DIAMOND FILMS DEPOSITED AT LOW TEMPERATURES MICROWAVE PLASMA-ASSISTED CVD METHOD

Low-temperature deposition of diamond thin films in the range of 280￣445℃ has been successfully carried out by microwave plasma-assisted CVD method.At lower deposition temperatures (280￣445℃),the large increase in the nucleation density and great improvement in the average surfae roughness of the diamond were observed. Results of low temperature deposition and characterization of diamond thin films obtained are presented.

Microwave Plasma Chemical Vapor Deposition of Diamond Films on Silicon From Ethanol and Hydrogen

Diamond films with very smooth surface and good optical quality have been deposited onto silicon substrate using microwave plasma chemical vapor deposition (MPCVD) from a gas mixture of ethanol and hydrogen at a low substrate temperature of 450 ℃. The effects of the substrate temperature on the diamond nucleation and the morphology of the diamond film have been investigated and observed with scanning electron microscopy (SEM). The microstructure and the phase of the film have been characterized using Raman spectroscopy and X-ray diffraction (XRD). The diamond nucleation density significantly decreases with the increasing of the substrate temperature. There are only sparse nuclei when the substrate temperature is higher than 800 ℃ although the ethanol concentration in hydrogen is very high. That the characteristic diamond peak in the Raman spectrum of a diamond film prepared at a low substrate temperature of 450 ℃ extends into broadband indicates that the film is of nanophase. No graphite peak appeared in the XRD pattern confirms that the film is mainly composed of SP3 carbon. The diamond peak in the XRD pattern also broadens due to the nanocrystalline of the film.

Preparation and Characterization of High Quality Diamond Films by DC ArcPlasma Jet CVD Method

Under optimal conditions free-standing high quality diamond films were prepared by DC arc plasma jet CVD method at a growth rate of 7-10 Pm/h. Surface and cross section morphologies of the diamond films were observed by SEM. Raman spectrometer wasused to characterize the quality of diamond films. The IR transmittivity measured by IR spectrometer is close to the theoretical value ofabout 71% in the far infrared band. The thermal conductivity measured by photothermal deflection exceeds 18 W/cm' K. <l 10> is thepreferential growth orientation of the films detected by X-ray diffractometer. As s result, the extremely high temperature of DC arc plasma jet can produce supersaturated atomic hydrogen, which played an important role in the process for the deposition of high quality diamond films.

Cytotoxicity of Boron-Doped Nanocrystalline Diamond Films Prepared by Microwave Plasma Chemical Vapor Deposition

Boron-doped nanocrystalline diamond（NCD） exhibits extraordinary mechanical properties and chemical stability,making it highly suitable for biomedical applications.For implant materials,the impact of boron-doped NCD films on the character of cell growth（i.e.,adhesion,proliferation） is very important.Boron-doped NCD films with resistivity of 10-2Ω·cm were grown on Si substrates by the microwave plasma chemical vapor deposition（MPCVD） process with H2 bubbled B2O3.The crystal structure,diamond character,surface morphology,and surface roughness of the boron-doped NCD films were analyzed using different characterization methods,such as X-ray diffraction（XRD）,Raman spectroscopy,scanning electron microscopy（SEM） and atomic force microscopy（AFM）.The contact potential difference and possible boron distribution within the film were studied with a scanning kelvin force microscope（SKFM）.The cytotoxicity of films was studied by in vitro tests,including fluorescence microscopy,SEM and MTT assay.Results indicated that the surface roughness value of NCD films was 56.6 nm and boron was probably accumulated at the boundaries between diamond agglomerates.MG-63 cells adhered well and exhibited a significant growth on the surface of films,suggesting that the boron-doped NCD films were non-toxic to cells.

Preparation of Nano-Crystalline Diamond Films on Poly-Crystalline Diamond Thick Films by Microwave Plasma Enhanced Chemical Vapor Deposition

Nano-crystalline diamond （NCD） films were prepared on poly-crystalline diamond （PCD） thick flims by the microwave plasma enhanced chemical vapor deposition （MPCVD） method. Free standing PCD thick film （50 mm in diameter） with a thickness of 413 μm was deposited in CHn/H2 plasma. It was then abraded for 2 hours and finally cut into pieces in a size of 10×10 mm^2 by pulse laser. NCD fihns were deposited on the thick film substrates by introducing a micro-crystalline diamond （MCD） interlayer. Results showed that a higher carbon concentration （5%） and a lower substrate temperature （650℃） were feasible to obtain a highly smooth interlayer, and the appropriate addition of oxygen （2%） into the gas mixture was conducive to obtaining a smooth nano-crystalline diamond film with a tiny grain size.

Fabrication and Characterization of FeNiCr Matrix-TiC Composite for Polishing CVD Diamond Film

Dynamic friction polishing （DFP） is one of the most promising methods appropriate for polishing CVD diamond film with high efficiency and low cost. By this method CVD diamond film is polished through being simply pressed against a metal disc rotating at a high speed utilizing the thermochemical reaction occurring as a result of dynamic friction between them in the atmosphere. However, the relatively soft materials such as stainless steel, cast iron and nickel alloy widely used for polishing CVD diamond film are easy to wear and adhere to diamond film surface, which may further lead to low efficiency and poor polishing quality. In this paper, FeNiCr matrix-TiC composite used as grinding wheel for polishing CVD diamond film was obtained by combination of mechanical alloying （MA） and spark plasma sintering （SPS）. The process of ball milling, composition, density, hardness, high-temperature oxidation resistance and wear resistance of the sintered piece were analyzed. The results show that TiC was introduced in MA-SPS process and had good combination with FeNiCr matrix and even distribution in the matrix. The density of composite can be improved by mechanical alloying. The FeNiCr matrix-TiC composite obtained at 1273 K was found to be superior to at 1173 K sinterin8 in hardness, high-temperature oxidation resistance and wearability. These properties are more favorable than SUS304 for the preparation of high-performance grinding wheel for polishing CVD diamond film.

Edge effect during microwave plasma chemical vapor deposition diamond-film:Multiphysics simulation and experimental verification

This study focused on the investigation of the edge effect of diamond films deposited by microwave plasma chemical vapor de-position.Substrate bulge height△h is a factor that affects the edge effect,and it was used to simulate plasma and guide the diamond-film deposition experiments.Finite-element software COMSOL Multiphysics was used to construct a multiphysics(electromagnetic,plasma,and fluid heat transfer fields)coupling model based on electron collision reaction.Raman spectroscopy and scanning electron microscopy were performed to characterize the experimental growth and validate the model.The simulation results reflected the experimental trends observed.Plasma discharge at the edge of the substrate accelerated due to the increase in△h(△h=0-3 mm),and the values of electron density(n_(c)),molar concentration of H(C_(H)),and molar concentration of CH_(3)(C_(CH_(3)))doubled at the edge(for the special concave sample with△h=−1 mm,the active chemical groups exhibited a decreased molar concentration at the edge of the substrate).At=0-3 mm,a high diamond growth rate and a large diamond grain size were observed at the edge of the substrate,and their values increased with.The uniformity of film thickness decreased with.The Raman spectra of all samples revealed the first-order characteristic peak of dia-mond near 1332 cm^(−1).When△h=−1 mm,tensile stress occurred in all regions of the film.When△h=1-3 mm,all areas in the film ex-hibited compressive stress.

Nanocrystalline Diamond Films Grown by Microwave Plasma Chemical Vapor Deposition and Its Biocompatible Property

Due to its unique properties such as high hardness, light transmittance, thermal conductance, chemical stability and corrosion resistance, diamond has drawn tremendous attention in last two decades. These specific properties made diamond film a promising material for cutting tools, microwave windows, heat sinks for electronic devices and diamond electrodes. However, the diamond film with grain sizes at microscale usually exhibits high surface roughness and hinders its applications in the microelectro mechanical system (MEMS) and biological field because it is difficult to be polished by mechanical and chemical methods. With the development of the chemical vapor deposition, the nanocrystalline diamond (NCD) film has been fabricated and found new applications. The grain size of NCD film is in the range of 10 to 100 nm, which inherits the properties of the diamond and possesses the unique properties of the nanoscale materials, and the morphology of the NCD film is granular or needle-like structure. The microwave plasma chemical vapor deposition (MPCVD) has been regarded as the most promising method to deposit NCD film at low temperature. Compared to the hot filament CVD, MPCVD can grow high quality NCD film avoiding of the contamination from the filament materials. The MPCVD technique has high plasma density to activate carbonaceous compound and grow NCD film in high growth rate and low substrate temperature. The unique properties of NCD film, such as the superior electrical, mechanical and biological properties facilitate their application in various fields. The biological application, especially as a biocompatible coating, mainly includes the joint replacement implants and protective coatings and the ophthalmological prosthesis.

OES study of the gas phase during diamond films deposition in high power DC arc plasma jet CVD system

This paper used optical emission spectroscopy （OES） to study the gas phase in high power DC arc plasma jet chemical vapour deposition （CVD） during diamond films growth processes. The results show that all the deposition parameters （methane concentration, substrate temperature, gas flow rate and ratio of H2/Ar） could strongly influence the gas phase. C2 is found to be the most sensitive radical to deposition parameters among the radicals in gas phase. Spatially resolved OES implies that a relative high concentration of atomic H exists near the substrate surface, which is beneficial for diamond film growth. The relatively high concentrations of C2 and CH are correlated with high deposition rate of diamond. In our high deposition rate system, C2 is presumed to be the main growth radical, and CH is also believed to contribute the diamond deposition.

Growth of mirror-like ultra-nanocrystalline diamond(UNCD)films by a facile hybrid CVD approach

In this study, growth of mirror-like ultra-nanocrystalline diamond（UNCD） films by a facile hybrid CVD approach was presented. The nucleation and deposition of UNCD films were conducted in microwave plasma CVD（MPCVD） and direct current glow discharge CVD（DC GD CVD） on silicon substrates, respectively. A very high nucleation density（about 1×10^11 nuclei cm^-2） was obtained after plasma pretreatment. Furthermore, large area mirrorlike UNCD films of Φ 50 mm were synthesized by DC GD CVD. The thickness and grain size of the UNCD films are 24 μm and 7.1 nm, respectively. In addition, the deposition mechanism of the UNCD films was discussed.

Study on the Dielectric Properties of Chemical Vapor Deposited Diamond Film

Aim To study the dielectric properties of diamond film. Methods Dielectric properties (the frequency dependenCe of conductance, permittivity, and loss factor) of diamond film preped by DC are plasma jet chemical vapor deposition (CVD) were studied. Resuls Dielectric properties of CVD diamond fAn depend mainly on its polycrystalline nature, and the presence of non-diamond disordered graphitic regions and impurities between diamond grains of the film. Annealing at 500℃ leads to the removal of greater part of disordered graphitic regions, but am not remove all disordered graphitic regions and impurities. Conclusion Much work nab to be done tO prepare or post-treat diamond films before using CVD diamond as a substrate for electronic devices.

Effects of Surface Pretreatment on Nucleation and Growth of Ultra-Nanocrystalline Diamond Films

The effects of different surface pretreatment nmthods on the nucleation and growth of ultra-nanocrystalline diamond （UNCD） fihns grown from focused microwave Ar/CHa/H2 （argon- rich） plasma were systematically studied. The surface roughness, nucleation density, mierostruc- ture, and crystallinity of the obtained UNCD films were characterized by atomic force microscope （AFM）, scanning electron microscopy （SEM）, X-ray diffraction （XRD）, and Raman spectroscopy. The results indicate that the nucleation enhancement was found to be sensitive to the different sur- face pretreatment methods, and a higher initial nucleation density leads to highly smooth UNCD films. When the silicon substrate was pretreated by a two-step method, i.e., plasma treatment followed by ultrasonic vibration with diamond nanopowder, the grain size of the UNCD films was greatly decreased： about 7.5 nm can be achieved. In addition, the grain size of UNCD films depends on the substrate pretreatment methods and roughness, which indicates that the surface of substrate profile has a ＂genetic characteristic＂.

Preparation and characterization of nano-crystalline diamond films on glass substrate

Adherent nano diamond films were successfully deposited on glass substrate bymicrowave plasma assisted CVD method in H_2-CH_4 and Ar-CH_4 environment. Raman, AFM (Atomic ForceMicroscope), TEM (Transmission Electron Microscope), FTIR, and Nano Indentation techniques were usedfor characterization of the obtained nano diamond films. It was found that the average grain sizewas less than 100 nm with a surface roughness value as low as 2 nm. The nano diamond films werefound to have excellent transparency in visible and IR spectrum range, and were as hard as naturaldiamond. Experimental results were presented. Mechanisms for nano diamond film deposition werediscussed.

Effects of deposition parameters on microstructure and thermal conductivity of diamond films deposited by DC arc plasma jet chemical vapor deposition

The uniform diamond films with 60 mm in diameter were deposited by improved DC arc plasma jet chemical vapor deposition technique. The structure of the film was characterized by scanning electronic microcopy(SEM) and laser Raman spectrometry. The thermal conductivity was measured by a photo thermal deflection technique. The effects of main deposition parameters on microstructure and thermal conductivity of the films were investigated. The results show that high thermal conductivity, 10.0 W/(K·cm), can be obtained at a CH4 concentration of 1.5% (volume fraction) and the substrate temperatures of 880-920 ℃ due to the high density and high purity of the film. A low pressure difference between nozzle and vacuum chamber is also beneficial to the high thermal conductivity.

Growth behavior of CVD diamond films with enhanced electron field emission properties over a wide range of experimental parameters

In this study, diamond films were synthesized on silicon substrates by microwave plasma enhanced chemical vapor deposition（CVD） over a wide range of experimental parameters. The effects of the microwave power,CH;/H;ratio and gas pressure on the morphology, growth rate, composition, and quality of diamond films were investigated by means of scanning electron microscope（SEM）, X-ray diffraction（XRD）, Raman spectroscopy and X-ray photoelectron spectroscopy（XPS）. A rise of microwave power can lead to an increasing pyrolysis of hydrogen and methane, so that the microcrystalline diamond film could be synthesized at low CH;/H;levels. Gas pressure has similar effect in changing the morphology of diamond films, and high gas pressure also results in dramatically increased grain size. However,diamond film is deteriorated at high CH;/H;ratio due to the abundant graphite content including in the films. Under an extreme condition of high microwave power of 10 kW and high CH;concentration, a hybrid film composed of diamond/graphite was successfully formed in the absence of N;or Ar,which is different from other reports. This composite structure has an excellent measured sheet resistance of 10-100 Ω/Sqr. which allows it to be utilized as field electron emitter. The diamond/graphite hybrid nanostructure displays excellent electron field emission（EFE） properties with a low turn-on field of 2.17 V/μm and β= 3160, therefore it could be a promising alternative in field emission applications.

THE EFFECT OF DIAMOND FILM NUCLEATION AND GROWTH IN DIFFERENT SUBSTRATE PRETREATMENT METHODS

The diamond film on single crystal silicon substrate in threekinds of substrate is deposited by pre- treatment method usingmicrowave plasma, the diamond film is analyzed using SEM and Raman,the reasons why substrate pretreatment affects nucleation and growthare probed. The results show that substrate pretreatment di- rectlyaffects nucleation and growth of diamond film, ho- mogeneousnucleation and growth can be formed only in suitable pretreatmentmethod.

Growth of Free-Standing Diamond Films on Stainless Steel

Free-standing diamond films have been successfully deposited on stainless steel substrates using microwave plasma-assisted chemical vapor deposition. Although iron, which is the main element of stainless steel, is known to inhibit the nucleation of diamond and enhance the formation of graphite, we were able to grow relatively thick films （-1.2 mm）. The films were easily detachable from the substrates. The poor adhesion made it possible to obtain free-standing diamond films without chemical etching. Raman spectroscopy showed the 1332 cm^-1 characteristic Raman peak of diamond and the 1580 cm^-1, 1350 cm^-1 bands of graphite on the growth surface and backside of the films, respectively. By energy dispersive X-ray spectroscopy it was only possible to detect iron on the back of the films, but not on the surface. The role of iron in the film growth is discussed.

采用DC Arc Plasma JetCVD方法沉积微/纳米复合自支撑金刚石膜

在30kW级直流电弧等离子体喷射化学气相沉积(DC Arc P lasm a Jet CVD)设备上,采用Ar-H2-CH4混合气体,通过调节甲烷浓度以及控制其他沉积参数,在Mo衬底上沉积出微/纳米复合自支撑金刚石膜。实验表明,当微米金刚石膜层沉积结束后,在随后的沉积中,随着甲烷浓度的增加,金刚石膜表面的晶粒大小是逐渐减小的。当甲烷浓度达到20%以上时,金刚石膜生长面晶粒呈现菜花状的小晶团,膜体侧面已经没有了粗大的柱状晶,而是呈现出光滑的断口,对该层进行拉曼谱分析显示,位于1145 cm-1附近有一定强度的散射峰出现。这说明所沉积的晶粒全部变为纳米级尺寸。

Effect of Seed Size, Suspension Recycling and Substrate Pre-Treatment on the CVD Growth of Diamond Coatings

CVD growth of uniform conformal polycrystalline diamond (PCD) coatings over complex three dimensional structures is very important material processing technique. It has been found that the nucleation and subsequent growth period is very critical for successful development of CVD diamond based technologies. There are many methods of enhancing diamond nucleation on foreign substrates-ultrasonic treatment with diamond seed suspension being the best among them. A combination of ultrasonic seeding (US) technique with prior treatment (PT) of the substrate under CVD diamond growth conditions for brief period of time, has found to be very effective in enhancing the diamond nucleation during CVD growth—together they are known as NNP. But successive usage of the same seeding suspension up to ten cycles deteriorates the seeding efficiency. 6th seeding cycle onwards the silicon substrates are barely get covered by diamond crystallites. Five different diamond micron grits were used for seeding the silicon substrates and it is observed that US with the sub-micron particles (0.25 μm) is very effective in efficient nucleation of PCD on Si substrates. PT of the substrate somewhat negates the effect of successive use of the same seeding slurry but it is best to avoid recycling of the same seeding suspension using micron size diamond grits.

线形同轴耦合式微波等离子体CVD法制备金刚石薄膜

线形同轴耦合式微波等离子体CVD装置是一种利用微波天线产生轴向分布的等离子体柱的新型微波等离子体CVD装置。由于它产生的等离子体是沿微波天线分布的 ,因而可避免石英管式、石英钟罩式以及不锈钢谐振腔式微波等离子体CVD装置中等离子体的分布容易受到金属工件位置干扰的缺点。本文将首先讨论线形同轴耦合式微波等离子体CVD装置的工作原理 ,其后介绍利用此装置进行的金刚石薄膜沉积实验的初步结果。实验结果表明 ,利用线形同轴耦合式微波等离子体CVD装置 。