Influence of the substrate nature on the properties of nanocrystalline diamond films

Nanocrystalline diamond/amorphous carbon (NCD/a-C) nanocomposite films have been deposited by microwave plasma CVD from CH₄/N₂ mixtures on a variety of substrates such as polycrystalline diamond, cubic boron nitride, silicon, titanium nitride, and Ti–6Al–4V. The study aimed to investigate the influence of the chemical nature of the substrate, the surface roughness, and the pretreatment of the substrate on the nucleation, the bulk structure, and the mechanical and tribological properties of the NCD/a-C films. The present paper is especially devoted to the bulk structure of the films. By means of X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) it is shown that the bulk properties of the films are not affected by the properties of the substrate although these have a strong influence on the nucleation behaviour. XRD measurements show that – irrespective of the substrate used – the films contain diamond nanocrystallites of 3–5 nm diameter. From the Raman spectra it can be inferred that the crystallite/matrix ratio does not vary. The XPS measurements, finally, show that there are no great changes in the sp²/sp³ ratio of the matrix. These findings are discussed in view of possible growth mechanisms of NCD/a-C nanocomposite films.     

Crystalline structures of carbon complexes in amorphous carbon films

Amorphous carbon (a-C) films, 20 nm thick, were deposited by sputtering on (001) Si substrates. A negative bias voltage was applied to the substrate during deposition to induce Ar⁺ ion bombardment with an energy of ∼230 eV. The film microstructure was investigated by conventional transmission electron microscopy as well as high-resolution electron microscopy. The films consist of an amorphous carbon matrix and crystallites with a platelet form. The crystallites are energetically metastable and easily degrade under electron beam irradiation. In addition, they are usually oriented along their sixfold or threefold axes, exhibiting lattice parameters larger than those of graphite and diamond. X-ray reflectivity density measurements and high-resolution electron microscopy observations indicate that these crystallites consist of packed complex carbon clusters. X-ray diffraction measurements in rocking curve geometry support the existence of oriented crystallites with interplanar spacings corresponding to those observed by transmission electron microscopy.     

Effect of deposition voltage on the microstructure of electrochemically deposited hydrogenated amorphous carbon films

Hydrogenated amorphous carbon (a-C:H) films were deposited on Si substrates by electrolysis in a methanol solution at ambient pressure and a low temperature (50 °C), using various deposition voltages. The influence of deposition voltage on the microstructure of the resulting films was analyzed by visible Raman spectroscopy at 514.5 nm and X-ray photoelectron spectroscopy (XPS). The contents of sp³ bonded carbon in the various films were obtained by the curve fitting technique to the C1s peak in the XPS spectra. The hardness and Young’s modulus of the a-C:H films were determined using a nanoindenter. The Raman characteristics suggest an increase of the ratio of sp³/sp² bonded carbon with increasing deposition voltage. The percentage of sp³-bonded carbon is determined as 33–55% obtained from XPS. Corresponding to the increase of sp³/sp², the hardness and Young’s modulus of the films both increase as the deposition voltage increases from 800 V to 1600 V.     

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.     

Tribological investigation of nanocrystalline diamond films at low load under different tribosystems

The mechanical and frictional properties of hydrogen- and oxygen-terminated nanocrystalline diamond films (NCD) grown by hot-filament chemical vapor deposition (HFCVD) have been investigated in the present work.The structure and morphology of the NCD films have been characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman-effect spectroscopy. In addition, X-ray photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS) have been used to investigate the surface chemical groups on the NCD surface. Mechanical and frictional properties are determined using atomic force microscopy (AFM), nano-indentation, nano-scratching and micro-tribometer. The friction behavior of these films in the load range of 25 to 200 mN under reciprocating sliding conditions, using steel counter-body material has been thoroughly studied.It is noted that these films are highly crystalline with nanometer size grains and contain a very high fraction of sp³ carbon bonds. They exhibit high hardness and high elastic modulus. The friction coefficient of the film is lower under unidirectional scratch with diamond indenter than the friction coefficient under low load reciprocating sliding against steel ball. Transfer of the film from the counter-body, oxidation of transfer film and mixing of transfer film with carbonaceous layer on the worn surfaces are responsible for such behavior. Although, the friction responses of H-terminated and O-terminated films are similar under unidirectional scratch with diamond indenter, the friction coefficient of O-terminated film is always higher than the friction coefficient of H-terminated film under reciprocating sliding condition against steel counter-body material.     

X-ray photoemission spectroscopic study of ultrananocrystalline diamond/hydrogenated amorphous carbon composite films prepared by pulsed laser deposition

Chemical bonding configurations of ultrananocrystalline diamond (UNCD)/hydrogenated amorphous carbon (a-C:H) composite films prepared by pulsed laser ablation of graphite were investigated by X-ray photoemission spectroscopy using synchrotron radiation. The spectra were decomposed using a Voigt function after the backgrounds were subtracted by Shirley's method. A narrow full-width half-maximum of the sp³ peak is specific, which might be attributed to existence of a large number of UNCD crystallites in the film. The width was immediately broadened by an argon ion bombardment. Its value became equivalent to that of the a-C:H film after the ion bombardment in the same manner. This implies that UNCD crystallites were easily damaged and destroyed by the ion bombardment.     

The role of pressure on thin amorphous carbon films deposited using microwave surface wave plasma CVD

We report the effects of gas composition pressure (GCP) on the optical, structural and electrical properties of thin amorphous carbon (a-C) films grown on p-type silicon and quartz substrates by microwave surface wave plasma chemical vapor deposition (MW SWP CVD). The films, deposited at various GCPs ranging from 50 to 110 Pa, were studied by UV/VIS/NIR spectroscopy, atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and current–voltage characteristics. The optical band gap of the a-C film was tailored to a relatively high range, 2.3–2.6 eV by manipulating GCPs from 50 to 110 Pa. Also, spin density strongly depended on the band gap of the a-C films. Raman spectra showed qualitative structured changes due to sp³/sp² carbon bonding network. The surfaces of the films are found to be very smooth and uniform (RMS roughness < 0.5 nm). The photovoltaic measurements under light illumination (AM 1.5, 100 mW/cm²) show that short-circuit current density, open-circuit voltage, fill factor and photo-conversion efficiency of the film deposited at 50 Pa were 6.4 μA/cm², 126 mV, 0.164 and 1.4 × 10^− 4% respectively.     

X-ray photoemission spectroscopy of nitrogen-doped UNCD/a-C:H films prepared by pulsed laser deposition

Nitrogen-doped ultrananocrystalline diamond (UNCD)/hydrogenated amorphous carbon (a-C:H) films were deposited by pulsed laser deposition (PLD). Nitrogen contents in the films were controlled by varying a ratio in the inflow amount between nitrogen and hydrogen gases. The film doped with a nitrogen content of 7.9 at.% possessed n-type conduction with an electrical conductivity of 18 Ω^? 1 cm^? 1 at 300 K. X-ray photoemission spectra, which were measured using synchrotron radiation, were decomposed into four component spectra due to sp², sp³ hybridized carbons, C=N and C–N. A full-width at half-maximum of the sp³ peak was 0.91 eV. This small value is specific to UNCD/a-C:H films. The sp²/(sp³ + sp²) value was enhanced from 32 to 40% with an increase in the nitrogen content from 0 to 7.9 at.%. This increment probably originates from the nitrogen incorporation into an a-C:H matrix and grain boundaries of UNCD crystallites. Since an electrical conductivity of a-C:H does not dramatically enhance for this doping amount according to previous reports, we believe that the electrical conductivity enhancement is predominantly due to the nitrogen incorporation into grain boundaries.     

Structural analysis of a-C:H and a-C:H:Si films under high-pressure and high-temperature by synchrotron X-ray diffraction

Amorphous carbon films have several outstanding tribology characteristics, including high hardness, surface smoothness, and low friction. Under tribological conditions, their surface is generally exposed to high-temperature and pressure. Although the structure of amorphous carbon films is likely changed by high temperature and pressure, there have been no reports on such structural changes of the films. To obtain information about their structural changes, synchrotron X-ray diffraction was used to analyze two kinds of amorphous carbon films, a-C:H and a-C:H:Si, under high-temperature and high-hydrostatic pressure conditions. Synchrotron X-ray diffraction was applied to films pressurized by a multi-anvil press installed in the PF-AR NE5C beamline at KEK at room temperature and at a high-temperature around 200 °C. The pair distribution functions derived by Fourier transformation of the obtained scattering intensity profiles showed that the sp²/sp³ ratios for both films decreased as the pressure increased and that the sp²/sp³ ratio for the a-C:H film increased as the temperature increased. This indicates that high-pressure creates sp³ stabilization in a-C:H and a-C:H:Si films while high-temperature creates sp² transition in a-C:H film. The sp²/sp³ ratio for the a-C:H:Si film did not change much even at high-temperature due to the high thermal-oxidative stability of a-C:H:Si.     

Residual stress relief of hard a-C films though buckling

To characterize the adhesive failure mode in amorphous-carbon (a-C) films, and to explore the effects of stress relief mechanism on the mechanical properties of the films, the microstructure and the morphologies of the buckled and peeled a-C films were characterized by various techniques, including transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman spectrum and X-ray photoelectron spectroscopy (XPS). Results indicated that there is obvious buckling between the stress relieved a-C films and Si substrates, and the development of the buckling blister was derived from the residual compressive stress. The as-deposited a-C films voluntarily buckled along the film growth direction above Si substrate when film thickness reached a certain size, and became more and more remarkable, resulting in eventual peeling. These buckling and peeling processes can relieve the residual stress of the a-C films by eliminating the mechanical restriction of Si substrates. The corresponding sp² hybridization transformation and the reconfiguring graphitic phase were detected in the stress relived a-C films, which can induce buckling and spalling in the a-C films.     

Surface composition,bonding, and morphology in the nucleation and growth of ultra-thin,high quality nanocrystalline diamond films

The morphology, composition, and bonding character (carbon hybridization state) of continuous, ultra-thin (thickness ∼ 60 nm) nanocrystalline diamond (NCD) membranes are reported. NCD films were deposited on a silicon substrate that was pretreated using an optimized, two-step seeding process. The surface after each of the two steps, the as-grown NCD topside and the NCD underside (revealed by etching away the silicon substrate) is examined by X-ray PhotoElectron Emission spectroMicroscopy (X-PEEM) combined with X-ray absorption near edge structure (XANES) spectroscopy, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The first step in the seeding process, a short exposure to a hydrocarbon plasma, induces the formation of SiC at the diamond/Si interface along with a thin, uniform layer of hydrogenated, amorphous carbon on top. This amorphous carbon layer allows for a uniform, dense layer of nanodiamond seed particles to be spread over the substrate in the second step. This facilitates the growth of a homogeneous, continuous, smooth, and highly sp³-bonded NCD film. We show for the first time that the underside of this film possesses atomic-scale smoothness (RMS roughness: 0.3 nm) and > 98% diamond content, demonstrating the effectiveness of the two-step seeding method for diamond film nucleation.     

Bioproperties of nanocrystalline diamond/amorphous carbon composite films

Nanocrystalline diamond/amorphous carbon (NCD/a-C) nanocomposite films have been deposited by microwave plasma chemical vapour deposition (MWCVD) from CH₄/N₂ mixtures. The films have been thoroughly characterized by a variety of methods with respect to their composition, morphology, structure and bonding environment. Thereafter, the bioproperties of these films have been investigated. Tests with osteoblast-like cells and pneumocytes proved that the NCD/a-C films are not cytotoxic. In addition, exposure of the films to a simulated body fluid revealed that they are bioinert. Further experiments addressed the question whether biomolecules such as RNA or proteins bind unspecifically on the surfaces of NCD/a-C films. By means of atomic force microscopy (AFM) and scanning force spectroscopy measurements it was established that, in contrast to control experiments with mica and glass, no interaction between the nanocrystalline diamond and either RNA or protein molecules took place. The results of these experiments concerning the biologically relevant properties of NCD/a-C films are discussed in view of possible future applications, e.g. as a material for the immobilization of biomolecules and their characterization by AFM measurements and related techniques.     

Boron doped amorphous carbon thin films grown by r.f. PECVD under different partial pressure

Boron doped hydrogenated amorphous carbon (a-C) thin films have been deposited by r.f.-plasma CVD with a frequency of 13.56 MHz at room temperature using pure methane as a precursor of carbon source mixed with hydrogen (H₂) as a carrier gas. The films were prepared by varying the r.f. power, different flow rates of CH₄, and partial pressure of mixed gas (CH₄/H₂) using solid boron as a target. The thickness, structural, bonding and optical properties of the as-deposited films were studied by Alpha step surface profiler, Raman, FT-IR, XPS and UV–visible spectroscopy. It was found that changing the deposition pressure in presence of solid boron dopant in the r.f. PECVD process has a profound effect on the properties of the deposited films, as evidenced from their Raman scattering and optical results. The grown p-C: B films were found very smooth and thickness in the range of 240 to 360 nm for 1 h deposition. Films deposited at lower pressure appear brownish color whereas those deposited at higher pressure appear pale yellowish. The as-deposited film is found to be dominated by sp² rather than sp³, which might be due to the formation of small crystallites. The optical band gap is found to be reduced from 2.601.58 eV as the partial pressure of CH₄/H₂ gas is reduced.     

NEXAFS characterization of nanocrystalline diamond thin films synthesized with high methane concentrations

Diamond thin films were deposited on silicon in gas mixtures of methane and hydrogen with different methane concentrations ranging from 1% to 100% using microwave plasma assisted chemical vapor deposition. Both Raman spectroscopy and synchrotron near edge extended X-ray absorption fine structure spectroscopy (NEXAFS) were used to characterize the electronic structure and chemical bonding of the synthesized films. The NEXAFS spectra of the nanocrystalline diamond (NCD) films exhibit clear spectral characteristics of diamond. Close observation reveals that the films (10% CH₄ or above) exhibit a slightly broadened exciton transition with a 0.25 eV blue shift. With the increase in methane concentration, the growth rate, the surface smoothness, and the sp² carbon concentration of the films increase while the grain size decreases. Well-faceted microcrystalline diamond films were synthesized with a methane concentration of 5% or lower, while NCD films were formed with a methane concentration of 10% or higher. Diamond thin films with low surface roughness and fine nanocrystalline structure have been synthesized with high methane concentrations (50% or above). It has been observed that the diamond growth rate increases with methane concentration. The growth rate at 100% methane concentration is approximately 10 times higher than at 1%.     

Surface and interface morphology and structure of amorphous carbon thin and multilayer films

We review the implementation of X-ray reflection (reflectivity and scattering) techniques for the study of amorphous Carbon (a-C, a-C:H, ta-C) thin and multilayer films and in particular in the determination of the film density and surface and interface morphology, which are intrinsically significant for ultra-thin films. We present studies of various a-C and a-C:H films, which include in particular: i) the morphology of a-C/Si interface, ii) the surface morphology and density evolution during sputter growth of a-C, iii) the morphology of the sp²-rich a-C/sp³-rich a-C interfaces in multilayer a-C films, iv) the universal correlation between the film density and the refractive index of a-C and a-C:H films. We also compare and validate the experimental results with relative results from Monte-Carlo simulations within an empirical potential scheme. The computational results shed light on the atomistic mechanisms determining the structure and morphology of the a-C interfaces between individual sp²- and sp³-rich a-C layers and between a-C and Si substrates.     

Preparation and microstructure properties of tetrahedral amorphous carbon films by pulsed laser deposition using camphoric carbon target

The properties of tetrahedral amorphous carbon (ta-C) films grown by pulsed laser deposition (PLD) using camphoric carbon (CC) target and their respective effects of diamond percentages by weight in the target (Dwt.%) are discussed. Scanning electron microscopy (SEM), atomic force microscopy (AFM), Visible-Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses indicated that the Dwt.% noticeably modified the sp³ bonds content and the morphology of the ta-C films. The optical gap (E_g) and electrical resistivity (ρ) increase with Dwt.% up to 1.6 eV and 5.63×10⁷ (Ω cm), respectively, for the ta-C films deposited using target with higher of 50 Dwt.%. We found that the Dwt.% has modified the surface morphological, structural, bonding and physical properties of the camphoric carbon films.     

Structural characterization and properties enhancement of diamond-like carbon films synthesized under low energy Ne bombardment

Diamond-like carbon (DLC) films were synthesized by Ar⁺ sputtering graphite with concurrent Ne⁺ bombardment. Transmission electron microscopy diffraction revealed that some diamond crystals were distributed in the amorphous matrix of DLC films synthesized under Ne⁺ bombardment at an energy of 200 eV and ion current density of 0.19 mA cm⁻². X-ray photo electron spectra showed that the valence band of the DLC films was similar to that of diamond, and the binding energy of electrons was 284.9 eV. The DLC films possessed a high hardness of 42.14 GPa and excellent wear resistance. It was confirmed that the wide atomic intermixed film-substrate interface meant that the DLC films would improve greatly the wear-resistant properties of AISI 52100 steel if the DLC films were coated on its surface.     

Guided assembly of nanoparticles on electrostatically charged nanocrystalline diamond thin films

We apply atomic force microscope for local electrostatic charging of oxygen-terminated nanocrystalline diamond (NCD) thin films deposited on silicon, to induce electrostatically driven self-assembly of colloidal alumina nanoparticles into micro-patterns. Considering possible capacitive, sp² phase and spatial uniformity factors to charging, we employ films with sub-100 nm thickness and about 60% relative sp² phase content, probe the spatial material uniformity by Raman and electron microscopy, and repeat experiments at various positions. We demonstrate that electrostatic potential contrast on the NCD films varies between 0.1 and 1.2 V and that the contrast of more than ±1 V (as detected by Kelvin force microscopy) is able to induce self-assembly of the nanoparticles via coulombic and polarization forces. This opens prospects for applications of diamond and its unique set of properties in self-assembly of nano-devices and nano-systems.     

Cathodoluminescence of fluorine doped amorphous carbon nanoparticles deposited by a filtered cathodic arc plasma system

The fluorine doped amorphous carbon nanoparticles (a-C:F NPs) films with sizes 50-100 nm were deposited on polyethylene terephthalate in an atmosphere of CF₄ by a 90°-bend magnetic filtered cathodic arc plasma system. The surface morphology of a-C:F NPs films was observed by field emission scanning electron microscope and atomic force microscope. The microstructure and chemical bonding nature of the a-C:F NPs films were investigated by Raman, X-ray diffraction and X-ray photoelectron spectroscopy. This work presents cathodoluminescence (CL) spectra of a-C:F NPs films obtained at 1.9-2.4 eV and verifies luminescence from a-C:F NPs films in the visible region. The incorporation of fluorine into the carbon network results in orange emission (∼2.03 eV) due to the transitions between fluorine-related electron levels and σ* states, and the red emission (∼1.97 eV) results from the recombination of carriers in the valence π and conduction π* states. The peak at ∼2.10 eV may result from the defects of the structures in a-C:F NPs films.     

Low-temperature thermionic emission from nitrogen-doped nanocrystalline diamond films on n-type Si grown by MPCVD

Temperature-dependent emission current–voltage measurements were carried out for nitrogen (N)-doped nanocrystalline diamond (NCD) films grown on n-type Si substrates by microwave plasma-assisted chemical vapor deposition (MP-CVD). Low threshold temperature (~ 260 °C) and low threshold electric field (~ 5 × 10^− 5 V/µm) were observed. Both the temperature dependence and the electric field dependence have shown that the obtained emission current was based on electron thermionic emission from N-doped NCD films. We have also studied the relation between nitrogen concentration and the saturation emission current. The saturation current obtained was as high as 1.4 mA at 5.6 × 10^− 3 V/µm at 670 °C when the nitrogen concentration was 2.4 × 10²⁰ cm^− 3. Low value of effective work function (1.99 eV) and relatively high value of Richardson constant (~ 70) were estimated by well fitting to Richardson–Dushman equation. The results of smaller φ and larger A′ suggest that N-doped NCD has great possibility of being a highly efficient thermionic emitter material.