Evolution and properties of adherent diamond films with ultra high nucleation density deposited onto alumina

In this work, we report on adherent diamond films with thickness of up to 4.5 μm grown on polycrystalline alumina substrates. Prior to deposition, alumina substrates were ultrasonically abraded with mixed poly-disperse slurry that allows high nucleation density of values up to ∼5×10¹⁰ particles/cm². It was estimated that the minimal film thickness achieved for continuous films was ∼320 nm, obtained after a deposition time of 15 min with diamond particles density (DPD) of ∼4×10⁹ particles/cm². Continuous adherent diamond films with high DPD (∼10⁹ particles/cm²) were obtained also on sapphire surface after abrasion with mixed slurry and 15 min of deposition. However, after longer deposition time, diamond films peeled off from the substrates during cooling.The poor adhesion between the diamond and sapphire is attributed to the weak interface interaction between the film and the substrate and to difference in coefficient of thermal expansion. On the other hand, it is suggested that the reason for good adhesion between diamond film and alumina substrate is that high carbon diffusivity onto alumina grain boundaries allows strong touch-points at the grooves of alumina grains, and this prevents the delamination of diamond film. This adhesion mechanism, promoted by sub-micron diamond grain-size, is allowed by initial high nucleation density.The surface properties, phase composition and microstructure of the diamond films deposited onto alumina were examined by electron energy loss spectroscopy (EELS), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and high-resolution scanning electron microscopy (HR-SEM). The residual stress in the diamond films was evaluated by diamond Raman peak position and compared to a theoretical model with good agreement. Due to the sub-micron grain-size, the intrinsic tensile stress is high enough to partially compensate the thermal compressive stress, especially in diamond films with thickness lower than 1 μm.     

Study on enhancement of diamond nucleation on fused silica substrate by ultrasonic pretreatment

Fused silica substrates were pretreated by the ultrasonic vibration in the diamond powder slurry (UVDS). The influence of UVDS parameters such as the grain size of diamond powder, the liquid medium used to form the slurry, the weight ratio of diamond powder to liquid medium and the pretreatment time on the diamond nucleation density (DND) were systemically investigated. The grain size of diamond powder greatly affected the DND, the larger the grain size the higher the DND in our experiment conditions. The DND was about the same using acetone or ethanol or hexane medium. The best weight ratio of diamond powder (grain size 20–40 μm) to liquid medium was ∼1/60. Under appropriate pretreatment and CVD conditions, the DND of ∼10¹⁰ cm⁻² was obtained on fused silica substrates. Continuous ultra-thin diamond films with uniform and smooth surface (diamond grain size: ∼150 nm and surface roughness: ∼6 nm) were synthesized in an improved hot filament chemical vapor deposition (HFCVD) system. Nano-damaged sites on the pretreated surface mainly enhanced the DND and shortened the incubation time of nucleation.     

Substrate pre-treatment by ultrasonication with diamond powder mixtures for nucleation enhancement in diamond film growth

Pre-treatment of silicon substrates by ultrasonic abrasion for nucleation enhancement in diamond film formation by hot-filament chemical vapour deposition is discussed. Scanning electron microscopy, atomic force microscopy and visible Raman spectroscopy were employed as analysis techniques. Ultrasonication was applied by suspensions of isopropanol with micro-or nanosized diamond powders, micro-sized metal and alumina particles and mixtures thereof. The root mean square roughness of the ultrasonically pre-treated samples varied from 0.2 to 12.0 nm depending on the applied powder mixture. All samples that were ultrasonically pre-treated had a larger diamond nucleation density than the untreated silicon wafer. As expected, for an effective increment of the diamond nucleation density by several orders of magnitude the application of diamond powder is necessary, since the generation of surface roughness alone is not sufficient to enhance the diamond nucleation kinetics satisfactorily. The simultaneous action of diamond powders and large alumina or titanium particles leads to an increase in diamond nucleation density up to a factor of 10⁶. When nano-diamond powder is used, the embedment of diamond fragments is best and in combination with titanium grains (50–75 µm) a diamond nucleation density of 8 × 10⁹ cm^− 2 is obtained. After 8 h of film growth, the diamond surface grains are significantly smaller for the samples that demonstrated higher nucleation densities, whereas the quality of the diamond layers is equal.     

The effect of ion bombardment on the nucleation of CVD diamond

The nucleation effect of CVD diamond by ion bombardment was studied by a two-step process. In the first step, hydrocarbon and hydrogen ion bombardment was used to induce nucleation on mirror-polished (001) Si substrates. In the second step, diamond films were subsequently deposited on the ion-bombarded substrates by a conventional hot filament chemical vapor deposition. It was found that after the ion bombardment, an amorphous layer embedded with nano-crystalline diamond particles formed on the Si substrate. These nano-crystalline diamond particles were proposed to serve as the nucleation centers for the growth in the second step. The nucleation density depended strongly on the ion dosage and a nucleation density of up to 2×10⁹ cm⁻² could be achieved under optimized conditions.     

Nano-particles seeding and its characterization by X-ray photoelectron spectroscopy (XPS)

We present a new procedure for pretreatment seeding by ultrasonic agitation of silicon substrates in diamond nano-powder suspensions to which HF and KOH were added X-ray photoelectron spectroscopy (XPS) was used to measure the surface coverage by diamond nuclei immediately after the pretreatment. Coverage percentages of 70, 40 and 55% were obtained for the HF, KOH and the original diamond slurry, respectively. The seeding density (S_D) was calculated from the known nano-particles size, determined independently from X-ray diffraction of the powder. For nano-particle size of ∼6 nm, we obtain nominal seeding densities of the order ∼10¹² cm⁻². The advantage of the high coverage was most evident for films deposited at low substrate temperature (570 °C). The potential of the new seeding procedure and the XPS characterization method are discussed.     

Influence of nucleation density on film quality,growth rate and morphology of thick CVD diamond films

The optimum growth parameters of our 5 kW microwave plasma CVD reactor were obtained using CH₄/H₂/O₂ plasma and high quality transparent films can be produced reproducibly. Among the films prepared in this system, the film of best quality has very smooth crystalline facets free of second nucleation and the full width at half maximum (FWHM) of the diamond Raman peak is 2.2 cm⁻¹, as narrow as that of IIa natural diamond. For this study, diamond films were grown on silicon substrates with low (10⁴–10⁵ cm⁻²) and high nucleation densities (>10¹⁰ cm⁻²), respectively. From the same growth run, a highly 〈110〉 textured 300 μm thick white diamond film with a growth rate of 2.4 μm/h was obtained from high nucleation densities (>10¹⁰ cm⁻²), and a white diamond film of 370 μm in thickness with a higher growth rate of 3 μm/h was obtained from low nucleation densities (5×10⁴–10⁵ cm⁻²) too. The effect of nucleation density on film quality, growth rate, texture and morphology was studied and the mechanism was discussed. Our results suggest that under suitable growth conditions, nucleation density has little effect on film quality and low nucleation density results in higher growth rate than high nucleation density due to less intense grain growth competition.     

Nucleation and growth of diamond films on single crystal and polycrystalline tungsten substrates

Silicon has been the most widely studied substrate for the nucleation and growth of CVD diamond films. However, other substrates are of interest, and in this paper, we present the results of a study of the biased nucleation and growth of diamond films on bulk single and polycrystalline tungsten. Diamond films were nucleated and grown, using a range of bias and reactor conditions, and characterized by Raman spectroscopy and scanning electron microscopy (SEM). High-quality (100) textured films (Raman FWHM<4 cm⁻¹) could be grown on both single and polycrystalline forms of the tungsten substrate. On carefully prepared substrates, by varying the bias treatment, it was possible to determine the nucleation density over a 4–5 order range, up to ∼10⁹ cm⁻². Raman measurements indicated that the diamond films grown on bulk tungsten exhibited considerable thermal stress (∼1.1 GPa), which, together with a thin carbide layer, resulted in film delamination on cooling. The results of the study show that nucleation and growth conditions can be used to control the grain size, nucleation density, morphology and quality of CVD diamond films grown on tungsten.     

Growth of diamond films with high surface smoothness

Diamond films with highly smooth backside surface have been deposited by positively biasing the substrate during diamond growth in a hot-filament chemical vapor deposition (HFCVD) system. By bonding the diamond film on the glass and wet etching to remove silicon, the highly smooth diamond surface can be exposed and used directly for the fabrication of diamond devices.Silicon substrate was first treated by diamond powder of 625 nm in an ultrasonic bath. By positively biasing the substrate, electron bombardment during diamond growth increases the nucleation density from 10⁸ ∼ 10⁹ cm^− 2 to 4 × 10¹¹ cm^− 2. The surface smoothness on the backside of diamond film has thus been improved significantly, inducing root-mean-square roughness of 5 nm. Owing to the extremely high surface smoothness and the high crystalline quality on the backside of diamond film and the high diamond growth rate, the backside surface of the diamond film grown under electron bombardment is particularly suitable for device fabrication.     

Mechanistic study of ion-induced diamond nucleation

The effect of low-energy ion bombardment of silicon on diamond nucleation was investigated. By bombarding 100 eV ions of methane and hydrogen on a silicon substrate prior to diamond growth by chemical vapor deposition, diamond nucleation can be immensely enhanced. The ion beam treatment deposited a layer of nano-crystalline graphitic carbon embedded with amorphous SiC. Diamond then nucleated on the graphite overlayer; the nucleation density increased with increasing ion dose. At 1×10¹⁹ ions cm⁻², a nuclei density of 4×10⁸ cm⁻² was obtained. These results show that ion bombardment of the substrate enhances diamond nucleation.     

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.     

Electron field emission from defective diamond films deposited on chrome electrode

Deposition of the good electron-emitting diamond films on a chrome electrode, which is essential for the development of the actual display device, was successfully carried out. Emission current densities of 1 μA/cm² and 1 mA/cm² were measured at the electric field of 6.6 and 12.3 V/μm, respectively. The emission images revealed that the emission site density was ∼10⁴ sites/cm². Both Raman spectroscopy and scanning electron microscopy showed that these were defective diamond films, similar to those deposited on silicon substrates under similar deposition conditions. Comparing the emission characteristics of the films deposited on silicon and on chrome, we conclude that the interface between the back contact and the film is not the current-limiting factor. Moreover, we discuss the importance of the inclusion of sp²-bonded carbons for good electron emission.     

Diamond nucleation and growth under very low-pressure conditions

The synthesis of thin diamond films using various chemical vapor deposition methods has received significant attention in recent years due to the unique characteristic of diamond, which make it an attractive candidate for a wide range of applications. In order to grow diamond epitaxially, the proper control of diamond nucleation on mirror-polished Si is essential. Adding the negative bias voltage to the substrate is the most popular method. This paper has proposed a new method to greatly enhance the nuclear density. Under very low pressure (1 torr), the high-density nucleation of diamond is achieved on mirror-polished silicon in a hot-filament chemical vapor deposition (HFCVD). Scanning electron microscopy has demonstrated that the nuclear density can be as high as 10¹⁰–10¹¹ cm⁻². Raman spectra of the sample have shown a dominant diamond characteristic peak at 1332 cm⁻¹. The pressure effect has been discussed in detail and it has been shown that the very low pressure is a very effective means to nucleate and grow diamond films on mirror-polished silicon. Extraordinary pure hydrogen (purity=99.9999%) was used as the source. Compared with the highly pure hydrogen (purity=99.99%), we found that the density of nucleation was greatly increased. The residual oxygen in the hydrogen displayed a very obvious negative effect on the nucleation of diamond, although it can accelerate the growth of diamond. Based on these results, it was suggested that the enhanced nucleation at very low pressure should be attributed to an increased mean free path, which induced a high density of atomic hydrogen and hydrocarbon radicals near the silicon surface. Atomic hydrogen can effectively etch the oxide layer on the surface of silicon and so greatly enhance the nucleation density.     

A new method for nucleation enhancement of diamond

Diamond nucleation of sufficient density to allow for the growth of continuous films requires substrate pretreatment either by abrasion with diamond particles or by in-situ biasing of the substrate, a method which applies only to electrically conductive materials. Even with the above methods, nucleation on materials which do not form carbides such as quartz is quite low. We report on a new method for increasing the abrasion effect using the ultrasonic cavitation method, through the use of slurry, which is composed of more than one component. Using this slurry, the nucleation density increases by up to several orders of magnitude, which shows the potential to enable the growth of continuous films on ceramic materials. A qualitative model to explain the mechanism of this nucleation enhancement phenomenon is suggested.     

Silicon carbide films from polycarbosilane and their usage as buffer layers for diamond deposition

Thin films of polycarbosilane (PCS) were coated on a Si (100) wafer and converted to silicon carbide (SiC) by pyrolyzing them between 800 and 1150 °C. Granular SiC films were derived between 900 and 1100 °C whereas smooth SiC films were developed at 800 and 1150 °C. Enhancement of diamond nucleation was exhibited on the Si (100) wafer with the smooth SiC layer generated at 1150 °C, and a nucleation density of 2 × 10¹¹ cm^− 2 was obtained. Nucleation density reduced to 3 × 10¹⁰ cm^− 2 when a bias voltage of − 100 V was applied on the SiC-coated Si substrate. A uniform diamond film with random orientations was deposited to the PCS-derived SiC layer. Selective growth of diamond film on top of the SiC buffer layer was demonstrated.     

Growth of {111}-oriented diamond on Pt/Ir/Pt substrate deposited on sapphire

Highly 〈111〉-oriented diamond films with azimuthal alignment were successfully deposited on platinum{111}/iridium{111}/platinum{111} formed on sapphire{0001} by microwave enhanced chemical vapor deposition. With oriented nucleation density of approximately 1×10⁸ cm⁻², the heteroepitaxial {111}-oriented diamond films were grown over a 10×10 mm² area without crack or delamination from the substrate. X-Ray diffraction rocking curve of diamond{111} has a full-width at half maximum value of 1.1°, which endorses a high crystal quality of the diamond film. The high density of oriented nucleation and improved adhesion of the diamond can be attributed to the Ir film inserted between the two Pt layers, which hinders diffusion of carbon through the Pt and graphite formation at the Pt/sapphire interface.     

Transmission electron microscopy study of diamond nucleation and growth on smooth silicon surfaces coated with a thin amorphous carbon film

Amorphous carbon (a-C) films with high contents of tetrahedral carbon bonding (sp³) were synthesized on smooth Si(100) surfaces by cathodic arc deposition. Before diamond growth, the a-C films were pretreated with a low-temperature methane-rich hydrogen plasma in a microwave plasma-enhanced chemical vapor deposition system. The evolution of the morphology and microstructure of the a-C films during the pretreatment and subsequent diamond nucleation and initial growth stages was investigated by high-resolution transmission electron microscopy (TEM). Carbon-rich clusters with a density of ∼10¹⁰ cm⁻² were found on pretreated a-C film surfaces. The clusters comprised an a-C phase rich in sp³ carbon bonds with a high density of randomly oriented nanocrystallites and exhibited a high etching resistance to hydrogen plasma. Selected area diffraction patterns and associated dark-field TEM images of the residual clusters revealed diamond fingerprints in the nanocrystallites, which played the role of diamond nucleation sites. The presence of non-diamond fingerprints indicated the formation of Si–C-rich species at C/Si interfaces. The predominantly spherulitic growth of the clusters without apparent changes in density yielded numerous high surface free energy diamond nucleation sites. The rapid evolution of crystallographic facets in the clusters observed under diamond growth conditions suggested that the enhancement of diamond nucleation and growth resulted from the existing nanocrystallites and the crystallization of the a-C phase caused by the stabilization of sp³ carbon bonds by atomic hydrogen. The significant increase of the diamond nucleation density and growth is interpreted in terms of a simple three-step process which is in accord with the experimental observations.     

Towards homogeneous and reproducible highly oriented diamond films

Diamond films have been deposited by the microwave plasma assisted chemical vapor deposition technique using an ultra short bias enhanced nucleation step to synthesize highly oriented diamond films on single silicon substrate. Firstly in this paper, we focus on the bias enhanced nucleation process to obtain homogeneous and reproducible diamond deposits. By optimizing the process, we obtained a crystal density value of 10⁹ cm⁻² on the whole substrate surface for a reduced polarization time of 60 s. Then, using scanning electron microscopy and image analysis, we report cartographies of crystal densities, covering rate and average radius on the whole sample surface. Next, we analyze a local area of the surface to produce a size distribution of the particles versus their type. Lastly, we present a discussion on the ratio of epitaxial crystals.     

Nucleation and growth of diamond films on aluminum nitride by hot filament chemical vapor deposition

Nucleation and growth of diamond films on aluminum nitride (ALN) coatings were investigated by scanning electron microscopy, Raman spectroscopy and scratch test. ALN films were grown in a magnetron sputtering deposition. The substrates were Si(111) and tungsten carbide (WC). Chemical vapor deposition (CVD) diamond films were deposited on ALN films by hot filament CVD. The nucleation density of diamond on ALN films was found to be approximately 10⁵ cm⁻², whereas over 10¹⁰ cm⁻² after negative bias pre-treatment for 35 min was −320 V, and 250 mA. The experimental studies have shown that the stresses were greatly minimized between diamond overlay and ALN films as compared with WC substrate. The results obtained have also confirmed that the ALN, as buffer layers, can notably enhance the adhesion force of diamond films on the WC.     

Influence of SiC particle addition on the nucleation density and adhesion strength of MPCVD diamond coatings on Si3N4 substrates

It is generally accepted that SiC layers are often involved in the adhesion efficiency of chemical vapour deposition (CVD) diamond films on Si-containing substrates. Si₃N₄–SiC composite substrates with different amounts of SiC particles (0–50 wt%) were then used for diamond deposition. Samples were produced by pressureless sintering (1750°C, N₂ atmosphere, 2–4 h). The diamond films were grown on a commercial MPCVD reactor using H₂/CH₄ mixtures. Despite there being no special substrate pre-treatment, the films were densely nucleated when SiC was added (N_d≈1×10¹⁰ cm⁻²) with primary nanosized (∼100 nm) particles, followed by a less dense (N_d≈1×10⁶ cm⁻²) secondary nucleation. Indentation experiments with a Brale tip of up to 588 N applied load corroborated the benefit of SiC inclusion for a strong adhesion. The low thermal expansion coefficient mismatch between Si₃N₄ and diamond resulted in very low compressive stresses in the film, as proved by micro-Raman spectroscopy.     

Influence of CF4 addition for HFCVD diamond growth on silicon nitride substrates

This work presents a study of CVD diamond growth on silicon nitride-based ceramics with the addition of carbon tetrafluoride (CF₄) in a hot filament-assisted reactor (HFCVD). Silicon nitride substrates were hot pressed under a nitrogen atmosphere for 90 min at 1750°C, giving specimens of very high density and good mechanical properties. The CF₄ addition is known to bring several advantages to diamond growth and, in particular, in this work, an important interaction of the CF₄-containing gas phase with the silicon nitride (Si₃N₄) substrates has been proven to be very beneficial for nucleation, growth and adherence of the diamond films. A basic gas mixture of H₂/1.5 vol.% CH₄/0.5 vol.% CF₄ was used in the growth experiments. The nucleation study reveals a strong interaction of the halogen-containing gas phase with the vitreous phase on the substrate surface. A strong erosion of the surface has been observed, which induced a high nucleation density (N_d) of the order of 10⁸ particles cm⁻², without any surface pre-treatment. Silicon nitride surface analysis was performed with Raman and infrared specular reflectance spectroscopy. Results suggest the erosion of the vitreous phase, mainly the silica (SiO₂) component, and the formation of silicon carbide, prior to diamond growth. Raman spectra and scanning electron microscopy (SEM) show better quality film grown with CF₄ addition. Indentation tests with a Rockwell C tip, at variable charge, show a better film adherence if grown with CF₄ addition.