Synthesis of diamond hexagonal nanoplatelets by microwave plasma chemical vapor deposition

Variation of diamond deposition with temperature gradient was studied using standing-up substrates embedded within the plasma ball in microwave plasma chemical vapor deposition (MPCVD). The substrate is a polycrystalline diamond coated with a 30-nm thick iron film before deposition. Surface morphologies of the deposits and their crystalline characteristics were characterized by scanning electron microscopy, transmission electron microscopy (TEM), and selected area diffraction. On the upper area of the specimen near the center of the plasma ball where the temperature is the highest (>1100 °C), formation of diamond nanoplatelets in hexagonal shape with a thickness of 20–60 nm and side length of several hundreds of nanometers is found. In the middle region, diamond nanoplatelets with some iron nanoparticles are observed. Around the bottom region with low temperature near the edge of the plasma ball, nanodiamonds, Fe nanoparticles, and carbon nanotubes coexisted. The relative temperature distributions of diamond and carbon nanotube growth are briefly discussed.     

Nucleation of diamond films by ECR-enhanced microwave plasma chemical vapor deposition

A novel nucleation technique based on electron cyclotron resonance microwave plasma was developed to enhance the nucleation of diamond. By choosing a suitable experimental condition, a nucleation density higher than 10⁸ nuclei cm⁻² was achieved on an untreated, mirror-polished silicon substrate. Uniform diamond films were obtained by combining this nucleation method with subsequent growth by the common microwave plasma chemical vapor deposition. Furthermore, the possibility of this new nucleation method to generate heteroepitaxial diamond nuclei on (001) silicon substrates was explored.     

Biased enhanced growth of nanocrystalline diamond films by microwave plasma chemical vapor deposition

Smooth nanocrystalline diamond thin films with rms surface roughness of ∼17 nm were grown on silicon substrates at 600°C using biased enhanced growth (BEG) in microwave plasma chemical vapor deposition (MPCVD). The evidence of nanocrystallinity, smoothness and purity was obtained by characterizing the samples with a combination of Raman spectroscopy, X-ray diffraction (XRD), atomic force microscopy and Auger electron spectroscopy. The Raman spectra of the films exhibit an intense band near 1150 cm⁻¹ along with graphitic bands. The former Raman band indicates the presence of nanocrystalline diamond. XRD patterns of the films show broad peaks corresponding to inter-planar spacing of (111) and (220) planes of cubic diamond supporting the Raman results. Auger line shapes closely match with the line shape of diamond suggesting high concentration of sp³ carbon on the surfaces of the films. The growth of dominantly sp³ carbon by BEG in the MPCVD system at the conditions used in the present work can be explained by the subsurface implantation mechanism while considering some additional effects from the high concentration of atomic hydrogen in the system.     

Synthesis of boron-doped homoepitaxial single crystal diamond by microwave plasma chemical vapor deposition

The deposition of boron-doped homoepitaxial single crystal diamond is investigated using a microwave plasma-assisted chemical vapor deposition system. The objective is to deposit high-quality boron-doped single crystal diamond and establish the relationships between the deposition conditions and the diamond growth rate and quality. Experiments are performed using type Ib HPHT diamond seeds as substrates and growing diamond with varying amounts of diborane in a methane–hydrogen gas mixture. The deposition system utilized is a 2.45 GHz microwave plasma-assisted CVD system operating at 135–160 Torr. Experiments are performed with methane concentrations of 4–6% and diborane concentrations of 5–50 ppm in the feedgas. Diamond is deposited with growth rates of 2 to 11 µm/h in this study. The deposited diamond is measured to determine its electrical conductivity and optical absorption versus wavelength in the UV, visible and IR portions of the spectrum. Data is presented that relates the growth rate and diamond properties to the deposition conditions including substrate temperature and feedgas composition.     

Growth of nanocrystalline diamond films by biased enhanced microwave plasma chemical vapor deposition

Nanocrystalline diamond (NCD) films were grown using biased enhanced growth (BEG) in microwave plasma chemical vapor deposition on mirror polished silicon substrates at temperatures in the range from 400 to 700°C. The films were characterized by Raman spectroscopy, X-ray diffraction (XRD), Auger electron spectroscopy and atomic force microscopy (AFM). Hardness of the films was measured by nano-indentor. Apart from graphitic D and G bands in the films, the Raman spectra exhibit NCD features near 1140 cm⁻¹. The relative intensity of the NCD to graphitic G band in the Raman spectra of the films is negligible in the films grown at 400°C. It increases with temperature and attains a maximum at 600°C following a sharp decrease in the films grown at higher temperatures. XRD results also indicate a maximum concentration of NCD in the film grown at 600°C. Average hardness of the films increases with temperature from ∼5 GPa to ∼40 GPa up to 600°C followed by a decrease (∼24 GPa) in the film grown at 700°C. Substrate temperature seems to play a crucial role in the growth of NCD in BEG processes. An increase in growth temperature may be responsible for evolving bonded hydrogen and increasing mobility of carbon atoms. Both factors help in developing NCD in the films grown at 500 and 600°C with a combination of subplantation mechanism, due to biasing, and a high concentration of H atoms in the gas-phase, typical of CVD diamond process. At 700°C the implanted carbon atoms may be migrating back to the surface resulting in domination of surface processes in the growth, which in turn should result in increase in graphitic content of the films at such a high methane concentration and continuous biasing used in the present study.     

Deposition of thick boron-doped homoepitaxial single crystal diamond by microwave plasma chemical vapor deposition

The deposition of high quality single crystal boron-doped diamond is studied. The experimental conditions for the synthesis of 1–2 mm thick boron-doped diamond are investigated using a high power density microwave plasma-assisted chemical vapor deposition reactor. The boron-doped diamond is deposited at a rate of 8–11.5 μm/h using 1 ppm diborane in the feed gas as the boron source, and the capability to overgrow defects is demonstrated. The experimental study also investigates the deposition of diamond with both 10 ppm diborane and 2.5–500 ppm of nitrogen added to the feedgas. Synthesized material properties are measured including the electrical conductivity using a four-point probe and the substitutional boron content using infrared absorption.     

High compressive stress in nanocrystalline diamond films grown by microwave plasma chemical vapor deposition

Hard and smooth nanocrystalline diamond (NCD) thin films were deposited on mirror polished silicon substrates by biased enhanced growth in a microwave plasma chemical vapor deposition system. The films were characterized by Raman spectroscopy, X-ray diffraction and atomic force microscopy. Stress in the films was calculated by measuring the radius of curvature of the films on substrates and hardness was measured using a Nanoindenter. Stress in the films increases, first, with decreasing methane concentration in the gas phase while keeping biasing voltage constant, and second, with increasing biasing voltage while keeping the methane concentration constant. Observation of enormous stress (∼30 GPa) was possible in the films, which is due to strong adhesion between the films and substrates. To the best of our knowledge, this is the maximum value of stress reported so far in any kind of carbon thin films. It was hypothesized that it is mostly hydrogen content of the films in the methane series and graphitic content of the films in voltage series that are responsible in generating compressive stress in the respective films. The hardness follows almost a reverse trend than stress with the two growth parameters and can be well-defined from the relative concentration of NCD to graphitic content of the films, as estimated from Raman spectroscopy.     

Comparative study of diamond films grown on silicon substrate using microwave plasma chemical vapor deposition and hot-filament chemical vapor deposition technique

Diamond films on the p-type Si(111) and p-type(100) substrates were prepared by microwave plasma chemical vapor deposition (MWCVD) and hot-filament chemical vapor deposition (HFCVD) by using a mixture of methane CH₄ and hydrogen H₂ as gas feed. The structure and composition of the films have been investigated by X-ray Diffraction, Raman Spectroscopy and Scanning Electron Microscopy methods. A high quality diamond crystalline structure of the obtained films by using HFCVD method was confirmed by clear XRD-pattern. SEM images show that the prepared films are poly crystalline diamond films consisting of diamond single crystallites (111)-orientation perpendicular to the substrate. Diamond films grown on silicon substrates by using HFCVD show good quality diamond and fewer non-diamond components.     

Structural and optical properties of diamond and nano-diamond films grown by microwave plasma chemical vapor deposition

We compare structural and optical properties of microcrystalline and nanocrystalline diamond (MCD and NCD, respectively) films grown on mirror polished Si(100) substrates by microwave plasma chemical vapor deposition. The films were characterized by SEM, Raman spectroscopy, XRD, and AFM. Optical properties were obtained from transmittance and reflectance measurements of the samples in the wavelength range of 200–2000 nm. Raman spectrum of the MCD film exhibits a strong and sharp peak near 1335 cm⁻¹, an unambiguous signature of cubic crystalline diamond with weak non-diamond carbon bands. Along with broad non-diamond carbon bands, Raman spectra of NCD films show features near 1140 cm⁻¹, the intensity of which is significantly higher in the film grown at 600°C compared to the NCD film grown at higher temperature. The Raman feature near 1140 cm⁻¹ is related to the calculated phonon density of states of diamond and has been assigned to nanocrystalline or amorphous phase of diamond. XRD patterns of the MCD film show sharp peaks and NCD films show broad features, corresponding to cubic diamond. The rms surface roughness of the films was observed to be approximately 60 nm for MCD film that reduced substantially to 17 and 34 nm in the NCD films grown at 600 and 700°C, respectively. Tauc's optical gap for the diamond film is found to be approximately 5.5 eV. NCD grown at 700°C has a high optical absorption coefficient in the whole spectral region and the NCD film grown at 600°C shows very high transmittance (∼78%) in the near IR region, which is close to that of diamond. This indicates that the NCD film grown at 600°C has the potential for applications as optical windows since its surface roughness is significantly low as compared to the MCD film.     

Fabrication of SiC/diamond composite coatings by electrophoretic deposition and chemical vapor deposition

In this research, SiC/diamond composite coatings were fabricated by a novel procedure that consisted of the electrophoretic deposition (EPD) of diamond particles onto graphite substrates followed by chemical vapor deposition (CVD) of SiC. Various concentrations of MgCl₂ were employed to increase the deposition rate and uniformity of the deposits during the EPD process by giving a positive charge to diamond particles. The CVD of SiC was found to have a tightly connected diamond‐graphite interface and spherical texture. With higher weight fraction of diamond particles deposits, the wear of steel ball increased, while the wear of SiC coating decreased.     

Synthesis of single crystal diamond by microwave plasma assisted chemical vapor deposition with in situ low-coherence interferometric control of growth rate

We performed synthesis of single crystal (SC) diamond by microwave plasma chemical vapor deposition in methane-enriched H₂–CH₄ gas mixtures, and achieved growth rates more than 30 μm/h, without adding nitrogen in reaction mixture. A low-coherence interferometry (LCI) was employed for precise measurements of the thickness and growth rate of the epitaxial diamond layers in the course of the process. The performance of this in situ technique is demonstrated by continuously monitoring the SC diamond thickness in a single growth run upon variation of CH₄ percentage in steps, up to 17%, without switching off the plasma, to produce a “multilayer” diamond film. In addition, etching rate of diamond in pure hydrogen plasma has been evaluated with the same method. The LCI technique allows quick collection of growth kinetics data upon systematic variation of a selected process parameter for the growth optimization.     

Diamond-graphite nanorods produced by microwave plasma chemical vapor deposition

One dimensional C–C nanostructure, diamond–graphite nanorods, was synthesized by the argon rich microwave plasma chemical vapor deposition method. The nanostructures were characterized by scanning electron microscopy and transmission electron microscopy techniques. The diamond nanorods (DNRs) consist of single-crystalline diamond cores of 2–5 nm in diameter and several tens of nanometer in length. The DNRs are encapsulated in a graphitic shell of variable thickness. Raman and X-ray diffraction spectra also indicated the coexistence of diamond and graphite phases in the film. The addition of nitrogen is considered to be helpful for the highly efficient formation of graphite shell. The high content of methane in the gas mixture in the presence of argon rich environment is suggested to be responsible for the one dimensional growth.     

Numerical analyses of a microwave plasma chemical vapor deposition reactor for thick diamond syntheses

We have carried out simulations of microwave plasmas inside a reactor for thick diamond syntheses. In a model reactor used in the calculation, a diamond substrate with finite thickness and area is taken into account. Distributions of electric field, density of microwave power absorbed by the plasma, temperatures and flow field of gas have been studied not only in a bulk region inside a reactor but also a local region around the substrate surface. Numerically predicted distributions of (1) microwave power density, (2) temperature on the top surface of the substrate, and (3) gas flow around the substrate imply that the adopted arrangement of the substrate is not desirable for continuous growth of large diamond crystals.     

Some novel aspects of nanocrystalline diamond nucleation and growth by direct current plasma assisted chemical vapor deposition

Some novel aspects of nanocrystalline diamond (NCD) film nucleation and growth by DC-PACVD were investigated, which focused on the effect of methane injection timing at ramp stage (see discussion in the text) and cathode temperature as well. NCD films were deposited for 4 h on a 4 in. Si wafer which was ultrasonically seeded in a methanol slurry of diamond powder with a 5 nm average diameter. The H₂/CH₄/N₂ gas mixture with a composition of 96.7%/3%/0.3% was used as precursor gas. The total gas flow rate and chamber pressure were 150 sccm and 150 Torr, respectively. Discharge voltage and current of 500 V and 45 A were used respectively at a substrate temperature of 800 °C. The nucleation density, microstructure, growth rate and crystallinity of the obtained NCD films were characterized by SEM, XRD, NEXAFS and Raman spectroscopy. The nucleation density was found to be sensitive to methane injection timing in the ramp stage. In addition, the cathode temperature greatly affected the nucleation density, grain size and growth rate.     

DLC films by plasma assisted chemical vapor deposition near room temperature

This work concentrates on the preparation of diamond-like amorphous carbon films using a d.c. glow discharge with and without coupling to a microwave source. Films were deposited on single crystal silicon, glass and several plastics at temperatures between room temperature and 150°C. A variety of carbon containing feed gases have been used at pressures ranging from few milliTorrs to 1 Torr with an applied electric field up to 3300 V in⁻¹. The films obtained range from transparent to semi-transparent and can be very hard as observed by an ASTM scratch tester. The visible, IR and Raman spectra of the films have been obtained, and these are related to their structure and hardness. The DLC films grown on plastics were found to suffer from deformations due to the flexibility of the underlying material, and hence their performance was judged to be less than ideal despite the hardness of the overlying material. The results are discussed in terms of chemical composition and growth kinetics of the films.     

Heteroepitaxial diamond nucleation and growth on silicon by microwave plasma-enhanced chemical vapor deposition synthesis

Heteroepitaxial diamond films were successfully nucleated and deposited on 1-inch diameter Si(001) substrates by microwave plasma-enhanced chemical vapor deposition (MPECVD). The precursor gases for the synthesis were methane and hydrogen. Before the application of a negative d.c. bias to the substrate, an in-situ carburization pre-treatment on the silicon was found to be an indispensable step towards the heteroepitaxial diamond on the silicon. Morphologies of the films were characterized by scanning electron microscopy (SEM). Interface observations based on the cross-sectional HRTEM directly reveal the heteroepitaxial diamond nucleation phenomena in detail. No interlayers of silicon carbide and/or amorphous carbon phases were observed. Tilt and azimuthal misorientation angles between the heteroepitaxial diamond crystals and the substrate were determined by combining the Ewald sphere construction in the reciprocal lattice space and the selected area diffraction (SAD) patterns taken across the interface.     

Growth and characterization of diamond films on TiN/Si(100) by microwave plasma chemical vapor deposition

Polycrystalline diamond films were deposited on silicon (100) substrate by microwave plasma chemical vapor disposition (MPCVD) using ~ 300 nm thick <001> textured titanium nitride (TiN) films as buffer layer which were prepared by radio-frequency reactive sputtering. The diamond/TiN films were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy. The results show that no apparent change can be observed for the <100> oriented TiN buffer layers after MPCVD even with a negative bias voltage applied onto the substrates.     

A novel microwave plasma reactor with a unique structure for chemical vapor deposition of diamond films

With the aid of numerical simulation, a novel microwave plasma reactor for diamond films deposition has been designed. The new reactor possesses a unique structure, neither purely cylindrical nor purely ellipsoidal, but a combination of the both. In this paper, the design strategy of the new reactor together with a simple but reliable phenomenological simulation method will be described. Preliminary experiments show that uniform diamond films of high quality could be deposited using the new reactor, and the deposition rate of diamond films is typically about 3 μm/h at 6 kW input power level on a 2 inch diameter silicon substrate.