热处理对PI基板铜薄膜金属化TiN阻挡层的影响

聚酰业胺(PI)材料具有介电常数低，分解温度高及化学稳定性好等优点，是很有前途的电子封装材料。Cu具有低的电阻和高的抗电迁移能力，足PI基板金属化的首选材料。采用物理气相沉积(PVD)方法在PI基板上沉积Cu薄膜，利用TiN陶瓷薄膜阻挡Cu向PI基板内部扩散。研究热处理条件下TiN陶瓷薄膜阻挡层的阻挡效果、Cu膜电阻变化以及Cu膜的结合强度，俄歇谱图分析表明TiN可以有效地阻挡Cu向PI内的扩散。300℃热处理消除了Cu膜内应力，提高了Cu膜的结合强度。     

偏压和氮分压对TiN膜层结构和膜/基体系性能的影响

采用多弧离子镀工艺在钛合金或低碳钢基材上制备TiN薄膜,研究了不同偏压及不同氮分压下制备的薄膜相结构、残余应力、膜/基体系硬度、膜/基结合及其摩擦磨损行为.结果表明:偏压影响TiN晶粒的择优取向,偏压绝对值越大则薄膜内部的残余应力也越大;偏压过高或过低都会降低薄膜与基材之间的结合强度,从而影响其摩擦学性能.氮分压上升,TiN熔滴粒度变大,Ti2N相减少,导致薄膜硬度提高;由过高或过低氮分压制备的膜/基体系在划痕试验中测得的临界载荷均较小;随着氮分压的增加,在试验范围内样品的摩擦因数下降但耐磨性并未获得预期的提高.     

多弧离子镀TiN/Cu纳米复合多层膜致硬机理的探讨

采用多弧离子镀技术制备单一的TiN薄膜和TiN/Cu纳米复合多层膜,研究了复合膜的硬度变化及相组成.初步探讨了TiN/Cu纳米复合多层膜的致硬机理.实验结果表明,Cu元素的掺人阻碍了TiN的生长,使复合膜硬度有了显著提高,制得硬度高达51GPa的TiN/Cu复合多层膜,其TiN以(111)和(200)两个晶面择优生长,且衍射峰强度极为接近,(200)面略高于(111)面.     

离子辅助沉积TiN/Ti复合膜提高TC17钛合金高温微动疲劳抗力

为提高钛合金高温微动疲劳抗力,利用离子辅助电弧沉积技术在TC17钛合金表面制各了TiN/Ti复合膜层,研究了膜层的剖面成分分布、膜基结合强度、膜层显微硬度、韧性、常规摩擦学性能以及抗高温微动疲劳性能.结果表明:利用离子辅助电弧沉积技术可以获得硬度高、韧性好、膜基结合强度和承载能力优异的TiN/Ti复合膜层,该膜层具有良好的抗磨和减摩性能,能够显著地提高TC17钛合金在350℃高温环境下的常规磨损和微动疲劳抗力.然而,TC17钛合金表面喷丸强化后进行离子辅助沉积TiN/Ti复合膜,由于喷丸层残余压应力的显著松弛以及膜层易于开裂和脱落的缘故,微动疲劳抗力则不及喷丸强化或TiN/Ti复合膜单独作用.     

CVD多层涂层断裂方式及失效的微观机理分析

本文以TiN/Al₂O₃/TiAlCNO/TiCN/TiN CVD多层涂层为对象研究了CVD多层涂层的断裂方式和失效机理。采用扫描电镜和透射电镜观察多层涂层的断裂形貌和涂层界面微观组织，结果表明多层涂层的断裂方式为沿晶断裂和穿晶断裂；Al₂O₃/TiAlCNO/TiCN涂层界面微观组织疏松有微裂纹等缺陷。采用电子探针分析了多层涂层界面的元素扩散行为，结果表明TiN/基体界面依靠机械结合、吸附结合、扩散结合和化学结合，界面强度高；Al₂O₃/TiAlCNO界面仅依靠吸附结合，界面强度低。通过计算得出多层涂层中存在残余热应力，它使多层涂层中产生较多微裂纹。因此，多层涂层失效源于涂层中微裂纹，界面结合强度低会加速涂层脱落。     

金属陶瓷及硬质合金表面CVD/PVD涂层的摩擦与切削性能

为研究涂层沉积方式对金属陶瓷和硬质合金性能的影响,采用粉末冶金技术制备了Ti(C,N)基金属陶瓷和YT15硬质合金,在基体表面先后采用CVD和PVD制备涂层。采用SEM、EDS等手段对涂层的微观组织和元素含量进行分析,并对涂层试样进行划痕、摩擦因数、切削性能检测。结果表明,通过复合CVD+PVD工艺,CVD涂层和PVD涂层结合良好。不论是金属陶瓷还是硬质合金,CVD涂层的膜基结合力和摩擦因数均为最大,PVD涂层最小,复合CVD+PVD涂层介于两者之间。对于金属陶瓷和硬质合金而言,复合CVD+PVD涂层的切削性能最好,CVD涂层最差,PVD涂层介于两者之间。切削过程中的磨损机理主要是氧化磨损和磨粒磨损。     

硬质合金基体上金刚石膜的XRD研究

采用直流等离子体射流CVD法在硬质合金 (WC + 8wt.%Co)基体上生长金刚石膜 ,主要借助XRD分析方法对CVD金刚石膜的微观结构和残余应力进行了研究 ,探讨了CVD金刚石膜中残余应力的形成及其对金刚石膜粘附性能的影响。研究结果表明 :CVD金刚石膜中通常存在GPa数量级的残余压应力 ,膜中存在适中的残余压应力 ,有利于CVD金刚石膜获得最佳的粘附性能     

等离子复合渗镀陶瓷层腐蚀磨损性能的研究

利用等离子渗金属技术、尖端放电、空心阴极效应和反应气相沉积技术，在碳钢表面形成具有扩散层和沉积层的新型复合渗镀TiN沉积层＋TiN析出相＋Ti扩散层，并在此基础上用磁控溅射PVD沉积TiB2薄膜，对其耐蚀性、耐磨性进行了检测和分析。结果表明：由于等离子TiN复合渗镀层的均匀性、致密度高于PVD沉积TiB2薄膜，在1mol／LH2S04溶液中耐腐蚀性能是PVD沉积TiB2＋等离子TiN复合渗镀层11．7倍。TiB2／TiN复合渗镀层与碳钢基体直接PVD沉积TiB2相比硬度高达2600HV，膜层比较厚，表面光滑、平整薄膜覆盖，膜基结合力也很强，有很好的减磨耐膜性能。说明等离子渗金属技术制备的TiN渗镀复合层不仅具有优异的耐腐蚀性能同时对TiB2陶瓷有着强有力的支撑作用。     

(SiC)TiN/Cu复合材料的热物理性能和焊接性能

以醇盐水解-氨气氮化法在SiC颗粒表面包覆TiN,然后采用放电等离子体烧结进行致密化,重点分析所制备的(SiC)TiN/Cu复合材料的热物理性能和焊接性能。结果表明:醇盐水解-氨气氮化法能够制备出TiN包覆SiC复合粉末,TiN包覆层均匀连续,能够提高材料的致密度并改善界面结合。(SiC)TiN/Cu复合材料的热膨胀系数介于8.1×10-6～11.9×10-6K-1之间,并且随着SiC体积分数的增加而降低。(SiC)TiC/Cu复合材料经过8次热循环以后的残余塑性应变为4.0×10-4。当SiC的体积分数为30%时,复合材料的热导率达到270W·m-1·K-1。Ag-Cu-Ti钎料在900℃时能在(SiC)TiN/Cu复合材料上完全铺展,具有良好的润湿性。(SiC)TiN/Cu复合材料与Ag-Cu-Ti钎料焊接接头的剪切强度高达56MPa。     

悬臂梁法测量不锈钢基体上铜膜和银膜残余应力

用悬臂梁法研究了不锈钢4Cr13基体上的Cu膜和Ag膜的平均残余应力和残余应力分布。结果表明，Cu膜和Ag膜的平均残余应力和分布残余应力随膜厚的增加而急剧减小。2种膜生长过程中界面应力很大，而生长应力很小。Cu膜在厚度较小时，残余应力值很大，超过了铜块材的断裂强度。     

离子束增强沉积TiN薄膜界面结合强度的研究

采用划痕法测定了离子束增强沉积ＴｉＮ薄膜的界面结合力。结果表明，由于在离子束增强沉积过程中ＴｉＮ薄膜和基体之间生成一层厚约３０～４０ｎｍ的过渡层，从而大大改善了涂层的界面结合强度，其临界载荷可达１４０Ｎ，为一般ＰＶＤ和ＣＶＤ方法所生成的ＴｉＮ膜的３～４倍，并且发现它并不随膜厚的增加而变化。     

铝合金表面沉积类金刚石薄膜的研究进展

类金刚石(Diamond-like Carbon,DLC)薄膜因其高硬度、良好的化学惰性以及优异的摩擦性能等优势,有望成为一种理想的铝合金表面防护涂层。对比了物理气相沉积(Physical vapor deposition,PVD)技术制备DLC改性材料与传统铝合金表面改性技术的优劣,概述了DLC薄膜在提升铝合金表面力学性能、减摩抗磨方面取得的最新成果,以及在复杂服役工况下面临的抗塑性变形差、易发生结合失效等瓶颈性问题。通过分析铝合金基体上生长高性能DLC薄膜的不利因素,指出界面化学结合强度低、薄膜残余应力大以及软基体/硬质薄膜的结构体系限制是导致上述问题产生的主要原因。在此基础上,重点综述了国内外研究学者为提高铝合金表面沉积DLC薄膜的膜基结合力所采取的有效措施及结果,包括:通过基体前处理增强基体力学性能与改善宏观表面缺陷;采用PVD或其他表面处理方法制备一层或多层的中间过渡层,缓解DLC薄膜与铝合金基体结构、性能之间的差异;调控DLC薄膜组分与结构以降低残余应力。最后展望了在铝合金基体表面制备DLC防护薄膜的发展趋势。     

管状构件内表面真空镀膜方法研究进展

综述了国内外真空镀膜方法,包括化学气相沉积与物理气相沉积方法对管状构件内表面镀膜的研究进展,介绍了热化学气相沉积及各种等离子体(包括直流、射频及电子自旋共振等离子体)增强化学气相沉积方法在管状构件内表面镀膜方面的应用,分析了这种方法的优缺点;重点阐述了溅射镀膜方法 (包括直流二极(或三极)溅射、磁控溅射及离子束(或激光束)溅射)及电弧离子镀技术在管状构件内表面镀膜时对薄膜种类、沉积速率、薄膜厚度轴向均匀性、膜/基结合力等方面的特点。最后对管状构件内表面各种真空镀膜方法进行了分析对比,指出了存在的问题及今后的发展方向。     

Roughness analysis of CVD Cu films on different substrates by AFM imaging

The roughness analysis of chemical vapor deposition (CVD) of copper (Cu) thin films on various substrates with and without seed layers was studied using atomic force microscopy (AFM). The effect of the seed layers on the film morphology was investigated, and none of the seed layers on the substrates improved the film morphology compared with TiN.     

TiSiO非晶结构光学薄膜的性能调控机理研究进展

TiSiO复合薄膜的制备方法主要包括溶胶-凝胶、物理气相沉积和化学气相沉积等,针对不同制备工艺条件下SiO2改性TiO2的微观结构与光学参量的调控机理的研究,仍处于探索阶段。综述了近年来国内外在不同工艺条件下沉积的TiSiO薄膜的结构和光学性质,从溶胶体系和热处理工艺两方面,对溶胶-凝胶工艺制备的TiSiO薄膜展开论述,分别归纳了溶胶体系和热处理工艺调控TiSiO薄膜的结构和光学性质的一般规律;从溅射工艺和蒸发工艺两方面对物理气相沉积工艺制备的TiSiO薄膜展开论述,分别阐述了在溅射工艺和蒸发工艺过程中,调控TiSiO薄膜的结构和光学性质的一般规律;从低（常）压化学气相沉积和等离子增强化学气相沉积等方面,对化学气相沉积工艺制备的TiSiO薄膜展开论述,分别阐述了在不同化学气相沉积技术中,通过调节一些重要参数调控薄膜结构和性能的一般规律。总结了不同工艺制备并调控TiSiO薄膜的一般规律的内在联系,并指出了这类薄膜制备工艺存在的问题和后续的研究方向。     

Effects of Ti- and Zr-based interlayer coatings on hot-filament chemical vapor deposition of diamond on high-speed steel

The prospect of obtaining good adhesion of diamond films onto steel substrates is highly exciting because the achievement of this objective will open up numerous new applications in industry. However, a major problem with depositing diamond onto steel is high diffusion of carbon into steel at chemical vapor deposition (CVD) temperatures leading to a very low nucleation density and cementite (Fe₃C) formation. Therefore, the study of the nucleation and growth processes is timely and will yield data that can be utilized to get a better understanding of how adhesion can be improved. This work focuses on the adhesion of thin diamond films onto high speed steel previously coated with various interlayers such as ZrN, ZrC, TiC, and TiC/Ti(C,N)/TiN. The role of seeding on nucleation density and the effect of diamond film thickness on stress development and adhesion has been investigated using scanning electron microscopy (SEM), x-ray diffraction (XRD), and Raman spectroscopy (RS). The main emphasis in this study lies with TiC, which for the first time proved to be a suitable layer for diamond CVD on high-speed steel (HSS). In fact, different from other interlayer materials investigated, no delamination was observed after 3 h of CVD at 650 °C when TiC was used. Nevertheless, the increase of diamond film thickness on TiC-coated HSS substrates led to delamination of small areas. This occurrence suggests that there was a distribution of adhesive toughness values at the diamond/TiC interface with the stress development being dependent on film thickness. This paper was presented at the fourth International Surface Engineering Congress and Exposition held August 1–3, 2005 in St. Paul, MN.     

退火温度对磁控溅射TiN/TiCN薄膜残余应力、结构及耐蚀性能的影响

采用反应磁控溅射在AZ31合金上制备了TiN/TiCN薄膜,并对沉积后的薄膜进行真空去应力退火。分别采用X射线荧光光谱仪(XRF)、扫描电镜(SEM)、掠入射X射线衍射(GIXRD)和电化学工作站对退火前后的薄膜进行表面化学成分、形貌结构、残余应力以及耐蚀性能分析。结果表明:薄膜由FCC结构的TiCN和TiN组成。退火后,薄膜的晶粒尺寸和结晶度增大,内部残余应力显著下降,电化学腐蚀区域的Ti、C、N元素含量下降,250 ℃退火薄膜的耐蚀性能与沉积态薄膜相当,300 ℃退火后薄膜的耐蚀性能下降。     

Evaluation of four commercially produced surface treatments

The paper reports the results of characterization of four commercial surface treatments on M2 tool steel substrates. The treatments characterized were (a) TiN deposited by physical vapor deposition (PVD), (b) TiCN/TiN multilayer also deposited by PVD, (c) diamond-like carbon (DLC) deposited by an ion-assisted technique, and (d) vanadium carbide (VC) produced by a thermal diffusion process. The surface treatments were evaluated for characteristics relevant to their tribological performance, such as thickness, roughness, chemical composition, micro- and nanohardness, coating-substrate adhesion, and wear resistance. In addition, a hardness model developed at the University of Newcastle upon Tyne (United Kingdom) to correct for substrate effects was successfully applied. Nanohardness tests also yielded the elastic modulus values of the surface treatments, while scratch testing used for determining coating-substrate adhesion provided qualitative information on their ductility.     

Study of adhesion of TiN grown on a polymer substrate

TiN films were deposited on polycarbonate substrates by cathodic vacuum arc using the plasma immersion ion implantation and deposition (PIII&D) method. The biaxial intrinsic stress in the film deposited using PIII&D with 3 kV applied bias was 0.3 GPa — much lower than that found in films deposited without the application of high-voltage pulsed bias. It was found that the dominant mechanism for generating stress in the TiN film was thermal stress arising from the large difference between the thermal expansion coefficient of TiN and that of the polymer. Tensile testing was used to ascertain film adhesion and a model was used to estimate the adhesion between the film and the substrate. It was found that PIII&D strongly reduced the stress in the TiN film and increased the adhesion to the polycarbonate. The ultimate shear strength of adhesion is of the same order of magnitude as that of TiN on stainless steel.