Anodic growth of highly ordered TiO2 nanotube arrays to 134 microm in length.

Described is the fabrication of self-aligned highly ordered TiO(2) nanotube arrays by potentiostatic anodization of Ti foil having lengths up to 134 mum, representing well over an order of magnitude increase in length thus far reported. We have achieved the very long nanotube arrays in fluoride ion containing baths in combination with a variety of nonaqueous organic polar electrolytes including dimethyl sulfoxide, formamide, ethylene glycol, and N-methylformamide. Depending on the anodization voltage, pore diameters of the resulting nanotube arrays range from 20 to 150 nm. Our longest nanotube arrays yield a roughness factor of 4750 and length-to-width (outer diameter) aspect ratio of approximately 835. The as-prepared nanotubes are amorphous but crystallize with annealing at elevated temperatures. In initial measurements, 45 mum long nanotube-array samples, 550 degrees C annealed, under UV illumination show a remarkable water photoelectrolysis photoconversion efficiency of 16.25%.

Self-assembled hybrid polymer-TiO2 nanotube array heterojunction solar cells.

Films comprised of 4 microm long titanium dioxide nanotube arrays were fabricated by anodizing Ti foils in an ethylene glycol based electrolyte. A carboxylated polythiophene derivative was self-assembled onto the TiO2 nanotube arrays by immersing them in a solution of the polymer. The binding sites of the carboxylate moiety along the polymer chain provide multiple anchoring sites to the substrate, making for a stable rugged film. Backside illuminated liquid junction solar cells based on TiO2 nanotube films sensitized by the self-assembled polymeric layer showed a short-circuit current density of 5.5 mA cm-2, a 0.7 V open circuit potential, and a 0.55 fill factor yielding power conversion efficiencies of 2.1% under AM 1.5 sun. A backside illuminated single heterojunction solid state solar cell using the same self-assembled polymer was demonstrated and yielded a photocurrent density as high as 2.0 mA cm-2. When a double heterojunction was formed by infiltrating a blend of poly(3-hexylthiophene) (P3HT) and C60-methanofullerene into the self-assembled polymer coated nanotube arrays, a photocurrent as high as 6.5 mA cm-2 was obtained under AM 1.5 sun with a corresponding efficiency of 1%. The photocurrent action spectra showed a maximum incident photon-to-electron conversion efficiency (IPCE) of 53% for the liquid junction cells and 25% for the single heterojunction solid state solar cells.

Vertically oriented Ti-Fe-O nanotube array films: toward a useful material architecture for solar spectrum water photoelectrolysis.

In an effort to obtain a material architecture suitable for high-efficiency visible spectrum water photoelectrolysis, herein we report on the fabrication and visible spectrum (380-650 nm) photoelectrochemical properties of self-aligned, vertically oriented Ti-Fe-O nanotube array films. Ti-Fe metal films of variable composition, iron content ranging from 69% to 3.5%, co-sputtered onto FTO-coated glass are anodized in an ethylene glycol + NH4F electrolyte. The resulting amorphous samples are annealed in oxygen at 500 degrees C, resulting in nanotubes composed of a mixed Ti-Fe-O oxide. Some of the iron goes into the titanium lattice substituting titanium ions, and the rest either forms alpha-Fe2O3 crystallites or remains in the amorphous state. Depending upon the Fe content, the band gap of the resulting films ranges from about 380 to 570 nm. The Ti-Fe oxide nanotube array films are utilized in solar spectrum water photoelectrolysis, demonstrating 2 mA/cm2 under AM 1.5 illumination with a sustained, time-energy normalized hydrogen evolution rate by water splitting of 7.1 mL/W.hr in a 1 M KOH solution with a platinum counter electrode under an applied bias of 0.7 V. The surface morphology, structure, elemental analysis, optical, and photoelectrochemical properties of the Ti-Fe oxide nanotube array films are considered.