氮离子轰击能量对ta-C:N薄膜结构的影响

利用磁过滤真空阴极电弧技术制备了sp³键含量不小于80%的四面体非晶碳薄膜(ta-C), 然后通过氮离子束改性技术制备了氮掺杂的四面体非晶碳(ta-C:N)薄膜. 利用Raman光谱和X射线光电子能谱对薄膜结构的分析,研究了氮离子轰击能量对ta-C:N薄膜结构的影响. 氮离子对ta-C薄膜的轰击,形成了氮掺杂的ta-C:N薄膜. 氮离子轰击诱导了薄膜中sp³键向sp²键转化, 以及CN键的形成.在ta-C:N薄膜中,氮掺杂的深度和浓度随着氮离子能量的增大而增大. ta-C:N薄膜中sp²键的含量和sp²键团簇的尺寸随着氮离子轰击能量的增大而增加; 在ta-C:N薄膜中, CN键主要由C-N键和C＝N键构成, C-N 键的含量随着氮离子轰击能量的增大而减小,但是C＝N 键含量随着氮离子轰击能量的增大而增大.在ta-C:N薄膜中不含有C≡N键结构.     

高能氮离子轰击对四面体非晶碳膜的表面改性和摩擦系数影响的研究

利用过滤阴极真空电弧技术制备了sp³键含量不小于80%的四面体非晶碳(ta-C)膜.利用冷阴极潘宁离子源产生不同能量的氮离子对制备的ta-C薄膜进行轰击,通过X射线光电子能谱和原子力显微镜对薄膜表面结构与形貌进行分析研究.研究表明,随着氮离子的轰击能量的增大,薄膜中的CN键结构略有增大,形成了轻N掺杂;同时,在薄膜表层发生了sp³键结构向sp²键结构的转化;薄膜的表面粗糙度在经过氮离子轰击后从0.2 nm减小至0.18 nm,然后随着轰击能 关键词： 四面体非晶碳 X射线光电子能谱 摩擦系数     

多样品法确定类金刚石薄膜的光学常数与厚度

采用乙烷气体辉光放电法在单晶Si衬底上制备了名义厚度分别为75,150和250nm的类金刚石碳(DLC)薄膜,除沉积时间外其他工艺参数完全一致。使用可变入射角光谱型椭偏仪(VASE)测量了380～1700nm波段的椭偏谱。该研究发现,对单一DLC样品的椭偏数据进行分析时,一定的范围内,假定不同的薄膜厚度均可以得到非常好的拟合结果。结果表明,采用单样品椭偏法拟合时,厚度与光学常数呈现出强烈的关联性,无法快速获得准确的结果。采用多样品椭偏法,对三个样品建立相同的物理模型,假定他们的光学常数相同,进行数据拟合。分析发现该方法可以快速、简便地获得精确的折射率、消光系数以及厚度值。经过检验,结果具有非常好的唯一性。     

N掺杂对非晶C薄膜的电子结构与光学性质的影响

用直流磁控溅射法制备了非晶C薄膜及N掺杂非晶C(a-C∶N)薄膜,用紫外-可见分光光谱仪、椭圆偏振仪、俄歇电子能谱(AES)等对薄膜进行了检测。结果表明:随源气体中N气含量的增加,透过率和折射率变小,而光学带隙先增大后减小;当薄膜中N的含量很少,N的掺入对sp3杂化C起稳定作用,使得薄膜光学带隙Eg增大。而较高量N的掺入抑制了sp3杂化C的形成,提高了薄膜中sp2键含量,使得薄膜光学带隙变小。参数D定义为俄歇电子能谱(AES)中最大正峰和最低负峰之间的距离,用俄歇电子能谱中的D值来计算薄膜的sp2键的百分含量,俄歇电子能谱(AES)表征也表明:较高量的N的掺入抑制了sp3杂化C的形成。所以应该考虑在较低N分压条件下掺N来改善非晶C薄膜的光学性能。     

光谱型椭偏仪精确表征非晶吸收薄膜的光学常数

采用光谱型椭偏仪(SE)和分光光度计分别测量了超薄类金刚石(DLC)薄膜和非晶硅(a-Si)薄膜的椭偏参数(y和D)和透射率T。由于薄膜的厚度与折射率、消光系数之间存在强烈的相关性,仅采用椭偏参数拟合,难以准确得到薄膜的光学常数。如果加入透射率同时进行拟合(以下简称SE+T法),可简单、快速得到薄膜的厚度和光学常数。但随机噪声、样品表面的轻微污染或衬底上任何小的吸收都可能影响SE+T法拟合的光学常数的准确性。因此将SE+T法和光学常数参数化法联用,实现DLC、a-Si薄膜光学常数的参数化,以消除测量数据中的噪声对光学常数的影响。结果显示,联用时的拟合结果具有更好的唯一性,而且拟合得到的光学常数变得平滑、连续且符合Kramers-Kronig(K-K)关系。这种方法特别适合于精确表征厚度仅为几十纳米的非晶吸收薄膜的光学常数。     

光谱型椭偏仪精确表征非晶吸收薄膜的光学常数EI北大核心CSCD

采用光谱型椭偏仪(SE)和分光光度计分别测量了超薄类金刚石(DLC)薄膜和非晶硅(a-Si)薄膜的椭偏参数(y和D)和透射率T。由于薄膜的厚度与折射率、消光系数之间存在强烈的相关性,仅采用椭偏参数拟合,难以准确得到薄膜的光学常数。如果加入透射率同时进行拟合(以下简称SE+T法),可简单、快速得到薄膜的厚度和光学常数。但随机噪声、样品表面的轻微污染或衬底上任何小的吸收都可能影响SE+T法拟合的光学常数的准确性。因此将SE+T法和光学常数参数化法联用,实现DLC、a-Si薄膜光学常数的参数化,以消除测量数据中的噪声对光学常数的影响。结果显示,联用时的拟合结果具有更好的唯一性,而且拟合得到的光学常数变得平滑、连续且符合Kramers-Kronig(K-K)关系。这种方法特别适合于精确表征厚度仅为几十纳米的非晶吸收薄膜的光学常数。     

a-C:H膜化学结构对光学性能的影响

选用体积分数为99.999 9%的H2及反式-2-丁烯(T2B)为工作气体,利用低压等离子体增强化学气相沉积法制备了a-C;H薄膜.利用傅里叶变换红外光谱仪和X射线光电子能谱对薄膜化学键和电子结构进行分析,并结合高斯分峰拟合分析了薄膜中sp3/sp2杂化键比值和sp3C杂化键分数.结果表明:薄膜中氢含量较高,主要以sp3C-H形式存在;工作气压越高,制备的薄膜中C=C键含量越少,薄膜中sp3/sp2杂化键比值和sp3C杂化键分数增加,薄膜稳定性提高.应用UV-VIS光谱仪,获得了波长在400～1 000 nm范围内薄膜的光吸收特性,结果显示:a-C:H薄膜透过率可达98%.光学常数公式计算得到工作压强为4～14 Pa时光学带隙在2.66～2.76之间,并均随着工作气压的升高而增大.结果表明,随工作气压的升高,薄膜内sp3键减小,从而促使透过率、光学带隙增大.     

一种可溯源的光谱椭偏仪标定方法

提出了一种用X射线反射术标定光谱椭偏仪的方法.作为一种间接测量方法,光谱椭偏术测得的薄膜厚度依赖于其光学常数,不具有可溯源性.在掠入射条件下,X射线反射术能测得薄膜的物理厚度,测量结果具有亚纳米量级的精密度且与薄膜光学常数无关.在单晶硅基底上制备了厚度分别为2nm,18nm,34nm,61nm及170nm的SiO2薄膜标样,并用强制过零点的直线拟合了两种方法的标样测量结果,拟合直线的斜率为1.013±0.013,表明该方法可在薄膜厚度测量中标定光谱椭偏仪.     

空心阴极放电沉积氮化碳薄膜的结构和成键性质

利用空心阴极放电等离子体源在Si(100)衬底上沉积了氮化碳薄膜.用XRD,SEM,XPS及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.XRD分析表明,制备的氮化碳薄膜为非晶结构.XPS分析证实了薄膜中以C—C,sp2CN和sp3CN键为主,并得出薄膜中的氮碳比为0.71,而sp3—CN相的含量也达到了0.39.拉曼和红外吸收光谱的结果也与XPS分析的键态结果一致.     

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     

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.     

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.     

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.     

椭偏与光度法联用精确测定吸收薄膜的光学常数与厚度

介绍了一种同时利用椭偏仪和分光光度计精确测量薄膜光学常数的方法, 并详细比较了该方法与使用单一椭偏仪拟合结果的可靠性.采用可变入射角光谱型椭偏仪（VASE）表征了250—1700 nm波段辉光放电法沉积的类金刚石薄膜,研究发现当仅用椭偏参数拟合时,由于厚度与折射率、消光系数的强烈相关性,无法得到吸收薄膜光学常数的准确解.如果加入分光光度计测得的透射率同时拟合,得到的结果具有很好的惟一性.该方法无需设定色散模型即可快速拟合出理想的结果,特别适合于确定透明衬底上较薄吸收膜的光学常数. 关键词： 光学常数 光谱型椭偏仪 吸收薄膜 透射率     

Effects of the ion-beam voltage on the properties of the diamond-like carbon thin film prepared by ion-beam sputtering deposition

Diamond-like carbon(DLC) thin film is one of the most widely used optical thin films.The fraction of chemical bondings has a great influence on the properties of the DLC film.In this work,DLC thin films are prepared by ion-beam sputtering deposition in Ar and CH4 mixtures with graphite as the target.The influences of the ion-beam voltage on the surface morphology,chemical structure,mechanical and infrared optical properties of the DLC films are investigated by atomic force microscopy(AFM),Raman spectroscopy,nanoindentation,and Fourier transform infrared(FTIR) spectroscopy,respectively.The results show that the surface of the film is uniform and smooth.The film contains sp2 and sp3hybridized carbon bondings.The film prepared by lower ion beam voltage has a higher sp3 bonding content.It is found that the hardness of DLC films increases with reducing ion-beam voltage,which can be attributed to an increase in the fraction of sp3 carbon bondings in the DLC film.The optical constants can be obtained by the whole infrared optical spectrum fitting with the transmittance spectrum.The refractive index increases with the decrease of the ion-beam voltage,while the extinction coefficient decreases.     

Synthesis and structure of nitrogenated tetrahedral amorphous carbon films prepared by nitrogen ion bombardment

The tetrahedral amorphous carbon (ta-C) films with more than 80% sp³ fraction firstly were deposited by filtered cathode vacuum arc (FCVA) technique. Then the energetic nitrogen (N) ion was used to bombard the ta-C films to fabricate nitrogenated tetrahedral amorphous carbon (ta-C:N) films. The composition and structure of the films were analyzed by visible Raman spectrum and X-ray photoelectron spectroscopy (XPS). The result shows that the bombardment of energetic nitrogen ions can induce the formation of CN bonds, the conversion of C-C bonds to CC bonds, and the increase of size of sp² cluster. The CN bonds are made of CN bonds and C-N bonds. The content of CN bonds increases with the increment of N ion bombardment energy, but the content of C-N bonds is inversely proportional to the increment of nitrogen ion energy. In addition, C≡N bonds are not existed in the films. By the investigation of AFM (atom force microscopy), the RMS (root mean square) of surface roughness of the ta-C film is about 0.21 nm. When the bombarding energy of N ion is 1000 eV, the RMS of surface roughness of the ta-C:N film decreases from 0.21 to 0.18 nm. But along with the increment of the N ion energy ranging from 1400 to 2200 eV again, the RMS of surface roughness of the ta-C:N film increases from 0.19 to 0.33 nm.     

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     

α-C∶H膜化学结构对光学性能的影响

 选用体积分数为99.999 9%的H₂及反式-2-丁烯（T2B）为工作气体,利用低压等离子体增强化学气相沉积法制备了α-C∶H薄膜。利用傅里叶变换红外光谱仪和X射线光电子能谱对薄膜化学键和电子结构进行分析,并结合高斯分峰拟合分析了薄膜中sp³/sp²杂化键比值和sp³C杂化键分数。结果表明：薄膜中氢含量较高,主要以sp³C—H形式存在;工作气压越高,制备的薄膜中C=C键含量越少,薄膜中sp³/sp²杂化键比值和sp³C杂化键分数增加,薄膜稳定性提高。应用UV-VIS光谱仪,获得了波长在400~1 000 nm范围内薄膜的光吸收特性,结果显示: α-C∶H薄膜透过率可达98%。光学常数公式计算得到工作压强为4~14 Pa时光学带隙在2.66~2.76之间,并均随着工作气压的升高而增大。结果表明,随工作气压的升高,薄膜内sp³键减小,从而促使透过率、光学带隙增大。     

α-C∶H膜化学结构对光学性能的影响

 选用体积分数为99.999 9%的H₂及反式-2-丁烯（T2B）为工作气体,利用低压等离子体增强化学气相沉积法制备了α-C∶H薄膜。利用傅里叶变换红外光谱仪和X射线光电子能谱对薄膜化学键和电子结构进行分析,并结合高斯分峰拟合分析了薄膜中sp³/sp²杂化键比值和sp³C杂化键分数。结果表明：薄膜中氢含量较高,主要以sp³C—H形式存在;工作气压越高,制备的薄膜中C=C键含量越少,薄膜中sp³/sp²杂化键比值和sp³C杂化键分数增加,薄膜稳定性提高。应用UV-VIS光谱仪,获得了波长在400~1 000 nm范围内薄膜的光吸收特性,结果显示: α-C∶H薄膜透过率可达98%。光学常数公式计算得到工作压强为4~14 Pa时光学带隙在2.66~2.76之间,并均随着工作气压的升高而增大。结果表明,随工作气压的升高,薄膜内sp³键减小,从而促使透过率、光学带隙增大。     

Effect of phosphorus content on structural properties of phosphorus incorporated tetrahedral amorphous carbon films

With phosphorus incorporated tetrahedral amorphous carbon (ta-C:P) films prepared using filtered cathodic vacuum arc technique with PH₃ as the dopant source, we investigate the effect of phosphorus content on the structural properties of the films by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. XPS analysis indicates that a function is established between the atomic fraction of phosphorus in the samples and the flow rate of PH₃ during deposition, and that phosphorus implantation increases the graphite-like trihedral sp² bonds deduced from fitted C 1s and P 2p core level spectra. Raman spectra of a broad range show that there are two notable features for all ta-C:P films: the first-order band centered at about 1560 cm^-1 and the second-order band between 2400 and 3400 cm^-1. The broad first-order band demonstrates that the amorphous structure of all samples does not remarkably change when a lower flow rate of PH₃ is implanted, while a higher concentration of phosphorus impurity enhances the clustering of sp² sites dispersed in sp³ skeleton and the evolution of structural ordering. Furthermore, the second-order Raman spectra confirm the formation of small graphitic crystallites in size due to a finite-crystal-size effect. PACS 81.05.Uw; 81.15.Ef; 63.50.+x