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     

DLC coating of textile blood vessels using PLD

Textile blood vessels with a length of 30 cm were coated with amorphous diamond-like carbon (DLC) layers with thicknesses up to 200 nm. The layers were created by pulsed laser deposition in vacuum or argon ambient. The percentage of sp³ carbon was evaluated using X-ray photoelectron spectroscopy, X-ray excited Auger electron spectroscopy and Raman spectroscopy. Depending on the deposition conditions the sp³ content varied from ∼40% to 60%. The adhesion of the DLC layers to the textile vessels was checked. The preliminary biocompatibility results from in vivo tests with sheep are also given.     

CO2 laser-induced crystallization of sol–gel-derived indium tin oxide films

Indium tin oxide (ITO) thin films prepared by the sol–gel method have been deposited by the dip-coating process on silica substrates. CO₂ laser is used for annealing treatments. The electrical resistivity of sol–gel-derived ITO thin films decreased following crystallization after exposure to CO₂ laser beam. The topological and electrical properties of the irradiated surfaces have been demonstrated to be strongly related to the coating solution and to the laser processing parameters. Optimal results have been obtained for 5 dip-coating layers film from 0.4 mol/l solution irradiated by 0.6 W/m² laser power density. In this case, homogeneous and optically transparent traces were obtained with a measured sheet resistance of 1.46×10² Ω/□.     

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.     

Chromium-doped diamond-like carbon films deposited by dual-pulsed laser deposition

Diamond-like carbon (DLC) and Cr-doped diamond-like carbon layers were studied. DLC and Cr-DLC were deposited on silicon and titanium substrates (Ti-6Al-4V) by dual-pulsed laser ablation using two KrF excimer lasers and two targets (graphite and chromium). The composition was analyzed using wavelength-dependent X-ray spectroscopy. The Cr content increased from 2.2 to 17.9 at%. The topology and surface properties as roughness of layers were studied using scanning electron microscopy and atomic force microscopy. With the chromium concentration increased the roughness and the number of droplets. Carbon and chromium bonds were determined by Raman spectroscopy. With an increase in chromium content the I _D/I _G ratio increased. Mechanical properties of DLC films with various chromium content were evaluated. Hardness (reduced Young’s modulus) was determined by nanoindentation and reached of 51 GPa (309 GPa). Films adhesion was studied using scratch test and with concentration of chromium increased up to 20 N.     

Power factor of very thin thermoelectric layers of different thickness prepared by laser ablation

Room temperature conductivity and the Seebeck coefficient of thin layers prepared by laser ablation from Bi₂Te₃ target were explored. The power factor was calculated for samples prepared at substrate temperature of 360°C with the density of the laser beam 5 J cm⁻² and at substrate temperature of 410°C with the density of the laser beam 2 J cm⁻² during the deposition. Oscillations of the conductivity and the power factor with the layer thickness were observed at room temperature. The oscillations of conductivity were also verified at the temperature of 77 K. The period of oscillations depends on the preparation conditions. This behavior has been theoretically explained by the quantum size effect in the layers containing different phases and in addition, it was demonstrated by the X-ray Diffraction measurement. The behavior of the power factor of the layers is compared to the behavior of the figure of merit of the layers published earlier.     

Characterization of the bonding structure of nanocrystalline diamond and amorphous carbon films prepared by plasma assisted techniques

Thin nanocrystalline diamond/amorphous carbon (NCD/a-C) composite films and amorphous diamond-like carbon (DLC) films were prepared by three methods: microwave plasma chemical vapour deposition (MWCVD) from methane/nitrogen mixtures (NCD/a-C), RF magnetron sputtering of a pure graphite target in argon/methane ambients, and pulsed laser deposition (PLD) in vacuum or argon atmosphere (DLC). The films prepared by the three techniques were comprehensively characterized with respect to their bonding structure by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). PACS 81.05.Uw; 82.80.Pv     

Phase transformation of graphite irradiated by high-intensity pulsed ion beams

The microstructure and morphology of graphite irradiated by high-intensity pulsed ion beams (HIPIB) has been studied by varying the ion current density as 200, 350 and 1500 A/cm² with one to five shots. Phase transformation from graphite to diamond-like carbon (DLC) on the HIPIB-irradiated graphite was confirmed by Raman spectroscopy where a typical broadened asymmetric peak appeared in the wavenumber range of 1100-1700 cm⁻¹. Formation of DLC on the irradiated graphite strongly depended on the HIPIB parameters and preferably took place at the medium ion current density of 350 A/cm² up to five shots. Numerical simulation of ablation process was performed to explore the transformation mechanism of DLC from graphite irradiated by HIPIB. The calculation showed that the temperature profile in irradiated graphite at 350 A/cm² is almost identical to that at 200 A/cm², showing a deeper heat-affected zone in comparison with that of 1500 A/cm². Moreover, the ablation depth per shot is around 0.8 μm at 350 A/cm², higher than that of 0.4 μm at 200 A/cm² and much lower than that of 8.4 μm at 1500 A/cm², respectively. The experimental and numerical results indicate that a proper temperature and pressure repetitively created in the top layer of ablated graphite during HIPIB irradiation facilitates the phase transformation.     

Target-plane deposition of diamond-like carbon in pulsed laser ablation of graphite

In pulsed Nd:YAG laser ablation of highly oriented pyrolytic graphite (HOPG) at 10⁻⁶ Torr, diamond-like carbon (DLC) are deposited at laser wavelengths of 1064, 532, and 355 nm on substrates placed in the target-plane. These target-plane samples are found to contain varying sp³ content and composed of nanostructures of 40-200 nm in size depending on the laser wavelength and laser fluence. The material and origin of sp³ in the target-plane samples is closely correlated to that in the laser-modified HOPG surface layer, and hardly from the backward deposition of ablated carbon plume. The surface morphology of the target-plane samples shows the columnar growth and with a tendency for agglomeration between nanograins, in particular for long laser wavelength at 1064 nm. It is also proposed that DLC formation mechanism at the laser-ablated HOPG is possibly via the laser-induced subsurface melting and resolidification.     

Optical properties of La2O3 doped diamond-like carbon films

A novel kind of La₂O₃ doped diamond-like carbon (DLC) films with thickness of 100-120 nm were deposited by unbalanced magnetron sputtering. Raman spectra and photoluminescence properties were measured by Raman spectrometer operated by 325 nm He-Cd laser and 514 nm Ar⁺ laser, respectively. The intensities of Raman spectra and photoluminescence are higher than those of pure DLC films. The La₂O₃ doped DLC films have the potential promising for the application of solar cell coatings.     

DLC/Ag/DLC复合多层薄膜光学性能

采用等离子体增强化学气相沉积类金刚石(DLC)薄膜、高真空磁控溅射镀膜设备溅射Ag靶的方法制备了不同厚度Ag、DLC层的DLC/Ag/DLC多层膜,分别用紫外可见分光光度计、四探针测试仪对样品的光学性能、电学性能进行了测试.结果表明,随着Ag层厚度的增加,DLC/Ag/DLC多层膜透射率先增后减,外层DLC薄膜和内层DLC薄膜对透射率影响基本一致,随着厚度增加透射率先增后减,在内外层厚度为40 nm,Ag夹层厚度为16 nm时,DLC(30 nm)/Ag(16 nm)/DLC(40 nm)膜在550 nm处的透射率高达94.4%,电气指数高达112.4 ×10-3Ω-1,远远超过现有透明导电膜的电气指数(FTC≈20×10-3Ω-1).     

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.     

XeCl（308nm）脉冲准分子激光淀积类金刚石薄膜

利用ＸｅＣｌ（３０８ｎｍ）脉冲准分子激光淀积技术在功率密度５×１０８Ｗ／ｃｍ２、室温、真空度１０－３Ｐａ的条件下，制备出不含氢成分的类金刚石薄膜，研究了类金刚石薄膜的特性及其随制备工艺条件的变化规律。研究了激光诱导的碳等离子体发射光谱，探讨了类金刚石薄膜的形成机理。     

Preparation of Y2O3:Eu thin films by excimer-laser-assisted metal organic deposition

Europium-doped yttrium oxide (Y₂O₃:Eu) thin films were successfully deposited on quartz and ITO/glass substrates by excimer-laser-assisted metal organic deposition (ELAMOD) at low temperatures. The effects of laser wavelength and thermal temperature on the films’ crystallinity and photoluminescence properties were investigated. Films irradiated by an ArF laser at 80 mJ/cm² and 400–500°C were highly crystallized compared with those prepared by thermal MOD. In contrast, when the film was irradiated by a KrF laser at 500°C, no crystalline Y₂O₃:Eu was formed. The Y₂O₃:Eu film irradiated by the ArF laser at 80 mJ/cm² and 500°C showed typical PL spectra of Eu³⁺ ions with cubic symmetry and a ⁵D₀→⁷F₂ transition at ∼612 nm. The PL intensity at 612 nm was much higher for the film prepared with ELAMOD than for that prepared by the thermal-assisted process, and the photoemission intensity of the film prepared with ELAMOD strongly depended on the substrate material.     

The influence of temperature on magnetic and microwave absorption properties of Fe/graphite oxide nanocomposites

Fe/graphite oxide nanocomposites were prepared by inserting Fe³⁺ into layers of graphite oxide and then reducing Fe³⁺/graphite oxide compound at different reduced reaction temperatures in H₂. The composition, crystal structure, magnetic and microwave absorption properties of Fe/graphite oxide nanocomposites were investigated using elemental analysis, transmission electron microscope (TEM), X-ray diffraction (XRD), magnetic hysteresis curve and electromagnetic parameter analysis. The results show that the densities of samples are 2.43–2.47 g/cm³ and the nanocomposites are soft magnetic materials. The optimum reduced reaction temperature for preparing Fe/graphite oxide nanocomposites is 600 °C. With the increase of the thickness of the sample, the matching frequency tends to shift to the lower frequency region, and theoretical reflection loss becomes less at the matching frequency. Microwave absorption property of Fe/graphite oxide nanocomposites prepared at 600  °C (FeGO600) is the best. When the thickness is 1 mm, the maximum theoretical reflection loss of FeGO600 is −9 dB and the frequency region in which the maximum reflection loss is more than −6.0 dB is 11–18 GHz. In conclusion, FeGO600 is a good candidate for microwave absorbent due to its low density, wide frequency region for microwave absorption and large reflection loss.     

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.     

Fabrication of completely filled carbon nanotubes with copper nanowires in a confined space

Carbon nanotubes (CNTs) filled completely with polycrystalline Cu nanowires were synthesized by laser vaporization of Cu and graphite under high-pressure Ar gas atmosphere. Depending on the Ar gas pressure (0.1–0.9 MPa) and the Cu content (1–40 at.%) in graphite targets for laser vaporization, various products with different morphologies were observed by scanning and transmission electron microscopy. The ratios of the Cu-filled CNTs and carbon nanocapsules particularly increased as Ar gas pressure was increased. The maximum ∼60% fraction of Cu-filled CNTs with outer diameter of 10–50 nm and length of 0.3–3 μm was achieved at 0.9 MPa from graphite containing 20 at.% Cu. Most of the encapsulated Cu-nanowires were surrounded by single, double, or triple graphitic layers. Although the yield of the Cu-filled CNTs was also dependent on the Cu content in the graphite targets, no unfilled CNTs were produced even for low Cu content. The growth of Cu-filled CNTs is explained by the formation of molten Cu–C composite particles with an unusually C-rich composition in a space confined by high-pressure Ar gas, followed by precipitating Cu and C from the particles and subjecting them to phase separation.     

Synthesis and tribological behaviors of diamond-like carbon films by electrodeposition from solution of acetonitrile and water

Diamond-like carbon (DLC) films were prepared on silicon substrates by liquid phase electrodeposition from a mixture of acetonitrile and deionized water. The deposition voltage was clearly reduced owing to the presence of deionized water in the electrolyte by changing the basic properties (dielectric constant and dipole moment) of the electrolyte. Raman spectra reveal that the ratio of sp³/sp² in the DLC films is related to the concentration of acetonitrile. The surface roughness and grain morphology determined by atomic force microscopy are also influenced by the concentration of the acetonitrile. The UMT-2 universal micro-tribometer was used to test the friction properties of the DLC films obtained from electrolytes with different concentration. The results convey that the DLC film prepared from the electrolyte containing 10 vol.% acetonitrile has the better surface morphology and friction behavior comparing with the other. In addition the growth mechanism of the film was also discussed.     

Thermal stability of amorphous carbon films deposited by pulsed laser ablation

Diamond-like carbon (DLC) films have been grown on Si substrates at ambient temperature by the pulsed-laser ablation technique, using pulses of different durations both in the nano- and picosecond ranges and at various energy fluences. The stability of these films was investigated as a function of thermal anneals performed in UHV conditions up to 1273 K. Their physico-chemical properties have been characterized by different techniques including X-ray photo-emission, Auger electron and electron-energy-loss spectroscopies, Raman scattering, spectroscopic ellipsometry and atomic-force microscopy. The thermal stability of the films has been demonstrated to be related to their initial structural (sp³/sp² ratio) and chemical (contaminant) properties. DLC layers prepared under optimized conditions have been found to show a very good thermal stability up to 900 K. Received: 4 Jule 2000 / Accepted: 6 July 2000 / Published online: 6 September 2000     

Production of biologically inert Teflon thin layers on the surface of allergenic metal objects by pulsed laser deposition technology

Allergic-type diseases are current nowadays, and they are frequently caused by certain metals. We demonstrated that the metal objects can be covered by Teflon protective thin layers using a pulsed laser deposition procedure. An ArF excimer laser beam was focused onto the surface of pressed PTFE powder pellets; the applied fluences were 7.5–7.7 J/cm². Teflon films were deposited on fourteen-carat gold, silver and titanium plates. The number of ablating pulses was 10000. Post-annealing of the films was carried out in atmospheric air at oven temperatures between 320 and 500 °C. The thickness of the thin layers was around 5 μm. The prepared films were granular without heat treatment or after annealing at a temperature below 340 °C. At 360 °C a crystalline, contiguous, smooth, very compact and pinhole-free thin layer was produced; a melted and re-solidified morphology was observed above 420 °C. The adhesion strength between the Teflon films and the metal substrates was determined. This could exceed 1–4 MPa depending on the treatment temperature. It was proved that the prepared Teflon layers can be suitable for prevention of contact between the human body and allergen metals and so for avoidance of metal allergy. Received: 12 June 2002 / Accepted: 13 June 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. E-mail: bhopp@physx.u-szeged.hu