Simulations of the Dependence of Gas Physical Parameters on Deposition Variables during HFCVD Diamond Films

During the growth of the hot filament chemical vapor deposition （HFCVD） diamond films, numerical simulations in a 2-D mathematical model were employed to investigate the influence of various deposition parameters on the gas physical parameters, including the temperature, velocity and volume density of gas. It was found that, even in the case of optimized deposition parameters, the space distributions of gas parameters were heterogeneous due primarily to the thermal blockage come from the hot filaments and cryogenic pump effect arisen from the cold reactor wall. The distribution of volume density agreed well with the thermal round-flow phenomenon, one of the key obstacles to obtaining high growth rate in HFCVD process. In virtue of isothermal boundary with high temperature or adiabatic boundary condition of reactor wall, however, the thermal roundflow was profoundly reduced and as a consequence, the uniformity of gas physical parameters was considerably improved, as identified by the experimental films growth.

Effect of Substrate Temperature on the Selective Deposition of Diamond Films

Selective deposition of diamond film on patterned Si (100) substrates has been achieved by using microwave plasma chemical vapor deposition (MPCVD) method. The films have been characterized by scanning electron microscope (SEM) and Raman spectrum. The influence of substrate temperature on the nucleation behavior of diamond was discussed in detail and the optimized deposition condition has been obtained.

Surface graphitization analysis of cerium-polished HFCVD diamond films with micro-raman spectra

The etching technique using Ce is a convenient and fast method for polishing and shaping diamond films. In this study, the influence of polishing parameters such as polishing temperature and time on the surface crystallinity and phase composition of diamond films was thoroughly investigated via the analysis of Raman spectra such as FWHM and ID/IG. Moreover, the issue on the graphitization of diamond after polishing with Ce was further researched through the detailed study of the depth distribution of Raman data including FWHM and ID/IG, and a result completely different from the hot-iron metal polished ones was obtained. The results showed that polished diamond films had considerably higher diamond content than those before polishing, and not a bit of graphitization was found in the polished ones, owing to a higher solubility of carbon in rare earth metal Ce than that in transition metals, and the original crystallinity of the films polished with Ce did not deteriorate.

Ohmic contact properties of p-type surface conductive layer on H-terminated diamond films prepared by DC arc jet CVD

With the advantages of high deposition rate and large deposition area, polycrystalline diamond films prepared by direct current （DC） arc jet chemical vapor deposition （CVD） are considered to be one of the most promising materials for high-frequency and high-power electronic devices. In this paper, high-quality self-standing polycrystalline diamond films with the diameter of 100 mm were prepared by DC arc jet CVD, and then, the p-type surface conductive layer with the sheet carrier density of 10^11-10^13 cm-2 on the H-terminated diamond film was obtained by micro-wave hydrogen plasma treatment for 40 min. Ti/Au and Au films were deposited on the H-terminated diamond surface as the ohmic contact electrode, respectively, afterwards, they were treated by rapid vacuum annealing at different temperatures. The properties of these two types of ohmic contacts were investigated by measuring the specific contact resistance using the transmission line method （TLM）. Due to the formation of Ti-related carbide at high temperature, the specific contact resistance of Ti/Au contact gradually decreases to 9.95 × 10^-5 Ω-cm2 as the temperature increases to 820℃. However, when the annealing temperature reaches 850℃, the ohmic contact for Ti/Au is degraded significantly due to the strong diffusion and reaction between Ti and Au. As for the as-deposited Au contact, it shows an ohmic contact. After annealing treatment at 550℃, low specific contact resistance was detected for Au contact, which is derived from the enhancement of interdiffusion between Au and diamond films.

Phase Transformation and Enhancing Electron Field Emission Properties in Microcrystalline Diamond Films Induced by Cu Ion Implantation and Rapid Annealing

Cu ion implantation and subsequent rapid annealing at 500℃ in N2 result in low surface resistivity of 1.611 ohm/sq with high mobility of 290 cm2 V-1S-1 for microcrystalline diamond （MCD） films. Its electrical field emission behavior can be turned on at Eo = 2.6 V/μm, attaining a current density of 19.5μA/cm2 at an applied field of 3.5 V/#m. Field emission scanning electron microscopy combined with Raman and x-ray photoelectron mi- croscopy reveal that the formation of Cu nanoparticles in MCD films can catalytically convert the less conducting disorder/a-C phases into graphitic phases and can provoke the formation of nanographite in the films, forming conduction channels for electron transportation.

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.

The Effect of Pressure on the Dissociation of H_2/CH_4Gas Mixture during Diamond Films Growth via Chemical Vapor Deposition

Monte Carlo simulations are adopted to study the electron motion in the mixture of H2 and CH4 during diamond synthesis via Glow Plasma-assisted Chemical Vapor Deposition (GPCVD). The non-uniform electric field is used and the avalanche of electrons is taken into account in this simulation. The average energy distribution of electrons and the space distribution of effective species such as CH3, CH+3, CH+ and H at various gas pressures are given in this paper, and optimum experimental conditions are inferred from these results.

Electrical and structural properties of diamond films implanted by various doses of oxygen ions

Oxygen-doped diamond films are prepared by implanting various dose oxygen ions into the diamond films synthesized by hot filament chemical vapour deposition, and their electrical and structural properties are investigated. Hall effect measurements show that lower dose oxygen ion implantation is beneficial to preparing n-type diamonds. The carrier concentration increases with the dose increasing, indicating that oxygen ions supply electrons to the diamonds. The results of AES spectrum indicate that oxygen ions are doped into the diamond films, and the O-implanted depth is around 0.1μm. Raman spectrum measurements indicate that the lower dose oxygen ion implantation at 10^14 cm^-2 or 10^15 cm^-2 is favourable for producing less damaged O-doDed diamond films.

Effect of metal nanoparticle doping concentration on surface morphology and field emission properties of nano-diamond films

Nano-diamond particles are co-deposited on Ti substrates with metal(Ti/Ni) nanoparticles(NPs) by the electrophoretic deposition(EPD) method combined with a furnace annealing at 800℃ under N_(2) atmosphere. Modifications of structural and electron field emission(EFE) properties of the metal-doped films are investigated with different metal NPs concentrations. Our results show that the surface characteristics and EFE performances of the samples are first enhanced and then reduced with metal NPs concentration increasing. Both the Ti-doped and Ni-doped nano-diamond composite films exhibit optimal EFE and microstructural performances when the doping quantity is 5 mg. Remarkably enhanced EFE properties with a low turn-on field of 1.38 V/μm and a high current density of 1.32 mA/cm^(2) at an applied field of 2.94 V/μm are achieved for Ni-doped nano-diamond films, and are superior to those for Ti-doped ones. The enhancement of the EFE properties for the Ti-doped films results from the formation of the TiC-network after annealing. However, the doping of electron-rich Ni NPs and formation of high conductive graphitic phase are considered to be the factor, which results in marvelous EFE properties for these Ni-doped nano-diamond films.

Influences of grain size and microstructure on optical properties of microcrystalline diamond films

Microcrystalline diamond(MCD)films with different grain sizes ranging from 160 nm to 2200 nm are prepared by using a hot filament chemical vapor deposition(HFCVD)system,and the influences of grain size and structural features on optical properties are investigated.The results show that the film with grain size in a range of 160 nm–310 nm exhibits a higher refractive index in a range of(2.77–2.92).With grain size increasing to 620±300 nm,the refractive index shows a value between 2.39 and 2.47,approaching to that of natural diamond(2.37–2.55),and a lower extinction coefficient value between 0.08 and 0.77.When the grain size increases to 2200 nm,the value of refractive index increases to a value between 2.66 and 2.81,and the extinction coefficient increases to a value in a range of 0.22–1.28.Visible Raman spectroscopy measurements show that all samples have distinct diamond peaks located in a range of 1331 cm-1–1333 cm-1,the content of diamond phase increases gradually as grain size increases,and the amount of trans-polyacetylene(TPA)content decreases.Meanwhile,the sp2 carbon clusters content and its full-width-at-half-maximum(FWHM)value are significantly reduced in MCD film with a grain size of 620 nm,which is beneficial to the improvement of the optical properties of the films.

Impact of nitrogen doping on growth and hydrogen impurity incorporation of thick nanocrystalline diamond films

A much larger amount of bonded hydrogen was found in thick nanocrystalline diamond （NCD） films produced by only adding 0.24% N2 into 4% CH4/H2 plasma, as compared to the high quality transparent microcrystalline diamond （MCD） films, grown using the same growth parameters except for nitrogen. These experimental results clearly evidence that defect formation and impurity incorporation （for example, N and H） impeding diamond grain growth is the main formation mechanism of NCD upon nitrogen doping and strongly support the model proposed in the literature that nitrogen competes with CHx （x = 1, 2, 3） growth species for adsorption sites.

Relationship between texture and residual macro-strain in CVD diamond films based on phenomenological analysis

The relationship between texture and elastic properties of chemical vapor deposition （CVD） diamond films was analyzed based on the phenomenological theory, which reveals the influence of crystalline orientation and texture on the residual macro-strain and macro-stress. The phenomenological calculations indicated that the difference in Young＇s modulus could be 15% in single diamond crystals and 5% in diamond films with homogeneously distributed strong fiber texture. The experimentally measured residual strains of free-standing CVD diamond films were in good agreement with the correspondingly calculated Young＇s modulus in connection with the multi-fiber textures in the films, though the difference in Young＇s modulus induced by texture was only around 1%. It is believed that texture should be one of the important factors influencing the residual stress and strain of CVD diamond films.

THE INTERFACE LAYERS AND CATHODOLUMINESCENCE STUDIES OF DIAMOND FILMS

Polycrystalline diamond films have been synthesized on various substrates by hot filament CVD from the mixture gases of methane and hydrogen. The interface layers between CVD diamond films and substrates have been investigated by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). In addition, visible luminescence between 2.0～3.5eV of undoped and boron-doped CVD diamond films has also been studied by cathodoluminescence.

Deposition of Diamond Films on Copper Substrate

The direct deposition of diamond films on copper substrate has been suffered fromadhesion problems due to the mismatch of the thermal expansion coefficients of diamond andcopper. In this paper nuclei with valuable density were directly introduced thirough a submicrondiamond powder layer. The diamond grits partially were buried in the copper substrate leadingto better adhesion. Another method with nickel intermediate layer for enhancing the adhesionwas studied here in detail. It was suggested that Cu-Ni eutectic between the copper substrate andNi interlayer might contribute to the adhesion improvement. The quality of the diamond filmsdeposited wlth rnckel interlayer was investigated by scanning electron microscopy and Ramanspectroscopy.

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.

Hydrogen distribution in CVD diamond films prepared by DC arcjet operating at gas recycling mode

Hydrogen distribution and content in diamond films deposited by DC arcjetunder gas recycling mode was evaluated by nuclear reaction analysis (NRA). The films werecharacterized using scanning electron microscopy, X-ray diffraction and Raman spectrometry. The NRAresults show that the hydrogen content in diamond films was approximately 0.6% (substratetemperature 770℃), and strongly depended on the substrate temperature. It was that the hydrogencontent increased with the increase of the substrate temperature. The possibility of hydrogentrapping in the films was also discussed.

MECHANISM OF THE GROWTH, NUCLEATION, AND HETEROEPITAXY OF METASTABLE DIAMOND FILMS ON ATOMIC SCALE

The mechanism of chemical-vapor-deposited (CVD) diamond film growth has attracted increasing attention recent years, mainly due to the fact that further technological advancement (such as obtaining high-quality films, controlling film growth, and heteroepitaxial growth, etc.) requires a more detailed understanding of the fundamental phenomena responsible for diamond growth.

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 appeare

A novel approach of deposition for uniform diamond films on circular saw blades

Uniform diamond films are highly desirable for cutting industries, due to their high performance and long lifetime used on cutting tools. Nevertheless, they are difficult to obtain on cutting tools with complicated shapes, greatly limiting the applications of diamond films. In this study, a novel approach of deposition for uniform diamond films is proposed, on circular saw blades made of cemented carbide using reflectors of brass sheets. Diamond films are deposited using hot filament chemical vapor deposition（HFCVD）. A novel concave structure of brass sheets is designed and fabricated, improving the distribution of temperature field, and overcoming the disadvantages of the conventional HFCVD systems. This increases the energy efficiency of use without changing the structure and increasing the cost of HFCVD. The grains are refined and the intensities of diamond peaks are strengthened obviously, which is confirmed by scanning electron microscopy and Raman spectra respectively.

Simulations of Temperature Field in HFCVD Diamond Films over Large Area

A three-dimensional model was developed to investigate the influence of various hot filaments parameters on substrate temperature fields that significantly affect the nucleation and growth of diamond films over large area by hot-filament chemical vapordeposition (HFCVD). Numerical simulated results indicated that substrate temperature varies as a function of hot filamentsnumber, radius, temperature, emissivity, the distance between filaments, and the distance between substrate and filamentsarrangement plane. When these filaments parameters were maintained at the optimal values, the homogeneous substrate temperature region of 76 mm×76 mm with the temperature fluctuation no more than 5% could be obtained by a 80 mm×80 mmhot filaments arrangement plane. Furthermore, the homogeneous region could be enlarged to 100 mm×100 mm under thecondition of supplementary hot filaments with appropriate parameters. All of these calculations provided the basis for speciallyoptimizing the hot filaments parameters to deposit uniform diamond film over large area by HFCVD.