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Singlet and triplet potential energy surfaces for the atmospheric ozonation of trans-2-chlorovnyldichloroarsine (lewisite) are investigated theoretically. Optimizations of the reactants, products, intermediates and transition states are carried out at the BHandHLYP/6-311+G(d,p) level. Single point energy calculations are performed at the CCSD(T)/6-311+G(d,p) level based on the optimized structures. The detailed mechanism is presented and discussed. Various possible H (or Cl)-abstraction and C (or As)-addition/elimination pathways are considered. The results show that the As-addition/elimination is more energetically favorable than the other mechanisms. Rice-Ramsperger-Kassel-Marcus (RRKM) theory is used to compute the rate constants over the possible atmospheric temperature range of 200-3000 K and the pressure range of 10(-8)-10(9) Torr. The calculated rate constant is in good agreement with the available experimental data. The total rate coefficient shows positive temperature dependence and pressure independence. The modified three-parameter Arrhenius expressions for the total rate coefficient and individual rate coefficients are represented. Calculation results show that major product is CHClCHAs(OOO)Cl2 (s-IM3) at the temperature below 600 K and O2 + CHClCHAsOCl2 (s-P9) play an important role at the temperature between 600 and 3000 K. Time-dependent DFT (TD-DFT) calculations indicate that CHCl(OOO)CHAsCl2 (s-IM3) and CHOAsCl2 (s-P5) can take photolysis easily in the sunlight. Due to the absence of spectral information for arsenide, computational vibrational spectra of the important intermediates and products are also analyzed to provide valuable evidence for subsequent experimental identification., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

We report the cw-laser-induced oxidation of molecular-beam-epitaxy grown GaAsBi bismuth surface microdroplets investigated in situ by micro-Raman spectroscopy under ambient conditions as a function of irradiation power and time. Our results reveal the surface droplets are high-purity crystalline bismuth and the resultant Bi 2 O 3 transformation to be β-phase and stable at room temperature. A detailed Raman study of Bi microdroplet oxidation kinetics yields insights into the laser-induced oxidation process and offers useful real-time diagnostics. The temporal evolution of new β-Bi 2 O 3 Raman modes is shown to be well described by Johnson-Mehl-Avrami-Kolmogorov kinetic transformation theory and while this study limits itself to the laser-induced oxidation of GaAsBi bismuth surface droplets, the results will find application within the wider context of bismuth laser-induced oxidation and direct Raman laser processing.

Multilayer anti-reflection (AR) coatings can be used to improve the efficiency of Gallium Arsenide (GaAs) solar cells. We propose an alternate method to obtain optical thin films with specified refractive indices, which is using a self-assembled nanoporous anodic aluminum oxide (AAO) template as an optical thin film whose effective refractive index can be tuned by pore-widening. Different kinds of double-layer AR coatings each containing an AAO layer were designed and investigated by finite difference time domain (FDTD) method. We demonstrate that a λ /4n - λ /4n AR coating consisting of a TiO(2) layer and an AAO layer whose effective refractive index is 1.32 realizes a 96.8% light absorption efficiency of the GaAs solar cell under AM1.5 solar spectrum (400 nm-860 nm). We also have concluded some design principles of the double-layer AR coating containing an AAO layer for GaAs solar cells.

We demonstrate an integrated autocorrelator based on two superconducting single-photon detectors patterned on top of a GaAs ridge waveguide. This device enables the on-chip measurement of the second-order intensity correlation function g(2)(τ). A polarization-independent device quantum efficiency in the 1% range is reported, with a timing jitter of 88 ps at 1300 nm. g(2)(τ) measurements of continuous-wave and pulsed laser excitations are demonstrated with no measurable crosstalk within our measurement accuracy.

We demonstrate a regrowth-free material platform to create monolithic InGaAsP/InP photonic integrated circuits (PICs) with high-gain active and low-loss passive sections via a PL detuning of >135 nm. We show 2.5 µm wide by 400 µm long semiconductor optical amplifiers with >40 dB/mm gain at 1570 nm, and passive waveguide losses <2.3 dB/mm. The bandgap in the passive section is detuned using low-energy 190 keV channelized phosphorous implantation and subsequent rapid thermal annealing to achieve impurity-induced quantum well intermixing (QWI). The PL wavelengths in the active and passive sections are 1553 and 1417 nm, respectively. Lasing wavelengths for 500 µm Fabry-Perot lasers are 1567 and 1453 nm, respectively.

We report the first InGaAsP-based uni-travelling carrier photodiode structure grown by Solid Source Molecular Beam Epitaxy; the material contains layers of InGaAsP as thick as 300 nm and a 120 nm thick InGaAs absorber. Large area vertically illuminated test devices have been fabricated and characterised; the devices exhibited 0.1 A/W responsivity at 1550 nm, 12.5 GHz -3 dB bandwidth and -5.8 dBm output power at 10 GHz for a photocurrent of 4.8 mA. The use of Solid Source Molecular Beam Epitaxy enables the major issue associated with the unintentional diffusion of zinc in Metal Organic Vapour Phase Epitaxy to be overcome and gives the benefit of the superior control provided by MBE growth techniques without the costs and the risks of handling toxic gases of Gas Source Molecular Beam Epitaxy.

The authors report on the fabrication of hybrid planar micro-resonators based on InGaAs microdisks with an evaporated organic material. Samples of InGaAs grown on InP(100) substrates are obtained by Chemical Beam Epitaxy, and microdisks of InGaAs with different diameters are fabricated by focused ion beam. The hybrid disks are obtained by the subsequent evaporation of 8-hydroxyquinoline aluminium doped with 4-Dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran on the InGaAs microdisks. The devices, characterized by micro- and confocal photoluminescence imaging and spectroscopy, exhibit emission around 650 nm, from the organic material for disks with different radius. Finally, simultaneous emission in the visible and at whispering gallery resonant modes in the 1350-1450 nm range are observed due to excitation transfer to InGaAs. These devices open the possibility to combine the flexibility of organics with the high gain of III-V compounds for wavelength down conversion and telecom applications.

InGaAs PIN photodetectors heterogeneously integrated on silicon-on-insulator waveguides are fabricated and characterized. Efficient evanescent coupling between silicon-on-insulator waveguides and InGaAs photodetectors is achieved. The fabricated photodetectors can work well without external bias and have a very low dark current of 10pA. The measured responsivity of a 40microm-long photodetector is 1.1A/W (excluding the coupling loss between the fiber and the SOI waveguide) at a wavelength of 1550nm and shows good linearity for an input power range of 40dB. Due to the large absorption coefficient of InGaAs and the efficient evanescent coupling, the fabricated photodetectors can cover the whole S, C and L communication bands.

Nonlinear transient absorption bleaching of intense few-cycle terahertz (THz) pulses is observed in photoexcited GaAs using opticalpump--THz-probe techniques. A simple model of the electron transport dynamics shows that the observed nonlinear response is due to THz-electric- field-induced intervalley scattering over sub-picosecond time scales as well as an increase in the intravalley scattering rate attributed to carrier heating. Furthermore, the nonlinear nature of the THz pulse transmission at high peak fields leads to a measured terahertz conductivity in the photoexcited GaAs that deviates significantly from the Drude behavior observed at low THz fields, emphasizing the need to explore nonlinear THz pulse interactions with materials in the time domain.

In this study we develop an efficient light harvesting scheme that can enhance the efficiency of GaAs solar cells using self-assembled microspheres. Based on the scattering of the microspheres and the theory of photonic crystals, the path length can be increased. In addition, the self-assembly of microspheres is one of the simplest and the fastest methods with which to build a 2D periodic structure. The experimental results are confirmed by the use of a simulation in which a finite-difference time-domain (FDTD) method is used to analyze the absorption and electric field of the 2D periodic structure. Both the results of the numerical simulations and the experimental results show an increase in the conversion power efficiency of GaAs solar cell of about 25% when 1 microm microspheres were assembled on the surface of GaAs solar cells.

We report a telecom-band single-photon detector for gigahertz clocked quantum key distribution systems. The single-photon detector is based on a sinusoidally gated InGaAs/InP avalanche photodiode. The gate repetition frequency of the single-photon detector reached 1.5 GHz. A quantum efficiency of 10.8 % at 1550 nm was obtained with a dark count probability per gate of 6.3 x 10(-7) and an afterpulsing probability of 2.8 %. Moreover, the maximum detection rate of the detector is 20 MHz.

Phenyl-substituted arsonic acids have been widely used as feed additives in the poultry industry. While very few studies have been reported on the environmental impact of these compounds, they have been introduced into the environment through land application of poultry litter in large quantities (about 10(6) kg/year). Phenylarsonic acid (PA) was used as a model for problematic arsonic acids. Dilute aqueous solutions of PA were subjected to gamma radiolysis under hydroxyl radical generating conditions, which showed rapid degradation of PA. Product studies indicate addition of (.)OH to the phenyl ring forms the corresponding phenols as the primary products. Arsenite, H3As(III)O3, and arsenate, H3As(V)O4, were also identified as products. The optimized structures and relative calculated energies (using GAUSSIAN 98, the B3LYP/6-31G(d) method) of the various transient intermediates are consistent with the product studies. Pulse radiolysis was used to determine the rate constants of PA with (.)OH (k = 3.2 x 10(9) M(-1) s(-1)) and SO4(.-) (k = 1.0 x 10(9) M(-1) s(-1)). PA reacts slower toward O(.-) (k = 1.9 x 10(7) M(-1) s(-1)) and N3(.) (no detectable transient), due to the lower oxidation potential of these two radicals. Our results indicate advanced oxidative processes employing (.)OH and SO4(.-) can be effective for the remediation of phenyl-substituted arsonic acids.

The potential energy surfaces corresponding to the photochemical reactions of pyridine, phosphinine, and arsabenzene have been investigated by employing the CAS(6,6)/6-311G(d,p) and MP2-CAS-(6,6)/6-311++G(3df,3pd)//CAS(6,6)/6-311G(d,p) methods. The thermal (or dark) reactions of these reactant species have also been examined using the same level of theory. The mechanisms of drastic structural change in the excited- and ground-state reactions of pyridine, phosphinine, and arsabenzene and the differences between them are elucidated. The theoretical investigations suggest that conical intersections play a crucial role in their photoisomerization reactions. The results obtained allow a number of predictions to be made.

We report on new schemes for terahertz (THz) generation. The THz efficiency of photoconducting antennas can be increased by using a cavity effect for the near-infrared pump beam. The cavity is formed by a molecular beam epitaxy grown semiconductor Bragg mirror below the photoconducting layer. The optical confinement is accompanied by an electrical confinement suppressing undesired leakage currents and providing a constant electric field in the active layers. The performance of this cavity-enhanced emitter is further improved by using a mobility optimized low-temperature GaAs layer. This emitter is successfully used in a femtosecond Ti:sapphire laser cavity for highly efficient intracavity THz generation, where the photoconductive layer serves also as a saturable absorber. The broadband THz pulses generated are used for time-resolved spectroscopy of nanostructures. We study the dynamics of intersubband transitions in semiconductor quantum wells. The relaxation of carriers excited by a near-infrared pump pulse is investigated by measuring the THz absorption between the different subbands with our THz pulses. For transition energies below the optical phonon energy we find relatively long relaxation times with a strong dependence on the excited carrier density.