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.     

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.     

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.     

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.     

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.     

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.     

Mechanical properties of nanocrystalline diamond/amorphous carbon composite films prepared by microwave plasma chemical vapour deposition

Nanocrystalline diamond films (NCD) have been deposited by microwave plasma chemical vapour deposition from CH₄/N₂ mixtures with varying methane content. They consist of diamond nanocrystallites with sizes of 3–5 nm embedded in an amorphous matrix with grain boundary widths of 1–1.5 nm. The CH₄ content in the gas phase has almost no influence on the microscopic structure but a strong effect on the macroscopic structure and morphology. The mechanical and tribological properties of these films have been investigated by nanoindentation, nano tribo tests, and nano scratch tests. The hardness of a 4-μm-thick film deposited with 17% methane was about 40 GPa, the indentation modulus 387 GPa, and the elastic recovery 75%. Ball-on-disk tests against an Al₂O₃ ball revealed, after initially higher values, a friction coefficient of ≤0.1. Tribo tests and scratch tests proved a strong adhesion and a protective effect on silicon substrates. Finally, the correlations between the macroscopic structure of the films and their mechanical and tribological properties are discussed.     

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.     

Doping of vanadium to nanocrystalline diamond films by hot filament chemical vapor deposition

Doping an impure element with a larger atomic volume into crystalline structure of buck crystals is normally blocked because the rigid crystalline structure could not tolerate a larger distortion. However, this difficulty may be weakened for nanocrystalline structures. Diamonds, as well as many semiconductors, have a difficulty in effective doping. Theoretical calculations carried out by DFT indicate that vanadium (V) is a dopant element for the n-type diamond semiconductor, and their several donor state levels are distributed between the conduction band and middle bandgap position in the V-doped band structure of diamond. Experimental investigation of doping vanadium into nanocrystalline diamond films (NDFs) was first attempted by hot filament chemical vapor deposition technique. Acetone/H₂ gas mixtures and vanadium oxytripropoxide (VO(OCH₂CH₂CH₃)₃) solutions of acetone with V and C elemental ratios of 1:5,000, 1:2,000, and 1:1,000 were used as carbon and vanadium sources, respectively. The resistivity of the V-doped NDFs decreased two orders with the increasing V/C ratios.     

Growth of microcrystalline and nanocrystalline diamond films by microwave plasmas in a gas mixture of 1% methane/5% hydrogen/94% argon

Well-faceted microcrystalline diamond (MCD) films were deposited along with nanocrystalline diamond (NCD) films on the same substrate by a microwave plasma in the gas mixture of 1% CH₄+5% H₂+94% Ar. This was achieved by forcing a microwave plasma ball generated at 170 torr gas pressure to touch a silicon substrate that was pre-seeded by nanocrystalline diamond powder resulting in a high concentration of atomic hydrogen on the surface of growing diamond. Previously reported compositional mapping of the argon–methane–hydrogen system for MCD and NCD growth was not valid in this process parameter space. The non-uniform concentrations of atomic hydrogen and carbon containing radicals such as C₂ as well as varied local substrate temperature resulted in the simultaneous deposition of well-faceted MCD films in some areas with nanograined NCD films in others. Dilution of methane/hydrogen microwave plasmas by as much as 94% of argon alone could not suppress the growth of MCD.     

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.     

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.     

Fracture mechanics of microcrystalline/nanocrystalline composited multilayer chemical vapor deposition self-standing diamond films

Though microwave plasma chemical vapor deposition (MPCVD) diamond films exhibit extraordinary strength, the toughness improvement is still a huge challenge. The catastrophic fracture of the diamond films is undesirable in many applications, especially for the application of fabricating cutting tools. In the present study, adopting the pre-notched and unnotched cantilever bending tests, fracture behaviors of monolayer microcrystalline diamond (m-M), monolayer nanocrystalline diamond (m-N), and microcrystalline/nanocrystalline composited multilayer diamond films were observed and compared. Typical fracture mechanics, including Young's modulus (E), fracture strength (${\sigma }_F$), and fracture toughness (K_IC) of different diamond films were investigated. Effects of diamond crystal structure, intrinsic stress, and tensile-side roughness were systematically analyzed. Grain size and graphite phase content dominated the E of self-standing diamond films. Tensive-side surface roughness and intergranular bonding strength affected the ${\sigma }_F$. When the growth side in tension, E of the multilayer film (modulation period Λ = 3 h) was 16.0% lower than m-M and 26.6% higher than m-N, ${\sigma }_F$ of multilayer film was 16.8% higher than m-M and 8.3% lower than m-N. At fixed Λ, doubling the total deposition period, E, ${\sigma }_F$, and K_IC of the multilayer film increased 72.3%, 22.3%, and 2.7%, respectively. MCD/NCD composited multilayer architecture presented significant strengthening and toughening effects on self-standing diamond films.     

Microwave plasma enhanced chemical vapor deposition of diamond in silicon pores

In this work, the feasibility of growing boron-doped diamond coatings, approximately 0.3 μm thick, on thin silicon substrates that have 50-μm diameter pores etched 125 μm deep has been demonstrated using deep reactive ion etching (DRIE) in combination with chemical–mechanical polishing (CMP). Using a microwave plasma enhanced chemical vapor deposition (MPECVD) cyclic growth process consisting of carburization, bias-enhanced nucleation, diamond growth and boron-doped diamond growth, uniform diamond coatings throughout the pores have been obtained. The coatings were characterized by Raman spectroscopy and scanning electron microscopy and the secondary electron emission coefficients were found to increase from 4 to 10 between 200 and 1000 V, in agreement with reported values for thicker polycrystalline diamond films grown under similar conditions.     

Synthesis of nanocrystalline diamond films by DC plasma-assisted argon-rich hot filament chemical vapor deposition

Continuous nanocrystalline diamond (NCD) films were grown in an argon-rich gas atmosphere with relatively high growth rates by sustaining a low power (5 W) DC plasma in a hot filament chemical vapor deposition system (HFCVD). The parameter window for the synthesis of NCD films was studied as a function of argon, methane and hydrogen concentrations, as well as substrate temperature and DC bias. The results are consistent with reports indicating that the DC plasma induces re-nucleation by ion bombardment during the initial growth step and helps to maintain the atomic H and hydrocarbon species near the growing surface. It was found that DC plasma-assisted HFCVD enables high NCD growth rates and expands the parameter window, rendering it unnecessary to heat the filament above 2800 K.     

Structure of copolymer films created by plasma enhanced chemical vapor deposition

The interface structure in copolymer films made using plasma enhanced chemical vapor deposition (PECVD) has been probed for the first time using X-ray reflectivity. Copolymer films made from comonomers benzene (B), octafluorocyclobutane (OFCB), and hexamethyldisiloxane (HMDS) show extremely sharp interfaces and scattering length density depth profiles that are uniform with depth, making them useful for optical applications. The polymer/air interface has an rms roughness (∼5 Å) that is only slightly larger than that of the supporting substrate (∼3 Å). Addition of either benzene or HMDS as a comonomer in the deposition of OFCB alters a transient deposition behavior at the silicon oxide interface that occurs when using only OFCB. For the B-OFCB copolymer films, a facile control of refractive index with monomer feed composition is achieved. A nonlinear variation in the X-ray scattering length density with composition for the HMDS-OFCB copolymer films is consistent with the nonlinear visible light refractive index (632.8 nm) variation reported earlier.     

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 graphene on Cu by plasma enhanced chemical vapor deposition

The growth of graphene on Cu substrates by plasma enhanced chemical vapor deposition (PE-CVD) was investigated and its growth mechanism was discussed. At a substrate temperature of 500 °C, formation of graphene was found to precede the growth of carbon nanowalls (CNWs), which are often fabricated by PE-CVD. The growth of graphene was investigated in various conditions, changing the plasma power, gas pressures, and the substrate temperature. The catalytic nature of Cu also affects the growth of monolayer graphene at high substrate temperatures, while the growth at low temperatures and growth of multilayer graphene are dominated mostly by radicals generated in the plasma.     

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.     

Fabrication of diamond micro-structures by ink-jet printed diamond seeding and microwave plasma assisted chemical vapor deposition

Ink-jet printing has the advantage of easy formation of micro-patterns on rigid as well as flexible surfaces without needing conventional lithographic processes. By means of printing in selected areas, diamond seeding in designed patterns and areas is achieved. Properly designed ink with a desirable composition helps the formation of patterned structures with tailored functions. Ink containing nano-diamond particles was designed and used to print micro-structures, which were applied for further CVD growth of diamond by means of microwave plasma CVD. Promising applications of this technique are discussed.