Studies on the electrical conductivity of molecular beam deposited carbon films after annealing of the carbon films have been carried out. Detailed temperature dependence of conductivity on the as-deposited and on annealed samples has been investigated. The results were interpreted in terms of a model which includes a variable range hopping and strongly scattering metallic components. A correlation between annealing behavior of the electrical conductivity and the results of x-ray photoelectron spectroscopy and Raman spectroscopy is presented.

Diamond-like carbon (DLC) films were deposited on various substrates using direct ion beam deposition from an RF IC hydrocarbon plasma source. Combinations of gases such as CH4. CH4–N2 were used to form plasma. The mechanical, electrical and optical properties of the films were examined as a function of deposition conditions and N2 content in gas mixture. A small amount of N2 (<8 sccm) did not markedly change hardness and stress, while electrical conductivity was significantly increased. In addition, a small amount of N2 improved wear performance of the films reducing amount of debris and wear track size. Introduction of high N2 flow into the system significantly deteriorates value of these parameters. It was found that N2 essentially increases absorption coefficient, and reduces optical band gap. Analysis of the experimental results shows that observed effects can be explained by incorporation of N2 into carbon-strained network that induces structural changes and. in turn, leads to an increase of sp2 fraction in the DLC films.

A novel approach to deposit amorphous carbon from the precursor CH2I2 at low cost and high efficiency is reported. The combination of thermal and quantum photo effects shows new interesting growth behaviour. The radiation of a halogen-lamp was used to heat the substrate material and to split photolytically the precursor molecules above the substrate surface. The deposition process was investigated as a function of lamp power, gas phase partial pressures and substrate materials. The films were analysed by Raman spectroscopy, scanning electron microscopy, energy dispersive x-ray spectroscopy, x-ray photon spectroscopy, transmission electron microscopy and atomic force microscopy.

Fluorinated diamond-like carbon (F-DLC) coatings were deposited on polished silicon substrates with plasma immersion ion processing (PIIP) technique. In the PIIP technique, pulsed glow discharge plasma from a mixture of acetylane and hexafluoroethane gases was used. Contact angle measurements were performed in order to see the un-wetting properties of the coatings. The film composition was measured with Rutherford Backscattering Spectroscopy (RBS) and Elastic Recoil Detection Analysis (ERDA) and the hardness was measured with a Nanoindenter® II. The results clearly show that the un-wetting properties and hardness are strongly dependent on the fluorine incorporation in the F-DLC coatings. With optimized gas ratio of acetylane and hexafluoroethane gases, a combination of extremely good un-wetting properties and high hardness was achieved.

Aromatic polyimide films are partially carbonized between 700°C and 1000°C. Electrical conductivity and Hall coeficient have been measured. Electrical conductivity is higher at higher measuring temperatures. The electrical conductivity σ can be expressed as σ= σ0exp (–E /kT), where k is the Boltzman constant. T is the absolute temperature. E depends upon the carborized temperature. The experimental data show the Hall coefficient RH is negative, and this implies the carriers are negatively charged, i.e. electrons. The specimens are n-type semiconductors. The carrier density η can be expressed by η= A1 exp (–E1/κT) and carrier mobility μ can be expressed by μ = A1exp ( E2/κT). E, E1andE2 depend upon the carbonized temperature

Grazing angle x-ray reflectivity (XRR) is used to study density, thickness, internal layering and roughness of a variety of carbon samples, with and without hydrogen and nitrogen. The bulk mass density of optimised tetrahedral amorphous carbon (ta-C) is 3.26 g/cm2, for which Electron Energy Loss Spectroscopy (EELS) found a sp3 fraction of 85%. Combining XRR and EELS we benchmark the dependence of sp3 fraction on density for hydrogen-free carbons. Hydrogenated ta-C (ta-C:H) deposited by electron cyclotron wave resonance (ECWR) reactor from acetylene gas, has a density of 2.35 g/cm3, 75% sp3 and ∼30% hydrogen. These data provide a similar validation for density and sp3 EELS data for hydrogenated DLCs. XRR can also reveal internal layering in films, and indeed less dense layers may be found at the surface or interface of ta-C films, but no such layers are found in ta-C:H films.

The factors controlling the position and intensity of the G3 and D peaks of the Raman spectra of disordered and amorphous carbons are separated in terms of a 3-stage model. The Raman spectra are shown to depend fundamentally on the degree of ordering of the sp2 sites, and only weakly or indirectly on the fraction of sp3 sites. Three factors control the G and D peaks; the perfection of graphitic order, replacing aromatic rings with olefinic chains and increasing the sp2 content. These rules allow us to state when the G3 peak position can be related reliably to sp3 content.

Mass-selected ion-beam deposition using 120 eV C+ ions has been used to grow a carbon film on a Si substrate held at 200° C. The structure of the film has been characterized by transmission electron microscopy and electron energy loss spectroscopy. The film is graphitic and highly oriented with the c-axis lying parallel to the substrate. Moreover, the film is under significant biaxial stress such that the graphitic layer spacing is reduced by 4% from that of ambient pressure graphite. This oriented structure evolves due to the mobility of the carbon atoms at 200 °C. The material is sufficiently crystalline on the nanometer scale so as to produce Bragg diffraction discs in a convergent beam electron diffraction pattern using a 2.5 nm probe.

The elastic constants of thin Diamond-Like Carbon (DLC) films supply important information, but their measurement is difficult. Standard nanoindentation does not directly measure the elastic constants and has strong limitations particularly in the case of hard thin films on softer substrates, such as tetrahedral amorphous carbon on Si. Surface acoustic waves provide a better mean to investigate elastic properties. Surface Brillouin scattering (SBS) intrinsically probes acoustic waves of the wavelength which is appropriate to test the properties of films in the tens to hundreds of nanometers thickness range. SBS can be used to derive all the isotropic elastic constants of hard-on-soft and soft-on-hard amorphous carbon films of different kinds, with thickness down to less than 10 nm. The results help to resolve the previous uncertainties in mechanical data. The Young's modulus of tetrahedral amorphous carbon (ta-C) turns out to be lower than that of diamond, while the moduli of hydrogenated ta-C (ta-C:H) are considerably lower than those of ta-C because of the weakening effect of C-H bonding.

A commonly used technique to compute mechanical properties from indentation tests is the Oliver and Pharr method. Using dimensional analysis and finite element modeling, this paper investigates errors when the Oliver and Pharr method is used to compute thin film properties.

Pure diamondlike carbon thin films largely bonded by four-fold coordination suffer from a large internal compressive stress that gives rise to a serious adhesion problem. In this work, functionally gradient (FG) diamondlike carbon thin coatings were prepared by pulsed laser deposition in a high vacuum chamber as an alternative approach to address the adhesion problem of diamondlike films. Copper, silver and titanium were incorporated into the growing films with their concentration as a function of the distance from the substrate surface. The top of the thin coating is pure DLC of about 400 nm in thickness. The total thickness of the functionally graded superhard DLC coatings can exceed 1.0 μm without buckling. Visible micro-Raman spectroscopy was used to characterize the bonding structure of the layers which contain alloy atoms. High resolution transmission electron microscopy was employed to study the microstructure of the coatings. Nanoscale mechanical characterizations using Nanoindenter XPTM were carried out to study the mechanical behavior of the functionally gradient DLC films.

Metal-doped diamond-like carbon films were produced for the purpose of an electrochemical nano-electrode. In this study we use Z-contrast scanning transmission electron microscopy to directly observe metal cluster formation and distributions within the chromium-doped carbon films. At low doping (∼6at%Cr), Cr is uniformly distributed; at high doping (∼12at%Cr), Cr-rich clusters are formed. Using electron energy loss spectroscopy, we find that the Cr clusters tend to be metallic-like at low doping levels and carbide-like at high doping levels according to the Cr L2.3 white line ratios. The carbon is more diamond-like at low doping and more graphite/carbide like at high doping according to the sp2/sp3 electron percentage measurements.

We have studied the growth and the properties of ta-C:F films prepared by the deposition of mass separated 12C+ and 19F+ ions as a function of the F concentration CF. The films are always strongly F-deficient due to the formation of volatile CFx, molecules during the deposition process. CF ≈ 25 at.% is obtained for an ion charge ratio of C+:F+ = 1:1. The mass density strongly decreases from 2.9 g/cm3 for ta-C to 1.1 g/cm3 for films with CF ≈ 23 at.%, whereas the electron density related plasmon energy only varies slightly between 31.8 eV and 29 eV. Therefore, films with small CF have both a high mass and high electron density resulting in diamond-like properties. The discrepancy between low mass density and high electron density for films with large cF can be explained by voids. The thickness and composition of films with CF below 20 at.% remains unchanged for vacuum annealing to temperatures of 600 °C for 10 minutes. Loss of F was observed for films with cF above 20 at.%. The compressive film stress decreases with increasing CF, and is further reduced by annealing.

This paper describes a comparison between capacitance-voltage (CV) and spectral ellipsometry (SE) measurements of the dielectric constant of fluorinated amorphous carbon films. Whereas CV measurements require the construction of metal-insulatorsemiconductor (MIS) structures, SE measurements can be made on as-deposited films, and are much easier to implement. An examination of the results indicate that under certain conditions, the SE measurements give values that are in reasonable agreement with the more direct measurements based on the electrical (CV) response of the dielectric layer. The films reported on here had dielectric constants ranging from 3 – 5, and, in some cases, show promising characteristics for use as low-k dielectrics in semiconductor devices.

The incorporation of fluorine into amorphous hydrogenated carbon films deposited by the plasma enhanced chemical vapor deposition technique (PECVD) was investigated. Different mixtures of CH4 and CF4 were employed as the plasma atmosphere, with the partial pressure of CF4 ranging from 0 to 100 %. For all depositions, the self-bias was kept at –350 V. In the case of atmospheres richer than ∼80 % of CF4, no film deposition but substrate erosion was observed. The composition of the films was determined by Ion Beam Analysis (IBA), revealing that fluorine is incorporated into the amorphous network by replacing hydrogen. Infrared (IR) transmission measurements confirmed these results. It was also found that the incorporation of fluorine has the effect of reducing both the internal stress and hardness due to atomic density reduction.

The organic carbon source –xylene(C6H6-C2H4), was used to fabricate a-C:H films in plasma enhanced chemical vapor deposition system. The structures and bonding configurations were characterized and compared with that of conventional methane-based samples by using Fourier Transform Infrared spectroscopy and Raman scattering technique. Strong room temperature luminescence in blue-green light range was found and the PL feature was quite different from that of methane-based a-C:H films.

Diamond-like carbon (DLC) films have been prepared by pulsed laser deposition (PLD) (wavelength 248 nm), ablating highly oriented pyrolytic graphite (HOPG) at room temperature in a vacuum of 10−2Pa, at fluences between 0.5 and 35 Jcm−2. Films have been deposited on Si(100) with and without a SiC interlayer. Structural analysis, such as visible and UV Raman, Infrared and Electron Energy Loss (EEL) spectroscopies show that the films are hydrogen-free and undergo a transition, from mainly disordered graphitic to up to 80% tetrahedral amorphous carbon (ta-C), above a laser threshold fluence of 5 J cm−2. The measured residual stresses of as deposited ta-C films do not exceed 2 GPa. Scratch tests show excellent adhesion properties. Low friction coefficients (0.05-0.1) have been measured in ambient humidity. Nanoindentation indicates that film hardness is as high as 70 GPa

Interaction of oxygen with three commercial activated carbons (GX203, P1400 and MEED50 supplied by PICA USA Inc., with BET surface areas of 1000, 1150 and 2000 m2/g respectively) is investigated using 9 GHz electron spin resonance (ESR) spectroscopy. All three carbons give a single ESR line with g = 2.0028(3), but the linewidth ΔH and the spin concentration Ns, are strongly affected by exposure to oxygen. The ESR parameters (g, ΔH, Ns) are measured for different partial pressures of oxygen. For the highly evacuated samples, δH ≃ 1.2 Oe and Ns ≃ 1019/gm and these results are interpreted in terms of uncompensated surface dangling bonds. Oxygen exposure broadens the line and reduces Ns, in direct relation to the surface areas of the carbons and the effect is reversible. Possible effects of the paramagnetic oxygen on dangling bonds are discussed.

Hydrogen free amorphous carbon (a-C) and carbon nitride (a-C:N) were synthesized by means of shielded arc ion plating in which a shielding plate was inserted between a target and a substrate in order to reduce macroparticle deposition onto the substrate. Using a graphite target as a cathode, thin films of a-C and a-C:N were prepared in an arc discharge plasma of argon or nitrogen gas, respectively, at a pressure of 1 Pa. Based on nanoindentation, mechanical properties of these films were studied in relation to substrate bias voltage (Vs). The a-C films prepared at Vs ranging from -50 to -200 V consisted of diamond-like phase and showed hardness higher than 20 GPa with its maximum of 35 GPa at Vs = -100 V. However, hardness of the films deposited at Vs < 300 V was less than 7 GPa indicating that the films were converted to graphite-like phase due to excessive ion impact in Ar plasma. Wear resistance of the a-C films was closely related to their hardness. Namely, a harder a-C film was more wear resistant. On the contrary, hardness of the a-C:N films was less dependent on Vs. It remained in the range of 10 to 15 GPa and was much lower than the maximum hardness of the a-C films. Nevertheless, the wear resistance of the a-C:N films was comparable to or much better than the a-C films. In particular, the a-C:N film prepared at Vs = -300 V was so wear resistant that the film showed no apparent wear when rubbed with a diamond tip less than 100 nm in tip-diameter at a contact force of 20μN. The presence of β-C3N4like phase characterized by a N1 s XPS peak at 400.5 eV has found to be crucial for high wear resistance of the a-C:N films

We have prepared pure diamondlike carbon films and Cu doped diamondlike carbon films through pulsed laser deposition. The Cu concentration does not exceed 3.0 atomic percent. Electrical conduction studies were carried out on the films to understand the electrical transport mechanism. It was found that both pure DLC and Cu doped DLC are of p-type conduction. Incorporation of Cu into the DLC films decreases the resistivity significantly. Transmission electron microscopy and radial distribution function analyses showed that the DLC films are typical tetrahedral amorphous carbon. The conductivity of Cu doped DLC films exhibited T1/2 temperature dependence, rather than the T1/4 dependence (Mott-Davis law). This dependence was observed within a wide temperature range (from below liquid nitrogen temperature to near room temperature). The T1/2 dependence was explained on the basis of the Efros-Shklovskii model which considers the long range Coulomb interaction between localized states