Novel low temperature atmospheric pressure plasma jet systems for silicon dioxide and poly-ethylene thin film deposition

In this study, both low-density plasma quartz tube (QT) and high-density plasma metallic tube (MT) jet-electrodes with pulsed-type alternating-voltage (AC) generator were used to investigate the influences of the process parameters and electrode types on the microstructures and the corrosion behaviors of silicon dioxide (SiO₂) or poly-ethylene (PE, (CH₂CH₂)n) thin films. Tetraethoxysilane (TEOS) and ethylene (C₂H₄) were used as precursors for SiO₂ and PE thin film deposition. The TEOS precursor was vaporized by an ultrasonic oscillator and introduced into the AP plasma systems by argon (Ar) carrier gas. The main plasma working gas was Ar gas mixed with or without oxygen gas. The pulsed-type AC generator, with a frequency of 30 kHz, a voltage of 10 kV and a wattage of 300 W, was used to deposit SiO₂ and PE thin films on the silicon and AISI 1005 low carbon steel substrates at the room temperature, respectively. The high-density plasma MT jet-electrode with an Ar gas flow rate of 6 slm, a precursor flow rate of 40 sccm and an oxygen flow rate of 40 sccm revealed optimal plasma dissociation and chemical reaction efficiencies to synthesize effective atomic stoichiometry of SiO₂ (in-organic films) thin films. However, the low-density plasma QT jet-electrode with an Ar gas flow rate of 6 slm and an ethylene flow rate of 15 sccm appeared optimal plasma-induced polymerization efficiency to exhibit reasonable atomic stoichiometry of PE (organic films) thin films. Moreover, the optimal SiO₂ thin films deposited by MT jet-electrode possessed better corrosion resistant integrity than the optimal PE thin films synthesized by QT jet-electrode. It was also found that SiO₂ and PE thin films synthesized by the AP plasma method possess effective corrosion barrier characteristics like other deposition techniques.     

Effects of oxygen partial pressure on doping properties of Ga-doped ZnO films prepared by ion-plating with traveling substrate

Polycrystalline Ga-doped ZnO (GZO) thin films were prepared by ion-plating on a traveling glass substrate at 200 °C. Effects of O₂ gas flow rate and Ga₂O₃ content in source on the electrical and structural properties of GZO films were investigated. GZO films having a low resistivity of 210^− 4 Ω cm order were obtained under the conditions of Ga₂O₃ contents of 3-5 wt.% and O₂ gas flow rates below 10 sccm. In particular, for GZO films prepared with a Ga₂O₃ content of 4 wt.% at an O₂ gas flow rate of 2.5 sccm, the lowest resistivity of 2.23 × 10^− 4 Ω cm was obtained; the carrier concentration and Hall mobility were 1.17 × 10²¹ cm^− 3 and 23.9 cm²/Vs, respectively. Excess Ga₂O₃ content in source (> 6 wt.%) cause deterioration both in crystallinity and in electric property most probably due to the solubility limit for Ga doping in ZnO at the glass substrate temperature of 200 °C. Excess O₂ gas flow rates (> 10 sccm) during the film growth also lower the electric properties of the GZO films.     

Reactive sputtering of TiOxNy coatings by the reactive gas pulsing process: Part II: The role of the duty cycle

The reactive gas pulsing process (RGPP) was used to deposit titanium oxynitride thin films by dc reactive magnetron sputtering. A titanium target was sputtered in a reactive atmosphere composed of Ar + O₂ + N₂. Argon and nitrogen gases were continuously introduced into the sputtering chamber whereas oxygen was injected with a well-controlled pulsing flow rate following a rectangular and periodic signal. A constant pulsing period T = 45 s was used for every deposition and the duty cycle α = t_ON/T was systematically changed from 0 to 100%. The operating conditions were investigated taking into account the poisoning phenomena of the target surface by oxygen and nitrogen. Kinetics of poisoning were followed from measurements of the total sputtering pressure and titanium target potential during the depositions. Deposition rate and optical transmittance of titanium oxynitride coatings were also analysed and correlated with the process parameters. Pulsing the oxygen flow rate with rectangular patterns and using suitable duty cycles, RGPP method allows working according to reversible nitrided-oxidised target conditions and leads to the deposition of a wide range of TiO_xN_y thin films, from metallic TiN to insulating TiO₂ compounds.     

Effect of ammoniating temperature on microstructure and optical properties of one-dimensional GaN nanowires doped with magnesium

One-dimensional GaN nanowires doped with Mg element have been successfully prepared on Si (1 1 1) substrates by magnetron sputtering through ammoniating Ga₂O₃/Mg thin films, and the effect of the ammoniating temperatures on the microstructure and optical properties of the GaN nanowires was investigated in detail. X-ray diffraction (XRD), X-ray photoelectron spectroscope (XPS), FT-IR spectrophotometer, Scanning electron microscope (SEM), high-resolution transmission electron microscope (TEM), and photoluminescence (PL) spectrum were carried out to characterize the microstructure, morphology, and optical properties of GaN nanowires. The results demonstrate that ammoniating temperature has a significant effect on microstructure, morphology and optical properties of GaN nanowires. GaN nanowires after ammoniation at 900 °C for 15 min are straight, smooth and of uniform thickness along spindle direction with the highest crystalline quality. The growth direction of these nanowires is parallel to [1 0 0] orientation.     

Investigation of novel low temperature atmospheric pressure plasma system for deposition photo-catalytic TiO2 thin film

The purpose of this study was to develop a novel low-temperature atmospheric pressure (AP) plasma system and to use the system to deposit photo-catalytic titanium dioxide (TiO₂) thin film. In this study, titanium tetraisopropoxide (TTIP) was used as a precursor for TiO₂ thin film deposition. The precursor was vaporized by ultrasonic oscillator and introduced into an atmospheric plasma system by argon (Ar) carrier gas. The main plasma working gas was Ar mixed with O₂. Microstructure evolutions of TiO₂ thin film were investigated by low-angle grazing-incidence x-ray diffraction (GID), x-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), and transmission electron microscope (TEM). The photo-catalytic properties were determined by contact angle and methylene orange de-coloration testing. In this study, the substrate temperature, the precursor flow rate and the O₂ flow rate were varied. TiO₂ thin film grown at a temperature of 350 °C, with precursor and O₂ flow rates of 20 sccm and 200 sccm, respectively, revealed the optimum photo-catalytic properties. It was also found that titanium dioxide thin films synthesized by the AP plasma method possess reasonable photo-catalytic characteristics like other deposition techniques.     

Structural and mechanical properties of amorphous silicon carbonitride films prepared by vapor-transport chemical vapor deposition

The deposition of amorphous silicon carbonitride (a-SiCN:H) films has been successfully achieved through an in-house developed vapor-transport chemical vapor deposition (VT-CVD) technique in a nitrogenated atmosphere. Polydimethylsilane (PDMS) was used as a single-source precursor for both silicon and carbon, while NH₃ was mixed with argon to ensure the in-situ nitrogenation of the films. The chemical bonding and the atomic composition of the a-SiCN:H films were systematically investigated, as a function of their N content, by means of Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). AFM was used to obtain 2-D and 3-D views of the films. The mechanical properties [(hardness (H) and Young's modulus (E)] of the freshly prepared films were investigated by the nanoindentation technique. It is shown that by controlling the NH₃/Ar gas flow ratio in the reactor, a-SiCN:H films with various N contents [(0-27) at.% range] are achieved. On the microstructural level, the increase incorporation of N in the a-SiCN:H films is found not only to lead to C atom substitution by N atoms in the local Si-C-N environment but also to an enhanced incorporation of hydrogen bonded to both Si and N. Furthermore, the increase incorporation of N in the a-SiCN:H films resulted in an increase of the average R_rms surface roughness from 4 to 12 nm. Moreover, the films became porous with pore size and density increase as a result of increasing N at.%. Ultimately, both H and E of the a-SiCN:H films were found to be sensitive to their N content, as they decrease (from ~ 17 GPa and 160 GPa to ~ 13 GPa and 136 GPa, respectively) when the N content is increased from 0 to 27 at.%. The formation of Si-N, Si-H, and N-H bonds at the detriment of the more stiff Si-C bonds is thought to account for the observed lowering of the mechanical properties of the a-SiCN:H films as their N content increased.     

Fabrication, microstructure and tribological behavior of pulsed laser deposited a-CNx/TiN multilayer films

a-CN_x/TiN multilayer films were deposited onto high-speed steel substrates by pulsed laser ablation of graphite and Ti target alternately in nitrogen gas. The composition, morphology and microstructure of the films were characterized by energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy. The tribological properties of the films in humid air were investigated using a ball-on-disk tribometer. The multilayer films consist of crystalline TiN, metallic Ti and amorphous CN_x (a-CN_x). With an increase in thickness ratio of CN_x to bilayer, the hardness of multilayer film decreases, friction coefficient decreases from 0.26 to 0.135, and wear rate increases. The film with thickness ratio of CN_x to bilayer of 0.47 exhibits a maximum hardness of 30 GPa and excellent wear rate of 2.5 × 10^− 7 mm³ N^− 1 m^− 1. The formation of tribo-layer was observed at contact area of Si₃N₄ ball. The film undergoes the combined wear mechanism of abrasion wear and adhesion wear.     

AC powered reactive magnetron deposition of indium tin oxide (ITO) films from a metallic target

Transparent highly conductive indium tin oxide (ITO) films for low cost applications were deposited by a reactive dual magnetron sputter process using metallic targets. The magnetrons were equipped with rectangular (130 × 400 mm²) In:Sn targets (90 wt.% In/10 wt.% Sn). A sine wave power supply was used at a frequency of about 70 kHz. All experiments were done in the transition mode at a constant argon flow of 40 sccm and an oxygen flow varied between 35 and 70 sccm. The total pressure was kept constant at 0.4 Pa.The films were deposited onto silicon and float glass substrates which were either moved in an oscillatory manner (dynamic deposition) or fixed in front of the targets (static mode) during deposition. A dynamic deposition rate of about 100 nm × m/min was obtained at an average power of 2 kW/cathode. The film thickness was adjusted to 500 nm. At an optimised Ar/O₂ gas flow ratio of 0.6 we found an electrical resistivity as low as 1.2 × 10^− 3 Ω cm. The refractive index of these films was about 2.05 indicating a dense film structure, while the optical absorption of k = 10^− 2 qualifies these ITO films for many low cost applications. Moreover, the film structure and texture were investigated by XRD methods.Applying a static deposition we have achieved a lower electrical resistivity with a minimum value of 6 × 10^− 4 Ω cm. In this case, the resistivity and the transparency, respectively, were not constant over the substrate but depend on the lateral position in front of the target. To explain this inhomogeneity we have performed spatially resolved deposition rate and Langmuir probe measurements and related their results to film structure and properties. In order to improve the film properties at dynamic deposition the growth conditions have to be homogenised at all substrate positions.     

Fabrication of finely structured silicon-supported SOFC with anode deposited by multi-phase plasma spraying

The mechanically mixed NiO/YSZ powder was usually used as the anode material of atmospheric plasma sprayed (APS) solid oxide fuel cells (SOFC). Big particles and the non-uniform distribution of the pores were observed in the resultant anode layer. To overcome the limitations, a method of fabricating anode layer by multi-phase plasma spraying (MPS) was proposed in this paper. The NiO and YSZ powders were delivered into plasma jet by a separate injection, where nitrogen carrier was employed to feed micrometer-sized NiO powder and liquid carrier was to feed submicrometer-sized YSZ powder. Suspension plasma spraying (SPS) was applied to fabricate dense electrolyte layer. The microstructure and composition of coatings were characterized by SEM and EDS. The results showed that finely structured anode layer with small particle size (d ∼ 2 μm) was achieved by the MPS method. The MPS anode layer was porous with the porosity of 32.1% while the APS anode layer was 22.6%. Three kinds of elements (Ni, Y, Zr) were observed in the MPS anode layer and the NiO content was calculated to be 49.6 wt%. In the SPS process, the suspension flow rate was matched to the plasma gas flow rate to obtain proper injection condition.     

Transparent conducting oxide films of heavily Nb-doped titania by reactive co-sputtering

Niobium-doped titania (TNO) films of various Nb content were deposited on glass and silicon substrates by reactive co-sputtering of Ti and Nb metal targets. Nb content in the TNO films was varied from 0 to ∼13 at.% (atomic percent), corresponding to Ti_1−xNb_xO₂ with x = 0-0.52, by modulating the Nb target power from 0 to 150 W (Watts). The influence of ion bombardment on the TNO films was investigated by applying an RF substrate bias from 0 to 25 W. The as-deposited TNO films were all amorphous and insulating, but after annealing at 600 °C for 1 h in hydrogen, they became crystalline and conductive. The annealed films crystallized into either pure anatase or mixed anatase and rutile structures. The as-deposited and the annealed films were transparent, with an average transmittance above 70%. Anatase TNO film (Ti_1−0.39Nb_0.39O₂) with Nb 9.7 at.% exhibited a dramatically reduced resistivity of 9.2 × 10⁻⁴ Ω cm, a carrier density of 6.6 × 10²¹ cm⁻³ and a carrier mobility around 1.0 cm² V⁻¹ s⁻¹. In contrast, the mixed-phase Ti_1−0.39Nb_0.39O₂ showed a higher resistivity of 1.2 × 10⁻¹ Ω cm. This work demonstrates that the anatase phase, oxygen vacancies, and Nb dopants are all important factors in achieving high conductivities in TNO films.     

Influence of air oxidation on the properties of decorative NbOxNy coatings prepared by reactive gas pulsing

In this work the oxidation resistance of DC reactive sputtered niobium oxynitrides and its influence on the properties of the films are studied. The depositions have been carried out by DC magnetron sputtering with a reactive gas pulsing process. The nitrogen flow was kept constant and the oxygen flow was pulsed. Pulse durations of 10 s produced multilayer coatings with a period of λ = 10 nm. Three sets of films with increasing duty cycle (= on-time of high oxygen flow / pulse duration) have been deposited. The films were subsequently annealed in air at 400, 500 and 600 °C, respectively.X-ray diffraction measurements showed a clear and progressive change from a roughly amorphous nature of the films to a crystalline oxide-type compound for those annealed at 600 °C, which was consistent with the composition analysis. For annealing temperatures of 500 and 600 °C, the coatings presented a significant reduction in hardness, approaching the values characteristic of Nb₂O₅-type films. Moreover, the residual stress measurements performed by using the deflection method revealed low values in all the coatings nearly independent on the annealing temperature.Color variation in the CIE − L^?a^?b^? color space and the reflectance in the UV-visible spectrum range of these niobium oxynitrides were investigated and correlated to their chemical composition and structural features. For both properties, the variation tendencies are quite similar, showing the transition from a nitride-type alloy to an oxide-type one with increasing annealing temperature.     

Study of bactericidal efficiency of magnetron sputtered TiO2 films deposited at varying oxygen partial pressure

TiO₂ thin films have been deposited at different Ar:O₂ gas ratios (20:80,70:30,50:50,and 40:60 in sccm) by rf reactive magnetron sputtering at a constant power of 200 W. The formation of TiO₂ was confirmed by X-ray photoelectron spectroscopy (XPS). The oxygen percentage in the films was found to increase with an increase in oxygen partial pressure during deposition. The oxygen content in the film was estimated from XPS measurement. Band gap of the films was calculated from the UV-Visible transmittance spectra. Increase in oxygen content in the films showed substantial increase in optical band gap from 2.8 eV to 3.78 eV. The Ar:O₂ gas ratio was found to affect the particle size of the films determined by a transmission electron microscope (TEM). The particle size was found to be varying between 10 and 25 nm. The bactericidal efficiency of the deposited films was investigated using Escherichia coli (E. coli) cells under 1 h UV irradiation. The growth of E. coli cells was estimated through the Optical Density measurement by UV-Visible absorbance spectra. The qualitative analysis of the bactericidal efficiency of the deposited films after UV irradiation was observed through SEM. A correlation between the optical band gap, particle size and bactericidal efficiency of the TiO₂ films at different argon:oxygen gas ratio has been studied.     

Optical and electrical properties of zinc oxide thin films with low resistivity via Li-N dual-acceptor doping

Zinc oxide thin films with low resistivity have been deposited on glass substrates by Li-N dual-acceptor doping method via a modified successive ionic layer adsorption and reaction process. The thin films were systematically characterized via scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction, ultraviolet-visible spectrophotometry and fluorescence spectrophotometry. The resistivity of zinc oxide film was found to be 1.04 Ω cm with a Hall mobility of 0.749 cm² V⁻¹ s⁻¹ and carrier concentration of 8.02 × 10¹⁸ cm⁻³. The Li-N dual-acceptor doped zinc oxide films showed good crystallinity with prior c-axis orientation, and high transmittance of about 80% in visible range. Moreover, the effects of Li doping level and other parameters on crystallinity, electrical and ultraviolet emission of zinc oxide films were investigated.     

Spatial stress distribution and optical properties of GaN films grown on convex shape-patterned sapphire substrate by metalorganic chemical vapor deposition

μ-Raman and μ-photoluminescence methods have been employed to investigate microscopic spatial stress distribution and optical properties of GaN films grown on the convex shape-patterned sapphire substrate (CSPSS). By comparison of the μ-Raman and μ-PL spectra, we found that significantly large difference, Δσ_xx ∼0.46 GPa, in biaxial compressive stress between the flat trench and convex regions in the side facet of the GaN film, around ∼2 μm below the surface whereas on the GaN surface, little difference with large residual stress was observed in both regions compared to those from the side facet. Temperature dependent and time-resolved photoluminescence spectra have shown that the GaN film grown on the CSPSS has improved crystal purity through the reduction of intrinsic point defects.     

Influence of oxygen partial pressure on electrical and optical properties of Zn0.93Mn0.07O thin films

The Zn_1−xMn_xO (x = 0.07) thin films were grown on glass substrates by direct current reactive magnetron cosputtering. The influence of oxygen partial pressure on the structural, electrical and optical properties of the films has been studied. X-ray-diffraction measurement revealed that all the films were single phase and had wurtzite structure with c-axis orientation. The experimental results indicated that there was an optimum oxygen partial pressure where the film shows relative stronger texture, better nano-crystallite and lower surface roughness. As the oxygen partial pressure increases, the carrier concentration systematically decreases and photoluminescence peaks related to zinc interstitials gradually diminish. The minimal resistivity of 70.48 Ω cm with the highest Hall mobility of 1.36 cm² V⁻¹ s⁻¹ and the carrier density of 6.52 × 10¹⁶ cm⁻³ were obtained when oxygen partial pressure is 0.4. All films exhibit a transmittance higher than 80% in the visible region, while the deposited films showed a lower transmittance when oxygen partial pressure is 0.4. With the increasing of oxygen partial pressure, the peak of near-band-edge emission has firstly a blueshift and then redshift, which shows a similar trend to the band gap in the optical transmittance measurement.     

Thermal stability of electrical properties of ZnO:Al films deposited by room temperature magnetron sputtering

In order to investigate the thermal stability of electrical properties for aluminum doped zinc oxide (ZnO:Al, AZO) films deposited by direct current reactive magnetron sputtering, AZO films deposited from an alloy target (0.8 wt.% Al) on soda-lime glasses were annealed in argon gas at different temperatures. A data capturer was applied to monitor and collect real-time sheet resistance (R_s) of the films throughout the annealing. Results revealed that R_s of the film heated at 100 °C was reduced throughout the annealing, however, conductivity of the films annealed over 100 °C was improved at early stage but then deteriorated all along to the end. Some novel R_s change points which need more penetrations were detected. The experimental results obtained from electron diffraction spectrum, X-ray diffraction pattern, X-ray photoelectron spectrum, and Hall measurement were analyzed to explore the effect of the annealing on the electrical properties of AZO films. It was found that the exotic element, which might influence the film properties, was not observed. It was also suggested that the transformation of the crystalline structure and surface chemical bonding states, which resulted in the decrease of carrier concentration and mobility could be the reason for the conductivity degeneration of the films annealed at higher temperature.     

Deep UV laser etching of GaN epilayers grown on sapphire substrate

The laser etching of GaN epilayers on sapphire substrate was carried out using a deep ultraviolet pulsed laser (157 nm wavelength, 20 ns pulse width). The quality and morphology of the etched GaN surface were evaluated by scanning electron microscopy, atomic force microscopy and scanning profilometer. Quadrate micro-hole and micro-trenches etched by the 157 nm laser exhibited clean and smooth edges, sharp side walls and very small heat affected zone (HAZ). In order to achieve controllable high-quality etching, the laser and processing parameters, such as laser repetition rate, scan speed, were systematically investigated and optimized. The mechanism analysis shows that, direct photoionization or photo-chemical reaction play predominant role within 157 nm laser etching of GaN epilayers.     

Effect of nitrogen pressure on structure and optical properties of pulsed laser deposited BCN thin films

Amorphous boron carbon nitride (BCN) thin films were deposited on Si (100) and quartz substrates by laser ablation of a boron carbide (B₄C) target in nitrogen atmosphere. The effects of the nitrogen pre ssure (p_N2) on the film deposition rate, composition, structure and optical properties were investigated. The film deposition rate was measured by a surface profiler, which increased from 3.4 to 6.25 nm/min at elevated p_N2. Structure and composition of the films were investigated by X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared (FTIR) spectroscopy. FTIR and XPS analyses indicated that the as-deposited BCN films contained B-C, N-C and B-N chemical bonds, implying the formation of ternary BCN compounds. The nitrogen content in the films increased gradually and then saturated up to ∼ 26 at.% at 10 Pa p_N2. The optical band gap (E_g) increased from 3.78 to 3.92 eV with increasing p_N2 from 2 to 15 Pa. The evolution of E_g is in accordance with the change of film compositions and bonding states.     

Conductive and transparent Bi-doped ZnO thin films prepared by rf magnetron sputtering

Bi-doped ZnO thin films were grown on glass substrates by ratio frequency (rf) magnetron sputtering technique and followed by annealing at 400 °C for 4 h in vacuum (~ 10^− 1 Pa). The effect of argon pressure on the structural, optical, and electrical properties of the Bi-doped films were investigated. The XRD patterns show that the thin films were highly textured along the c-axis and perpendicular to the surface of the substrate. Some excellent properties, such as high transmittance (about 85%) in visible region, low resistivity value of 1.89 × 10^− 3 W cm and high carrier density of 3.45 × 10²⁰ cm^− 3 were obtained for the film deposited at the argon pressure of 2.0 Pa. The optical band gap of the films was found to increase from 3.08 to 3.29 eV as deposition pressure increased from 1 to 3 Pa. The effects of post-annealing treatments had been considered. In spite of its low conductivity comparing with other TCOs, Bi-doping didn't appreciably affect the optical transparency in the visible range of ZnO thin films.     

Study of post annealing influence on structural, chemical and electrical properties of ZTO thin films

Zinc-Tin-Oxide (ZTO) thin films were deposited on glass substrate with varying concentrations (ZnO:SnO₂; 100:0, 90:10, 70:30 and 50:50 wt.%) at room temperature by flash evaporation technique. These deposited ZTO films were annealed at 450 °C in vacuum. These films were characterized to study the effect of annealing and addition of SnO₂ concentration on the structural, chemical and electrical properties. The XRD analysis indicates that crystallization of the ZTO films strongly depends on the concentration of SnO₂ and post annealing where annealed films showed polycrystalline nature. Atomic force microscopy (AFM) images manifest the surface morphology of these ZTO thin films. The XPS core level spectra of Zn(2p), O(1s) and Sn(3d) have been deconvoluted into their Gaussian component to evaluate the chemical changes, while valence band spectra reveal the electronic structures of these films. A small shift in Zn(2p) and Sn(3d) core level towards higher binding energy and O(1s) core level towards lower binding energy have been observed. The minimum electrical resistivity (ρ ≈ 3.69 × 10⁻² Ω-cm), maximum carrier concentration (n ≈ 3.26 × 10¹⁹ cm⁻³) and Hall mobility (μ ≈ 5.2 cm² v⁻¹ s⁻¹) were obtained for as-prepared ZTO (50:50) film thereafter move towards lowest resistivity (ρ ≈ 1.12 × 10⁻³ Ω-cm), highest carrier concentration (n ≈ 2.96 × 10²⁰ cm⁻³) and mobility (μ ≈ 18.8 cm² v⁻¹ s⁻¹) for annealed ZTO (50:50) thin film.