rotational force exerted on the ions by the magnetic field. With a fixed magnetic field, increasing the angle of the magnetic field, θ, with respect to the electric field produced a continuous increase in current density in the y direction from zero to its maximum at θ = 90° but the current density in the z direction could be described as saddle-shaped being zero at both ends.     

新一代全方位离子注入及增强沉积工业机

本文报告了核工业西南物理研究院最近研制开发的新一代全方位离子注入及增强沉积工业机。该机直径 90 0 m m,高 10 5 0 m m,立式放置 ,抽气系统由分子泵及机械泵构成并且实现了 PL C控制 ,本底真空小于 4× 10 - 4Pa。气体和金属等离子体可分别由热阴极放和三个高效磁过滤式金属等离子体源产生。真空室顶部预留了法兰口并配有冷却靶台。该机的负高压脉冲幅值为 10～ 80 k V,重复频率为 5 0～ 5 0 0 Hz,脉冲上升沿小于 2 μs,并且可根据需要产生脉冲串。一般地等离子体密度为 10 8～ 10 1 0 cm- 3,膜沉积速率为0 .1～ 0 .5 nm/s。文中亦报道了一些实验结果     

Dynamic nitrogen and titanium plasma ion implantation/deposition at different bias voltages

Titanium oxynitride films were prepared on AISI 304 stainless steel samples employing dual titanium and nitrogen plasmas in an immersion configuration. The vacuum arc source provided the titanium plasma and the nitrogen plasma was sustained by hot filament glow discharge. A 30 μs implantation duration and 270 μs titanium arc duration were used in our plasma ion implantation and deposition (PIID) process. The impact of the implantation voltages (8 kV, 16 kV and 23 kV) on the film was investigated. The treated samples were characterized using Auger electron spectroscopy (AES) and atomic force microscopy (AFM). Our results reveal that the thickness of the coating is not changed significantly by the applied voltage. However, the surface morphology varies substantially with the implantation voltage. The 8-kV sample shows the highest titanium content and a smooth island-shaped surface whereas the 23-kV sample features peaks with sharper edges.     

9Cr18轴承钢氮等离子体浸没离子注入表面改性工艺及机理的研究

采用不同怕等离子体浸没离子注入工艺对９Ｃｒ１８轴承钢进行了氮离子注入,结果发现,不同条件下的氮离子注入均能显著提高９Ｃｒ１８钢表面的显微硬度和耐磨性,同时耐磨蚀性也明显改善。实验分析结果表明、氮离子注入后试样表面形成了大量的氮化物相,它们在改善材料表面特性中起到了关键的作用。     

Wear resistant and anti-corrosive treatment for TI-6AL-4V using metal vapor vacuum arc source in comparison with plasma immersion ion implantation

This study utilizes two ion-implantation methods, plasma immersion ion implantation (PIII) and metal vapor vacuum arc (MeVVA), to prepare Ti-N phases on the surface of Ti-6Al-4V. By the nitrogen PIII method, both nitrogen and minor oxygen species are simultaneously attracted by the negatively charged substrate. The penetration of N and O interstitial elements to an extensible depth is possible owing to the effect from the negatively charged target. The nitrogen PIII treatment does not produce a novel Ti-N phase. As a result, the modified surface does not behave anticorrosive. The H_n and the E determined by nanoindentation also remain unchanged. It is still potential to apply this non-directional treatment by increasing bias voltage of the target, coating pure titanium on Ti-6Al-4V, and adjusting the regeneration process of nitrogen ions. The MeVVA treatment creates a novel αTiN_0.3 (011) phase on Ti-6Al-4V in present study. It signifies that the interactions between kinetic Ti ions of varied energies and minor nitrogen molecules, with minor participation of oxygen, are highly feasible. The novel ion-implanted Ti-N phase is corrosion resistant, which is capable to reduce passivation current density by forming a passive film. Moreover, the MeVVA-treated surface is surface-hardened; the E is simultaneously increased. The increase of nano mechanical properties can be visualized by 3D images using Nano Vision and determined by analyzing the tip/surface impact structure on the indentation site.     

等离子体浸没式离子注入-离子束增强沉积TiN膜研究

本文采用一种新型的等离子体浸没式离子注入 离子束增强沉积的技术(PIII IBAD),在Cr12MoV钢基体上制备出了TiN膜,对沉积膜的组织进行了光电子能谱分析,并对沉积膜进行了硬度检测、摩擦试验及磨痕形貌分析。试验结果表明,沉积膜中的组织为TiN、TiO2和Ti2O3,TiN膜具有高达Hv3200的高硬度和极其优良的摩擦性能。     

脉冲宽度对偏转电场法内表面等离子体浸没离子注入的影响

近年来 ,采用等离子体浸没离子注入 (PIII)对零部件内表面进行改性处理引起了各国研究工作者的广泛关注 .研究表明 ,提出的偏转电场法是进行内表面注入处理的有效方法 ,可以极大提高内表面注入的注入剂量和注入能量 .研究了采用偏转电场法注入时注入电压脉冲宽度对注入效果的影响 .结果表明 ,长注入脉宽可以提高内表面注入能量 ,但对注入剂量影响不大 ;脉冲宽度对注入峰值深度和注入剂量的分布有很大影响 ,长注入脉宽使注入峰值深度和注入剂量的最大值向筒内部移动 ;采用适当的不同宽度脉冲进行注入 ,可以改善注入均匀性 .     

不同能量离子束辅助沉积对形成氮化钛薄膜性能的影响

用不同能量离子束辅助沉积方法在医用不锈钢317L和Si(100)基底上沉积TiN薄膜。通过X射线光电子能谱(XPS)、X射线衍射(XRD)和俄歇电子能谱(AES)分析研究了薄膜的结构特征;测试了薄膜与基底的附着力和耐磨性;用电化学腐蚀的方法检测了薄膜在Hank’s模拟体液中的耐腐蚀性能;最后采用成纤堆细胞、骨髓细胞体外培养试验考察了生长于不同薄膜表面的细胞粘附、增殖、展布情况及细胞的形态。研究结果表明：用高、低能氮离子兼用的IBAD方法制备的TiN多晶薄膜比只用高能或低能沉积的薄膜具有更强的附着力和耐磨性,在Hank’s模拟体液中显示出更强的抗腐蚀能力,并在细胞体外培养中显示出良好的细胞相容性。     

Microstructural and frictional control of diamond-like carbon films deposited on acrylic rubber by plasma assisted chemical vapor deposition

In this paper we concentrate on the microstructure of diamond-like carbon films prepared by plasma assisted chemical vapor deposition on acrylic rubber. The temperature variation produced by the ion impingement during plasma cleaning and subsequent film deposition was monitored and controlled as a function of bias voltage and treatment time. Its influence during film growth on the appearance of patterns of cracks and wrinkles, caused by the thermal stresses is evaluated. Different growth modes are proposed in order to explain the smaller patch sizes observed at negative variations of temperature. The coefficient of friction (CoF) of the samples is measured using a pin-on-disk tribometer in non-lubricated conditions. Much lower CoF values than unprotected rubber are seen, which can be correlated with the observed patch size.     

离子注N对6061铝合金表层晶粒取向的影响

通过掠入射X射线衍射及面探扫描实验研究了经氮离子注入后，6061铝合金表层的晶粒取向。结果表明离子注入对铝合金表层的晶粒取向有较大影响，并且随着注入时间的增加，其晶粒取向也发生变化。同时对离子注入层中晶粒取向的形成进行了探讨。     

Thin-film photo-catalytic TiO2 phase prepared by magnetron sputtering deposition, plasma ion implantation and metal vapor vacuum arc source

This study utilizes three methods, magnetron sputtering deposition (MSD), plasma ion implantation (PIII), and metal vapor vacuum arc (MeVVA), to prepare a thin-film TiO₂. The formation of stoichiometrical TiO₂-polymorphs as a layer is regularly relevant to the characteristic of the photo-catalytic effect. TiO₂-polymorphs created at the outermost surface and initiated by efficient photons are still capable to produce superficial hydroxyl groups for subsequent photo-catalytic reactions. The MSD-treated surface with the majority of TiO₂-anatase (101) surface is presently photo-catalytic. The PIII or MeVVA treatment results in an ion-implanted layer of different Ti / O ratios along with the detecting depths, whereas the Ti and O elements in TiO₂ phase at the outermost surface of the layer can be distinguished. Although the PIII- or MeVVA-treated surface is relatively insignificant in photo-catalytic reactions assessed by water droplet contact angle, the consumption of methylene blue in water and antibacterial test, it is still potential to adjust their surface chemistry by improving the quality of the ion-implanted layer, roughening the contact surface area, and increasing the efficiency to regenerate the photo-catalytic reactions. In addition, the ion implantation methods do not alter the size and dimension of a substrate that is a great advantage to employ them for various advanced applications.     

X射线测量高速钢上不同厚度氮化钛涂层残余应力

采用多弧离子镀在AISIM2高速钢(HSS)上沉积了TiN硬涂层,试样中基体厚度为1mm,涂层厚度分别为3.0、5.0、7.0、9.0和11.0μm.应用X射线衍射(XRD)分析了TiN涂层中残余应力,测量了TiN(220)衍射晶面在五种不同倾斜角(Ψ=0°,20.7°,30°,37.8°和45°)下的X射线衍射峰.结果表明:在3～11μm涂层厚度范围内,TiN涂层中均表现出残余压应力且残余压应力值较大.TiN涂层中残余应力大致分布在-3.22～-2.04GPa之间,本征应力分布在-1.32～-0.14GPa,热应力约为-1.86～-1.75GPa.TiN涂层中残余应力值随涂层厚度变化是非线性增加的,随厚度增加表现出先增大后减小的变化趋势,多项式拟合后发现约在8.5μm厚时残余应力达到最大值.     

离子束辅助沉积引发互不固溶系非晶相和亚稳晶相形成

利用离子束辅助沉积技术（IBAD）研究了在互不固溶的Cu-Ta和Cu-Nb系统中获得非晶相和亚稳晶体的可能性,结果表明：r(Cu)为30％时Cu含量的Cu-Ta薄膜得到了非晶相;r(Cu)为25％－35％时Cu-Nb薄膜中随辅助等离子束能量的改变出现了fcc相－非晶相转变;r(Cu）和20％时Cu-Nb薄膜中得到了bcc相,说明IBAD技术可以在互不固溶二元合金系统中制备非晶和亚稳晶相,非晶或亚稳晶的形成是由薄膜沉积过程中辅助离子束的作用引起的。     

Synthesis and characterization of HfO2 and ZrO2 thin films deposited by plasma assisted reactive pulsed laser deposition at low temperature

A plasma assisted reactive pulsed laser deposition process was demonstrated for low-temperature deposition of thin hafnia (HfO₂) and zirconia (ZrO₂) films from metallic hafnium or zirconium with assistance of an oxygen plasma generated by electron cyclotron resonance microwave discharge. The structure and the interface of the deposited films on silicon were characterized by means of Fourier transform infrared spectroscopy, which reveals the monoclinic phases of HfO₂ and ZrO₂ in the films with no interfacial SiO_x layer between the oxide film and the Si substrate. The optical properties of the deposited films were investigated by measuring the refractive indexes and extinction coefficients with the aid of spectroscopic ellipsometry technique. The films deposited on fused silica plates show excellent transparency from the ultraviolet to near infrared with sharp ultraviolet absorption edges corresponding to direct band gap.