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.

Electron field emission characteristics of nano-catkin carbon films deposited by electron cyclotron resonance microwave plasma chemical vapour deposition

This paper reported that the nano-catkin carbon films were prepared on Si substrates by means of electron cyclotron resonance microwave plasma chemical vapour deposition in a hydrogen and methane mixture. The surface morphology and the structure of the fabricated films were characterized by using scanning electron microscopes and Raman spectroscopy, respectively. The stable field emission properties with a low threshold field of 5V/μm corresponding to a current density of about 1μA/cm^2 and a current density of 3.2mA/cm^2 at an electric field of 10V/μm were obtained from the carbon film deposited at CH4 concentration of 8%. The mechanism that the threshold field decreased with the increase of the CH4 concentration and the high emission current appeared at the high CH4 concentration was explained by using the Fowler-Nordheim theory.

Field emission characteristics of nano-sheet carbon films deposited by quartz-tube microwave plasma chemical vapour deposition

Nano-sheet carbon films are prepared on Si wafers by means of quartz-tube microwave plasma chemical vapour deposition （MPCVD） in a gas mixture of hydrogen and methane. The structure of the fabricated films is investigated by using field emission scanning electron microscope （FESEM） and Raman spectroscopy. These nano^carbon films are possessed of good field emission （FE） characteristics with a low threshold field of 2.6 V/μm and a high current density of 12.6 mA/cm^2 at an electric field of 9 V/μm. As the FE currents tend to be saturated in a high E region, no simple Fowler-Nordheim （F-N） model is applicable. A modified F N model considering statistic effects of FE tip structures and a space-charge-limited-current （SCLC） effect is applied successfully to explaining the FE data observed at low and high electric fields, respectively.

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.

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.

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.

SYNTHESIS OF PPCuPc FILM BY MICROWAVE PLASMA CHEMICAL VAPORIZATION DEPOSITION(MPCVD)

Using a low power microwave generator(W_(max)=100W) and a Surfatron discharge device, Plasma-polymerized copper phthalocyanine (PPCuPc) film was synthesised from monomer copper phthalocyanine(CuPc) by microwave plasma chemical vaporization deposition(MPCVD) with Ar as incorporation gas. The film was characterized by FTIR and ESCA. The role of dissociation of chemical bond in the polymerization process and the influence of substrate temperature and material on deposition were investigated in some detail.

Influence of oxygen on the growth of cubic boron nitride thin films by plasma-enhanced chemical vapour deposition

Cubic boron nitride thin films were deposited on silicon substrates by low-pressure inductively coupled plasmaenhanced chemical vapour deposition. It was found that the introduction of 02 into the deposition system suppresses both nucleation and growth of cubic boron nitride. At a B2H6 concentration of 2.5% during film deposition, the critical O2 concentration allowed for the nucleation of cubic boron nitride was found to be less than 1.4%, while that for the growth of cubic boron nitride was higher than 2.1%. Moreover, the infrared absorption peak observed at around 1230- 1280 cm^-1, frequently detected for cubic boron nitride films prepared using non-ultrahigh vacuum systems, appears to be due to the absorption of boron oxide, a contaminant formed as a result of the oxygen impurity. Therefore, the existence of trace oxygen contamination in boron nitride films can be evaluated qualitatively by this infrared absorption peak.

Diagnosis of gas phase near the substrate surface in diamond film deposition by high-power DC arc plasma jet CVD

Optical emission spectroscopy （OES） was used to study the gas phase composition near the substrate surface during diamond deposition by high-power DC arc plasma jet chemical vapor deposition （CVD）. C2 radical was determined as the main carbon radical in this plasma atmosphere. The deposition parameters, such as substrate temperature, anode-substrate distance, methane concentration, and gas flow rate, were inspected to find out the influence on the gas phase. A strong dependence of the concentrations and distribution of radicals on substrate temperature was confirmed by the design of experiments （DOE）. An explanation for this dependence could be that radicals near the substrate surface may have additional ionization or dissociation and also have recombination, or are consumed on the substrate surface where chemical reactions occur.

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.

Significant suppression of residual nitrogen incorporation in diamond film with a novel susceptor geometry employed in MPCVD

This work proposed to change the structure of the sample susceptor of the microwave plasma chemical vapor deposition(MPCVD)reaction chamber,that is,to introduce a small hole in the center of the susceptor to study its suppression effect on the incorporation of residual nitrogen in the MPCVD diamond film.By using COMSOL multiphysics software simulation,the plasma characteristics and the concentration of chemical reactants in the cylindrical cavity of MPCVD system were studied,including electric field intensity,electron number density,electron temperature,the concentrations of atomic hydrogen,methyl,and nitrogenous substances,etc.After introducing a small hole in the center of the molybdenum support susceptor,we found that no significant changes were found in the center area of the plasma,but the electron state in the plasma changed greatly on the surface above the susceptor.The electron number density was reduced by about 40%,while the electron temperature was reduced by about 0.02 eV,and the concentration of atomic nitrogen was decreased by about an order of magnitude.Moreover,we found that if a specific lower microwave input power is used,and a susceptor structure without the small hole is introduced,the change results similar to those in the surface area of the susceptor will be obtained,but the spatial distribution of electromagnetic field and reactant concentration will be changed.

Deposition and Boron Doping of Nano-Crystalline Diamond Thin Films on Poly-Crystalline Diamond Thick Films

Boron-doped nano-crystalline diamond （NCD） thin films have been successfully deposited on well-polished poly-crystalline diamond （PCD） thick films in a microwave plasma enhanced chemical vapor deposition （MPCVD） reactor for the first time. Different surface pretreatment techniques are carried out under different gas conditions （CH4, H2, Ar, and CH4/H2） to eliminate the effect of grain boundaries on the growth of a smooth NCD intrinsic layer. Well doped NCD films have been fabricated in CH4/H2/B2H6 plasma by varying the atomic ratio of B/C and the substrate temperature. Atomic force microscopy （AFM） results show that pretreatment in pure CH4 plasma at 1000℃ is most effective for NCD growth, while hydrogen containing plasma is harmful to the surface smoothness of NCD thin fihns. Doping research indicates that the optimum parameters for the boron-doping of high-quality NCD thin films are B/C=300 ppm （10-6） and 800℃.

Plasma Processing of Boron-Doped Nano-Crystalline Diamond Thin Film Fabricated on Poly-Crystalline Diamond Thick Film

Plasma treatments of boron-doped nano-crystalline diamond （NCD） thin films were carried out in order to improve their electrical properties of the films. Boron-doped NCD thin films were fabricated on well polished poly-crystalline diamond （PCD） thick films in a microwave plasma enhanced chemical vapor deposition （MPCVD） reactor, then they were processed in methane, ar- gon, hydrogen and B2H~ （0.1% diluted by H~） plasmas, respectively. Scanning electron microscopy （SEM） and atomic force microscope （AFM） results show that the surface morphology changed lit- tle during the 10 min treatment. Secondary ion mass spectroscopy （SIMS） results indicate that B2H6 plasma was efficient for increasing boron concentration in NCD films, while the carrier anal- yses demonstrates that CH4 plasma processing was effective to activate the dopants and resulted in good electrical properties.

Electroluminescence of double-doped diamond thin films

A new electroluminescence device is fabricated by microwave plasma chemical vapour deposition system and electron beam vapour deposition system. It is comprised of highly doped silicon/diamond/boron/nitrogen-doped diamond/indium tin oxide thin films. Effects of process parameters on morphologies and structures of the thin films are detected and analysed by scanning electron microscopy, Raman spectrometer and x-ray photoelectron spectrometer. A direct-current （DC） power supply is used to drive the electroluminescence device. The blue light emission with a luminance of 1.2 cd·m^-2 is observed from this double-doped diamond thin film electroluminescence device at an applied voltage of 105 V.

Pinhole defects in MPCVD diamond films

Diamond films were deposited in microwave plasma chemical vapor deposition (MPCVD) method on plain silicon substrates with (100) orientation. And the pinhole defects on them were investigated by optical microscopy and scanning electron microscopy (SEM). X-ray masks were fabricated with the films deposited by us. We found the pinhole defects in the film destroyed the gold absorber. The corrosion-resistance tests conducted in 30% KOH solution under 80℃showed that the diamond films with pinhole defects have lower corrosion-resistance. In addition, the possible mechanism of the formation of pinhole defects in diamond films was discussed. And we deduced that the defects on substrates, competitive growth of multi-phase in diamond films, lattice dislocation between substrates and diamond films could be associated with the defect formation.

Toughness enhancement of single-crystal diamond by the homoepitaxial growth of periodic nitrogen-doped nano-multilayers

Periodic nitrogen-doped homoepitaxial nano-multilayers were grown by microwave plasma chemical vapor deposition. The residual time of gases(such as CH4and N2) in the chamber was determined by optical emission spectroscopy to determine the nano-multilayer growth process, and thin, nanoscale nitrogen-doped layers were obtained. The highest toughness of 18.2 MPa·m^(1/2)under a Young’s modulus of1000 GPa is obtained when the single-layer thickness of periodic nitrogen-doped nano-multilayers is about 96 nm. The fracture toughness of periodic nitrogen-doped CVD layer is about 2.1 times that of the HPHT seed substrate. Alternating tensile and compressive stresses are derived from periodic nitrogen doping;hence, the fracture toughness is significantly improved. Single-crystal diamond with a high toughness demonstrates wide application prospects for high-pressure anvils and single-point diamond cutting tools.

Study of relationship between structure and transmittance of diamond-like carbon (DLC) films

In this paper, the transparent hard diamond-like carbon (DLC) films were deposited on glass substrate by magnetic confined radio-frequency plasma chemical vapor deposition. The structure of films was studied by Raman spectra and X-ray photoelectron spectra (XPS), the transmittance of films by Spectrophotometer. The mechanism of the influence of films structure on transmittance of the films was discussed. The results show that the thickness of films was lower than 100nm, and the transmittance was over 90% in 380-780 nm region. Discussion in theory on the influence of film structure on transmittance was correspondence to experiment results.

SiC基GaN上多晶金刚石散热膜生长及其影响

通过微波等离子体化学气相沉积(MPCVD)法,在SiC基GaN高电子迁移率晶体管(HEMT)异质结构材料上生长多晶金刚石散热膜,采用光学显微镜(OM)、拉曼光谱、非接触霍尔测试系统、X射线衍射(XRD)和扫描电子显微镜(SEM)对生长样品进行表征,研究了生长温度、多晶金刚石散热膜厚度对GaN HEMT异质结构材料性能的影响。测试结果表明,当多晶金刚石生长温度为625℃,散热膜厚度为20μm时,GaN材料载流子迁移率降低9.8%,载流子浓度上升5.3%,(002)衍射峰半高宽增加40%。生长温度越高,金刚石散热膜的生长速率越快。当金刚石散热膜厚度相差不大时,生长温度越高,GaN所受拉应力越大,材料电特性衰退越明显。多晶金刚石高温生长过程中,金刚石引入的应力未对GaN结构产生破坏作用,GaN材料中没有出现孔洞等缺陷。

氮硅共掺对类金刚石薄膜组织及性能影响

为了研究不同掺杂元素对类金刚石(DLC)薄膜改性的协同影响,利用等离子体增强化学气相沉积技术在2024铝合金表面制备N、Si共掺的DLC薄膜,研究N_(2)与TMS流量比对N/Si-DLC薄膜结构和性能的影响规律及相应机制。结果表明,随着N_(2)与TMS流量比值在一定范围内增大,N/Si-DLC薄膜与基体结合强度、硬度及弹性模量逐渐升高,但当N_(2)与TMS流量比继续增加后薄膜的力学性能反而出现下降趋势。N_(2)与TMS流量比为30∶30时,薄膜具有最高的硬度和弹性模量,分别为11.58 GPa和108.4 GPa。同时,N/Si-DLC薄膜耐蚀性能随N_(2)与TMS流量比值增大先升高后降低。N_(2)与TMS流量比为30∶30时,薄膜较致密,缺陷较少,耐腐蚀性能较好。