Atomic layer deposited protective layers

This paper reviews the use of Atomic Layer Deposition (ALD) in protective coatings. Because of the growth principle ALD allows the deposition of dense conformal films on substrates of different size and shape. Recently, ALD has received increasingly interest in deposition of protective coatings. In protective coatings oxides are the most common materials and especially Al, Ti, and Ta oxides have been applied. The use of nanolaminates enables improving the protection properties. Since ALD films are pinhole-free and often thin they are used to protect against moisture, radiation, out-gassing but not often against corrosion of metals. Very good moisture barriers are obtained with thin ALD oxide layers on polymers and cardboard. This property is also very attractive in encapsulation of OLEDs. In studies of energy technology materials protection of electrodes in Li-ion batteries, fuel cells and supercapacitors by ALD has been reported and significant improvement in the stability has been achieved. Yet another area is protection of silver jewelry from tarnishing by a thin oxide layer. In traditional corrosion protection of metals ALD films have proven to be useful in tailoring of interfaces and sealing of defects in coatings made by other techniques. © 2017 Trans Tech Publications, Switzerland.Peer reviewe

Ambient pressure x-ray photoelectron spectroscopy setup for synchrotron-based in situ and operando atomic layer deposition research

An ambient pressure cell is described for conducting synchrotron-based x-ray photoelectron spectroscopy (XPS) measurements during atomic layer deposition (ALD) processes. The instrument is capable of true in situ and operando experiments in which it is possible to directly obtain elemental and chemical information from the sample surface using XPS as the deposition process is ongoing. The setup is based on the ambient pressure XPS technique, in which sample environments with high pressure (several mbar) can be created without compromising the ultrahigh vacuum requirements needed for the operation of the spectrometer and the synchrotron beamline. The setup is intended for chemical characterization of the surface intermediates during the initial stages of the deposition processes. The SPECIES beamline and the ALD cell provide a unique experimental platform for obtaining new information on the surface chemistry during ALD half-cycles at high temporal resolution. Such information is valuable for understanding the ALD reaction mechanisms and crucial in further developing and improving ALD processes. We demonstrate the capabilities of the setup by studying the deposition of TiO2 on a SiO2 surface by using titanium(IV) tetraisopropoxide and water as precursors. Multiple core levels and the valence band of the substrate surface were followed during the film deposition using ambient pressure XPS.Peer reviewe

TiO2 Photocatalyzed Oxidation of Drugs Studied by Laser Ablation Electrospray Ionization Mass Spectrometry

In drug discovery, it is important to identify phase I metabolic modifications as early as possible to screen for inactivation of drugs and/or activation of prodrugs. As the major class of reactions in phase I metabolism is oxidation reactions, oxidation of drugs with TiO2 photocatalysis can be used as a simple non-biological method to initially eliminate (pro)drug candidates with an undesired phase I oxidation metabolism. Analysis of reaction products is commonly achieved with mass spectrometry coupled to chromatography. However, sample throughput can be substantially increased by eliminating pretreatment steps and exploiting the potential of ambient ionization mass spectrometry (MS). Furthermore, online monitoring of reactions in a time-resolved way would identify sequential modification steps. Here, we introduce a novel (time-resolved) TiO2-photocatalysis laser ablation electrospray ionization (LAESI) MS method for the analysis of drug candidates. This method was proven to be compatible with both TiO2-coated glass slides as well as solutions containing suspended TiO2 nanoparticles, and the results were in excellent agreement with studies on biological oxidation of verapamil, buspirone, testosterone, andarine, and ostarine. Finally, a time-resolved LAESI MS setup was developed and initial results for verapamil showed excellent analytical stability for online photocatalyzed oxidation reactions within the set-up up to at least 1h.Peer reviewe

Molecular organization of the tear fluid lipid layer

The tear fluid protects the corneal epithelium from drying out as well as from invasion by pathogens. It also provides cell nutrients. Similarly to lung surfactant, it is composed of an aqueous phase covered by a lipid layer. Here we describe the molecular organization of the anterior lipid layer of the tear film. Artificial tear fluid lipid layers (ATFLLs) composed of egg yolk phosphatidylcholine (60 mol %), free fatty acids (20 mol %), cholesteryl oleate (10 mol %), and triglycerides (10 mol %) were deposited on the air-water interface and their physico-chemical behavior was compared to egg-yolk phosphatidylcholine monolayers by using Langmuir-film balance techniques, x-ray diffraction, and imaging techniques as well as in silico molecular level simulations. At low surface pressures, ATFLLs were organized at the air-water interface as heterogeneous monomolecular films. Upon compression the ATFLLs collapsed toward the air phase and formed hemispherelike lipid aggregates. This transition was reversible upon relaxation. These results were confirmed by molecular-level simulations of ATFLL, which further provided molecular-scale insight into the molecular distributions inside and dynamics of the tear film. Similar type of behavior is observed in lung surfactant but the folding takes place toward the aqueous phase. The results provide novel information of the function of lipids in the tear fluid

Beam-induced damage on diffractive hard X-ray optics

Beam-induced damage on diffractive hard X-ray optics is studied by means of X-ray diffraction and scanning electron microscopy

Ultrathin Oxide Films by Atomic Layer Deposition on Graphene

In this paper, a method is presented to create and characterize mechanically robust, free standing, ultrathin, oxide films with controlled, nanometer-scale thickness using Atomic Layer Deposition (ALD) on graphene. Aluminum oxide films were deposited onto suspended graphene membranes using ALD. Subsequent etching of the graphene left pure aluminum oxide films only a few atoms in thickness. A pressurized blister test was used to determine that these ultrathin films have a Young's modulus of 154 \pm 13 GPa. This Young's modulus is comparable to much thicker alumina ALD films. This behavior indicates that these ultrathin two-dimensional films have excellent mechanical integrity. The films are also impermeable to standard gases suggesting they are pinhole-free. These continuous ultrathin films are expected to enable new applications in fields such as thin film coatings, membranes and flexible electronics.Comment: Nano Letters (just accepted

Programming nanostructured soft biological surfaces by atomic layer deposition

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

Intercalation of Lithium Ions from Gaseous Precursors into beta-MnO2 Thin Films Deposited by Atomic Layer Deposition

LiMn2O4 is a promising candidate for a cathode material in lithium-ion batteries because of its ability to intercalate lithium ions reversibly through its three-dimensional manganese oxide network. One of the promising techniques for depositing LiMn2O4 thin-film cathodes is atomic layer deposition (ALD). Because of its unparalleled film thickness control and film conformality, ALD helps to fulfill the industry demands for smaller devices, nanostructured electrodes, and all-solid-state batteries. In this work, the intercalation mechanism of Li+ ions into an ALD-grown beta-MnO2 thin film was studied. Samples were prepared by pulsing (LiOBu)-Bu-t and H2O for different cycle numbers onto about 100 nm thick MnO2 films at 225 degrees C and characterized with X-ray absorption spectroscopy, X-ray diffraction, X-ray reflectivity, time-of-flight elastic recoil detection analysis, and residual stress measurements. It is proposed that forPeer reviewe

Role of ALD Al2O3 Surface Passivation on the Performance of p-Type Cu2O Thin Film Transistors

High-performance p- type oxide thin film transistors (TFTs) have great potential for many semiconductor applications. However, these devices typically suffer from low hole mobility and high off-state currents. We fabricated p-type TFTs with a phase-pure polycrystalline Cu2O semiconductor channel grown by atomic layer deposition (ALD). The TFT switching characteristics were improved by applying a thin ALD Al2O3 passivation layer on the Cu2O channel, followed by vacuum annealing at 300 degrees C. Detailed characterization by transmission electron microscopy-energy dispersive X-ray analysis and X-ray photoelectron spectroscopy shows that the surface of Cu2O is reduced following Al2O3 deposition and indicates the formation of a 1-2 nm thick CuAlO2 interfacial layer. This, together with field-effect passivation caused by the high negative fixed charge of the ALD Al2O3, leads to an improvement in the TFT performance by reducing the density of deep trap states as well as by reducing the accumulation of electrons in the semiconducting layer in the device off-state.Peer reviewe