ABSTRACT
In this work, we report the successful growth of high-quality SiO2 films by low-temperature plasma-enhanced atomic layer deposition using an oxidant which is compatible with moisture/oxygen sensitive materials. The SiO2 films were grown at 90 °C using CO2 and Bis(tertiary-butylamino)silane as process precursors. Growth, chemical composition, density, optical properties, and residual stress of SiO2 films were investigated. SiO2 films having a saturated growth-per-cycle of ~ 1.15 Å/cycle showed a density of ~ 2.1 g/cm3, a refractive index of ~ 1.46 at a wavelength of 632 nm, and a low tensile residual stress of ~ 30 MPa. Furthermore, the films showed low impurity levels with bulk concentrations of ~ 2.4 and ~ 0.17 at. % for hydrogen and nitrogen, respectively, whereas the carbon content was found to be below the measurement limit of time-of-flight elastic recoil detection analysis. These results demonstrate that CO2 is a promising oxidizing precursor for moisture/oxygen sensitive materials related plasma-enhanced atomic layer deposition processes.
ABSTRACT
Corrosion protection of steel obtained with physical vapor deposition (PVD) coatings can be further improved by sealing the intrinsic pinholes with atomic layer deposition (ALD) coatings. In this work, the effect of surface wear on corrosion protection obtained by a hybrid PVD CrN/ALD Al2O3/TiO2 nanolaminate coating was studied. The samples were investigated by alternating surface wear steps and exposure to salt solution and consecutively the progression of corrosion after each wear and each corrosion step was evaluated. Optical microscopy, scanning electron microscopy (SEM), and energy-dispersive spectroscopy showed that the rust spots were almost exclusively located on positions at which the wear steps had removed the top surface of the PVD CrN coating. Nevertheless, even after complete removal of the ALD nanolaminate from the top of the CrN surface by sandpaper grinding, the corrosion current density was less than half compared to the PVD CrN coating alone without surface wear. Cross-sectional SEM images obtained with focused ion beam milling showed not only the presence of the ALD coating at the CrN defects but also the opening of new pathways for the corrosion to attack the substrate. A mechanism for the effect of wear on the structure and corrosion protection of hybrid PVD/ALD coatings is proposed on the basis of this investigation.
ABSTRACT
In this paper, we have optimized a low-temperature atomic layer deposition (ALD) of SiO2 using AP-LTO® 330 and ozone (O3) as precursors, and demonstrated its suitability to surface-modify temperature-sensitive bio-based films of cellulose nanofibrils (CNFs). The lowest temperature for the thermal ALD process was 80°C when the silicon precursor residence time was increased by the stop-flow mode. The SiO2 film deposition rate was dependent on the temperature varying within 1.5-2.2 Å cycle-1 in the temperature range of 80-350°C, respectively. The low-temperature SiO2 process that resulted was combined with the conventional trimethyl aluminium + H2O process in order to prepare thin multilayer nanolaminates on self-standing CNF films. One to six stacks of SiO2/Al2O3 were deposited on the CNF films, with individual layer thicknesses of 3.7 nm and 2.6 nm, respectively, combined with a 5 nm protective SiO2 layer as the top layer. The performance of the multilayer hybrid nanolaminate structures was evaluated with respect to the oxygen and water vapour transmission rates. Six stacks of SiO2/Al2O with a total thickness of approximately 35 nm efficiently prevented oxygen and water molecules from interacting with the CNF film. The oxygen transmission rates analysed at 80% RH decreased from the value for plain CNF film of 130 ml m-2 d-1 to 0.15 ml m-2 d-1, whereas the water transmission rates lowered from 630 ± 50 g m-2 d-1 down to 90 ± 40 g m-2 d-1This article is part of a discussion meeting issue 'New horizons for cellulose nanotechnology'.
