Quantum Dot-Sensitized Solar Cells Based on Directly Adsorbed Zinc Copper Indium Sulfide Colloids

Heavy metal-based quantum dots (QDs) have demonstrated to behave as efficient sensitizers in QD-sensitized solar cells (QDSSCs), as attested by the countless works and encouraging efficiencies reported so far. However, their intrinsic toxicity has arisen as a major issue for the prospects of commercialization. Here, we examine the potential of environmentally friendly zinc copper indium sulfide (ZCIS) QDs for the fabrication of liquid-junction QDSSCs by means of photoelectrochemical measurements. A straightforward approach to directly adsorb ZCIS QDs on TiO2 from a colloidal dispersion is presented. Incident photon-to-current efficiency (IPCE) spectra of sensitized photoanodes show a marked dependence on the adsorption time, with longer times leading to poorer performances. Cyclic voltammograms point to a blockage of the channels of the mesoporous TiO2 film by the agglomeration of QDs as the main reason for the decrease in efficiency. Photoanodes were also submitted to the ZnS treatment. Its effects on electron recombination with the electrolyte are analyzed through electrochemical impedance spectroscopy and photopotential measurements. The corresponding results bring out the role of the ZnS coating as a barrier layer preventing electron leakage toward the electrolyte, as argued in other QD-sensitized systems. The beneficial effect of the ZnS coating is ultimately reflected on the power conversion efficiency of complete devices, reaching values of 2 %. In a more general vein, through these findings, we aim to call the attention to the potentiality of this quaternary alloy, virtually unexplored as a light harvester for sensitized devices.

Improving the Photoelectrochemical Response of TiO2 Nanotubes upon Decoration with Quantum-Sized Anatase Nanowires

TiO2 nanotubes (NTs) have been widely used for a number of applications including solar cells, photo(electro)chromic devices, and photocatalysis. Their quasi-one-dimensional morphology has the advantage of a fast electron transport although they have a relatively reduced interfacial area compared with nanoparticulate films. In this study, vertically oriented, smooth TiO2 NT arrays fabricated by anodization are decorated with ultrathin anatase nanowires (NWs). This facile modification, performed by chemical bath deposition, allows to create an advantageous self-organized structure that exhibits remarkable properties. On one hand, the huge increase in the electroactive interfacial area induces an improvement by 1 order of magnitude in the charge accumulation capacity. On the other hand, the modified NT arrays display larger photocurrents for water and oxalic acid oxidation than bare NTs. Their particular morphology enables a fast transfer of photogenerated holes but also efficient mass and electron transport. The importance of a proper band energy alignment for electron transfer from the NWs to the NTs is evidenced by comparing the behavior of these electrodes with that of NTs modified with rutile NWs. The NT-NW self-organized architecture allows for a precise design and control of the interfacial surface area, providing a material with particularly attractive properties for the applications mentioned above.

Photogeneration of Hydrogen from Water by Hybrid Molybdenum Sulfide Clusters Immobilized on Titania

Two new hybrid molybdenum(IV) Mo3S7 cluster complexes derivatized with diimino ligands have been prepared by replacement of the two bromine atoms of [Mo3S7Br6]2− by a substituted bipyridine ligand to afford heteroleptic molybdenum(IV) Mo3S7Br4(diimino) complexes. Adsorption of the Mo3S7 cores from sample solutions on TiO2 was only achieved from the diimino functionalized clusters. The adsorbed Mo3S7 units were reduced on the TiO2 surface to generate an electrocatalyst that reduces the overpotential for the H2 evolution reaction by approximately 0.3 V (for 1 mA cm−2) with a turnover frequency as high as 1.4 s−1. The nature of the actual active molybdenum sulfide species has been investigated by X-ray photoelectron spectroscopy. In agreement with the electrochemical results, the modified TiO2 nanoparticles show a high photocatalytic activity for H2 production in the presence of Na2S/Na2SO3 as a sacrificial electron donor system.

Physics of hydrogen radiation.

"A & ES 62-12."

On the quantum theory of line-spectra,

Issued in three parts.

Quantum transport and integrability of the Anderson model for a quantum dot with multiple leads

We show that an Anderson Hamiltonian describing a quantum dot connected to multiple leads is integrable. A general expression for the nonlinear conductance is obtained by combining the Bethe ansatz exact solution with Landauer-Buttiker theory. In the Kondo regime, a closed form expression is given for the matrix conductance at zero temperature and when all the leads are close to the symmetric point. A bias-induced splitting of the Kondo resonance is possible for three or more leads. Specifically, for N leads, with each at a different chemical potential, there can be N-1 Kondo peaks in the conductance.

Experimental tests of quantum nonlinear dynamics in atom optics

Cold atoms in optical potentials provide an ideal test bed to explore quantum nonlinear dynamics. Atoms are prepared in a magneto-optic trap or as a dilute Bose-Einstein condensate and subjected to a far detuned optical standing wave that is modulated. They exhibit a wide range of dynamics, some of which can be explained by classical theory while other aspects show the underlying quantum nature of the system. The atoms have a mixed phase space containing regions of regular motion which appear as distinct peaks in the atomic momentum distribution embedded in a sea of chaos. The action of the atoms is of the order of Planck's constant, making quantum effects significant. This tutorial presents a detailed description of experiments measuring the evolution of atoms in time-dependent optical potentials. Experimental methods are developed providing means for the observation and selective loading of regions of regular motion. The dependence of the atomic dynamics on the system parameters is explored and distinct changes in the atomic momentum distribution are observed which are explained by the applicable quantum and classical theory. The observation of a bifurcation sequence is reported and explained using classical perturbation theory. Experimental methods for the accurate control of the momentum of an ensemble of atoms are developed. They use phase space resonances and chaotic transients providing novel ensemble atomic beamsplitters. The divergence between quantum and classical nonlinear dynamics is manifest in the experimental observation of dynamical tunnelling. It involves no potential barrier. However a constant of motion other than energy still forbids classically this quantum allowed motion. Atoms coherently tunnel back and forth between their initial state of oscillatory motion and the state 180 out of phase with the initial state.

Quantum dynamics with stochastic gauge simulations

The general idea of a stochastic gauge representation is introduced and compared with more traditional phase-space expansions, like the Wigner expansion. Stochastic gauges can be used to obtain an infinite class of positive-definite stochastic time-evolution equations, equivalent to master equations, for many systems including quantum time evolution. The method is illustrated with a variety of simple examples ranging from astrophysical molecular hydrogen production, through to the topical problem of Bose-Einstein condensation in an optical trap and the resulting quantum dynamics.

Progress in silicon-based quantum computation

We review progress at the Australian Centre for Quantum Computer Technology towards the fabrication and demonstration of spin qubits and charge qubits based on phosphorus donor atoms embedded in intrinsic silicon. Fabrication is being pursued via two complementary pathways: a 'top-down' approach for near-term production of few-qubit demonstration devices and a 'bottom-up' approach for large-scale qubit arrays with sub-nanometre precision. The 'top-down' approach employs a low-energy (keV) ion beam to implant the phosphorus atoms. Single-atom control during implantation is achieved by monitoring on-chip detector electrodes, integrated within the device structure. In contrast, the 'bottom-up' approach uses scanning tunnelling microscope lithography and epitaxial silicon overgrowth to construct devices at an atomic scale. In both cases, surface electrodes control the qubit using voltage pulses, and dual single-electron transistors operating near the quantum limit provide fast read-out with spurious-signal rejection.

Entangled subspaces and quantum symmetries

Entanglement is defined for each vector subspace of the tensor product of two finite-dimensional Hilbert spaces, by applying the notion of operator entanglement to the projection operator onto that subspace. The operator Schmidt decomposition of the projection operator defines a string of Schmidt coefficients for each subspace, and this string is assumed to characterize its entanglement, so that a first subspace is more entangled than a second, if the Schmidt string of the second majorizes the Schmidt string of the first. The idea is applied to the antisymmetric and symmetric tensor products of a finite-dimensional Hilbert space with itself, and also to the tensor product of an angular momentum j with a spin 1/2. When adapted to the subspaces of states of the nonrelativistic hydrogen atom with definite total angular momentum (orbital plus spin), within the space of bound states with a given total energy, this leads to a complete ordering of those subspaces by their Schmidt strings.

Enhanced optical properties of the GaAsN/GaAs quantum-well structure by the insertion of InAs monolayers

Microstructural and optical properties of InAs-inserted and reference single GaAsN/GaAs quantum-well (QW) structures grown by metalorganic chemical vapor deposition were investigated using cross-sectional transmission electron microscopy and photoluminescence (PL). Significant enhancement of PL intensity and a blueshift of PL emission were observed from the InAs-inserted GaAsN/GaAs QW structure, compared with the single GaAsN/GaAs QW structure. Strain compensation and In-induced reduction of N incorporation are suggested to be two major factors affecting the optical properties. (C) 2004 American Institute of Physics.

Stress corrosion cracking and hydrogen embrittlement of an Al-Zn-Mg-Cu alloy

The age hardening, stress corrosion cracking (SCC) and hydrogen embrittlement (HE) of an Al-Zn-Mg-Cu 7175 alloy were investigated experimentally. There were two peak-aged states during ageing. For ageing at 413 K, the strength of the second peak-aged state was slightly higher than that of the first one, whereas the SCC susceptibility was lower, indicating that it is possible to heat treat 7175 to high strength and simultaneously to have high SCC resistance. The SCC susceptibility increased with increasing Mg segregation at the grain boundaries. Hydrogen embrittlement (HE) increased with increased hydrogen charging and decreased with increasing ageing time for the same hydrogen charging conditions. Computer simulations were carried out of (a) the Mg grain boundary segregation using the embedded atom method and (b) the effect of Mg and H segregation on the grain boundary strength using a quasi-chemical approach. The simulations showed that (a) Mg grain boundary segregation in Al-Zn-Mg-Cu alloys is spontaneous, (b) Mg segregation decreases the grain boundary strength, and (c) H embrittles the grain boundary more seriously than does Mg. Therefore, the SCC mechanism of Al-Zn-Mg Cu alloys is attributed to the combination of HE and Mg segregation induced grain boundary embrittlement. (C) 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Crystallography of zirconium hydrides in recrystallized Zircaloy-2 fuel cladding lay electron backscatter diffraction

Precipitation morphology and habit planes of the delta-phase Zr hydrides, which were precipitated within the a-phase matrix grains and along the grain boundaries of recrystallized Zircaloy-2 cladding tube, have been examined by electron backscatter diffraction (EBSD). Radially-oriented hydrides, induced by residual tensile stress, precipitated in the outside region of the cladding, and circumferentially-oriented hydrides in the stress-free middle region of the cladding. The most common crystallographic relationship for both types of the hydrides precipitated at the inter- and intra-granular sites was identical at (0001)(alpha) // {111}(delta), with {1017}(alpha) // {111}(delta) being the occasional exception only for the inter-granular radial hydrides. When tensile stress was loaded, the intra-granular hydrides tended to preferentially precipitate in the grains with circumferential basal pole textures. The inter-granular hydrides tended to preferentially precipitate on the grain faces opposite to tensile axis. The change of prioritization in the precipitation sites for the hydrides due to tensile stress could be explained in terms of the relaxation effect of constrained elastic energy on the terminal solid solubility of hydrogen at hydride precipitation.

Microstructure of MmM(5)/Mg multi-layer hydrogen storage films prepared by magnetron sputtering

Multi-layer hydrogen storage thin films with Mg and MmNi(3.5)(CoAlMn)(1.5) (here Mm denotes La-rich mischmetal) as alternative layers were prepared by direct current magnetron sputtering. Transmission electron microscopy investigation shows that the microstructure of the MmNi(3.5)(CoAlMn)(1.5) and Mg layers are significantly different although their deposition conditions are the same. The MmNi(3.5)(CoAlMn)(1.5) layer is composed of two regions: one is an amorphous region approximately 4 nm thick at the bottom of the layer and the other is a nanocrystalline region on top of the amorphous region. The Mg layer is also composed of two regions: one is a randomly orientated nanocrystalline region 50 nm thick at the bottom of the layer and the other is a columnar crystallite region on top of the nanocrystalline region. These Mg columnar crystallites have their [001] directions parallel to the growth direction and the average lateral size of these columnar crystallites is about 100 nm. A growth mechanism of the multi-layer thin films is discussed based on the experiment results. Wiley-Liss, Inc.

The effects of J-gate potential and interfaces on donor exchange coupling in the Kane quantum computer architecture

We calculate the electron exchange coupling for a phosphorus donor pair in silicon perturbed by a J-gate potential and the boundary effects of the silicon host geometry. In addition to the electron-electron exchange interaction we also calculate the contact hyperfine interaction between the donor nucleus and electron as a function of the varying experimental conditions. Donor separation, depth of the P nuclei below the silicon oxide layer and J-gate voltage become decisive factors in determining the strength of both the exchange coupling and hyperfine interaction-both crucial components for qubit operations in the Kane quantum computer. These calculations were performed using an anisotropic effective-mass Hamiltonian approach. The behaviour of the donor exchange coupling as a function of the parameters varied in this work provides relevant information for the experimental design of these devices.