We present an optimized approach for the deposition of Al2O3 (as a model secondary material) coating into high aspect ratio (≈180) anodic TiO2 nanotube layers using the atomic layer deposition (ALD) process. In order to study the influence of the diffusion of the Al2O3 precursors on the resulting coating thickness, ALD processes with different exposure times (i.e., 0.5, 2, 5, and 10 s) of the trimethylaluminum (TMA) precursor were performed. Uniform coating of the nanotube interiors was achieved with longer exposure times (5 and 10 s), as verified by detailed scanning electron microscopy analysis. Quartz crystal microbalance measurements were used to monitor the deposition process and its particular features due to the tube diameter gradient. Finally, theoretical calculations were performed to calculate the minimum precursor exposure time to attain uniform coating. Theoretical values on the diffusion regime matched with the experimental results and helped to obtain valuable information for further optimization of ALD coating processes. The presented approach provides a straightforward solution toward the development of many novel devices, based on a high surface area interface between TiO2 nanotubes and a secondary material (such as Al2O3).

The first catalytic enantioselective Reissert reaction of pyridine derivatives that affords products with excellent regio- and enantioselectivity is described. The key for success is the development of new Lewis acid-Lewis base bifunctional asymmetric catalysts containing an aluminum as a Lewis acid and sulfoxides or phosphine sulfides as a Lewis base. These reactions are useful for the synthesis of a variety of chiral piperidine subunits, and catalytic enantioselective formal synthesis of CP-293,019, a selective D4 receptor antagonist, was achieved. Preliminary mechanistic studies indicated that both sulfoxides and phosphine sulfides can activate TMSCN as a Lewis base. In addition, the sulfoxides with appropriate stereochemistry might stabilize a highly enantioselective bimetallic complex (a presumed active catalyst) through internal coordination to aluminum.

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An efficient palladium catalyst supported on fibrous silica nanospheres (KCC‐1) has been developed for the hydrogenation of alkenes and α,β‐unsaturated carbonyl compounds, providing excellent yields of the corresponding products with remarkable chemoselectivity. Comparison (high‐resolution TEM, chemisorption) with analogous mesoporous (MCM‐41, SBA‐15) silica‐supported Pd nanocatalysts prepared under identical conditions, demonstrates the advantage of employing the fibrous KCC‐1 morphology versus traditional supports because it ensures superior accessibility of the catalytically active cores along with excellent Pd dispersion at high metal loading. This morphology ultimately leads to higher catalytic activity for the KCC‐1‐supported nanoparticles. The protocol developed for hydrogenation is advantageous and environmentally benign owing to the use of HCOOH as a source of hydrogen, water as a solvent, and because of efficient catalyst recyclability and durability. The recycled catalyst has been analyzed by XPS spectroscopy and TEM showing only minor changes in the oxidation state of Pd and in the morphology after the reaction, thus confirming the robustness of the catalyst.

The water vapor barrier properties of low-temperature atomic layer deposited (ALD) AlOx thin-films are observed to be unstable if exposed directly to high or even ambient relative humidities. Upon exposure to humid atmospheres, their apparent barrier breaks down and their water vapor transmission rates (WVTR), measured by electrical calcium tests, deteriorate by several orders of magnitude. These changes are accompanied by surface roughening beyond the original thickness, observed by atomic force microscopy. X-ray reflectivity investigations show a strong decrease in density caused by only 5 min storage in a 38 °C, 90% relative humidity climate. We show that barrier stabilities required for device applications can be achieved by protection layers which prevent the direct contact of water condensing on the surface, i.e., the sensitive ALD barrier. Nine different protection layers of either ALD materials or polymers are tested on the barriers. Although ALD materials prove to be ineffective, applied polymers seem to provide good protection independent of thickness, surface free energy, and deposition technique. A glued-on PET foil stands out as a low-cost, easily processed, and especially stable solution. This way, 20 nm single layer ALD barriers for organic electronics are measured. They yield reliable WVTRs down to 2×10(-5) g(H2O) m(-2) day(-1) at 38 °C and 90% relative humidity, highlighting the great potential of ALD encapsulation.

In this work, a process for the thermal activated atomic layer deposition (ALD) of ruthenium from the organometallic heteroleptic precursor [(ethylcyclopentadienyl)(pyrrolyl)ruthenium] with molecular oxygen was developed and characterized. Silicon substrates were precleaned in hydrofluoric acid and preheated to a specific temperature before coating with ruthenium. The corresponding cycle-by-cycle growth was monitored throughout the entire ALD process time, utilizing an in-situ real-time spectroscopic ellipsometer. Transmission electron microscopy and atomic force microscopy were applied at a reference sample to generate an appropriate optical model for the translation of the ellipsometric spectra into Ru film thicknesses. Given a representative set of process parameters the cycle-by-cycle growth was studied in detail, obtaining information about incubation, nucleation, linear growth and delamination. In order to determine the ALD characteristic dependencies, the following process parameters were varied while applying ellipsometry during the linear film growth regime on as-deposited ruthenium film surfaces; thus excluding effects from the initial foreign substrate material: both reactant doses and purging times, the substrate temperature and the total pressure. During the respective film growth experiments, one process parameter-setting was changed each 15 ALD cycles, which enabled a fast and extensive process development.

Plasma-enhanced atomic layer deposition (PE-ALD) of cobalt (Co) using cyclopentadienylcobalt dicarbonyl [CpCo(CO)2] combined with hydrogen, nitrogen, ammonia, and argon based plasma gases was investigated. The utilized ALD tool was clustered to an ultrahigh vacuum analytic system for direct surface analyses including X-ray photoelectron spectroscopy (XPS). The combination with a nondestructive surface analysis system enabled a sample transfer without vacuum break and thereby a direct qualification and quantification of the chemical surface composition under quasi in situ conditions. The authors studied the influence of process parameters (e.g., pulse times, plasma power, and substrate temperature) on film compositions and film properties. The occurrence and prevention of sputtering effects due to ion bombardment at high plasma powers were discussed. Beyond those results, precise information about the impact of different plasma gas compositions on the resulting film properties was obtained. Cobalt films grown using a hydrogen/nitrogen (H2/N2) plasma as a coreactant showed a stable film composition (CoNx) with a high Co content of 75 at. %. Using scanning electron microscopy and four point probe measurements, a moderate electrical resistivity of about 56 μΩ cm was calculated for a 20 nm film. The high sensitivity of in vacuo XPS measurements allowed investigations of interface reactions for a single PE-ALD pulse as well as investigations of the initial film growth mechanisms. The nucleation of CoNx films during PE-ALD using H2/N2 plasma as a coreactant was investigated on several substrate materials by XPS. After the very first cycle of the PE-ALD process, no Co could be detected on all the investigated substrates. XPS revealed that the plasma pulse was needed to provide active binding sites for the adsorption reaction of precursor molecules due to the formation of Si-Nx or Si-NxOy surfaces. Therefore, the plasma pulse plays an important role in the PE-ALD process of Co on silicon surfaces. The early cycles were characterized by the onset of Co—O bonds. The homogeneous film body on all substrates consisted of Co-nitride compounds.

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