Ludek Hromadko

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).

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 20×20 μm2 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 2 μm over the whole area of the pattern.

Self-organized double-wall oxide nanotube layers on glass-forming Ti-Zr-Si(-Nb) alloys

In this work, we report for the first time on the use of melt spun glass-forming alloys - Ti75Zr10Si15 (TZS) and Ti60Zr10Si15Nb15 (TZSN) - as substrates for the growth of anodic oxide nanotube layers. Upon their anodization in ethylene glycol based electrolytes, highly ordered nanotube layers were achieved. In comparison to TiO2 nanotube layers grown on Ti foils, under the same conditions for reference, smaller diameter nanotubes (~116nm for TZS and ~90nm for TZSN) and shorter nanotubes (~11.5μm and ~6.5μm for TZS and TZSN, respectively) were obtained for both amorphous alloys. Furthermore, TEM and STEM studies, coupled with EDX analysis, revealed a double-wall structure of the as-grown amorphous oxide nanotubes with Ti species being enriched in the inner wall, and Si species in the outer wall, whereby Zr and Nb species were homogeneously distributed.

Bismuth Oxychloride Nanoplatelets by Breakdown Anodization

Abstract Herein, the synthesis of BiOCl nanoplatelets of various dimensions is demonstrated. These materials were prepared by anodic oxidation of Bi ingots in diluted HCl under dielectric breakdown conditions, triggered by a sufficiently high anodic field. Additionally, it is shown that the use of several other common diluted acids (HNO3, H2SO4, lactic acid) resulted in the formation of various different nanostructures. The addition of NH4F to the acidic electrolytes accelerated the growth rate resulting in bismuth‐based nanostructures with comparably smaller dimensions and an enormous volume expansion observed during the growth. On the other hand, the addition of lactic acid to the acidic electrolytes decelerated the oxide growth rate. The resulting nanostructures were characterized using SEM, XRD and TEM. BiOCl nanoplatelets received by anodization in 1 M HCl were successfully employed for the photocatalytic decomposition of methylene blue dye and showed a superior performance compared to commercially available BiOCl powder with a similar crystalline structure, confirming its potential as a visible light photocatalyst.