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.     

脉冲偏压对电弧离子镀Ti/TiN纳米多层薄膜显微硬度的影响

采用脉冲偏压电弧离子镀方法在高速钢基体上沉积Ti／TiN纳米多层薄膜,采用正交实验法设计脉冲偏压电参数,考察脉冲偏压对Ti／TiN纳米多层薄膜显微硬度的影响．结果表明,在所有偏压参数（脉冲偏压幅值、占空比和频率）和几何参数（调制周期和周期比）中,脉冲偏压幅值是影响显微硬度的最主要因素;当沉积工艺中脉冲偏压幅值为900V、占空比为50％及频率为30kHZ时,薄膜硬度可高达34．1GPa,此时多层膜调制周期为84nm,TiN和Ti单元层厚度分别为71和13nm;由于薄膜中的单层厚度较厚,纳米尺寸的强化效应并未充分体现于薄膜硬度的贡献中,硬度的提高主要与脉冲偏压工艺,尤其是脉冲偏压幅值对薄膜组织的改善有关．     

多弧离子镀制备TiN-Cu超硬纳米复合涂层的研究

采用多弧离子镀技术制备了TiN—Cu超硬纳米复合涂层,并对涂层断口形貌、相组成、择优取向、硬度等进行了测试分析。试验结果表明,用多弧离子镀技术的分层沉积和混合沉积方式都可以制备出硬度高达40．8GPa以上的TiN—Cu超硬复合纳米涂层。涂层中TiN晶粒尺寸普遍〈15nm,达到了纳米晶水平,且涂层中的Cu含量、TiN择优取向等因素均对涂层硬度有重要影响。     

脉冲偏压电弧离子镀Ti/TiN纳米多层薄膜的结构与硬度

采用脉冲偏压电弧离子镀设备在高速钢基体上沉积Ti／TiN纳米多层硬质薄膜,通过仅改变偏压幅值的方法进行对比实验。XRD分析和薄膜断截面SEM形貌显示出薄膜的纳米多层组织结构;硬度测试表明纳米多层薄膜硬度随脉冲偏压升高而升高。在-900V时超过同等条件制备的TiN单层薄膜,硬度高达34．1GPa;分析表明硬度的提高主要与脉冲偏压工艺对薄膜组织的改善有关;用脉冲偏压电弧离子镀可以制备纳米多层硬质薄膜,并且在工艺控制上相对简单。     

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采用MEVVA离子源技术对由磁过滤阴极真空电弧沉积的TiN薄膜注入不同剂量的Si元素,利用XPS和纳米硬度仪表征Si离子注入后化学成分、元素键合状态以及硬度的变化。结果表明,Si离子注入后,薄膜表面硬度得到提高,5×1016 ions/cm2的样品硬度峰值从27.18GPa增加到39.85GPa,随着注入剂量的增加,纳米硬度峰值有下降的趋势,1×1017 ions/cm2的样品硬度峰值为33.27GPa,但表面改性层的深度增加,纳米硬度在一定的深度范围内得到了整体的提高。离子注入使薄膜表面层的弹性模量显著提高,表层弹性模量随注入剂量的增加而提高。并且由于Si元素的注入,形成了新的微结构相Si3N4,新相的含量与注入剂量有关。     

低能量离子束辐照磁控溅射沉积超硬质nc-TiN/nc-Cu纳米复合膜

利用诱导型等离子体辅助双靶磁控溅射法在Si（100）基板表面沉积Cu含量（原子分数）为0～10．0％的Ti—Cu—N膜,研究了Cu含量对薄膜结构及硬度的影响．结果表明,添加少量Cu可极大地提高薄膜硬度．Cu含量为2．0％的Ti—Cu—N薄膜具有超硬特性,硬度HV达到42,约为纯TiN薄膜硬度的2倍．超硬质Ti—Cu—N薄膜为nc-TiN／nc—Cu纳米复合薄膜,具有柱状晶结构．薄膜的超硬特性源于薄膜的纳米复合结构．     

低能Si离子注入对TiN硬质薄膜性能的影响

采用低能MEVVA离子源技术对由磁过滤阴极真空弧沉积的TiN硬质膜进行了Si离子注入.采用场发射扫描电子显微镜、纳米硬度测试等方法,研究了基体离子注入剂量对薄膜性能的影响.结果表明,Si离子注入能在薄膜表面形成均匀细小的纳米颗粒.使基体及薄膜硬度从33 GPa提高到56 GPa,弹性模量从360 GPa提高到750 GPa.对薄膜进行多(4)次注入,硬度和弹性模量的提高并不显著,但对基体离子注入充分,薄膜的整体硬度和吸收塑性变形能的能力均有显著提高.     

Ti-Si-N纳米复相薄膜及Si含量对脉冲直流PCVD镀膜质量的影响

用工业型脉冲直流等离子体增强化学气相沉积(PCVD)设备，在高速钢(W18Cr4V)表面沉积Ti-Si-N三元薄膜，研究了不同N2流量对薄膜组织及性能的影响，结果表明：随N2流量增大，膜层沉积速率及膜层中Si含量减少，薄膜组织趋于致密，膜层颗粒尺寸明显减小，划痕法临界载荷和显微硬度显著增加，硬度最高可达50GPa以上。研究发现，对应N2流量，薄膜相组成发生变化，依次存在有TiN／a-Si3N4／Si，TiN／a—Si3N4／TiSi2／Si，TiN／a—Si3N4／TiSi2三种相组成形式，分析认为，低N2或高Si效果不佳的原因在于直流PCVD是以工件为阴极，膜层中过多的Si3N4和Si将严重劣化阴极的电导性，致使膜层疏松，说明脉冲直流PCVD与射频PCVD存在很大的区别。     

TiN薄膜的合成及其性能研究

用电子束蒸发沉积钛和40keV氮离子束轰击交替进行的办法合成了TiN薄膜。用RBS,AES,TEM,XPS,和X射线衍射研究TiN薄膜的组分和结构表明:用离子束增强沉积制备的TiN薄膜主要由TiN相构成;晶粒大小为30—40um,无择优取向;而非离子束轰击沉积的薄膜则是无定形的;用离子束增强沉积制备的TiN薄膜,其氧含量明显小于无离子束轰击薄膜的值;在TiN薄膜和衬底之间存在一个界面混合区,厚度为40um左右。机械性能测试表明,TiN薄膜具有高的显微硬度,低的摩擦系数。     

纳米复合Ti-B-N薄膜的结构和摩擦学性能

研究了射频等离了体辅助化学气相沉积（PCVD）技术获得的Ti-B-N薄膜的组织结构和力学性能。结果发现，B元素的加入使薄膜中出现TiN纳米晶和BN非晶（nc-TiN／a-BN）的复合结构，其硬度显著高于TiN薄膜，最高可达40GPa。用球盘式摩擦磨损实验考察了薄膜的磨损特性。结果表明：与TiN薄膜相比，Ti-B-N薄膜抗磨损性能有显著提高，磨损机制与TiN薄膜不同，摩擦系数较TiN稍高。     

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。     

金刚石上不同晶体结构Y2O3膜性质与增透性能研究

目的研究不同晶体结构Y_2O_3薄膜的性质及其对金刚石增透性能的影响规律。方法采用反应磁控溅射的方法,通过控制氧氩比,在金刚石膜上制备立方与单斜两种不同晶体结构的Y_2O_3薄膜,随后系统研究两种Y_2O_3薄膜的性质与增透性能。结果在低氧氩比下获得了立方结构Y_2O_3薄膜,在高氧氩比下获得了单斜结构Y_2O_3薄膜,二者表面粗糙度分别为2.57、1.07nm。两种晶体结构均呈现出符合Y_2O_3原子配比的价态。立方和单斜结构的Y_2O_3薄膜硬度分别为17.4、12.6 GPa;弹性模量分别为248.1、214.6 GPa。双面镀制立方结构Y_2O_3薄膜后,金刚石膜在10.0μm透过率最大,达89.1%,增透24.5%;单斜结构Y_2O_3薄膜在7.4μm透过率最大,达90.4%,增透25.4%。结论通过控制氧氩比可以获得热力学稳定的立方Y_2O_3薄膜和亚稳态的单斜Y_2O_3薄膜。立方和单斜结构的Y_2O_3薄膜中O与Y原子价态均符合其化学计量比。立方结构Y_2O_3薄膜呈现出更高的硬度与弹性模量。两种结构对金刚石窗口均呈现出良好的增透效果。单斜结构Y_2O_3薄膜增透效果更佳与其较低的折射率有关,且相比于立方结构Y_2O_3薄膜,增透最佳值向低波长方向移动。     

Mechanical and tribological properties of coatings sputtered from SiC target in the presence of CH4 gas

Amorphous hydrogen-free silicon carbide (a-SiC) coatings demonstrate good adhesion to different steel substrates, low intrinsic stress and high hardness however show quite high coefficient of friction in comparison with carbon-based coatings. Some addition of carbon to SiC can promote the decrease of friction coefficient.In the present work the amorphous hydrogenated silicon-carbide (a-SiC:H) films with different C/Si ratio were prepared at room temperature using DC magnetron sputtering in two ways: (i) sputtering of silicon target; (ii) sputtering of SiC target, both in the gas mixture of Ar and CH₄. In the latter case the films contained less hydrogen at the same C/Si ratio. The mechanical and tribological properties of these films were studied to find their optimum combination.The hardness, elastic modulus (nanoindentation), intrinsic stress (Stoney's formula) and coefficient of friction (pin on disc tribometer) were examined in dependence on the technological parameters, film structure and composition (Raman spectra, electron probe microanalysis). An increase of carbon in the films from 50 to 70 at.% resulted in decrease of hardness and friction coefficient. In the first case (i) the hardness decreased from 13 to10 GPa and in the second case (ii) from 23 to 16 GPa. Thus sputtering of SiC target in the gas mixture of Ar and CH₄ allows obtaining at room temperature the films with C/Si > 1 in which relatively high hardness (16-18 GPa) and low friction coefficient (~ 0.15) are combined.     

MICROBRIDGE TESTING OF YOUNG＇S MODULUS AND RESIDUAL STRESS OF NICKEL FILM ELECTROPLATED ON SILICON WAFER

Microbridge testing is used to measure the Young's modulus and residual stresses of metallic films. Nickel film microbridges with widths of several hundred microns are fabricated by Microelectromechanical Systems. In order to measure the mechanical properties of nickel film microbridges, special shaft structure is designed to solve the problem of getting the load-deflection curves of metal film microbridge by Nanoindenter XP system with normal Berkovich probe. Theoretical analysis of the microbridge load-deflection curve is proposed to evaluate the Young's modulus and residual stress of the films simultaneously. The calculated results based on the experimental measurements show that the average Young's modulus and residual stress are around 190GPa and 175MPa respectively, while the Young's modulus measured by Nano- hardness method on nickel film with silicon substrate is 186.8±7.34GPa.     

Zr掺杂类金刚石薄膜摩擦性能及耐腐蚀性能的影响

目的改善不锈钢摩擦性能及耐腐蚀性能。方法通过线性阳极层离子源辅助非平衡磁控溅射法,制备了不同Zr含量的类金刚石(DLC)薄膜,采用扫描电子显微镜、拉曼光谱仪、纳米硬度仪、高温销盘磨损仪、电化学工作站,对薄膜的化学成分、显微结构、纳米硬度、薄膜摩擦性能及耐腐蚀性能进行测试研究。结果随着Zr靶功率的增大,Zr含量线性增加。Zr含量从4.9%增加至16.3%时,I_D/I_G增大,薄膜硬度从12.1 GPa逐渐下降至8.4 GPa;Zr含量增大至21.2%时,I_D/I_G减小,薄膜硬度增大至11.4 GPa。涂镀类金刚石薄膜的不锈钢基体比无涂层的不锈钢基体有更低的摩擦系数,更好的耐磨损性能。Zr掺杂DLC薄膜的最小摩擦系数为0.07。Zr含量从4.9%增加至16.3%,DLC薄膜的耐腐蚀性能减弱;Zr含量继续增加,DLC薄膜的耐腐蚀性能增强。当Zr含量不大于11.9%时,沉积Zr掺杂DLC膜的不锈钢基体的耐腐蚀性能比不锈钢基体的更强。结论 Zr含量不大于11.9%时,Zr掺杂类金刚石薄膜既可以有效地改善不锈钢基体的摩擦磨损性能,又可以大幅提高耐腐蚀性能。     

Microstructure and mechanical properties of quaternary Cr–Si–O–N films by a hybrid coating system

Quaternary Cr–Si–O–N films were deposited by a hybrid coating system using a Cr cathodic arc target and a Si sputtering target in an Ar/N₂/O₂ gaseous mixture. The influence of oxygen flux rate on the microstructure and properties of the Cr–Si–O–N films were investigated. The results indicated that the oxygen-free Cr–Si–N film exhibited nanocolumnar microstructure containing CrN nano columns and amorphous Si₃N₄ phase. The Cr–Si–O–N films exhibit equiaxed CrN nanocrystallites likely surrounded by amorphous SiO₂ and Si₃N₄ phases. Further increasing the oxygen content gives films containing Cr₂O₃ crystallites. The hardness first increases from 30 GPa for the Cr–Si–N film to a maximum value of approximately 50 GPa for the oxygen content of 16 at.% and then decreases for larger oxygen content. All the Cr–Si–O–N films exhibit low friction coefficient (0.22–0.26) and low residual stress (− 0.03–0.08 GPa). The influence of the oxygen content on the microstructure and mechanical properties of the Cr–Si–O–N films is discussed.     

Facile synthesis of CNTs-doped diamond-like carbon film by electrodeposition

A simple and effective process for synthesis of carbon nanotubes (CNTs)-doped diamond-like carbon (DLC) film via electrodeposition has been reported. Transmission electron microscope (TEM), Raman, X-ray photoelectron spectroscopy (XPS), and Fourier transformation infrared spectrometry (FTIR) were employed to investigate the microstructure, chemical composition, and various carbon phases of the films. The experimental results clearly showed that the CNTs were well dispersed in the carbon film and the D and G bands of the composite carbon film both downshifted comparing with those of the undoped carbon film. The hardness of the carbon film was improved with the incorporation of CNTs from 10.28 to 12.47 GPa, while the Young's modulus was decreased from 253.64 to 206.66 GPa. Simultaneously, the residual stress of the carbon film was greatly reduced from 1.2 to 0.83 GPa after the incorporation of CNTs.     

Structure and mechanical properties of TiAlN-WNx thin films

A combinatorial method was employed to grow TiAlN-WNx films by DC sputtering as well as by High Power Pulsed Magnetron Sputtering (HPPMS) where the W concentration was varied between 10-52 at.% and 7-54 at.%, respectively. Experiments were paired with ab initio calculations to investigate the correlation between composition, structure, and mechanical properties. During all depositions the time averaged power was kept constant. As the W concentration was increased, the lattice parameter of cubic TiAlN-WNx films first increased and then decreased for W concentrations above ≈ 29 at.% (DCMS) and ≈ 27 at.% (HPPMS) as the N concentration decreased. Calculations helped to attribute the increase to the substitution of Ti and Al by W and the decrease to the presence of N vacancies. Young's modulus and hardness were around 385-400 GPa and 29-31 GPa for DCMS and 430-480 GPa and 34-38 GPa for HPPMS, respectively, showing no significant trend as the W concentration was increased, whereas calculations showed a continuous decrease in Young's modulus from 440 to 325 GPa as the W concentration was increased from 0 to 37.5 at.%. The presence of N vacancies was shown to increase the calculated Young's modulus. Hence, the relatively constant values measured may be understood based on N vacancy formation as the W concentration was increased. HPPMS-deposited films exceed DCMS films in Young's modulus and hardness, which may be a consequence of the larger degree of ionization in the HPPMS plasma. It is reasonable to assume that especially the ionized film forming species may contribute towards film densification and N vacancy formation.     

Synthesis and characterization of nanocrystalline ZrNxOy thin films on Si by ion plating

Based on the optimum deposition conditions of ZrN thin film from our previous study, by varying oxygen flow rate ranging from 0 to 8 sccm, nanocrystalline ZrN_xO_y thin films were deposited on p-type (100) Si substrates using hollow cathode discharge ion-plating (HCD-IP) system. The objective of this study was to investigate the effect of oxygen content on the composition, structure and properties of the ZrN_xO_y thin films. The oxygen content of the thin film, determined using X-ray photoelectron spectroscopy (XPS), increased with increasing oxygen flow rate. As the oxygen content increased, the color of the ZrN_xO_y thin film changed from golden yellow to blue and then slate blue, and the microstructure observed by scanning electron microscopy (SEM) varied from columnar structure to finer grains and finally flat and featureless structure. Phase separation of ZrN_xO_y to ZrN and monoclinic ZrO₂ was found from X-ray diffraction (XRD) patterns when the oxygen content was higher than 9.7 at.%. The hardness of the film slightly increased as the oxygen content was less than 9.7% and then decreased to 15.7 GPa, a typical hardness of ZrO₂ phase, as the oxygen content further increased. The total residual stress of the film was measured using an optical method, and the residual stresses of ZrN and ZrO₂ phases were determined separately using modified XRD sin²ψ method. The total stress was close to the stress in ZrN phase as the ZrO₂ fraction was less than 30%, and was close to that in ZrO₂ phase as the ZrO₂ fraction was over 30%. The electrical resistivity of the film increased significantly with the increase of oxygen content. The film properties showed consistent trend with phase separation. As the fraction of ZrO₂ phase was small, the apparent properties of the films were more close to those in ZrN. When ZrO₂ fraction was over 30%, the films mainly exhibited the properties of ZrO₂.     

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。