[en] Nanotubular titanium dioxide thin films were prepared by anodization of titanium metal films evaporated on indium tin oxide (ITO) coated glass. A facile method to enhance the adhesion of the titanium film to the ITO glass was developed. An optimum thickness of 550 nm for the evaporated titanium was found to keep the film adhered to ITO during the anodization. The films were further modified by growing amorphous titania, alumina and tantala thin films conformally in the nanotubes by atomic layer deposition (ALD). The optical, electrical and physical properties of the different structures were compared. It was shown that even 5 nm thin layers can modify the properties of the nanotubular titanium dioxide films. (paper)

[en] Nanotubular Ta₂O₅- and TiO₂-based structures were prepared by atomic layer deposition of Ta₂O₅ and TiO₂ thin films, conformally on pore walls of porous alumina membranes. Both self-supporting alumina membranes and Si-supported thin-film membranes were studied as templates. Long Ta₂O₅ and TiO₂ nanotubes were prepared successfully with the self-supporting membranes. The TiO₂ nanotubes showed photocatalytic activity in methylene blue degradation under UV illumination. The Ta₂O₅ and TiO₂ nanotubes were further modified by depositing Pt nanoparticles inside them. The Si-supported thin-film membranes were used as templates for the preparation of robust Ta₂O₅-coated Ni nanorod arrays on a Si substrate using electrodeposition, chemical etching and atomic layer deposition. In addition to photocatalysis, the nanostructures prepared in this work may find applications as other catalysts and as solid-state or electrochemical capacitors.

[en] Here, we present the first successful attempt to programme the surface properties of nanostructured soft biological tissues by atomic layer deposition (ALD). The nanopatterned surface of lotus leaf was tuned by 3–125 nm TiO₂ thin films. The lotus/TiO₂ composites were studied by SEM-EDX, XPS, Raman, TG-DTA, XRR, water contact angle and photocatalysis measurements. While we could preserve the superhydrophobic feature of lotus, we managed to add a new property, i.e. photocatalytic activity. We also explored how surface passivation treatments and various ALD precursors affect the stability of the sensitive soft biological tissues. As we were able to gradually change the number of nanopatterns of lotus, we gained new insight into how the hollow organic nanotubes on the surface of lotus influence its superhydrophobic feature. (paper)

[en] The effect of H_2–Ar plasma pre-treatment prior to thermal atomic layer deposition (ALD) and plasma-enhanced atomic layer deposition (PEALD) of Al_2O_3 films on steel for corrosion protection was investigated. Time-of-flight secondary ion mass spectrometry and transmission electron microscopy were used to observe the changes in the interface. The electrochemical properties of the samples were studied with polarization measurements, and the coating porosities were calculated from the polarization results for easier comparison of the coatings. Prior to thermal ALD the plasma pre-treatment was observed to reduce the amount of impurities at the interface and coating porosity by 1–3 orders of magnitude. The anti-corrosion properties of the PEALD coatings could also be improved by the pre-treatment. However, exposure of the pre-treatment plasma activated steel surface to oxygen plasma species in PEALD led to facile oxide layer formation in the interface. The oxide layer formed this way was thicker than the native oxide layer and appeared to be detrimental to the protective properties of the coating. The best performance for PEALD Al_2O_3 coatings was achieved when, after the plasma pre-treatment, the surface was given time to regrow a thin protective interfacial oxide prior to exposure to the oxygen plasma. The different effects that thermal and plasma-enhanced ALD have on the substrate-coating interface were compared. The reactivity of the oxygen precursor was shown to have a significant influence on substrate surface in the early stages of film growth and thereafter also on the overall quality of the protective film. - Highlights: • Influence of H_2–Ar plasma pre-treatment to ALD coatings on steel was studied. • The pre-treatment modified the coating–substrate interface composition and thickness. • The pre-treatment improved the barrier properties of the coatings

[en] Highlights: ► 5 to 50 nm Al₂O₃ and Ta₂O₅ coatings grown by ALD for protection of stainless steel. ► Lower OH and C trace contamination by precursors at higher growth temperature. ► Iron and chromium oxide present at the buried coating/alloy interface. ► Decrease of coating porosity over four orders of magnitude with thickness increase. ► Marked effect of the coating and interface contaminants on the sealing performance. - Abstract: Ultra-thin (5–50 nm) layers of aluminium and tantalum oxides deposited by atomic layer deposition (ALD) on a stainless steel substrate (316L) for corrosion protection have been investigated by electrochemical methods (linear scan voltammetry, LSV, and electrochemical impedance spectroscopy, EIS) and time-of-flight secondary ion mass spectrometry, ToF-SIMS. The effects of the deposition temperature (250 °C and 160 °C) and coating thickness were addressed. ToF-SIMS elemental depth profiling shows a marked effect of the organic and water precursors used for deposition and of the substrate surface contamination on the level of C and OH trace contamination in the coating, and a beneficial effect of increasing the deposition temperature. The polarization data show a decrease of the current density by up to four orders of magnitude with increasing coating thickness from 5 to 50 nm. The 50 nm films block the pitting corrosion in 0.8 M NaCl. The uncoated surface fraction (quantified from the current density and allowing a ranking of the efficiency of the coating, also confirmed by the capacitance and resistance values extracted from the EIS data) was 0.03% with a 50 nm thick Al₂O₃ film deposited at 250 °C. The correlation between the porosity values of the coatings and the level of C and OH traces observed by ToF-SIMS points to a marked effect of the coating contaminants on the sealing performance of the coatings and on the corrosion resistance of the coated systems.

[en] Highlights: ► 50 nm Ta₂O₅ coatings grown by ALD at 160 °C and FCAD for protection of steel. ► Combined analysis by ToF-SIMS, XPS, polarization curves and EIS. ► Relation between chemical architecture and corrosion protection properties studied. ► Localized corrosion by pitting with absence of coating dissolution demonstrated. ► Origin and role of spurious interfacial oxide promoting coating breakdown emphasized. -- Abstract: A comparative study by Time-of-Flight Secondary Ions Mass Spectrometry and X-ray Photoelectron Spectroscopy, i–E polarization curves and Electrochemical Impedance Spectroscopy of the corrosion protection of low alloy steel by 50 nm thick tantalum oxide coatings prepared by low temperature Atomic Layer Deposition (ALD) and Filtered Cathodic Arc Deposition (FCAD) is reported. The data evidence the presence of a spurious oxide layer mostly consisting of iron grown by transient thermal oxidation at the ALD film/substrate interface in the initial stages of deposition and its suppression by pre-treatment in the FCAD process. Carbonaceous contamination (organic and carbidic) resulting from incomplete removal of the organic precursor is the major cause of the poorer sealing properties of the ALD film. No coating dissolution is demonstrated in neutral or acid 0.2 M NaCl solutions. In acid solution localized corrosion by pitting proceeds faster with the ALD than with the FCAD coating. The roles of the pre-existing channel defects exposing the substrate surface and of the spurious interfacial oxide promoting coating breakdown and/or delamination are emphasized

[en] Highlights: • 40–50 nm mixed alumina–tantala coatings were grown by atomic layer deposition. • Effects of substrate surface finish and oxide mix were analysed. • Nanolaminate stacks are better resistant to breakdown. • Localised corrosion occurs at pre-existing coating defects exposing substrate sites. • Substrate brushing and H₂–Ar plasma pre-treatment hinder pit initiation. - Abstract: A comprehensive study of the corrosion properties of low alloy steel protected by 40–50 nm aluminium and tantalum mixed oxide coatings grown by atomic layer deposition is reported. Electrochemical and surface analysis was performed to address the effect of substrate surface finish and whether an oxide mixture or nanolaminate was used. There was no dissolution or breakdown for nanolaminate alumina/tantala stacks in acidic NaCl solution. Localised corrosion (pitting) took place when defects exposing the substrate pre-existed in the coating. Substrate pre-treatment by brushing and H₂–Ar plasma was instrumental to block or slow down pit initiation by reducing the defect dimensions

[en] Highlights: → 10-100 nm Alumina coatings grown by ALD at 160 ^oC for protection of steel. → Al₂O₃ stoichiometry of the coating and trace contamination by growth precursors. → Iron oxide and siloxane presence at the buried coating/steel interface. → Exponential decay of coating porosity over four orders of magnitude with thickness increase. → Coating thickness increase required to seal the defective first deposited 10 nm. - Abstract: ToF-SIMS, XPS, voltammetry and EIS investigation of the anti-corrosion properties of thin (10, 50 and 100 nm) alumina coatings grown by atomic layer deposition at 160 ^oC on steel is reported. Surface analysis shows a thickness-independent Al₂O₃ stoichiometry of the coating and trace contamination by the growth precursors. The buried coating/alloy interface has iron oxide formed in ambient air and/or resulting from the growth of spurious traces in the initial stages of deposition. Electrochemical analysis yields an exponential decay of the coating porosity over four orders of magnitude with increasing thickness, achieved by sealing of the more defective first deposited 10 nm.

[en] Combined analysis by electrochemical impedance spectroscopy (EIS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and field emission scanning electron microscopy (FESEM) of the corrosion protection provided to carbon steel by thin (50 nm) Al₂O₃ coatings grown by atomic layer deposition (ALD) and its failure mechanism is reported. In spite of excellent sealing properties, the results show an average dissolution rate of the alumina coating of ∼7 nm h^-1 in neutral 0.2 M NaCl and increasing porosity of the remaining layers with increasing immersion time. Alumina dissolution is triggered by the penetration of the solution via cracks/pinholes through the coating to the substrate surface where oxygen reduction takes place, raising the pH. At defective substrate surface sites of high aspect ratio and concentrated residual mechanical stress (along scratches) presumably exposing a higher steel surface fraction, localized dissolution of the coating is promoted by a more facile access of the solution to the substrate surface enhancing oxygen reduction. De-adhesion of the coating is also promoted in these sites by the ingress of the anodic dissolution trenching the steel surface. Localized corrosion of the alloy (i.e. pitting) is triggered prior to complete dissolution of the alumina film on the elsewhere still coated surface matrix.