Katherine T. Fountaine

Photoelectrochemistry of core–shell tandem junction n–p^+-Si/n-WO_3 microwire array photoelectrodes

Tandem junction (n–p^+-Si/ITO/WO_3/liquid) core–shell microwire devices for solar-driven water splitting have been designed, fabricated and investigated photoelectrochemically. The tandem devices exhibited open-circuit potentials of E_(∝) = −1.21 V versus E^0′(O_2/H_2O), demonstrating additive voltages across the individual junctions (n–p^+-Si E_(∝) = −0.5 V versus solution; WO_3/liquid E_(∝) = −0.73 V versus E^0′(O_2/H_2O)). Optical concentration (12×, AM1.5D) shifted the open-circuit potential to E_(∝) = −1.27 V versus E^0′(O_2/H_2O) and resulted in unassisted H_2 production during two-electrode measurements (anode: tandem device, cathode: Pt disc). The solar energy-conversion efficiencies were very low, 0.0068% and 0.0019% when the cathode compartment was saturated with Ar or H_2, respectively, due to the non-optimal photovoltage and band-gap of the WO_3 that was used in the demonstration system to obtain stability of all of the system components under common operating conditions while also insuring product separation for safety purposes.

Optical, electrical, and solar energy-conversion properties of gallium arsenide nanowire-array photoanodes

Periodic arrays of n-GaAs nanowires have been grown by selective-area metal–organic chemical-vapor deposition on Si and GaAs substrates. The optical absorption characteristics of the nanowire-arrays were investigated experimentally and theoretically, and the photoelectrochemical energy-conversion properties of GaAs nanowire arrays were evaluated in contact with one-electron, reversible, redox species in non-aqueous solvents. The radial semiconductor/liquid junction in the nanowires produced near-unity external carrier-collection efficiencies for nanowire-array photoanodes in contact with nonaqueous electrolytes. These anodes exhibited overall inherent photoelectrode energy-conversion efficiencies of � 8.1% under 100 mW cm � 2 simulated Air Mass 1.5 illumination, with open-circuit photovoltages of 590 � 15 mV and short-circuit current densities of 24.6 � 2.0 mA cm � 2 . The high optical absorption, and minimal reflection, at both normal and off-normal incidence of the GaAs nanowire arrays that occupy <5% of the fractional area of the electrode can be attributed to efficient incoupling into radial nanowire guided and leaky waveguide modes. Broader context Due to the voltage requirements to produce fuels from sunlight, water, and CO2 as the inputs, two light-absorbing materials, with band gaps of 1.7 eV and 1.1 eV, respectively, are attractive as the foundation for high-efficiency articial photosynthesis. The integration of materials with 1.7 and 1.1 eV band gaps is, however, very challenging. Accordingly, a nanowire-growth strategy has been developed to integrate single crystal III–V nanowires (e.g. GaAs) with highly mismatched Si substrates. In this work, GaAs nanowire arrays grown on Si were studied using a non-destructive contact method involving non-aqueous photoelectrochemistry. The approach has allowed us to understand the interplay of nanowire growth with the optical absorption and electrical properties of such systems, and will aid in the design and optimization of nanowire-based systems for solar energy-conversion applications. Photoelectrolysis of water for the production of renewable H2 from sunlight faces a constraint in that a potential difference of 1.23 V is required thermodynamically to sustain the watersplitting reaction under standard conditions. In an integrated photoelectrochemical system for water splitting, the operating voltage produced by the light absorber should exceed the sum of

Resonant absorption in semiconductor nanowires and nanowire arrays: Relating leaky waveguide modes to Bloch photonic crystal modes

We present a unified framework for resonant absorption in periodic arrays of high index semiconductor nanowires that combines a leaky waveguide theory perspective and that of photonic crystals supporting Bloch modes, as array density transitions from sparse to dense. Full dispersion relations are calculated for each mode at varying illumination angles using the eigenvalue equation for leaky waveguide modes of an infinite dielectric cylinder. The dispersion relations along with symmetry arguments explain the selectivity of mode excitation and spectral red-shifting of absorption for illumination parallel to the nanowire axis in comparison to perpendicular illumination. Analysis of photonic crystal band dispersion for varying array density illustrates that the modes responsible for resonant nanowire absorption emerge from the leaky waveguide modes.

Experimental Demonstration of >230° Phase Modulation in Gate-Tunable Graphene–Gold Reconfigurable Mid-Infrared Metasurfaces

Metasurfaces offer significant potential to control far-field light propagation through the engineering of the amplitude, polarization, and phase at an interface. We report here the phase modulation of an electronically reconfigurable metasurface and demonstrate its utility for mid-infrared beam steering. Using a gate-tunable graphene-gold resonator geometry, we demonstrate highly tunable reflected phase at multiple wavelengths and show up to 237° phase modulation range at an operating wavelength of 8.50 μm. We observe a smooth monotonic modulation of phase with applied voltage from 0° to 206° at a wavelength of 8.70 μm. Based on these experimental data, we demonstrate with antenna array calculations an average beam steering efficiency of 23% for reflected light for angles up to 30° for this range of phases, confirming the suitability of this geometry for reconfigurable mid-infrared beam steering devices. By incorporating all nonidealities of the device into the antenna array calculations including absorption losses which could be mitigated, 1% absolute efficiency is achievable up to 30°.

Efficiency limits for photoelectrochemical water-splitting

Theoretical limiting efficiencies have a critical role in determining technological viability and expectations for device prototypes, as evidenced by the photovoltaics communitys focus on detailed balance. However, due to their multicomponent nature, photoelectrochemical devices do not have an equivalent analogue to detailed balance, and reported theoretical efficiency limits vary depending on the assumptions made. Here we introduce a unified framework for photoelectrochemical device performance through which all previous limiting efficiencies can be understood and contextualized. Ideal and experimentally realistic limiting efficiencies are presented, and then generalized using five representative parameters—semiconductor absorption fraction, external radiative efficiency, series resistance, shunt resistance and catalytic exchange current density—to account for imperfect light absorption, charge transport and catalysis. Finally, we discuss the origin of deviations between the limits discussed herein and reported water-splitting efficiencies. This analysis provides insight into the primary factors that determine device performance and a powerful handle to improve device efficiency.

Modeling, Simulation, and Implementation of Solar-Driven Water-Splitting Devices.

An integrated cell for the solar-driven splitting of water consists of multiple functional components and couples various photoelectrochemical (PEC) processes at different length and time scales. The overall solar-to-hydrogen (STH) conversion efficiency of such a system depends on the performance and materials properties of the individual components as well as on the component integration, overall device architecture, and system operating conditions. This Review focuses on the modeling- and simulation-guided development and implementation of solar-driven water-splitting prototypes from a holistic viewpoint that explores the various interplays between the components. The underlying physics and interactions at the cell level is are reviewed and discussed, followed by an overview of the use of the cell model to provide target properties of materials and guide the design of a range of traditional and unique device architectures.

Current-voltage characteristics of coupled photodiode-electrocatalyst devices

Analytical expressions for the illuminated current-voltage characteristics of coupled photodiode-electrocatalyst fuel forming devices are derived. The approach is based on combining solid-state diode behavior with metal electrochemistry via the diode equation and the Butler-Volmer equation (charge transfer coefficients: α_A = α_C = α) or the Tafel equation ( |η|≥^(118mV)_(ne)), respectively. The analytical expression for the current-voltage behavior of the coupled photodiode-electrocatalyst device (α_A = α_C = 0.5) and an isolated photodiode is plotted, compared, and augmented with band diagrams at equilibrium, open circuit, short circuit, and the maximum power point to illustrate the effect of coupling an electrocatalyst to a photodiode. The applicability of the derived equations is then demonstrated by comparing with a recently reported high efficiency, thin film InP/InO_xP_y/Rh photoelectrosynthetic hydrogen evolution device.

Interplay of light transmission and catalytic exchange current in photoelectrochemical systems

We develop an analytic current-voltage expression for a variable junction photoelectrochemical (PEC) cell and use it to investigate and illustrate the influence of the optical and electrical properties of catalysts on the optoelectronic performance of PEC devices. Specifically, the model enables a simple, yet accurate accounting of nanostructured catalyst optical and electrical properties through incorporation of an optical transmission factor and active catalytic area factor. We demonstrate the utility of this model via the output power characteristics of an exemplary dual tandem solar cell with indium gallium phosphide and indium gallium arsenide absorbers with varying rhodium catalyst nanoparticle loading. The approach highlights the importance of considering interactions between independently optimized components for optimal PEC device design.

Mesoscale modeling of photoelectrochemical devices: light absorption and carrier collection in monolithic, tandem, Si|WO_3 microwires

We analyze mesoscale light absorption and carrier collection in a tandem junction photoelectrochemical device using electromagnetic simulations. The tandem device consists of silicon (E(g,Si) = 1.1 eV) and tungsten oxide (E(g,WO3) = 2.6 eV) as photocathode and photoanode materials, respectively. Specifically, we investigated Si microwires with lengths of 100 µm, and diameters of 2 µm, with a 7 µm pitch, covered vertically with 50 µm of WO3 with a thickness of 1 µm. Many geometrical variants of this prototypical tandem device were explored. For conditions of illumination with the AM 1.5G spectra, the nominal design resulted in a short circuit current density, J(SC), of 1 mA/cm(2), which is limited by the WO3 absorption. Geometrical optimization of photoanode and photocathode shape and contact material selection, enabled a three-fold increase in short circuit current density relative to the initial design via enhanced WO3 light absorption. These findings validate the usefulness of a mesoscale analysis for ascertaining optimum optoelectronic performance in photoelectrochemical devices.

Achieving near-unity broadband absorption in sparse arrays of GaAs NWs via a fundamental understanding of localized radial modes

We report a fundamental understanding of the mechanism for enhanced light absorption in sparse semiconductor nanowire arrays and design methods to achieve near-unity broadband absorption, demonstrated by GaAs nanowire arrays on a Si substrate. The sparse nanowire arrays absorb strongly into localized radial modes of individual nanowires, enabled by efficient scattering of incident light from neighboring nanowires. The radius-dependent localized modes led to two basic design approaches towards achieving near unity broadband absorption: (i) including multiple wire radii within an array for a 21% increase in absorbed current, and (ii) tapering the nanowires for a 23% increase in absorbed current.