Surface Stoichiometry and Depth Profile of Tix-CuyNz Thin Films Deposited by Magnetron Sputtering.

We report the surface stoichiometry of Tix-CuyNz thin film as a function of film depth. Films are deposited by high power impulse (HiPIMS) and DC magnetron sputtering (DCMS). The composition of Ti, Cu, and N in the deposited film is investigated by X-ray photoelectron spectroscopy (XPS). At a larger depth, the relative composition of Cu and Ti in the film is increased compared to the surface. The amount of adventitious carbon which is present on the film surface strongly decreases with film depth. Deposited films also contain a significant amount of oxygen whose origin is not fully clear. Grazing incidence X-ray diffraction (GIXD) shows a Cu3N phase on the surface, while transmission electron microscopy (TEM) indicates a polycrystalline structure and the presence of a Ti3CuN phase.

Spectroscopic Study of Plasma Polymerized a-C:H Films Deposited by a Dielectric Barrier Discharge.

Plasma polymerized a-C:H thin films have been deposited on Si (100) and aluminum coated glass substrates by a dielectric barrier discharge (DBD) operated at medium pressure using C2Hm/Ar (m = 2, 4, 6) gas mixtures. The deposited films were characterized by Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS), Raman spectroscopy, and ellipsometry. FT-IRRAS revealed the presence of sp³ and sp² C-H stretching and C-H bending vibrations of bonds in the films. The presence of D and G bands was confirmed by Raman spectroscopy. Thin films obtained from C2H4/Ar and C2H6/Ar gas mixtures have ID/IG ratios of 0.45 and 0.3, respectively. The refractive indices were 2.8 and 3.1 for C2H4/Ar and C2H6/Ar films, respectively, at a photon energy of 2 eV.

Effects of reactive oxygen species on single polycation layers.

Positively charged, branched polyethylenimine (PEI) adsorbed onto silicon wafers and silica surfaces are attacked by free hydroxyl radicals. With AFM colloid probe technique, the surface forces between PEI layers are measured. Force profiles show that an electrostatic repulsion dominates the surface forces between freshly deposited PEI layers. After radical attack, both surface potential and surface charge density are reduced by a factor of about 0.5, while the Debye length remains unchanged. Adsorbed gold nanoparticles and force volume measurements show a homogeneous distribution of the surface charge on length scales between 40 nm and 30 µm. For radical attacked PEI layers, we find a 10% decrease of saturation coverage of gold nanoparticles. This is consistent with the decreased surface charge density, if the electrostatic three-body interaction is taken into account. Nevertheless, the NP adsorption kinetics are slowed down suggesting that the PEI layer is inhomogeneous on the nm-scale after radical attack.

In vivo examination of the local inflammatory response after implantation of Ti6Al4V samples with a combined low-temperature plasma treatment using pulsed magnetron sputtering of copper and plasma-polymerized ethylenediamine.

Copper (Cu) could serve as antibacterial coating for Ti6Al4V implants. An additional cell-adhesive layer might compensate Cu cytotoxicity. This study aimed at in vitro and in vivo evaluation of low-temperature plasma treatment of Ti6Al4V plates with Ti/Cu magnetron sputtering (Ti6Al4V-Ti/Cu), plasma-polymerized ethylenediamine (Ti6Al4V-PPEDA), or both (Ti6Al4V-Ti/Cu-PPEDA). Ti6Al4V-Ti/Cu and Ti6Al4V-Ti/Cu-PPEDA had comparable in vitro Cu release and antibacterial effectiveness. Following intramuscular implantation of Ti6Al4V-Ti/Cu, Ti6Al4V-PPEDA, Ti6Al4V-Ti/Cu-PPEDA and Ti6Al4V controls for 7, 14 and 56 days with 8 rats/day, peri-implant tissue was immunohistochemically examined for different inflammatory cells. Ti6Al4V-PPEDA had more mast cells and NK cells than Ti6Al4V, and more tissue macrophages, T lymphocytes, mast cells and NK cells than Ti6Al4V-Ti/Cu-PPEDA. Ti6Al4V-Ti/Cu had more mast cells than Ti6Al4V and Ti6Al4V-Ti/Cu-PPEDA. Results indicate that PPEDA-mediated cell adhesion counteracted Cu cytotoxicity. Ti6Al4V-Ti/Cu-PPEDA differed from Ti6Al4V only for mast cells on day 56. Altogether, implants with both plasma treatments had antibacterial properties and did not increase inflammatory reactions.

Analysis of the release characteristics of cu-treated antimicrobial implant surfaces using atomic absorption spectrometry.

New developments of antimicrobial implant surfaces doped with copper (Cu) ions may minimize the risk of implant-associated infections. However, experimental evaluation of the Cu release is influenced by various test parameters. The aim of our study was to evaluate the Cu release characteristics in vitro according to the storage fluid and surface roughness. Plasma immersion ion implantation of Cu (Cu-PIII) and pulsed magnetron sputtering process of a titanium copper film (Ti-Cu) were applied to titanium alloy (Ti6Al4V) samples with different surface finishing of the implant material (polished, hydroxyapatite and corundum blasted). The samples were submersed into either double-distilled water, human serum, or cell culture medium. Subsequently, the Cu concentration in the supernatant was measured using atomic absorption spectrometry. The test fluid as well as the surface roughness can alter the Cu release significantly, whereby the highest Cu release was determined for samples with corundum-blasted surfaces stored in cell medium.

Role of nitrogen in the formation of HC-N films by CH(4)/N(2) barrier discharge plasma: aliphatic tendency.

We have studied the influence of nitrogen on the chemical properties of the hydrogenated carbon nitride (a-CN(x):H) film deposited by CH(4)/N(2) dielectric barrier discharge (DBD) plasma. X-ray photoelectron spectroscopy (XPS) indicates that carbon and nitrogen form an unpolarized covalent bond in these C-N(x) materials, and the observed chemical shift in the C 1s and N 1s binding energy is explained with respect to N 1s incorporation. Furthermore, the average nitrogen content (N/C approximately 0.76) in the films was systematically varied by changing the nitrogen partial pressure (CH(4)/N(2) approximately from 5:1 to 1:7) which is well supported by the elemental analysis. Fourier transform infrared (FTIR) absorption spectra exhibit significant changes in different C-N, C identical withN, and NH/OH molecular bands at higher nitrogen concentration in the film. The isonitrile and nitrile groups (-NC and -CN) are increased with the increase of deposition time. In addition, the elemental analysis, proton NMR, and thermolysis mass spectrum show that the composition of the film with the ratio CH(4)/N(2) approximately 1:1 is C, 67.68; H, 9.88; N, 16.53 (in wt %) and that the film is composed of polymers, probably containing linear chains which are cleaved off on heating in vacuum.

Development of metal nanocluster ion source based on dc magnetron plasma sputtering at room temperature.

A simple and cost effective nanocluster ion source for the deposition of size selected metal nanocluster has been developed based on the dc magnetron discharge (including pulsed dc discharge). The most important and interesting feature of this cluster source is that it is working at room temperature, cooled by chilled water during the experiment. There is no extraction unit in this device and the cluster streams flow only due to the pressure gradient from source chamber to substrate via quadrupole mass filter. It has provision of multiple substrate holders in the deposition chamber, which can be controlled manually. The facility consists of quadrupole mass filter (QMF 200), which can select masses in the range of 2-125 000 atoms depending on the target materials, with a constant mass resolution (M/DeltaM approximately 25). The dc magnetron discharge at a power of about 130 W with Ar as feed/buffer gas was used to produce the Cu nanocluster in an aggregation tube and deposited on Si (100) wafer temperature.

Flow of nanosize cluster-containing plasma in a magnetron discharge.

A magnetron source of silver clusters captured by an argon flow with the quadrupole mass filter is used for the analysis of charged clusters after an orifice of the magnetron chamber, and the size distribution function follows from the analysis of clusters deposited on a silicon substrate by an atomic force microscope. Cluster charge near an orifice results from attachment of ions of a secondary plasma that is a tail of a magnetron plasma, and the cluster charge is mostly positive. The character of passage of a buffer gas flow with metal clusters through an orifice is studied both theoretically and experimentally. Assuming the cone shape of the drift chamber near the orifice, we analyze drift of charged clusters in a buffer gas flow towards the orifice if the electric field inside the drift chamber is created by charged rings on the cone surface. Under experimental conditions, when an equilibrium between the buffer gas flow and cluster flux is violated, a typical voltage of rings and parameters of corona discharge for cluster charging are estimated if the electric field does not allow for clusters to reach walls of the drift chamber. The number density of clusters near the orifice is estimated that increases both due to violation of an equilibrium for the cluster flux inside the buffer gas flow and owing to focusing of the cluster by the electric field that is created by electrodes located near walls and due to diffusion motion of clusters. Processes of cluster charging in the magnetron chamber are analyzed.

Development of dielectric barrier discharge plasma processing apparatus for mass spectrometry and thin film deposition.

Cost effective and a very simple dielectric barrier discharge plasma processing apparatus for thin film deposition and mass spectroscopic analysis of organic gas mixture has been described. The interesting features of the apparatus are the construction of the dielectric electrodes made of aluminum oxide or alumina (Al(2)O(3)) and glass and the generation of high ignition voltage from the spark plug transformer taken from car. Metal capacitor is introduced in between ground and oscilloscope to measure the executing power during the discharge and the average electron density in the plasma region. The organic polymer films have been deposited on Si (100) substrate using several organic gas compositions. The experimental setup provides a unique drainage system from the reaction chamber controlled by a membrane pump to suck out and remove the poisonous gases or residuals (cyanogens, H-CN, CH(x)NH(2), etc.) which have been produced during the discharge of CH(4)N(2) mixture.

Chemical reaction studies in CH4/Ar and CH4/N2 gas mixtures of a dielectric barrier discharge.

Chemical reactions in a dielectric barrier discharge at medium pressure of 250-300 mbar have been studied in CH(4)/Ar and CH(4)/N(2) gas mixtures by means of mass spectrometry. The main reaction scheme is production of H(2) by fragmentation of CH(4), but also production of higher order hydrocarbon molecules such as C(n)H(m) with n up to 9 including formation of different functional CN groups is observed. Formation of C(2)H(2), C(2)H(4), and C(2)H(6) molecules has been investigated in some detail. Significant differences are noted in comparison to a theoretical estimate.