The properties of N-doped diamond-like carbon films prepared by helicon wave plasma chemical vapor deposition

In this paper, N-doped diamond-like carbon(DLC) films were deposited on silicon substrates by using helicon wave plasma chemical vapor deposition(HWP-CVD) with the Ar/CH_4/N_2 mixed gas. The surface morphology, structural and mechanical properties of the N-doped DLC films were investigated in detail by scanning electron microscopy(SEM), x-ray photoelectron spectroscopy(XPS), Raman spectra, and atomic force microscopy(AFM). It can be observed from SEM images that surface morphology of the films become compact and uniform due to the incorporation of N. The maximum of the deposition rate of the films is 143 nm min~(-1), which is related to the high plasma density. The results of XPS show that the N incorporates in the films and the C-C sp~3 bond content increases firstly up to the maximum(20%) at 10 sccm of N_2 flow rate, and then decreases with further increase in the N_2 flow rate. The maximum Young's modulus of the films is obtained by the doping of N and reaches 80 GPa at 10 sccm of N_2 flow rate, which is measured by AFM in the scanning probe microscope mode. Meanwhile, friction characteristic of the N-doped DLC films reaches a minimum value of 0.010.     

氢气流量对类金刚石薄膜结构与性能的影响

采用直流/射频耦合反应磁控溅射法在Si（100）衬底上成功制备出类金刚石（DLC）薄膜。利用表面轮廓仪、Raman光谱仪、X射线光电子能谱仪表征所制备薄膜在不同氢气流量下的沉积速率和化学结构,讨论了氢气流量对薄膜沉积速率和化学结构的影响;利用纳米压痕技术及曲率弯曲法表征薄膜的力学性能;利用扫描电镜和原子力显微镜表征薄膜的表面形貌与粗糙度。研究表明：随着氢气流量的增加,所制备薄膜的沉积速率逐渐减小,而薄膜中sp³键的含量逐渐增大。当氢气流量为25 mL/min时,薄膜中sp³键的含量为36.3%,薄膜的硬度和体弹性模量分别达到最大值17.5 GPa和137 GPa。同时,所制备薄膜的内应力均低于0.5 GPa,有望成功制备出低内应力的高质量DLC厚膜。随着氢气流量的增加,DLC薄膜的表面变得更致密光滑,且表面均方根粗糙度由5.40 nm降为1.46 nm。     

Low Friction-Coefficient TiBCN Nanocomposite Coatings Prepared by Cathode Arc Plasma Deposition

TiBCN nanocomposite coatings were deposited on cemented carbide and Si（100）by a cathode arc plasma system,in which TiB₂ cathodes were used in mixture gases of N₂ and C₂H₂.X-ray diffraction shows that TiB₂ and Ti₂B₅ peaks enhance at low flow rates of C₂H₂,but they shrink when the flow rate is over 200 seem.An increase of deposition rate was obtained from different TiBCN thicknesses for the same deposition time measured by scanning electron microscopy.Atomic force microscopy shows that the surface roughnesses are ¹0 nm and ²0 nm at C₂H₂ flow rates of 0-100 sccm and of 150-300 sccm,respectively.High resolution transmission electron microscopy and X-ray photoelectron spectroscopy show that the coatings consist of nanocrystal phases Ti₂B₅,TiB₂ and TiN,and amorphous phase carbon and BN.The average crystal sizes embedded in the amorphous matrices are 200 nm and 10 nm at C₂H₂ flow rates of200 sccm and 300 sccm,respectively.In Raman spectra,the D- and G-bands increase with C₂H₂flows at low flow rates,but weaken at high flow rates.The microhardness of the coatings decreases from 28.6 GPa to 20 GPa as the C₂H₂ increases from 0 sccm to 300 sccm,and the ball-on-disk measurement shows a dramatic decrease of the friction coefficient from 0.84 to 0.13.The reason for the reduced hardness and friction coefficient with the change of C₂H₂ flow rates is discussed.     

Mechanism of high growth rate for diamond-like carbon films synthesized by helicon wave plasma chemical vapor deposition

A high growth rate fabrication of diamond-like carbon(DLC)films at room temperature was achieved by helicon wave plasma chemical vapor deposition(HWP-CVD)using Ar/CH_4gas mixtures.The microstructure and morphology of the films were characterized by Raman spectroscopy and scanning electron microscopy.The diagnosis of plasma excited by a helicon wave was measured by optical emission spectroscopy and a Langmuir probe.The mechanism of high growth rate fabrication for DLC films by HWP-CVD has been discussed.The growth rate of the DLC films reaches a maximum value of 54μm h~(-1)at the CH_4flow rate of 85 sccm,which is attributed to the higher plasma density during the helicon wave plasma discharge.The CH and H_αradicals play an important role in the growth of DLC films.The results show that the H_αradicals are beneficial to the formation and stabilization of C=C bond from sp~2to sp~3.     

Effect of Fe ion implantation on tribological properties and Raman spectra characteristics of diamond-like carbon film

1 Introduction It is well known that DLC (diamond-like carbon)prepared by physical vapor deposition, plasma en-hanced chemical vapor deposition (PECVD) and otherplasma processing is an amorphous carbon materialcontaining sp2 and sp3 bonded carbon atoms. DLCfilm possesses some interesting properties, such ashigh hardness and Young's modulus, chemical inert-ness and low friction coefficient. The property andstructure of DLC film can be modified by addingsome metals. Ion implantation…     

Incorporation of Nitrogen into Amorphous Carbon Films Produced by Surface-Wave Plasma Chemical Vapor Deposition

In order to study the influence of nitrogen incorporated into amorphous carbon films, nitrogenated amorphous carbon films have been deposited by using surface wave plasma chemical vapor deposition under various ratios of N2/CH4 gas flow. Optical emission spectroscopy has been used to monitor plasma features near the deposition zone. After deposition, the samples are checked by Raman spectroscopy and x-ray photo spectroscopy (XPS). Optical emission intensities of CH and N atom in the plasma are found to be enhanced with the increase in the N2/CH4 gas flow ratio, and then reach their maximums when the N2/CH4 gas flow ratio is 5%. A contrary variation is found in Raman spectra of deposited films. The intensity ratio of the D band to the G band (ID/IG) and the peak positions of the G and D bands all reach their minimums when the N2/CH4 gas flow ratio is 5%. These show that the structure of amorphous carbon films has been significantly modified by introduction of nitrogen。     

Intense Yellow Photoluminescence from Silicon Oxynitride Films Prepared by Dual Ion Beam Sputtering

In this work, results on the study of the structure and photoluminescence (PL) properties of SiOxNy thin films are presented. The films were deposited at room temperature using a dual-ion-beam co-sputtering system. The XRD and TEM results show that the deposited films have an amorphous structure. In the XPS result, we find N 1 s spectra consist of one symmetric single peak at 397.8 eV, indicating that the nitrogen atoms are mainly bonded to silicon. It is in agreement to the result of FTIR. In SiOxNy films, an intense single PL peak at 590 nm is observed. Furthermore, with the increase of the N content in the SiOxNy films, the intensity of the PL peak at 590 nm increases a lot. The PL peak of 590 nm is suggested to originate from N-related defects.     

Influence of Microwave Power on the Properties of Hydrogenated Diamond-Like Carbon Films Prepared by ECR Plasma Enhanced DC Magnetron Sputtering

Electron cyclotron resonance (ECR) plasma was applied to enhance the direct current magnetron sputtering to prepare hydrogenated diamond-like carbon (H-DLC) films. For different microwave powers, both argon and hydrogen gas are introduced separately as the ECR working gas to investigate the influence of microwave power on the microstructure and electrical property of the H-DLC films deposited on P-type silicon substrates. A series of characterization methods including the Raman spectrum and atomic force microscopy are used. Results show that, within a certain range, the increase in microwave power affects the properties of the thin films, namely the sp3 ratio, the hardness, the nanoparticle size and the resistivity all increase while the roughness decreases with the increase in microwave power. The maximum of resistivity amounts to 1.1×109 Ωcm. At the same time it is found that the influence of microwave power on the properties of H-DLC films is more pronounced when argon gas is applied as the ECR working gas, compared to hydrogen gas.     

The effect of nitrogen concentration on the properties of N-DLC prepared by helicon wave plasma chemical vapor deposition

Nitrogen-doped diamond-like carbon (N-DLC) films were synthesized by helicon wave plasma chemical vapor deposition (HWP-CVD). The mechanism of the plasma influence on the N-DLC structure and properties was revealed by the diagnosis of plasma. The effects of nitrogen doping on the mechanical and hydrophobicity properties of DLC films were studied. The change in the ratio of precursor gas flow reduces the concentration of film-forming groups, resulting in a decrease of growth rate with increasing nitrogen flow rate. The morphology and structure of N-DLC films were characterized by scanning probe microscopy, Raman spectroscopy, and X-ray photoemission spectroscopy. The mechanical properties and wettability of N-DLC were analyzed by an ultra-micro hardness tester and JC2000DM system. The results show that the content ratio of N+ and ${{\rm{N}}}_{2}^{+}$ is positively correlated with the mechanical properties and wettability of N-DLC films. The enhancement hardness and elastic modulus of N-DLC are attributed to the increase in sp3 carbon–nitrogen bond content in the film, reaching 26.5 GPa and 160 GPa respectively. Water contact measurement shows that the increase in the nitrogen-bond structure in N-DLC gives the film excellent hydrophobic properties, and the optimal water contact angle reaches 111.2°. It is shown that HWP technology has unique advantages in the modulation of functional nanomaterials.     

Effects of composition and structure on hydrogen incorporation in tungsten oxide films deposited by sputtering

The effects of composition and structure on hydrogen incorporation in tungsten oxide films were investigated. Films were deposited on carbon and SiO₂ substrates using a reactive sputtering by varying the substrate temperature from 30 to 600 °C in argon and oxygen mixture. The films were characterized using X-ray diffraction (XRD), Rutherford backscattering spectroscopy (RBS), elastic recoil detection analysis (ERDA) and Raman scattering. XRD patterns showed amorphous structure in the films deposited below 400 °C and (0 1 0) oriented monoclinic WO₃ in the films deposited beyond 400 °C. The results of RBS and ERDA indicated that hydrogen concentration in the amorphous films increased from 0.1 to 0.7 H/W with changing the composition from WO_0.25 to WO₃. The hydrogen concentration in WO₃ films decreased to 0.4 H/W with increasing the substrate temperature during deposition. The Raman spectra of the WO₃ films revealed that decreasing of W⁶⁺O terminals was related to decreasing of the hydrogen concentration. It was considered that the incorporated hydrogen in tungsten oxide films was bonded at the end of W⁶⁺O terminals.     

Growth and surface morphology of ion-beam sputtered Ti-Ni thin films

Titanium-nickel thin films have been deposited on float glass substrates by ion beam sputtering in 100% pure argon atmosphere. Sputtering is predominant at energy region of incident ions, 1000 eV to 100 keV. The as-deposited films were investigated by X-ray photoelectron spectroscopy (XPS) and atomic force microscope (AFM). In this paper we attempted to study the surface morphology and elemental composition through AFM and XPS, respectively. Core level as well as valence band spectra of ion-beam sputtered Ti-Ni thin films at various Ar gas rates (5, 7 and 12 sccm) show that the thin film deposited at 3 sccm possess two distinct peaks at binding energies 458.55 eV and 464.36 eV mainly due to TiO₂. Upon increasing Ar rate oxidation of Ti-Ni is reduced and the Ti-2p peaks begin approaching those of pure elemental Ti. Here Ti-2p peaks are observed at binding energy positions of 454.7 eV and 460.5 eV. AFM results show that the average grain size and roughness decrease, upon increasing Ar gas rate, from 2.90 μm to 0.096 μm and from 16.285 nm to 1.169 nm, respectively.     

感应耦合等离子体源制备硬质类金刚石膜的研究

采用感应耦合等离子体源(ICPS)成功地实现化学气相沉积硬质类金刚石(DLC)膜,并考察了基片负偏压对类金刚石膜沉积过程和薄膜性质的影响。薄膜的微观形貌、显微硬度、沉积速率以及结构成分分析表明感应耦合等离子体源适于制备硬质类金刚石膜,并且在相对较低的基片负偏压条件就可以获得高硬度的类金刚石膜。基片负偏压对类金刚石膜化学气相沉积过程和薄膜性质都有显著影响。     

Surface characteristics and electrochemical corrosion behavior of fluorinated diamond-like carbon (F-DLC) films on the NiTi alloys

Fluorinated diamond-like carbon (F-DLC) films with different CF₄ flux were deposited on polished NiTi alloys by plasma immersion ion implantation and deposition (PIIID). The results show CF_x bond is formed in the F-DLC films. With the increase of the CF₄ flux, the fluorine content and surface hydrophilicity of the F-DLC films are increased, while their sp³/sp² ratio and surface roughness are decreased. The F-DLC films improve the surface corrosion resistance of NiTi alloys, and the corrosion resistance of the F-DLC films on the NiTi alloys first increase and then decrease with increasing the CF₄ flux. Moreover, the relationship between the corrosion resistance and its structure and surface hydrophilicity of the F-DLC films is also clarified.     

Tarnish Testing of Copper-Based Alloys Coated with SiO_2-Like Films by PECVD

The tarnishing test in the presence of hydrogen sulfide（H2S） vapors has been used to investigate the tarnish resistance capability of copper-based alloys coated with Si02-like films by means of plasma-enhanced chemical vapor deposition（PECVD） fed with a tetraethoxysilane/oxygen mixture.The chemical and morphological properties of the films have been characterized by using infrared absorption spectroscopy（IR） and scanning electron microscopy（SEM）with energy disperse spectroscopy（EDS）.The corrosion products of the samples after the tarnishing test have been identified by X-ray diffraction analysis（XRD）.It has been found that SiO2-like films formed via PECVD with a high O2 flow rate could protect copper-based alloys from H2S vapor tarnishing.The alloys coated at the O2 flow rate of 20 sccm remain uncorroded after 54days of H2S vapor tarnish testing.The corrosion products for the alloys deposited at a low O2flow rate after 54 days of tarnish testing are mainly composed of brochantite.     

Effect of Plasma Boronitriding on Diamond Nucleation and Growth onto Cemented Carbide Substrates

Plasma boronitriding has been successfully employed to overcome the difficulty in diamond growth on ferrous-based substrates,Commercial cobalt-sintered,tungsten-cemented carbides(WC (Co) were pretreated by a plasma boronitriding method,diamond was then deposited by microwave-enhanced chemical vapor deposition (MPCVD) ,The deposited films were characterized by scanning electron microsopy and Raman spectroscopy,Conitinuous diamond films with a sharp characteristic Raman Peak of 1334 cm^-1 were grown and adhered well on the boronitrided region of the cemented carbide substrates,On,the other hand,a mixture of diamond crystallites,amorphous carbon and graphitic carbon was loosely deposited on the unboronitrided region A cobalt inert thin layer formed after plasma bornitriding pretreatment enabled the subsequent nucleation and growht of a high-quality CVD iamond.     

STUDY OF HYDROGEN IN ANNEALED AMORPHOUS SILICON AND IMPLANTED AMORPHOUS CARBON

Hydrogen contents and its depth profiles, obtained by nuclear reaction induced by fluorine ion, have been investigated for a series of thermal annealed amorphous silicon and implanted amorphous carbon (diamond-like carbon) films. For dual layer amorphous silicon films, it is shown that hydrogen of either a-Si:H or a-SiNx:H sublayer moves obviously at different annealing conditions. For diamond-like carbon (DLC) films, measurements show that, by argon implantation, hydrogen contents decrease obviously with the increase of implanting dose. The decrease of hydrogen contents results in the decrease of diamond- like (SP3) and graphite-like (SP2) components of DLC films. But, the ratios of SP2 and SP3 increased, and the resistivities decrease with the increase of implanting dose.     

Modification of DLC films by Ni ions implantation

Enhanced diamond-like carbon (DLC) multilayer films were produced by a method of alternating the magnetic filtered vacuum cathode arc deposition and the metal vapor vacuum arc (MEVVA) implantation of Ni⁺ ions. The microstructure and mechanical properties of these multilayer films were studied by XPS, Raman, SEM, AFM, XRD, nano-intender and internal stress measurement. The results reveal that with the increasing dose of implanted Ni⁺ ions, the sp³ contents are declining and reduction of the nanohardness and release of the internal stress are observed.     

C注入GaN光致发光和微区拉曼散射的研究

使用光致发光谱和微区拉曼散射谱的测量,研究了C离子注入原生无黄光发射的GaN。C离子的注入剂量范围为1013-1017cm-2。发光谱的研究表明,C注入的GaN经950℃高温退火后出现了黄光发射,而近带边发射峰的峰位则由于C注入产生的某种缺陷而发生了蓝移。拉曼谱的测量表明,GaN薄膜的应力不随C注入而改变。当注入剂量增加至1015cm-2时,出现了与无序激活拉曼散射相关的300cm-1峰,但随着注入剂量进一步增加,300cm-1峰减弱并未消失,这被归因于注入束流强度随注入剂量增大。     

Effect of Gas Sources on the Deposition of Nano-Crystalline Diamond Films Prepared by Microwave Plasma Enhanced Chemical Vapor Deposition

Nano-crystalline diamond (NCD) films were deposited on silicon substrates by a microwave plasma enhanced chemical vapor deposition (MPCVD) reactor in C2H5OH/H2 and CH4/H2/O2 systems, respectively, with a constant ratio of carbon/hydrogen/oxygen. By means of atomic force microscopy (AFM) and X-ray diffraction (XRD), it was shown that the NCD films deposited in the C2H5OH/H2 system possesses more uniform surface than that deposited in the CH4/H2/O2 system. Results from micro-Raman spectroscopy revealed that the quality of the NCD films was different even though the plasmas in the two systems contain exactly the same proportion of elements. In order to explain this phenomenon, the bond energy of forming OH groups, energy distraction in plasma and the deposition process of NCD films were studied. The experimental results and discussion indicate that for a same ratio of carbon/hydrogen/oxygen, the C2H5OH/H2 plasma was beneficial to deposit high quality NCD films with smaller average grain size and lower surface roughness.     

A direct current glow discharge plasma source for inner surface modification of metallic tube

A dc glow discharge plasma source was developed for inner surface modification of metallic tubes with an inner diameter of 10 mm. A tungsten wire of 30 μm thick was stretched inside the tube to form coaxial electrodes. DC glow discharge plasma was generated inside the tube by applying a negative high dc voltage to the tube. It was found that the length of the cylindrical plasma bulk depends linearly on the applied voltage. The electron excitation temperature of Ar plasma was measured as 12830 ± 550 K by optical emission spectroscopy method. As a preliminary application, diamond-like carbon (DLC) films were deposited onto the inner surface of stainless steel tube of 100 mm in length and 10 mm in inner diameter by using CH₄/Ar mixture with 40% CH₄ at 40 Pa pressure. The chemical structure of the DLC film deposited on the substrate was analyzed by Raman spectroscopy. The integrated intensity ratio (I_D:I_G) was obtained as 1.62 from the Raman spectra. The thickness of the DLC film deposited on the substrate was estimated as 1.5 μm by scanning electron microscopy (SEM) observation.