Ray optical light trapping in silicon microwires: exceeding the 2n^2 intensity limit

We develop a ray optics model of a silicon wire array geometry in an attempt to understand the very strong absorption previously observed experimentally in these arrays. Our model successfully reproduces the n^2 ergodic limit for wire arrays in free space. Applying this model to a wire array on a Lambertian back reflector, we find an asymptotic increase in light trapping for low filling fractions. In this case, the Lambertian back reflector is acting as a wide acceptance angle concentrator, allowing the array to exceed the ergodic limit in the ray optics regime. While this leads to increased power per volume of silicon, it gives reduced power per unit area of wire array, owing to reduced silicon volume at low filling fractions. Upon comparison with silicon microwire experimental data, our ray optics model gives reasonable agreement with large wire arrays (4 μm radius), but poor agreement with small wire arrays (1 μm radius). This suggests that the very strong absorption observed in small wire arrays, which is not observed in large wire arrays, may be significantly due to wave optical effects

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

Gating NO Release from Nitric Oxide Synthase

We have investigated the kinetics of NO escape from Geobacillus stearothermophilus nitric oxide synthase (gsNOS). Previous work indicated that NO release was gated at position 223 in mammalian enzymes; our kinetics experiments include mutants at that position along with measurements on the wild type enzyme. Employing stopped-flow UV–vis methods, reactions were triggered by mixing a reduced enzyme/N-hydroxy-l-arginine complex with an aerated buffer solution. NO release kinetics were obtained for wt NOS and three mutants (H134S, I223V, H134S/I223V). We have confirmed that wt gsNOS has the lowest NO release rate of known NOS enzymes, whether bacterial or mammalian. We also have found that steric clashes at positions 223 and 134 hinder NO escape, as judged by enhanced rates in the single mutants. The empirical rate of NO release from the gsNOS double mutant (H134/I223V) is nearly as rapid as that of the fastest mammalian enzymes, demonstrating that both positions 223 and 134 function as gates for escape of the product diatomic molecule

Solar Water Splitting Cells

No abstract

Composite Adaptive Lyapunov-Based Deep Neural Network (Lb-DNN) Controller

Recent advancements in adaptive control have equipped deep neural network (DNN)-based controllers with Lyapunov-based adaptation laws that work across a range of DNN architectures to uniquely enable online learning. However, the adaptation laws are based on tracking error, and offer convergence guarantees on only the tracking error without providing conclusions on the parameter estimation performance. Motivated to provide guarantees on the DNN parameter estimation performance, this paper provides the first result on composite adaptation for adaptive Lyapunov-based DNN controllers, which uses the Jacobian of the DNN and a prediction error of the dynamics that is computed using a novel method involving an observer of the dynamics. A Lyapunov-based stability analysis is performed which guarantees the tracking, observer, and parameter estimation errors are uniformly ultimately bounded (UUB), with stronger performance guarantees when the DNN's Jacobian satisfies the persistence of excitation (PE) condition. Comparative simulation results demonstrate a significant performance improvement with the developed composite adaptive Lb-DNN controller in comparison to the tracking error-based Lb-DNN

Report on Second Activations with the Lead Slowing Down Spectrometer

Summary On August 18 and 19 2011, five items were irradiated with neutrons using the Lead Slowing Down Spectrometer (LSDS). After irradiation, dose measurements and gamma-spectrometry measurements were completed on all of the samples. No contamination was found on the samples, and all but one provided no dose. Gamma-spectroscopy measurements qualitatively agreed with expectations based on the materials. As during the first activation run, we observed activation in the room in general, mostly due to 56Mn and 24Na. Most of the activation of the samples was short lived, with half-lives on the scale of hours to days, except for 60Co which has a half-life of 5.3 y

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

Report on First Activations with the Lead Slowing Down Spectrometer

On Feb. 17 and 18 2011, six items were irradiated with neutrons using the Lead Slowing Down Spectrometer. After irradiation, dose measurements and gamma-spectrometry measurements were completed on all of the samples. No contamination was found on the samples, and all but one provided no dose. Gamma-spectroscopy measurements qualitatively agreed with expectations based on the materials, with the exception of silver. We observed activation in the room in general, mostly due to 56Mn and 24Na. Most of the activation was short lived, with half-lives on the scale of hours, except for 198Au which has a half-life of 2.7 d

Hydrogen-evolution characteristics of Ni–Mo-coated, radial junction, n+p-silicon microwire array photocathodes

The photocathodic H_2-evolution performance of Ni–Mo-coated radial n+p junction Si microwire (Si MW) arrays has been evaluated on the basis of thermodynamic energy-conversion efficiency as well as solar cell figures of merit. The Ni–Mo-coated n^(+)p-Si MW electrodes yielded open-circuit photovoltages (V_oc) of 0.46 V, short-circuit photocurrent densities (J_sc) of 9.1 mA cm^(−2), and thermodynamically based energy-conversion efficiencies (η) of 1.9% under simulated 1 Sun illumination. Under nominally the same conditions, the efficiency of the Ni–Mo-coated system was comparable to that of Pt-coated n+p-Si MW array photocathodes (V_oc = 0.44 V, J_sc = 13.2 mA cm^(−2_, η = 2.7%). This demonstrates that, at 1 Sun light intensity on high surface area microwire arrays, earth-abundant electrocatalysts can provide performance comparable to noble-metal catalysts for photoelectrochemical hydrogen evolution. The formation of an emitter layer on the microwires yielded significant improvements in the open-circuit voltage of the microwire-array-based photocathodes relative to Si MW arrays that did not have a buried n^(+)p junction. Analysis of the spectral response and light-intensity dependence of these devices allowed for optimization of the catalyst loading and photocurrent density. The microwire arrays were also removed from the substrate to create flexible, hydrogen-evolving membranes that have potential for use in a solar water-splitting device