Titanium oxide thin films synthesis by pulsed – DC magnetron sputtering

Titanium oxide thin films (1–4 μm) were deposited on the porous Hastelloy-X substrates using the pulsed – DC magnetron sputtering technique and characterized by X–ray diffraction (XRD) and scanning electron microscopy (SEM) methods. Firstly, the films were deposited at different distances between the magnetron and the substrate, as magnetron current and pressure in the deposition chamber were constant. The distance between the magnetron and the substrate was changed from 3 cm to 7 cm, and the deposition rate varied between 10.1 nm/min to 6.0 nm/min. Secondly, pressure influence for the deposition rate was investigated. The deposition rate decreased nearly 15% with the decrease of oxygen pressure from 1.3 to 6.0 Pa. Finally, the influence of the bias (applied to the substrate for the increase of deposition rate) on thin films phase and microstructure was investigated.The experimental results showed that formation of pure titanium oxide thin films was observed in all experimental cases. Only crystallite sizes and orientation were changed. The results showed that there is a possibility to change porosity and uniformity of the growing film by changing oxygen partial pressure during deposition or bias application to the substrate. The existence of columnar boundaries and nanocrystalline structure in the films was observed.     

The effects of pulse frequency and substrate bias to the mechanical properties of CrN coatings deposited by pulsed DC magnetron sputtering

The chromium nitride coatings have been prepared by the bipolar symmetric pulsed DC magnetron reactive sputtering process at 2 kHz and 20 kHz pulse frequencies, respectively. Different substrate bias was applied with a pulsed DC bias unit with 50 kHz pulse frequency. Oscilloscope traces of the I–V waveforms indicate high power and high current density outputs during the symmetric bipolar pulsed mode. It is concluded that the (200) orientation of CrN films is observed. The grain size decreases with increasing pulse frequency and substrate bias. The substrate bias has a strong influence on the mechanical properties of CrN films. The scratch tests of the CrN coatings show that almost only tiny chipping failure is occurred. Sufficient adhesion strength quality of the coating is also observed. The substrate bias for the deposition of CrN films with sufficient hardness and adhesion properties combination is − 290 V at 20 kHz and − 408 V at 2 kHz pulse frequency, respectively.     

An investigation of nitrided layer prepared by direct current nitrogen arc discharge

A simple direct current (DC) nitrogen arc discharge method is presented, which allows for in situ nitriding of titanium at atmospheric pressure. The microstructure and microhardness of the nitrided layer and effects of the arc discharge current were investigated. The nitrided layer was mainly composed of TiN dendrites and small amounts of TiN_0.3. The density and size of the TiN dendrites gradually decreased from the surface towards the titanium substrate. The layer had a good adhesion with titanium. With an increase of the arc discharge current from 40 to 80 A, the TiN dendrites coarsened, the layer thickness and amount of TiN increased and the layer hardness enhanced. The nitrided layer with the highest hardness value of 1600 HV and thickness of 1800 μm was obtained for an arc discharge current of 80 A.     

Tuning exchange bias in epitaxial Ni/MgO/TiN heterostructures integrated on Si(1 0 0)

Epitaxial Ni thin films are integrated with tunneling barrier MgO on Si(1 0 0) substrate. During pulsed laser deposition, early island-like structure transformed into uniform thin film with increasing number of laser pulses. This led to transitions in exchange bias from positive to negative and back to positive, which is ascribed to morphology associated residual strain. The Ni island structure has a coercive field as high as 3 times of that of the continuous film. The current work holds a tremendous promise in the realization of magnetic devices integrated with the Si-platform.     

Deposition of TiB2 onto X40 CrMoV 5-1-1 steel substrates by DC magnetron sputtering

Titanium diboride (TiB₂) films are being investigated due to their promising uses not only in electronic devices but also for mechanical purposes. Its excellent corrosion resistance and chemical stability, as well as high hardness and wear resistance, makes TiB₂ particularly suitable for aluminium processing (e.g. extrusion, die-casting and machining). In the present work, TiB₂ coatings were produced by non-reactive DC magnetron sputtering from a TiB₂ target on a tool steel substrate (AISI H13 premium/EN X40 CrMoV 5-1-1). Substrates similar to those frequently found on the aluminium injection industry were produced by vacuum quenching and tempering. The deposition parameters, namely the target/substrate distance, discharge current and substrate bias, were varied in order to obtain crystalline and well-structured films, suiting the substrate composition and microstructure. The coatings were characterized by X-ray diffraction (XRD) and scanning electron microscopy/EDS.A deposition rate of 23 nm/min was obtained for 0.85 A cathode current intensity and 70 mm substrate–magnetron distance. For positively biased substrates, all films are dense, without a columnar structure and show a (0 0 1) texture. For negatively biased substrates, there are less surface heating effects due to a much lower electron current through the substrate, and an ordered structure appears only at −150 V.     

Deposition of B4C/BCN/c-BN multilayered thin films by r.f. magnetron sputtering

Thin films of cubic boron nitride (c-BN) and B₄C/BCN/c-BN multilayers, were deposited by r.f. (13.56 MHz) multi-target magnetron sputtering from high-purity (99.99%) h-BN and a (99.5%) B₄C targets, in an Ar (90%)/N₂ (10%) gas mixture. Films were deposited onto silicon substrates with (100) orientations at 300 °C, with r.f. power density near 7 W/cm². In order to obtain the highest fraction of the c-BN phase, an r.f. substrate bias voltage between − 100 and − 300 V was applied during the initial nucleation process and − 50 to − 100 V during the film growth. Additionally, B₄C and BCN films were deposited and analyzed individually. For their deposition, we varied the bias voltage of the B₄C films between − 50 and − 250 V, and for the BCN coatings, the nitrogen gas flow from 3% to 12%. A 300-nm-thick TiN buffer layer was first deposited to improve the adhesion of all samples. X-ray diffraction patterns revealed the presence of c-BN (111) and h-BN phases. FTIR spectroscopy measurements indicate the presence of a peak at 780 cm^− 1 referred to as “out-of-plane” h-BN vibration mode; another peak at 1100 cm^− 1 corresponds to the c-BN TO mode and the “in-plane” vibration mode of the h-BN at 1400 cm^− 1. BN films deposited at 300 °C at a pressure of 4.0 Pa and under − 150 V of nucleation r.f. bias, applied for 35 min, presented the highest c-BN fraction, near 85%. By using 32 layers, it was possible to deposit a 4.6-μm-thick c-BN film with adequate mechanical properties and good adhesion to the substrate.     

Effect of the target bias voltage during off-pulse period on the impulse magnetron sputtering

With a high-power impulse magnetron sputtering (HiPIMS) apparatus, it has been studied how the target bias voltage during the off-pulse period affects the stability of the generated plasma. We have prepared an electrical pulse power source which can control the target voltage during the pulse off period, in addition to the pulse voltage, repetition frequency and a duty ratio of the pulse. Time-resolved current-voltage characteristic was monitored by an oscilloscope, and plasma generation behavior was elucidated. With titanium target and at Ar gas pressures of 0.6–5 Pa, pulse-off bias voltage was changed between −300 and +100 V, and the I-V characteristics were recorded. On increasing the negative bias voltage, the time at which the target current began to rise was gradually delayed. And at a certain voltage, the delay suddenly disappeared. This voltage was found to be the sustain voltage of the dc discharge in the same condition. Applying positive bias voltage resulted in a much longer delay. These results suggest that the minimal discharge during the pulse-off period helps the initiation of high-density plasma, while the bias voltage which can not maintain the plasma contrarily hampers it.     

Investigation of in vitro bone cell adhesion and proliferation on Ti using direct current stimulation

Our objective was to establish an in vitro cell culture protocol to improve bone cell attachment and proliferation on Ti substrate using direct current stimulation. For this purpose, a custom made electrical stimulator was developed and a varying range of direct currents, from 5 to 25 μA, was used to study the current stimulation effect on bone cells cultured on conducting Ti samples in vitro. Cell–material interaction was studied for a maximum of 5 days by culturing with human fetal osteoblast cells (hFOB). The direct current was applied in every 8 h time interval and the duration of electrical stimulation was kept constant at 15 min for all cases. In vitro results showed that direct current stimulation significantly favored bone cell attachment and proliferation in comparison to nonstimulated Ti surface. Immunochemistry and confocal microscopy results confirmed that the cell adhesion was most pronounced on 25 μA direct current stimulated Ti surfaces as hFOB cells expressed higher vinculin protein with increasing amount of direct current. Furthermore, MTT assay results established that cells grew 30% higher in number under 25 μA electrical stimulation as compared to nonstimulated Ti surface after 5 days of culture period. In this work we have successfully established a simple and cost effective in vitro protocol offering easy and rapid analysis of bone cell–material interaction which can be used in promotion of bone cell attachment and growth on Ti substrate using direct current electrical stimulation in an in vitro model.     

Effects of substrate parameters on structure and optical properties of ZnO thin films fabricated by pulsed laser deposition

Highly oriented zinc oxide thin films have been grown on quartz, Si (1 1 1) and sapphire substrates by pulsed laser deposition (PLD). The effect of temperature and substrate parameter on structural and optical properties of ZnO thin films has been characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), optical transmission spectra and PL spectra. The experimental results show that the best crystalline thin films grown on different substrate with hexagonal wurtzite structure were achieved at growth temperature 400–500 °C. The growth temperature of ZnO thin film deposited on Si (1 1 1) substrate is lower than that of sapphire and quartz. The band gaps are increasing from 3.2 to 3.31 eV for ZnO thin film fabricated on quartz substrate at growth temperature from 100 to 600 °C. The crystalline quality and UV emission of ZnO thin film grown on sapphire substrate are significantly higher than those of other ZnO thin films grown on different substrates.     

Structural and biocompatible characterization of TiC/a:C nanocomposite thin films

In this work, sputtered TiC/amorphous C thin films have been developed in order to be applied as potential barrier coating for interfering of Ti ions from pure Ti or Ti alloy implants. Our experiments were based on magnetron sputtering method, because the vacuum deposition provides great flexibility for manipulating material chemistry and structure, leading to films and coatings with special properties. The films have been deposited on silicon (001) substrates with 300 nm thick oxidized silicon sublayer at 200 °C deposition temperature as model substrate. Transmission electron microscopy has been used for structural investigations. Thin films consisted of ~ 20 nm TiC columnar crystals embedded by 5 nm thin amorphous carbon matrix. MG63 osteoblast cells have been applied for in vitro study of TiC nanocomposites. The cell culture tests give strong evidence of thin films biocompatibility.     

Fabrication of ZnO nanoneedle arrays by direct microwave irradiation

We report a method for the fabrication of ZnO nanoneedle arrays by direct microwave irradiation on the Zn sheet under O₂ and Ar atmosphere (the total pressure: 1 atm). Pure hexagonal-phase ZnO structures were grown on the Zn substrate through this synthetic method. Dimensions of synthesized needle-like ZnO structures are ~ 500 nm in length and ~ 50 and ~ 100 nm in diameter at the tip and the pillar, respectively. This method needs relatively low microwave irradiation power (300 W) and a short reaction time (3 min). Also, it does not require any template or catalyst. The results of this research allow us to propose the growth mechanism of ZnO nanoneedles on the Zn substrate by direct microwave irradiation.     

Anodic oxide film growth on thin magnetron sputter-deposited titanium layer

A ~ 100 nm thick sputter-deposited titanium layer on electropolished aluminium is used for the investigation of anodic film growth in 1 M H₃PO₄. It is found that the thin titanium layer could not provide sufficient current efficiency for titanium anodic film growth when anodized to the voltage over 80 V due to the occurrence of oxygen evolution. The ruptures of titanium anodic film and the sputtering layer are induced by the development of oxygen bubbles. The penetrated phosphoric acid electrolyte in the ruptured regions of sputtering titanium layer contacts with the aluminium substrate, which is leading to the anodic oxide growth of aluminium. The thickness of the titanium anodic film increases from 10 to 100 V, however, it is reduced from 100 to 150 V due to the thinning of titanium layer. Over 80 V, the sputtering layer at some regions where it is completely ruptured, the anodic film growth of titanium could not be created. A thicker aluminium anodic film is formed on such regions due to the direct connection with the electrolyte.     

Enhanced dielectric properties of Mn doped Ba0.6Sr0.4TiO3 thin films fabricated by pulsed laser deposition

Pure and 2 mol% Mn doped Ba_0.6Sr_0.4TiO₃ (BST) thin films have been deposited on La_0.67Sr_0.33MnO₃ (LSMO) coated single-crystal (001) oriented LaAlO₃ substrates using pulsed-laser deposition technique. The bilayer films of BST and LSMO were epitaxially grown in pure single-oriented perovskite phases for both samples, and an enhanced crystallization effect in the BST film was obtained by the addition of Mn, which were confirmed by X-ray diffraction (XRD) and in situ reflective high energy electron diffraction (RHEED) analyses. The dielectric properties of the BST thin films were measured at 100 kHz and 300 K with a parallel-plate capacitor configuration. The results have revealed that an appropriate concentration acceptor doping is very effective to increase dielectric tunability, and to reduce loss tangent and leakage current of BST thin films. The figure-of-merit (FOM) factor value increases from 11 (undoped) to 40 (Mn doped) under an applied electric field of 200 kV/cm. The leakage current density of the BST thin films at a negative bias field of 200 kV/cm decreases from 2.5 × 10^− 4 A/cm² to 1.1 × 10^− 6 A/cm² by Mn doping. Furthermore, a scanning-tip microwave near-field microscope has been employed to study the local microwave dielectric properties of the BST thin films at 2.48 GHz. The Mn doped BST film is more homogeneous, demonstrating its more potential applications in tunable microwave devices.     

Oxygen plasma power dependence on ZnO grown on porous silicon substrates by plasma-assisted molecular beam epitaxy

ZnO thin films were deposited on porous silicon by plasma-assisted molecular beam epitaxy using different radio frequency power settings. Optical emission spectrometry was applied to study the characteristics of the oxygen plasma, and the effects of the radio frequency power on the properties of the ZnO thin films were evaluated by X-ray diffraction, scanning electron microscopy, and photoluminescence. The grain sizes for radio frequency powers of 100, 200, and 300 W were 46, 48, and 62 nm, respectively. In addition, the photoluminescence intensities of the ultraviolet and the visible range increased at 300 W, because the density of the atomic oxygen transitions increased. The quality of the ZnO thin films was enhanced, but the deep-level emission peaks increased with increasing radio frequency power. The structural and optical properties of the ZnO thin films were improved at the radio frequency power of 300 W. Moreover, the optical properties of the ZnO thin films were improved with porous silicon, instead of Si.     

DC substrate bias effects on the physical properties of hydrogenated amorphous carbon films grown by plasma-assisted chemical vapour deposition

Hydrogenated amorphous carbon (a-C:H) films have been grown from argon/methane gas mixtures by electron cyclotron resonance chemical vapour deposition (ECR-CVD) on silicon substrates. The effects of the application of a DC substrate bias on the structural, morphological and mechanical properties of the films have been explored by multiple analysis techniques such as infrared and micro-Raman spectroscopy, atomic force microscopy, nanoindentation and pin-on-disk wear testing. In general, within the range of applied substrate bias (i.e. from −300 up to +100 V) we have observed a strong correlation between all measured properties of the a-C:H films and the ion energy. This work shows that the properties can differ greatly and indicates a threshold energy in the order of 90 eV. For the production of hard, low-friction coatings energies above this value are required.     

Photoelectrochemical characterization of Bi2Se3 thin films deposited by SILAR technique

Bi₂Se₃ thin films have been deposited by simple and less investigated successive ionic layer adsorption and reaction (SILAR) technique onto fluorine-doped tin oxide (FTO) coated glass substrates at room temperature (27 °C). The X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies indicate that Bi₂Se₃ thin films are nanocrystalline. These films are used for photoelectrochemical (PEC) characterization in cell with configuration as n-Bi₂Se₃/0.1 M polysulfide/C. The studies such as current–voltage characteristics in dark and light, photovoltaic power output, transient photoresponse, and capacitance–voltage have been carried out. The study reveals that fill factor and power conversion efficiency of the cell are low (0.43 and 0.032%, respectively).The flat bond potential is found to be −0.04 V (SCE).     

Fabrication of LiCoO2 thin film cathodes by DC magnetron sputtering method

LiCoO₂ thin films were fabricated on Al substrate by direct current magnetron sputtering method. The effects of Ar/O₂ gas rates and annealing temperatures were investigated. Crystal structures and surface morphologies of the deposited films were investigated by X-ray diffraction, Raman scattering spectroscopy and field emission scanning electron microscopy. The as-deposited LiCoO₂ thin films exhibited amorphous structure. The crystallization starts at the annealing temperature over 400 °C. However, the annealed films have the partially disordered structure without completely ordered crystalline structure even at 600 °C annealing. The electrochemical properties of the LiCoO₂ films were investigated by the charge–discharge and cycle measurements. The 500 °C annealing film has the highest capacity retention rate of 78.2% at 100th cycles.     

New natively textured surface Al-doped ZnO-TCOs for thin film solar cells via magnetron sputtering

Natively textured surface aluminum doped zinc oxide (ZnO:Al) thin films were directly deposited via pulsed direct current (DC) reactive magnetron sputtering on glass substrates. During the reactive sputtering process, the oxygen gas flow rate was varied from 8.5 sccm to 11.0 sccm. The influences of oxygen flow rate on the structural, electrical and optical properties of naturally textured ZnO:Al TCO thin films with milky surface were investigated in detail. Gradual oxygen growth (GOG) technique was developed in the reactive sputtering process for textured ZnO:Al thin films. The light-scattering ability and optical transmittance of the natively textured ZnO:Al TCO thin films can be improved through gradual oxygen growth method while maintaining a low sheet resistance. Typical natively textured ZnO:Al TCO thin film with crater-like surface exhibits low sheet resistance (R_s ～ 4 Ω), high transmittance (T_a > 85%) in visible optical region and high haze value (12.1%).     

Feasibility study on preparation of coatings on Ti–6Al–4V by combined ultrasonic impact treatment and electrospark deposition

A novel method combining ultrasonic impact treatment (UIT) with electrospark deposition was developed to prepare coatings on Ti–6Al–4V substrates. The microstructure, phase composition, residual stress, microhardness, and wear performance of the coating were studied, and new amorphous and nanocrystalline phases (titanium carbide nitride and iron titanium oxide) were found. In addition, the residual stress in the coating and in the substrate near the coating is compressive stress. The maximum compressive residual stress is about −717 MPa, and its depth is about 470 μm. Because of contributions from multiple factors, the wear volume loss of the sample subjected to combined UIT and electrospark processing was reduced by four orders of magnitude compared with that of the base material.     

Wide bandgap Mg-doped ZnAlO thin films for optoelectronic applications

Magnesium-doped ZnAlO thin films were grown on quartz substrate by ablating the sintered target with a KrF excimer laser. The effect of growth temperature from 30 °C to 700 °C on structural, optical, and electrical properties has been studied. These films are highly transparent in visible spectrum with average transmittance of 82%. The films grown at low temperature are amorphous while films grown at high temperature are crystalline in nature. These films are highly oriented along (0 0 2) direction. The electrical conductivity, carrier concentration, and electron mobility is found to increase with increase in temperature and then decreases with further increase in temperature. The bandgap is found to vary from 3.86 eV to 4.00 eV for various films.