Structure, hardness and thermal stability of TiAlBN coatings grown by alternating deposition of TiAlN and BN

Hardness and thermal stability of TiAlBN coatings prepared by alternating deposition of TiAlN and BN with high rotation speed of substrate holder (∼7 rpm) have been investigated. The TiAlN and BN were deposited by reactive sputtering of Ti_0.5Al_0.5 and BN targets with N₂ and Ar reactive gases, respectively. Despite alternating deposition, the TiAlBN coating did not show layered structure due to high rotation speed of substrate holder. By TEM analysis, the TiAlBN coating was observed to be nanocomposite with grain less than 10 nm in size. Compared to TiAlN coating, the TiAlBN nanocomposite coating showed superior hardness. Furthermore, the hardness of the coating increased after the heat-treatment in N₂ atmosphere up to 800 °C. By comparison with TiAlN/BN nanoscale multilayered coating prepared by the same deposition method except the lower rotation speed of substrate holder (∼1 rpm), the hardness enhancement after annealing, ‘self-hardening’, of the TiAlBN nanocomposite coating is believed to be due to the sharpness in chemical composition at the interface between TiAlN and BN phase.     

Ar + H2 plasma etching for improved adhesion of PVD coatings on steel substrates

Ar + H₂ plasma cleaning has been described for the surface modification of the steel substrates, which removes oxides and other contaminants from substrate surface effectively leading to a better adhesion of the physical vapor deposited (PVD) coatings. Approximately 1.1-1.3 μm thick TiAlN coatings were deposited on plasma treated (Ar and Ar + H₂) and untreated mild steel (MS) substrates. A mechanism has been put forward to explain the effect of plasma treatment on the substrate surface based upon the data obtained from X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). The XPS measurements on untreated and Ar + H₂ plasma etched MS substrates indicated that the untreated substrate surface mainly consisted of Fe₃O₄, whereas, after etching the concentration of oxides decreased considerably. The FESEM and the AFM results showed changes in the surface morphology and an increase in the substrate roughness as a result of Ar + H₂ plasma etching. Removal of oxide/contaminants, formation of coarser surface and increased substrate surface roughness as a result of Ar + H₂ plasma etching facilitate good mechanical interlocking at the substrate surface, leading to a better adhesion of the deposited PVD coatings. The adhesion of TiAlN coating could be increased further by incorporating a very thin Ti interlayer.     

Ion beam deposition of α-Ta films by nitrogen addition and improvement of diffusion barrier property

Ta thin films were deposited on Si (100) substrates by an ion beam deposition method at various substrate bias voltages under Ar + N₂ atmosphere with different pressure ratios of Ar and N₂. The effects of nitrogen pressure in the plasma gas and the substrate bias voltage on the surface morphology, crystalline microstructure, electrical resistivity and diffusion barrier property were investigated. It was found that the fraction of a metastable β-phase in the Ta film deposited at the substrate bias voltage of − 50 V films decreased by adding nitrogen gas, while the α-Ta phase became dominant. As a result, the Ta films deposited at the substrate bias voltage of − 50 V under Ar (9 Pa) + N₂ (3 Pa) atmosphere showed a dominant α-phase with good surface morphology, low resistivity, and superior thermal stability as a diffusion barrier.     

The etching characteristics of Al2O3 thin films in an inductively coupled plasma

In this study, the etching characteristics of ALD deposited Al₂O₃ thin film in a BCl₃/N₂ plasma were investigated. The experiments were performed by comparing the etch rates and the selectivity of Al₂O₃ over SiO₂ as functions of the input plasma parameters, such as the gas mixing ratio, the DC-bias voltage, the RF power, and the process pressure. The maximum etch rate was obtained at 155.8 nm/min under a 15 mTorr process pressure, 700 W of RF power, and a BCl₃ (6 sccm)/N₂ (14 sccm) plasma. The highest etch selectivity was 1.9. We used X-ray photoelectron spectroscopy (XPS) to investigate the chemical reactions on the etched surface. Auger electron spectroscopy (AES) was used for the elemental analysis of the etched surfaces.     

Dry etching process of GaAs in capacitively coupled BCl3-based plasmas

Dry etching of GaAs was investigated in BCl₃, BCl₃/N₂ and BCl₃/Ar discharges with a mechanical pump-based capacitively coupled plasma system. Etched GaAs samples were characterized using scanning electron microscopy and surface profilometry. Optical emission spectroscopy was used to monitor the BCl₃-based plasma during etching. Pure BCl₃ plasma was found to be suitable for GaAs etching at > 100 mTorr while producing a clean and smooth surface and vertical sidewall. Adding N₂ or Ar to the BCl₃ helped increase the etch rates of GaAs. For example, the GaAs etch rate was doubled with 20% N₂ composition in the BCl₃/N₂ plasma compared to the pure BCl₃ discharge at 150 W CCP power and 150 mTorr chamber pressure. The GaAs etch rate was ∼ 0.21 µm/min in the 20 sccm BCl₃ plasma. The BCl₃/Ar plasma also increased etch rates of GaAs with 20% of Ar in the discharge. However, the surface morphology of GaAs was strongly roughened with high percentage (> 30%) of N₂ and Ar in the BCl₃/N₂ and BCl₃/Ar plasma, respectively. Optical emission spectra showed that there was a broad BCl₃-related molecular peak at 450-700 nm wavelength in the pure BCl₃ plasma. When more than 50% N₂ was added to the BCl₃ plasma, an atomic N peak (367.05 nm) and molecular N₂ peaks (550-800 nm) were detected. Etch selectivity of GaAs to photoresist decreased with the increase of % N₂ and Ar in the BCl₃-based plasma.     

Deposition and characterization of TiAlN/Si3N4 superhard nanocomposite coatings prepared by reactive direct current unbalanced magnetron sputtering

Superhard nanocomposite coatings of TiAlN/Si₃N₄ with varying silicon contents were synthesized using reactive direct current (DC) unbalanced magnetron sputtering. The Si and TiAl targets were sputtered using an asymmetric bipolar-pulsed DC power supply and a DC power supply, respectively, in Ar+N₂ plasma. The structural and mechanical properties of the coatings were characterized using X-ray diffraction (XRD) and nanoindentation techniques, respectively. The elemental composition of the TiAlN/Si₃N₄ nanocomposite coatings was determined using energy-dispersive X-ray analysis and the bonding structure was characterized by X-ray photoelectron spectroscopy. The surface morphology of the coatings was studied using atomic force microscopy. The XRD data showed that the nanocomposite coatings exhibited (1 1 1) and (2 0 0) reflections of cubic TiAlN phase. The broadening of the diffraction peaks with an increase in the silicon content in the nanocomposite coatings, suggested a decrease in the average crystallite size. The TiAlN/Si₃N₄ nanocomposite coatings exhibited a maximum hardness of 43 GPa and an elastic modulus of 350 GPa at a silicon concentration of approximately 11 at%. The hardness and the elastic modulus of the nanocomposite coatings decreased significantly at higher silicon contents. Micro-Raman spectroscopy was used to characterize the structural changes as a result of heating of the nanocomposite coatings in air (400-850 °C) and in vacuum (900 °C). The Raman data of the nanocomposite coatings annealed in air and vacuum showed better thermal stability as compared to that of the TiAlN coatings. Similarly, the nanocomposite coatings deposited on mild steel substrates exhibited improved corrosion resistance.     

Comparison of the optical and structural properties of nickel oxide-based thin films obtained by chemical bath and sputtering

Nickel oxide thin films were prepared using chemical bath deposition and reactive magnetron dc-sputtering. Through the chemical route, Ni(OH)₂ films were deposited with a nano-porous structure providing large specific surface area. Subsequent annealing at 300 °C transformed the films into NiO. These films showed high absorption in the visible range and low crystallinity due to Ni vacancies. Annealing at higher temperatures removes Ni vacancies improving transmittance and crystallinity. Sputtered films were obtained in Ar + O₂ and Ar + H₂ + O₂ atmospheres at different flux ratios. During deposition in the former atmosphere, substrate temperature was 300 °C producing dense polycrystalline films with excellent optical properties. In the hydrogen containing atmosphere, the substrate was at room temperature and polycrystalline films with a dark-yellowish color and expanded lattice were obtained.     

Growth and surface characterization of magnetron sputtered zinc nitride thin films

Zinc nitride films were deposited on Si(100) substrates at room temperature using RF-magnetron sputtering in pure N₂ and in Ar + N₂ atmospheres. Two active phonon modes (270.81 and 569.80 cm^− 1) are observed in Raman spectra for films deposited in Ar + N₂ atmosphere. Atomic force microscopy showed that the average surface roughness of the films deposited in pure N₂ atmosphere (1.3-3.33 nm) was less than for those deposited in a mixed Ar + N₂ atmosphere (10.3-12.8 nm). Low temperature cathodoluminescence showed two emission bands centered at 2.05 eV and 3.32 eV for both types of films.     

Influence of hydrogen introduction on structure and properties of ZnO thin films during sputtering and post-annealing

ZnO thin films were prepared in Ar and Ar + H₂ atmospheres by rf magnetron sputtering, and then they were annealed in vacuum and Ar + H₂ atmosphere, respectively. The structure and optical-electrical properties of the films were investigated by X-ray diffraction, transmittance spectra, and resistivity measurement, and their dependences on deposition atmosphere, annealing treatment, and aging were studied. The results showed that adding H₂ in deposition atmosphere improved the crystallinity of the films, decreased lattice constant, increased band gap, decreased the resistivity by the order of 10⁴ Ω cm, but exhibited poor conductive stability with aging. After Ar + H₂ and vacuum annealing, crystallinity of the films deposited in Ar and Ar + H₂ was further improved; their resistivity was decreased by the order of 10⁵ and 10¹ Ω cm, respectively, and exhibited high conductive stability with aging. We suggest that the formed main defect is V_O and H_i when H₂ is introduced during deposition, which decreases the resistivity but cannot improve the conductive stability; hydrogen would remove negatively charged oxygen species near grain boundaries during Ar + H₂ annealing to decrease the resistivity, and grain boundaries are passivated by formation of a number of V_O-H complex (H_O) to improve the conductive stability at the same time. Under vacuum annealing, the hydrogen that is introduced non-intentionally from deposition chamber maybe plays an important role; it exists as H_O in the films to improve the conductive stability of the films.     

p-type doping of ZnO by means of high-density inductively coupled plasmas

A custom-designed inductively coupled plasma assisted radio-frequency magnetron sputtering deposition system has been used to fabricate N-doped p-type ZnO (ZnO:N) thin films on glass substrates from a sintered ZnO target in a reactive Ar + N₂ gas mixture. X-ray diffraction and scanning electron microscopy analyses show that the ZnO:N films feature a hexagonal crystal structure with a preferential (002) crystallographic orientation and grow as vertical columnar structures. Hall effect and X-ray photoelectron spectroscopy analyses show that N-doped ZnO thin films are p-type with a hole concentration of 3.32 × 10¹⁸ cm^− 3 and mobility of 1.31 cm² V^− 1 s^− 1. The current-voltage measurement of the two-layer structured ZnO p-n homojunction clearly reveals the rectifying ability of the p-n junction. The achievement of p-type ZnO:N thin films is attributed to the high dissociation ability of the high-density inductively coupled plasma source and effective plasma-surface interactions during the growth process.     

A study of the nanostructure and hardness of electron beam evaporated TiAlBN Coatings

TiAlBN coatings have been deposited by electron beam (EB) evaporation from a single TiAlBN material source onto AISI 316 stainless steel substrates at a temperature of 450 °C and substrate bias of − 100 V. The stoichiometry and nanostructure have been studied by X-ray photoelectron spectroscopy, X-ray diffraction and transmission electron microscopy. The hardness and elastic modulus were determined by nanoindentation. Five coatings have been deposited, three from hot-pressed TiAlBN material and two from hot isostatically pressed (HIPped) material. The coatings deposited from the hot-pressed material exhibited a nanocomposite nc-(Ti,Al)N/a-BN/a-(Ti,Al)B₂ structure, the relative phase fraction being consistent with that predicted by the equilibrium Ti-B-N phase diagram. Nanoindentation hardness values were in the range of 22 to 32 GPa. Using the HIPped material, coating (Ti,Al)B_0.29N_0.46 was found to have a phase composition of 72-79 mol.% nc-(Ti,Al)(N,B)_1 − x+ 21-28 mol.% amorphous titanium boride and a hardness of 32 GPa. The second coating, (Ti,Al)B_0.66N_0.25, was X-ray amorphous with a nitride+boride multiphase composition and a hardness of 26 GPa. The nanostructure and structure-property relationships of all coatings are discussed in detail. Comparisons are made between the single-EB coatings deposited in this work and previously deposited twin-EB coatings. Twin-EB deposition gives rise to lower adatom mobilities, leading to (111) (Ti,Al)N preferential orientation, smaller grain sizes, less dense coatings and lower hardnesses.     

Al-doped ZnO thin films deposited by reactive frequency magnetron sputtering: H2-induced property changes

Al-doped ZnO (AZO) transparent conductive thin films have been prepared by radio-frequency magnetron sputtering with a ceramic target (98 wt.% ZnO, 2 wt.% Al₂O₃) in different Ar + H₂ ambient at a substrate temperature of 200 °C. To investigate the influence of H₂-flow on the properties of AZO films, H₂-flow was changed during the growth process with a fixed Ar-flow of 60 sccm. The results indicate that H₂-flow has a considerable influence on the transparent conductive properties of AZO films. The low resistivity in the order of 10^− 4 Ω cm and the high average transmittance more than 92% in the visible range were obtained for the samples prepared in the optimal H₂-flow range from 0.4 sccm to 1.0 sccm. In addition, the influence of H₂-flow on the structure and composition of AZO films have also been studied.     

Blue-violet phosphate phosphor thin films for EL

Photoluminescence (PL) and electroluminescence (EL) in blue-violet emission were observed in newly developed phosphate phosphor thin films such as Ba₃(PO₄)₂:Eu and Ba₃(PO₄)₂:Ti. These phosphate phosphor thin films were first deposited on thick BaTiO₃ ceramic sheets by r.f. magnetron sputtering using powder targets and then post-annealed in various atmospheres. Blue-violet PL and EL emissions were obtained in Ba₃(PO₄)₂:Eu and Ba₃(PO₄)₂:Ti phosphor thin films that were deposited in an Ar + H₂ (10%) gas atmosphere and then post-annealed above about 900 °C in an Ar + H₂ (10%) gas atmosphere. In particular, the EL observed in Ba₃(PO₄)₂:Eu thin films exhibited two peaks, a red emission peaking at about 615 nm and a blue-violet emission peaking at about 420 nm. A luminance of 2.0 cd/m² in blue-violet emission was obtained in a thin-film EL device using a two step post-annealed Ba₃(PO₄)₂:Eu thin-film emitting layer: step 1, post-annealing at 1000 °C in air for 1 h, and step 2, post-annealing at 1000 °C in an Ar + H₂ atmosphere.     

Influence of substrate temperature on N-doped ZnO films deposited by RF magnetron sputtering

Nitrogen-doped ZnO films were deposited by RF magnetron sputtering in 75% of N₂ / (Ar + N₂) gas atmosphere. The influence of substrate temperature ranging from room temperature (RT) to 300 °C was analyzed by X-ray diffractometry (XRD), spectrophotometry, X-ray photoelectron spectroscopy (XPS), secondary-ion mass spectrometry (SIMS) and Hall measurements setup. The XRD studies confirmed the hexagonal ZnO structure and showed that the crystallinity of these films increased with increasing substrate temperature (T_s). The optical studies indicate the average visible transmittance in the wavelength ranging 500-800 nm increases with increasing T_s. A minimum transmittance (9.84%) obtained for the films deposited at RT increased with increasing T_s to a maximum of 88.59% at 300 °C (500-800 nm). Furthermore, it was understood that the band gap widens with increasing T_s from 1.99 eV (RT) to 3.30 eV (250 °C). Compositional analyses (XPS and SIMS) confirmed the nitrogen (N) incorporation into the ZnO films and its decreasing concentration with increasing T_s. The negative sign of Hall coefficients confirmed the n-type conducting.     

Dry etching characteristics of HfAlO3 thin films in BCl3/Ar plasma using inductively coupled plasma system

In this study, we monitored the HfAlO₃ etch rate and selectivity to SiO₂ as a function of the etch parameters (gas mixing ratio, RF power, DC-bias voltage, and process pressure). A maximum etch rate of 52.6 nm/min was achieved in the 30% BCl₃/(BCl₃ + Ar) plasma. The etch selectivity of HfAlO₃ to SiO₂ reached 1.4. As the RF power and the DC-bias voltage increased, the etch rate of the HfAlO₃ thin film increased. As the process pressure decreased, the etch rate of the HfAlO₃ thin films increased. The chemical state of the etched surfaces was investigated by X-ray Photoelectron Spectroscopy (XPS). According to the results, the etching of HfAlO₃ thin films follows the ion-assisted chemical etching mechanism.     

Photoelectrochemical and optical properties of N-doped TiO2 thin films prepared by oxidation of sputtered TiNx films

Nitrogen-doped titanium dioxide thin films with visible light photoresponse were prepared by oxidation of sputtered TiN_x films, whose nitrogen contents can be easily changed by controlling the volume ratio of N₂/(Ar + N₂) during reactive direct current (DC) magnetron sputtering process. The reference TiO₂ sample was also deposited by the same method under Ar/O₂ gas mixture. The as-prepared films were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoemission spectroscopy, UV-vis spectrophotometry and photoelecrochemical measurements. The formation of anatase type TiO₂ is confirmed by XRD. SEM measurement indicates a rough surface morphology with sharp, protruding modules after annealing treatment. Optical properties reveal an extended tailing of the absorption edge toward the visible region due to nitrogen presence. The band gap of the N-doped sample is reduced from 3.36 eV to 3.12 eV compared with the undoped one. All the N-doped samples show red shift in photoresponse towards visible region and improved photocurrent density under visible irradiance is observed for the N-doped samples.     

Structure, hardness and thermal stability of TiAlN and nanolayered TiAlN/CrN multilayer films

TiAlN films were deposited on silicon (1 1 1) substrates from a TiAl target using a reactive DC magnetron sputtering process in Ar+N₂ plasma. Films were prepared at various nitrogen flow rates and TiAl target compositions. Similarly, CrN films were prepared from the reactive sputtering of Cr target. Subsequently, nanolayered TiAlN/CrN multilayer films were deposited at various modulation wavelengths (Λ). X-ray diffraction (XRD), energy dispersive X-ray analysis, nanoindentation and atomic force microscopy were used to characterize the films. The XRD confirmed the formation of superlattice structure at low modulation wavelengths. The maximum hardness of TiAlN/CrN multilayers was 3900 kg/mm², whereas TiAlN and CrN films exhibited maximum hardnesses of 3850 and 1000 kg/mm², respectively. Thermal stability of TiAlN and TiAlN/CrN multilayer films was studied by heating the films in air in the temperature range (T_A) of 500-900 °C for 30 min. The XRD spectra revealed that TiAlN/CrN multilayers were stable up to 800 °C and got oxidized substantially at 900 °C. On the other hand, the TiAlN films were stable up to 700 °C and got completely oxidized at 800 °C. Nanoindentation measurements performed on the films after heat treatment showed that TiAlN retained a hardness of 2200 kg/mm² at T_A=700 °C and TiAlN/CrN multilayers retained hardness as high as 2600 kg/mm² upon annealing at 800° C.     

Thermal stability of nanocomposite CrC/a-C:H thin films

The thermal stability of low-friction Me-C/a-C:H coatings is important for their potential applications in the tool and automotive industry. Recently we showed that CrC_x/a-C:H coatings prepared by unbalanced magnetron sputtering of a Cr target in Ar + CH₄ glow discharges exhibit a nanocomposite structure where metastable fcc CrC nanocrystals are encapsulated by an a-C:H phase. Here, we present the structural evolution of these nanocomposite CrC/a-C:H coatings during annealing. High-temperature X-ray diffraction in vacuum and differential scanning calorimetry (DSC) combined with thermo-gravimetric analysis in Ar atmosphere indicate decomposition of the formed metastable fcc CrC phase and subsequent formation of Cr₃C₂ and Cr₇C₃ and structural transformation of the a-C:H matrix phase towards higher sp² bonding contents at temperatures above 450 °C. Combined DSC and mass spectrometer analysis as well as elemental profiling after annealing in vacuum by elastic recoil detection analysis relate this transformation to the loss of bonded hydrogen at temperatures above 200 °C.Due to these structural changes the coefficient of friction depends on the annealing temperature of the nanocomposite a-C:H coatings and shows a minimum of ∼ 0.13 for T = 200 °C. The more complex tribochemical reactions, influenced by the hydrogen loss from the coating during in-situ high temperatures ball-on disc tests, result in coefficient of friction values below 0.05 for T < 120 °C.     

Effect of heating conditions on the magnetic properties of micron-sized carboxyl modified-magnetite particles synthesized by a spray pyrolysis and heating process

Superparamagnetic carboxyl (COOH) modified-magnetite (Fe₃O₄) (COOH-Fe₃O₄) micrometer-sized porous particles were synthesized by the spray pyrolysis of a 0.1 M Fe(NO₃)₃·9H₂O and 0.2 M citric acid solution and a subsequent heating process in either an Ar + 1% H₂ (P_O2 = 10^?20 Pa) or N₂ (P_O2 = 1 Pa) gas atmosphere. Fe₃O₄ formed due to carbon and hydrogen gas generation of thermal decomposition of citric acid, even under reduction conditions with a P_O2 below 10^?23 Pa. The COOH-Fe₃O₄ particles heated in an Ar + 1% H₂ or N₂ atmosphere were porous (40% porosity) and about 1.2 to 1.3 μm in diameter. The particles consist of nano-sized COOH-Fe₃O₄ crystallite about 7 nm in diameter. The specific surface area increased from 116 to 127 m²/g by increasing the heating time in an Ar + 1% H₂ atmosphere from 10 to 20 h. The saturation magnetization of the COOH-Fe₃O₄ particles (38.7 A·m²/kg) heated in Ar + 1% H₂ for 10 h was much higher than that of commercial magnetic microbeads (17 A·m²/kg) and the coercivity was 0 kA/m. These superparamagnetic COOH-Fe₃O₄ particles dispersed in distilled water were attracted to a NdFeB magnet for 7–10 s under a 400 Mt external magnetic field, compared with 10 s for commercial magnetic microbeads.