Arthur J. Frank

Microstructure and Pseudocapacitive Properties of Electrodes Constructed of Oriented NiO-TiO2 Nanotube Arrays

We report on the synthesis and electrochemical properties of oriented NiO-TiO(2) nanotube (NT) arrays as electrodes for supercapacitors. The morphology of the films prepared by electrochemically anodizing Ni-Ti alloy foils was characterized by scanning and transmission electron microscopies, X-ray diffraction, and photoelectron spectroscopies. The morphology, crystal structure, and composition of the NT films were found to depend on the preparation conditions (anodization voltage and postgrowth annealing temperature). Annealing the as-grown NT arrays to a temperature of 600 °C transformed them from an amorphous phase to a mixture of crystalline rock salt NiO and rutile TiO(2). Changes in the morphology and crystal structure strongly influenced the electrochemical properties of the NT electrodes. Electrodes composed of NT films annealed at 600 °C displayed pseudocapacitor (redox-capacitor) behavior, including rapid charge/discharge kinetics and stable long-term cycling performance. At similar film thicknesses and surface areas, the NT-based electrodes showed a higher rate capability than the randomly packed nanoparticle-based electrodes. Even at the highest scan rate (500 mV/s), the capacitance of the NT electrodes was not much smaller (within 12%) than the capacitance measured at the slowest scan rate (5 mV/s). The faster charge/discharge kinetics of NT electrodes at high scan rates is attributed to the more ordered NT film architecture, which is expected to facilitate electron and ion transport during the charge-discharge reactions.

Rapid Charge Transport in Dye-Sensitized Solar Cells Made from Vertically Aligned Single-Crystal Rutile TiO2 Nanowires†

A rapid solvothermal approach was used to synthesize aligned 1D single-crystal rutile TiO(2) nanowire (NW) arrays on transparent conducting substrates as electrodes for dye-sensitized solar cells. The NW arrays showed a more than 200 times faster charge transport and a factor four lower defect state density than conventional rutile nanoparticle films.

Spatial location of transport-limiting traps in TiO2 nanoparticle films in dye-sensitized solar cells

The dependence of the electron diffusion coefficient and photoinduced electron density on the internal surface area of TiO2 nanoparticle films in dye-sensitized solar cells was investigated by photocurrent transient measurements. The internal surface area was varied by altering the average particle size of the films. The density of electron traps in the films is found to change in direct proportion with the internal surface area, indicating that the traps are located predominately at the surface of TiO2 particles instead of in the bulk of the particles or at interparticle grain boundaries. The observed scaling of the electron diffusion coefficient with the internal surface area suggests that surface traps limit transport in TiO2 nanoparticle films. These results address a long-standing issue in the understanding of electron transport in dye-sensitized TiO2 solar cells.

General Strategy for Fabricating Transparent TiO2 Nanotube Arrays for Dye-Sensitized Photoelectrodes: Illumination Geometry and Transport Properties

We report on the preparation of transparent oriented titania nanotube (NT) photoelectrodes and the effect of illumination direction on light harvesting, electron transport, and recombination in dye-sensitized solar cells (DSSCs) incorporating these electrodes. High solar conversion efficiency requires that the incident light enters the cell from the photoelectrode side. However, it has been synthetically challenging to prepare transparent TiO(2) NT electrodes by directly anodizing Ti metal films on transparent conducting oxide (TCO) substrates because of the difficulties of controlling the synthetic conditions. We describe a general synthetic strategy for fabricating transparent TiO(2) NT films on TCO substrates. With the aid of a conducting Nb-doped TiO(2) (NTO) layer between the Ti film and TCO substrate, the Ti film was anodized completely without degrading the TCO. The NTO layer was found to protect the TCO from degradation through a self-terminating mechanism by arresting the electric field-assisted dissolution process at the NT-NTO interface. The illumination direction and wavelength of the light incident on the DSSCs were shown to strongly influence the incident photon-to-current conversion efficiency, light-harvesting, and charge-collection properties, which, in turn, affect the photocurrent density, photovoltage, and solar energy conversion efficiency. Effects of NT film thickness on the properties and performance of DSSCs were also examined. Illuminating the cell from the photoelectrode substantially increased the conversion efficiency compared with illuminating it from the counter-electrode side.

Determining the locus for photocarrier recombination in dye-sensitized solar cells

We present intensity-modulated photocurrent and infrared transmittance measurements on dye-sensitized solar cells based on a mesoporous titania (TiO2) matrix immersed in an iodine-based electrolyte. Under short-circuit conditions, we show that an elementary analysis accurately relates the two measurements. Under open-circuit conditions, infrared transmittance, and photovoltage measurements yield information on the characteristic depth at which electrons recombine with ions (the “locus of recombination”). For one particular series of samples recombination occurred near the substrate supporting the titania film, as opposed to homogeneously throughout the film.

Constructing Ordered Sensitized Heterojunctions : Bottom-Up Electrochemical Synthesis of p-Type Semiconductors in Oriented n-TiO2 Nanotube Arrays

Fabrication of efficient semiconductor-sensitized bulk heterojunction solar cells requires the complete filling of the pore system of one semiconductor (host) material with nanoscale dimensions (<100 nm) with a different semiconductor (guest) material. Because of the small pore size and electrical conductivity of the host material, it is challenging to employ electrochemical approaches to fill the entire pore network. Typically, during the electrochemical deposition process, the guest material blocks the pores of the host, precluding complete pore filling. We describe a general synthetic strategy for spatially controlling the growth of p-type semiconductors in the nanopores of electrically conducting n-type materials. As an illustration of this strategy, we report on the facile electrochemical deposition of p-CuInSe(2) in nanoporous anatase n-TiO(2) oriented nanotube arrays and nanoparticle films. We show that by controlling the ambipolar diffusion length the p-type semiconductors can be deposited from the bottom-up, resulting in complete pore filling.

Voltage-Enhancement Mechanisms of an Organic Dye in High Open-Circuit Voltage Solid-State Dye-Sensitized Solar Cells

Sensitization of solid-state dye-sensitized solar cells (SSDSSCs) with a new, organic donor-π-acceptor dye with a large molar absorption coefficient led to an open-circuit voltage of over 1 V at AM1.5 solar irradiance (100 mW/cm(2)). Recombination of electrons in the TiO(2) film with the oxidized species in the hole-transfer material (HTM) was significantly slower with the organic dye than with a standard ruthenium complex dye. Density functional theory indicated that steric shielding of the electrons in the TiO(2) by the organic dye was important in reducing recombination. Preventing the loss of photoelectrons resulted in a significant voltage gain. There was no evidence that the organic dye contributed to the high voltage by shifting the band edges to more negative electrode potentials. Compared with an iodide-based liquid electrolyte, however, the more positive redox potential of the solid-state HTM used in the SSDSSCs favored higher voltages.

Electrochemical and Optical Characterization of Poly(3‐methylthiophene) Effects of Solvent, Anion, and Applied Potential

The electrochemical and optical properties of poly(3‐methylthiophene) (PMeT) coatings on electrodes exposed to different electrolytes, solvents, redox species, and applied potential were investigated. Electroanalytical (cyclic voltammetry, chronoamperometry, chronocoulometry, electrode admittance) and spectrophotometric measurements show that the nature of the charge‐compensating dopant anion, the solvent (acetonitrile vs. water), and the applied potential have a profound effect on charge transport through the film. The oxidation (doping) of PMeT films, in contrast to its reduction (undoping), depends on the size of the dopants (, , , and ). The film suffers irreversible loss of electrochemical activity, to varying degrees, in aqueous solutions with ions, such as , , , and phthalate. Ion trapping and slow structural relaxation in the polymeric films introduce hysteresis in the electrochemical and optical data. The doping of the film and the structural relaxation time, associated with its oxidation and reduction, depend strongly on the solvent. The electrochemical activity of PMeT films, in the electronic insulative state, is found to display an unusual dependence on the solvent and the applied potential. The nature of the polymer‐dopant and polymer‐solvent interactions and the mechanism of charge transport in PMeT are discussed.

Synthesis of CdSe-TiO2 nanocomposites and their applications to TiO2 sensitized solar cells.

CdSe-TiO(2) nanocomposites were synthesized via aminolysis of Ti-oleate complexes in the presence of CdSe nanocrystals, and their application as sensitizers for TiO(2) solar cells was investigated. The formation of CdSe-TiO(2) nanocomposites was confirmed using transmission electron microscopy and Raman spectroscopy. The emission spectrum of CdSe-TiO(2) nanocomposites revealed photoinduced charge separation at the CdSe-TiO(2) interface of the composite. The photocurrent-voltage properties of CdSe-TiO(2)-sensitized TiO(2) particle films compared favorably with those of CdSe-sensitized TiO(2) films. Evidence was also found indicating that the TiO(2) component of the composite protects CdSe against degradation during film annealing.

Hole transport in sensitized CdS–NiO nanoparticle photocathodes

A general chemical approach was used to synthesise NiO-CdS core-shell nanoparticle films as photocathodes for p-type semiconductor-sensitized solar cells. Compared to dye-sensitized NiO photocathodes, the CdS-sensitized NiO cathodes exhibited two orders of magnitude faster hole transport (attributable to the passivation of surface traps by the CdS) and almost 100% charge-collection efficiencies.