Gregory McMahon

Growth of p-Type Hematite by Atomic Layer Deposition and Its Utilization for Improved Solar Water Splitting

Mg-doped hematite (α-Fe(2)O(3)) was synthesized by atomic layer deposition (ALD). The resulting material was identified as p-type with a hole concentration of ca. 1.7 × 10(15) cm(-3). When grown on n-type hematite, the p-type layer was found to create a built-in field that could be used to assist photoelectrochemical water splitting reactions. A nominal 200 mV turn-on voltage shift toward the cathodic direction was measured, which is comparable to what has been measured using water oxidation catalysts. This result suggests that it is possible to achieve desired energetics for solar water splitting directly on metal oxides through advanced material preparations. Similar approaches may be used to mitigate problems caused by energy mismatch between water redox potentials and the band edges of hematite and many other low-cost metal oxides, enabling practical solar water splitting as a means for solar energy storage.

Hematite‐Based Water Splitting with Low Turn‐On Voltages

Sunlight-driven photoelectrochemical (PEC) water splitting offers promise as a method for effective solar-energy harvesting and storage. To transform the reaction into economically competitive technology, we need materials that can absorb sunlight broadly, transfer the energy to excited charges at high efficiencies, and catalyze specific reduction and oxidation reactions. Furthermore, the materials should be inexpensive and stable against photocorrosion. To date, an ideal material that satisfies all of these considerations remains elusive. This challenge can, in principle, be addressed by combining various material components, each purposedesigned to offer desired properties with respect to photovoltage generation, charge transport, and catalytic activity. For example, it has recently been shown that the performance of hematite (a-Fe2O3)-based water splitting can indeed be improved by introducing dedicated charge collectors, buried homoand heterojunctions, and oxygen-evolution catalysts. Hematite was chosen as a prototypical system for these proof-of-concept demonstrations because it is an earth-abundant material with great promise for high-efficiency, low-cost water splitting. To realize the potential of hematite, however, we still need to address a key issue concerning its low photovoltage (Vph, typically 0.4 V), which is unreasonably low given that the bandgap of hematite is 2.0 eV. For successful integration with a small-bandgap photocathode, the photovoltage generated at the photoanode needs to be significantly higher so that a total (combined) photovoltage of 1.61 V (or greater, with a minimum overpotential of 0.38 V) is produced. Herein we show that this issue may be addressed by modifying the hematite surface. When decorated with an amorphous NiFeOx layer (Figure 1), hematite produces photovoltages as high as 0.61 V, which enable the observation of turn-on voltages (Von) as low as 0.62 V (versus the reversible hydrogen electrode, RHE) without the need for a second absorber (unless otherwise noted, all electrochemical potentials reported herein are relative to RHE). When a second absorber, Si, was added, a record-low turn-on voltage of 0.32 V was measured. The basis for our approach is illustrated schematically in Figure 2. The fundamental reason for the observed limited photovoltage generation by hematite lies in the relatively positive positions of its valenceand conduction-band edges. However, even within these limits, the Vph value of 0.6–0.8 V calculated for reported flat-band potentials (Vfb) of 0.4–0.6 V has not been reached.We understand the cause of this discrepancy to be a partial Fermi level pinning effect. That is, owing to the existence of surface states, a nonnegligible potential drop takes place within the Helmholtz layer (hH, Figure 2a). [22] The effect is manifested as a more positive Von value, since a significant portion of the applied potential is used to overcome the overpotential hH (Figure 2c). Appropriate surface modification enables the hH to be minimized or eliminated (Figure 2b) and a less positive Von value to be measured (Figure 2d). The effect of the NiFeOx overlayer was profound: it led to a Von shift from approximately 1.0 V to approximately 0.6 V (Figure 1b). Although the apparent effect of the cathodic Von shift is similar to the effect of reducing the kinetic over[*] C. Du, Dr. X. Yang, Dr. M. T. Mayer, H. Hoyt, J. Xie, Dr. G. McMahon, G. Bischoping, Prof. Dr. D. Wang Department of Chemistry Merkert Chemistry Center, Boston College 2609 Beacon Street, Chestnut Hill, MA, 20467 (USA) E-mail: dunwei.wang@bc.edu Homepage: http://www2.bc.edu/dunwei-wang [] These authors contributed equally to this work.

Enabling unassisted solar water splitting by iron oxide and silicon

Photoelectrochemical (PEC) water splitting promises a solution to the problem of large-scale solar energy storage. However, its development has been impeded by the poor performance of photoanodes, particularly in their capability for photovoltage generation. Many examples employing photovoltaic modules to correct the deficiency for unassisted solar water splitting have been reported to-date. Here we show that, by using the prototypical photoanode material of haematite as a study tool, structural disorders on or near the surfaces are important causes of the low photovoltages. We develop a facile re-growth strategy to reduce surface disorders and as a consequence, a turn-on voltage of 0.45 V (versus reversible hydrogen electrode) is achieved. This result permits us to construct a photoelectrochemical device with a haematite photoanode and Si photocathode to split water at an overall efficiency of 0.91%, with NiFeOx and TiO2/Pt overlayers, respectively.

Forming Buried Junctions to Enhance the Photovoltage Generated by Cuprous Oxide in Aqueous Solutions

Whereas wide-bandgap metal oxides have been extensively studied for the photooxidation of water, their utilization for photoreduction is relatively limited. An important reason is the inability to achieve meaningful photovoltages with these materials. Using Cu2 O as a prototypical photocathode material, it is now shown that the photovoltage barrier can be readily broken by replacing the semiconductor/water interface with a semiconductor/semiconductor one. A thin ZnS layer (ca. 5 nm) was found to form high-quality interfaces with Cu2 O to increase the achievable photovoltage from 0.60 V to 0.72 V. Measurements under no net exchange current conditions confirmed that the change was induced by a thermodynamic shift of the flatband potentials rather than by kinetic factors. The strategy is compatible with efforts aimed at stabilizing the cathode that otherwise easily decomposes and with surface catalyst decorations for faster hydrogen evolution reactions. A combination of NiMo and CoMo dual-layer alloy catalysts was found to be effective in promoting hydrogen production under simulated solar radiation.

Ultrasensitive chemical detection using a nanocoax sensor.

We report on the design, fabrication, and performance of a nanoporous, coaxial array capacitive detector for highly sensitive chemical detection. Composed of an array of vertically aligned nanoscale coaxial electrodes constructed with porous dielectric coax annuli around carbon nanotube cores, this sensor is shown to achieve parts per billion level detection sensitivity, at room temperature, to a broad class of organic molecules. The nanoscale, 3D architecture and microscale array pitch of the sensor enable rapid access of target molecules and chip-based multiplexing capabilities, respectively.

Direct-write, focused ion beam-deposited, 7 K superconducting C–Ga–O nanowire

We have fabricated C–Ga–O nanowires by gallium focused ion beam-induced deposition from the carbon-based precursor phenanthrene. The electrical conductivity of the nanowires is weakly temperature dependent below 300 K and indicates a transition to a superconducting state below Tc=7 K. We have measured the temperature dependence of the upper critical field Hc2(T) and estimate a zero temperature critical field of 8.8 T. The Tc of this material is approximately 40% higher than that of any other direct write nanowire, such as those based on C–W–Ga, expanding the possibility of fabricating direct-write nanostructures that superconduct above liquid helium temperatures.

Imprint-Templated Nanocoax Array Architecture: Fabrication and Utilization

Arrays of vertically-oriented cylindrical, coaxial and triaxial nanostructures are fabricated from polymer nanopillar arrays prepared by nanoimprint lithography. With particular process modifications, these arrays have wide potential utility, including as molecular-scale biological (biomarker, pathogen, etc.) and chemical (explosives, environmental agents, etc.) sensors, high density neuroelectronic interfaces and retinal prostheses, radial junction photovoltaic solar cells, ultracapacitors, and optical metastructures. We report on their fabrication and example utilizations in the latter of these areas, with arrays of typical area density 106 mm−2.