Amorphous carbon films in direct current magnetron sputtering from regenerative sooting discharge

We present results of carbon coatings on metal substrates in cylindrical hollow cathode (CHC) direct current magnetron sputtering. This is a new technique for making amorphous carbon films by CHC magnetron sputtering from a regenerative sooting discharge. The carbon films are deposited on Cu and Al substrates in a Ne atmosphere and compared with the films of carbon soot on the same materials produced from a conventional 80A arc discharge between graphite electrodes in a He background gas. Raman spectroscopy reveals the existence of graphite and diamond-like structures from the arc discharge while in CHC magnetron sputtering, graphite-like structures are dominant. X-ray diffraction data of samples from the arc discharge show nano-size precipitates of Al₄C₃ of rhombohedral and hexagonal form for the aluminium sample and probable formation of diamond and hexagonal carbon in copper whilst in magnetron sputtering we obtain amorphous carbon films. Scanning electron microscope images of the surface show a collection of loose agglomerates of carbon particles in the arc discharge whereas, for magnetron sputtering, structures are regular with smooth edges and fine grains.     

Synthesis and characterization of thin Ba-M hexagonal ferrite films

It is demonstrated that Ba-M hexagonal ferrite films with a thickness of ～100 nm and the properties required for the data recording at a superhigh density can be synthesized on an amorphous substrate. The films are obtained on SiO₂/Si substrates by magnetron sputtering of a Ba-M ferrite ceramic target in a gas mixture of Ar and O₂ taken at the partial pressures of 3.5 and 0.5 mTorr, respectively. In order to obtain the required crystal and magnetic structure, the films were annealed for 1 h at 700, 800, or 900°C. The experimental data show that the annealing at 800°C leads to crystallization of the amorphous deposit into a hexagonal ferrite of the Ba-M type.     

Properties of amorphous carbon films produced by magnetron sputtering

Amorphous carbon films were prepared by magnetron sputtering of a graphite target. Their electrical and optical properties obey the relationship governing the conduction mechanisms in amorphous semiconductors. Their microscopic and structural properties are characteristic of physically vapour-deposited films. A scattering of single crystals of carbon in an amorphous carbon matrix was obtained by triode sputtering of a graphite target.     

Deposition of nickel oxide by direct current reactive sputtering: Effect of oxygen partial pressure

Nickel oxide thin films were deposited by Direct Current magnetron reactive sputtering from Ni target onto SnO₂:F conductive glass substrates. The process was carried out without intentional heating, in an argon/oxygen gas mixture with various oxygen contents and discharge currents. The polycrystalline NiO thin films were deposited with controlled growth of the structure along [111] and [200] crystallographic directions for chosen conditions. Morphology of as-deposited films was found to depend on the preferentially oriented NiO crystals. Moreover, on the basis of discharge voltage as a function of the O₂ partial pressure for a constant discharge current, we present here the method to estimate the deposition conditions allowing us to achieve the desired preferential growth of transparent p-type semiconductor NiO, by Direct Current magnetron reactive sputtering.     

Catalyst-free synthesis of carbon and boron nitride nanoflakes using RF-magnetron sputtering

Catalyst-free boron nitride (BN) and carbon (C) nanoflakes have been produced by direct radio frequency (RF)-magnetron sputtering on molybdenum and tungsten substrates at or above temperatures of 1000 °C and 800 °C, respectively. Selected-area electron diffraction (SAED) shows that the films are polycrystalline and contain disordered graphite and hexagonal BN. Transmission electron microscopy (TEM) reveals curved or twisted flakes up to several hundred nanometres in length. High resolution transmission electron microscopy (HRTEM) confirms the nanoflake structure to be turbostratic, which is intermediate between an amorphous phase and the ordered layered phases of hexagonal BN or graphite.     

High-power impulse magnetron sputtering of Ti-Si-C thin films from a Ti3SiC2 compound target

We have deposited Ti-Si-C thin films using high-power impulse magnetron sputtering (HIPIMS) from a Ti₃SiC₂ compound target. The as-deposited films were composite materials with TiC as the main crystalline constituent. X-ray diffraction and photoelectron spectroscopy indicated that they also contained amorphous SiC, and for films deposited on inclined substrates, crystalline Ti₅Si₃C_x. The film morphology was dense and flat, while films deposited with direct-current magnetron sputtering under comparable conditions were rough and porous. We show that, due to the high degree of ionization of the sputtered species obtained in HIPIMS, the film composition, in particular the C content, depends on substrate inclination angle and Ar process pressure.     

Crystalline hydroxyapatite thin films produced at room temperature — An opposing radio frequency magnetron sputtering approach

Hydroxyapatite (HA) films have been widely recognized for their biocompatibility and utility in promoting biointegration of implants in both osseous and soft tissue. Conventional sputtering techniques have shown some advantages over the commercially available plasma spraying method; however, the as-sputtered films are usually amorphous which can cause some serious adhesion problems when post-deposition heat treatment is necessitated. In this paper we present an opposing radio frequency (RF) magnetron sputtering approach for the preparation of HA thin films on various substrates at low power levels. Using this alternative RF magnetron geometry, as-sputtered HA films are nearly stoichiometric, highly crystalline, and strongly bound to the substrate. Post-deposition heat treatment under 800 °C did not result in a marked improvement in the degree of crystallinity of the films. In addition, dissolution experiments show that as-sputtered films are more stable than annealed ones. As-sputtered films grown on amorphous silica substrates exhibit X-ray diffraction (XRD) patterns similar to those of randomly orientated HA powder. On the other hand, films deposited on oriented substrates such as Si(100) and Si(111) show a polycrystalline HA XRD pattern but with some strongly preferred orientations, indicating that HA crystallization is sensitive to the nature of the substrate. The results suggest that the opposing RF magnetron sputtering approach has some potential to produce high quality HA films on metallic implants.     

Al-Mg-B thin films prepared by magnetron sputtering

Hard, nanocomposite aluminum magnesium boride thin films were prepared on Si (100) substrates with a three target magnetron sputtering system. The films were characterized by X-ray diffraction, atomic force microscope, electron micro-probe, Fourier transform infrared spectroscopy and nanoindentation. The results show that the maximum hardness of the as-deposited films is about 30.7 GPa and these films are all X-ray amorphous with smooth surfaces. The influences of substrate temperature and boron sputtering power on the quality of the films are discussed. From the results of this work, magnetron sputtering is a promising method to deposit Al-Mg-B thin films.     

Electrochemical corrosion behavior of amorphous carbon nitride thin films

The corrosion behavior along with biocompatibility and mechanical properties plays an important role in determining of biomedical implants feasibility. Diamond-like carbon seems to be the promising material in which all these three requirements can be achieved. In this study nitrogen doped amorphous carbon (a-C:N) films were deposited on silicon and medical CoCrMo alloy substrates by vacuum glow discharge sputtering technique using different deposition conditions from graphite target. Potentiodynamic polarization tests were employed to assess the corrosion performances of the films at room temperature in 0.89 wt. % NaCl solution. The influence of substrate bias on the electrochemical corrosion behavior was investigated. The highest value off E_corr for CoCrMo substrate was measured on the coating deposited with substrate bias around −0.6 kV. The shift of E_corr to more positive values was about 350 mV.     

Preparation and antibacterial properties of Ag-containing diamond-like carbon films prepared by a combination of magnetron sputtering and plasma source ion implantation

Ag-containing diamond-like carbon (DLC) films were prepared on austenitic type stainless steel SUS316L and silicon wafer substrates by a process combining reactive magnetron sputtering with plasma source ion implantation (PSII). An Ag disc was used as a target for the sputter source with an RF power of 100 W. A mixture of the gases Ar and C₂H₂ was introduced into the discharge chamber while a negative high voltage pulse was applied to the substrate holder. By changing the gas flow ratios the resulting Ag content of the films could be varied. The prepared films were composed of amorphous carbon with crystalline Ag, as observed by X-ray diffractometry and TEM. Additional sample characterizations were performed by X-ray photoelectron spectroscopy, secondary ion mass spectrometry and Raman spectroscopy. The surface morphology was observed by scanning electron microscopy. The antibacterial activity was determined using Staphylococcus aureus bacteria. All Ag-containing diamond-like carbon films exhibited an antibacterial activity with only small variations depending on the Ag content.     

Investigation on preparation and diffusion barrier properties of W-Ti thin films

An W-10 wt.%Ti alloy target was prepared by the W-Ti ball-milled powders, and W-Ti thin ?lms were deposited by dc magnetron sputtering on Si substrates. Then Cu/W-Ti/Si structures were prepared after Cu films were deposited on the W-Ti/Si structures. The results show that W-Ti alloy has a single phase structure with fine grain size. The structures of W-Ti thin films evolved from an amorphous film to a dual phase structure with bcc W and hcp Ti, followed by W-Ti solid solution with increasing sputtering powers. W-Ti thin ?lms can effectively block against Cu diffusion and maintain good adhesion strength with Cu ?lms at 600 °C. The failure mechanism of the crystal W-Ti films is related to the grain boundary which provides fast diffusion paths for Cu and Si atoms, while the amorphous W-Ti diffusion barrier layer is directly related to the thermal stress and interface reaction.     

Deposition and characterization of magnetron sputtered amorphous Cr-C films

Thin films in the Cr-C system with carbon content of 25-85 at.% have been deposited using non-reactive DC magnetron sputtering from elemental targets. Analyses with X-ray diffraction and transmission electron microscopy confirm that the films are completely amorphous. Also, annealing experiment show that the films had not crystallized at 500 °C. Furthermore, X-ray spectroscopy and Raman spectroscopy show that the films consist of two phases, an amorphous CrC_x phase and an amorphous carbon (a-C) phase. The presence of two amorphous phases is also supported by the electrochemical analysis, which shows that oxidation of both chromium and carbon contributes to the total current in the passive region. The relative amounts of these amorphous phases influence the film properties. Typically, lower carbon content with less a-C phase leads to harder films with higher Young’s modulus and lower resistivity. The results also show that both films have lower currents in the passive region compared to the uncoated 316L steel substrate. Finally, our results were compared with literature data from both reactively and non-reactively sputtered chromium carbide films. The comparison reveals that non-reactive sputtering tend to favour the formation of amorphous films and also influence e.g. the sp²/sp³ ratio of the a-C phase.     

Study of adhesion of carbon nitride thin films on medical alloy substrates

The adhesion improvement of biocompatible thin films on medical metal alloy substrates commonly used for joint replacement implants is studied. Diamond-like carbon (DLC) and carbon nitride (CN) thin films are, because of their unique properties such as high hardness, wear resistance and low friction coefficient, candidates for coating of medical implants. However, poor adhesion on substrates with high thermal expansion coefficient limits their application. We deposited CN films by pulsed DC discharge vacuum sputtering of graphite target on CoCrMo and Ti6Al4V substrates. Surface nitridation of the substrate, changing the deposition parameters and use of interlayer led to improved adhesion properties of the films. Argon and nitrogen gas flow, thickness of the film and frequency of the deposition pulses had significant influence on the adhesion to the substrate. Properties of deposited films were analyzed using Scanning Electron Microscopy, Raman spectroscopy and tribology tests.     

Ordered, self-organized cobalt nanodots in Co-diamond-like carbon thin films

A formation process for ordered, self-organized cobalt (Co) nanodots in diamond-like carbon (DLC) thin films deposited by magnetron sputtering in a plasma-assisted Ar/CH4 discharge is presented. episilon-Co dots -5 nm in diameter, separated by 1-2 nm DLC boundaries and arranged in hexagonal arrays were produced on Si substrates. The formation mechanism relies on a self-organization process which is based on surface energy minimization and local magnetic field interaction. The proposed plasma-assisted process presents a controlled and cost-effective bottom-up nanofabrication approach for the production of well-ordered magnetic nanodots based on self-organization.     

Preparation of amorphous FexSi(1 − x) film using unbalanced magnetron sputtering

The preparation of iron-silicon films was performed onto Si (100) substrates by microwave electron cyclotron resonance (ECR) plasma source enhanced unbalance magnetron sputtering. The compositions, microstructures and properties of films under different sputtering powers and annealing conditions were characterized by AES, GAXRD, TEM and absorption spectrum techniques. The results described that the amorphous iron silicon films can be easily prepared by unbalance magnetron sputtering. Even the Fe/Si ratio deviated far from 1:2, such as Fe/Si = 1:14.8 or 1:10, the amorphous iron silicon film with semiconductor properties can also be obtained, which suggests that the Fe/Si ratio is not the only factor to determine whether the samples have semiconducting properties in iron silicon amorphous. After annealing at 850 °C for 4 h, the microstructure of nanometer β-FeSi₂ embedded into amorphous Si still possesses semiconducting characteristics.     

Non-magnetic hexagonal nanocrystalline ni films grown by radio frequency magnetron sputtering

Nanoscale Ni films in the thickness range 15-500 nm were grown on various substrates, such as amorphous glass, single crystalline silicon and sapphire, and polycrystalline alumina, at a temperature of about 350 K by radio frequency magnetron sputtering. It is demonstrated, via X-ray diffraction and high-resolution transmission electron microscopy, that there is an Ar-gas pressure window that favors the growth of stable single-phase hexagonal nanocrystalline Ni films regardless of the film thickness and the kind of the substrate. At lower or higher Ar pressures the films grow in the regular face centered cubic phase of Ni. The structural habits are attributed to differences in the kinetic energy of the Ni atoms impinging on the substrates. Superconducting quantum interference device magnetometry measurements reveal that the hexagonal films show zero magnetic response down to liquid Helium temperature. This result is discussed with respect to earlier first principle calculations and to experimental results on Ni nanoparticles.     

无定型CNx超硬薄膜的生长过程研究

利用直流磁控溅射方法,在高纯石墨衬底上沉积制备碳氮薄膜.借助于SEM对溅射沉积的碳氮薄膜微观形貌进行观察,并对碳氮薄膜的生长过程进行研究.结果表明:沉积所得的碳氮薄膜为无定型结构,且由大量的团簇所组成.在碳氮薄膜的形成过程中,先是在某些局部位置优先形成突起,继而延伸发展成棒状或纤维状结构,并桥联于相邻的CNx团簇间,伴随着这些桥联结构在径向、轴向的扩展,逐渐演变成新的团簇,并毗连成膜;同时,又不断衍生出新的突起,如此反复,实现了碳氮薄膜的持续增厚或生长.     

Comparison of hydrophilic properties of TiO2 thin films prepared by sol-gel method and reactive magnetron sputtering system

This article reports on preparation, characterization and comparison of TiO₂ films prepared by sol-gel method using the titanium isopropoxide sol (TiO₂ coating sol 3%) as solvent precursor and reactive magnetron sputtering from substoichiometric TiO_2 − x targets of 50 mm in diameter. Dual magnetron supplied by dc bipolar pulsed power source was used for reactive magnetron sputtering. Depositions were performed on unheated glass substrates. Comparison of photocatalytic properties was based on measurements of hydrophilicity, i.e. evaluation of water contact angle on the film surface after UV irradiation. It is shown, that TiO₂ films prepared by the sol-gel method exhibited higher hydrophilicity in the as-deposited state but has significant deterioration of hydrophilicity during aging, compared to TiO₂ films prepared by magnetron sputtering. To explain this effect AFM, SEM and high resolution XPS measurements were performed. It is shown that the deterioration of hydrophilicity of sol-gel TiO₂ films can be suppressed if as-deposited films are exposed to the plasma of microwave oxygen discharge.     

Evidence of hexagonal diamond in plasma-deposited carbon films

Hexagonal diamond grains of 30 nm diameter together with graphite and SiC are seen in predominantly amorphous carbon films deposited at low temperature on Si substrates from a CH₄ plasma vapour source. The different crystalline phases are identified by grazing-angle X-ray diffraction which allows for substrate rotation and tilting to enable the 2 peaks to be correlated with the angular displacements of specific planes. Electron energy-loss spectroscopy shows the chemical composition of the films to be predominantly carbon with traces of oxygen. Raman spectroscopy shows the peaks to be associated with amorphous carbon and graphite, together with a peak at 1170 cm^–1 which is attributed to microcrystalline hexagonal diamond.     

Structural, mechanical and tribological behavior of fullerene-like carbon film

Hydrogenated carbon films containing fullerene-like structures (FL-C:H) were synthesized using magnetron sputtering of a graphite target in methane and argon atmospheres. The results indicate clearly that a substantial part of the film is made up of fragments of such fullerene-like structures mixed in a hydrogenated amorphous carbon matrix. The film exhibits excellent mechanical properties with a hardness of 27.4 GPa and almost complete elastic recovery (as high as 95%). The tribological properties of the FL-C:H film were tested and compared with a-C:H and a-C films. The results show that the lowest friction coefficient of the FL-C:H film, about 0.02, is recorded in oxygen environment. The ranges of dispersion of the friction coefficient for the FL-C:H film are merely 0.02 in different testing environments, much lower than that of a-C:H and a-C films, which indicates the friction-coefficient-insensitivity of the FL-C:H film to different atmospheres.