Gopal K. Mor

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

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.

Fabrication of tapered, conical-shaped titania nanotubes

Using anodic oxidation with a time-dependent linearly varying anodization voltage, we have made films of tapered, conical-shaped titania nanotubes. The tapered, conical-shaped nanotubes were obtained by anodizing titanium foil in a 0.5% hydrofluoric acid electrolyte, with the anodization voltage linearly increased from 10-23 V at rates varying from 2.0-0.43 V/min. The linearly increasing anodization voltage results in a linearly increasing nanotube diameter, with the outcome being an array of conical-shaped nanotubes approximately 500 nm in length. Evidence provided by scanning electron-microscope images of the titanium substrate during the initial stages of the anodization process enabled us to propose a mechanism of nanotube formation.

High Carrier Density and Capacitance in TiO2 Nanotube Arrays Induced by Electrochemical Doping

The paper describes the electronic charging and conducting properties of vertically oriented TiO 2 nanotube arrays formed by anodization of Ti foil samples. The resulting films, composed of vertically oriented nanotubes approximately 10 mum long, wall thickness 22 nm, and pore diameter 56 nm, are analyzed using impedance spectroscopy and cyclic voltammetry. Depending on the electrochemical conditions two rather different electronic behaviors are observed. Nanotube array samples in basic medium show behavior analogous to that of nanoparticulate TiO 2 films used in dye-sensitized solar cells: a chemical capacitance and electronic conductivity that increase exponentially with bias potential indicating a displacement of the Fermi level. Nanotube array samples in acidic medium, or samples in a basic medium submitted to a strong negative bias, exhibit a large increase in capacitance and conductivity indicating Fermi level pinning. The contrasting behaviors are ascribed to proton intercalation of the TiO 2. Our results suggest a route for controlling the electronic properties of the ordered metal-oxide nanostructures for their use in applications including supercapacitors, dye-sensitized solar cells, and gas sensing.

Visible to near-infrared light harvesting in TiO2 nanotube array-P3HT based heterojunction solar cells.

The development of high-efficiency solid-state excitonic photovoltaic solar cells compatible with solution processing techniques is a research area of intense interest, with the poor optical harvesting in the red and near-IR (NIR) portion of the solar spectrum a significant limitation to device performance. Herein we present a solid-state solar cell design, consisting of TiO(2) nanotube arrays vertically oriented from the FTO-coated glass substrate, sensitized with unsymmetrical squaraine dye (SQ-1) that absorbs in the red and NIR portion of solar spectrum, and which are uniformly infiltrated with p-type regioregular poly(3-hexylthiophene-2,5-diyl) (P3HT) that absorbs higher energy photons. Our solid-state solar cells exhibit broad, near-UV to NIR, spectral response with external quantum yields of up to 65%. Under UV filtered AM 1.5G of 90 mW/cm(2) intensity we achieve typical device photoconversion efficiencies of 3.2%, with champion device efficiencies of 3.8%.

Highly Efficient Solar Cells using TiO2 Nanotube Arrays Sensitized with a Donor-Antenna Dye

Donor antenna dyes provide an exciting route to improving the efficiency of dye sensitized solar cells owing to their high molar extinction coefficients and the effective spatial separation of charges in the charge-separated state, which decelerates the recombination of photogenerated charges. Vertically oriented TiO(2) nanotube arrays provide an optimal material architecture for photoelectrochemical devices because of their large internal surface area, lower recombination losses, and vectorial charge transport along the nanotube axis. In this study, the results obtained by sensitizing TiO(2) nanotube arrays with the donor antenna dye Ru-TPA-NCS are presented. Solar cells fabricated using an antenna dye-sensitized array of 14.4 microm long TiO(2) nanotubes on Ti foil subjected to AM 1.5 one sun illumination in the backside geometry exhibited an overall conversion efficiency of 6.1%. An efficiency of 4.1% was obtained in the frontside illumination geometry using a 1 microm long array of transparent TiO(2) nanotubes subjected to a TiCl(4) treatment and then sensitized with the Ru-TPA-NCS dye. Open circuit voltage decay measurements give insight into the recombination behavior in antenna-dye sensitized nanotube photoelectrodes, demonstrating outstanding properties likely due to a reduction in the influence of the surface traps and reduced electron transfer from TiO(2) to ions in solution.

P-type Cu--Ti--O nanotube arrays and their use in self-biased heterojunction photoelectrochemical diodes for hydrogen generation.

Copper and titanium remain relatively plentiful in the earths crust; hence, their use for large-scale solar energy conversion technologies is of significant interest. We describe fabrication of vertically oriented p-type Cu-Ti-O nanotube array films by anodization of copper rich (60% to 74%) Ti metal films cosputtered onto fluorine doped tin oxide (FTO) coated glass. Cu-Ti-O nanotube array films 1 mum thick exhibit external quantum efficiencies up to 11%, with a spectral photoresponse indicating that the complete visible spectrum, 380 to 885 nm, contributes significantly to the photocurrent generation. Water-splitting photoelectrochemical pn-junction diodes are fabricated using p-type Cu-Ti-O nanotube array films in combination with n-type TiO 2 nanotube array films. With the glass substrates oriented back-to-back, light is incident upon the UV absorbing n-TiO 2 side, with the visible light passing to the p-Cu-Ti-O side. In a manner analogous to photosynthesis, photocatalytic reactions are powered only by the incident light to generate fuel with oxygen evolved from the n-TiO 2 side of the diode and hydrogen from the p-Cu-Ti-O side. To date, we find under global AM 1.5 illumination that such photocorrosion-stable diodes generate a photocurrent of approximately 0.25 mA/cm (2), at a photoconversion efficiency of 0.30%.

High efficiency double heterojunction polymer photovoltaic cells using highly ordered TiO2 nanotube arrays

Vertically oriented TiO2 nanotube arrays formed by anodization offer a highly ordered material architecture for efficient charge generation and collection in photoelectrochemical devices. A blend of regioregular poly(3-hexylthiophene) and a methanofullerene (phenyl C71-butyric acid methyl ester) was infiltrated into transparent TiO2 nanotube films. The heterojunction poly(3-hexylthiophene) (P3HT)-([6,6]-phenyl-C71-butyric acid methyl ester) and P3HT-TiO2 interfaces both result in charge separation. The resulting solid state solar cells show a short-circuit current density of 12.4mA∕cm2, 641mV open circuit potential, and a 0.51 fill factor, yielding power conversion efficiencies of 4.1% under AM 1.5 sun.

Water-photolysis properties of micron-length highly-ordered titania nanotube-arrays.

We report the water photoelectrolysis and photoelectrochemical properties of the titania nanotube arrays as a function of nanotube crystallinity, length (up to 6.4 microm), and pore size. Most noteworthy of our results, under 320-400 nm illumination (98 mW/cm2) the titania nanotube-array photoanodes (area 1 cm2), pore size 110 nm, wall thickness 20 nm, and 6 microm length, generate hydrogen by water photoelectrolysis at a rate of 7.6 mL/hr, with a photoconversion efficiency of 12.25%. The energy-time normalized hydrogen evolution rate is 80 mL/hrW, the largest reported hydrogen photoelectrolysis generation rate for any material system by a factor of four. The highly-ordered nanotubular architecture appears to allow for superior charge separation and charge transport, with a calculated quantum efficiency of over 80% for incident photons with energies larger than the titania bandgap.

Ta3N5 Nanotube Arrays for Visible Light Water Photoelectrolysis

Tantalum nitride (Ta3N5) has a band gap of approximately 2.07 eV, suitable for collecting more than 45% of the incident solar spectrum energy. We describe a simple method for scale fabrication of highly oriented Ta3N5 nanotube array films, by anodization of tantalum foil to achieve vertically oriented tantalum oxide nanotube arrays followed by a 700 degrees C ammonia anneal for sample crystallization and nitridation. The thin walled amorphous nanotube array structure enables transformation from tantalum oxide to Ta3N5 to occur at relatively low temperatures, while high-temperature annealing related structural aggregation that commonly occurs in particle films is avoided. In 1 M KOH solution, under AM 1.5 illumination with 0.5 V dc bias typical sample (nanotube length approximately 240 nm, wall thickness approximately 7 nm) visible light incident photon conversion efficiencies (IPCE) as high as 5.3% were obtained. The enhanced visible light activity in combination with the ordered one-dimensional nanoarchitecture makes Ta3N5 nanotube arrays films a promising candidate for visible light water photoelectrolysis.

Synthesis and photoelectrochemical properties of nanoporous iron (III) oxide by potentiostatic anodization

We report the synthesis of self-organized nanoporous iron (III) oxide (haematite) via potentiostatic anodization of iron foil. Dependent upon the applied potential and electrolytic composition, the pore diameters range from 50 to 250 nm with a pore depth of approximately 500 nm. We examine the effect of electrolytic composition, anodization bath temperature and applied potential on the dimensions of the as-synthesized nanoporous structure. Crystallization and structural retention of the synthesized structure are achieved upon annealing the initial amorphous sample in a nitrogen atmosphere at 400 °C. The crystallized nanoporous film, having a 2.2 eV bandgap, exhibited a net photocurrent density of 0.51 mA cm−2 in 0.5 M H2O2+1 M NaOH at 0.6 V versus Ag/AgCl under simulated AM 1.5 sunlight. Factors limiting the photoresponse and strategies of improvement are discussed.