Room temperature preparation of c axis oriented ZnO films on Si(100), SiO2, and ZnO substrates by rf magnetron sputtering

Abstract

Growth of ZnO thin films with c axis (002) orientation has been demonstrated at room temperature on Si(100), SiO₂, and amorphous ZnO substrates by the rf magnetron sputtering method. The structural properties of the ZnO thin films were investigated with varying rf power. X-ray diffraction analysis revealed that increasing rf power helped to increase the c axis lattice constant and grain size, regardless of substrate material. Scanning electron microscopy indicated that the structural morphology of the ZnO films was not dependent on the substrate material.     

Effects of plasma gas composition on bond strength of hydroxyapatite/titanium composite coatings prepared by rf-plasma spraying

The effects of plasma gas composition on the bond-strength of HA/Ti composite coatings were investigated. HA/Ti composite coatings were deposited on titanium substrates by a radio-frequency (rf) thermal plasma spraying method with input powers of 10–30 kW. The ratio of the HA and Ti powders supplied into the plasma was precisely controlled by two microfeeders so as to change the coating's composition from Ti-rich at the bottom to HA-rich at its upper layer. The bond (tensile) strength of the obtained HA/Ti composite coatings was 40–65 MPa when sprayed with plasma gas containing N₂ (i.e., Ar–N₂). On the other hand, HA/Ti composite coatings prepared with plasma gas containing O₂ (i.e., Ar–O₂) had significantly lower bond strength (under 30 MPa). XRD patterns of Ti coatings without HA showed that titanium nitride and titanium dioxide formed, respectively, on titanium deposits sprayed with Ar–N₂ and Ar–O₂ plasma. Scanning electron microscopic (SEM) observation showed an acicular texture on the Ti deposits prepared with Ar–N₂ plasma. SEM observations implied that, when sprayed with Ar–O₂ plasma, a thin TiO₂ layer formed at the interfaces between the Ti splats in the deposits.     

TiO2/ZnO double-layer broadband antireflective and down-shifting coatings for solar applications

Making full use of sunlight in solar cells requires reducing the reflection of light and minimizing spectral mismatch. Here, a TiO₂/ZnO double-layer coating with both wider band antireflection and down-shifting performance was prepared. TiO₂ sols and ZnO nanoparticles were synthesized via the sol-gel method and then successively coated on the surface of the Si substrate by dip-coating. Computational simulations were used to obtain the optimal refractive index and thickness of the coatings. In the experiments, the thicknesses of the TiO₂ and ZnO coatings were adjusted by changing the lifting speed, and the refractive index of the TiO₂ and ZnO coatings were adjusted by adding the porosity inducing agent and varying the concentration of the solution. The TiO₂/ZnO coating reduces the reflectivity of the silicon substrate by 24.97% in the 400–1100 nm band, and the ZnO nanoparticles can convert light at approximately 345 nm–527 nm, reducing the spectral mismatch of the solar cell. The photocurrent of solar cells coated with TiO₂/ZnO coatings was markedly improved, with an increase of 29% in the average photocurrent at 300–800 nm. Herein, TiO₂/ZnO coatings have the potential to benefit the development of multifunctional coatings that are important for improving the efficiency of solar cells.     

Cadmium sulfide activated zinc oxide coatings deposited by liquid plasma spray for room temperature nitrogen dioxide detection under visible light illumination

Zinc oxide (ZnO) is well-known to be used as a gas sensing material. However, due to its high operation temperature, the chemical and thermal stability of ZnO based gas sensors are relatively low. In recent years, some researchers adopt light illumination as activated source to replace heating and obtain high gas sensing performance at low temperature. The study that follows is an attempt to use cadmium sulfide (CdS) as sensitizer to activate ZnO at room temperature with assistance of visible-light illumination. CdS–ZnO coatings were deposited by liquid plasma spray with aqueous solution containing zinc acetate and cadmium sulfide as precursors. The crystal structure of as-sprayed CdS–ZnO coatings was characterized by X-ray diffractometer (XRD) and field-emission scanning electron microscopy (FE-SEM). The sensing performance of sensors based on CdS–ZnO coatings were tested with 1 ppm nitrogen dioxide (NO₂) at room temperature illuminated under various visible lights. The results demonstrated that the LPS process was a straightforward method for deposition of high performance CdS–ZnO sensitive layers and the obtained sensors showed high responses to NO₂ at room temperature.     

Deposition of silicon oxide hard coatings by low‐temperature radio‐frequency plasmas

In this study, the deposition of silicon oxide (SiOx) hard coatings on polycarbonate (PC) substrates was attempted with low‐temperature radio‐frequency (RF) plasmas from tetramethyldisiloxane (TMDSO) with the addition of oxygen. The coating uniformity and deposition rate were investigated in terms of substrate size, glow uniformity, and RF power input. The hardness of the resulting SiOx plasma coatings was examined by the ASTM pencil hardness test method. The hardness of the resulting SiOx plasma coatings was mainly determined by the TMDSO–O₂ ratio in the plasma gas mixture. Ultraviolet–visible transmission spectra showed that these plasma coatings were transparent in the visible light region. Fourier transform infrared–attenuated total reflection analysis results indicated that the resulting SiOx plasma coatings were inorganic in nature. The interfacial adhesion, which is a common problem in the deposition of hard protective coatings on polymeric substrates, was also significantly improved by the deposition of an ultrathin plasma polymer interlayer from TMDSO before the deposition of the SiOx plasma coatings on the PC substrates. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Characterization and property of bifunctional Zn-incorporated TiO2 micro-arc oxidation coatings: The influence of different Zn sources

In the present work, Zn-incorporated TiO₂ coatings are prepared through a one-step micro-arc oxidation (MAO) method on a grade 4 pure titanium with the addition of either Na₂Zn-EDTA solution or ZnO nanoparticles (NPs) as Zn sources. The microstructural features of both Zn-incorporated TiO₂ coatings were systematically examined. It is revealed that different Zn sources result in significant difference of phase component, chemical state, composition and morphology between the resultant Zn-incorporated MAO coatings. Zn species could be present as ZnO and Zn(OH)₂ in the coating when Na₂Zn-EDTA was used as Zn source whereas the presence of ZnO nano-clusters is obvious on the coating surface with ZnO NPs as Zn source. The addition of ZnO NPs during the MAO process also leads to a lower Zn content of the resultant coating, which is more defective with increased thickness in comparison to that of Na₂Zn-EDTA. Further, antibacterial property and osteogenic activity of both Zn-incorporated coatings were examined. Both Zn-incorporated coatings exhibit favourable bacterial inhibition ability and bone formability, suggesting the successful synthesis of bifunctional coatings through the facile one-step micro-arc oxidation method.     

Adhesion and fatigue resistance of Ta-doped MoS2 composite coatings deposited with pulsed-DC magnetron sputtering

MoS₂–Ta composite coatings were deposited using the pulsed-DC magnetron sputtering technique. X-ray diffraction (XRD), scanning electron microscopy, energy dispersive spectroscopy, and atomic force microscopy were used to determine the structural properties of the MoS₂–Ta composite coatings. The hardness values and adhesion and fatigue features of the coatings were determined using a microindentation hardness test and a scratch test, respectively. The scratch tests were evaluated using two modes: a standard mode (under a progressive load) and a multimode (sliding-fatigue with a constant sub-critical load within the same scratch track). Failure mechanisms of the scratch tracks were determined by examining the resulting micrographs. The MoS₂–Ta coatings have a dense columnar microstructure. XRD patterns of the coatings revealed MoS₂ (0?0?2), MoS₂ (1?0?0), MoS₂ (1?0?3), and α-Ta (1?1?0) reflections. The thickness, roughness, hardness, and elemental ratio values of the coatings were significantly affected by the target currents. The adhesion of the coatings dramatically increased with an increase in the thickness, hardness, and Ta/Mo ratio and with decreases in the roughness. The MoS₂–Ta composite coatings with a high load-bearing capacity exhibited excellent fatigue resistance.     

Wear-resistant Ti–Al–Ni–C–N coatings produced by magnetron sputtering of SHS-targets in the DC and HIPIMS modes

The hard wear-resistant nanocomposite Ti–Al–Ni–C–N coatings were deposited by direct current magnetron sputtering (DCMS) and high power impulse magnetron sputtering (HIPIMS) in the Ar, Ar+15%N_2, and Ar+25%N₂ atmospheres. The structure of coatings was analyzed using the X-ray diffraction analysis, glow discharge optical emission spectroscopy, and scanning electron microscopy. Mechanical and tribological properties were measured using the nanoindentation and scratch testing as well as by tribological testing using the “pin-on-disc” scheme. Electrochemical corrosion resistance and oxidation resistance of coatings were investigated. The results suggest that the coatings are based on the FCC phases TiCN and Ni₃Al with crystallites size ~3 and ~15 nm, correspondingly. DCMS coatings with optimal composition were characterized by hardness 34 GPa, stable friction coefficient <0.26 and wear rate <5 × 10^-6 mm³N^-1m^-1. Application of HIPIMS mode allowed the increase of adhesion strength, tribological properties and corrosion resistance of coatings.     

Conducting polymer based hybrid nano-composites for enhanced corrosion protective coatings

Hybrid composite coatings containing zinc oxide (ZnO) and polyaniline (PANI) as nano-additives dispersions were prepared with poly(vinyl acetate) (PVAc) as the major matrix. The steel plates dip-coated with these formulations were tested for corrosion protection by immersion in saline water over long periods. The Tafel plots for the determination of open circuit potential (OCP) and corrosion current (I_corr) were recorded. The coatings containing both ZnO and PANI showed improved corrosion resistance as compared to the single component coating. The I_corr values of PVAc–ZnO–PANI are found to be two-order magnitude lower than that of PVAc and PVAc–ZnO coatings. The results are explained on the basis of enhancement in barrier properties due to nano-particulate additives in PVAc–ZnO–PANI film together with the redox behaviour of PANI and protective oxide layer formation near the substrate.     

Sol–gel preparation and characterization of antibacterial and self-cleaning hybrid nanocomposite coatings

ZnO–TiO₂, SiO₂–TiO₂, and SiO₂–TiO₂–ZnO hybrid nanocomposite coatings were synthesized based on sol–gel precursors including tetramethoxysilane (TMOS), 3-glycidoxypropyl trimethoxysilane (GPTMS), tetra(n-butyl orthotitanate) (TBT), and zinc acetate dihydrate. The hybrid network was characterized by FTIR, FESEM, and EDAX techniques. Results indicated that inorganic particles’ size was of nanoorder (20–30 nm), with very uniform distribution and dispersion. Photocatalytic and self-cleaning activities of these coatings were further investigated by degradation of methylene blue in an aqueous solution (20 ppm) at visible light irradiation, indicating photocatalytic performance of the coatings containing ZnO and TiO₂ nanoparticles. The antibacterial effect of the coatings was investigated for inhibition and inactivation of cell growth, with the results showing the same antibacterial activity for ZnO–TiO₂ and SiO₂–TiO₂–ZnO coatings against Escherichia coli and Staphylococcus aureus; the activity was, however, higher than that of SiO₂–TiO₂ hybrid nanocomposite coatings.     

TiO2–ZnO/Ni–5wt.%Al composite coatings on GH4169 superalloys by atmospheric plasma spray techniques and theirs elevated-temperature tribological behavior

Ni–based composite coatings with different amounts of TiO₂–ZnO were fabricated by atmospheric plasma spraying (APS) to protect GH4169 superalloy substrates against excess wear and friction at elevated temperatures. In addition, the influence of the simultaneous addition of the oxides on the microstructure, microhardness, and wear behaviour was investigated. According to the results, the simultaneous addition of TiO₂/ZnO provides anti-friction and wear inhibition over 600 °C. In particular at 800 °C, the TiO₂–ZnO/Ni–5wt.%Al composite coating (10 wt% TiO₂ and 10 wt% ZnO were incorporated within Ni–5wt.%Al matrix) exhibits a superior lubricity and wear resistance compared to the Ni–5wt.%Al based coatings. The XRD, Raman, and TEM characterisations reveal the formation of a glaze oxide layer consisting of NiO, TiO₂, ZnO and the in-situ production of ternary oxide (Zn₂TiO₄), which was primarily responsible for the tribological performance of the sliding wear contacts at the specific temperature.     

Characterization of luminescent properties of ZnO:Er thin films prepared by rf magnetron sputtering

ZnO:Er thin films were deposited on c-plane sapphire substrates by rf magnetron sputtering and annealed at 700 °C under air and H₂ atmospheres for the luminescent improvement. The effects of sputtering parameters and the annealing conditions on visible and 1.54 μm IR emissions were investigated. Structural and luminescent properties strongly depended on the deposition conditions and annealing atmospheres. By tuning the excitation wavelength, ZnO:Er thin films exhibited a strong emission band at around 465 nm and a weak emission at 525 nm originated from the energy transition of ⁴I_15/2–⁴F_5/2 and ⁴I_15/2–²H_11/2, respectively, while 1.54 μm IR emissions due to ⁴I_15/2–⁴I_13/2 transition.     

Zinc oxide films deposited by radio frequency plasma magnetron sputtering technique

Zinc oxide (ZnO) is a wide band gap transparent conductive oxide (TCO) material with a lot of potential applications including transparent thin-film sensors, transistors (TFTs), solar cells, and window insulation systems. In this work, ZnO films were deposited on glass substrates by the radio frequency (RF) plasma magnetron sputtering deposition technique. The effects of the RF power on the properties of the ZnO films were elucidated. The influences of the RF power on the surface morphology, structural, and optical properties of the ZnO films were investigated by Mahr surface profilometer, Atomic Force Microscopy (AFM), X-ray diffractometer (XRD), and ultraviolet–visible (UV–VIS) spectrophotometer. To allow for accurate comparison of the power effects, ZnO films with similar thickness deposited at different RF powers were examined. The RF power effects on the properties of the ZnO films are revealed and discussed in this paper.     

Preparation of multilayered C–Si–Al2O3 coatings on continuous carbon fibers and C–Si–Al2O3-coated carbon-fiber-reinforced hydroxyapatite composites

Multilayered C–Si–Al coatings with various morphologies were deposited on carbon fibers (CFs) using magnetron sputtering. The thickness of the coatings was increased from 0.5 to 1.5 μm by magnetron sputtering between 90 and 120 min. C–Si–Al coatings of suitable thickness were heat-treated at 600 °C and transformed into C–Si–Al₂O₃ coatings by one-step anodic oxidation (AO). The oxidation time for the one/two-step anodic oxidation and the ratio of oxidation time for the two-step anodic oxidation significantly influenced the morphologies of the C–Si–Al₂O₃(AO) coatings. Al₂O₃ coatings with satisfactory morphologies and structures were prepared by two-step anodic oxidation with a total time of 30 min and a ratio of 1:1 between the initial and secondary oxidation times. The multilayered C–Si–Al₂O₃(AO) coatings were modified to C–Si–Al₂O₃ coatings by secondary heat treatment at 1050 °C. Subsequently, hot-press sintering was used to prepare CFs with multilayered C–Si–Al₂O₃ coating-reinforced hydroxyapatite (CF/C–Si–Al₂O₃/HA) composites. The multilayered C–Si–Al₂O₃-coated CFs demonstrated good resistance to oxidation and thermal shock. This could effectively protect CFs from oxidative damage and maintain its strengthening effect during sintering. The multilayered C, Si, and Al₂O₃ coatings effectively reduced the difference between the coefficient of thermal expansion of the CFs and HA matrixes. The interfacial gaps between the multilayered coatings and HA were reduced. This could enhance the mechanical performance of the composites. The CF/C–Si–Al₂O₃/HA composites exhibited improved mechanical properties with a bending strength of 83.94 ± 12.29 MPa, and fracture toughness of 2.45 ± 0.08 MPa m^1/2. This study can broaden the application of CF/C–Si–Al₂O₃/HA biocomposites as bone-repair materials and help obtain CF-reinforced composites with excellent mechanical properties that are fabricated or serviced at high temperatures.     

Plasma-sprayed TiO2 coatings: Hydrophobicity enhanced by ZnO additions

Titanium dioxide (TiO₂) powder mixed individually with 10 and 30 weight percentage (wt%) ZnO was thermally sprayed onto a grade B API 5 L carbon steel substrate by atmospheric plasma spraying. The effect of the addition of ZnO (10 wt% and 30 wt%) on the microstructures and wettability properties of the TiO₂/ZnO coatings was investigated. The characterization of the coatings was carried out using scanning electron microscopy, X-ray diffraction (XRD), laser confocal microscope, and sessile droplet system. The XRD analysis of the coating revealed that the anatase phase of TiO₂ in the powder state transformed into rutile phases for the produced TiO₂/ZnO coatings. Surface microstructure analysis revealed that the coatings had typical micro-roughened surfaces of plasma spraying products. The coating with 30 wt% ZnO produced a coating with remarkable pores and microcracks compared with the TiO₂ coating and coating with 10 wt% ZnO. Additionally, the increase in the wt% of ZnO increased the surface roughness value of the produced coatings and substantially changed the wettability properties of the TiO₂ coating from hydrophilic to hydrophobic.     

Micromechanical and microtribological properties of BCN thin films near the B4C composition deposited by r.f. magnetron sputtering

Ternary materials with compositions in the B–C–N system offer properties of great interest. In particular, mechanical and tribological properties are expected to be excellent, as they can combine some of the specific properties of BN, B₄C and C₃N₄. In this paper, BCN thin films deposited by r.f. magnetron sputtering are characterized by their micromechanical and microtribological behavior. BCN coatings with different composition were obtained by varying the N₂/Ar proportion in the sputtering gas. Hardness and elastic modulus of the coatings were measured by nanoindentation. The adhesion and friction coefficient against diamond have been evaluated by microscratch and the coatings have been characterized in their wear behavior at the nanometric scale. These mechanical and tribological properties have been related to film composition and structure, which have been studied in a previous work. It is found that the measured wear resistance at the nanometric scale is directly related to the coating microhardness rather than friction behavior or adhesion of the coating to the substrate, which are the determinant factors in the macroscopic scale wear behavior.     

Evaluation of halogenated polyimide etching for optical waveguide fabrication by using inductively coupled plasma

Oxygen plasma etching of a series of halogenated polyimides was carried out for low‐loss waveguide fabrication by using inductively coupled plasma (ICP). The effects of etching parameters such as ICP power, rf power, and O₂ flow rate on the etching rate and etching profile of polymer films were investigated. The increase in the etch rate with the ICP power and the rf power was observed. Both the vertical profile and sidewall roughness were found to be related to the ion energy (dc bias). By optimizing these parameters, a vertical profile and a smooth sidewall were obtained by 500 W of ICP power, 150 W of rf power, 5 mTorr of chamber pressure, and 40 sccm of the O₂ flow rate. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 176–182, 2001     

Influence of ZnO buffer layer on AZO film properties by radio frequency magnetron sputtering

Transparent conductive films of Al-doped zinc oxide (AZO) were deposited on glass substrates under various ZnO buffer layer deposition conditions (radio frequency (r.f.) power, sputtering pressure, thickness, and annealing) using r.f. magnetron sputtering at room temperature. This work investigates the influence of ZnO buffer layer on structural, electrical, and optical properties of AZO films. The use of grey-based Taguchi method to determine the ZnO buffer layer deposition processing parameters by considering multiple performance characteristics has been reported. Findings show that the ZnO buffer layer improves the optoelectronic performances of AZO films. The AZO films deposited on the 150-nm thick ZnO buffer layer exhibit a very smooth surface with excellent optical properties. Highly c-axis-orientated AZO/ZnO/glass films were grown. Under the optimized ZnO buffer layer deposition conditions, the AZO films show lowest electrical resistivity of 6.75 × 10⁻⁴ Ω cm, about 85% optical transmittance in the visible region, and the best surface roughness of R_a = 0.933 nm.     

Improvement of anti-erosion performance of TiN coatings through using a filtration cathode vacuum arc deposition method

Sand erosion is a major factor that shortens the service life of aircraft in desert regions. The anti-erosion performance of titanium alloys may be improved using TiN coatings. However, few studies have employed Ti sputtering on Ti transition layers to improve the erosion resistance of the coatings. Herein, TiN coatings with a sputtering layer between the Ti transition layer and the TiN layer were deposited on a Ti–6Al–4V alloy by filtered cathodic vacuum arc deposition. For comparison, another group of TiN coatings without a Ti sputtering layer but processed using the same deposition parameters were prepared. The effects of the nanoscale sputtering layer on the microstructure, mechanical properties, and anti-erosion performance of the coatings were investigated using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and nanoindentation. The results show that the introduction of a Ti sputtering layer promoted the growth of TiN grains, leading to the formation of finer and denser TiN columnar grains. The preferred orientation of the coatings with the sputtering layer is (111) plane, whereas that of the coatings without the sputtering layer is (200) plane. The TiN coatings containing a sputtering layer exhibit higher hardness, elastic modulus, and H³/E² ratio, which enhances the anti-erosion performance of the coatings. The coatings with a sputtering layer exhibited better erosion resistance (erosion rate reduced by 75%) than the coatings without a sputtering layer. The underlying mechanism to understand the effect of the sputtering layer on the erosion resistance was discussed based on variations in the microstructure and mechanical properties of the coatings with and without the Ti sputtering layer. Ti sputtering layer was finally proved to be an effective method to improve the erosion resistance of TiN coatings.     

Strongly adherent Al2O3 coating on SS 316L: Optimization of plasma spray parameters and investigation of unique wear resistance behaviour under air and nitrogen environment

Plasma spray deposition of Al₂O₃ is a well-established technique for thick ceramic coatings on various substrates to shield them from corrosion and wear. Owing to its high hardness, aluminum oxide is known to protect stainless steel substrates from wear. However, the plasma process requires optimization for desired coating thickness and adhesion strength. It is also necessary to understand the sensitivity of friction and wear resistance of the deposited coating on exposed environment for evaluation of service life. The study offers comprehensive investigation on plasma process parameters for the development of strongly adherent aluminium oxide coatings on SS 316L substrate. Impact of environment like dry air and dry nitrogen on tribological properties of the coatings was also investigated. Dense adherent coatings of alumina could be deposited on SS 316L at a plasma power of 20 kW with an intermediate bond coat of NiCrAlY to enhance the adhesion properties. The effects of stand-off distance and bond coat thickness on adhesion strength were additionally examined. Further, the coatings were characterised for phase composition, microstructure, microhardness and wear resistance potential. Reciprocating wear tests of the coatings were carried out using ball on disc reciprocating tribometer at different loading conditions (5, 10 and 15 N) at constant (5 Hz) sliding frequency. Unlike the coefficient of friction (COF), wear volume was found to increase with an increase in normal load. These adherent coatings revealed promising properties for the applications where the tribological failure of SS 316L in dry air or dry nitrogen environment is to be controlled.