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。     

调制周期对TiN/Ti多层膜组织结构和结合力的影响

为了阐明调制周期对薄膜微观组织及薄膜与基体结合力的影响,采用反应磁控溅射在Ti6Al4V基板上交替沉积了Ti层及TiN层制备了TiN/Ti多层膜。利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、显微硬度仪和划痕仪测量分析了薄膜的晶体结构、微观组织、硬度以及薄膜与基体之间的结合力。研究结果表明:TiN/Ti多层膜中均存在TiN,Ti和Ti2N 3种相。TiN/Ti多层膜均以柱状晶方式生长,在调制周期较大(5层)时,TiN和Ti层的界面清晰;随着调制周期的减小(层数增加),TiN和Ti层的界面逐渐消失。与单层TiN薄膜相比,多层TiN/Ti薄膜的硬度显著提高;但随着薄膜层数的增加,多层TiN/Ti薄膜硬度略微降低。当调制周期为80nm(30层)时,薄膜与基体的结合力明显提高,达到73N。     

ZrN及其多层膜的性质和耐腐蚀性能

用磁过滤电弧制备了ZrN和ZrN／TiN多层膜，磁控溅射制备了ZrN薄膜。结果表明，ZrN／TiN多层膜，由于纳米多层化作用，硬度高于ZrN和TiN的26GPa和2lGPa，平均值达到34．5GPa。X射线衍射分析表明，ZrN／TiN多层膜由ZrN和TiN组成。过滤电弧制备的ZrN和ZrN／TiN多层膜的结合力为8lN和77N，磁控溅射制备的ZrN薄膜的结合力为26N。极化曲线的结果显示，过滤电弧制备的ZrN和ZrN／TiN多层膜的耐腐蚀性显著优于磁控溅射制备的ZrN薄膜，讨论了两种方法制备薄膜性能差异的原因。     

The evolution of diffusion barriers in copper metallization

Refractory metal nitride thin films have been widely developed as the diffusion barriers for the aluminum or copper interconnects in integrated circuits. This study reviewed the evolution of diffusion barriers in copper metallization. First, materials characteristics and electrical properties of various diffusion barriers, titanium nitride (TiN), tantalum nitride (TaN), and titanium zirconium nitride (TiZrN), were examined. These diffusion barriers were prepared by reactive magnetron sputtering in N₂/Ar gas mixtures. Next, barrier performance was evaluated by annealing the Cu/barrier/Si systems at 400–1,000°C for 60 min. in vacuum as well as the measurements of copper diffusion coefficients. The results suggest that TiZrN films can be used as a diffusion barrier for copper metallization better than the well-known TaN films. Therefore, the evolution of diffusion barriers in copper metallization, from TiN to TaN and then from TaN to TiZrN, is addressed.     

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。     

磁控溅射Cu-Cr合金薄膜与Sn-Ag-Cu焊料在时效处理时的界面反应

采用磁控溅射的方式沉积不同Cr含量的Cu-Cr合金薄膜,通过与Sn-Ag-Cu(SAC)焊料在240 ℃下回焊形成焊点结构,然后将试样置于180 ℃下进行真空时效处理。研究Cu-Cr合金作为凸点下金属化(UBM)层时与SAC形成焊点的焊接可靠性。使用配备能量色散X射线光谱仪的场发射扫描电镜和多功能推力测试仪等分析界面金属间化合物(IMC)的形貌及焊点的剪切强度。结果表明,SAC/Cu-Cr焊点结构在回焊后形成了不同于传统的SAC/Cu焊点扇贝状IMC的针状IMC。在时效处理后,Cr在晶界处的偏析形成了富铬层,其作为扩散阻挡层阻碍Cu扩散到IMC中,使得Cu₃Sn和柯肯达尔空洞的生长受到抑制。剪切强度测试结果表明,回焊后SAC/Cu-Cr试样比SAC/Cu试样具有更高的剪切强度。Cr靶电流为1.5 A的Cu-Cr合金UBM层形成的焊点结构具有较小的IMC厚度,且拥有最高的焊点剪切强度。证实了Cu-Cr 合金UBM层有利于提高焊接可靠性。     

脉冲频率对HiPIMS制备TiN薄膜组织和力学性能的影响EI北大核心CSCD

为探究脉冲频率对通过高功率脉冲磁控溅射制备TiN薄膜组织力学性能的影响,选用Ti靶和N2气体,采用反应磁控溅射技术通过改变高功率脉冲磁控溅射(HiPIMS)电源脉冲频率在Si(100)晶片上制备不同种TiN薄膜。利用X射线衍射仪(XRD)、X射线光电子能谱仪和扫描电子显微镜(SEM)对所制薄膜晶体结构和成分、表面和断面形貌进行分析,利用纳米压痕仪对薄膜的硬度和弹性模量进行表征,并计算H/E和H^(3)/E^(2)。结果表明,高离化率Ti离子轰击促使薄膜以低应变能的晶面优先生长,所制TiN薄膜具有(111)晶面择优取向。薄膜平均晶粒尺寸均在10.3 nm以下,随着脉冲频率增大晶粒尺寸增大,结晶度和沉积速率降低,柱状生长明显,致密度下降,影响薄膜力学性能。在9 kHz时,TiN薄膜的晶粒尺寸可达8.9 nm,薄膜组织致密具有最高硬度为30 GPa,弹性模量374 GPa,弹性恢复为62.9%,具有最优的力学性能。     

痕法测定 TiAlN 涂层结合强度的研究

采用磁控溅射法在不锈钢表面制备了TiAlN涂层,采用压入法及划痕法表征了涂层的结合强度。分析表明,压入法只能作为一种定性的测定方法,该法测得TiAlN涂层的结合强度达到HF3。划痕法结合了声信号、摩擦力信号和划痕微观形貌,可以定量测定结合强度,该法测得在压头曲率半径为200μm的情况下,TiAlN涂层的临界载荷达到13 N,比传统TiN涂层提高了45%。     

钛合金表面离子束增强沉积MoS2基膜层及其性能

将离子束增强沉积（IBED）技术与离子束溅射的沉积技术相结合,在钛合金表面制备了MoS2,MoS2-Ti复合膜。研究了膜层的形态、结构、膜基结合强度、硬度、摩擦学性能及抗微动（fretting）损伤性能。结果表明;所获膜层较纯溅射膜结合强度高、致密性好,复合膜中允许的金属元素含量大。通过恰当地控制复合膜中Ti的含量,可获得以（002）基面择优取向的MoS2-Ti复合膜,该膜层有较好的减摩和抗磨综合性能,能够显著地改善钛合金的常规磨损、微动摩员（FW)和微动疲劳（FF）性能,特别是在磨损严重的大位移整体滑条件下,MoS2-Ti复合膜对钛合金FF抗力的提高作用可大于喷丸形变强化处理。     

磁控溅射ZrSiN涂层对钛瓷结合强度的影响

探讨采用射频磁共溅射氮硅锆(ZrSiN)涂层作为扩散阻挡层(钛与瓷间的中间层),增强钛/瓷结合强度的可行性.结果表明:ZrSiN是含纳米结晶相ZrN和非晶相SiNx的纳米复合扩散阻挡层.无ZrSiN扩散阻挡层的钛经热循环后表面明显氧化,有ZrSiN扩散阻挡层处理后的钛表面经热循环后没有氧化钛,只有锆、硅、氮和氧元素,表明ZrSiN扩散阻挡层可有效阻挡钛在瓷烧结温度下氧化.三点弯曲试验表明ZrSiN涂层还可提高钛瓷结合强度.高硅含量的ZrSiN涂层处理的钛瓷结合强度更高,这与非晶相SiNx增多有关.     

Fabrication and diffusion barrier properties of nanoscale Ta/Ta-N bi-layer

One of the most important processes in Cu metallization for ultra large scale integrated circuits (ULSI) is to fabricate better diffusion barrier. In this paper, Ta/Ta-N films were fabricated by dc magnetron reactive sputtering (DCMS) in N₂/Ar ambient, then Cu/Ta/Ta-N/Si multi-structures were prepared in suite. The thin-film samples were rapid thermal annealed (RTA) at variational temperatures in N₂ ambient. Alpha-Step IQ Profiler, four-point probe (FPP) sheet resistance measurer, atomic force microscope (AFM), scanning electron microscope (SEM), X-ray diffraction (XRD) and tape test were used to characterize the microstructure and diffusion properties of the thin-films. The results show that the nanoscale Ta/Ta-N thin-films have smooth surface, and the thermal stability and barrier performance are good. After 600 °C/300 s RTA, Ta (40 nm)/Ta-N (60 nm) thin-films can effectively block against Cu diffusion and keep good adhesion strength with Cu films. After higher temperature RTA process, Cu atoms penetrated through the barrier and reacted with silicon, the barrier fail.     

Bond strength of W-Cu/CuCr integrated material

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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...     

Effect of TiN/Ti multilayer on fretting fatigue resistance of Ti-811 alloy at elevated temperature

The TiN/Ti multilayer was deposited on Ti-811 alloy surface by magnetron sputtering(MS) technique for improving fretting fatigue(FF) resistance of the titanium alloy at elevated temperature. The element distribution, bonding strength, micro-hardness and ductility of the TiN/Ti multilayer were measured. The effects of the TiN/Ti multilayer on the tribological property and fretting fatigue resistance of the titanium alloy substrate at elevated temperature were compared. The results indicate that by MS technique a TiN/Ti multilayer with high hardness, good ductility and high bearing load capability can be prepared. The MS TiN/Ti multilayer, for its good toughness and tribological behavior, can significantly improve the wear resistance and FF resistance of the Ti-811 alloy at 350 ℃.     

锆合金表面涂层耐高温高压动水腐蚀性能的研究

目的 提高锆合金在高温高压环境中耐动水腐蚀性能。方法 利用多弧离子镀技术（MAIP）在Zr-4合金表面分别制备了Al2O3涂层和Cr/TiAlN复合涂层,利用磁控溅射技术（MS）在Zr-4合金表面制备了TiN涂层。通过堆外高压釜实验,对比研究了三种不同涂层的耐高温高压动水腐蚀性能,利用自动划痕仪检测膜基结合力,利用XRD分析涂层的物相成分,利用SEM观察涂层腐蚀前后的微观形貌,利用EDS对涂层元素种类与含量进行分析。结果 多弧离子镀技术制备的Al2O3涂层和Cr/TiAlN涂层致密度较高,但表面存在少量大颗粒与微孔洞;磁控溅射技术制备的TiN涂层均匀平整,表面大颗粒较少。Al2O3涂层、TiN涂层和Cr/TiAlN涂层可承受的临界载荷分别为26、16、26.5 N。在实验条件下,Cr/TiAlN涂层和TiN涂层表面均发生了剥落或腐蚀现象,且这两种试样表面均检测出大量的ZrO2,而Al2O3涂层几乎未被破坏,基体得到了充分防护。结论 利用多弧离子镀技术在Zr-4合金表面制备的Al2O3涂层和Cr/TiAlN涂层的膜基结合力较高,利用磁控溅射技术制备的TiN涂层的膜基结合性能较差,其中Al2O3涂层具备良好的耐腐蚀性能,在高温高压动水腐蚀环境中能够有效地保护锆合金基体。     

Study on Properties of Ti(C,N)/TiN Multi-Element-layer Films Plus Nanometer Lubrication Dry Films

STARTING from the binary TiN wear-resistancecoating system,multi-element PVD superhard films,e.g.(Ti,Al)N films,(Ti,Cr)N films and Ti(C,N)films,may possess better tribological properties'1"41.Forexample,Ti(C,N)films showed higher hardness andbetter thermal-wear resistance properties than TiNfilms[4-5].However,due to mismatch of physical andmicro-structural properties of the multi-element filmsand the substrate,premature failure may occur duringfilm deposition process or in applicatio…     

氮气流量对反应磁控溅射TiN薄膜微结构与力学性能的影响

利用磁控溅射镀膜技术分别在硬质合金YG6X和单晶Si片表面制备TiN薄膜,分析N2流量对薄膜相组成、表面形貌、显微硬度和膜基结合力的影响。结果表明,N2流量对薄膜的微结构以及力学性能具有重要影响。随着N2流量的降低,TiN薄膜表面孔洞和台阶明显减少,表面平整度得到明显改善;薄膜的物相组成在N2流量为0.2sccm时为TiN和TiN0.61两相;N2流量的变化改变了薄膜表面的能量状态,因此,降低N2流量导致TiN薄膜的生长取向由(200)面向(111)面转变。同时,N2流量为2.4 sccm时TiN薄膜的膜基结合力最高,此时TiN薄膜也具有最高的显微硬度。     

AZ91C镁合金表面Ti-TiN复合镀层的阴极多弧离子镀法制备与表征

采用阴极多弧离子镀膜技术,在AZ91C镁合金基底上首次成功镀制了结合力强的以Ti为过渡层的TiN复合膜层,并利用高分辨扫描电子显微镜(SEM)、X射线能谱仪(EDS)、显微划痕测试等技术对复合膜层的形貌、组织结构及性能进行分析研究。结果表明,采用多弧离子镀膜工艺,能在经过恰当预处理的镁合金基底上制备出性能良好的TiN膜,膜层均匀、致密,膜基结合力达130 mN以上,复合硬度达500 HV左右(AZ91镁合金基底为125 HV)。此外中性盐雾强化实验表明,经该方法处理后的镁合金在ASTM-B117标准测试条件下,腐蚀速率明显降低,经过200 h后,表面无明显腐蚀现象。真空多弧离子镀膜技术有望在镁合金表面防护领域得到应用。     

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.