Effect of ion bombardment on the phase composition and mechanical properties of diamond-like carbon films

It is established that the addition of hydrogen to methane in the reaction mixture upon the fabrication of diamond-like carbon films via the plasma-enhanced chemical vapor deposition method decreases residual stresses in the obtained films and significantly reduces their growth rate. The films were investigated via atomic force microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. Irradiation of the prepared films with P⁺ and PF ₄ ⁺ ions results in strong sample swelling with increasing dose, as well as in a decrease in the compressive stress up to transition to tensile one reaching saturation. Moreover, the fraction of sp ³ bonds increases with increasing ion dose while the fraction of sp ² bonds decreases symmetrically with the processes proceeding faster upon irradiation with molecular ions. Qualitative mechanisms explaining the experimental results are proposed.     

Electrically conducting ion tracks in diamond-like carbon films for field emission

Electrically conducting channels in an insulating carbon matrix were produced by 140-MeV Xe ion irradiation. The high local energy deposition of the individual ions along their pathes causes a rearrangement of the carbon atoms and leads to a transformation of the insulating, diamond-like (sp³-bonding) form of carbon into the conducting, graphitic (sp²-bonding) configuration. The conducting ion tracks are clearly seen in the current mapping performed with an atomic force microscope (AFM). These conducting tracks are of possible use in field emission applications. Received: 4 May 1999 / Accepted: 5 May 1999 / Published online: 1 July 1999     

Influence of a magnetic field on deposition of diamond-like carbon films

Received: 17 February 1998/Accepted: 25 May 1998     

Stability of subatomic carbon films on metal surfaces against low-energy gas ion bombardment

The earlier developed original experimental technique for measuring and analyzing the parameters of low-frequency fluctuations of the field-emission current in metal film systems is used to measure the sputtering yield Y _f of carbon films (with a coverage Θ ranging from 1 to 4) applied on Fe, Nb, Ta, and U substrates. The value of Y _f is calculated by an expression derived within a theoretical model developed. The sputtering ratios were measured for the case when the carbon films are sputtered by H⁺ and He⁺ ions with an energy E _i between 2 and 10 keV. With Θ fixed, the energy dependences of Y _f are obtained for each of the ions. In addition, for each of the ions, the Θ dependences of Y _f are found for several values of E _i. In all the cases, the measured values of Y _f far exceed those for pure carbon. With another original technique that combines field-ion microscopy (FIM) and precise measurement of current and/or luminous properties of local regions in FIM images, the energy thresholds E _th of sputtering carbon films applied on the metal surfaces are found. The energy distributions of Y _f in the near-threshold energy range for various Θ are obtained.     

Laser-induced spallation in diamond-like carbon films

Laser-induced multilevel spallation in diamond-like carbon films is observed and studied for a wide range of laser parameters (=539, 800, 1064, and 1078 nm; =100 fs, 300 ps, 10 ns, and 150 ns; E>0.1 J/cm²). Laser irradiation causes the detachment and removal of material layers, whose lateral size is comparable with the irradiated area and whose thickness of 10–200 nm is much less than the DLC film thickness. The influence of the laser parameters on the thickness, size, and number of removed layers is examined. A qualitative explanation of laser-induced spallation in DLC films is proposed, which is based on the fact that the absorbed laser pulse produces a rapidly expanding surface layer of modified structure and reduced density. PACS 42.62.Cf; 61.80.Ba; 81.40.Wx     

Influence of ion bombardment on growth and properties of PLD created DLC films

A hybrid PLD system with ion bombardment of films was developed. Growing DLC films were modified during the laser deposition (10 J?cm^?2) by argon ions with energy in the range from 40 eV to 210 eV and cathode current of 0.15 A and 0.5 A. The content of sp² “graphitic” and sp³ “diamond” bonds was measured using XPS. Sp³ bonds changed from 60 % to 81 %. We found the highest sp³ content for energy of 40 eV. Hardness (and reduced Young’s modulus) were determined by nanoindentation and reached 49 GPa (277 GPa). Film adhesion was studied using the scratch test and was up to 14 N for titanium substrates. Relations among deposition conditions and measured properties are presented.     

Residual stress in diamond-like carbon films: Role of growth conditions and ion irradiation

The dependence of the internal residual stress in thin diamond-like carbon films grown by the plasma-enhanced chemical vapor deposition technique on the most important growth parameters, namely, the radio-frequency (RF) power and direct-current (DC) bias voltage, was studied. It was shown that the compressive stress reaches its highest value of 2.7 GPa at the low RF power and DC bias values. Both increase and decrease of these parameters result in stress decrease. The stress increases with increase in the growth temperature from 250 to 350°C. Thermal annealing of up to 350°C does not affect the stress value. Subsequent irradiation of the films by In⁺ and P⁺ ions with the energy of 350 and 120 keV, respectively, results in the decrease in the compressive stress followed by its inversion to the tensile one. The stress linearly depends on the effective dose of up to 0.5 DPA with the slope of (8.7 ± 1.3) Gpa/DPA.     

Nanoindentation measurements on modified diamond-like carbon thin films

In the present study, we explored the effect of metallic interlayers (Cu and Ti) and indentation loads (5-20 mN) on the mechanical properties of plasma produced diamond-like carbon (DLC) thin films. Also a comparison has been made for mechanical properties of these films with pure DLC and nitrogen incorporated DLC films. Introduction of N in DLC led to a drastic decrease in residual stress (S) from 1.8 to 0.7 GPa, but with expenses of hardness (H) and other mechanical properties. In contrast, addition of Cu and Ti interlayers between substrate Si and DLC, results in significant decrease in S with little enhancement of hardness and other mechanical properties. Among various DLC films, maximum hardness 30.8 GPa is observed in Ti-DLC film. Besides hardness and elastic modulus, various other mechanical parameters have also been estimated using load versus displacement curves.     

Study of colors of diamond-like carbon films

Reflective and transmissive film interference colors were calculated for DLC films on the Si and SiO 2 substrates.The calculated interference colors were compared with photographed colors of the prepared DLC samples.The observed film colors were found to match reasonably well with the corresponding calculated colors,indicating that DLC film colors come from interference instead of color center effects.Color charts for DLC films on the Si and SiO 2 substrates with various optical gaps were constructed,and the relationship between interference color and film properties such as optical gap,thickness and substrate were investigated.Usefulness of the calculated color charts in estimating optical gap or thickness of DLC films were demonstrated.     

Raman study of W-doped diamond-like carbon films

Amorphous diamond-like carbon (DLC) films prepared by the plasma chemical method on glass substrates SiO₂-Al₂O₃-TiO₂ have been studied by Raman spectroscopy. W-doped DLC films show a considerable increase in the G-band frequency up to 1592 cm^?1 and an enhanced surface hardness. The DLC films doped with W and atoms of semiconductors exhibit high transparency and a higher G-band shift to the high-frequency range (up to 1611 cm^?1).     

Evaluation of bacterial adhesion on Si-doped diamond-like carbon films

Diamond-like carbon (DLC) films as biomaterial for medical devices have been attracting great interest due to their excellent properties such as hardness, low friction and chemical inertness. It has been demonstrated that the properties of DLC films can be further improved by the addition of silicon into DLC films, such as thermal stability, compressive stress, etc. However no research work on anti-bacterial properties of silicon-doped diamond-like carbon films has been reported. In this paper the surface physical and chemical properties of Si-doped diamond-like carbon films with various Si contents on 316 stainless steel substrate prepared by a magnetron sputtering technique were investigated, including surface topography, surface chemistry, the sp³/sp² ratio, contact angle, surface free energy, etc. Bacterial adhesion to Si-doped DLC films was evaluated with Pseudomonas aeruginosa, Staphylococcus epidermidis and Staphylococcus aureus which frequently cause medical device-associated infections. The experimental results showed that bacterial adhesion decreased with increasing the silicon content in the films. All the Si-doped DLC films performed much better than stainless steel 316L on reducing bacterial attachment.     

Synthesis and structure of nitrogenated tetrahedral amorphous carbon films prepared by nitrogen ion bombardment

The tetrahedral amorphous carbon (ta-C) films with more than 80% sp³ fraction firstly were deposited by filtered cathode vacuum arc (FCVA) technique. Then the energetic nitrogen (N) ion was used to bombard the ta-C films to fabricate nitrogenated tetrahedral amorphous carbon (ta-C:N) films. The composition and structure of the films were analyzed by visible Raman spectrum and X-ray photoelectron spectroscopy (XPS). The result shows that the bombardment of energetic nitrogen ions can induce the formation of CN bonds, the conversion of C-C bonds to CC bonds, and the increase of size of sp² cluster. The CN bonds are made of CN bonds and C-N bonds. The content of CN bonds increases with the increment of N ion bombardment energy, but the content of C-N bonds is inversely proportional to the increment of nitrogen ion energy. In addition, C≡N bonds are not existed in the films. By the investigation of AFM (atom force microscopy), the RMS (root mean square) of surface roughness of the ta-C film is about 0.21 nm. When the bombarding energy of N ion is 1000 eV, the RMS of surface roughness of the ta-C:N film decreases from 0.21 to 0.18 nm. But along with the increment of the N ion energy ranging from 1400 to 2200 eV again, the RMS of surface roughness of the ta-C:N film increases from 0.19 to 0.33 nm.     

Influence of sulfidation treatment on the structure and tribological properties of nitrogen-doped diamond-like carbon films

The nitrogen-doped diamond-like carbon (DLC) films were deposited on high speed steel (HSS) substrates in the direct current unbalanced magnetron sputtering system. Sulphurized layer was formed on the surface of DLC films by means of liquid sulfidation in the intermixture of urea and thiourea solution in order to improve the tribological properties of DLC films. The influence of sulfidation treatment on the structure and tribological properties of DLC films was investigated in this work. The structure and wear surface morphology of DLC films were analyzed by Raman spectroscopy, XPS and SEM, respectively. It reveals that the treated films are smooth and uniform; and sulfur atoms are bonded chemically. The treated films have broader distribution of Raman spectra in the range of 1000-1800 cm⁻¹ and higher I_D/I_G ratio than the untreated films as a result of the appearance of the crystalline graphite structure after the sulfidation treatment. It is showed that the sp² relative content increase in the treated films from the XPS measurement. The Raman results are consistent with the XPS results. The tribological properties of DLC films were investigated using a ball-on-disk rotating friction and wear tester under dry friction conditions. It is found that the sulfidation concentration plays an important part in the tribological properties of the treated DLC films. The results showed the treated films with low sulfidation concentration have a lower friction coefficient (0.1) than the treated films with high sulfidation concentration (0.26) and the untreated films (0.27) under the same friction testing conditions, which can be attributed to both the presence of sulfur-containing materials and the forming of the mechanical alloyed layer on the wear surface. Adding the dry nitrogen to the sliding surface in the testing system helps the friction coefficient of the treated films with low sulfidation concentration to decrease to 0.04 further in this work. On the basis of the experimental results, it is indicated that the liquid sulfidation technique, which is low-cost, non-polluting and convenience, would be an appropriate method for the surface treatment of DLC films.     

Nanoindentation testing on copper/diamond-like carbon bi-layer films

In the present work, the effect of indentation load on nano-mechanical properties of copper/diamond-like carbon (Cu/DLC) bi-layer films was explored. In addition, effect of Cu interlayer and influence of self bias on residual stress and various other nano-mechanical properties such as hardness (H) and elastic modulus (E) of Cu/DLC bi-layer films were also discussed. These Cu/DLC bi-layer films were deposited, using hybrid system involving radio frequency (RF)-plasma enhanced chemical vapor deposition and RF-sputtering units, under varied self biases from −125 to −225 V. The effect of penetration depth with varied load from 5 to 20 mN on H and E of these Cu/DLC bi-layer films was also analyzed.     

射频功率对类金刚石薄膜性能的影响

在不同射频功率条件下,实验研究了射频等离子体化学气相沉积类金刚石薄膜的金刚石相分数、光学常数和硬度。利用Raman光谱仪、椭圆偏振仪、数字式显微硬度计分别测试了不同条件下单层类金刚石薄膜的金刚石相分数、光学常数和硬度。实验表明,随着功率的增加,金刚石相的相对分数减少,薄膜的折射率先减小再增加然后减小,射频功率大于910 W时,沉积速率急剧增大。而薄膜的硬度先增加后减小,在射频功率为860 W处获得最大值。     

Short-pulse laser deposition of diamond-like carbon thin films

The high intensities present in and the non-thermal nature of ultrashort-pulse laser ablation provide a nearly ideal source for thin-film deposition. The high kinetic energies and high ion content in the ablation plume suggest that it would be useful for the creation of diamond thin films. We used a 120 fs, 3 W, 1 kHz laser to ablate a graphite target and characterized the resulting films. We were able to grow amorphous films of up to 18 7m thick and free from graphite particulates with no annealing necessary and at rates up to 25 7m/hr. The films had 40-50% sp³ bonds as measured by using EELS and had properties typical of PLD-generated diamond-like carbon films.     

Resistance changes in thin metallic films under ion bombardment

Resistance changes in thin films of copper, aluminium and bismuth have been studied under the bombardment of nitrogen, carbon and argon ions. Variations in resistance with implantation dose have been observed upto doses of ∼ 3 × 10¹⁷ ions/cm² for ion energies in the range 40 to 120 keV. The results are discussed in terms of desorption of gases from the film and a composite action of sputter removal of the film and its structural changes upon ion bombardment. A simple theoretical model is discussed which can qualitatively explain the experimental observations.     

射频功率对类金刚石薄膜性能的影响

在不同射频功率条件下,实验研究了射频等离子体化学气相沉积类金刚石薄膜的金刚石相分数、光学常数和硬度。利用Raman光谱仪、椭圆偏振仪、数字式显微硬度计分别测试了不同条件下单层类金刚石薄膜的金刚石相分数、光学常数和硬度。实验表明,随着功率的增加,金刚石相的相对分数减少,薄膜的折射率先减小再增加然后减小,射频功率大于910 W时,沉积速率急剧增大。而薄膜的硬度先增加后减小,在射频功率为860 W处获得最大值。     

Femtosecond pulsed laser ablation of diamond-like carbon films on silicon

Femtosecond pulsed laser ablation (τ = 120 fs, λ = 800 nm, repetition rate = 1 kHz) of thin diamond-like carbon (DLC) films on silicon was conducted in air using a direct focusing technique for estimating ablation threshold and investigating the influence of ablation parameter on the morphological features of ablated regions. The single-pulse ablation threshold estimated by two different methods were ?_th(1) = 2.43 and 2.51 J/cm². The morphological changes were evaluated by means of scanning electron microscopy. A comparison with picosecond pulsed laser ablation shows lower threshold and reduced collateral thermal damage.     

Electrodeposition of diamond-like amorphous carbon films on aluminum from acetonitrile

Diamond-like carbon (DLC) films were electrodeposited on aluminum from acetonitrile with a pulse-modulated power at room temperature. The films were grey with 1 7m in thickness. The resistivity of the films was of the order of 10⁷ Q cm The films were characterized by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. XPS shows that the main composition of the films is carbon. Raman spectra indicate that typical DLC films were formed when high potential (>800 V) was applied.