Study of optical properties and biocompatibility of DLC films characterized by sp3 bonds

Optical and biomedical properties of diamond-like carbon (DLC) films of various sp², sp³ bonds were studied. The layers were prepared by pulsed laser deposition (PLD) for laser energy densities from 4 J?cm^?2 to 14 J?cm^?2. The percentage of sp² and sp³ bonds was calculated using X-ray photoelectron spectroscopy (XPS). In dependence on density the films contained up to 70 % of sp³ bonds. Optical properties were measured using spectroscopic ellipsometry in region from 250 nm to 1000 nm (n=2.6–2.7; k=0.07–0.25) and by transmission measurement (from 200 nm to 1100 nm). The adhesion and growth of human fibroblasts and keratinocytes of DLC films were tested in vitro.     

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.     

Synthesis of DLC films by PLD from liquid target and dependence of film properties on the synthesis conditions

DLC (Diamond-like carbon films) were prepared by pulsed laser ablation of a liquid target at substrate temperatures from 18 to 600°C using 248 nm KrF excimer laser. The sp³ hybridization state carbon formation was additionally promoted by gaseous H₂O₂ flow through the reaction chamber and substrate excitation by the same laser beam. Deposited DLC films were characterised by Raman scattering spectroscopy and atomic force microscopy (AFM). Comparative AFM and Raman study shows that the increase in the content of sp³ type bonding in DLC is in correlation with the increase of the surface roughness of the samples prepared.     

PLD方法制备的超硬非晶碳薄膜研究

 用脉冲激光沉积在不同条件下制备非晶碳超硬薄膜，研究了非晶碳超硬薄膜的表面形貌、结构、应力、硬度以及能谱等。原子力显微镜和扫描电镜图像显示，薄膜表面平整、致密且光滑,均方根粗糙度最大为0.877 nm。在高激光重复频率、高激光通量条件下，薄膜有很大的应力，致使膜层褶皱甚至破裂，小角X射线衍射表明薄膜为非晶态且最大残余应力达30 GPa以上,但300 ℃温度的原位退火可以有效降低残余应力；纳米压痕测试表明薄膜硬度大于20 GPa，弹性模量大于200 GPa；X射线光电子能谱表明薄膜中sp3的含量在39%~53%之间变化，并且与激光通量成正比。     

Fabrication of diamond-like carbon thin films by femtosecond laser ablation of frozen acetone

Diamond-like carbon (DLC) thin films were fabricated by the ablation of frozen acetone with a 790 nm, 130 fs Ti:sapphire laser. Compared to a solid carbon target, frozen acetone could significantly reduce the number of fragments mixed into the films. The optical and mechanical properties of the fabricated DLC films were determined when the laser fluence was varied from 3 to 470 J/cm². With the increase in laser fluence, the films tinged with brown and the optical bandgap of the films decreased from 2.0 to 1.2 eV. Also, the refractive index and hardness of the films increased from 1.75 to 1.99 and from 10 to 16 GPa, respectively. The sp³ content was not changed even if the laser fluence was varied. The change in properties resulted from the hydrogen content of the films. PACS 81.05.Uw; 81.15.Fg     

脉冲激光气相沉积法制备的非晶CH薄膜特性分析

采用脉冲激光气相沉积(PLD)法,研究了氢气压强对非晶CH薄膜性能的影响。原子力显微镜图和白光干涉图显示,薄膜表面平整致密,随着氢气压强增大,粗糙度变大。拉曼光谱分析表明,氢气压强增加,G峰和D峰位置都在向高波数方向移动。傅里叶变换红外光谱分析显示,薄膜中存在sp3—CH2和sp2—CH等基团。最后,采用PLD漂浮法在最优参数氢气压强为0.3 Pa下,成功制备了不同厚度(100~300 nm)、满足一定力学强度、无明显宏观缺陷的自支撑CH薄膜。     

Adjusting chemical bonding of hard amorphous CSixNy thin films by N*-plasma-assisted pulsed laser deposition

Hard amorphous carbon silicon nitride thin films have been grown by pulsed laser deposition (PLD) of various carbon silicon nitride targets by using an additional nitrogen RF plasma source on [100] oriented silicon substrates at room temperature. The influence of the number of laser shots per target site on the growth rate and film surface morphology was studied. Up to about 30 at. % nitrogen and up to 20 at. % silicon were found in the films by Rutherford backscattering spectroscopy (RBS) and X-ray photoelectron spectroscopy (XPS). The XPS of the films showed a clear correlation of binding energy to the variation of PLD parameters. The films show a universal hardness value up to 23 GPa (reference value for silicon substrate 14 GPa) in dependence on target composition and PLD parameters. The results emphasise the possibility of variation of chemical bonding and corresponding properties, such as nanohardness, of amorphous CSi_xN_y thin films by the plasma-assisted PLD process.     

Preparation of super-hard coatings by pulsed laser deposition

Amorphous diamond-like carbon (DLC) films and nanocrystalline cubic boron nitride (c-BN) films were prepared by pulsed laser deposition. DLC films with 80 to 85% sp³ bonds prepared at a laser fluence above 6 J/cm² and a substrate temperature below 100 °C show high compressive stresses in the range of 8 to 10 GPa. Those stresses can be completely removed by means of pulsed laser annealing, allowing the preparation of DLC films with several-micrometre thickness. c-BN films were prepared with additional ion-beam bombardment at a substrate temperature of 250 °C. The properties of DLC and c-BN films deposited at high growth rates up to 100 nm/min are presented . PACS 81.15.Fg; 68.60.Bs: 62.40.+i     

Thermal conductive performance of deposited amorphous carbon materials by molecular dynamics simulation

A series of diamond-like carbon (DLC) films with different microstructure were prepared by depositing carbon atoms on diamond surface with incident energy ranging from 1 to 100 eV. The thermal conductivity of the deposited films and the Kapitza resistance between the film and the diamond substrate were investigated. Results show that the average density, the average fraction of sp³ bonding and the thermal conductivity of the DLC films increase first, reaching a maximum around 20–40 eV before decreasing, while the Kapitza resistance decreases gradually with increased deposition energy. The analysis suggests that the thermal resistance of the interface layer is in the order of 10^?10 m²K/W, which is not ignorable when measuring the thermal conductivity of the deposited film especially when the thickness of the DLC film is not large enough. The fraction of sp³ bonding in the DLC film decreases gradually normal to the diamond surface. However, the thermal conductivity of the film in normal direction is not affected obviously by this kind of structural variation but depends linearly on the average fraction of sp³ bonding in the entire film. The dependence of the thermal conductivity on the fraction of sp³ bonding was analysed by the phonon theory.     

Low energy repetitive miniature plasma focus device as high deposition rate facility for synthesis of DLC thin films

Diamond-like carbon (DLC) films were deposited on Si (1 0 0) substrate using a low energy (219 J) repetitive (1 Hz) miniature plasma focus device. DLC thin film samples were deposited using 10, 20, 50, 100 and 200 focus shots with hydrogen as filling gas at 0.25 mbar. The deposited samples were analyzed by XRD, Raman Spectroscopy, SEM and XPS. XRD results exhibited the diffraction peaks related to SiO₂, carbon and SiC. Raman studies verified the formation amorphous carbon with D and G peaks. Corresponding variation in the line width (FWHM) of the D and G positions along with change in intensity ratio (I_D/I_G) in DLC films was investigated as a function of number of deposition shots. XPS confirmed the formation sp² (graphite like) and sp³ (diamond like) carbon. The cross-sectional SEM images establish the 220 W repetitive miniature plasma focus device as the high deposition rate facility for DLC with average deposition rate of about 250 nm/min.     

Biocompatible film deposition by using Nd:YAG pulsed laser

A Nd:YAG laser operating at the fundamental wavelength (1064 nm) and at the second harmonic (532 nm), with 9 ns pulse duration, 100–900 mJ pulse energy, and 30 Hz repetition rate mode, was employed to ablate in vacuum (10^?6 mbar) biomaterial targets and to deposit thin films on substrate backings. Titanium target was ablated at the fundamental frequency and deposited on near-Si substrates. The ablation yield increases with the laser fluence and at 40 J/cm ² the ablation yield for titanium is 1.2×10¹⁶ atoms/pulse. Thin film of titanium was deposited on silicon substrates placed at different distance and angles with respect to the target and analysed with different surface techniques (optical microscopy, scanning electron spectrosopy (SEM), and surface profile).

Hydroxyapatite (HA) target was ablated to the second harmonic and thin films were deposited on Ti and Si substrates. The ablation yield at a laser fluence of 10 J/cm ² is about 5×10¹⁴ HA molecules/pulse. Thin film of HA, deposited on silicon substrates placed at different distance and angles with respect to the target, was analysed with different surface techniques (optical microscopy, SEM, and Raman spectroscopy).

Metallic films show high uniformity and absence of grains, whereas the bio-ceramic film shows a large grain size distribution. Both films found special application in the field of biomaterial coverage.     

Diamond-like-carbon films produced by magnetically guided pulsed laser deposition

We have compared the quality of carbon films deposited with magnetically guided pulsed laser deposition (MGPLD) and conventional pulsed laser deposition (PLD). In MGPLD, a curved magnetic field is used to guide the plasma but not the neutral species to the substrate to deposit the films while, in conventional PLD, the film is deposited with a mixture of ions, neutral species and clusters. A KrF laser pulse (248 nm) was focused to intensities of 10 GW/cm² on a carbon source target and a magnetic field strength of 0.3 T was used to steer the plasma around a curved arc to the deposition substrate. Electron energy loss spectroscopy was used in order to measure the fraction of sp³ bonding in the films produced. It is shown that the sp³ fraction, and hence the diamond-like character of the films, increased when deposited only with the pure ion component by MGPLD compared with films produced by the conventional PLD technique. The dependence of film quality on the laser intensity is also discussed. Received: 7 December 2000 / Accepted: 20 August 2001 / Published online: 2 October 2001     

The influence of the number of pulses on the morphological and photoluminescence properties of SrAl2O4:Eu,Dy thin films prepared by pulsed laser deposition

The current work reports on the influence of the number of laser pulses on the morphological and photoluminescence properties of SrAl₂O₄:Eu²⁺,Dy³⁺ thin films prepared by the pulsed laser deposition (PLD) technique. Atomic force microscopy (AFM) was used to study the surface topography and morphology of the films. The AFM data showed that the film deposited using a higher number of laser pulses was packed with a uniform layer of coarse grains. In addition, the surface of this film was shown to be relatively rougher than the films deposited at a lower number of pulses. Photoluminescence (PL) data were collected using the Cary Eclipse fluorescence spectrophotometer equipped with a monochromatic xenon lamp. An intense green photoluminescence was observed at 517 nm from the films prepared using a higher number of laser pulses. Consistent with the PL data, the decay time of the film deposited using a higher number of pulses was characteristically longer than those of the other films. The effects of laser pulses on morphology, topography and photoluminescence intensity of the SrAl₂O₄:Eu²⁺,Dy³⁺ thin films are discussed.     

Pulsed laser deposition of Mg–Al layered double hydroxide with Ag nanoparticles

Powdered layered double hydroxides (LDHs)—also known as hydrotalcite-like (HT)—compounds have been widely studied due to their applications as catalysts, anionic exchangers or host materials for inorganic or organic molecules. Assembling thin films of nano-sized LDHs onto flat solid substrates is an expanding area of research, with promising applications as sensors, corrosion-resistant coatings, components in optical and magnetic devices. The exploitation of LDHs as vehicles to carry dispersed metal nanoparticles onto a substrate is a new approach to obtain composite thin films with prospects for biomedical and optical applications. We report the deposition of thin films of Ag nanoparticles embedded in a Mg–Al layered double hydroxide matrix by pulsed laser deposition (PLD). The Ag-LDH powder was prepared by co-precipitation at supersaturation and pH = 10 using aqueous solutions of Mg and Al nitrates, Na hydroxide and carbonate, and AgNO₃, having atomic ratios of Mg/Al = 3 and Ag/Al = 0.55. The target to be used in laser ablation experiments was a dry pressed pellet obtained from the prepared Ag-LDH powder. Three different wavelengths of a Nd:YAG laser (266, 532 and 1064 nm) working at a repetition rate of 10 Hz were used. X-Ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), and secondary ions mass spectrometry (SIMS) were used to investigate the structure, surface morphology and composition of the deposited films.     

Morphological and optical properties of silicon thin films by PLD

Silicon thin films have been prepared on sapphire substrates by pulsed laser deposition (PLD) technique. The films were deposited in vacuum from a silicon target at a base pressure of 10⁻⁶ mbar in the temperature range from 400 to 800 °C. A Q-switched Nd:YAG laser (1064 nm, 5 ns duration, 10 Hz) at a constant energy density of 2 J × cm⁻² has been used. The influence of the substrate temperature on the structural, morphological and optical properties of the Si thin films was investigated.Spectral ellipsometry and atomic force microscopy (AFM) were used to study the thickness and the surface roughness of the deposited films. Surface roughness values measured by AFM and ellipsometry show the same tendency of increasing roughness with increased deposition temperature.     

Diamond-like phase formation in an amorphous carbon films prepared by periodic pulsed laser deposition and laser irradiation method

Diamond-like carbon (DLC) films were fabricated by pulsed laser ablation of a liquid target. During deposition process the growing films were exited by a laser beam irradiation. The films were deposited onto the fused silica using 248 nm KrF eximer laser at room temperature and 10⁻³ mbar pressure. Film irradiation was carried out by the same KrF laser operating periodically between the deposition and excitation regimes. Deposited DLC films were characterized by Raman scattering spectroscopy. The results obtained suggested that laser irradiation intensity has noticeable influence on the structure and hybridization of carbon atoms deposited. For materials deposited at moderate irradiation intensities a very high and sharp peak appeared at 1332 cm⁻¹, characteristic of diamond crystals. At higher irradiation intensities the graphitization of the amorphous films was observed. Thus, at optimal energy density the individual sp³-hybridized carbon phase was deposited inside the amorphous carbon structure. Surface morphology for DLC has been analyzed using atomic force microscopy (AFM) indicating that more regular diamond cluster formation at optimal additional laser illumination conditions (∼20 mJ per impulse) is possible.     

The effect of argon gas pressure on structural,morphological and photoluminescence properties of pulsed laser deposited KY<Subscript>3</Subscript>F<Subscript>10</Subscript>:Ho<Superscript>3+</Superscript> thin films

KY₃F₁₀:Ho³⁺ thin films were deposited by a pulsed laser deposition technique with Nd–YAG laser radiation (λ = 266 nm) on (100) silicon substrate. The XRD and FE-SEM results show improved crystalline structure for the film deposited at a pressure of 1 Torr. The AFM results show that the RMS roughness of the films increases with rise in argon gas pressure. The EDS elemental mapping shows Y-excess for all the films deposited under all pressures, and this is attributed to its higher mass and low volatility as compared to K and F. XPS analysis further confirmed Y-excess in the deposited films. Green PL emission at 540 nm was investigated at three main excitation wavelengths, namely 362, 416 and 454 nm. The PL emission peaks increase with rise in background argon gas pressure for all excitation wavelengths. The highest PL intensity occurred at excitation of 454 nm for all the thin films. In addition, faint red (near infrared) emission was observed at 750 nm for all the excitations. The green emission at 540 nm is ascribed to the ⁵F₄–⁵I₈ and ⁵S₂–⁵I₈ transitions, and the faint red emission at 750 nm is due to the ⁵F₄–⁵I₇ and ⁵S₂–⁵I₇ transitions of Ho³⁺.     

Pulsed laser deposition of hard coatings in atmospheric air

A new laser plasma technique for non-vacuum deposition of thin films has been proposed and experimentally realized. It is based on the fact that the plasma plume, which occurs under ablation of a target in air by high-intensity short laser pulses, can penetrate through a dense gas environment without significant cooling at the distance of about 1 mm. The technique has been applied to deposit diamond-like carbon (DLC) coatings on stainless steel substrates using four different values of pulse duration: 10 ns, 300 ps, 5 ps and 130 fs. Optimization of different experimental parameters including distance between the target and the substrate, laser intensity and gases (He, Ar, N₂, compressed air) blown in the deposition zone, has been performed. The deposition rate in the experiments was estimated as 2–5×10^-4 nm/(cm²pulse) for the pulse energy of 1–4 mJ. The deposited amorphous carbon films with thickness of several hundred nanometers have shown high average nanohardness (10–25 GPa depending on the irradiation conditions) and good adhesion to substrates (60 MPa). According to X-ray electron spectroscopy analysis the films consist of both sp²- and sp³-bonded carbon and contain 3–7% of free oxygen in bulk. The mechanisms of DLC non-vacuum laser deposition are discussed. To demonstrate the large potential of this technique, the first results on deposition of titanium nitride using ablation of titanium in air with nitrogen jet assistance are also presented. PACS 52.38.Mf; 81.15.Fg; 81.05.Uw     

Improving the conductivity of diamond-like carbon films with zinc doping and its material properties

Zinc doped diamond-like carbon (DLC) nanocomposite thin films are fabricated by KrF pulsed laser deposition. Carbon targets containing 3.0, 5.0 and 10.0 atomic percentages of zinc are used as the source for the laser system. Investigation of electrical properties by the four-point probe shows that doping zinc into DLC can lower the electrical sheet resistivity. Microstructural analysis by Raman spectroscopy and XPS show a lower sp³ content but a higher SiC content with an increasing amount of zinc incorporation. The increase of SiC leads to an increase in adhesion strength. Surface roughness of the films also increases while the coefficients of friction for the films do not change.     

The protective properties of ultra-thin diamond like carbon films for high density magnetic storage devices

With the increase of magnetic storage density, the thickness of the protective diamond like carbon (DLC) film on the surfaces of head and disk is required as thin as possible. In this paper, the structure, mechanical properties and corrosion and oxidation resistance of ultra-thin DLC films are investigated. The ultra-thin DLC films were deposited by using filtered cathodic vacuum arc (FCVA) technique. The exact thickness of the ultra-thin DLC film was determined by high resolution transmission electron microscope (HRTEM). Raman analysis indicates that the ultra-thin DLC film presents ta-C structure with high sp³ fraction. In the wear test, a diamond tip was used to simulate a single-asperity contact with the film surface and the wear marks were produced on the film surface. The wear depths decrease with film thickness increasing. If the film thickness was 1.4 nm or above, the wear depth was much lower than that of Si substrate. This indicates that the ultra-thin DLC film with thickness of 1.4 nm shows excellent wear resistance. Corrosion tests in water and oxidation tests in air were carried out to investigate the diffusion barrier effect of the ultra-thin DLC films. The results show that the DLC film with thickness of 1.4 nm provides adequate coverage on the substrate and has good corrosion and oxidation resistance.