Gas sensing properties of nanocrystalline diamond films

Toxic gas sensing device with metal electrodes built into nanocrystalline diamond (NCD) is investigated. The NCD morphology is controlled via seeding and/or deposition time. The surface properties and morphology of NCD are studied using scanning electron microscopy (SEM) and atomic force microscopy (AFM). AFM measurements reveal increase in NCD surface area by up to 13%. Gas sensing properties of H-terminated NCD device show high sensitivity towards oxidizing species where the surface conductivity is increased by an order of magnitude for humid air and by three orders of magnitude for COCl₂. The surface conductivity exhibits a small decrease to reducing spices (CO₂, NH₃).     

Influence of hydrogen on the residual stress in nanocrystalline diamond films

Nanocrystalline films were deposited by microwave-plasma CVD at a pressure of 200 mbar from an Ar/H₂/CH₄ plasma where the hydrogen fraction in the process gas was varied between 2 and 7%.Residual stress is a critical parameter in thin film deposition and especially important for technical applications of nanocrystalline diamond because high residual stress can lead to cracking or even to delamination of the film from the substrate. An ex-situ optical device was used to measure the residual stress of the substrate.It is shown that by controlling the process parameters the residual stress in the NCD films can be adjusted in a wide range even from compressive to tensile.The films were characterized by two wavelength scanning micro Raman spectroscopy and SEM.In this work a correlation is made between the intrinsic stress measurements and the Transpolyacetylene peaks (around 1120 cm^− 1 and 1450 cm^− 1) in the Raman spectra of NCD films. It is shown that the intensity and the FWHM of the peaks correlate with the tensile stress in the films. A model correlating the Raman spectra to the grain size and thus to the intrinsic stress measurements is given in this paper.     

Effect of metallic seed layers on the properties of nanocrystalline diamond films

Three metallic films (Mo, Ti and W) were sputtered on Si substrates and ultrasonically seeded in diamond powder suspension. Nanocrystalline diamond (NCD) films were deposited using a dc arc plasma jet CVD system on the seeded metallic layers and, for comparison, a seeded Si without any metallic layer. The effect of metallic seed layers on the nucleation, microstructure, composition and mechanical properties of NCD films was investigated by atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy and nanoindentation. We found that the metallic seed layers were transformed into metallic carbide or/and metallic silicide during the deposition of NCD films at high temperature. Adding metallic seed layers had no obvious effect on the bonding structure of the NCD films but significantly improved their surface roughness and mechanical properties. The NCD film deposited on W seed layer displays the lowest root-mean-square roughness of 19 nm while that on Ti seed layer has the highest compactness, hardness and elastic modulus.     

The effects of nitrogenation on the electrochemical properties of nanocrystalline diamond films

The effect of the nitrogenation on the electrochemical properties of nanocrystalline diamond films produced by microwave plasma CVD in CH₄–Ar–H₂–N₂ gas mixtures was studied systematically, using cyclic voltammetry and electrochemical impedance spectroscopy measurements, for the first time. Differential capacitance, kinetic parameters of reactions in [Fe(CN)₆]^3-/4-redox system and potential window were found to be sensitive to the nitrogen concentration in the process gas. With its increase (from 0 to 25%), a transition of the NCD film behavior from “poor conductor” to metal-like character takes place. The heavily N-doped nanocrystalline diamond films have satisfactory electrochemical properties to be used as electrodes.     

Nitrogenated nanocrystalline diamond films: Thermal and optical properties

Ultrananocrystalline diamond films have been grown by microwave plasma CVD using CH₄/H₂/Ar mixtures with N₂ added in plasma in amounts up to 25%. The films were characterized with AFM, Raman, XRD, and UV–IR optical absorption spectroscopy mainly focusing on optical and thermal properties. In comparison with polycrystalline CVD diamond the UNCD are very smooth (R_a < 10 nm), have low thermal conductivity ( 0.10 W/cm K), high optical absorption ( 10³ cm^− 1 at 500 nm) and high concentration of bonded hydrogen ( 9 at.%). The nitrogen presence in the plasma has a profound impact on UNCD structure and properties, particularly leading to a decrease in resistivity (by 12 orders of magnitude), thermal conductivity, Tauc band gap, optical transmission and H content. The UNCD demonstrated rather good thermal stability in vacuum: the diamond phase still was present in the films subjected to annealing to 1400 °C.     

Wettability of nanocrystalline diamond films

The wettability of nanocrystalline CVD diamond films grown in a microwave plasma using Ar/CH₄/H₂ mixtures with tin melt (250–850 °C) and water was studied by the sessile-drop method. The films showed the highest contact angles θ of 168 ± 3° for tin among all carbon materials. The surface hydrogenation and oxidation allow tailoring of the θ value for water from 106 ± 3° (comparable to polymers) to 5° in a much wider range compared to microcrystalline diamond films. Doping with nitrogen by adding N₂ in plasma strongly affects the wetting presumably due to an increase of sp²-carbon fraction in the films and formation of C–N radicals.     

Thermal analysis of submicron nanocrystalline diamond films

The thermal properties of sub-μm nanocrystalline diamond films in the range of 0.37–1.1 μm grown by hot filament CVD, initiated by bias enhanced nucleation on a nm-thin Si-nucleation layer on various substrates, have been characterized by scanning thermal microscopy. After coalescence, the films have been outgrown with a columnar grain structure. The results indicate that even in the sub-μm range, the average thermal conductivity of these NCD films approaches 400 W m^− 1 K^− 1. By patterning the films into membranes and step-like mesas, the lateral component and the vertical component of the thermal conductivity, k_lateral and k_vertical, have been isolated showing an anisotropy between vertical conduction along the columns, with k_vertical ≈ 1000 W m^− 1 K^− 1, and a weaker lateral conduction across the columns, with k_lateral ≈ 300 W m^− 1 K^− 1.     

AC behavior of intrinsic nanocrystalline diamond films

Nanocrystalline diamond was prepared by hot filament assisted chemical vapor deposition technique. The nanometer sized dimension of diamond grains was determined by X-ray line broadening. AC electrical response of deposits, constituted by well formed diamond grains, was studied by admittance spectroscopy at different temperatures. Grain boundary and grain surface were considered different regions able to influence differently the frequency dependent AC response. Observed variations in admittance spectra were attributed to a modification of the grain surface response as frequency and temperature rise. A semiconductor to metal-like transition was evidenced in admittance spectra increasing the frequency of applied signal at lower temperatures.     

Subgap photoluminescence spectroscopy of nanocrystalline diamond films

We report on the effect of ambient conditions and UV irradiation on the subgap photoluminescence of nanocrystalline diamond prepared by microwave plasma enhanced chemical vapour deposition. We measured the photoluminescence of self-supporting membranes of thickness about 290 nm with the grain size up to 40 nm under variable ambient conditions – pressure, temperature, air, nitrogen and helium atmospheres. We have found that intensity of photoluminescence of samples kept under low pressure increases during the time. The photoluminescence intensity of samples under low pressure depends on sample temperature with maximum at about 260 K. The photoluminescence increase can be enhanced substantially by UV irradiation (325 nm) of the sample under certain conditions: temperature greater than ~ 280 K, low pressure of ambient atmosphere. We interpret the experimental results in terms of desorption of water molecules and their interaction with the of individual diamond nanocrystals in the membrane.     

Transparent ultrananocrystalline diamond films on quartz substrate

Highly transparent ultrananocrystalline diamond (UNCD) films were deposited on quartz substrates using microwave plasma enhanced chemical vapor deposition (MPECVD) method. Low temperature growth of high quality transparent UNCD films was achieved by without heating the substrates prior to the deposition. Additionally, a new method to grow NCD and microcrystalline diamond (MCD) films on quartz substrates has been proposed. Field emission scanning electron microscopy (FESEM) and Raman spectroscopy were used to analyze the surface and structural properties of the films. The surface morphology of UNCD film shows very smooth surface characteristics. The transparent property studies of UNCD film on quartz substrate showed 90% transmittance in the near IR region. The transparent and dielectric properties of UNCD, NCD, and MCD films on quartz substrates were compared and reported.     

Grain size dependent mechanical properties of nanocrystalline diamond films grown by hot-filament CVD

Nanocrystalline diamond (NCD) films with a thickness of ~ 6 µm and average grain sizes ranging from 60 to 9 nm were deposited on silicon wafers using a hot-filament chemical vapor deposition (HFCVD) process. These samples were then characterized in order to identify correlations between grain size, chemical composition and mechanical properties. The characterization reveals that our films are phase pure and exhibit a relatively smooth surface morphology. The levels of sp²-bonded carbon and hydrogen impurities are low, showing a systematic variation with the grain size. The hydrogen content increases with decreasing grain size, whereas the sp² carbon content decreases with decreasing grain size. The material is weaker than single crystalline diamond, since both stiffness and hardness decrease with the reduction in crystal size. These trends suggest gradual changes in the nature of the grain boundaries, from graphitic in case of 60 nm grain size material to hydrogen terminated sp³ carbon in 9 nm grain size material. The films exhibit low levels of internal stress and free-standing structures with a length of several centimeters could be fabricated without noticeable bending     

Effects of plasma treatments on the nitrogen incorporated nanocrystalline diamond films

The nitrogen incorporated nanocrystalline diamond (NCD) films were grown on n-silicon (100) substrates by microwave plasma enhanced chemical vapor deposition (MPECVD) using CH₄/Ar/N₂ gas chemistry. The effect of surface passivation on the properties of NCD films was investigated by hydrogen and nitrogen-plasma treatments. The crystallinity of the NCD films reduced due to the damage induced by the plasma treatments. From the crystallographic data, it was observed that the intensity of (111) peak of the diamond lattice reduced after the films were exposed to the nitrogen plasma. From Raman spectra, it was observed that the relative intensity of the features associated with the transpolyacetylene (TPA) states decreased after hydrogen-plasma treatment, while such change was not observed after nitrogen-plasma treatment. The hydrogen-plasma treatment has reduced the sp²/sp³ ratio due to preferential etching of the graphitic carbon, while this ratio remained same in both as-grown and nitrogen-plasma treated films. The electrical contacts of the as-grown films changed from ohmic to near Schottky after the plasma treatment. The electrical conductivity reduced from ~ 84 ohm^– 1 cm^− 1 (as-grown) to ~ 10 ohm^– 1 cm^− 1 after hydrogen-plasma treatment, while the change in the conductivity was insignificant after nitrogen-plasma treatment.     

Influence of substrate nature on the d.c.-glow discharge induced nucleation of diamond

The nature of the nucleation centers, formed during the so called bias enhanced nucleation (BEN) of chemical vapor deposition (CVD) diamond is still an open question. We address this question by investigating the chemical composition and structure of the material deposited during the “nucleation” stage on various substrates by near edge X-ray absorption fine structure technique (NEXAFS) and Raman spectroscopy.The key step of the BEN of diamond in hot filament CVD systems is the generation of a stable d.c.-glow discharge between the grounded substrate and a positively biased electrode. This process results in the deposition of a carbon based film which contains the diamond nucleation and growth centers. Different materials, such as Si(100), CVD diamond films, and Si(100) onto which thin films of Ni were evaporated were used as substrates.It was found that the structure of the material deposited during the d.c.-glow discharge process is affected by the nature of the substrate. The d.c.-glow discharge process applied to the Si substrate resulted in the formation of a graphite-like film in the earlier stages (5 min), which after prolonged treatment time (30 min) was predominantly composed of nanosized diamond. The CVD diamond film, used as a substrate, promoted the formation of nanosized diamond particles even after 5 min of the d.c.-glow discharge process. However, C-13 labeling experiments have shown that microcrystalline diamond does not grow on the pre-existing CVD diamond substrate under the d.c.-glow discharge conditions. In the case of the Ni modified Si, the deposited film was graphitic in nature both after short and prolonged d.c.-glow discharge treatment times.     

Effect of substrate temperature on microstructure and optical properties of nanocrystalline alumina thin films

Aluminum oxide (Al₂O₃) thin films were deposited on silicon (100) and quartz substrates by pulsed laser deposition (PLD) at an optimized oxygen partial pressure of 3.0×10^?3 mbar in the substrate temperatures range 300–973 K. The films were characterized by X-ray diffraction, transmission electron microscopy, atomic force microscopy, spectroscopic ellipsometry, UV–visible spectroscopy and nanoindentation. The X-ray diffraction studies showed that the films deposited at low substrate temperatures (300–673 K) were amorphous Al₂O₃, whereas those deposited at higher temperatures (≥773 K) were polycrystalline cubic γ-Al₂O₃. The transmission electron microscopy studies of the film prepared at 673 K, showed diffuse ring pattern indicating the amorphous nature of Al₂O₃. The surface morphology of the films was examined by atomic force microscopy showing dense and uniform nanostructures with increased surface roughness from 0.3 to 2.3 nm with increasing substrate temperature. The optical studies were carried out by ellipsometry in the energy range 1.5–5.5 eV and revealed that the refractive index increased from 1.69 to 1.75 (λ=632.8 nm) with increasing substrate temperature. The UV–visible spectroscopy analysis indicated higher transmittance (>80%) for all the films. Nanoindentation studies revealed the hardness values of 20.8 and 24.7 GPa for the films prepared at 300 K and 973 K respectively.     

Electrical contacts to nitrogen incorporated nanocrystalline diamond films

The effect of surface plasma treatment on the nature of the electrical contact to the nitrogen incorporated nanocrystalline diamond (n-NCD) films is reported. Nitrogen incorporated NCD films were grown in a microwave plasma enhanced chemical vapor deposition (MPECVD) reactor using CH₄ (1%)/N₂ (20%)/Ar (79%) gas chemistry. Raman spectra of the films showed features at ∼ 1140 cm^− 1, 1350 cm^− 1(D-band) and 1560 cm^− 1(G-band) respectively with changes in the bonding configuration of G-band after the plasma treatment. Electrical contacts to both untreated and surface plasma treated films are formed by sputtering and patterning Ti/Au metal electrodes. Ohmic nature of these contacts on the untreated films has changed to non-ohmic type after the hydrogen plasma treatment. The linear current–voltage characteristics could not be obtained even after annealing the contacts. The nature of the electrical contacts to these films depends on the surface conditions and the presence of defects and sp² carbon.     

Local boron environment in B-doped nanocrystalline diamond films

Thin films of heavily B-doped nanocrystalline diamond (B:NCD) have been investigated by a combination of high resolution annular dark field scanning transmission electron microscopy and spatially resolved electron energy-loss spectroscopy performed on a state-of-the-art aberration corrected instrument to determine the B concentration, distribution and the local B environment. Concentrations of ～1 to 3 at.% of boron are found to be embedded within individual grains. Even though most NCD grains are surrounded by a thin amorphous shell, elemental mapping of the B and C signal shows no preferential embedding of B in these amorphous shells or in grain boundaries between the NCD grains, in contrast with earlier work on more macroscopic superconducting polycrystalline B-doped diamond films. Detailed inspection of the fine structure of the boron K-edge and comparison with density functional theory calculated fine structure energy-loss near-edge structure signatures confirms that the B atoms present in the diamond grains are substitutional atoms embedded tetrahedrally into the diamond lattice.     

Effect of XeF laser treatment on structure of nanocrystalline diamond films

Nanocrystalline diamond (NCD) films were deposited on Si substrates by microwave plasma-enhanced chemical vapor deposition (MPECVD) using methane/hydrogen/oxygen (30/169/0.2 sccm) as process gases. Subsequently a thin (0.33 μm) and a thick (1.01 μm) NCD films were irradiated with XeF excimer laser (λ = 351 nm) with 300 and 600 mJ cm^? 2 of energy densities in air. The NCD films became rougher after laser irradiations. Fraction of graphitic clusters decreased but oxygen content increased in the thin NCD film after laser irradiation. Opposite phenomena were observed for the thick NCD films. Effect of laser irradiation to oxygenation and graphitization of NCD films was correlated with structural properties of free surface and grain boundaries of the thin and thick NCD films.     

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.     

Synthesis of nanocrystalline diamond films using microwave plasma CVD

Diamond is one of the most valuable materials for the industrial applications because of its excellent properties including high hardness, with good electrical insulation and thermal conductivity. Mechanical polishing processes of diamond are difficult and very costly. To limit those costs, it is reasonable to think that the surface roughness of the as-grown diamond film should be as small as possible. In this study, a nanocrystalline diamond film was synthesized on a 4-inch Si wafer at 923 K and methane concentration of 10 vol.%, (H₂/CH₄=100/10 sccm) using a microwave plasma CVD system. In order to increase the nucleation density, the substrate was pretreated by dry scratch method with diamond powder of two sizes (250 nm and 5 nm). The nucleation density was approximately 1×10¹¹ cm⁻². The grown diamond films were analyzed by Raman spectroscopy and X-ray diffraction (XRD). The grain size was observed to be approximately 10 nm by FE-SEM observation. Surface roughness was measured as Rms=8.4 nm by atomic force microscope (AFM). The as-grown properties of those nanocrystalline diamond films were almost efficient for tribological and the optical applications.     

Characterization of nanocrystalline diamond films implanted with nitrogen ions

Nanocrystalline diamond films, prepared by a microwave plasma-enhanced CVD, were implanted using 110-keV nitrogen ions under fluence ranging from 10¹⁶–10¹⁷ ions cm⁻². AFM, XRD, XPS and Raman spectroscopy were used to analyze the changes in surface structure and chemical state of the films before and after implantation. Results show that high-fluence nitrogen ions implanted in the nanocrystalline diamond film cause a decline in diamond crystallinity and a swelling of the crystal lattice; the cubic-shaped diamond grains in the film transform into similar roundish-shaped grains due to the sputtering effect of implanted nitrogen ions. Nitrogen-ion implantation changes the surface chemical state of the nanocrystalline diamond film. After high-fluence implantation, the surface of the film is completely covered by a layer of oxygen-containing groups. This phenomenon plays an importance role in the reduction of the adhesive friction between an Al₂O₃ ball and the nanocrystalline diamond film.