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     

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.     

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     

Platelet adhesion on phosphorus-incorporated tetrahedral amorphous carbon films

The haemocompatibility of phosphorus-incorporated tetrahedral amorphous carbon (ta-C:P) films, synthesized by filtered cathodic vacuum arc technique with PH₃ as the dopant source, was assessed by in vitro platelet adhesion tests. Results based on scanning electron microscopy and contact angle measurements reveal that phosphorus incorporation improves the wettability and blood compatibility of ta-C film. Our studies may provide a novel approach for the design and synthesis of doped ta-C films to repel platelet adhesion and reduce thrombosis risk.     

Properties of boron and phosphorous incorporated tetrahedral amorphous carbon films grown using filtered cathodic vacuum arc process

This paper reports the electrical, mechanical, structural and field emission properties of as grown and also boron and phosphorous incorporated tetrahedral amorphous carbon (ta-C) films, deposited using a filtered cathodic vacuum arc process. The effect of varying boron and phosphorous content (up to 2.0 at.% in to ta-C) on the conductivity (σ_D), activation energy (ΔE₁), hardness, microstructure, emission threshold (E_turn-ON) and emission current density (J) at 12.5 V/μm of ta-C: B and ta-C: P films deposited at a high negative substrate bias of −300 V are reported. It is observed that both boron and phosphorous incorporation leads to a nearly an order increase in σ_D and corresponding decrease in ΔE₁ and a slight increase in hardness as compared to as grown ta-C films. In the case of field assisted electron emission, it is observed that E_turn-ON increases and J decreases. The changes are attributed to the changes in the sp³/sp² ratio of the films due to boron and phosphorous incorporation. The effect of boron on ta-C is to give a p-type effect whereas the effect of phosphorous gives n-type doping effect.     

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。     

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.     

X-ray photoelectron spectroscopic study of nitrogen incorporated amorphous carbon films embedded with nanoparticles

The effect of substrate bias on X-ray photoelectron spectroscopy (XPS) study of nitrogen incorporated amorphous carbon (a-C:N) films embedded with nanoparticles deposited by filtered cathodic jet carbon arc technique is discussed. High resolution transmission electron microscope exhibited initially the amorphous structure but on closer examination the film was constituted of amorphous phase with the nanoparticle embedded in the amorphous matrix. X-ray diffraction study reveals dominantly an amorphous nature of the film. A straight forward method of deconvolution of XPS spectra has been used to evaluate the sp³ and sp² contents present in these a-C:N films. The carbon (C 1s) peaks have been deconvoluted into four different peaks and nitrogen (N 1s) peaks have been deconvoluted into three different peaks which attribute to different bonding state between C, N and O. The full width at half maxima (FWHM) of C 1s peak, sp³ content and sp³/sp² ratio of a-C:N films increase up to −150 V substrate bias and beyond −150 V substrate bias these parameters are found to decrease. Thus, the parameters evaluated are found to be dependent on the substrate bias which peaks at −150 V substrate bias.     

Bonding configurations in amorphous carbon and nitrogenated carbon films synthesised by femtosecond laser deposition

The effect of nitrogen addition and laser fluence on the atomic structure of amorphous carbon films (a-C) synthesized by femtosecond pulsed laser deposition has been studied. The chemical bonding in the films was investigated by means of X-ray photoelectron (XPS) and Raman spectroscopies. XPS studies revealed a decrease in the sp³ bonded carbon sites and an associated increase in the N-sp²C bonding sites with increasing nitrogen content in the CN_x films. An increase in laser fluence from 0.36 to 1.7 J/cm² led to a rise in sp³C sites. These results were further confirmed by Raman spectroscopy. The I_D/I_G ratio increased monotonically and G line-width decreased with the increase of nitrogen content in the films indicating a rise in either the number or the size of the sp² clusters. Furthermore a visible excitation wavelength dependence study established the resonant Raman process in a-C and CN_x films. PACS 81.05.Uw; 81.15.Fg; 82.80     

Structure and mechanical properties of low stress tetrahedral amorphous carbon films prepared by pulsed laser deposition

Tetrahedral amorphous carbon films have been produced by pulsed laser deposition, at a wavelength of 248 nm, ablating highly oriented pyrolytic graphite at room temperature, in a 10^-2 Pa vacuum, at fluences ranging between 0.5 and 35 Jcm^-2. Both (100) Si wafers and wafers covered with a SiC polycrystalline interlayer were used as substrates. Film structure was investigated by Raman spectroscopy at different excitation wavelength from 633 nm to 229 nm and by transmission Electron Energy Loss Spectroscopy. The films, which are hydrogen-free, as shown by Fourier Transform Infrared Spectroscopy, undergo a transition from mainly disordered graphitic to up to 80% tetrahedral amorphous carbon (ta-C) above a threshold laser fluence of 5 J cm^-2. By X-ray reflectivity roughness, density and cross-sectional layering of selected samples were studied. Film hardness as high as 70 GPa was obtained by nanoindentation on films deposited with the SiC interlayer. By scratch test film adhesion and friction coefficients between 0.06 and 0.11 were measured. By profilometry we obtained residual stress values not higher than 2 GPa in as-deposited 80% sp³ ta-C films. Received 25 June 2001     

Synthesis of DLC films by PLD from liquid target and dependence of film properties on the synthesis conditions

DLC (Diamond-like carbon films) were prepared by pulsed laser ablation of a liquid target at substrate temperatures from 18 to 600°C using 248 nm KrF excimer laser. The sp³ hybridization state carbon formation was additionally promoted by gaseous H₂O₂ flow through the reaction chamber and substrate excitation by the same laser beam. Deposited DLC films were characterised by Raman scattering spectroscopy and atomic force microscopy (AFM). Comparative AFM and Raman study shows that the increase in the content of sp³ type bonding in DLC is in correlation with the increase of the surface roughness of the samples prepared.     

Nitrogen 1s electron binding energy assignment in carbon nitride thin films with different structures

Carbon nitride thin films deposited by dc unbalanced magnetron sputtering have been analyzed by high-resolution X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The XPS data show that N 1s binding states depend on substrate temperature (T_s). By comparison with the Raman spectra, N 1s binding states are assigned in which nitrogen atoms are mainly bound to sp² and sp³ carbon atoms at T_s = 100°C, whereas at T_s = 500°C nitrogen atoms are mainly bonded to sp², sp³ and sp¹ carbon atoms.     

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     

Opto-electrical properties of amorphous carbon thin film deposited from natural precursor camphor

A simple thermal chemical vapor deposition technique is employed for the pyrolysis of a natural precursor “camphor” and deposition of carbon films on alumina substrate at higher temperatures (600-900 °C). X-ray diffraction measurement reveals the amorphous structure of these films. The carbon films properties are found to significantly vary with the deposition temperatures. At higher deposition temperature, films have shown predominately sp²-bonded carbon and therefore, higher conductivity and lower optical band gap (Tauc gap). These amorphous carbon (a-C) films are also characterized with Raman and X-ray photoelectron spectroscopy. In addition, electrical and optical properties are measured. The thermoelectric measurement shows these as-grown a-C films are p-type in nature.     

Structural and optical properties of nitrogen-containing tetrahedral amorphous carbon films

Tetrahedral amorphous carbon films (ta-C) and nitrogen-containing ta-C films have been prepared using a magnetic-filtered plasma-deposition method in pure Ar, and Ar with N₂ ambient, respectively. The structural and optical properties of these films have been studied using UV-visible optical absorption spectroscopy, Raman spectroscopy, and measurements of electrical conductivity in the temperature range from 300 to 500 K. The value of the optical band gap for the ta-C films deposited at suitable conditions were found to be larger than 3 eV. For nitrogen-containing ta-C films deposited at low partial pressure of nitrogen, the incorporation of a small amount of nitrogen will result in a slight drop in activation energy of conductivity and a decrease in band gap, which indicates that there are evidently both doping effect of nitrogen and graphitization of bonding. The study of surface morphology has been performed using atomic force microscopy (AFM), and results show that the surface roughness increases with the amount of nitrogen incorporated in ta-C films. The correlation between surface roughness and configuration of N atoms in ta-C network is also discussed.     

脉冲偏压电弧离子镀CNx薄膜研究

用脉冲偏压电弧离子镀通过控制不同的氮流量在(100)单晶Si基片上制备了不同成分的CN_x薄膜.用光学显微镜,XPS,XRD,激光Raman和Nanoindenter等方法研究了薄膜的形貌、成分、结构和性能.结果表明,薄膜表面平整致密、氮含量随着氮流量的降低而降低、结构为非晶且为类金刚石薄膜;随着氮含量从18.9%降低到5.3%(摩尔百分比,全文同),薄膜的硬度和弹性模量单调增加而且增幅较大,其中硬度从15.0 GPa成倍增加到30.0 GPa;通过氮流量的调整能够敏感地改变薄膜中的sp³键的含量,是CN_x薄膜的硬度和弹性模量获得大幅度调整的本质原因. 关键词： x薄膜')" href="#">CN_x薄膜 脉冲偏压 电弧离子镀 硬度     

Evaluation of carbon films electrodeposited on different substrates from different organic solvents

Diamond-like-carbon (DLC) films have been deposited on Si, aluminum and indium tin oxide-coated glass from several organic solvents with pulse-modulated power. The films are characterized by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. XPS spectra show that the main composition of the films is carbon and Raman spectra show that the films are typical DLC films and a high potential is preferable in the formation of sp ³-structure carbon. Comparing the results from different solvents and different substrates we deduce that the methyl group of the solvents has a critical function in forming the DLC films. However, the formation process and the characters of the films, such as appearance, resistivity and thickness, are mainly determined by the substrate. We may call this deposition a substrate-controlled reaction. Received: 31 May 2000 / Accepted: 9 January 2001 / Published online: 3 April 2001     

Effect of nickel on the structure and bond type in amorphous diamond-like carbon films

Experimental data are presented from studies of the structure and bond type of carbon atoms in amorphous carbon-nickel films deposited from pulsed vacuum-arc discharge plasma sources. X-ray photoelectron spectroscopy was used. The characteristics of the plasmon loss spectra depend significantly on the deposition parameters. Carbon exists in a mixed sp²+sp³ hybridized state in the carbon–nickel films. The ratio of sp³/sp² carbon bonds increases when the nickel content is reduced (from 5.5 to 1.0 atomic %) and the deposition angle is increased. The structure closest to that of diamond was with a substrate bias voltage of –80 to –100 V and a deposition angle of 90°.     

Polymeric like carbon films prepared from liquid gas and the effect of nitrogen

Polymeric like carbon (PLC) films are grown by a capacitance coupled RF-PECVD on the grounded electrode at room temperature from liquid gas (40% propane and 60% butane) in two regimes with nitrogen and without nitrogen gas. Films are characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), Fourier transform infrared (FTIR) absorption and Raman spectroscopy. The result of FTIR analyses indicates that more than 90% of hydrogen atoms are bonded to carbon with sp³ hybridization. The abundance of CH₃ is more than that of CH₂ and this one is more than that of CH for carbon with sp³ hybridization in these films. The C 1s line of the XPS spectra is deconvoluted to several peaks that are attributed to the CH₃, CH₂ and CH terminations. The result of this deconvolution is consistent with FTIR results. AFM images show that the mean nanoparticle size is reduced from about 100 nm for films without nitrogen to less than 80 nm for films with nitrogen. This is in agreement with our Raman results. By addition of nitrogen to the feed gas, no variation in the C-H stretching vibration mode is observed. The effect of N-H bonds is observable in both FTIR and XPS spectra and a very small trace of N-C bonds is present only in deconvolution of N 1s line of XPS spectra. These results indicate that by addition of nitrogen to feed gas, internal structure of a-C:H nanoparticles is not changed but particle size is decreased. We suggest that the internal stress reduction due to nitrogen addition in the feed gas for PLC films can be related to decreasing of the a-C:H particle size.