Raul Zazpe

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).

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.

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.

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.

A 1D conical nanotubular TiO2/CdS heterostructure with superior photon-to-electron conversion

Herein, a new strategy to efficiently harvest photons in solar cells is presented. A solar cell heterostructure is put forward, based on a 1D conical TiO2 nanotubular scaffold of high aspect ratio, homogenously coated with a thin few nm layer of CdS light absorber using atomic layer deposition (ALD). For the first time, a large variety of conical nanotube layers with a huge span of aspect ratios was utilized and ALD was used for the preparation of a uniform CdS coating within the entire high surface area of the TiO2 nanotubes. The resulting 1D conical CdS/TiO2 tubular heterostructure acts as a sink for photons. Due to the multiple light scattering and absorption events within this nanotubular sink, a large portion of photons (nearly 80%) is converted into electrons. It is the combination of the scaffold architecture and the light absorber present on the high surface area as a very thin layer, the optimized charge transport and multiple optical effects that make this heterostructure very promising for the next generation of highly performing solar cells.A novel 1D conical nanotubular CdS/TiO2 heterostructure possesses synergic effects that yield a superior photon-to-electron conversion and shows promising perspectives in photovoltaics.

Spaced TiO2 Nanotubes Enable Optimized Pt Atomic Layer Deposition for Efficient Photocatalytic H2 Generation

Abstract In the present work, we report the use of TiO2 nanotube (NT) layers with a regular intertube spacing that are decorated by Pt nanoparticles through the atomic layer deposition (ALD) of Pt. These Pt‐decorated spaced (SP) TiO2 NTs are subsequently explored for photocatalytic H2 evolution and are compared to classical close‐packed (CP) TiO2 NTs that are also decorated with various amounts of Pt by using ALD. On both tube types, by varying the number of ALD cycles, Pt nanoparticles of different sizes and areal densities are formed, uniformly decorating the inner and outer walls from tube top to tube bottom. The photocatalytic activity for H2 evolution strongly depends on the size and density of Pt nanoparticles, driven by the number of ALD cycles. We show that, for SP NTs, a much higher photocatalytic performance can be achieved with significantly smaller Pt nanoparticles (i.e. for fewer ALD cycles) compared to CP NTs.