Nathan S. Lewis

Solar Water Splitting Cells

Energy harvested directly from sunlight offers a desirable approach toward fulfilling, with minimal environmental impact, the need for clean energy. Solar energy is a decentralized and inexhaustible natural resource, with the magnitude of the available solar power striking the earth’s surface at any one instant equal to 130 million 500 MW power plants.1 However, several important goals need to be met to fully utilize solar energy for the global energy demand. First, the means for solar energy conversion, storage, and distribution should be environmentally benign, i.e. protecting ecosystems instead of steadily weakening them. The next important goal is to provide a stable, constant energy flux. Due to the daily and seasonal variability in renewable energy sources such as sunlight, energy harvested from the sun needs to be efficiently converted into chemical fuel that can be stored, transported, and used upon demand. The biggest challenge is whether or not these goals can be met in a costeffective way on the terawatt scale.2

Powering the planet: Chemical challenges in solar energy utilization

Global energy consumption is projected to increase, even in the face of substantial declines in energy intensity, at least 2-fold by midcentury relative to the present because of population and economic growth. This demand could be met, in principle, from fossil energy resources, particularly coal. However, the cumulative nature of CO2 emissions in the atmosphere demands that holding atmospheric CO2 levels to even twice their preanthropogenic values by midcentury will require invention, development, and deployment of schemes for carbon-neutral energy production on a scale commensurate with, or larger than, the entire present-day energy supply from all sources combined. Among renewable energy resources, solar energy is by far the largest exploitable resource, providing more energy in 1 hour to the earth than all of the energy consumed by humans in an entire year. In view of the intermittency of insolation, if solar energy is to be a major primary energy source, it must be stored and dispatched on demand to the end user. An especially attractive approach is to store solar-converted energy in the form of chemical bonds, i.e., in a photosynthetic process at a year-round average efficiency significantly higher than current plants or algae, to reduce land-area requirements. Scientific challenges involved with this process include schemes to capture and convert solar energy and then store the energy in the form of chemical bonds, producing oxygen from water and a reduced fuel such as hydrogen, methane, methanol, or other hydrocarbon species.

Nanostructured Nickel Phosphide as an Electrocatalyst for the Hydrogen Evolution Reaction

Nanoparticles of nickel phosphide (Ni2P) have been investigated for electrocatalytic activity and stability for the hydrogen evolution reaction (HER) in acidic solutions, under which proton exchange membrane-based electrolysis is operational. The catalytically active Ni2P nanoparticles were hollow and faceted to expose a high density of the Ni2P(001) surface, which has previously been predicted based on theory to be an active HER catalyst. The Ni2P nanoparticles had among the highest HER activity of any non-noble metal electrocatalyst reported to date, producing H2(g) with nearly quantitative faradaic yield, while also affording stability in aqueous acidic media.

Comparison of the device physics principles of planar and radial p-n junction nanorod solar cells

A device physics model has been developed for radial p-n junction nanorod solar cells, in which densely packed nanorods, each having a p-n junction in the radial direction, are oriented with the rod axis parallel to the incident light direction. High-aspect-ratio (length/diameter) nanorods allow the use of a sufficient thickness of material to obtain good optical absorption while simultaneously providing short collection lengths for excited carriers in a direction normal to the light absorption. The short collection lengths facilitate the efficient collection of photogenerated carriers in materials with low minority-carrier diffusion lengths. The modeling indicates that the design of the radial p-n junction nanorod device should provide large improvements in efficiency relative to a conventional planar geometry p-n junction solar cell, provided that two conditions are satisfied: (1) In a planar solar cell made from the same absorber material, the diffusion length of minority carriers must be too low to allow for extraction of most of the light-generated carriers in the absorber thickness needed to obtain full light absorption. (2) The rate of carrier recombination in the depletion region must not be too large (for silicon this means that the carrier lifetimes in the depletion region must be longer than ~10 ns). If only condition (1) is satisfied, the modeling indicates that the radial cell design will offer only modest improvements in efficiency relative to a conventional planar cell design. Application to Si and GaAs nanorod solar cells is also discussed in detail.

Enhanced absorption and carrier collection in Si wire arrays for photovoltaic applications

Si wire arrays are a promising architecture for solar-energy-harvesting applications, and may offer a mechanically flexible alternative to Si wafers for photovoltaics. To achieve competitive conversion efficiencies, the wires must absorb sunlight over a broad range of wavelengths and incidence angles, despite occupying only a modest fraction of the arrays volume. Here, we show that arrays having less than 5% areal fraction of wires can achieve up to 96% peak absorption, and that they can absorb up to 85% of day-integrated, above-bandgap direct sunlight. In fact, these arrays show enhanced near-infrared absorption, which allows their overall sunlight absorption to exceed the ray-optics light-trapping absorption limit for an equivalent volume of randomly textured planar Si, over a broad range of incidence angles. We furthermore demonstrate that the light absorbed by Si wire arrays can be collected with a peak external quantum efficiency of 0.89, and that they show broadband, near-unity internal quantum efficiency for carrier collection through a radial semiconductor/liquid junction at the surface of each wire. The observed absorption enhancement and collection efficiency enable a cell geometry that not only uses 1/100th the material of traditional wafer-based devices, but also may offer increased photovoltaic efficiency owing to an effective optical concentration of up to 20 times.

Amorphous TiO2 coatings stabilize Si, GaAs, and GaP photoanodes for efficient water oxidation

Keeping semiconductors safe from harm Solar cells harvest the energy of sunlight to create electricity, but electricity is hard to store. Solar cells could also be used to make hydrogen from water, which can be stored as a fuel. Separating water into hydrogen and oxygen, however, presents challenges, especially if this is done directly by illuminating the anode that oxides water. Under the acidic or alkaline conditions needed for practical devices, semiconducting anode materials corrode during operation. Hu et al. now show that amorphous titanium dioxide coatings can protect semiconductors from alkaline corrosion while still allowing light through. Science, this issue p. 1005 An amorphous titanium oxide coating protects semiconductors by conducting photogenerated charge carriers to nickel catalysts. Although semiconductors such as silicon (Si), gallium arsenide (GaAs), and gallium phosphide (GaP) have band gaps that make them efficient photoanodes for solar fuel production, these materials are unstable in aqueous media. We show that TiO2 coatings (4 to 143 nanometers thick) grown by atomic layer deposition prevent corrosion, have electronic defects that promote hole conduction, and are sufficiently transparent to reach the light-limited performance of protected semiconductors. In conjunction with a thin layer or islands of Ni oxide electrocatalysts, Si photoanodes exhibited continuous oxidation of 1.0 molar aqueous KOH to O2 for more than 100 hours at photocurrent densities of >30 milliamperes per square centimeter and ~100% Faradaic efficiency. TiO2-coated GaAs and GaP photoelectrodes exhibited photovoltages of 0.81 and 0.59 V and light-limiting photocurrent densities of 14.3 and 3.4 milliamperes per square centimeter, respectively, for water oxidation.

Highly Active Electrocatalysis of the Hydrogen Evolution Reaction by Cobalt Phosphide Nanoparticles

Nanoparticles of cobalt phosphide, CoP, have been prepared and evaluated as electrocatalysts for the hydrogen evolution reaction (HER) under strongly acidic conditions (0.50 M H2SO4, pH 0.3). Uniform, multi-faceted CoP nanoparticles were synthesized by reacting Co nanoparticles with trioctylphosphine. Electrodes comprised of CoP nanoparticles on a Ti support (2 mg cm(-2) mass loading) produced a cathodic current density of 20 mA cm(-2) at an overpotential of -85 mV. The CoP/Ti electrodes were stable over 24 h of sustained hydrogen production in 0.50 M H2SO4. The activity was essentially unchanged after 400 cyclic voltammetric sweeps, suggesting long-term viability under operating conditions. CoP is therefore amongst the most active, acid-stable, earth-abundant HER electrocatalysts reported to date.

Photovoltaic Measurements in Single-Nanowire Silicon Solar Cells

Single-nanowire solar cells were created by forming rectifying junctions in electrically contacted vapor-liquid-solid-grown Si nanowires. The nanowires had diameters in the range of 200 nm to 1.5 microm. Dark and light current-voltage measurements were made under simulated Air Mass 1.5 global illumination. Photovoltaic spectral response measurements were also performed. Scanning photocurrent microscopy indicated that the Si nanowire devices had minority carrier diffusion lengths of approximately 2 microm. Assuming bulk-dominated recombination, this value corresponds to a minimum carrier lifetime of approximately 15 ns, or assuming surface-dominated recombination, to a maximum surface recombination velocity of approximately 1350 cm s(-1). The methods described herein comprise a valuable platform for measuring the properties of semiconductor nanowires, and are expected to be instrumental when designing an efficient macroscopic solar cell based on arrays of such nanostructures.

Photoelectrochemical Hydrogen Evolution Using Si Microwire Arrays

Arrays of B-doped p-Si microwires, diffusion-doped with P to form a radial n(+) emitter and subsequently coated with a 1.5-nm-thick discontinuous film of evaporated Pt, were used as photocathodes for H(2) evolution from water. These electrodes yielded thermodynamically based energy-conversion efficiencies >5% under 1 sun solar simulation, despite absorbing less than 50% of the above-band-gap incident photons. Analogous p-Si wire-array electrodes yielded efficiencies <0.2%, largely limited by the low photovoltage generated at the p-Si/H(2)O junction.

Energy-Conversion Properties of Vapor-Liquid-Solid–Grown Silicon Wire-Array Photocathodes

Silicon Microwires as Photocathodes Solar hydrogen generation will require the development of photocathodes with high surface area, durability, and efficiency. Silicon microwire arrays, which allow for greater light penetration, could achieve this goal if the carrier mobilities are sufficiently high so that surface reactions occur before charges recombine. Boettcher et al. (p. 185) report the electronic properties on positively doped silicon microwire arrays that were grown with copper catalysts and used in a methyl viologen redox system. Although equivalent efficiencies for normal solar fluxes were only 2 to 3%, the high internal efficiencies and low use of the available optical flux suggest that further improvements are possible. The use of copper catalysts helps to increase charge-carrier mobilities in silicon microwire growth. Silicon wire arrays, though attractive materials for use in photovoltaics and as photocathodes for hydrogen generation, have to date exhibited poor performance. Using a copper-catalyzed, vapor-liquid-solid–growth process, SiCl4 and BCl3 were used to grow ordered arrays of crystalline p-type silicon (p-Si) microwires on p+-Si(111) substrates. When these wire arrays were used as photocathodes in contact with an aqueous methyl viologen2+/+ electrolyte, energy-conversion efficiencies of up to 3% were observed for monochromatic 808-nanometer light at fluxes comparable to solar illumination, despite an external quantum yield at short circuit of only 0.2. Internal quantum yields were at least 0.7, demonstrating that the measured photocurrents were limited by light absorption in the wire arrays, which filled only 4% of the incident optical plane in our test devices. The inherent performance of these wires thus conceptually allows the development of efficient photovoltaic and photoelectrochemical energy-conversion devices based on a radial junction platform.