Interface control of atomic layer deposited oxide coatings by filtered cathodic arc deposited sublayers for improved corrosion protection

Sublayers grown with filtered cathodic arc deposition (FCAD) were added under atomic layer deposited (ALD) oxide coatings for interface control and improved corrosion protection of low alloy steel. The FCAD sublayer was either Ta:O or Cr:O–Ta:O nanolaminate, and the ALD layer was Al₂O₃–Ta₂O₅ nanolaminate, Al_xTa_yO_z mixture or graded mixture. The total thicknesses of the FCAD/ALD duplex coatings were between 65 and 120 nm. Thorough analysis of the coatings was conducted to gain insight into the influence of the FCAD sublayer on the overall coating performance. Similar characteristics as with single FCAD and ALD coatings on steel were found in the morphology and composition of the duplex coatings. However, the FCAD process allowed better control of the interface with the steel by reducing the native oxide and preventing its regrowth during the initial stages of the ALD process. Residual hydrocarbon impurities were buried in the interface between the FCAD layer and steel. This enabled growth of ALD layers with improved electrochemical sealing properties, inhibiting the development of localized corrosion by pitting during immersion in acidic NaCl and enhancing durability in neutral salt spray testing.     

Deposition of dielectrics using a matrix distributed electron cyclotron resonance plasma enhanced chemical vapor deposition system

We have studied the deposition of silicon oxide, oxynitrides and silicon nitride in a novel, scalable, low-pressure high-density plasma system based on the ECR effect and the matrix arrangement of microwave antennas. Silane, nitrogen and oxygen gases were used as precursors. Films were deposited onto different heated and unheated substrates, including silicon, glass and polymer. The influence of the magnetic field configuration, gas flows, reactor pressure, microwave power and radio frequency bias on the uniformity and properties of the films was studied. Ex-situ and in-situ UV-visible spectroscopic phase-modulated ellipsometry and FTIR spectroscopy were used to study the properties of materials and the uniformity of the depositions, along with electrical measurements to evaluate the dielectric properties of the films. Optimizing the magnetic field configuration and applying an RF bias, we were able to achieve an uniformity better than 3.3% across the 200 mm wafers. Stoichiometric silicon oxide films with index values matching that of thermal silica were grown on unheated substrates with rates exceeding 2 nm/s.     

Synthesis and optical characterization of amorphous carbon nitride thin films by hot filament assisted RF plasma CVD

Carbon nitride thin films were synthesized by hot filament assisted radio frequency plasma chemical vapour deposition using methane and nitrogen gas mixture on silicon and glass substrates. The films were deposited at different substrate bias and at different substrate temperatures. At higher substrate bias (>−120 V) there was no deposition on the substrate, but complete etching of the deposited layer was observed. X-ray diffraction studies indicated the films were amorphous. The Fourier transform infrared spectra showed that the films produced exhibited high transmittance with the presence of the C-N stretching band at 1260 cm⁻¹. For the films deposited at a lower substrate temperature C=N peaks were also present. Raman spectroscopic study indicated the presence of D and G peaks whose relative height varied with substrate temperature. The transmittance versus wavelength measurement in the UV-VIS-NIR region showed the high transmittance in the NIR region. The optical band gap of the films was calculated to be 2.0 eV and the refractive index varied within 1.6-1.7 for the wavelength range 800-1800 nm.     

Low refractive index silicon oxide coatings at room temperature using atmospheric-pressure very high-frequency plasma

Low refractive index silicon oxide films were deposited using atmospheric-pressure He/SiH₄/CO₂ plasma excited by a 150-MHz very high-frequency power. Significant increase in deposition rate at room temperature could prevent the formation of dense SiO₂ network, decreasing refractive index of the resulting film effectively. As a result, a silicon oxide film with the lowest refractive index, n = 1.24 at 632.8 nm, was obtained with a very high deposition rate of 235 nm/s. The reflectance and transmittance spectra showed that the low refractive index film functioned as a quarter-wave anti-reflection coating of a glass substrate.     

In situ Fourier transform P-polarized infrared reflection absorption spectroscopic investigation of an interface properties of SiO2/Si(100) deposited using electron cyclotron resonance microwave plasma at room temperature

Amorphous SiO₂ films have been deposited onto the Si substrate, without heating, using sputtering-type electron cyclotron resonance (ECR) microwave plasma. In situ Fourier transform P-polarized infrared reflection absorption spectroscopy (ISFT-PIRRAS) has been used to study the properties of a-SiO₂/Si interface. The results from ISFT-PIRRAS monitoring indicated that the interface stress led to significant distortion in the local structure, which resulted in the broadening of a transverse optical mode (TO₃) located at 1050 cm⁻¹. The interface stress decreased with increased film thickness. In addition, the longitudinal optical phonon mode (LO₃, located at 1223 cm⁻¹) related to TO₃ mode was observed due to Berreman effect [B. Harbecke, Appl. Phys. A: Solids Surf. 38 (1985) 263]. This phonon mode is very sensitive to SiO₂ film thickness, which enables it to be used to detect and characterize ultra thin SiO₂ film. When the film thickness is over 30 nm, a non-linear dependence of the intensity of LO₃ mode on film thickness was observed. However, the TO₃ mode has a near linear dependence on film thickness. Thus, it is more accurate and suitable to detect thick film by monitoring TO₃ mode intensity.     

Silicon nitride films synthesized by reactive pulsed laser deposition in an electron cyclotron resonance nitrogen plasma

We report a film synthesis method called electron cyclotron resonance (ECR) plasma aided reactive pulsed laser deposition. Silicon nitride films were synthesized at low temperature by means of laser ablation of a silicon target in an ECR microwave discharge in pure nitrogen gas. It is found that silicon and nitrogen are well-distributed in the deposited films with a composition of near stoichiometric Si₃N₄. Optical emission spectroscopy indicated that nitrogen in the ECR plasma was highly activated. The presence of the ECR nitrogen plasma during the deposition is considered to lead to enhanced nitridation of the ablated silicon in the plume as well as at the substrate, and to be responsible for the effective incorporation of nitrogen in the films.     

Properties of fluorinated silica glass deposited at low temperature by atmospheric plasma-enhanced chemical vapor deposition

The atmospheric pressure plasma-enhanced chemical vapor deposition of fluorinated silica glass was demonstrated at a temperature of 120 °C. The process was carried out by simultaneously feeding tetramethylcyclotetrasiloxane (TMCTS) and triethoxyfluorosilane (TEOFS) into the afterglow of helium and oxygen plasma. The effect of the flow rate of the fluorinated precursor on the growth rate, composition, and optical properties was examined. The ratio of atomic fluorine to atomic silicon increased up to 10% at a TEOFS/TMCTS atomic Si feed ratio of 1.3 and then leveled off. Coatings made from pure TMCTS and both precursors showed higher surface roughness and porosity, and more hydroxyl content compared to coatings made from pure TEOFS. The refractive indices at 633 nm of films produced using pure TMCTS, a TEOFS/TMCTS atomic Si feed ratio of 1.3 and pure TEOFS were 1.457, 1.449, and 1.411, respectively.     

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.     

Growth and optical properties of uniform tungsten oxide nanowire bundles via a two-step heating process by thermal evaporation

Tungsten oxide (WO₃) nanowires with diameters of 15-40 nm and lengths of hundreds of nanometers were synthesized by thermal chemical vapor deposition (CVD) without using any catalyst in a low-temperature zone (200-300 °C) of a tube furnace via a two-step heating process. The morphology, composition, and crystal structure were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS), Raman, ultraviolet UV-visible, and cathodoluminescence (CL) spectroscopy. XRD and TEM confirmed that the nanowires were triclinic WO₃ with growth direction along [001]. Blue emission was observed in both the UV-visible and CL spectrum, indicating that the WO₃ nanowires exhibited a red-shift at an optical absorption wavelength due to oxygen deficiencies. The crystallinity and size distribution of the nanowires influenced the bandgap. In the CL spectrum, the blue emission was at shorter wavelengths than reported previously, which can be attributed to the nanoscale size effect.     

Effects of precursor evaporation temperature on the properties of the yttrium oxide thin films deposited by microwave electron cyclotron resonance plasma assisted metal organic chemical vapor deposition

Yttrium oxide thin films are deposited using indigenously developed metal organic precursor (2,2,6,6-tetra methyl-3,5-hepitane dionate) yttrium, commonly known as Y(thd)₃ (synthesized by ultrasound method). Microwave electron cyclotron resonance plasma assisted metal organic chemical vapor deposition process was used for these depositions. Depositions were carried out at a substrate temperature of 350 °C with argon to oxygen gas flow rates fixed to 1 sccm and 10 sccm respectively throughout the experiments. The precursor evaporation temperature (precursor temperature) was varied over a range of 170-275 °C keeping all other parameters constant. The deposited coatings are characterized by X-ray photoelectron spectroscopy, glancing angle X-ray diffraction and infrared spectroscopy. Thickness and refractive index of the coatings are measured by the spectroscopic ellipsometry. Hardness and elastic modulus of the films are measured by load depth sensing nanoindentation technique.C-Y₂O₃ phase is deposited at lower precursor temperature (170 °C). At higher temperature (220 °C) cubic yttrium oxide is deposited with yttrium hydroxide carbonate as a minor phase. When the temperature of the precursor increased (275 °C) further, hexagonal Y₂O₃ with some multiphase structure including body centered cubic yttria and yttrium silicate is observed in the deposited film. The properties of the films drastically change with these structural transitions. These changes in the film properties are correlated here with the precursor evaporation characteristics obtained at low pressures.     

Hard a-SiC:H films formed by remote hydrogen microwave plasma chemical vapor deposition using a novel single-source precursor

The a-SiC:H films were produced by remote hydrogen plasma chemical vapor deposition (RP-CVD) from bis(dimethylsilyl)ethane as a novel single-source precursor. The effect of substrate temperature (T_S) on the kinetics of RP-CVD, chemical composition, structure, surface morphology, and properties of resulting films (density, refractive index, photoluminescence, hardness, elasticity, and resistance to wear) is reported. The T_S dependence of film growth rate implies that RP-CVD is an adsorption controlled process. The increase of T_S from 30 °C to 400 °C causes the elimination of organic moieties from the film and the formation of SiC network structure. The relationships between the relative integrated intensity of SiC IR band and film properties were determined. The films deposited at T_S = 300 °C appear to be very hard materials exhibiting small surface roughness and low intensity of blue photoluminescence (PL). They seem to be suitable protective coatings for metals to increase their wear strength.     

The influence of CH4 addition on composition, structure and optical characteristics of SiCN thin films deposited in a CH4/N2/Ar/hexamethyldisilazane microwave plasma

Amorphous silicon carbonitride (a-SiCN) thin films were synthesized in a microwave plasma assisted chemical vapor deposition system using N₂, Ar, CH₄ and hexamethyldisilazane vapor (HMDSN). Composition, morphology and optical constants of the layers have been studied as a function of CH₄ rate in the range 0 to 9%. It was found that films are mainly composed of silicon nitride like compound whatever the CH₄ rate. However, CH₄ addition leads to less hydrogenated and denser films. In addition, a refractive index augmentation from 1.7 to 2.0 and a Tauc gap decrease from 5.2 eV to 4.8 eV is measured with CH₄ rate increase. It is believed that the refractive index augmentation is due to higher thin film density whereas hydrogen bonds decrease is assumed to contribute to the band gap narrowing. Besides, CH₄ addition to the gaseous mixture increases thin film oxidation resistance. These results show the ability of varying composition, structure and optical constants of a-SiCN films by modifying CH₄ rate in a N₂/Ar/HMDSN plasma.     

Characterization of thin TiO2 films prepared by plasma enhanced chemical vapour deposition for optical and photocatalytic applications

Thin titanium oxide films were deposited using a radio frequency (RF) plasma enhanced chemical vapour deposition method. Their optical properties and thickness were determined by means of ultraviolet-visible absorption spectrophotometry. Films of the optical parameters very close to those of titanium dioxide have been obtained at the high RF power input. Their optical quality is high enough to allow for their use in a construction of stack interference optical filters. At the same time, these materials exhibit strong photocatalytic effects. The results of structural analysis, carried out by Raman Shift Spectroscopy, show that the coatings posses amorphous structure. However, Raman spectra of the same films subjected to thermal annealing at 450 °C disclose an appearance of a crystalline form, namely that of anatase. Surface morphology of the films has also been characterized by Atomic Force Microscopy revealing granular, broccoli-like topography of the films.