Jan M. Macak

Down-scaling of resistive switching to nanoscale using porous anodic alumina membranes

An advanced approach for resistive switching memory cells based on porous anodic alumina (Al2O3) membranes is reported. The effective resistive switching resulting in 6 orders of magnitude difference in resistivity between “on” and “off” states of the cell is achieved by specific electronic and ionic interaction between Ag nanowires filled in the membrane and an ionic conductor (AgxAsS2) deposited on the membrane by thermal evaporation. This easy and robust approach can be exploited for deposition of other ionic conductors for novel types of memories.

Challenges in the surface analytical characterisation of anodic TiO2 films : a review

Abstract Surface analytical findings of thick anodic passive layers on titanium are discussed and analysed in order to give a critical overview about possible artefacts for the system Ti/TiO2. In line with previous studies, the pretreatment of the surface can have an influence on the morphology of the passive film. On polycrystalline surfaces, the oxide film shows a different composition and morphology on differently oriented grains, but although the crystallographic orientation of the substrate influences the thickness and the morphology of the passive layer the defect density does not seem to depend so strongly on the substrate condition. Ion sputtering strongly alters the TiO2 surface morphology and composition which can be directly seen in SEM images of the surface and indirectly from the change in XPS spectra throughout a sputter depth profile. The material removal is not homogeneous and sputtering leads to reduction of the surface oxide. In AES experiments the passive layer on titanium undergoes changes induced by the primary electron beam that is used for the analysis. All these effects make the Ti/Ti-oxide a challenging system particularly when employing surface analytical methods for its investigation. Recent developments like the growth of nanotube structures on titanium give the system a renewed importance.

Atomic Layer Deposition for Coating of High Aspect Ratio TiO2 Nanotube Layers

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).

Polymethacrylate monolithic columns for hydrophilic interaction liquid chromatography prepared using a secondary surface polymerization

Zwitterionic methacrylate based polymeric monolithic columns were prepared in two-step polymerizations, with reduced polymerization times. Characteristic properties such as hydrodynamic permeability, porosity, retention factors, and pore size distribution charts were used for column evaluation. A scaffold column was fabricated by polymerization of poly(lauryl methacrylate-co-tetraethyleneglycol dimethacrylate) and was used without further modification as a support for a poly(N,N-dimethyl-N-methacryloxyethyl-N-(3-sulfopropyl)ammonium betaine-co-bisphenol A glycerolate dimethacrylate) second monolith layer with zwitterionic functionality, for HILIC separations. An additional internal structure was formed by the second monolithic layer. The fabrication procedure was reproducible with RSD<5%. Field emission scanning electron microscopy has also been used to investigate column pore morphology, using a novel technique where the polymeric material is imaged directly, without coverage with a conducting film or particles. The new polar monolithic columns were used for HILIC separations of phenolic acids, flavones, nucleosides, and bases of nucleic acids, with similar efficiencies but different selectivities for zwitterionic methacrylate monolithic columns recently prepared by single step polymerization.

Atomic Layer Deposition Al2O3 Coatings Significantly Improve Thermal, Chemical, and Mechanical Stability of Anodic TiO2 Nanotube Layers

We report on a very significant enhancement of the thermal, chemical, and mechanical stability of self-organized TiO2 nanotubes layers, provided by thin Al2O3 coatings of different thicknesses prepared by atomic layer deposition (ALD). TiO2 nanotube layers coated with Al2O3 coatings exhibit significantly improved thermal stability as illustrated by the preservation of the nanotubular structure upon annealing treatment at high temperatures (870 °C). In addition, a high anatase content is preserved in the nanotube layers against expectation of the total rutile conversion at such a high temperature. Hardness of the resulting nanotube layers is investigated by nanoindentation measurements and shows strongly improved values compared to uncoated counterparts. Finally, it is demonstrated that Al2O3 coatings guarantee unprecedented chemical stability of TiO2 nanotube layers in harsh environments of concentrated H3PO4 solutions.

Fast and robust infiltration of functional material inside titania nanotube layers: case study of a chalcogenide glass sensitizer

Fast and robust infiltration of anodic TiO2 nanotube layers with a model chalcogenide As3S7 glass via spin-coating is reported for the first time. Effective sensitization leads to a significant visible light photocurrent response. This easy and cheap infiltration method can be extended for deposition of other absorbers into nanotubular layers.

Electrochemical Infilling of CuInSe2 within TiO2 Nanotube Layers and Subsequent Photoelectrochemical Studies

Abstract Anodic self‐organized TiO2 nanotube layers (with different aspect ratios) were electrochemically infilled with CuInSe2 nanocrystals with the aim to prepare heterostructures with a photoelectrochemical response in the visible light. The resulting heterostructure assembly was confirmed by field‐emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and X‐ray diffraction (XRD). High incident photon‐to‐electron conversion efficiency values exceeding 55% were obtained in the visible‐light region. The resulting heterostructures show promise as a candidate for solid‐state solar cells.

Evaluation of impedance spectra of ionic-transport materials by a random-walk approach considering electrode and bulk response

Analysis of impedance spectra by a random-walk approach is proposed for the study of ionic-transport materials with a silver-containing chalcogenide glass as a case example. Through a full analysis of complex impedance spectra including the electrode polarization effect, some important physical parameters, such as the number of mobile ions in bulk and interface regions, the diffusion coefficient, etc., are extracted without using the conventional equivalent electric circuit analysis. A detailed discussion on electrode polarization, which is highly dependent on signal amplitude, is also presented.

ALD Al2O3-Coated TiO2 Nanotube Layers as Anodes for Lithium-Ion Batteries

The utilization of the anodic TiO2 nanotube layers, with uniform Al2O3 coatings of different thicknesses (prepared by atomic layer deposition, ALD), as the new electrode material for lithium-ion batteries (LIBs), is reported herein. Electrodes with very thin Al2O3 coatings (∼1 nm) show a superior electrochemical performance for use in LIBs compared to that of the uncoated TiO2 nanotube layers. A more than 2 times higher areal capacity is received on these coated TiO2 nanotube layers (∼75 vs 200 μAh/cm2) as well as higher rate capability and coulombic efficiency of the charging and discharging reactions. Reasons for this can be attributed to an increased mechanical stability of the TiO2 nanotube layers upon Al2O3 coating, as well as to an enhanced diffusion of the Li+ ions within the coated nanotube layers. In contrast, thicker ALD Al2O3 coatings result in a blocking of the electrode surface and therefore an areal capacity decrease.

Ideally Hexagonally Ordered TiO2 Nanotube Arrays

Abstract Ideally hexagonally ordered TiO2 nanotube layers were produced through the optimized anodization of Ti substrates. The Ti substrates were firstly covered with a TiN protecting layer prepared through atomic layer deposition (ALD). Pre‐texturing of the TiN‐protected Ti substrate on an area of 20×20u2005μm2 was carried out by focused ion beam (FIB) milling, yielding uniform nanoholes with a hexagonal arrangement throughout the TiN layer with three different interpore distances. The subsequent anodic nanotube growth using ethylene‐glycol‐based electrolyte followed the pre‐textured nanoholes, resulting in perfectly ordered nanotube layers (resembling honeycomb porous anodic alumina) without any point defects and with a thickness of approximately 2u2005μm over the whole area of the pattern.