Synthesis of aluminum nitride thin films by filtered arc ion plating deposition

Thin films of aluminum nitride (AlN) were deposited on stainless steel and glass substrates by a modified deposition technique, filtered arc ion plating, at an enhanced deposition rate. X-ray diffraction spectra confirmed the exclusive presence of AlN hexagonal wurtzite phase. Under a mixed gas (Ar + N₂) pressure of 0.90 Pa and a bias voltage of − 400 V, the deposited films exhibited a fairly low surface roughness of 2.23 nm. The thin films were proved higher than 75% transparent in the visible spectral region. The bonding strength between the film and substrate was verified higher than 20 N. Thus high performance of such AlN thin films can be expected in applications.     

Comparing internal stress in diamond-like carbon films with different structure

Diamond-like carbon (DLC) films with different structures were deposited on Si (100) and stainless steel substrates in a hybrid deposition system with Ar and CH₄ as the feedstocks. The effects of the bias voltage, Ti-interlayer, Ti functional gradient layer and Ti-doping on the internal stress in DLC films were investigated. The results show that the internal stress in DLC films arises from both the intrinsic stress generated during the film growth and the thermal stress generated due to the mismatching of the thermal expansion coefficient between the DLC films and the substrate materials. The intrinsic stress can be released through doping titanium element at the expense of reducing the sp³/sp² ratio. The thermal stress in DLC films can be decreased through introducing Ti-interlayer or Ti functional gradient layer. Noticeably, DLC films with very low internal stress deposited on stainless steel can be obtained through the combination of Ti-doping and Ti functional gradient layer.     

Preparation of La0.8Sr0.2Cr0.97V0.03O3 − δ films for solid oxide fuel cell application

La_0.8Sr_0.2Cr_0.97V_0.03O_3 − δ (LSC) is commonly studied as a ceramic interconnect material as well as a coating material for metallic interconnects for solid oxide fuel cell applications. However, it is difficult to sinter this type of material to high density. In order to overcome this problem and to study the material in form of a thin film we have used Pulsed Laser Deposition to obtain a dense, uniform film with the right stochiometry. Investigation of preparation-parameter dependence of the LSC films deposited on a stainless steel substrate during pulsed-laser deposition was carried out. The LSC films were deposited with KrF excimer laser (248 nm) on a stainless steel substrate at different oxygen pressure and substrate temperatures. The substrate temperature (873-1073 K) and the oxygen background pressure (5-20 Pa) were varied in order to obtain optimal growth conditions. The surface morphology and structural information of the films were obtained using scanning electron microscope (SEM) and X-ray diffraction, respectively. Under the optimal preparation-parameter conditions: substrate temperature of 1023 K and an oxygen pressure of 10 Pa the structure of the film agreed with the target structure and the SEM micrographs show that the surfaces are homogeneous, smooth, crack-free and dense.     

SiO2 film deposition on the inner wall of a narrow polymer tube by a capacitively coupled μplasma

SiO₂ thin films were deposited on the inner wall of a narrow commercial poly(propylene) tube with inner/outer diameters of 1.0 mm/3.0 mm by plasma-enhanced chemical vapor deposition using He or Ar carrier gases and tetraethoxysilane (TEOS)/O₂ feedstock gases at high pressures from 30 kPa to atmospheric pressure and at room temperature. A glow μplasma was generated inside the tube by a radio frequency (RF 13.56 MHz) capacitively coupled discharge. X-ray photoelectron spectra and infrared spectra revealed that the inner surface of the plasma-treated tube was covered by a SiO₂ film. Scanning electron microscopy images indicated that the film produced by He/TEOS/O₂ μplasma had a smooth surface whereas the surface of the film produced by Ar/TEOS/O₂ μplasma appeared granulated. Typical deposition rates of approximately 300 nm/min were obtained by He/TEOS/O₂ μplasma at atmospheric pressure and a RF power of 11 W.     

The influence of fluorine doping on the optical properties of diamond-like carbon thin films

Optical properties of fluorine doped diamond-like carbon (F:DLC) films deposited by the direct current plasma enhanced chemical vapor deposition (PECVD) technique were studied in detail. Surface morphologies of the F:DLC films were studied by an atomic force microscope, which indicated surface roughness increased with increase in at.% of F in the films. The chemical binding was investigated by X-ray photoelectron spectroscopic studies. Fourier transformed infrared spectroscopic studies depicted the presence of CF_x (x = 1,2,3) and CH_n (n = 1,2) bonding within the F:DLC films. Optical transparency and the optical band gap decreased with the fluorine incorporation in the DLC film. Optical band gap calculated from the transmittance spectra decreased from 2.60 to 1.95 eV with a variation of 0-14.8 at.% of F concentration in the diamond-like carbon films. Urbach parameter determined from the band tail of the transmittance spectra showed that it increased with the doping concentration.     

ZnO nanostructured film deposition using the separated pulsed laser deposition (SPLD) assisted by electric and magnetic drift motion

We have developed the separated pulsed laser deposition (SPLD) technique to prepare high quality ZnO based films exhibiting uniform and droplet-free properties. This SPLD consists of an ablation chamber and a deposition chamber which can be independently evacuated under different ambient gases.The gas species and the pressures in both chambers can be arbitrarily chosen for the specific deposition such as nanostructured films and nanoparticles. The ablation chamber is a stainless steel globe and the deposition chamber is a quartz tube connected to a metallic conic wall with an orifice. We used a KrF excimer laser with λ = 248 nm and 25 ns pulse duration. The different gas conditions in two chambers allow us to realize optimal control of the plasma plume, the gas phase reaction and the film growth by applying the bias voltage between the conic wall and the substrate under the magnetic field. We can expect that at appropriate pressures the electric and magnetic field motion (E × B azimuthal drift velocity) gives significant influences on film growth.We have deposited ZnO thin films at various pressures of ablation chamber (Pab) and deposition chamber (Pd). The deposition conditions used here were laser fluence of 3 J/cm², laser shot number of 30,000, Pab of 0.67-2.67 Pa (O₂ or Ar), Pd of 0.399-2.67 Pa (O₂), and substrate temperature of 400 °C. Particle-free and uniform ZnO films were obtained at Pab of 0.67 Pa (Ar) and Pd of 1.33 Pa (O₂). The ZnO film showed high preferential orientation of (002) plane, optical band gap of 2.7 eV, grain size of 42 nm and surface roughness of 1.2 nm.     

Advances in DLC coatings by hybrid PSII and PECVD as a barrier to corrosion in simulated body fluid*

In this study, diamond-like carbon (DLC) films were deposited on biomedical AISI316L stainless steel by hybrid plasma source ion implantation (PSII) and plasma-enhanced chemical vapour deposition (PECVD). Potentiodynamic polarization tests and Electrochemical Impedance Spectroscopy (EIS) have been employed to investigate the corrosion performance of different DLC films in Tyrode's simulated body fluid (pH = 7.4). The corrosion resistance of the DLC films by PECVD deteriorated rapidly after 24 h of immersion, but those made by hybrid PSII and PECVD offered more effective barrier for AISI316L stainless steel during 72 h of immersion. The test results demonstrated that the DLC film by hybrid PSII and PECVD possessed less corrosion current density, greater corrosion resistance, and more positive breakdown potential in simulated body fluid.     

Bias effects on microstructure, mechanical properties and corrosion resistance of arc-evaporated CrTiAlN nanocomposite films on AISI 304 stainless steel

CrTiAlN films were deposited on AISI 304 stainless steel by cathodic arc evaporation under a systematic variation of the substrate bias voltage. The effects of substrate bias on the coating morphology and mechanical properties, such as structure, composition, adhesion, hardness and Young's modulus, were studied in details using field emission scanning electron microscopy, X-ray diffraction, electron probe microanalysis and indenter. Polarization test and immersion test were also carried out to evaluate the corrosion behavior of the various films. CrTiAlN films are nanocrystalline that exhibit a CrN/TiAlN multi-layered morphology. At the optimal value of substrate bias voltage (i.e., − 150 V), the CrTiAlN film showed an increased Cr content and improved properties, such as higher adhesion, higher hardness (38 ± 2 GPa), and greater Young's modulus (319 ± 16 GPa) vs. the films deposited at other substrate bias voltages. Moreover, the optimum film has better corrosion resistance in 3.5 wt.% NaCl and 20 vol.% HCl solutions.     

不锈钢衬底两面同时液相电沉积类金刚石薄膜及其沉积机理研究

为了利用液相电沉积技术实现在金属衬底表面全方位电沉积类金刚石(DLC)薄膜,采用不同尺度的不锈钢片作为衬底,在表面电沉积了DLC薄膜,利用X射线光电子能谱、Raman光谱和扫描电子显微镜分别对衬底两面薄膜的化学成分、微观结构和表面形貌进行了分析。结果显示:对于尺度大于石墨阳极的不锈钢衬底,仅在衬底正对着阳极的一面实现了DLC薄膜的沉积;而对于尺度小于阳极的不锈钢衬底,在衬底两面都有DLC薄膜沉积,且两面薄膜结构相似,形貌相近。利用准静态电场理论对实验结果进行了解释,提出在金属衬底表面实现液相电沉积DLC薄膜的前提条件是存在垂直于衬底表面的电场分量,为进一步实现在复杂形状的导电性衬底表面沉积DLC薄膜提供了理论依据。     

Improved electrochemical performance of nitrocarburised stainless steel by hydrogenated amorphous carbon thin films for bone tissue engineering

In this study, hydrogenated amorphous carbon thin films, structurally similar to diamond‐like carbon (DLC), were deposited on the surface of untreated and plasma nitrocarburised (Nitrocarburizing‐treated) stainless steel medical implants using a plasma‐enhanced chemical vapour deposition method. The deposited DLC thin films on the nitrocarburising‐treated implants (CN+DLC) exhibited an appropriate adhesion to the substrates. The results clearly indicated that the applied DLC thin films showed excellent pitting and corrosion resistance with no considerable damage on the surface in comparison with the other samples. The CN+DLC thin films could be considered as an efficient approach for improving the biocompatibility and chemical inertness of metallic implants.Inspec keywords: tissue engineering, bone, biomedical materials, electrochemistry, amorphous state, carbon, hydrogen, thin films, plasma CVD, adhesion, corrosion resistance, surface hardeningOther keywords: electrochemical performance, plasma nitrocarburised stainless steel medical implants, hydrogenated amorphous carbon thin films, bone tissue engineering, plasma‐enhanced chemical vapour deposition method, adhesion, corrosion resistance, biocompatibility, chemical inertness, metallic implants, C:H     

Fabrication of high frequency ZnO thin film SAW devices on silicon substrate with a diamond-like carbon buffer layer using RF magnetron sputtering

Diamond-like carbon (DLC) film is a promising candidate for surface acoustic wave (SAW) device applications because of its higher acoustic velocity. A zinc oxide (ZnO) thin film has been deposited on DLC film/Si substrate by RF magnetron sputtering; the optimized parameters for the ZnO sputtering are RF power density of 0.55 W/cm², substrate temperature of 380 °C, gas flow ratio (Ar/O₂) of 5/1 and total sputter pressure of 1.33 Pa. The results showed that when the thickness of the ZnO thin films was decreased, the phase velocity of the SAW devices increased significantly.     

The effects of plasma pre-treatment and post-treatment on diamond-like carbon films synthesized by RF plasma enhanced chemical vapor deposition

Diamond-like carbon (DLC) films were synthesized by RF plasma enhanced chemical vapor deposition and the effects of plasma pre-treatment and post-treatment on the DLC films were investigated. Experimental results show that the surface roughness of the substrate, ranging from 0.2 to 1.2 nm, created by the plasma pre-treatment, will affect the surface roughness of the DLC films deposited using methane as the carbon source. However, the film surface roughness (0.1-0.4 nm) is much smaller than that of the substrate. Raman analysis and hardness measurement by nanoindentation indicate that the structure and the hardness of the DLC films are relatively unchanged for the film surface roughness investigated. For the argon or hydrogen plasma post-treatment of the DLC films deposited using acetylene as the carbon source, it is found that surface roughness decreases with the post-treatment time. Although the hardness decreases after post-treatment, it remains relatively constant with increasing post-treatment time.     

Titanium oxy-nitride films deposited on stainless steel by an ion beam assisted deposition technique

Surfaces of stainless steel SUS304 were coated with titanium oxy-nitride (TiON) films at temperatures of 400–770°C using an ion-beam assisted deposition technique constructed from an electron beam evaporator for Ti evaporation and a microwave ion source for ionizing nitrogen gas. The N ions were accelerated at energies of 0.5–2.0 keV. Most of the deposited TiON films consisted of (60–80)% TiN and (40–20)% TiO₂, and the fraction of TiO₂ increased with increasing substrate temperature. Hardness of the TiNO films varied in the range from 160 GPa to 260 GPa with increasing substrate temperature. The titanium oxy-nitride film could be deposited on stainless steel without a significant deterioration surface layer at 600°C. However, when TiNO films were deposited at temperatures higher than 700°C, the thickness of the TiNO films were significantly thinner and a thick layer containing nitride such as Cr₂N, CrFe, Fe₂N and Fe₄N was formed in a near surface region of stainless steel because more nitrogen diffused into stainless steel.     

Thermal stability of amorphous molybdenum trioxide films prepared at different oxygen partial pressures by reactive DC magnetron sputtering

Thin films of MoO₃ were prepared on quartz and Si (1 0 0) substrates by reactive dc magnetron sputtering of a Mo target in an oxygen and argon atmosphere. The structural and optical changes induced in the films due to post-growth annealing have been systematically studied by Rutherford backscattering (RBS), X-ray diffraction (XRD), X-ray reflectivity (XRR) and by optical methods. RBS studies reveal no change in composition of the films upon annealing at high temperatures. Grazing angle XRD studies show that the as-deposited films are amorphous and crystallize to β-MoO₃ phase with small contribution of α-MoO₃ upon annealing at 300 °C. The film prepared at 0.40 Pa transforms to α-MoO₃ upon annealing at 650 °C, while the film deposited at 0.19 Pa still has some β-MoO₃ phase contribution. XRR measurements reveal that the film thickness decreases upon annealing with simultaneous increase of film density. The surface roughness of the films strongly increases after crystallization. The contraction of the film deposited at 0.40 Pa is much greater than the contraction of the film prepared at 0.19 Pa. The mass variation of the film deposited at 0.19 Pa and that deposited at 0.40 Pa are completely different. The optical properties of MoO₃ films deposited at 0.19 and 0.40 Pa are changed strongly by annealing.     

Application of plasma polymerized siloxane films for the corrosion protection of titanium alloy

Organosilicon film and SiO_x-like film are deposited on titanium alloy (Ti6Al4V) surfaces by atmospheric pressure (~ 10⁵ Pa) dielectric barrier discharge to improve its corrosion resistance in Hanks solution. Hexamethyldisiloxane (HMDSO) is used to be the chemical precursor. The organosilicon film deposited in Ar/HMDSO system has high growth rate (75 nm/min) and low surface roughness (3 nm), while the SiO_x-like film deposited in Ar/O₂/HMDSO system has lower growth rate (35 nm/min) and slightly higher surface roughness (9 nm). The potentiodynamic polarization tests show that both the two siloxane films coated Ti6Al4V samples have more positive corrosion potential and one order of magnitude lower corrosion current density than the substrate, indicating the corrosion resistance of Ti6Al4V can be improved by depositing siloxane film on its surface. In particular, as the surface is more compact and cross-linked, the SiO_x-like film has better corrosion resistance than the organosilicon film.     

Multi-phase structured silicon carbon nitride thin films prepared by hot-wire chemical vapour deposition

In this work, Silicon Carbon Nitride (Si-C-N) thin films were deposited by Hot Wire Chemical Vapour Deposition (HWCVD) technique from a gas mixture of silane (SiH₄), methane (CH₄) and nitrogen (N₂). Six sets of Si-C-N thin films were produced and studied. The component gas flow rate ratio (SiH₄:CH₄:N₂) was kept constant for all film samples. The total gas flow-rate (SiH₄ + CH₄ + N₂) was changed for each set of films resulting in different total gas pressure which represented the deposition pressure for each of these films ranging from 40 to 100 Pa. The effects of deposition pressure on the chemical bonding, elemental composition and optical properties of the Si-C-N were studied using Fourier transform infrared (FTIR) spectroscopy, Auger Electron Spectroscopy (AES) and optical transmission spectroscopy respectively. This work shows that the films are silicon rich and multi-phase in structure showing significant presence of hydrogenated amorphous silicon (a-Si:H) phase, amorphous silicon carbide (a-SiC), and amorphous silicon nitride (a-SiN) phases with Si-C being the most dominant. Below 85 Pa, carbon content is low, and the films are more a-Si:H like. At 85 Pa and above, the films become more Si-C like as carbon content is much higher and carbon incorporation influences the optical properties of the films. The properties clearly indicated that the films underwent a transition between two dominant phases and were dependent on pressure.     

Effect of oxygen plasma treatment on bonding states for columnar structured a-CNx thin films prepared by reactive sputtering

Amorphous carbon nitride (a-CN) thin films were deposited on silicon single crystal substrates by rf-reactive sputtering method using a graphite target and nitrogen gas. The substrate temperature was varied from room temperature (RT) to 853 K. After deposition, the effect of oxygen plasma treatment on bonding structures of the film surface has been studied by using an oxygen discharge at 16 Pa and rf power of 85 W. The chemical bonding states and film composition were analyzed by X-ray photoelectron spectroscopy (XPS), while film thickness was obtained from scanning electron microscopy (SEM) and ellipsometer. XPS study revealed that the films have NO₂ and NO₃ bonding structures when the films are deposited at temperatures higher than 673 K. After exposure to oxygen plasma, carbon in the film surface was etched selectively and this phenomenon was observed in all films. In contrast, the surface concentration of nitrogen was ket at constant values before and after oxygen plasma treatment. The NO₃ bonding state had dramatically increased after oxygen plasma treatment for films deposited at higher deposition temperatures. The film surfaces have been observed to change the function from hydrophobic to hydrophilic after oxygen plasma treatment.     

Effect of boron incorporation on the structure and electrical properties of diamond-like carbon films deposited by femtosecond and nanosecond pulsed laser ablation

The influence of the incorporation of boron in diamond-like carbon (DLC) films on the microstructure of the coatings has been investigated. The boron-containing DLC films (a-C:B) have been deposited by pulsed laser deposition (PLD) at room temperature in high vacuum conditions, by ablating graphite and boron targets either with a femtosecond pulsed laser (800 nm, 150 fs, fs-DLC) or with a nanosecond pulsed laser (248 nm, 20 ns, ns-DLC). Alternative ablation of the graphite and boron targets has been carried out to deposit the a-C:B films. The film structure and composition have been highlighted by coupling Field Emission Scanning Electron Microscopy, Electron Energy Loss Spectroscopy and High Resolution Transmission Electron Microscopy. Using the B K-edge, EELS characterization reveals the boron effect on the carbon bonding. Moreover, the plasmon energy reveals a tendency of graphitization associated to the boron doping. Pure boron particles have been characterized by HRTEM and reveal that those particles are amorphous or crystallized. The nanostructures of the boron-doped ns-DLC and the boron-doped fs-DLC are thus compared. In particular, the incorporation of boron in the DLC matrix is highlighted, depending on the laser used for deposition. Electrical measurements show that some of these films have potentialities to be used in low temperature thermometry, considering their conductivity and temperature coefficient of resistance (TCR) estimated within the temperature range 160-300 K.     

Influence of sputtering parameters and nitrogen on the microstructure of chromium nitride thin films deposited on steel substrate by direct-current reactive magnetron sputtering

Chromium nitride thin films were deposited on SA-304 stainless steel substrates by using direct-current reactive magnetron sputtering. The influence of process conditions such as nitrogen content in the fed gas, substrate temperature, and different sputtering gases on microstructural characteristics of the films was investigated. The films showed (200) preferred orientation at low nitrogen content (< 30%) in the fed gas. The formation of Cr₂N and CrN phases was observed when 30% and 40% N₂ were used, with a balance of Ar, respectively. Field emission scanning electron microscopy and atomic force microscopy were used to characterize the morphology and surface topography of the thin films, respectively. Microhardness tests showed a maximum hardness of 16.95 GPa for the 30% nitrogen content.     

Evolution of optical properties with deposition time of silicon nitride and diamond-like carbon films deposited by radio-frequency plasma-enhanced chemical vapor deposition method

The paper presents investigations of the optical properties of thin high-refractive-index silicon nitride (SiN_x) and diamond-like carbon (DLC) films deposited by the radio-frequency plasma-enhanced chemical vapor deposition method for applications in tuning the functional properties of optical devices working in the infrared spectral range, e.g., optical sensors, filters or resonators. The deposition technique offers the ability to control the film's optical properties and thickness on the nanometer scale. We obtained thin, high-refractive-index films of both types at deposition temperatures below 350 °C, which is acceptable under the thermal budget of most optical devices. In the case of SiN_x films, it was found that for short deposition processes (up to 5 min long) the refractive index of the film increases in parallel with its thickness (up to 50 nm), while for longer processes the refractive index becomes almost constant. For DLC films, the effect of refractive index increase was observed up to 220 nm in film thickness.