Deposition of tungsten nitride thin films by plasma focus device at different axial and angular positions

Tungsten nitride thin films were deposited on stainless steel-304 substrates by using a low energy (2 kJ) Mather type plasma focus device. X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and microhardness are used to study the surface of treated samples. The XRD analysis shows that the degree of crystallinity of deposited thin films strongly depends on axial and angular positions of samples. The SEM micrographs of the deposited films at different angular positions (0°, 10° and 30°) and axial position of 8 cm show that the content of WN sub-micro crystalline structures on the surface of deposited films decreased with increasing the angle with respect to anode axis. From AFM results we observe that for the sample deposited at 8 cm and 0° axial and angular positions, respectively, the most uniform surface and the most homogenous distribution of grains are obtained. Also the hardness results show that the highest mechanical hardness is obtained when the film is deposited at 8 cm and 0° axial and angular positions, respectively.     

Synthesis of composite TiN/Ni3N/a-Si3N4 thin films using the plasma focus device

Composite films of TiN/Ni₃N/a-Si₃N₄ were synthesized using the Mather-type plasma focus device with varying numbers of focus deposition shots (5, 15, and 25) at 0° and 10° angular positions. The composition and structural analysis of these films were analyzed by using Rutherford backscattering (RBS) and X-ray diffraction (XRD). Scanning electron microscope and atomic force microscope were used to study the surface morphology of films. XRD patterns confirm the formation of composite TiN/Ni₃N/a-Si₃N₄ films. The crystallite size of TiN (200) plane is 11 and 22 nm, respectively, at 0° and 10° angular positions for same 25 focus deposition shots. Impurity levels and thickness were measured using RBS. Scanning electron microscopy results show the formation of net-like structures for multiple focus shots (5, 15, and 25) at angular positions of 0° and 10°. The average surface roughness of the deposited films increases with increasing focus shots. The roughness of the film decreases at higher angle 10° and the films obtained are smoother as compared with the films deposited at 0° angular positions.     

Synthesis of titanium nitride thin films deposited by a new shielded arc ion plating

Thin films of titanium nitride (TiN) were deposited on stainless steel substrates by a modified deposition technique, double-layered shielded arc ion plating with vicarious circular holes (DL-SAIP). The results show that the TiN film with the distance of 10 mm between the double-layered shield plates had the least droplets. The deposition rate of the films prepared with the new technique was more homogeneous than that of all the other shielded arc ion plating. The film/substrate adhesion and microhardness values of the TiN films were higher than 40 N and 18 GPa, respectively. Thus such TiN thin films can be expected in applications.     

Characterization of ZnO-SnO2 thin film composites prepared by pulsed laser deposition

Thin films of ZnO-SnO₂ composites have been deposited on Si(1 0 0) and glass substrates at 500 °C by pulsed laser ablation using different composite targets with ZnO amount varying between 1 and 50 wt%. The effect of increasing ZnO-content on electrical, optical and structural properties of the ZnO-SnO₂ films has been investigated. X-ray diffraction analysis indicates that the as-deposited ZnO-SnO₂ films can be both crystalline (for ZnO <1 wt%) and amorphous (for ZnO ≥ 10 wt%) in nature. Atomic force microscopy studies of the as-prepared composite films indicate that the surfaces are fairly smooth with rms roughness varying between 3.07 and 2.04 nm. The average optical transmittance of the as-deposited films in the visible range (400-800 nm), decreases from 90% to 72% for increasing ZnO concentration in the film. The band gap energy (E_g) seems to depend on the amount of ZnO addition, with the maximum obtained at 1 wt% ZnO. Assuming that the interband electron transition is direct, the optical band gap has been found to be in the range 3.24-3.69 eV for as-deposited composite films. The lowest electrical resistivity of 7.6 × 10⁻³ Ω cm has been achieved with the 25 wt% ZnO composite film deposited at 500 °C. The photoluminescence spectrum of the composite films shows a decrease in PL intensity with increasing ZnO concentration.     

Anatase TiO2 films based CO gas sensor: Film thickness, substrate and temperature effects

Electrical response of anatase TiO₂ films is discussed for different concentrations of CO gas (20-100 ppm) in a nitrogen gas ambient. We investigated temperature (100-300 °C) and film thickness (100-1000 nm) effects for films deposited on glass, sapphire (0 0 0 1) and, Si(1 0 0) substrates. In general, there is a drop in resistance of the device when exposed to CO gas. Films deposited on sapphire showed a larger decrease in the resistance at 300 °C compared to those deposited on glass and silicon substrates. However, films grown on glass and silicon substrates showed a larger decrease in the resistance values for temperature around 200 °C when CO (ppm) values are greater than 40. The change in resistance of the films varies as square root of the CO gas concentration at 200 °C for films deposited on all the three substrates. In general, the decrease in resistance for thicker films is large compared to thinner ones, indicating participation of the bulk in the detection of CO gas. In the presence of O₂, film loses its sensitivity to CO gas when the concentration level of O₂ approaches 1800 ppm.     

Low energy repetitive miniature plasma focus device as high deposition rate facility for synthesis of DLC thin films

Diamond-like carbon (DLC) films were deposited on Si (1 0 0) substrate using a low energy (219 J) repetitive (1 Hz) miniature plasma focus device. DLC thin film samples were deposited using 10, 20, 50, 100 and 200 focus shots with hydrogen as filling gas at 0.25 mbar. The deposited samples were analyzed by XRD, Raman Spectroscopy, SEM and XPS. XRD results exhibited the diffraction peaks related to SiO₂, carbon and SiC. Raman studies verified the formation amorphous carbon with D and G peaks. Corresponding variation in the line width (FWHM) of the D and G positions along with change in intensity ratio (I_D/I_G) in DLC films was investigated as a function of number of deposition shots. XPS confirmed the formation sp² (graphite like) and sp³ (diamond like) carbon. The cross-sectional SEM images establish the 220 W repetitive miniature plasma focus device as the high deposition rate facility for DLC with average deposition rate of about 250 nm/min.     

Effect of the oxygen flow rate on the structure and the properties of Ag-Cu-O sputtered films deposited using a Ag/Cu target with eutectic composition

Ag-Cu-O films were deposited on glass substrates by reactive sputtering of a composite Ag₆₀Cu₄₀ target in various Ar-O₂ mixtures. The films were characterised by energy dispersive X-ray analysis, X-ray diffraction, UV-visible spectroscopy and using the four point probe method. The structure of the films is strongly dependent on the oxygen flow rate introduced in the deposition chamber. The variation of the oxygen flow rate allows the deposition of the following structures: Ag-Cu-(O) solid solution, nc-Ag + nc-Cu₂O, nc-Ag + nc-(Ag,Cu)₂O and finally X-ray amorphous. UV-visible reflectance measurements confirm the occurrence of metallic silver into the deposited films. The increase of the oxygen flow rate induces a continuous increase of the film oxygen concentration that can be correlated to the evolution of the film reflectance and the film electrical resistivity. Finally, the structural changes vs. the oxygen content are discussed in terms of reactivity of sputtered atoms with oxygen.     

Nano-structured Fe thin film deposition using plasma focus device

This paper reports the deposition of nano-structured Fe thin films using 3.3 kJ Mather-type plasma focus. The conventional hollow copper anode was replaced by anode fitted with solid Fe top and the deposition was done using different numbers of deposition shots at two different angular positions. Scanning Electron Microscopy shows that the size of nano-phase agglomerate is smaller when the sample is deposited using either lesser number of deposition shots or at higher angular position with respect to anode axis. X-ray Diffraction shows that crystal structure characteristics change with increase in number of deposition shots. Measurements of magnetic properties using Vibrating Sample Magnetometer identify intermediate magnetization and coercivity in Fe thin films deposited at smaller angular position with respect to anode axis. It is concluded that the morphological, structural and magnetic characteristics of Fe thin films deposited using plasma focus device depend not only on the number of focus deposition shots but also on the angular position of the sample.     

Influence of deposition parameters on hard Cr-Al-N coatings deposited by multi-arc ion plating

The Cr-Al-N coatings were synthesized at various substrate bias voltages and nitrogen partial pressures by multi-arc ion plating (M-AIP). The relationships between deposition parameters and coating properties were investigated. Morphologies, phase structures, hardness and adhesion strength of the coatings were analyzed by SEM, XRD, XPS, nano-indenter and scratch tester. The results indicated that with the increase of substrate bias voltages, the surface macroparticles and deposition rate reduced mainly for the resputtering phenomenon. The (Cr, Al)N solid-solution phase kept unchanged, but the Cr₂N and AlN phases disappeared gradually. Due to the change of phase structures and residual compressive stress, the hardness values decreased and the adhesion strength decreased initially and then increased. Similarly, with the increase of nitrogen partial pressures, the phase structures of CrAlN coatings varied from Cr + Cr₂N + (Cr,Al)N to Cr₂N + (Cr,Al)N. The surface macroparticles increased due to the decreasing resputtering efficiency, and the deposition rate increased initially and then decreased due to the resputtering phenomenon. With increasing nitrogen partial pressures, adhesion strength decreased initially and then increased. The microhardness increased mainly due to the increase of Cr₂N contents and decrease of metal macroparticles.     

Characteristics of Ni films deposited on SiO2/Si(1 0 0) and MgO(0 0 1) by direct current magnetron sputtering system with the oblique target

280 nm-thick Ni films were deposited on SiO₂/Si(1 0 0) and MgO(0 0 1) substrates at 300 K, 513 K and 663 K by a direct current magnetron sputtering system with the oblique target. The films deposited at 300 K mainly have a [1 1 0] crystalline orientation in the film growth direction. The [1 1 0]-orientation weakens and the [1 1 1]- and [1 0 0]-orientations enhance with increasing deposition temperature. The lattice constant of the Ni films is smaller than that of the Ni bulk, except for the film grown on MgO(0 0 1) at 663 K. Furthermore, as the deposition temperature increases, the lattice constant of the films grown on the SiO₂/Si(1 0 0) decreases whereas that of the films grown on the MgO(0 0 1) increases. The films deposited at 300 K and 513 K grow with columnar grains perpendicular to the substrate. For the films deposited at 663 K, however, the columnar grain structure is destroyed, i.e., an about 50 nm-thick layer consisting of granular grains is formed at the interface between the film and the substrate and then large grains grow on the layer. The Ni films deposited at 300 K consist of thin columnar grains and have many voids at the grain boundaries. The grains become thick and the voids decrease with increasing deposition temperature. The resistivity of the film decreases and the saturation magnetization increases with increasing deposition temperature.     

Exchange coupling in CoO–Co bilayer

In this work, exchange bias and coercivity enhancement in ferromagnet (FM)–antiferromagnet (AFM) bilayer have been investigated. CoO film (50 nm) was deposited by sputtering with a relatively high oxygen partial pressure. The deposited films were subsequently annealed at varied temperature up to 973 K in the air atmosphere. The CoO film shows a disordered structure in the as-deposited state and an increase of crystallinity after annealing characterized by XRD and Raman spectra. A 40-nm Co film was deposited on the as-deposited CoO and annealed films. The Co–CoO bilayer shows a large exchange bias up to 1600 Oe and relatively high coercivity up to 3200 Oe (H_C−) at 5 K, which is much larger than that of crystalline Co–CoO bilayer films without any treatment. The spin glass behavior combined with increasing crystallinity, surface roughness of CoO after annealing may be attributed to the large exchange bias and high coercivity.     

Effects of seed layer on the structure and property of zinc oxide thin films electrochemically deposited on ITO-coated glass

ZnO films with different morphologies were deposited on the ITO-coated glass substrate from zinc nitrate aqueous solution at 65 °C by a seed-layer assisted electrochemical deposition route. The seed layers were pre-deposited galvanostatically at different current densities (i_sl) ranging from −1.30 to −3.0 mA/cm², and the subsequent ZnO films had been done using the potentiostatic technique at the cathode potential of −1.0 V. Densities of nucleation centers in the seed layers varied with increasing the current density, and the ZnO films on them showed variable morphologies and optical properties. The uniform and compact nanocrystalline ZnO film with (0 0 2) preferential orientation was obtained on seed layer that was deposited under the current density (i_sl) of −1.68 mA/cm², which exhibited good optical performances.     

Properties of barium hexa-ferrite thin films dependent on sputtering pressure

M-type barium ferrite thin films were deposited onto sapphire (0 0 l) substrates by radio frequency magnetron sputtering. An ultra-thin layer about 20 nm was deposited and annealed before continuous deposition of the films up to 500 nm under different sputtering pressures: 0.2, 0.5, 0.8 and 1.0 Pa, respectively. It was found that the atomic ratios of Fe to Ba increased from 9.3 to 15.0 with the increase of the pressure. The films sputtered at all pressures have c-axis normal to the film plane by a four circle X-ray diffractometer, which is an improvement of the films directly sputtered on the substrate. Needle-like grains were formed on the surface of the films under higher sputter pressure with bubble domains, which is originated from high magnetocrystalline anisotropy of the film. Magnetic hysteresis loops recorded by vibrating sample magnetometer agree with them, where in-plane and out-of-plane loops of the samples prepared under high sputtering pressures are quite different, while they are almost identical of the samples under low pressures. The influence of the sputtering pressure was understood by that with the increase of the pressure, resputtering of the films was increased. Nucleation with c-axis normal to the film plane was deteriorated. Thus samples prepared under high pressure have more needle-like crystallites which have c-axis parallel to the film plane.     

Microstructure, hydrogenation and optical behavior of Mg-Ni multilayer films deposited by magnetron sputtering

Mg-Ni multilayer films with sequential Mg and Ni layers were prepared by direct current magnetron sputtering. The substrate temperature influences the microstructure of the films greatly. The film deposited at 298 K exhibits multilayered structure, while the film shows nanocrystalline/amorphous composite structure at the deposition temperature of 473 K. The optical properties between hydrogenation/dehydrogenation states of the films were performed using spectrophotometer in visible light region. The film deposited at 473 K can switch from mirror-like metallic state towards brownish yellow transparent state under 0.6 MPa H₂ at 298 K, and the optical transmittance modulation reaches up to 20% both at a wavelength of 770 nm and IR region, while the film deposited at 298 K exhibits low optical change, and the optical switching behavior can hardly be found. The extra free energy stored in the boundary of the nanocrystallines benefits the formation of magnesium-based hydride, resulting in the enhancement of the optical switching properties of the Mg-Ni film deposited at 473 K.     

Synthesis of anodizing composite films containing superfine Al2O3 and PTFE particles on Al alloys

Anodized composite films containing superfine Al₂O₃ and PTFE particles were prepared on 2024 Al alloy using an anodizing method. The microstructures and properties of the films were studied by scanning electron microscopy, optical microscopy and X-ray diffraction. Friction wear tests were performed to evaluate the mechanical properties of the composites. Results indicate that the composite films with reinforced Al₂O₃ and PTFE two-particles have reduced friction coefficients and relatively high microhardness. The friction coefficient can be as small as 0.15, which is much smaller than that of an oxide film prepared under the same conditions but without adding any particles (0.25), while the microhardness can reach as high as 404 HV. When rubbed at room temperature for 20 min during dry sliding friction tests, the wear loss of the film was about 16 mg, which is about the half of that of the samples without added particles. The synthesized composite films that have good anti-wear and self-lubricating properties are desirable for oil-free industrial machinery applications.     

Electrodeposition and growth mechanism of SnSe thin films

Tin selenide (SnSe) thin films were electrochemically deposited onto Au(1 1 1) substrates from an aqueous solution containing SnCl₂, Na₂SeO₃, and EDTA at room temperature (25 °C). The electrochemical behaviors and the codeposition potentials of Sn and Se were explored by cyclic voltammetry. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and UV-vis absorption spectroscopy were employed to characterize the thin films. When the electrodeposition potential increased, the Se content in the films decreased. It was found that the stoichiometric SnSe thin films could be obtained at −0.50 V. The as-deposited films were crystallized in the preferential orientation along the (1 1 1) plane. The morphologies of SnSe films could be changed from spherical grains to platelet-like particles as the deposition potential increases. The SEM investigations show that the film growth proceeds via nucleation, growth of film layer and formation of needle-like particles on the overlayer of the film. The optical absorption study showed the film has direct transition with band gap energy of 1.3 eV.     

Growth and structure of MBE grown TiO2 anatase films with rutile nano-crystallites

We have explored the systematics of TiO₂ polymorph nucleation during film growth by molecular beam epitaxy on perovskite substrates. The accidental lattice match between anatase (0 0 1) and LaAlO₃(0 0 1) or SrTiO₃(0 0 1) typically results in anatase nucleation at the interface. However, the growth conditions dictate whether or not rutile also nucleates, and the associated morphological and structural properties of the composite film. Four symmetry equivalent epitaxial orientations of rutile on anatase are observed when rutile nucleates as discrete particles on LaAlO₃(0 0 1). Such films constitute model systems for studying the anatase/rutile interface, which is of considerable current interest in photochemistry.     

Atomic layer deposition of HfO2: Effect of structure development on growth rate, morphology and optical properties of thin films

HfO₂ films were grown by atomic layer deposition from HfCl₄ and H₂O on Si(1 0 0), Si(1 1 1) and amorphous SiO₂ substrates at 180-750 °C and the effect of deposition temperature and film thickness on the growth rate and optical properties of the film material was studied. Crystallization, texture development and surface roughening were demonstrated to result in a noticeable growth rate increase with increasing film thickness. Highest surface roughness values were determined for the films deposited at 350-450 °C on all substrates used. The density of the film material increased with the concentration of crystalline phase but, within experimental uncertainty, was independent of orientation and sizes of crystallites in polycrystalline films. Refractive index increased with the material density. In addition, the refractive index values that were calculated from the transmission spectra depended on the surface roughness and crystallite sizes because the light scattering, which directly influenced the extinction coefficient, caused also a decrease of the refractive index determined in this way.     

The photocatalytic application and regeneration of anatase thin films with embedded commercial TiO2 particles deposited on glass microrods

Anatase thin films (<200 nm in thickness) embedding Degussa P25 TiO₂ were prepared by sol-gel method. TiO₂-anatase thin films were deposited on a fiberglass substrate and then ground to obtain glass microrods containing the composite films. The film structure was characterized using Raman spectroscopy, atomic absorption and UV-vis spectrophotometry, and atomic force microscopy. The photocatalytic activity of the composite films, calcined at 450 °C, and the regeneration of the activity under the same experimental conditions, were assessed using gas chromatography to study the photodegradation of phenol, an industrial pollutant, in water under 365 nm irradiation. The film with 15.0 wt.% of P25 TiO₂ was found to be more photoactive (54 ppm of degraded phenol at 6 h of illumination) than the other ones.     

Superhard Nb-Si-N composite films synthesized by reactive magnetron sputtering

By means of the reactive magnetron sputtering method, a series of Nb-Si-N composite films with different Si contents were deposited in an Ar, N₂ and SiH₄ mixture atmosphere. These films’ chemical composition, phase formation, microstructure and mechanical properties were characterized by the energy dispersive spectroscopy, X-ray diffraction, transmission electron microcopy, atomic force microscopy and nanoindentation. The experimental results showed that the silicon content in the Nb-Si-N composite films can be conveniently controlled by adjusting the SiH₄ partial pressure in mixed gas. The hardness and elastic modulus of the Nb-Si-N films were remarkably increased with a small amount of silicon addition and reached their maximum values of 53 and 521 GPa, respectively, at 3.4 at.% Si. Such an obvious enhancement of mechanical properties is related to the increment of crystal defects in the Nb-Si-N films. With silicon content increasing in the films further, the mechanical properties decreased gradually to somewhat a bit lower than those of the NbN film.