Nathan R. Neale

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.

Size and Bandgap Control in the Solution-Phase Synthesis of Near-Infrared-Emitting Germanium Nanocrystals

We present a novel colloidal synthesis of alkyl-terminated Ge nanocrystals based on the reduction of GeI(4)/GeI(2) mixtures. The size of the nanocrystals (2.3-11.3 nm) was controlled by adjusting both the Ge(IV)/Ge(II) ratio and the temperature ramp rate following reductant injection. The near-infrared absorption (1.6-0.70 eV) and corresponding band-edge emission demonstrate the highly tunable quantum confinement effects in Ge nanocrystals prepared using this mixed-valence precursor method. A mechanism is proposed for the observed size control, which relies upon the difference in reduction temperatures for Ge(II) versus Ge(IV).

Water reduction by a p-GaInP2 photoelectrode stabilized by an amorphous TiO2 coating and a molecular cobalt catalyst.

Producing hydrogen through solar water splitting requires the coverage of large land areas. Abundant metal-based molecular catalysts offer scalability, but only if they match noble metal activities. We report on a highly active p-GaInP2 photocathode protected through a 35-nm TiO2 layer functionalized by a cobaloxime molecular catalyst (GaInP2-TiO2-cobaloxime). This photoelectrode mediates H2 production with a current density of ∼9 mA cm(-2) at a potential of 0 V versus RHE under 1-sun illumination at pH 13. The calculated turnover number for the catalyst during a 20-h period is 139,000, with an average turnover frequency of 1.9 s(-1). Bare GaInP2 shows a rapid current decay, whereas the GaInP2-TiO2-cobaloxime electrode shows ≤5% loss over 20 min, comparable to a GaInP2-TiO2-Pt catalyst particle-modified interface. The activity and corrosion resistance of the GaInP2-TiO2-cobaloxime photocathode in basic solution is made possible by an atomic layer-deposited TiO2 and an attached cobaloxime catalyst.

Hypervalent surface interactions for colloidal stability and doping of silicon nanocrystals

Colloidal semiconductor nanocrystals have attracted attention for cost-effective, solution-based deposition of quantum-confined thin films for optoelectronics. However, two significant challenges must be addressed before practical nanocrystal-based devices can be realized. The first is coping with the ligands that terminate the nanocrystal surfaces. Though ligands provide the colloidal stability needed to cast thin films from solution, these ligands dramatically hinder charge carrier transport in the resulting film. Second, after a conductive film is achieved, doping has proven difficult for further control of the optoelectronic properties of the film. Here we report the ability to confront both of these challenges by exploiting the ability of silicon to engage in hypervalent interactions with hard donor molecules. For the first time, we demonstrate the significant potential of applying the interaction to the nanocrystal surface. In this study, hypervalent interactions are shown to provide colloidal stability as well as doping of silicon nanocrystals.

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.

Control of plasmonic and interband transitions in colloidal indium nitride nanocrystals.

We have developed a colloidal synthesis of 4-10 nm diameter indium nitride (InN) nanocrystals that exhibit both a visible absorption onset (∼1.8 eV) and a strong localized surface plasmon resonance absorption in the mid-infrared (∼3000 nm). Chemical oxidation and reduction reversibly modulate both the position and intensity of this plasmon feature as well as the band-to-band absorption onset. Chemical oxidation of InN nanocrystals with NOBF4 is found to red-shift the absorption onset to ∼1.3 eV and reduce the plasmon absorption energy (to 3550 nm) and intensity (by an order of magnitude at 2600 nm). Reduction of these oxidized species with Bu4NBH4 fully recovers the original optical properties. Calculations suggest that the carrier density in these InN nanocrystals decreases upon oxidation from 2.89 × 10(20) cm(-3) to 2.51 × 10(20) cm(-3), consistent with the removal of ∼4 electrons per nanocrystal. This study provides a unique example of the ability to tune the optical properties of colloidal nanomaterials, and in particular the LSPR absorption, with reversible redox reactions that do not affect the semiconductor chemical composition or phase.

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.

Perturbation of the electron transport mechanism by proton intercalation in nanoporous TiO2 films.

This study addresses a long-standing controversy about the electron-transport mechanism in porous metal oxide semiconductor films that are commonly used in dye-sensitized solar cells and related systems. We investigated, by temperature-dependent time-of-flight measurements, the influence of proton intercalation on the electron-transport properties of nanoporous TiO(2) films exposed to an ethanol electrolyte containing different percentages of water (0-10%). These measurements revealed that increasing the water content in the electrolyte led to increased proton intercalation into the TiO(2) films, slower transport, and a dramatic change in the dependence of the thermal activation energy (E(a)) of the electron diffusion coefficient on the photogenerated electron density in the films. Random walk simulations based on a microscopic model incorporating exponential conduction band tail (CBT) trap states combined with a proton-induced shallow trap level with a long residence time accounted for the observed effects of proton intercalation on E(a). Application of this model to the experimental results explains the conditions under which E(a) dependence on the photoelectron density is consistent with multiple trapping in exponential CBT states and under which it appears at variance with this model.

Semiconductor Interfacial Carrier Dynamics via Photoinduced Electric Fields

Charge separation viewed in reflection When light strikes a semiconductor, excited electrons travel across the interface. Y. Yang et al. applied ultrafast reflection spectroscopy to probe this process in a gallium indium phosphide system used for hydrogen generation from water (see the Perspective by Hansen et al.). Platinum and titanium dioxide (TiO2) coatings enhanced charge separation of the excited electrons from the positive holes they left behind. TiO2, however, was more effective at suppressing the reverse process of unproductive recombination. Science, this issue p. 1061; see also p. 1030 Reflection spectroscopy offers insights into the boost to charge separation conferred by TiO2 coatings on photoelectrodes. [Also see Perspective by Hansen] Solar photoconversion in semiconductors is driven by charge separation at the interface of the semiconductor and contacting layers. Here we demonstrate that time-resolved photoinduced reflectance from a semiconductor captures interfacial carrier dynamics. We applied this transient photoreflectance method to study charge transfer at p-type gallium-indium phosphide (p-GaInP2) interfaces critically important to solar-driven water splitting. We monitored the formation and decay of transient electric fields that form upon photoexcitation within bare p-GaInP2, p-GaInP2/platinum (Pt), and p-GaInP2/amorphous titania (TiO2) interfaces. The data show that a field at both the p-GaInP2/Pt and p-GaInP2/TiO2 interfaces drives charge separation. Additionally, the charge recombination rate at the p-GaInP2/TiO2 interface is greatly reduced owing to its p-n nature, compared with the Schottky nature of the p-GaInP2/Pt interface.