Jan Remsa

Chromium-doped DLC for implants prepared by laser-magnetron deposition.

Diamond-like carbon (DLC) thin films are frequently used for coating of implants. The problem of DLC layers lies in bad layer adhesion to metal implants. Chromium is used as a dopant for improvement of adhesion of DLC films. DLC and Cr-DLC layers were deposited on silicon, Ti6Al4V and CoCrMo substrates by a hybrid technology using combination of pulsed laser deposition (PLD) and magnetron sputtering. The topology of layers was studied using SEM, AFM and mechanical profilometer. Carbon and chromium content and concentration of trivalent and toxic hexavalent chromium bonds were determined by XPS and WDS. It follows from the scratch tests that Cr doping improved adhesion of DLC layers. Ethylene glycol, diiodomethane and deionized water were used to measure the contact angles. The surface free energy (SFE) was calculated. The antibacterial properties were studied using Pseudomonas aeruginosa and Staphylococcus aureus bacteria. The influence of SFE, hydrophobicity and surface roughness on antibacterial ability of doped layers is discussed.

Bonding and bio-properties of hybrid laser/magnetron Cr-enriched DLC layers.

Chromium-enriched diamond-like carbon (DLC) layers were prepared by a hybrid technology using a combination of pulsed laser deposition (PLD) and magnetron sputtering. XRD revealed no chromium peaks, indicating that the layers are mostly amorphous. Carbon (sp(2) and sp(3) bonds) and chromium bonds were determined by XPS from C 1s, O 1s, and Cr 2p photoelectron peaks. Depending on the deposition conditions, the concentration of Cr in DLC layers moved from zero to 10 at.% for as-received sample surfaces, and to about 31 at.% after mild sputter-cleaning by argon ion cluster beam. It should be noted that the most stable Cr(3+) bonding state is in Cr2O3 and Cr(OH)3, and that there is the toxic Cr(6+) state in CrO3. The surface content of hexavalent chromium in the Cr 2p3/2 spectra is rather low, but discernible. The population density of Saos-2 cells was the highest in samples containing higher concentrations of chromium 7.7 and 10 at.%. This means that higher concentrations of chromium supported the cell adhesion and proliferation. In addition, as revealed by a LIVE/DEAD viability/cytotoxicity kit, the cells on all Cr-containing samples maintained high viability (96 to 99%) on days 1 and 3 after seeding. However, this seemingly positive cell behavior could be associated with the risk of dedifferentiation and oncogenic transformation of cells.

PLD prepared bioactive BaTiO3 films on TiNb implants

BaTiO3 (BTO) layers were deposited by pulsed laser deposition (PLD) on TiNb, Pt/TiNb, Si (100), and fused silica substrates using various deposition conditions. Polycrystalline BTO with sizes of crystallites in the range from 90nm to 160nm was obtained at elevated substrate temperatures of (600°C-700°C). With increasing deposition temperature above 700°C the formation of unwanted rutile phase prevented the growth of perovskite ferroelectric BTO. Concurrently, with decreasing substrate temperature below 500°C, amorphous films were formed. Post-deposition annealing of the amorphous deposits allowed obtaining perovskite BTO. Using a very thin Pt interlayer between the BTO films and TiNb substrate enabled high-temperature growth of preferentially oriented BTO. Raman spectroscopy and electrical characterization indicated polar ferroelectric behaviour of the BTO films.

Influence of diamond and graphite bonds on mechanical properties of DLC thin films

Mechanical properties of diamond-like carbon thin films with various ratios of sp3/sp2 bonds were studied. The films were prepared in argon atmosphere (0.25 Pa) by laser deposition method for laser energy densities from 4 Jcm−2 to 14 Jcm−2. The sp2 and sp3 bonds were calculated by X-ray photoelectron spectroscopy. Films contained sp3 bonds up to 70 %. Surface properties as roughness and atomic force microscopy topology were measured. Hardness (and reduced Youngs modulus) were determined by nanoindentation and reached of 30 GPa (203 GPa). Films adhesion was studied using scratch test and was up to 12 N for biomedical alloy (titanium substrates – Ti-6Al-4V). Relations among deposition conditions and measured properties are presented.

Growth of a TiNb adhesion interlayer for bioactive coatings

Surface bioactivity has been under intensive study with reference to its use in medical implants. Our study is focused on coatings prepared from an electroactive material which can support bone cell adhesion. Until now, hydroxyapatite films have usually been utilized as a chemically-active surface agent. However, electrically-active films could set a new direction in hard tissue replacement. As a base for these films, it is necessary to prepare an intermediate film, which can serve as a suitable barrier against the possible diffusion of some allergens and toxic elements from the substrate. The intermediate film also improves the adaptation of the mechanical properties of the basic material to an electroactive film. The aim of our work was to select an implantable and biocompatible material for this intermediate film that is suitable for coating several widely-used materials, to check the possibility of preparing an electroactive film for use on a material of this type, and to characterize the structure and several mechanical properties of this intermediate film. TiNb was selected as the material for the intermediate film, because of its excellent chemical and mechanical properties. TiNb coatings were deposited by magnetron sputtering on various substrates, namely Ti, Ti6Al4V, stainless steel, and bulk TiNb (as standard), and important properties of the layers, e.g. surface morphology and surface roughness, crystalline structure, etc., were characterized by several methods (SEM, EBSD, X-ray diffraction, nanoindentation and roughness measurement). It was found that the structure and the mechanical properties of the TiNb layer depended significantly on the type of substrate. TiNb was then used as a substrate for depositing a ferroelectrically active material, e.g., BaTiO3, and the adhesion, viability and proliferation of human osteoblast-like Saos-2 cells on this system were studied. We found that the electroactive BaTiO3 film was not only non-cytotoxic (i.e. it did not affect the cell viability). It also enhanced the growth of Saos-2 cells in comparison with pure TiNb and with standard tissue culture polystyrene wells, and also in comparison with BaTiO3 films deposited on Ti, i.e. a material clinically used for implantation into the bone.

Study of Yb-Doped CoSb3 Thermoelectric Thin Films Prepared by Laser

Thin films of Yb filled CoSb3 were prepared on fused silica substrates using pulsed laser deposition method. The stoichiometric Yb0.19Co4Sb12 target was prepared by hot pressing method. The deposition conditions were changed with the goal to reach layers of smooth morphology. The target-to substrate distance was kept equal to 4 cm. The ambient argon pressure moved from 0.5 Pa to 13 Pa, laser repetition rate from 3 Hz to 10 Hz, and substrate temperature from 250 °C to 400 °C. We tested laser fluencies from 0.8 J·cm-2 to 5 J·cm-2. Films roughness was determined by mechanical profilometer and by atomic force microscopy. The lowest roughness of about 5 nm – 10 nm was reached for low laser fluencies but mechanical quality of films was poor and growth rate low (about 0.1 A/pulse). From WDX analysis follows that there is an excess of Yb and Sb compared to Yb0.19Co4Sb12 target.

Adhesion and differentiation of Saos-2 osteoblast-like cells on chromium-doped diamond-like carbon coatings

Diamond-like carbon (DLC) thin films are promising for use in coating orthopaedic, dental and cardiovascular implants. The problem of DLC layers lies in their weak layer adhesion to metal implants. Chromium is used as a dopant for improving the adhesion of DLC films. Cr-DLC layers were prepared by a hybrid technology, using a combination of pulsed laser deposition (PLD) from a graphite target and magnetron sputtering. Depending on the deposition conditions, the concentration of Cr in the DLC layers moved from zero to 10.0 at.%. The effect of DLC layers with 0.0, 0.9, 1.8, 7.3, 7.7 and 10.0 at.% Cr content on the adhesion and osteogenic differentiation of human osteoblast-like Saos-2 cells was assessed in vitro. The DLC samples that contained 7.7 and 10.0 at.% of Cr supported cell spreading on day 1 after seeding. On day three after seeding, the most apparent vinculin-containing focal adhesion plaques were also found on samples with higher concentrations of chromium. On the other hand, the expression of type I collagen and alkaline phosphatase at the mRNA and protein level was the highest on Cr-DLC samples with a lower concentration of Cr (0−1.8 at.%). We can conclude that higher concentrations of chromium supported cell adhesion; however DLC and DLC doped with a lower concentration of chromium supported osteogenic cell differentiation.Graphical Abstract

Scanning Thermal Microscopy of Thermoelectric Nanostructures

We present the development and results of a new simple method for thermal conductivity characterization of thin films and thermoelectric structures using a scanning thermal microscope in pulsed current mode. The presented method does not allow measurement of absolute thermal conductivity of the studied system, but only relative to the Si substrate. We present the results of the method on the Si substrate/layer step boundary. The nano-layers of different thickness and different materials were prepared for the experiments by the pulsed laser deposition from hot-pressed targets.

Characterization of laser prepared Bi2Te3 nano-layers

A method for relative thermal conductivity characterization of thin thermoelectric layers and multi-layered structures in nanometre range using a scanning thermal microscope working in an active constant current mode is suggested. The method requires a very smooth and high quality surface of the studied thermoelectric system. To fulfil these requirements a study of the influence of principal deposition conditions including substrate temperature and laser beam density on surface quality of Bi2Te3 layers prepared by pulsed laser deposition was performed and its results are presented.

Biocompatible layers fabricated using KrF laser

Thin films of hydroxyapatite, hydroxyapatite doped with silver and thin diamond like carbon layers were prepared using KrF excimer laser deposition. Tooth prostheses, textile blood vessels and artificial heart valves were covered and tested. Examples of physical tests, and in vitro and in vivo analysis using minipigs and sheep are presented.