Surface modification of 316L stainless steel with magnetron sputtered TiN/VN nanoscale multilayers for bio implant applications

Nanoscale multilayered TiN/VN coatings were developed by reactive dc magnetron sputtering on 316L stainless steel substrates. The coatings showed a polycrystalline cubic structure with (111) preferential growth. XPS analysis indicated the presence of peaks corresponding to Ti2p, V2p, N1s, O1s, and C1s. Raman spectra exhibited the characteristic peaks in the acoustic range of 160–320 cm⁻¹ and in the optic range between 480 and 695 cm⁻¹. Columnar structure of the coatings was observed from TEM analysis. The number of adherent platelets on the surface of the TiN/VN multilayer, VN, TiN single layer coating exhibit fewer aggregation and pseudopodium than on substrates. The wear resistance of the multilayer coatings increases obviously as a result of their high hardness. Tafel plots in simulated bodily fluid showed lower corrosion rate for the TiN/VN nanoscale multilayer coatings compared to single layer and bare 316L SS substrate.     

Crystallography of magnetron sputtered TiN coatings on steel substrates

Structure formation processes in TiN coatings deposited by reactive CFUBMS on steel substrates have been investigated by X-ray diffraction experiments in symmetric Bragg-Brentano (B-B) and grazing incidence asymmetric Bragg diffraction (GIABD) modes and by SEM. The results show that the deposits with thicknesses of 500 and 4000 nm are built-up of polycrystalline stoichiometric TiN, in addition to which, some negligible amount of Ti-O and Ti-N-O phases have also been observed predominantly at their surfaces. In the thinner 500 nm films only columnar crystallites with {1 1 1}, {2 0 0} and {2 2 0} crystallographic planes parallel to the surface were formed. The share of the micro-volumes belonging to the 〈1 1 1〉 out-of-plane texture component varied between 70% and 80% depending on the target current (I_d) used (4 or 8 A in the present experiments). During the more advanced stages of growth the 〈1 1 1〉 texture weakens and new texture components appear; the process being more pronounced when the application has been performed at higher I_d values. The obtained crystallographic texture results for the thinner films and their changes during the more advanced stages of the coatings formation are discussed with particular consideration of the crystallography of the TiN lattice and the anisotropy of its elastic parameters. Based on a precise estimation of the interplanar distances, d_{〈u v w〉}, corresponding to the main texture components of the investigated films in the direction along the surface macro-normal, it has been revealed that the elastic strain, ε_{〈u v w〉}, caused by the compressive residual macro-stresses acting parallel to the film surfaces and the corresponding elastic stored energy, U_{〈u v w〉}, values obey the following relationships: ε_{〈1 1 1〉}>ε_{〈2 2 0〉}> ε_{〈2 0 0〉} and U_{〈1 1 1〉}>U_{〈2 2 0〉}>U_{〈2 0 0〉}, respectively. The observed ε_{〈u v w〉} and U_{〈u v w〉} anisotropy is found to be more pronounced in the thinner coatings and is such that, at more advanced stages of growth, it would be expected to favour the transition from 〈1 1 1〉 to 〈2 0 0〉 out-of-plane preferred orientation. However, the experimental results do not confirm this expectation, which points out that the texture-formation at these stages is not governed solely by the minimization of the stored elastic energy, but is a rather complicated process depending on a larger number of factors, some of which are discussed in the paper.     

Mo/Si multilayers for EUV lithography by ion beam sputter deposition

Mo/Si multilayers for applications in extreme ultraviolet (EUV) lithography have been prepared on Si wafer substrates using ion beam deposition. The multilayers were characterised by transmission electron microscopy, secondary ion mass spectroscopy, atomic force microscopy, photoelectron spectroscopy, X-ray reflectometry at grazing incidence, and EUV-reflectivity measurements at nearly normal incidence. The surface and the interfaces of the multilayers are rather smooth with only small roughness. The material properties of the layers are characterised by some intermixing and silicide formation at the Mo-Si interfaces and a polycrystalline grain structure of the Mo layers, which is in agreement with prior studies. Appearance of multilayer diffraction spots, well-resolved Kiessig fringes and other diffraction evidence indicate very good coherence of the wave fields and in this manner a good reproducibility of the multilayer period of 6.7 nm. Normal incidence peak reflectivities of 64-65% in the EUV spectral range were routinely obtained at 13.4 nm wavelength. This reflectivity value and the formation of an EUV standing wave field are confirmed using photoelectron spectroscopy, and an application for defect particle analysis is proposed. The obtained results are discussed in comparison to literature data of multilayers prepared by other deposition techniques and considering new attempts of interface engineering.     

Epitaxial growth of MgO/TiN multilayers on Cu

The growth of epitaxial MgO/TiN multilayer films on (001) Cu has been investigated. In particular, epitaxial structures were grown on (001) Cu layers that were epitaxial on (001) SrTiO₃. X-ray diffraction and reflection high-energy electron diffraction indicate that the multilayer structures are epitaxial on the (001) Cu surface. The motivation is the use of crystalline MgO/TiN multilayers as a diffusion barrier to both copper and oxygen. MgO/TiN multilayers are potentially useful as diffusion barriers for Cu interconnects on semiconductors as well as for superconducting wires based on the epitaxial growth of cuprate superconductors on biaxially textured copper.     

Nature in corrosion-erosion surface for [TiN/TiAlN]n nanometric multilayers growth on AISI 1045 steel

The aim of this work is to characterize the electrochemical behavior of [TiN/TiAlN]n multilayer coatings under corrosion-erosion condition. The multilayers with bilayer numbers (n) of 2, 6, 12, and 24 and/or bilayer period (Λ) of 1500 nm, 500 nm, 250 nm, 150 nm and 125 nm were deposited by magnetron sputtering technique on Si (100) and AISI 1045 steel substrates. Both, the TiN and the TiAlN structures for multilayer coatings were evaluated via X-ray diffraction analysis. Mechanical and tribological properties were evaluated via nanoindentation measurements and scratch test respectively. Silica particles were used as abrasive material on corrosion-erosion test in 0.5 M of H₂SO₄ solution at impact angles of 30° and 90° over surface. The electrochemical characterization was carried out using polarization resistance technique (Tafel), in order to observe changes in corrosion rate as a function of the bilayer number (n) or the bilayer period (Λ) and the impact angle. Corrosion rate values of 9115 μm y for uncoated steel substrate and 2615 μm y for substrate coated with n = 24 (Λ = 125 nm) under an impact angle of 30° were found. On the other hand, for an impact angle of 90° the corrosion rate exhibited 16401 μm y for uncoated steel substrate and 5331 μm y for substrate coated with n = 24 (Λ = 125 nm). This behavior was correlated with the curves of mass loss for both coated samples and the surface damage was analyzed via scanning electron microscopy images for the two different impact angles. These results indicate that TiN/TiAlN multilayer coatings deposited on AISI 1045 steel represent a practical solution for applications in corrosive-erosive environments.     

Nucleation and growth of ion beam sputtered metal films

Transmission electron microscope observations have been made on ion beam sputtered (IBS) films of Cu, Au, Pt and Ni (of predetermined thicknesst 0.5 nm) deposited on amorphous carbon substrates. The influence of IBS parameters on particle size distribution and deposition rate has been measured, also the fractional substrate coveragef as a function oft which indicates three-dimensional island growth in Au, Cu films and two-dimensional growth in Pt, Ni films. Electron diffraction measurements appear to show that the f.c.c. metal particles grow with (1 1 0) parallel to the substrate with, in the case of Ni, a critical island thickness of 0.8 nm.     

Magnetic properties of sputtered multilayers of Mo/Ni

We have studied the d.c. magnetization of Mo/Ni artificial superlattices in the temperature range 5–300 K and in magnetic fields of up to 10⁷/4πAm^-1 (10kG). The saturation magnetization and the Curie temperature behavior are consistent with expectations based on thin film effects. However, there are indications of ferromagnetic coupling across the normal metal and the coercive field shows an unexpected peak at a layer thickness of 25 Å.     

Polymer pre-treatment by linear anode layer source plasma for adhesion improvement of sputtered TiN coatings

The pre-treatment of work-piece surfaces is decisive for improved adhesion of tribological, decorative, sensor, biocompatible, etc. coatings subsequently deposited by vacuum coating techniques. Most current industrial techniques (mainly glow discharges) miss the requirements for activating temperature-sensitive and electrically insulating materials. Gridless plasma sources like the linear anode layer ion source are an excellent alternative due to their low investment and operating costs and scalability to many industrial applications, and also due to the measured plasma characteristics (low surface charging, broad energy distribution). The appreciable increase of adhesion by anode layer source plasma pre-treatment and the effects of ion energy and gas composition are presented for room temperature sputtered titanium nitride coatings polyamide, polycarbonate, and poly(ethyleneterephtalate). For these polymers, the oxygen-based functionalization (chain-scissoring and cross-linking) strongly influence the wetting behaviour and improve the adhesion by suppressing adhesive cracking at low scratching loads. Low O₂ contents in Ar-O₂ discharge of ∼400 eV average ion energy lead to best coating adhesion.     

Electrical and structural properties of ion beam sputtered silver-SiO2 cermet films

Thin silver-SiO₂ cermet films containing 55–92 wt.% silver were deposited by co-sputtering using ion beam techniques. The resistivity and its temperature coefficient varied from 10^-6 to 10¹ Ω m and from +600 to -3500 ppm K^-1, respectively. Electron microscope examination revealed that films with a high silver content are of the capillary type whereas with increasing proportions of SiO₂ a transition to island structure is observed. In the latter case good agreement between measured and calculated electrical parameters was found.     

Investigation of dual ion beam sputtered transparent conductive Ga-doped ZnO films

Ga-doped ZnO (GZO) transparent conducting films were deposited on sapphire (0001) substrates using dual ion beam sputtering deposition system. The impact of growth temperature on the structural, morphological, elemental, optical, and electrical properties was thoroughly investigated and reported. X-ray diffraction measurements explicitly confirmed that all GZO films had (002) preferred crystal orientation. The film deposited at 400 °C exhibited the narrowest full-width at half-maximum value of 0.24° for (002) crystalline plane and the lowest room temperature electrical resistivity of 4.11 × 10^?3 Ω cm. The Raman spectra demonstrated the vibrational modes at 576 and 650–670 cm^?1, associated with native oxygen vacancies and elemental Ga doping in ZnO lattice, respectively. All doped films showed an overall transmittance of above 95 % in the visible spectra. A correlation between structural, optical, elemental, and electrical properties with GZO growth temperature was established.     

Oxidation behavior of TiN/ZrN multilayers annealed in air

Using reactive radio frequency magnetron sputtering, TiN/ZrN multilayers were deposited on Si (111) substrates at 550 °C. The multilayers were annealed at different temperatures ranging from 500 to 1100 °C in air. The variation of the annealed multilayers has been investigated by X-ray diffraction and transmission electron microscopy. A layer-by-layer oxidation behavior is found in the multilayers annealed at temperatures below 900 °C. The oxidation mechanism of multilayers is discussed in the paper.     

Magnetic and structural properties of ion beam sputtered Fe-Zr-Nb-B-Cu thin films

Magnetic and structural properties of Fe-Zr-Nb-B-Cu thin films, prepared by ion beam sputtering on silicon substrates by using a target made up of amorphous ribbons of nominal composition Fe₈₄Zr_3.5Nb_3.5B₈Cu₁, are reported. As-deposited thin film samples exhibit an in-plane uniaxial anisotropy, which can be ascribed to the preparation technique and the coupling of quenched-in internal stresses. Structural measurements indicate no significant variation of the grain size with thickness and with the annealing temperature. Increase in surface irregularities with annealing temperature and oxidation results in aggregates that would act as pinning centers, affecting the magnetic properties leading to magnetic hardening of the specimens. The role of the magnetic anisotropy is thoroughly discussed with the help of magnetic and ferromagnetic resonance measurements.     

Investigation of reactively sputtered TiN films for diffusion barriers

Two groups of reactively sputtered TiN films, gold-yellow films (G films) with low resistivity and high compressive internal stress and brown-black films (B films) with high resistivity, which are formed with and without a negative substrate bias, were examined as potential diffusion barriers.The microstructures and compositions were investigated by Auger electron spectroscopy, electron probe microanalysis and X-ray diffraction. The G films and the B films have a fine-grained and a columnar-arranged morphological structure respectively. Both films exhibit the cubic NaCl-type crystallographic structure strongly oriented towards the (111) plane which is parallel to the substrate surface. They also exhibit a superstoichiometric composition having excess nitrogen atoms. In addition, the B films contain a large number of oxygen atoms.The compressive internal stress in the G film originates from lattice expansion which is probably due to the incorporation of the excess nitrogen atoms. Using the experimental value of the Young's modulus, the expanded lattice parameter in this film was calculated from the corrected interplanar spacing after the silicon substrate had been removed.The superior diffusion barrier capability of the B film is demonstrated through the application of the TiN films to an Au/Pt/TiN/Ti metal system on thick polysilicon. It is assumed that the higher diffusion barrier capability of the B film is due to the reduction of grain boundary diffusion by the oxygen atoms located in the intercolumnar layers. This is supported by film analysis, the peculiar etching behaviour and hardness studies.     

Characterization of sputtered nickel/carbon multilayers with soft-x-ray reflectivity measurements

Several sputtered Ni/C multilayer mirrors with periods between 3.8 and 6.0 nm were investigated with the HASYLAB reflectometer to determine the peak reflectivity and the internal structure of the multilayers. The enhanced reflectivity in the Bragg maximum, especially below 284 eV (carbon K edge), is interesting for practical applications. For both materials (Ni and C), the optical constants were previously obtained from angular-dependent reflectivity measurements. The layer thicknesses, interface roughnesses, and mean thickness errors of multilayer mirrors are obtained from least-squares fits of theoretical reflectivity curves. A model is presented to describe the influence of interface roughness on other parameters obtained from the analysis. All Ni/C multilayers, with Ar as the sputter gas, were produced in the low-pressure triode-assisted sputtering facility of Sincrotrone Trieste.     

Behavior of dual ion beam sputtered MgZnO thin films for different oxygen partial pressure

Mg-doped ZnO (MgZnO) films were grown on p-Si (001) substrates by dual ion beam sputtering deposition system at a constant growth temperature of 600 °C for different oxygen partial pressure. The impact of oxygen partial pressure on the structural, electrical, elemental and morphological properties was thoroughly investigated. X-ray diffraction (XRD) spectra revealed that the deposited MgZnO films were polycrystalline in nature with preferred (002) crystal orientation. The peak of MgZnO (101) plane was reduced significantly as oxygen partial pressure was increased and disappeared completely at 80 and 100 % O₂. The maximum electron concentration was evaluated to be 5.79 × 10¹⁸ cm^?3 with resistivity of 0.116 Ω cm and electron mobility of 9.306 cm²/V s at room temperature, for MgZnO film grown with 20 % O₂. Raman spectra shows a broad peak at 434 cm^?1 corresponded to E ₂ ^high phonons mode of MgZnO wurtzite structure. The peak at 560 cm^?1 corresponded to the E₁ (LO) mode and was associated with oxygen deficiency in MgZnO films. Raman intensity at 560 cm^?1 reduced, on increasing oxygen partial pressure. A correlation between structural, electrical, elemental and morphological properties with oxygen partial pressure was also established.     

Bactericidal and biocompatible properties of TiN/Ag multilayered films by ion beam assisted deposition

Nanoscale TiN/Ag multilayered films of thickness 500 nm were synthesized on AISI317 stainless steel by ion beam assisted deposition (IBAD) with the modulation period of 4, 5, 6, 7.5, and 12 nm. The bactericidal and biocompatible properties of TiN/Ag multilayered films were investigated through Gram negative E. coli bacteria and L929 cells (mice fibroblast) as well as human umbilical vein endothelial cells (HUVEC). The results show that the TiN/Ag multilayered films with the modulation period of 7.5 nm possess the strongest bactericidal property. The cytotoxicity grade of TiN/Ag multilayered coating with the modulation periods of 7.5 nm, 12 nm is in 0–1 scope, which indicates this film has no cytotoxicity to L929. HUVEC on TiN/Ag multilayered film grows well and shows good cellularity. Auger electronic spectroscopy reveals the relationship between the structure of TiN/Ag multilayered film and the biomedical properties.     

Bactericidal and biocompatible properties of TiN/Ag multilayered films by ion beam assisted deposition

Nanoscale TiN/Ag multilayered films of thickness 500 nm were synthesized on AISI317 stainless steel by ion beam assisted deposition (IBAD) with the modulation period of 4, 5, 6, 7.5, and 12 nm. The bactericidal and biocompatible properties of TiN/Ag multilayered films were investigated through Gram negative E. coli bacteria and L929 cells (mice fibroblast) as well as human umbilical vein endothelial cells (HUVEC). The results show that the TiN/Ag multilayered films with the modulation period of 7.5 nm possess the strongest bactericidal property. The cytotoxicity grade of TiN/Ag multilayered coating with the modulation periods of 7.5 nm, 12 nm is in 0-1 scope, which indicates this film has no cytotoxicity to L929. HUVEC on TiN/Ag multilayered film grows well and shows good cellularity. Auger electronic spectroscopy reveals the relationship between the structure of TiN/Ag multilayered film and the biomedical properties.     

Growth and characterizations of dual ion beam sputtered CIGS thin films for photovoltaic applications

The growth of CIGS thin films on soda-lime glass substrates at different substrate temperatures by dual ion beam sputtering system in a single-step route from a single quaternary sputtering target with the composition of Cu (In_0.70 Ga_0.30) Se₂ was reported. The effects of the substrate temperature on structural, optical, morphological and electrical properties of CIGS films were investigated. Stoichiometry of one such film was investigated by X-ray photoelectron spectroscopy. All CIGS films had demonstrated a strong (112) orientation located at 2θ ~26.70^o, which indicated the chalcopyrite structure of films. The value of full-width at half-maximum of (112) peak was reduced from 0.58° to 0.19° and crystallite size was enlarged from 14.98 to 43.05 nm as growth temperature was increased from 100 to 400 °C. However, atomic force microscope results showed a smooth and uniform surface at lower growth temperature and the surface roughness was observed to increase with increasing growth temperature. Hall measurements exhibited the minimum film resistivity of 0.09 Ω cm with a hole concentration of 2.42 × 10¹⁸ cm^?3 and mobility of 28.60 cm² V^?1 s^?1 for CIGS film grown at 100 °C. Film absorption coefficient was found to enhance nominally from 1 × 10⁵ to 2.3 × 10⁵ cm^?1 with increasing growth temperature from 100 to 400 °C.     

Influence of growth rate on the structural and morphological properties of TiN, ZrN and TiN/ZrN multilayers

The effect of the deposition rate on the structural and morphological properties of TiN and ZrN single layers and TiN/ZrN multilayers deposited by radiofrequency reactive magnetron sputtering has been studied. The total pressure was kept constant and the growth rate variation was obtained by small difference of nitrogen concentration in the fed gas. The decreasing deposition rate results in a structural change in the thin films from (111) orientation to (100) one. As consequence the surface morphology becomes smoother. Films roughness is strongly related with texture and it decreases with an increase in the (100) X-ray diffraction line intensity. In order to achieve a clear interpretation of our experimental results, the ratio between the N⁺ ions of the plasma and the atoms number reaching the substrate was considered. At high deposition rate with respect to the N⁺ concentration, the chemical potential of transition metal on (100) growth surface is higher than (111) one favouring the (111) orientation of the films. On the contrary, when the growth rate is low with respect to the nitrogen concentration, the chemical potential of transition metal on (111) growth surface is higher than the (100) one leading to a preferential growth in the (100) direction.