Photoelectrochemical water splitting: silicon photocathodes for hydrogen evolution

The development of low cost, scalable, renewable energy technologies is one of today's most pressing scientific challenges. We report on progress towards the development of a photoelectrochemical water-splitting system that will use sunlight and water as the inputs to produce renewable hydrogen with oxygen as a by-product. This system is based on the design principle of incorporating two separate, photosensitive inorganic semiconductor/liquid junctions to collectively generate the 1.7-1.9 V at open circuit needed to support both the oxidation of H_2O (or OH^-) and the reduction of H^+ (or H_2O). Si microwire arrays are a promising photocathode material because the high aspect-ratio electrode architecture allows for the use of low cost, earth-abundant materials without sacrificing energy-conversion efficiency, due to the orthogonalization of light absorption and charge-carrier collection. Additionally, the high surfacearea design of the rod-based semiconductor array inherently lowers the flux of charge carriers over the rod array surface relative to the projected geometric surface of the photoelectrode, thus lowering the photocurrent density at the solid/liquid junction and thereby relaxing the demands on the activity (and cost) of any electrocatalysts. Arrays of Si microwires grown using the Vapor Liquid Solid (VLS) mechanism have been shown to have desirable electronic light absorption properties. We have demonstrated that these arrays can be coated with earth-abundant metallic catalysts and used for photoelectrochemical production of hydrogen. This development is a step towards the demonstration of a complete artificial photosynthetic system, composed of only inexpensive, earth-abundant materials, that is simultaneously efficient, durable, and scalable

pH-Independent, 520 mV Open-Circuit Voltages of Si/Methyl Viologen^(2+/+) Contacts Through Use of Radial n^+p-Si Junction Microwire Array Photoelectrodes

The effects of introducing an n^+-doped emitter layer have been evaluated for both planar Si photoelectrodes and for radial junction Si microwire-array photoelectrodes. In contact with the pH-independent, one-electron, outer-sphere, methyl viologen redox system (denoted MV^(2+/+)), both planar and wire array p-Si photoelectrodes yielded open-circuit voltages, V_(oc), that varied with the pH of the solution. The highest V_(oc) values were obtained at pH = 2.9, with V_(oc) = 0.53 V for planar p-Si electrodes and V_(oc) = 0.42 V for vapor−liquid−solid catalyzed p-Si microwire array samples, under 60 mW cm^(−2) of 808 nm illumination. Increases in the pH of the electrolyte produced a decrease in V_(oc) by approximately −44 mV/pH unit for planar electrodes, with similar trends observed for the Si microwire array electrodes. In contrast, introduction of a highly doped, n^+ emitter layer produced V_(oc) = 0.56 V for planar Si electrodes and V_(oc) = 0.52 V for Si microwire array electrodes, with the photoelectrode properties in each system being essentially independent of pH over six pH units (3 < pH < 9). Hence, formation of an n^+ emitter layer not only produced nearly identical photovoltages for planar and Si microwire array photoelectrodes, but decoupled the band energetics of the semiconductor (and hence the obtainable photovoltage) from the value of the redox potential of the solution. The formation of radial junctions on Si microwire arrays thus provides an approach to obtaining Si-based photoelectrodes with high-photovoltages that can be used for a variety of photoelectrochemical processes, including potentially the hydrogen evolution reaction, under various pH conditions, regardless of the intrinsic barrier height and flat-band properties of the Si/liquid contact

10 µm minority-carrier diffusion lengths in Si wires synthesized by Cu-catalyzed vapor-liquid-solid growth

The effective electron minority-carrier diffusion length, L_(n,eff), for 2.0 µm diameter Si wires that were synthesized by Cu-catalyzed vapor-liquid-solid growth was measured by scanning photocurrent microscopy. In dark, ambient conditions, L_(n,eff) was limited by surface recombination to a value of ≤ 0.7 µm. However, a value of L_(n,eff) = 10.5±1 µm was measured under broad-area illumination in low-level injection. The relatively long minority-carrier diffusion length observed under illumination is consistent with an increased surface passivation resulting from filling of the surface states of the Si wires by photogenerated carriers. These relatively large L_(n,eff) values have important implications for the design of high-efficiency, radial-junction photovoltaic cells from arrays of Si wires synthesized by metal-catalyzed growth processes

Solar Water Splitting Cells

No abstract

Evaluation of Pt, Ni, and Ni–Mo electrocatalysts for hydrogen evolution on crystalline Si electrodes

The dark electrocatalytic and light photocathodic hydrogen evolution properties of Ni, Ni–Mo alloys, and Pt on Si electrodes have been measured, to assess the viability of earth-abundant electrocatalysts for integrated, semiconductor coupled fuel formation. In the dark, the activities of these catalysts deposited on degenerately doped p^+-Si electrodes increased in the order Ni < Ni–Mo ≤ Pt. Ni–Mo deposited on degenerately doped Si microwires exhibited activity that was very similar to that of Pt deposited by metal evaporation on planar Si electrodes. Under 100 mW cm^(−2) of Air Mass 1.5 solar simulation, the energy conversion efficiencies of p-type Si/catalyst photoelectrodes ranged from 0.2–1%, and increased in the order Ni ≈ Ni–Mo < Pt, due to somewhat lower photovoltages and photocurrents for p-Si/Ni–Mo relative to p-Si/Ni and p-Si/Pt photoelectrodes. Deposition of the catalysts onto microwire arrays resulted in higher apparent catalytic activities and similar photoelectrode efficiencies than were observed on planar p-Si photocathodes, despite lower light absorption by p-Si in the microwire structures

High-performance Si microwire photovoltaics

Crystalline Si wires, grown by the vapor–liquid–solid (VLS) process, have emerged as promising candidate materials for lowcost, thin-film photovoltaics. Here, we demonstrate VLS-grown Si microwires that have suitable electrical properties for high-performance photovoltaic applications, including long minority-carrier diffusion lengths (L_n » 30 µm) and low surface recombination velocities (S « 70 cm·s^(-1)). Single-wire radial p–n junction solar cells were fabricated with amorphous silicon and silicon nitride surface coatings, achieving up to 9.0% apparent photovoltaic efficiency, and exhibiting up to ~600 mV open-circuit voltage with over 80% fill factor. Projective single-wire measurements and optoelectronic simulations suggest that large-area Si wire-array solar cells have the potential to exceed 17% energy-conversion efficiency, offering a promising route toward cost-effective crystalline Si photovoltaics

Si microwire-array solar cells

Si microwire-array solar cells with Air Mass 1.5 Global conversion efficiencies of up to 7.9% have been fabricated using an active volume of Si equivalent to a 4 μm thick Si wafer. These solar cells exhibited open-circuit voltages of 500 mV, short-circuit current densities (J_(sc)) of up to 24 mA cm^(-2), and fill factors >65% and employed Al_2O_3 dielectric particles that scattered light incident in the space between the wires, a Ag back reflector that prevented the escape of incident illumination from the back surface of the solar cell, and an a-SiN_x:H passivation/anti-reflection layer. Wire-array solar cells without some or all of these design features were also fabricated to demonstrate the importance of the light-trapping elements in achieving a high J_(sc). Scanning photocurrent microscopy images of the microwire-array solar cells revealed that the higher J_(sc) of the most advanced cell design resulted from an increased absorption of light incident in the space between the wires. Spectral response measurements further revealed that solar cells with light-trapping elements exhibited improved red and infrared response, as compared to solar cells without light-trapping elements

Des langes pour Artémis?

Metal (oxy)­hydroxides (MO_<i>x</i>H_<i>y</i>, M = Fe, Co, Ni, and mixtures thereof) are important materials in electrochemistry. In particular, MO_<i>x</i>H_<i>y</i> are the fastest known catalysts for the oxygen evolution reaction (OER) in alkaline media. While key descriptors such as overpotentials and activity have been thoroughly characterized, the nanostructure and its dynamics under electrochemical conditions are not yet fully understood. Here, we report on the structural evolution of Ni_1−δCo_δO_<i>x</i>H_<i>y</i> nanosheets with varying ratios of Ni to Co, in operando using atomic force microscopy during electrochemical cycling. We found that the addition of Co to NiO_<i>x</i>H_<i>y</i> nanosheets results in a higher porosity of the as-synthesized nanosheets, apparently reducing mechanical stress associated with redox cycling and hence enhancing stability under electrochemical conditions. As opposed to nanosheets composed of pure NiO_<i>x</i>H_<i>y</i>, which dramatically reorganize under electrochemical conditions to form nanoparticle assemblies, restructuring is not found for Ni_1−δCo_δO_<i>x</i>H_<i>y</i> with a high Co content. Ni_0.8Fe_0.2O_<i>x</i>H_<i>y</i> nanosheets show high roughness as-synthesized which increases during electrochemical cycling while the integrity of the nanosheet shape is maintained. These findings enhance the fundamental understanding of MO_<i>x</i>H_<i>y</i> materials and provide insight into how nanostructure and composition affect structural dynamics at the nanoscale

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_2O junction