磁控溅射偏压对Zr-Si-N扩散阻挡层组织结构的影响

用反应磁控溅射法在不同偏压下沉积了Zr-Si-N扩散阻挡层.结果表明:Zr-Si-N膜的成分、电阻率和结构均随偏压的改变而不同;随着溅射偏压的增加,Zr-Si-N膜的表面粗糙度值增大;Zr/Si比值也随着偏压的增加而增大;电阻率随偏压的增加显著降低;Zr-Si-N膜的结构为类似Si3N4的氮硅化物非晶相与ZrN组成的复合结构,随着偏压的升高ZrN由非晶转变为纳米晶,而且ZrN晶体相增加.     

磁控溅射氮分压对Nb-Si-N薄膜结构和性能的影响

用反应磁控溅射法在不同的氮分压下沉积了Nb-Si-N薄膜.结果表明：Nb-Si-N膜的成分、结构和性能随氮分压的改变而不同.随氮分压的增加,Nb-Si-N膜的Nb/Si比和表面粗糙度减小;薄膜的电阻值和微硬度增加.Nb-Si-N膜的结构为纳米晶NbN与类似Si3N4非晶相组成的纳米复合结构,且随着氮分压的增加,Nb-Si-N膜的非晶倾向增强,晶粒尺寸减小.     

Zr靶功率对(WMoTaNb)ZrxN薄膜微观组织及性能的影响

目的 提高(WMoTaNb)ZrxN薄膜的硬度与弹性模量、膜基结合力、摩擦磨损及抗烧蚀性能。方法 采用反应磁控溅射技术,通过对Zr靶功率的调控,在单晶Si和M2高速钢基体上制备不同Zr含量的(WMoTaNb)ZrxN薄膜。采用FESEM对薄膜的表面及截面形貌进行观察,利用XRD对薄膜的物相组成进行分析,采用纳米压痕仪、划痕仪和摩擦磨损试验机分别对薄膜的硬度、膜基结合力及摩擦磨损性能进行表征,通过氧–乙炔烧蚀试验对薄膜的抗烧蚀性能进行测定。结果 (WMoTaNb)ZrxN薄膜主要由FCC和BCC固溶体结构组成,Zr元素引入后,薄膜FCC(200)晶面衍射峰消失,FCC(111)与(311)晶面衍射峰强度增强。随着Zr靶功率的增加,薄膜中Zr元素含量逐渐增加,薄膜的硬度与弹性模量先增大、后减小,膜基结合力呈现不规律变化,薄膜的抗烧蚀性能逐渐提升。薄膜的摩擦系数随着Zr靶功率的增加而增大,但维持在0.65~0.95。当Zr靶功率为40 W时,制备的薄膜硬度、弹性模量及膜基结合力均达到最大,分别为27.9 GPa、291.3 GPa、84 N,此时薄膜的磨痕深度最小为227 nm。结论 Zr靶功率为40 W时制备的薄膜硬度、弹性模量、膜基结合力、摩擦磨损与抗烧蚀性能最佳。     

电弧离子镀法制备高硬度Cr-Si-C-N薄膜

采用电弧离子反应沉积技术在SCM415渗碳淬火钢基片上沉积了Cr-Si-C-N薄膜,三甲基硅烷(TMS)反应气体作为Si和C掺杂源,通过改变TMS流量实现了薄膜中si和C含量的调节.利用XPS,XRD,HRTEM和显微硬度计研究了Cr-Si-C-N薄膜的化学状态、显微组织和显微硬度.Cr-Si-C-N薄膜中的Si和C含量随TMS流量的增加而单调增加.在TMS流鼍小于:90 mL/min时,薄膜中Si和C含量较少,薄膜由Cr(C,N)纳米晶与Si_3N_4非品(nc-Cr(C,N)/a-Si_3N_4)组成,薄膜硬度随流量的增加而单调增大,最大至4500 HK.硬度的增加源于固溶强化及薄膜中纳米晶/非晶复合结构的形成;当TMS流量大于90 mL/min时,薄膜中Si和C含量较多,多余的C以游离态形式存在,且随TMS流量的增加而增多,薄膜硬度下降.     

Ti-Si-N纳米复合薄膜的结构与性能

用工业型脉冲直流等离子体增强化学气相沉积技术,在高速钢(W18Cr4V)表面沉积了Ti-Si-N复合薄膜,研究了Ti-Si-N复合薄膜的微观组织和力学性能.结果显示,薄膜相结构为纳米晶TiN和纳米晶或非晶TiSi2以及非晶相Si3N4;在Si含量为5.0 at%～28.0 at%范围内,薄膜的晶粒尺寸逐渐变大;Ti-Si-N薄膜的显微硬度相对于TiN有明显增加,最高硬度可达40 GPa;高温退火后,Ti-Si-N纳米复合薄膜的显微硬度与晶粒尺寸在800℃高温下仍然保持稳定.     

静电纺丝制备连续SiC亚微米/纳米纤维

采用镶嵌靶反应磁控溅射技术,通过调节氮分压及基体偏压在M2高速钢基体表面制备了一系列耐热的(Ti,Al)N硬质薄膜,并用XRD,EDS及纳米压入法、划痕法等方法研究了(Ti,Al)N薄膜的成分、相结构与力学性能的关系。结果表明,氮分压和基体偏压对(Ti,Al)N薄膜取向及Ti、Al、N原子含量有明显影响,从而导致薄膜硬度及膜基结合性能发生变化。研究中,在氮分压为33.3×10-3Pa、基体偏压为-100V时制备的(Ti,Al)N薄膜力学性能最优,其纳米硬度为43.4GPa,达到40GPa超硬薄膜的要求。     

反应磁控溅射碳化铪薄膜的微结构与力学性能

为满足不同加工方式和加工条件下刀具对涂层的特殊要求,获得硬度高和耐摩擦性能优异的刀具涂层,采用反应磁控溅射方法制备了一系列不同碳含量的碳化铪薄膜。利用EDX,XRD,SEM,AFM和微力学探针表征了薄膜的微结构和力学性能,研究了C2H2分压(Ar和C2H2混合气体)对薄膜成分、相组成、微结构以及硬度和弹性模量的影响。结果表明,反应磁控溅射可以方便地制备碳化铪薄膜,但是,只有在C2H2分压为混合气体总压约3.0%附近很窄的范围内才可获得高硬度和高弹性模量的单相碳化铪薄膜,其最高硬度和弹性模量分别为27.9 GPa和255 GPa;低C2H2分压下所得薄膜由金属Hf和HfC两相组成,硬度较低;而过高的C2H2分压将导致薄膜形成非晶态,其硬度和弹性模量亦随之降低。     

Si含量对电弧离子镀Ti-Al-Si-N薄膜组织结构和力学性能的影响

利用磁过滤电弧离子镀技术在高速钢基体上制备了不同Si含量的Ti-Al-Si-N薄膜,研究了Si含量对薄膜组织结构以及力学性能的影响.结果表明,Ti-Al-Si-N薄膜主要由晶态TiAlN和非晶态的Si₃N₄组成,随着Si含量的增加,XRD衍射峰强度减弱,晶粒尺寸减小;薄膜的显微组织也由明显的柱状晶转变为致密的纳米晶结构.利用纳米硬度仪对薄膜的硬度和弹性模量进行了分析,结果表明,薄膜的硬度和弹性模量有着相似的变化趋势,随着Si含量的增加,两者都先增加,当Si含量达到一定程度时.它们会逐渐稳定在一定范围内,而后又随Si含量的继续增加呈下降趋势.通过划痕测试对薄膜结合强度进行了分析,结果表明,薄膜与基体的结合强度随Si含量的增加先减小而后增加.     

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.     

N2流量比对复合磁控溅射Zr-B-N薄膜结构和性能的影响

目的 在反应沉积时补充金属离子,增加薄膜中金属氮化物硬质相的数量,优化复合磁控溅射Zr-B-N薄膜的制备工艺,揭示N2流量比（N2/(N2+Ar)）对Zr-B-N薄膜结构和性能的影响规律,进一步强化Zr-B-N纳米复合薄膜。方法 采用高功率脉冲磁控溅射和脉冲直流磁控溅射复合镀膜技术沉积Zr-B-N薄膜,借助X射线衍射仪、能谱仪、扫描电镜、纳米压痕仪、划痕测试仪和摩擦试验机,研究N2流量比对Zr-B-N薄膜成分、微观结构、力学性能和摩擦性能的影响。结果 Zr-B-N薄膜具有典型的纳米复合结构,即BN非晶层包裹着ZrB2、Zr3N4、Zr2N、ZrN等纳米晶,所有Zr-B-N薄膜均沿（100）晶面择优生长。随着N2流量的增加,（100）晶面的衍射峰宽化加剧;薄膜硬度由36.2 GPa下降到21.0 GPa;膜/基结合力逐渐增强,临界载荷从34.8 N增加到55.8 N;摩擦系数逐渐增大。当N2流量比为42.9%时,摩擦系数相对较低,约为0.48,归因于薄膜内形成了沿（220）晶面生长的ZrN相,从而起到了良好的减摩作用。结论 当N2流量比为42.9%时,Zr-B-N薄膜具有纳米复合结构和良好的各项性能。     

Effect of Annealing Ambience on the Chemical Stability of Zr-Si-N Diffusion Barrier

Cu has been drawn much attention as a newinterconnect material in ULSI due to its low resistivity,high resistance to electromigration and stress migration[1].However,Cu can easily diffuse into Si wafer evenat temperature below200°C,which degrades thereliability of the devices.It is well recognized that adiffusion barrier between Cu and Si is necessary toprevent the diffusion.Diffusion barriers are usuallychosen among refractory metals and their nitrides suchas Ta,TiN,TaN,and ZrN[2,5].R…     

Zr-Si-N扩散阻挡层及其热稳定性的研究

用反应磁控溅射法在不同偏压下沉积了Zr-Si-N扩散阻挡层,结果表明:Zr-Si-N膜的Si含量、电阻率随偏压的升高而降低;Zr-Si-N膜的晶体相随溅射偏压的升高而增加;Zr-Si-N扩散阻挡层的热稳定性高,在850℃时仍能有效阻挡Cu的扩散.     

Control of morphology (ZrN crystallite size and SiNx layer thickness) in Zr-Si-N nanocomposite thin films

DC reactive magnetron sputtering was used for the deposition of Zr-Si-N thin films. Four series of samples have been deposited at various substrate temperatures T_S: 300 K, 510 K, 710 K and 910 K. Depending on T_S, different N₂ partial pressures p_N2 were required to obtain nearly stoichiometric ZrN films. Si content (C_Si) was varied in each series by changing the power applied on the Si target, whereas the power on the Zr target was kept constant. The microstructure of the coatings was examined by XRD and in cross-section by transmission electron microscopy (TEM). Depending on T_S and p_N2, the deposition rate showed significant variations from 0.04 to 0.18 nm/s. The correlation between film morphology (preferential orientation of crystallites, grain size, column dimensions, thickness of the SiN_x layer covering ZrN crystallites) and the deposition conditions (power applied on Si target, temperature, nitrogen partial pressure and deposition rate) provides useful information for optimizing the deposition process.     

Structure, morphology and electrical properties of sputtered Zr-Si-N thin films: From solid solution to nanocomposite

DC reactive magnetron co-sputtering was used for the deposition of Zr-Si-N thin films. Si content (C_Si) was varied by changing the power applied on the Si target, whereas that on Zr target was kept constant. Three series of samples have been deposited at various substrate temperatures: room temperature, 240 °C and 440 °C. The evolution of morphology, crystalline structure, grain size and lattice constant has been investigated by X-ray diffraction analyses. Nanohardness, stress and resistivity measurements provide complementary information, which validate the proposed 3-step model for the film formation of the Zr-Si-N system deposited by reactive magnetron co-sputtering. For low Si content the Si atoms substitute the Zr atoms in the ZrN lattice. Above the solubility limit, a nanocomposite film containing ZrN:Si nanocrystallites and amorphous SiN_y is formed. Further increase of Si content results in a reduction of grain size (D), while the thickness of the SiN_y layer at the crystallite surface remains constant. The increasing amount of the SiN_y amorphous phase in the films is realized by increasing the surface to volume ratio of the crystallites. In this concentration range, the size of the crystallites in the Zr-Si-N films decreases according to the relationship C_Si ∼ 1 / D. With increasing substrate temperature, the solubility limit of Si in ZrN decreases whereas the films' global nitruration (C_N / (C_Si + C_Zr)) increases. The concentration dependence of the electrical resistivity is interpreted in terms of the variation of the SiN_y layer thickness.     

STRUCTURE AND BINDING STATE OF CN x FILMS SYNTHESIZED BY FACING TARGETS SPUTTERING

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Al元素对Zr-Si-N复合膜的微结构与力学性能的影响

采用反应磁控溅射方法制备了一系列不同铝含量的Zr-Al-Si-N复合膜,用能谱仪、X射线衍射仪和显微硬度计对复合膜进行表征,研究了铝元素对Zr-Si-N复合膜的微结构和力学性能的影响.结果表明,当铝的原子分数N_(Al) ≤10.84%时,Zr-Al-Si-N复合膜中fcc-(ZrAlSi)N为主要相;当N_(Al) ≥14.67%时,Zr-Al-Si-N复合膜是fcc-(ZrAlSi)N和h-AlN的混合相;铝原子分数为4.80%时,Zr-Al-Si-N复合膜的显微硬度达到最大值43.92 GPa;随着铝原子含量的进一步增加,Zr-Al-Si-N复合膜的显微硬度迅速下降.对复合膜的致硬机理进行了讨论.     

Formation of composite ternary nitride thin films by magnetron sputtering co-deposition

Thin films of M-X-N (M stands for early transition metal and X = Si, Ge, Sn) are studied as protective coatings. To extend the knowledge about the formation of nanocomposite films, various M-X-N systems have been compared. Ti-Si-N, Ti-Ge-N, Ti-Sn-N, Nb-Si-N, Zr-Si-N and Cr-Si-N thin films were deposited by reactive magnetron sputtering, from confocal targets in a mixed Ar/N₂ atmosphere. The chemical reactivity of germanium and tin with nitrogen is significantly lower than that of Si and Ti. Therefore, the Ti-Ge-N and Ti-Sn-N systems are different from Ti-Si-N. Important changes in the morphology and structure of M-X-N films are induced by X addition. Nanocrystalline composite films are formed in all these investigated ternary systems.As a function of increasing X content (C_X), the size of the crystallites D in the Ti-Si-N, Ti-Ge-N, Nb-Si-N and Zr-Si-N films decreases (from tens of nm to 2 nm) following the relationship C_X ∼ 1 / D. The segregation of X atoms on the MN crystallite surface is responsible for the limitation of their growth. It results in the formation of a SiN_y or TiGe_y amorphous phase on the crystallite surfaces. In the case of Nb-Si-N and Zr-Si-N systems, Si atoms can substitute metal atoms in the cubic MN lattice up to a critical concentration (solubility limit). Ti-Si-N, Ti-Ge-N and Ti-Sn-N systems are different: no solubility of Si, Ge and Sn in the TiN lattice is observed. For every composite film, the morphology changes result in a maximum hardness value at a typical concentration 2 ≤ C_X ≤ 12 at.%. Resistivity measurements provide experimental mean for determining the limit of Si solubility in M-Si-N ternary systems and for following the thickness evolution of the SiN_y coverage layer in the composite films.     

X-ray photoelectron spectroscopy analysis of zirconium nitride-like films prepared on Si(100) substrates by ion beam assisted deposition

Thin zirconium nitride films were prepared on Si(100) substrates at room temperature by ion beam assisted deposition with a 2 keV nitrogen ion beam. Arrival rate ratios ARR(N/Zr) used were 0.19, 0.39, 0.92, and 1.86. The chemical composition and bonding structure of the films were analyzed with X-ray photoelectron spectroscopy (XPS). Deconvolution results for Zr 3d, Zr 3p_3/2, N 1s, O 1s, and C 1s XPS spectra indicated self-consistently the presence of metal Zr⁰, nitride ZrN, oxide ZrO₂, oxynitride Zr₂N₂O, and carbide ZrC phases, and the amounts of these compounds were influenced by ARR(N/Zr). The chemical composition ratio N/Zr in the film increased with increasing ARR(N/Zr) until ARR(N/Zr) reached 0.92, reflecting the high reactivity of nitrogen in the ion beam, and stayed almost constant for ARR(N/Zr) ≥ 1, the excess nitrogen being rejected from the growing film. A considerable incorporation of contaminant oxygen and carbon into the depositing film was attributed to the getter effect of zirconium.