Effects of argon and oxygen flow rate on water vapor barrier properties of silicon oxide coatings deposited on polyethylene terephthalate by plasma enhanced chemical vapor deposition

Plasma polymer coatings were deposited from hexamethyldisiloxane on polyethylene terephthalate (PET) substrates while varying the operating conditions, such as the Ar and O₂ flow rates, at a fixed radio frequency power of 300 W. The water vapor transmission rate (WVTR) of the untreated PET was 54.56 g/m²/day and was decreased after depositing the silicon oxide (SiO_x) coatings. The minimum WVTR, 0.47 g/m²/day, was observed at Ar and O₂ flow rates of 4 and 20 sccm, respectively, with a coating thickness of 415.44 nm. The intensity of the peaks for the Si-O-Si bending at 800-820 cm^− 1 and Si-O-Si stretching at 1000-1150 cm^− 1 varied depending on the Ar and O₂ flow rates. The contact angle of the SiO_x coated PET increased as the Ar flow rate was increased from 2 to 8 sccm at a fixed O₂ flow rate of 20 sccm. It decreased gradually as the oxygen flow rate increased from 12 to 28 sccm at a fixed Ar carrier gas flow rate. The examination by atomic force microscopy revealed a correlation of the SiO_x morphology and the water vapor barrier performance with the Ar and O₂ flow rates. The roughness of the deposited coatings increased when either the O₂ or Ar flow rate was increased.     

Characterization of nanocrystalline indium tin oxide thin films prepared by ion beam sputter deposition method

Indium tin oxide (ITO) thin films were deposited on glass substrates by ion beam sputter deposition method in three different deposition conditions [(i) oxygen (O₂) flow rate varied from 0.05 to 0.20 sccm at a fixed argon (1.65 sccm) flow rate, (ii) Ar flow rate changed from 1.00 to 1.65 sccm at a fixed O₂ (0.05 sccm) flow rate, and (iii) the variable parameter was the deposition time at fixed Ar (1.65 sccm) and O₂ (0.05 sccm) flow rates]. (i) The X-ray diffraction (XRD) patterns show that the ITO films have a preferred orientation along (400) plane; the orientation of ITO film changes from (400) to (222) direction as the O₂ flow rate is increased from 0.05 to 0.20 sccm. The optical transmittance in the visible region increases with increasing O₂ flow rate. The sheet resistance (R_s) of ITO films also increases with increasing O₂ flow rate; it is attributed to the decrease of oxygen vacancies in the ITO film. (ii) The XRD patterns show that the ITO film has a strong preferred orientation along (222) direction. The optical transmittance in the visible spectral region increases with an increase in Ar flow rate. The R_s of ITO films increases with increasing Ar flow rate; it is attributed to the decrease of grain size in the films. (iii) A change in the preferred orientations of ITO films from (400) to (222) was observed with increasing film thickness from 314 to 661 nm. The optical transmittance in the visible spectral region increases after annealing at 200 °C. The R_s of ITO film decreases with the increase of film thickness.     

Atmospheric pressure PECVD of SiO2 thin film at a low temperature using HMDS/O2/He/Ar

SiO₂-like thin films were deposited at a low temperature (< 50 °C) by a remote-type, atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD) using a pin-to-plate-type, dielectric barrier discharge with gas mixtures containing hexamethyldisilazane (HMDS)/O₂/He/Ar. The film characteristics were investigated according to the HMDS and O₂ flow rates. To obtain a more SiO₂-like thin film, an adequate combination of HMDS and oxygen flow rates was required to remove the -(CH₃)_x bonding in the HMDS and to oxidize the Si in HMDS effectively. At the optimized flow rates, the surface roughness of the SiO₂-like thin film was also the lowest. By using HMDS (50 sccm) and O₂ (500 sccm) flow rates in the gas mixture of HMDS/O₂/He (2 slm)/Ar (600 sccm), SiO₂-like thin films with a low impurity (< 6.35% C) were obtained at a deposition rate of approximately 10.7 nm/min.     

Oxygen atom density in capacitively coupled RF oxygen plasma

The density of neutral oxygen atoms was determined in a plasma reactor for surface functionalization of polymer materials. Plasma was created in a stainless steel chamber by capacitively coupled RF generator at 13.56 MHz and adjustable forward power up to 100 W. Measurements were performed with a classical nickel catalytic probe. Systematic measurements were performed at a constant pumping speed, different flow rates from 15 to 100 sccm corresponding to pressures between 30 and 110 Pa, different powers between 40 and 100 W and different probe positions in the discharge chamber. The results showed that the O atom density did not depend much on probe position as long as it was between the powered electrode and grounded housing facing the electrode. The O density depended rather linearly with power at fixed pressure. At low power, the O density did not depend much on pressure, but at high power, it was increasing with increasing pressure. The O density was of the order of 10¹⁹ m⁻³ and increased slightly over 10²⁰ m⁻³ at the highest power and pressure. The results were explained by gas phase and surface reactions.     

Characteristics of SiOx thin films deposited by atmospheric pressure chemical vapor deposition as a function of HMDS/O2 flow rate

SiO₂-like thin films were deposited using a modified dielectric barrier discharge with a gas mixture of hexamethyldisilazane (HMDS)/O₂/He/Ar and their film characteristics were investigated as functions of the HMDS and O₂ flow rates. As the HMDS flow rate was increased, higher amounts of Si-(CH₃)_x bonds and lower amounts of Si-OH bonds were observed in the deposited SiO_x, due to the increase in the amount of the less dissociated HMDS, which also caused an increase of the surface roughness. The addition and increase of the oxygen flow to HMDS/He/Ar brought the stoichiometry of SiO_x close to SiO₂ and decreased the surface roughness by decreasing the amount of Si-(CH₃)_x bonds through the increased decomposition and oxidation of HMDS, even though the deposition rate was decreased. However, when the O₂ flow rate was higher than a certain threshold, the surface roughness increased again, possibly due to the decrease in the extent of HMDS dissociation caused by the decreased plasma density at the higher oxygen flow rate. By using an optimized gas mixture of HMDS (150 sccm)/O₂ (14 slm)/He (5 slm)/Ar (3 slm), SiO₂-like thin films with a very low impurity level and having a smooth surface could be obtained with a deposition rate of approximately 42.7 nm/min.     

Structure and mechanical properties of ZrO2 films deposited by gas flow sputtering

ZrO₂ films were deposited by reactive gas flow sputtering (GFS) where voltage is applied to a cyindrical hollow-cathode target from a DC source, the discharge being produced at relatively high sputtering pressure. In this system, secondary electrons form a major component of the total current flow and lead to heating of the substrate which in turn has an effect on the properties of deposited films. The present experiments were carried out under the following conditions: Ar gas flow rate of 200 sccm, O₂ flow rate FO₂ in the range between 0.003 and 1 sccm, and sputtering power (P_S) in the range of 50-800 W. The reults showed that the crystal structure of the films deposited for P_S below 200 W was monoclinic but for P_S above 400 W, the films included tetragonal cystals of stable structure formed at high temperature by the electron bombardment. The films were formed with grains of 20-100 nm in diameter in a porous structure. The mechanical properties of the films were determined by a nanoindentation technique. Martens hardness (H_M) of the porous films was found to be in the range between 220 and 330 MPa which is substantially less than that of films typically deposited by rf magnetron sputtering.     

Dry etching of TiN in N2/Cl2/Ar adaptively coupled plasma

We investigated the N₂ additive effect on the etch rates of TiN and SiO₂ and etch profile of TiN in N₂/Cl₂/Ar adaptively coupled plasma (ACP). The mixing ratio of Cl₂ and Ar was fixed at 75 and 25 sccm, respectively. The N₂ flow rate was increased from 0 to 9 sccm under the constant pressure of 10 mTorr. As N₂ flow rate was increased in N₂/Cl₂/Ar plasma, the etch rate of TiN was linearly increased, but that of SiO₂ was increased non-monotonically. The etch profile and the compositional changes of TiN was investigated with field emission-scanning electron microscope (FE-SEM), FE-Auger electron spectroscopy (FE-AES) and x-ray photoelectron spectroscopy (XPS). When 9 sccm N₂ was added into Cl₂/Ar, a steep etch profile and clean surface of TiN was obtained. In addition, the signals of TiN and Ti were disappeared in FE-AES and XPS when N₂ additive flow into Cl₂/Ar was above 6 sccm. From the experimental data, the increase in TiN etch rate was mainly caused by the increase of desorption and evacuation rate of etch by products because of the increased effective pumping speed. The etch mechanism of TiN in N₂/Cl₂/Ar ACP plasma can be concluded as the ion enhanced chemical etch.     

Dry etching of TiN in N2/Cl2/Ar adaptively coupled plasma

We investigated the N₂ additive effect on the etch rates of TiN and SiO₂ and etch profile of TiN in N₂/Cl₂/Ar adaptively coupled plasma (ACP). The mixing ratio of Cl₂ and Ar was fixed at 75 and 25 sccm, respectively. The N₂ flow rate was increased from 0 to 9 sccm under the constant pressure of 10 mTorr. As N₂ flow rate was increased in N₂/Cl₂/Ar plasma, the etch rate of TiN was linearly increased, but that of SiO₂ was increased non-monotonically. The etch profile and the compositional changes of TiN was investigated with field emission-scanning electron microscope (FE-SEM), FE-Auger electron spectroscopy (FE-AES) and x-ray photoelectron spectroscopy (XPS). When 9 sccm N₂ was added into Cl₂/Ar, a steep etch profile and clean surface of TiN was obtained. In addition, the signals of TiN and Ti were disappeared in FE-AES and XPS when N₂ additive flow into Cl₂/Ar was above 6 sccm. From the experimental data, the increase in TiN etch rate was mainly caused by the increase of desorption and evacuation rate of etch by products because of the increased effective pumping speed. The etch mechanism of TiN in N₂/Cl₂/Ar ACP plasma can be concluded as the ion enhanced chemical etch.     

Highly flexible indium zinc oxide electrode grown on PET substrate by cost efficient roll-to-roll sputtering process

We have investigated the characteristics of flexible indium zinc oxide (IZO) electrode grown on polyethylene terephthalate (PET) substrates using a specially designed roll-to-roll (RTR) sputtering system for use in flexible optoelectronics. It was found that both electrical and optical properties of the flexible IZO electrode were critically dependent on the DC power and Ar/O₂ flow ratio during the roll-to-roll sputtering process. At optimized conditions (constant working pressure of 3 mTorr, Ar/O₂ flow ratio of Ar at only 30 sccm, DC power 800 W and rolling speed at 0.1 cm/s) the flexible IZO electrode exhibits a sheet resistance of 17.25 Ω/sq and an optical transmittance of 89.45% at 550 nm wavelength. Due to the low PET substrate temperature, which is effectively maintained by cooling drum system, all IZO electrodes showed an amorphous structure regardless of the DC power and Ar/O₂ flow ratio. Furthermore, the IZO electrodes grown at optimized condition exhibited superior flexibility than the conventional amorphous ITO electrodes due to its stable amorphous structure. This indicates that the RTR sputter grown IZO electrode is a promising flexible electrode that can substitute for the conventional ITO electrode, due to its low resistance, high transparency, superior flexibility and fast preparation by the RTR process.     

Structural and optical properties of Ti oxide cluster-assembled films prepared by plasma-gas-condensation

Ti and Ti oxide cluster-assembled films have been prepared using a plasma-gas-condensation apparatus. Transmission electron microscopy and electron diffraction measurement indicates that their structures vary from a face-centered-cubic (fcc) Ti phase, via an NaCl-type TiO_x phase, to an amorphous and rutile-type TiO₂ mixture phase with increasing the O₂ flow rate in the Ar/He gas mixture. Cluster shapes are spherical for the fcc phase, cubic for the NaCl-type, and spherical for the amorphous and rutile-type mixture, while the cluster size monotonically decreases with increasing O₂ flow rate. The Ti and Ti oxide cluster-assembled films have a sooty appearance, showing a very porous morphology in the scanning electron microscopy images. The electrical resistivity dramatically increases between R_O2 = 0.065 and 0.075 sccm, while the optical transmittance spectra in the visible wavelength range rapidly increases between R_O2 = 0.1 and 0.12 sccm, well reflecting the structure variations in these Ti and Ti oxide cluster-assembled films.     

Preparation and characterization of α-Fe2O3 polyhedral nanocrystals via annealing technique

Polyhedral nanocrystals of α-Fe₂O₃ are successfully synthesized by annealing FeCl₃ on silicon substrate at 1000 °C in the presence of H₂ gas diluted with argon (Ar). Uniformly shaped polyhedral nanoparticles (diameter ~ 50-100 nm) are observed at 1000 °C and gases flow rate such as; Ar = 200 ml/min and H₂ = 150 ml/min. Non-uniform shaped nanoparticles (diameter ~ 20-70 nm) are also observed at an annealing temperature of 950 °C with lower gases flow rate (Ar = 100 ml/min and H₂ = 75 ml/min). Nanoparticles are characterized in detail by field-emission electron microscopy (FE-SEM), energy dispersive X-ray (EDX) and high resolution transmission electron microscopy (HRTEM) techniques. HRTEM study shows well resolved (110) fringes corresponding to α-Fe₂O₃, and selected area diffraction pattern (SADP) confirms the crystalline nature of α-Fe₂O₃ polyhedral nanoparticles. It is observed that polyhedral formation of α-Fe₂O₃ nanocrystals depends upon annealing temperature and the surface morphology highly rely on the gas flow rate inside the reaction chamber.     

The effect of the backscattered energetic atoms on the stress generation and the surface morphology of reactively sputtered vanadium nitride films

During the reactive magnetron sputtering of transition metal nitrides in an Ar-N₂ ambient, Ar⁺ and N₂⁺ plasma ions are neutralized upon impingement on the target and are backscattered towards the growing film as neutral Ar and N species, respectively. Based on simulations, as well as on plasma and on film characterization techniques we manifest the relationship between the bombardment by the backscattered energetic atoms and the properties of reactively sputtered vanadium nitride (VN) films. Depending on the N₂ flow (q_N2) two bombardment regimes are established. In the first regime, (q_N2 < 20 sccm) the contribution of the N species to the energetic bombardment is insignificant. The major bombarding species in this regime are the backscattered Ar species, as well as positive plasma ions and sputtered atoms. These species have relatively low energies and subplantation ratios and thus, their energy is transferred to the surface of the growing film. In the second regime (q_N2 > 20 sccm) the backscattered N atoms are the major bombarding species and their flux to the growing film increases with increasing the N₂ flow. We argue that the backscattered N atoms have higher energy and subplantation ratio in comparison to the other bombarding species. As a result, a higher part of their energy is dissipated in the bulk of the film. The two bombarding regimes correlate well with the residual compressive stresses and the surface roughness of the films. Films grown at q_N2 < 20 sccm exhibit low compressive stresses and their roughness drops when q_N2 is increased. This consistent with the low subplantation ratio and the transfer of the energy of the bombarding species to surface the growing film. The compressive stresses of films grown at q_N2 > 20 sccm are higher, than those of the films grown in the first regime, and increase with increasing N₂ flow. This is attributed to the subplantation of the bombarding N species in the growing film.     

Influence of N2 flow rate on the mechanical properties of SiNx films deposited by microwave electron cyclotron resonance magnetron sputtering

Hydrogen-free amorphous silicon nitride (SiN_x) films were deposited at room temperature by microwave electron cyclotron resonance plasma-enhanced unbalance magnetron sputtering. Varying the N₂ flow rate, SiN_x films with different properties were obtained. Characterization by Fourier-transform infrared spectrometry revealed the presence of Si-N and Si-O bonds in the films. Growth rates from 1.0 to 4.8 nm/min were determined by surface profiler. Optical emission spectroscopy showed the N element in plasma mainly existed as N⁺ species and N₂⁺ species with 2 and 20 sccm N₂ flow rate, respectively. With these results, the chemical composition and the mechanical properties of SiN_x films strongly depended on the state of N element in plasma, which in turn was controlled by N₂ flow rate. Finally, the film deposited with 2 sccm N₂ flow rate showed no visible marks after immersed in etchant [6.7% Ce(NH₄)₂(NO₃)₆ and 93.3% H₂O by weight] for 22 h and wear test for 20 min, respectively.     

Plasmachemical synthesis of maghemite nanoparticles in atmospheric pressure microwave torch

The powder of γ − Fe₂O₃ nanoparticles was synthesized in microwave torch at atmospheric pressure from 0.05 sccm of Fe(CO)₅ vapors in 670 sccm of argon. The optimization of the torch reactor design and deposition conditions allowed continual synthesis of γ − Fe₂O₃ nanoparticles at low power consumption. The synthesized powder was collected at the reactor walls and analyzed by TEM, X-ray diffraction and Raman spectroscopy without any further purification or treatment. The mean diameter of NPs, as observed by TEM, was 12 nm with a 90% confidence interval 5.5-22 nm.     

Optical constants of silicone-like (Si:Ox:Cy:Hz) thin films deposited on quartz using hexamethyldisiloxane in a remote RF hollow cathode discharge plasma

Deposition of amorphous silicone-like (Si:O_x:C_y:H_z) thin films in a remote RF hollow cathode discharge plasma using hexamethyldisoloxane as monomer and Ar as feed gas has been investigated for films optical constants and plasma diagnostic as a function of RF power (100-300 W) and precursor flow rate (1-10 sccm). Plasma diagnostic has been performed using Optical Emission Spectroscopy (OES). The optical constants (refractive index, extinction coefficient and dielectric constant) have been obtained by reflection/transmission measurements in the range 300-700 nm. It is found that the refractive index increases from 1.92 to 1.97 with increasing power from 100 to 300 W, and from 1.70 to 1.92 with increasing precursor flow rate from 1 to 10 sccm. The optical energy band gap E_g and the optical-absorption tail ΔE have been estimated from optical absorption spectra, it is found that E_g decreases from 3.28 to 3.14 eV with power increase from 100 to 300 W, and from 3.54 to 3.28 eV with precursor flow rate increase from 1 to 10 sccm. ΔE is found to increase with applied RF power and precursor flow rate increase. The dependence of optical constants on deposition parameters has been correlated to plasma OES.     

Synthesis of CuCr and CuCrAg alloy with nano-ceramic dispersion by mechanical alloying and consolidation by laser assisted sintering

Cu-4.5Cr and Cu-4.5Cr-3Ag (in wt%) alloys without or with 10 wt% nanocrystalline Al₂O₃ and ZrO₂ dispersion have been synthesized by mechanical alloying or milling and consolidated by laser assisted sintering in Ar atmosphere. Microstructural characterization by scanning and transmission electron microscopy and phase analysis by X-ray diffraction suggest that the alloyed matrix undergoes significant grain growth after sintering while the dispersoids retain their ultrafine size and uniform distribution in the matrix. The dispersion of nano-Al₂O₃ is more effective than that of nano-ZrO₂ in enhancing the mechanical properties due to the smaller initial particle size of Al₂O₃ than that of ZrO₂. In general, laser sintering of mechanically alloyed Cu-4.5Cr and Cu-4.5Cr-3Ag alloys with 10 wt% nanocrystalline Al₂O₃ at 100 W laser power and 1-2 mm s⁻¹ scan speed yields the optimum combination of high density (7.1-7.5 mg m⁻³), hardness (165-225 VHN), wear resistance and electrical conductivity (13-20% IACS).     

Effect of sintering process on the microstructures of Bi2O3-doped yttria stabilized zirconia

Variations of microstructures in Bi₂O₃-doped yttria stabilized zirconia (YSZ) with conventional furnace and microwave sintering were investigated in this work. The results demonstrated that a small amount of addition of Bi₂O₃ was effective in reducing the sintering temperature of YSZ from 1500 °C to 1200 °C and promoting the densification rate of the ceramics. It is interesting that microwave sintering is found to suppress the evaporation rate of Bi₂O₃ and formation of the monoclinic-ZrO₂ or other amorphous phases. Compared to conventional furnace sintering, significant improvement in density of Bi₂O₃-doped YSZ at lower sintering temperatures with microwave sintering was observed. Rapid heating rate and short sintering time for restricting serious segregation at grain boundary were observed as well. Employing microwave sintering at the same sintered condition, the density of a specimen was evidently increased by 4.59% in comparison to the specimen sintered with a conventional furnace sintering.     

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.     

Refraction properties of PECVD of silicon nitride film

Using a neural network, the refractive index of a film deposited in a plasma enhanced chemical vapor deposition is characterized. The deposition process was characterized by a 2^6-1 fractional factorial experiment. Experimental variables and ranges include 20-40 W radio frequency (RF) power, 80-160 Pa pressure, 180-260 sccm SiH₄ flow rate, 1-1.4 sccm NH₃ flow rate, 0-1000 sccm N₂ flow rate, and 200-300°C substrate temperature. To examine the effect of the interaction between variables on the refractive index, a predictive neural network model was constructed. Prediction accuracy was optimized as a function of training factors. Model predictions were certified experimentally. Many complex interactions between the variables not reported previously were revealed. The power effect was transparent only in such plasma conditions as high SiH₄ or NH₃ flow rate. The temperature effect was conspicuous under high pressure. Deposition mechanisms were qualitatively estimated in conjunction with the reported linear dependency of refractive index on SiH/NH ratio.     

Synthesis of well-crystallized birnessite using ethylene glycol as a reducing reagent

Well-crystallized birnessite sheets containing K⁺ in the interlayers have been prepared using KMnO₄, ethylene glycol and KOH by microwave heating at 90 °C for 10 min. Ethylene glycol was used as a reducing agent. The effect of KOH concentration on the formation of birnessite was studied. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TG), differential scanning calorimetric analysis (DSC) and Fourier transform infrared (FTIR). Birnessites were converted to cryptomelane upon heating at 400-800 °C and completely collapsed to form Mn₃O₄ at 1000 °C.