过滤电弧沉积非晶金刚石薄膜的光谱椭偏研究

为了深入理解过滤阴极电弧沉积非晶金刚石薄膜的光学性质,利用光谱椭偏仪研究了薄膜光学常数随测试偏振光波长变化的谱学关系,进而分析了薄膜折射率、消光系数和光学带隙与沉积能量之间的变化规律。实验表明,非晶金刚石薄膜的折射率高于金刚石晶体的折射率,薄膜的吸收光谱在高吸收区可以用抛物线型函数描述,并由此计算Tauc带隙。随着波长向红外延伸,非晶金刚石薄膜的消光系数渐次降低并趋近于零,光学常数因沉积能量变化而实现的调整幅度也逐渐缩小。随着衬底偏压的增加,折射率和光学带隙都是先升高后减小,并在负偏压为80 V时有最大值;而消光系数却是先减小再升高,在负偏压为80 V时有最小值。     

偏压对空心阴极放电等离子体溅射制备氮化碳薄膜的影响

利用空心阴极放电等离子体源在Si（100）单晶衬底上沉积了氮化碳薄膜．薄膜的表面形貌表明所得的薄膜非常的均匀光滑，用X光电子能谱、拉曼和红外吸收光谱对薄膜的结构、成分和化学键等进行了研究．在拉曼光谱中可以看到典型的G，D和C=N键的峰．当偏压为250V时．薄膜拉曼光谱中的D峰完全消失，此时薄膜的N／C比达到了0．81．通过对薄膜的XPS分析也表明薄膜中C—C，sp^2 CN和sp^3 CN键的组分也发生了明显的变化．当偏压为250V时薄膜的sp^3 CN相的含量达到了最大值为40％，同时氮含量也达到了最大值．实验结果给出了直接的证据：薄膜的结构模式可以通过改变偏压来得到控制．     

FCVAD合成Ta-C(N)薄膜及其Raman和XPS分析

掺N非晶金刚石Ta—C(N)薄膜是合成β—C3N4研究中出现的一种新型固体薄膜材料,近年来由于其优异的电化学性能受到越来越多的关注。我们用磁过滤阴极真空弧等离子体沉积(FCVAD)方法在不同N2分压下,在Si衬底上合成了Ta—C(N)薄膜。Raman和XPS分析表明Ta—C：N薄膜中的N主要以C—N的方式与C结合。N2分压越大,N／C原子比越高,最高可达31．1％。但同时sp^3键含量越低,并且合成Ta-C：N薄膜的速度越慢。     

椭偏法表征四面体非晶碳薄膜的化学键结构

采用自主研制的双弯曲磁过滤阴极真空电弧(FCVA)技术,在不同衬底负偏压下制备了四面体非晶碳(ta-C)薄膜。通过分光光度计和椭偏(SE)联用技术精确测量了薄膜厚度,重点采用椭偏法对不同偏压下制备的ta-C薄膜sp3 C键和sp2 C键结构进行了拟合表征,并与X射线光电子能谱(XPS)和拉曼光谱的实验结果相对比,分析了非晶碳结构的椭偏拟合新方法可靠性。结果表明,在-100V偏压时薄膜厚度最小,为33.9nm;随着偏压的增加,薄膜中的sp2 C含量增加,sp3 C含量减小,光学带隙下降。对比结果发现,椭偏法作为一种无损、简易、快速的表征方法,可用于ta-C薄膜中sp2 C键和sp3 C键含量的准确测定,且在采用玻璃碳代表纯sp2 C的光学常数及拟合波长选取250～1700nm时的椭偏拟合条件下,拟合数值最佳。     

非晶金刚石薄膜的场致电子发射性能研究

利用真空磁过滤弧沉积技术制备出一种高sp³含量的非晶碳膜———非晶金刚石薄膜，并对这种非晶金刚石薄膜的场电子发射特性及其发射机理进行了研究．实验结果表明，在阈值电场低于20V/μm情况下，得到的场发射电流达20—40μA，薄膜的电子发射行为符合Fowler-Nordheim场发射理论．研究表明，这种非晶金刚石薄膜具有负的电子亲合势和较小的有效功函数以及相对较低的禁带宽度 关键词：     

磁控溅射CNx薄膜的附着力、粗糙度与衬底偏压的关系

对磁控溅射生长在单晶Si(001)衬底上的CNx薄膜的附着力、粗糙度与衬底偏压的关系进行了研究。CNx薄膜沉积实验在纯N2的环境下进行．衬底温度(Ts)保持在350℃．衬底偏压(Vb)在0～-150V之间变化。利用原子力显微镜(AFM)和划痕试验机来测量CNx薄膜的表面粗糙度及对衬底的附着力。AFM和划痕实验的结果显示衬底偏压Vb对CNx薄膜的附着力和表面粗糙程度的影响很大，在-100V偏压下生长的CNx薄膜表面最光滑(粗糙度最小)，同时对Si(001)衬底的附着力最好。最后根据实验结果确定了在单晶Si(001)衬底上生长光滑而且附着力好的CNx薄膜的最佳实验条件。     

负偏压对磁控溅射Ti膜沉积速率和表面形貌的影响

 采用直流磁控溅射加负偏压的方法制备了Ti膜,研究了不同偏压条件对Ti膜沉积速率、密度、生长方式及表面形貌的影响。随着偏压逐渐增大,Ti膜沉积速率分三个阶段变化:0~ -40 V之间沉积速率基本不变; -40~ -80 V之间沉积速率迅速降低;超过-80 V后沉积速率随偏压的下降速度又放缓。Ti膜密度随偏压增加而增大,负偏压为-119.1 V时开始饱和并趋于块体Ti材密度。加负偏压能够抑制Ti膜的柱状生长方式;偏压可以改善Ti膜的表面形貌,对于40 W和100 W的溅射功率,负偏压分别在-100 V和-80 V左右时制备出表面光洁性能较佳的Ti膜。     

化学气相沉积法制备金刚石膜截面微区Raman分析

采用微区Raman散射分析方法研究化学气相沉积法制备的金刚石膜的横截面.金刚石膜从衬底面到生长面不同位置具有不同特征的Raman谱,依此对膜中的金刚石、石墨和非晶碳成分进行分析.衬底面附近区域对应金刚石膜生长过程的成核阶段,非晶碳成分含量较高,相应于1200—1600cm^-1波段较大的散射强度和存在较强的荧光背底.膜厚增大,非晶碳成分中sp³结构成分首先减少,而sp²结构成分和石墨成分的减少相对缓慢.而生长面附近区域只有比较单纯的晶体金刚石 关键词：     

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利用在线椭偏仪对非晶碳氢膜进行了光学常数、沉积率和刻蚀率的测量。在无直流负偏压或偏压较小时,薄膜呈现聚合物结构,折射率和消光系数较小;当增加直流负偏压时,薄膜的折射率和消光系数显著提高,所成膜为硬质非晶碳氢膜。在以CH4作为气源进行沉积时,随着偏压的增加,沉积率先升高再降低,在偏压为-100V时,沉积率为最大。H2/N2(30%N2)的混合气体的刻蚀率要比单独用H2作为刻蚀气体的刻蚀率要大。对于CH4/N2(30%N2),在偏压从0V增加到300V过程中,在大约50V时,基底上的薄膜有一个从沉积到刻蚀的转化过程。     

W过渡层结合界面对金刚石薄膜在WC-6%Co上的附着力的影响

 在微波等离子体化学气相沉积装置中,采用负偏压形核等方法,研究两种不同的W过渡层/基体结合界面对金刚石薄膜与WC-6%Co附着力的影响。采用氢等离子体脱碳、磁控溅射镀W、高偏压碳化等方法,在YG6衬底表面形成化学反应型界面,W膜在碳化时和基体WC连为一体,极大地增加了W膜与基体的附着力,明显优于直接镀钨、碳化形成的物理吸附界面。在高负偏压下碳化,能提高表面粗糙度,增加膜与基体机械钳合,而负偏压形核增加核密度,从而增加膜与基体的接触面积,结果极大地提高了金刚石薄膜的附着力。     

Influence of sp 3 fraction on the field emission properties of tetrahedral amorphous carbon films formed by magnetic filtered plasma stream

Electron field emission properties of tetrahedral amorphous carbon films (ta-C) with various sp³ fractions, [sp³]/([sp²]+[sp³]), prepared by magnetic filtered plasma deposition system, were investigated. The ta-C films were deposited on (100) n-Si wafer with a resistivity of 0.01–0.02 cm in a substrate bias voltage V_b range from +20 V to -80 V. The relative fraction of sp³-bonded carbon in these films was qualitatively and quantitatively estimated by a fitting of the Raman and XPS spectra, respectively. Results show that ta-C films of high sp³ fraction, more than 80%, can be formed with a substrate bias voltage V_b in the range from -10 to -50 V. A remarkably low turn-on field of about 1.7 V/m was observed for these samples. For V_b outside this range, the sp³ fraction is lower. The surface of such ta-C films was found to be smooth and uniform from the images of atomic force microscopy. The sp³ fraction of the sample is believed to be the main factor affecting field emission properties of ta-C films. PACS 79.70; 78.30; 73.90.+f     

不同能级加速过滤电弧沉积四面体非晶碳膜的结构和性能

采用过滤阴极真空电弧技术，通过施加0—2000 V衬底负偏压使沉积离子获得不同能级的入射能量，在单晶硅上制备了四面体非晶碳薄膜.拉曼光谱分析表明，薄膜的结构为非晶sp³骨架中镶嵌着平面关联长度小于1 nm的sp²团簇.原子力显微镜研究表明：在低能级、富sp³能量窗口和次高能级，薄膜中sp³的含量越多，其表面就越光滑，应用sp³浅注入生长机制能够圆满地解释薄膜表面形态与离子入射能量之间的关系；但在高 关键词： 四面体非晶碳 过滤阴极真空电弧 能级     

The preparation and evaluation of graded multilayer ta-C films deposited by FCVA method

In this study, a series of graded multilayer ta-C films were investigated by varying their sublayer thickness ratios, in which each film sublayer was prepared at different substrate bias by filtered cathode vacuum arc (FCVA) method. The experimental results show that the graded multilayer film structure can effectively decrease the internal stress level of deposited ta-C film, and meanwhile the graded multilayer ta-C films still have high sp³ fractions. The applied substrate bias voltage and sublayer thickness ratio can apparently influence the microstructure characteristics and internal stress of the graded multilayer ta-C films. The graded multilayer ta-C film has larger sp³ fraction when applying a larger negative substrate bias voltage and having a thicker outer sublayer during the film deposition process. However, the internal stress in the as-deposited film also increases with larger thickness of the outer sublayer, and the optimal ratio of sublayer thicknesses is 1:1:1:1 for graded ta-C film with four sublayers.     

Stress, microstructure and mechanical properties of graded multilayer tetrahedral amorphous carbon films

Tetrahedral amorphous carbon (ta-C) films deposited using a filtered cathodic vacuum arc (FCVA) system, have high intrinsic stress which limits their application as protective coatings. To reduce the film stress and to improve the adhesion, a multilayer structure is deposited at a gradient substrate negative bias from 1500 V to 80 V. This paper investigates the stress, microstructure and nano-mechanical properties of graded multilayer ta-C film on Si substrates. Compared with that of single-layer films deposited at optimised bias, the graded multilayer film has low stress without a decline in hardness and Young’s modulus. Microstructural evaluation of the multilayer film using visible Raman spectra shows that the average content of the sp³ bonds of the multilayer film remain at a high level. Nanoscratch testing illustrates favorable scratch resistance and good adhesion of the multilayer film. Scanning electron microscope (SEM) observation confirms the collapse of the film surface along the scratching trace. Finally, deposition on single crystal germanium substrates of a durable coating ∼ 1100 nm thick, and composed of three graded multilayer films is demonstrated. PACS 81.05.Uw; 81.15.Jj; 68.65.Ac; 68.55.Nq; 68.60.Bs     

氮化铬过渡层对四面体非晶碳薄膜在高速钢基底上附着特性影响的研究

利用磁过滤阴极电弧与磁控溅射相结合的薄膜沉积技术在高速钢基底上 制备了氮化铬/四面体非晶碳(CrN/ta-C)复合涂层, 通过改变过渡层氮化铬(CrN)的制备工艺, 研究了四面体非晶碳(ta-C)薄膜在钢基底材料上的附着特性的变化. 结果表明, 随着氮气流量的增大, CrN/ta-C复合涂层中的氮化铬经过了Cr-Cr₂N-CrN的相变过程. 同时涂层的附着力也随着氮气流量的增大而增加, 但是当氮气流量超过30 sccm时, 涂层附着力会有所下降; 通过改变基片偏压, 复合涂层中氮化铬的择优取向与晶粒结构发生改变, 随着偏压的增大, 涂层附着力也会大大改善, 但是当偏压超过200 V, 涂层附着特性会略微降低. 通过涂层耐磨性的测试也表明, 在高速钢基底上, CrN涂层能显著提高ta-C薄膜在高速钢基底上的附着力, 同时显著提高耐磨特性. 关键词： 附着力 四面体非晶碳薄膜 X射线衍射 拉曼光谱     

Effect of ECR-assisted microwave plasma nitriding treatment on the microstructure characteristics of FCVA deposited ultra-thin ta-C films for high-density magnetic storage applications

There are higher technical requirements for protecting layer of magnetic heads and disks used in future high-density storage fields. In this paper, ultra-thin (2 nm thickness) tetrahedral amorphous carbon (ta-C) films were firstly prepared by filtered cathodic vacuum arc (FCVA) method, then a series of nitriding treatments were performed with nitrogen plasma generated using electron cyclotron resonance (ECR) microwave source. Here it highlighted the influence of nitrogen flow and applied substrate bias voltage on the structural characteristics of ta-C films during the plasma nitriding process. The chemical compositions, element depth distribution profiles, physical structures and bonding configurations of plasma-nitrided ta-C films were investigated by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and UV-vis Raman spectroscopy. The experimental results show that the carbon nitride compounds (CN_x) are formed in nitrogenated ta-C films in which the N content and its depth distribution depends on bias voltage to large extent rather than N₂ flow. The N content of nitrogenated ta-C films can reach 16 at.% for a substrate bias of −300 V and a N₂ flow of 90 sccm. With increasing nitrogen content, there is less G peak dispersion and more ordering of structure. Furthermore, appropriate nitriding treatment (substrate bias: −100 V, N₂ flow: 150 sccm) can greatly increase the fraction of sp³ and sp³C-N bonds, but the values begin to fall when the N content is above 9.8 at.%. All these indicate that suitable ECR-assisted microwave plasma nitriding is a potential modification method to obtain ultra-thin ta-C films with higher sp³ and sp³C-N fractions for high-density magnetic storage applications.     

Correlation between substrate bias, growth process and structural properties of phosphorus incorporated tetrahedral amorphous carbon films

We investigate the growth process and structural properties of phosphorus incorporated tetrahedral amorphous carbon (ta-C:P) films which are deposited at different substrate biases by filtered cathodic vacuum arc technique with PH₃ as the dopant source. The films are characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, Raman spectroscopy, residual stress measurement, UV/VIS/NIR absorption spectroscopy and temperature-dependent conductivity measurement. The atomic fraction of phosphorus in the films as a function of substrate bias is obtained by XPS analysis. The optimum bias for phosphorus incorporation is about −80 V. Raman spectra show that the amorphous structures of all samples with atomic-scaled smooth surface are not remarkably changed when PH₃ is implanted, but some small graphitic crystallites are formed. Moreover, phosphorus impurities and higher-energetic impinging ions are favorable for the clustering of sp² sites dispersed in sp³ skeleton and increase the level of structural ordering for ta-C:P films, which further releases the compressive stress and enhances the conductivity of the films. Our analysis establishes an interrelationship between microstructure, stress state, electrical properties, and substrate bias, which helps to understand the deposition mechanism of ta-C:P films.     

The effects of dc bias voltage on the crystal size and crystal quality. of cBN films

For the deposition of cubic boron nitride thin films in Ar–N₂–BF₃–H₂ system by dc jet plasma chemical vapor deposition, the role of dc substrate bias ranging from -70 V to -150 V was investigated. A critical bias voltage was observed for the formation of cBN phase. The cBN content in the film increased with bias voltage and reached a maximum at the bias voltage of -85 V. Increasing the bias voltage further caused a decrease in cBN content and peeling of the films from the substrate. By combining the results of infrared spectroscopy, Raman spectroscopy and X-ray diffraction, the bias voltage was also found to strongly affect the crystal size, crystal quality and residual stress of the deposited films. A bias voltage a little higher than the critical value was demonstrated to be favorable for the deposition of a high-quality cBN film with large crystal size and low residual stress. Received: 13 June 2000 / Accepted: 21 June 2000 / Published online: 23 August 2000     

基底表面纳米织构对非晶四面体碳膜结构和摩擦特性的影响研究

本文利用离子束表面改性技术对基底表面进行不同时间的轰击, 形成不同规则的纳米织构, 对不同织构的变化规律进行了研究, 同时, 利用磁过滤真空阴极电弧技术, 在具有不同纳米织构的各基底上沉积相同时间的四面体非晶碳薄膜. 采用原子力显微镜对各基底的织构进行形貌分析, 结果表明, 高能粒子束的轰击对基底表面形貌有较大的影响, 根据离子束轰击时间的不同, 可以在基底表面形成各种不同规则的纳米织构, 轰击15 min后发现基底表面形成点阵纳米织构, 之后随着时间的增加, 基本维持点阵结构. 通过X射线光电子能谱仪和摩擦磨损试验仪对沉积在具有不同织构的基底上的ta-C薄膜进行测试, 研究表明, 基底表面纳米织构的非晶层结构引起薄膜内部sp³键的含量降低, 释放了薄膜的内应力, 同时发现基底表面纳米织构将ta-C薄膜磨损时间从不足10 min提高到约70 min, 有效提高了薄膜的耐磨性.