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Vicinal dithiol-containing proteins (VDPs) play a significant role in maintaining the cellular redox homeostasis and are implicated in many diseases. To provide new chemical tools for VDPs imaging, we report here a ratiometric fluorescent probe CAsH2 for VDPs using 7-diethylaminiocoumarin as the fluorescent reporter and cyclic 1,3,2-dithiarsenolane as the specific ligand. CAsH2 shows peculiar dual fluorescence emission from the excited intramolecular charge transfer (ICT) and twisted intramolecular charge transfer (TICT) states in aqueous media. However, upon selective binding of protein vicinal dithiols to the trivalent arsenical of CAsH2, the probe was brought from the polar water media into the hydrophobic protein domain, causing the excited state ICT to TICT conversion to be restricted; as a result, an increase from the ICT emission band and a decrease from the TICT emission band were observed simultaneously. The designed probe shows high selectivity toward VDPs over other proteins and biological thiols. Preliminary experiments show that CAsH2 can be used for the ratiometric imaging of endogenous VDPs in living cells. So far as we know, this is a rare example of the ratiometric fluorescent probe designed via modulating the ICT-TICT conversion process, which provides a new way to construct various protein-specific ratiometric fluorescent probes.

Plasmonics offers the opportunity of tailoring the interaction of light with single quantum emitters. However, the strong field localization of plasmons requires spatial fabrication accuracy far beyond what is required for other nanophotonic technologies. Furthermore, this accuracy has to be achieved across different fabrication processes to combine quantum emitters and plasmonics. We demonstrate a solution to this critical problem by controlled positioning of plasmonic nanoantennas with an accuracy of 11 nm next to single self-assembled GaAs semiconductor quantum dots, whose position can be determined with nanometer precision. These dots do not suffer from blinking or bleaching or from random orientation of the transition dipole moment as colloidal nanocrystals do. Our method introduces flexible fabrication of arbitrary nanostructures coupled to single-photon sources in a controllable and scalable fashion.

Over the past decade, the properties of plasmonic waveguides have extensively been studied as key elements in important applications that include biosensors, optical communication systems, quantum plasmonics, plasmonic logic, and quantum-cascade lasers. Whereas their guiding properties are by now fairly well-understood, practical implementation in chipscale systems is hampered by the lack of convenient electrical excitation schemes. Recently, a variety of surface plasmon lasers have been realized, but they have not yet been waveguide-coupled. Planar incoherent plasmonic sources have recently been coupled to plasmonic guides but routing of plasmonic signals requires coupling to linear waveguides. Here, we present an experimental demonstration of electrically driven GaAs nanowire light sources integrated with plasmonic nanostrip waveguides with a physical cross-section of 0.08λ(2). The excitation and waveguiding of surface plasmon-polaritons (SPPs) is experimentally demonstrated and analyzed with the help of full-field electromagnetic simulations. Splitting and routing of the electrically generated SPP signals around 90° bends are also shown. The realization of integrated plasmon sources greatly increases the applicability range of plasmonic waveguides and routing elements.

Heterogeneous photocatalytic reduction of As(V) and As(III) at different concentrations over TiO(2) under UV light in deoxygenated aqueous suspensions is described. For the first time, As(0) was unambiguously identified together with arsine (AsH(3)) as reaction products. As(V) reduction requires the presence of an electron donor (methanol in the present case) and takes place through the hydroxymethyl radical formed from methanol oxidation by holes or hydroxyl radicals. On the contrary, As(III) reduction takes place through direct reduction by the TiO(2)-conduction band electrons. Detailed mechanisms for the photocatalytic processes are proposed. Although reduction to solid As(0) is convenient for purposes of As removal from water as a deposit on TiO(2), attention must be paid to formation of AsH(3), one of the most toxic forms of As, and strategies for AsH(3) treatment should be considered.

The oscillating piezoelectric field of a surface acoustic wave (SAW) is employed to transport photoexcited carriers, as well as to spatially control exciton recombination in GaAs-based nanowires (NWs) on a subns time scale. The experiments are carried out in core-shell NWs transferred to a SAW delay line on a LiNbO(3) crystal. Carriers generated in the NW by a focused laser spot are acoustically transferred to a second location, leading to the remote emission of subns light pulses synchronized with the SAW phase. The dynamics of the carrier transport, investigated using spatially and time-resolved photoluminescence, is well-reproduced by computer simulations. The high-frequency contactless manipulation of carriers by SAWs opens new perspectives for applications of NWs in opto-electronic devices operating at gigahertz frequencies. The potential of this approach is demonstrated by the realization of a high-frequency source of antibunched photons based on the acoustic transport of electrons and holes in (In,Ga)As NWs., (© 2011 American Chemical Society)

We present a novel technique for the manipulation of the energy spectrum of hard-wall InAs/InP nanowire quantum dots. By using two local gate electrodes, we induce a strong transverse electric field in the dot and demonstrate the controlled modification of its electronic orbitals. Our approach allows us to dramatically enhance the single-particle energy spacing between the first two quantum levels in the dot and thus to increment the working temperature of our InAs/InP single-electron transistors. Our devices display a very robust modulation of the conductance even at liquid nitrogen temperature, while allowing an ultimate control of the electron filling down to the last free carrier. Potential further applications of the technique to time-resolved spin manipulation are also discussed.

We report a novel method for probing the gate-voltage dependence of the surface potential of individual semiconductor nanowires. The statistics of electronic occupation of a single defect on the surface of the nanowire, determined from a random telegraph signal, is used as a measure for the local potential. The method is demonstrated for the case of one or two switching defects in indium arsenide (InAs) nanowire field effect transistors at temperatures T=25-77 K. Comparison with a self-consistent model shows that surface potential variation is retarded in the conducting regime due to screening by surface states with density Dss≈10(12) cm(-2) eV(-1). Temperature-dependent dynamics of electron capture and emission producing the random telegraph signals are also analyzed, and multiphonon emission is identified as the process responsible for capture and emission of electrons from the surface traps. Two defects studied in detail had capture activation energies of EB≈50 meV and EB≈110 meV and cross sections of σ∞≈3×10(-19) cm2 and σ∞≈2×10(-17) cm2, respectively. A lattice relaxation energy of Sℏω=187±15 meV was found for the first defect.

We demonstrate strong coupling between a surface plasmon and intersublevel transitions in self-assembled InAs quantum dots. The surface plasmon mode exists at the interface between the semiconductor emitter structure and a periodic array of holes perforating a metallic Pd/Ge/Au film that also serves as the top electrical contact for the emitters. Spectrally narrowed quantum-dot electroluminescence was observed for devices with varying subwavelength hole spacing. Devices designed for 9, 10, and 11 μm wavelength emission also exhibit a significant spectral splitting. The association of the splitting with quantum-dot Rabi oscillation is consistent with results from a calculation of spontaneous emission from an interacting plasmonic field and quantum-dot ensemble. The fact that this Rabi oscillation can be observed in an incoherently excited, highly inhomogeneously broadened system demonstrates the utility of intersublevel transitions in quantum dots for investigations of coherent transient and quantum coherence phenomena.

We demonstrate an organic/inorganic solar cell architecture based on a blend of poly(3-hexylthiophene) (P3HT) and narrow bandgap GaAs nanowires. The measured increase of device photocurrent with increased nanowire loading is correlated with structural ordering within the active layer that enhances charge transport. Coating the GaAs nanowires with TiO(x) shells passivates nanowire surface states and further improves the photovoltaic performance. We find that the P3HT/nanowire cells yield power conversion efficiencies of 2.36% under white LED illumination for devices containing 50 wt % of TiO(x)-coated GaAs nanowires. Our results constitute important progress for the use of nanowires in large area solution processed hybrid photovoltaic cells and provide insight into the role of structural ordering in the device performance.

While ferromagnetic nanodots are being widely studied from fundamental as well as application points of views, so far all the dots have been physically defined; once made, one cannot change their dimension or size. We show that ferromagnetic nanodots can be electrically defined. To realize this, we utilize an electric field to modulate the in-plane distribution of carriers in a ferromagnetic semiconductor (Ga,Mn)As film with a meshed gate structure having a large number of nanoscaled windows.

In this paper, we report a successful realization and integration of a gold two-dimensional hole array (2DHA) structure with semiconductor InAs quantum dot (QD). We show experimentally that a properly designed 2DHA-QD photodetector can facilitate a strong plasmonic-QD interaction, leading to a 130% absolute enhancement of infrared photoresponse at the plasmonic resonance. Our study indicates two key mechanisms for the performance improvement. One is an optimized 2DHA design that permits an efficient coupling of light from the far-field to a localized plasmonic mode. The other is the close spatial matching of the QD layers to the wave function extent of the plasmonic mode. Furthermore, the processing of our 2DHA is amenable to large scale fabrication and, more importantly, does not degrade the noise current characteristics of the photodetector. We believe that this demonstration would bring the performance of QD-based infrared detectors to a level suitable for emerging surveillance and medical diagnostic applications.

A phase-stable superposition of femtosecond pulses from a compact erbium-doped fiber source and their second harmonic is shown to induce ultrashort approximately microA current bursts in single unbiased GaAs nanowires. Current injection relies on a quantum interference of one- and two-photon absorption pathways. The vector direction of the current is solely dictated by the polarization and relative phase of the harmonically related light components while its power dependence is consistent with a third order optical nonlinearity.

We report the use of Te as an n-type dopant in GaAs core-shell p-n junction nanowires for use in photovoltaic devices. Te produced significant change in the morphology of GaAs nanowires grown by the vapor-liquid-solid process in a molecular beam epitaxy system. The increase in radial growth of nanowires due to the surfactant effect of Te had a significant impact on the operating characteristics of photovoltaic devices. A decrease in solar cell efficiency occurred when the Te-doped GaAs growth duration was increased.

Optical control of the lateral quantum confinement and number of electrons confined in nanofabricated GaAs/AlGaAs quantum dots is achieved by illumination with a weak laser beam that is absorbed in the AlGaAs barrier. Precise tuning of energy-level structure and electron population is demonstrated by monitoring the low-lying transitions of the electrons from the lowest quantum-dot energy shells by resonant inelastic light scattering. These findings open the way to the manipulation of single electrons in these quantum dots without the need of external metallic gates.

GaAs:Mn nanowires were obtained on GaAs(001) and GaAs(111)B substrates by molecular beam epitaxial growth of (Ga,Mn)As at conditions leading to MnAs phase separation. Their density is proportional to the density of catalyzing MnAs nanoislands, which can be controlled by the Mn flux and/or the substrate temperature. After deposition corresponding to a 200 nm thick (Ga,Mn)As layer the nanowires are around 700 nm long. Their shapes are tapered, with typical diameters around 30 nm at the base and 7 nm at the tip. The wires grow along the 111 direction, i.e., along the surface normal on GaAs(111)B and inclined on GaAs(001). In the latter case they tend to form branches. Being rooted in the ferromagnetic semiconductor (Ga,Mn)As, the nanowires combine one-dimensional properties with the magnetic properties of (Ga,Mn)As and provide natural, self-assembled structures for nanospintronics.

Through the utilization of index-matched GaAs immersion lens techniques, we demonstrate a record extinction (12%) of a far-field focused laser beam by a single InAs/GaAs quantum dot. This contrast level enables us to report for the first time resonant laser transmission spectroscopy on a single InAs/GaAs quantum dot without the need for phase-sensitive lock-in detection.

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 have synthesized ternary InGaAs nanowires on (111)B GaAs surfaces by metal-organic chemical vapor deposition. Au colloidal nanoparticles were employed to catalyze nanowire growth. We observed the strong influence of nanowire density on nanowire height, tapering, and base shape specific to the nanowires with high In composition. This dependency was attributed to the large difference of diffusion length on (111)B surfaces between In and Ga reaction species, with In being the more mobile species. Energy dispersive X-ray spectroscopy analysis together with high-resolution electron microscopy study of individual InGaAs nanowires shows large In/Ga compositional variation along the nanowire supporting the present diffusion model. Photoluminescence spectra exhibit a red shift with decreasing nanowire density due to the higher degree of In incorporation in more sparsely distributed InGaAs nanowires.

We report on spectrally resolved photocurrent measurements on single self-assembled nanowire heterostructures. The wires, typically 3 microm long with an average diameter of 85 nm, consist of InAs with a 1 microm central part of InAsP. Two different sets of wires were prepared with phosphorus contents of 15+/-3% and 35+/-3%, respectively, as determined by energy-dispersive spectroscopy measurements made in transmission electron microscopy. Ohmic contacts are fabricated to the InAs ends of the wire using e-beam lithography. The conduction band offset between the InAs and InAsP regions virtually removes the dark current through the wires at low temperature. In the optical experiments, interband excitation in the phosphorus-rich part of the wires results in a photocurrent with threshold energies of about 0.65 and 0.82 eV, respectively, in qualitative agreement with the expected band gap of the two compositions. Furthermore, a strong polarization dependence is observed with an order of magnitude larger photocurrent for light polarized parallel to the wire than for light polarized perpendicular to the wire. We believe that these wires form promising candidates as nanoscale infrared polarization-sensitive photodetectors.

We have fabricated and characterized surface-emitting, spin-polarized light-emitting diodes with a Mn-doped InAs dilute magnetic quantum dot spin-injector and contact region grown by low-temperature molecular beam epitaxy, and an In(0.4)Ga(0.6)As quantum dot active region. Energy-dispersive X-ray and electron energy loss spectroscopies performed on individual dots indicate that the Mn atoms incorporate within the dots themselves. Circularly polarized light is observed up to 160 K with a maximum degree of circular polarization of 5.8% measured at 28 K, indicating high-temperature spin injection and device operation.

Images of a single-electron quantum dot were obtained in the Coulomb blockade regime at liquid He temperatures using a cooled scanning probe microscope (SPM). The charged SPM tip shifts the lowest energy level in the dot and creates a ring in the image corresponding to a peak in the Coulomb-blockade conductance. Fits to the line shape of the ring determine the tip-induced shift of the energy of the electron state in the dot. SPM manipulation of electrons in quantum dots promises to be useful in understanding, building, and manipulating circuits for quantum information processing.