高功率脉冲磁控溅射制备的TiN薄膜 应力释放及其结合稳定性研究

目的 探究高功率脉冲磁控溅射（HPPMS）制备的氮化钛（TiN）薄膜在自然时效过程中,应力、薄膜/基体结合性能随时间的变化规律。方法 采用高功率脉冲磁控溅射（HPPMS）技术,通过调控基体偏压（-50、-150 V）,制备出具有不同残余压应力（3.18、7.46 GPa）的TiN薄膜,并采用基片曲率法、X射线衍射法、划痕法和超显微硬度计评价了薄膜的应力、薄膜/基体结合性能、硬度随时间的变化规律。结果 在沉积完成后1 h内,-50 V和-150 V基体偏压下制备的TiN薄膜压应力分别在3.12~3.39 GPa和7.40~7.55 GPa范围内波动,薄膜压应力没有发生明显变化;沉积完成后1~7天,平均每天分别下降28.57 MPa和35.71 MPa;7~30天,平均每天分别下降2.08 MPa和2.50 MPa;30~60天内,平均每天分别下降1.67 MPa和7.00 MPa。其压应力连续下降,且均表现出前期下降速率快,后期下降逐渐放缓的趋势。自然放置60天后,应力基本释放完毕,薄膜性质基本保持稳定。同时,薄膜/基体结合性能随时间逐渐变差,薄膜硬度下降。结论 HPPMS制备的TiN薄膜在自然时效过程中,其残余应力会随时间增加,连续下降,进而影响薄膜的力学性能。     

Annealing of intrinsic stresses in sputtered TiN films: The role of thickness-dependent gradients of point defect density

Morphology, structure and thermal behavior of magnetron sputtered TiN thin films with the thickness in the range 100-2900 nm are characterized. The films are thermally cycled and the relationship between film thickness, defect density and the intrinsic stress relaxation is analyzed. The results indicate that the residual stresses in the as-deposited films and the amount of stress relaxation depend decisively on the specific depth gradient of point defects originating from film evolution during growth. The compressive stresses, representing different driving forces and the amount of stress relaxation decrease, while the onset temperature of stress relaxation increases with increasing film thickness.     

热处理对两种铜膜结合强度的影响

采用PVD和CVD技术制备Cu/TiN/PI试样，研究表明，TiN薄膜可以有效地阻挡Cu向PI基板内部扩散，CVD工艺制备的Cu膜内部残余应力很小，Cu膜有相对高的结合强度；而PVD制备的Cu膜，在有TiN阻挡层存在的情况下，Cu膜内存在拉应力，拉应力降低了Cu膜结合强度，300℃退火可以消除膜内残余应力，结合强度提高。     

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。     

Effects of titanium-implanted pre-treatments on the residual stress of TiN coatings on high-speed steel substrates

This investigation examined how titanium ion implantation pre-treatment affects the residual stress of TiN coatings on M2 high-speed steel. Ions were implanted by metal plasma ion implantation. The adhesion strength of the TiN coatings was enhanced by pre-treatment that implanted Ti into the M2 tool steel substrate. The implanted substrate functioned as a buffer layer between the deposited TiN and the tool steel substrate, resulting in variations of the residual stress. The residual stress determined by glancing-angle XRD demonstrates that the deposited TiN films on ion-implanted substrates exhibited reduced compressive stress, from − 3.95 to − 2.41 GPa, which corresponded to a decrease in the grain size of the TiN films. The texture of the TiN film was clearly transformed from the preferred orientation of (220) to (111), subsequently enhancing wear resistance against a tungsten ball.     

Experimental tests and numerical simulation studies on nano-indentation of TiN film deposited on N-implanted aluminum

Nitrogen was implanted into aluminum substrate prior to magnetron sputtering of TiN films to introduce a modified layer between the TiN film and Al substrate. In another sample, a Ti interlayer was produced on the untreated substrate by means of magnetron sputtering. From the load-displacement curves obtained by the nano-indentation tests, the ring-like cracks appeared at 38 mN on the TiN/N⁺-implanted aluminum sample, 25 mN on the TiN/Ti/aluminum sample, and 18 mN on the TiN/untreated aluminum sample. The finite element method (FEM) was used to analyze the stress distribution at the interface of the various samples. The decline in the film base tensile stress and shear stress revealed the advantages of the pre-implanted substrate. All the numerical simulation results are consistent with the increased loading capacity obtained from the load-displacement curves.     

Si和316L基片上TiN薄膜微观结构和应力的对比分析

目的 比较Si和316L基片上TiN薄膜的微观结构和应力,分析基片材料和基片初始曲率对薄膜应力的影响.方法 采用电弧离子镀技术在Si基片和316L基片上制备了TiN薄膜,实测了薄膜应力,通过XRD、SEM、TEM等方法对薄膜的微观结构进行了分析.运用有限元分析技术,以结构力学为原理,分别对不同初始曲率的Si基片和316...     

低模量Ti6Al4V表面Ti(Al/Pt)N薄膜强化改性

为解决硬质薄膜因与软基体硬度和模量差较大导致的薄膜失效问题,提高硬质薄膜在Ti6Al4V(TC4)钛合金基体上的适应性,使用掺杂氮化钛（TiN）陶瓷薄膜对低模量Ti6Al4V合金表面强化。采用热丝增强等离子体磁控溅射技术在Ti6Al4V合金表面制备Ti(Al/Pt)N薄膜：包括本征TiN、Al&Pt掺杂TiAlN和TiAl(Pt)N薄膜。采用扫描电子显微镜、X-射线衍射仪、纳米压痕仪、洛氏硬度计和摩擦磨损测试仪分别表征三种薄膜组织形貌、能谱分析、相结构和内应力、纳米硬度和模量及耐磨性。结果表明：Al元素掺杂使TiN薄膜柱状晶细化,截面形貌柱状晶更致密;同时微量Pt掺杂后,截面断口呈韧性撕裂。本征TiN和TiAlN薄膜衍射峰图谱呈现TiN(111)取向,TiAl(Pt)N薄膜的衍射峰呈TiN(200)主峰位。Al元素掺杂使TiN薄膜晶格畸变增多,内应力从-13 MPa增大到-115 MPa,导致膜-基结合力恶化,洛氏压痕和摩擦磨损实验中均出现薄膜剥落。Pt掺杂后薄膜内应力降低到-66 MPa,在洛氏压痕试验中TiAl(Pt)N薄膜与基体结合良好,仅有少许环形裂纹。摩擦磨损试验中本...     

气相沉积 Ti / TiN 多层薄膜的力学及耐腐蚀性能研究

目的研究多层薄膜的界面对薄膜性能的影响。方法通过直流磁控溅射法在45#钢表面制备Ti N及Ti/Ti N多层薄膜,采用扫描电镜和XRD衍射分析仪对薄膜表面形貌及相结构进行观察和分析,使用纳米压痕仪、电子薄膜应力分布测试仪对Ti N及Ti/Ti多层薄膜的力学性能以及残余应力大小进行研究,并运用电化学设备对Ti N及不同调制周期的Ti/Ti多层薄膜的耐腐蚀性能进行研究。结果制备的Ti N及Ti/Ti N多层薄膜表面光滑且结构致密,Ti N晶粒细小且为非晶相;薄膜力学性能良好,内部均存在残余压应力。随着调制周期的减小,弹性模量和硬度先减小后增大,内部残余应力逐渐减小且分布不均匀程度逐渐增大。薄膜在H_2SO_4中的腐蚀试验表明:当Ti/Ti N多层薄膜调制周期为1μm时,多层薄膜的耐腐蚀性能不如Ti N薄膜,随着Ti/Ti N多层薄膜随调制周期的减小,多层薄膜的耐腐蚀性能逐渐升高;当调制周期为0.5μm时,Ti/Ti N多层薄膜的耐蚀性能已超过Ti N薄膜。结论 Ti/Ti N多层薄膜界面的增多有助于减小薄膜的残余应力,并且可提高薄膜的耐蚀性能。     

基体温度对磁控溅射TiN薄膜电化学性能的影响

采用直流反应磁控溅射方法在AISI 304不锈钢和Si(100)表面沉积了TiN薄膜,利用场发射扫描电镜、X射线衍射仪和电化学技术研究了基体温度对TiN薄膜结构与电化学性能的影响。结果表明:TiN薄膜为柱状结构,表面平整、致密,但基体温度高于300℃时膜表面存在微裂纹。薄膜为面心立方结构δ-TiN并存在择优取向,室温和150℃时的薄膜择优取向为(111)晶面,300℃和450℃时为(200)晶面;基体为室温时薄膜厚度为0.63μm,温度提高到150℃后膜厚增加到1μm左右,但继续升温对膜厚影响并不明显。薄膜在NaCl溶液中的腐蚀为点蚀,基体温度为150℃时的TiN薄膜具有最高的开路电位和点蚀电位以及最低的腐蚀速率,因此具有最佳的耐蚀性。     

薄膜厚度对HfO2薄膜残余应力的影响

HfO2薄膜是用电子束蒸发方法制备的，利用ZYGO干涉仪测量了基片镀膜前后曲率半径的变化，计算了薄膜应力。对样品进行了XRD测试，讨论了膜厚对薄膜残余应力的影响。结果发现不同厚度HfO2薄膜的残余应力均为张应力，应力值随薄膜厚度的增加而减小，当薄膜厚度达到一定值后，应力值趋于稳定。从微观结构变化对实验结果进行了分析，发现微结构演变引起的本征应力变化是引起薄膜残余应力改变的主要因素。     

Effects of residual stress distribution on the cracking of thick freestanding diamond films produced by DC arc jet plasma chemical vapor deposition operated at gas recycling mode

Chemical vapor deposited diamond thick films for electronic and optical applications must be released without cracks from substrates as freestanding wafers. In the present investigation, the residual stress distribution of diamond thin films deposited by DC arc jet plasma chemical vapor deposition (CVD) at gas recycling mode was analyzed based on wave number shifts in their Raman spectra. The results show that residual compressive stress concentrates at the film's edge, and this residual stress increases with the increase in deposition temperature. Experimental observation also showed that cracks initiated at the edge of the diamond thick wafer and then propagated towards the center. Effects of the residual stress distribution on diamond thick films detachment were discussed. To release the residual stress, sandwich structure was designed and the metal interlayer was inserted between the diamond films and the substrate. Thick freestanding diamond films (more than 1 mm thick, 60 mm in diameter) were produced by DC arc jet plasma CVD process using Mo substrate with Ti interlayer.     

Room-temperature growth of high-purity titanium nitride by laser ablation of titanium in a nitrogen atmosphere

Thin films of titanium nitride (TiN) were deposited on glass substrates by KrF excimer laser ablation of titanium over a very broad nitrogen pressure range with different target–substrate distances at room temperature. The as-deposited TiN thin films were analyzed by X-ray diffraction and transmission electron microscopy. It was found that the as-deposited thin films are normally a mixture of TiN and metallic titanium, and the TiN-to-Ti ratio of the as-deposited thin film depends on both the nitrogen pressure and the target–substrate distance. High-purity TiN thin films can be obtained only in a very narrow deposition parameter range. A compound parameter (the product of the nitrogen pressure and the target–substrate distance) is proposed to optimize the deposition of high-purity TiN thin films, and the possible mechanism is also discussed. It was also revealed that the as-deposited TiN thin films are polycrystalline with an average grain size of about 20 nm.     

Improvement in adhesion of diamond film on Cu substrate with an inlay structured interlayer

Diamond films were fabricated by using a two-step process on copper substrates in this study. The first step involved electroplating a chromium (Cr)–diamond composite interlayer on copper substrate and in the second step continuous diamond film was deposited on top using the hot-filament chemical vapor deposition (HFCVD) method. The interfacial characteristics was investigated by indentation tests and the thin film surface morphology, phase structure and residual stress analyzed by scanning electron microscopy (SEM), X ray diffraction (XRD) and Raman spectroscopy. The results show that the diamond particles are deeply imbedded in the chromium layer and the amorphous Cr in the composite interlayer was carburized to Cr₃C₂ during the CVD process. Low residual stress was detected in the diamond film and good adhesive strength between film and substrate was obtained due to the diamond particles anchored deep in the Cr₃C₂ matrix. Concentric cracks but no delaminated areas and radial cracks were observed on the periphery of the indentation at indentation load of 441 N.     

梯度基体温度法和反应溅射TiC过渡层对钛合金基体沉积金刚石薄膜的影响

以H2和CH4作为反应气体,采用热丝化学气相沉积法(HFCVD)在钛合金(Ti6Al4V)平板基体上制备金刚石薄膜,利用扫描电镜(SEM)、X射线衍射仪(XRD)、激光拉曼光谱(Raman)和洛氏硬度仪分析薄膜的表面形貌、结构、成分和附着性能,研究了高温形核-低温生长的梯度降温法对原始钛合金和反应磁控溅射TiC过渡层的钛合金表面沉积金刚石薄膜的影响。结果表明:原始基体区和TiC过渡层区沉积的金刚石薄膜平均尺寸分别为0.77μm和0.75μm,薄膜内应力分别为-5.85GPa和-4.14GPa,TiC层的引入可以有效提高金刚石的形核密度和晶粒尺寸的均匀性,并减少薄膜残余应力;高温形核-低温生长的梯度降温法可以有效提高金刚石的形核密度和质量,并提高原始基体上沉积金刚石薄膜的附着性能。     

Relation between delamination of thin flims and backward deviation of load–displacement curves under repeating nanoindentation

The delamination behavior of sputter coated TiN and AlN films have been examined from the load–displacement curves under repeated nanoindentation loading. When the penetration depth is either much larger or much smaller than the film thickness, the curve progresses in forward direction that represents the deformation of the substrate or film. On the other hand, a backward deviation is observed when the penetration depth is comparable with the film thickness. Observation of the indents by a scanning electron microscope (SEM) and an atomic force microscope (AFM) shows that cracking and extrusion of the film occur when the backward deviation appears. It suggests that the partially delaminated film releases the compressive residual stress and causes an upward bending due to the elongation of the delamintated film, which resists the penetration of the indenter in the consecutive cycle.     

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.     

具有TiN过渡层的BCN薄膜制备与力学性能

用电弧增强磁控溅射(AEMS)装置在高速钢(W18Cr4V)和Si(100)基体上制备了具有TiN过渡层的BCN薄膜,用X射线衍射(XRD)仪和傅里叶红外光谱(FTIR)分析了薄膜的微观结构,用划痕仪测试了薄膜的结合力,用显微硬度计和销盘式摩擦磨损实验仪测试了薄膜的硬度和摩擦学性能。结果表明:本实验条件下制备的具有Ti N过渡层的BCN薄膜的硬度为23 GPa,薄膜与GCr15钢球对磨的摩擦系数为0.3,具有TiN过渡层的BCN薄膜的结合力和摩擦学性能较BCN单层薄膜有明显提高。     

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.     

IBED Si_3N_4和TiN薄膜的成份、结构与摩擦学性能

本文考察了工艺参数对离子束增强沉积（IBED）氮化硅、氮化钛薄膜的成分和微观组织的影响。测定了薄膜的硬度以及薄膜与基体之间结合力，分析了成分和结构与薄膜的硬度和结合力的关系。考察了在不同载荷和速度条件下St_3N_4、TiN薄膜和52100钢试样的摩擦系数和耐磨性。结果显示，与无膜的52100相比，IBEDSt_3N_4和IBEDTiN的耐磨性成倍提高。探讨了薄膜的磨损机理。