A review on highly ordered, vertically oriented TiO2 nanotube arrays: Fabrication, material properties, and solar energy applications

Described is the fabrication of self-aligned highly ordered TiO2 nanotube arrays by potentiostatic anodization of Ti foil having lengths up to 134 μm, representing well over an order of magnitude i...

Anodic Growth of Highly Ordered TiO2 Nanotube Arrays to 134 μm in Length

The fabrication of highly-ordered TiO2 nanotube arrays up to 134 µm in length by anodization of Ti foil has recently been reported (Paulose et al 2006 J. Phys. Chem. B 110 16179). This work reports an extension of the fabrication technique to achieve TiO2 nanotube arrays up to 220 µm in length, with a length-to-outer diameter aspect ratio of ≈1400, as well as their initial application in dye-sensitized solar cells and hydrogen production by water photoelectrolysis. The highly-ordered TiO2 nanotube arrays are fabricated by potentiostatic anodization of Ti foil in fluoride ion containing baths in combination with non-aqueous organic polar electrolytes including N-methylformamide, dimethyl sulfoxide, formamide, or ethylene glycol. Depending upon the anodization voltage, the inner pore diameters of the resulting nanotube arrays range from 20 to 150 nm. As confirmed by glancing angle x-ray diffraction and HRTEM studies, the as-prepared nanotubes are amorphous but crystallize with annealing at elevated temperatures.

https://iopscience.iop.org/article/10.1088/0957-4484/18/6/065707/pdf

Highly-ordered TiO2 nanotube arrays up to 220 µm in length: use in water photoelectrolysis and dye-sensitized solar cells

Anodization of titanium in a fluorinated dimethyl sulfoxide (DMSO) and ethanol mixture electrolyte is investigated. The prepared anodic film has a highly ordered nanotube-array surface architecture. Using a 20 V anodization potential (vs Pt) nanotube arrays having an inner diameter of 60 nm and 40 nm wall thickness are formed. The overall length of the nanotube arrays is controlled by the duration of the anodization, with nanotubes appearing only after approximately 48 h; a 72 h anodization results in a nanotube array approximately 2.3 μm in length. The photoelectrochemical response of the nanotube-array photoelectrodes is studied using a 1 M KOH solution under both UV and visible (AM 1.5) illumination. Enhanced photocurrent density is observed for samples obtained in the organic electrolyte, with an UV photoconversion efficiency of 10.7%.

Fabrication of Highly Ordered TiO2 Nanotube Arrays Using an Organic Electrolyte

Since first introduced by Zwilling and co-workers in 1999, titania nanotube arrays (TNTAs) fabricated by simple electrochemical anodization method have attracted great interest due to their outstanding photoelectrochemical properties which render them the most promising candidate for many solar energy harvesting applications. In this contribution, the fabrication, properties, and applications of TiO2 nanotube arrays have been reviewed, with special focus on synthesis by anodization in fluoride-containing electrolytes. The effect of anodization process parameters such as electric potential, pH, anodization duration and electrolyte composition on the size, and morphology of TNTAs has been discussed in detail. Electronic property modification strategies of the wide band gap TNTAs to enhance the material responsiveness to visible light irradiation have also been reviewed. Modification strategies include nonmetal doping such as nitrogen, carbon, boron and sulfur; metal ion doping such as Fe, Zn, Zr and Cr; surface decoration with precious metal nanoparticles such as Pt, Ag, Au; and sensitization with CdS nanoparticles.

Modified TiO2 nanotube arrays (TNTAs): progressive strategies towards visible light responsive photoanode, a review

The aim of this work is to explain the influence of the solvent molecules on silicon dissolution using several hydrofluoric acid containing organic electrolytes. The investigations focus on the morphology of the mesopores and macropores and the electrochemical valence of the overall reaction. Some basic properties of the electrolyte (polarity, tendency to form silicon oxide, and the H donor properties) were found to dominate the macropore formation in p-type silicon. For macropore formation the correct balance between the two main dissolution paths (direct silicon dissolution and dissolution via an anodic oxide) is very important. For mesopores in highly doped p- and n-type silicon the direct dissolution is dominant. The consequences of mixing organic and aqueous solutions are discussed.

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K. Voigt

Papers

Organic and aqueous electrolytes used for etching macro- and mesoporous silicon