TiN/Si3N4纳米多层膜的生长结构与超硬效应

采用磁控溅射方法制备了一系列不同Si3N4和TiN层厚的TiN/Si3N4纳米多层膜,采用X射线衍射、高分辨电子显微分析和微力学探针表征了薄膜的微结构和力学性能,研究了Si3N4和TiN层厚对多层膜生长结构和力学性能的影响.结果表明:当Si3N4层厚小于0.7 nm时,原为非晶的Si3N4在TiN的模板作用下晶化并与之形成共格外延生长的柱状晶,使TiN/Si3N4多层膜产生硬度和弹性模量异常升高的超硬效应.最高硬度和弹性模量分别为34.0 GPa和353.5 GPa.当其厚度大于1.3 nm时,Si3N4呈现非晶态,阻断了TiN的外延生长,多层膜的力学性能明显降低.此外,TiN层厚的增加也会对TiN/Si3N4多层膜的生长结构和力学性能造成影响,随着TiN层厚的增加,多层膜的硬度和弹性模量缓慢下降.     

评Veprek的nc-TiN/a-Si_3N_4模型和其“超过金刚石硬度”的实验基础

由于报道获得了超过金刚石的硬度,TiN/Si3N4纳米复合薄膜成为十多年来超硬材料和薄膜材料的重要热点。本文从实验基础方面对这类薄膜的Veprek模型和"超高硬度"进行了评述。在微结构方面,Veprek提出的非晶Si3N4包裹TiN纳米晶的结构模型(即nc-TiN/a-Si3N4)缺乏足够的实验依据,直接观察表明:高硬度薄膜中的TiN晶粒并非等轴晶,而是纳米直径的柱状晶。就Si3N4界面相来说也并非以1个单分子层(~0.3 nm)的非晶态存在,而是厚度约3个分子层(~0.7 nm)的晶体态,更重要的是Si3N4界面相与相邻的TiN晶体形成了共格结构。在制备技术方面,十余年来始终没有人在这类材料中重复出Veprek超过金刚石硬度的结果,Veprek不仅将其归咎于缺乏足够高的沉积温度和氮分压,甚至归咎于薄膜中存在不可避免的微量氧,但也缺乏足够的直接证据。在超高硬度的样品方面,Veprek所报道超过金刚石硬度(最高达138.9 GPa)的样品不但未经任何他人检测确认,而且现在这些样品已经不存在了。     

反应溅射HfC/Si3N4纳米多层膜的微结构与力学性能

通过反应磁控溅射制备了一系列不同Si3N4层厚的HfC/Si3N4纳米多层膜,采用X射线光电子能谱、X射线衍射、扫描电子显微镜和微力学探针表征了多层膜的微结构、硬度与弹性模量,研究了Si3N4层厚度变化对纳米多层膜微结构与力学性能的影响。结果表明,溅射的Si3N4粒子不与C2H2气体反应,因NaCl结构HfC晶体调制层的模板效应,溅射态为非晶的Si3N4层在厚度小于约1 nm时被强制晶化,并与HfC晶体层形成共格外延生长结构,多层膜呈现强烈的(111)择优取向柱状晶,其硬度和弹性模量显著上升,最高值分别达到38.2 GPa和343 GPa。进一步增加Si3N4层的厚度后,Si3N4层转变为以非晶态生长,多层膜的共格外延生长结构受到破坏,其硬度和模量也相应降低。     

反应溅射Ti-Si-N纳米晶复合薄膜的微结构与力学性能

采用Ar、N2 和SiH4混合气体反应溅射制备了一系列不同Si含量的Ti Si N复合膜 ,用EDS、XRD、TEM和微力学探针研究了复合膜的微结构和力学性能。结果表明 ,通过控制混合气体中SiH4分压可以方便地获得不同Si含量的Ti Si N复合膜。当Si含量为 (4～ 9)at%时 ,复合膜得到强化 ,最高硬度和弹性模量分别为 34 2GPa和 398GPa。进一步增加Si含量 ,复合膜的力学性能逐步降低。微结构研究发现 ,高硬度的Ti Si N复合膜呈现Si3 N4界面相分隔TiN纳米晶的微结构特征 ,其中TiN纳米晶的直径约为 2 0nm ,Si3 N4界面相的厚度小于 1nm。     

SiO2层晶化对TiN/SiO2纳米多层膜结构和性能的影响

采用多靶磁控溅射法制备了一系列具有不同SiO2调制层厚的TiN/SiO2纳米多层膜.利用X射线衍射、X射线能量色散谱、扫描电子显微镜、高分辨电子显微镜和微力学探针表征和研究了多层膜的生长结构和力学性能.结果表明,具有适当厚度(0.45～0.9 nm)的SiO2调制层,在溅射条件下通常为非晶态,在TiN层的模板作用下晶化并与TiN层共格外延生长,形成具有强烈(111)织构的超晶格柱状晶多层膜;与此相应,纳米多层膜产生了硬度和弹性模量异常增高的超硬效应(最高硬度达45 GPa).随着SiO2层厚度的继续增加,SiO2层转变为非晶态,阻断了多层膜的共格外延生长,使纳米多层膜形成非晶SiO2层和纳米晶TiN层的多层结构,多层膜的硬度和弹性模量逐渐下降.     

纳米多层膜中的非晶晶化与超硬效应

通过对TiN/SiC、TiN/TiB₂和TiN/SiO₂纳米多层膜微结构和力学性能的研究, 展示了通常溅射沉积态为非晶的SiC、TiB2和SiO₂薄膜, 在立方结构的TiN晶体层模板作用下的晶化现象, 以及多层膜由此产生的生长结构和力学性能的变化. 结果表明: SiC在层厚0.6nm时晶化为立方结构后,可以反过来促进TiN/SiC多层膜中TiN层的晶体完整性; TiB₂在层厚2.9nm时晶化为六方结构, 并与TiN形成{111} _TiN//{0001} _TiB2, <100> _TiN//<11-20> _TiB2 的共格关系; SiO₂在层厚0.9nm 时晶化为立方结构的赝晶. 多层膜中SiC、TiB₂和SiO₂晶化后都与TiN形成共格外延的生长结构, 并相应产生了硬度升高的超硬效应. 随着SiC、TiB₂和SiO₂层厚的增加, 它们又转变为非晶态, 多层膜的共格外延生长受到破坏, 其硬度亦明显降低.     

Ti-Al-Si-N涂层界面微结构研究

采用多元等离子体浸没离子注入与沉积装置制备Ti-Al-Si-N涂层,借助X射线衍射仪、X射线光电子能谱、透射电子显微镜、纳米探针和原子力显微镜等系统研究涂层界面微结构与力学性能。研究结果表明:Ti-Al-Si-N涂层具有Si3N4界面相包裹TiAlN纳米晶复合结构,Si元素掺杂诱发涂层发生明显晶粒细化效应。随涂层Si含量增加,TiAlN晶粒尺寸显著降低,界面Si3N4层厚度增加。当Si3N4界面层厚度小于1nm并与TiAlN晶粒共格外延生长时,Ti-Al-Si-N涂层表现超高硬度约40GPa,当Si3N4界面相厚度增至2nm并呈非晶态存在时,涂层硬度降至约29GPa。     

(AlCrTiZrNb)N/Si3N4纳米多层膜的微观结构和力学性能研究

采用多靶磁控溅射系统,使用AlCrTiZrNb合金靶和Si靶制备了不同Si_3N_4厚度的(AlCrTiZrNb)N/Si_3N_4纳米多层膜,样品基底为单晶硅。通过X射线衍射仪(XRD)、高透射电子显微镜(HRTEM)、扫描电子显微镜(SEM)和纳米压痕仪对样品进行微观组织的表征和力学性能的测量。实验结果表明,随着Si_3N_4层厚度的增加,样品的结晶度和力学性能均先增加后减小,XRD图谱中出现面心立方相结构。在Si_3N_4层厚度为0.5 nm时,(111)衍射峰强度达到最大值。说明薄膜结晶度最强,薄膜的硬度和弹性模量也达到最高值,分别为30.6,298 GPa。通过对样品的横截面的形貌观察,发现当Si_3N_4层厚度为0.5 nm时,多层膜的多层结构生长良好。在(AlCrTiZrNb)N层的模板作用下,Si_3N_4层从非晶态转变为面心立方结构,与(AlCrTiZrNb)N层之间形成共格外延生长结构,(AlCrTiZrNb)N/Si_3N_4纳米多层膜的强化可归因于两调制层之间形成的共格界面。     

磁控溅射Ti-Si-N纳米复合超硬膜的研究

传统的TiN膜具有硬度高、耐磨、耐腐蚀及其他优良的性能,在刀具、工磨具等已经有了广泛的应用。随着科技的发展,近年来许多科技工作者都企图采用多种方法来进一步改善TiN薄膜,其中包括添加Al,Si,C,B等合金元素至TiN膜中,以改善起组织结构和性能。自从S.Veprek首先报道采用CVD的方法制备Ti-Si-N纳米复合膜后,由于Ti-Si-N膜具有nc-TiN/a-Si_3N_4组织结构,即纳米尺寸的TiN嵌镶在非晶Si_3N_4基体中,Ti-Si-N类纳米复合超硬膜以其高硬度、耐磨性、优良的热稳定性和化学稳定性引起了人们的普遍关注。采用钛硅复合靶,通过控制反应磁控溅射的各工艺参数制得了一系列Ti-Si-N膜,并借助能谱仪(EDS)、X射线衍射(XRD)、纳米压入仪和划痕仪对膜层的成分、结构和力学性能进行了分析。结果发现,可方便地通过改变氮气分压的方法来调整Ti、Si元素含量比、微观组织结构及力学性能。少量氮气的加入能制得纳米硬度高达53GPa的Ti-Si-N超硬膜,而随着氢气分压的增加,膜层中TiN相和Si_3N_4相的比例减小,纳米硬度逐渐下降,同时,TiN晶粒的平均尺寸也逐渐减少。     

磁控溅射技术制备硅纳米晶多层膜及微观结构表征

在室温下,分别利用常规磁控溅射和反应磁控溅射技术交替沉积Si薄膜和Si1-xNx薄膜在单晶硅基体上制备了Si/Si1-xNx纳米多层膜。接下来,在高温下对Si/Si1-xNx多层膜进行退火诱发各层中形成硅纳米晶。研究了Si1-xNx层厚度和N2流量沉积对Si/Si1-xNx多层膜中Si量子点形成的影响。TEM检测结果表明,N2流量为2.5mL/min时沉积的多层膜退火后形成了尺寸为20～30nm的等轴Si3N4纳米晶;N2流量为5.0mL/min时沉积的多层膜退火后在Si层和Si1-xNx多层中均形成了硅纳米晶,而在7.5mL/min N2流量下沉积的Si/Si1-xNx多层膜退火后仅在Si层中形成了硅纳米晶。     

Microstructure and hardening mechanisms in a-Si3N4/nc-TiN nanostructured multilayers

Amorphous/nanocrystalline Si₃N₄/TiN nanostructured multilayer films were fabricated by radio-frequency reactive magnetron sputtering. The microstructure and properties of these films were measured using an X-ray diffractometer, X-ray photoelectron spectroscope, high-resolution transmission electron microscopy and nanoindenter. The superhardness effect was found in Si₃N₄/TiN multilayers. The hardness of Si₃N₄/TiN multilayers is affected not only by modulation periods, but also by layer thickness ratio and deposition temperature. The hardness value is about 40% higher than the value calculated from the rule of mixtures at a deposition temperature of 500 °C and a layer thickness ratio (l_Si3N4/l_TiN) of 3/1. The hardening mechanisms in this system are discussed in the light of our experimental results. Results of calculation of the theoretical stress distribution in the multilayers suggests that alternating stress fields caused by thermal mismatching between Si₃N₄ and TiN is one of the main reasons for the superhardness effect observed in Si₃N₄/TiN multilayers.     

TiN/Si_3N_4复相导电陶瓷的制备及其性能

以铁尾矿为主要原料经碳热还原氮化制成的Si3N4粉和高钛渣作为原料,常压烧结制备了TiN/Si3N4复相导电陶瓷。利用XRD对其相组成进行了表征,研究了初始原料中TiO2加入量对材料致密度、力学性能和导电性能的影响。结果表明,烧结产物主要由Si3N4和TiN组成,随初始原料中TiO2加入量的增加,烧结产物中TiN相含量增加;初始原料中TiO2加入量为25%(质量分数)时烧结试样的体积密度为3.32g/cm3,硬度为8.97GPa,抗弯强度为79MPa。最少需加入20%左右的TiO2,材料中的TiN才能形成导电网络,此时材料的电阻率为4.25×10-2Ω.cm。     

衬底偏压对CrN／Si3N4纳米多层膜结构和力学性能的影响

采用磁控溅射法在不同基底偏压条件下制备了CrN／Si3N4纳米多层膜,用x射线衍射仪、原子力显微镜及纳米压痕仪表征,结果表明,衬底偏压对CrN／Si3N4纳米多层膜微观结构、界面结构、硬度和磨损性能有重要影响;漂浮电位时,导致多层膜界面粗糙,CrN呈（200）、（111）共同生长,硬度和弹性模量低;当偏压变化时,界面宽度和粗糙度变化不大,硬度和模量变化的主要原因是不同衬底偏压下的晶格畸变导致两层材料弹性模量变化和晶粒尺寸变化。与漂浮电位相比,涂层的屈服应力和断裂韧性有所增强。     

Influence of multi-interfacial structure on mechanical and tribological properties of TiSiN/Ag multilayer coatings

The TiSiN/Ag multilayer coatings with bilayer periods of ~50, 65, 80, 115, 150, and 410 nm have been deposited on Ti6Al4 V alloy by arc ion plating. In order to improve the adhesion of the TiSiN/Ag multilayer coatings, TiN buffer layer was first deposited on titanium alloy. The multi-interfacial TiSiN/Ag layers possess alternating TiSiN and Ag layers. The TiSiN layers display a typical nanocrystalline/amorphous microstructure, with nanocrystalline TiN and amorphous Si₃N₄. TiN nanocrystallites embed in amorphous Si₃N₄ matrix exhibiting a fine-grained crystalline structure. The Ag layers exhibit ductile nanocrystalline metallic silver. The coatings appear to be a strong TiN (200)-preferred orientation for fiber texture growth. Moreover, the grain size of TiN decreases with the decrease of the bilayer periods. Evidence concluded from transmission electron microscopy revealed that multi-interfacial structures effectively limit continuous growth of single (200)-preferred orientation coarse columnar TiN crystals. The hardness of the coatings increases with the decreasing bilayer periods. Multi-interface can act as a lubricant, effectively hinder the cracks propagation and prevent aggressive seawater from permeating to substrate through the micro-pores to some extent, reducing the friction coefficient and wear rates. It was found that the TiSiN/Ag multilayer coating with a bilayer period of 50 nm shows an excellent wear resistance due to the fine grain size, high hardness, and silver-lubricated transfer films formed during wear tests.     

Mechanical Properties and Microstructure of Si3N4-TiC Nanocomposites

1. IntroductionSilicon nitride is one of the promising structural ma-terials for high-temperature applications because of itshigh resistance to thermal shock, as well as high strength,high fracture toughness, and high resistance to chemicalattack[1~3]. However, wider application has been lim-ited mainly due to its inherent brittleness. Many effortshave been made to improve its properties by control-ling the microstructure or by fabricating various typesof composites[4~7].The silicon nitride wi…     

Complex Permittivity and Microwave Absorbing Property of Si3N4-SiC Composite Ceramic

Si3N4-SiC composite ceramics were fabricated by chemical vapor infiltration using porous Si3N4 ceramic as preform. The average grain size of SiC was 30 nm. Relationship between SiC content and relative complex permittivity of Si3N4-SiC within the frequency range of 8.2-12.4 GHz (X-band) was investigated. The average real part of relative complex permittivity ε of Si3N4-SiC increased from 3.7 to 14.9 and the relative imaginary part ε increased from 0.017 to 13.4 when the content of SiC increased from 0 to 10 vol.%. The Si3N4-SiC ceramic with 3 vol.% SiC achieved a reflection loss below 10 dB (90% absorption) at 8.6-11.4 GHz, and the minimum value was 27.1 dB at 9.8 GHz when the sample thickness was 2.5 mm. The excellent microwave absorbing abilities of Si3N4-SiC ceramic were attributed to the interfacial polarization at interface between Si3N4 and SiC and at grain boundary between SiC nanocrystals.     

磁约束电感耦合等离子体增强反应溅射沉积nc-TiN/a-Si3N4纳米复合薄膜

介绍一种新型磁束缚电感耦合等离子体增强的物理化学气相沉积复合系统，并用该系统通过反应磁控溅射TiSi合金靶，在氩气和氮气等离子体作用下，在单晶硅衬底上制备了nc—TiN／a—Si3N4纳米复合薄膜．扫描电子显微镜、X射线衍射仪、X射线光电子谱仪和高分辨率透射电子显微镜的分析和观察结果清晰地表明该薄膜是具有纳米结构的复合薄膜，主要由镶嵌在非晶态Si3N4基体中的TiN纳米晶粒组成，TiN晶粒的尺寸约为3nm。     

Microstructure and mechanical properties of reactively sputtered Ti–Si–N nanocomposite films

A series of Ti–Si–N nanocomposite films with different Si content were deposited by reactive sputtering in a gas mixed with Ar, N₂ and SiH₄. Energy dispersive spectroscope, X-ray diffraction, transmission electron microscope and nanoindentation technique were employed to characterize the microstructure and mechanical properties of the films. The results reveal that Ti–Si–N nanocomposite films with different Si content can be easily obtained by controlling SiH₄ partial pressure in the mixed gas. With Si content ranging from 4 at.% to 9 at.%, the films are strengthened and reach the highest hardness and elastic modulus of 34.2 GPa and 398 GPa, respectively. With a further increase of Si content, the mechanical properties of films decrease gradually. The microstructure of Ti–Si–N films with high hardness shows the existence of TiN nanocrystals surrounded by Si₃N₄ interphase. The grain size of TiN is about 20 nm and the thickness of Si₃N₄ interphase is less than 1 nm.