Directed C-H Halogenation Reactions Catalysed by PdII Supported on Polymers under Batch and Continuous Flow Conditions.

A new generation of N-heterocyclic carbene palladium(II) complexes containing vinyl groups in different positions in the backbone of the N-heterocycle have been developed. The fully characterised monomers were copolymerised with divinylbenzene to fabricate robust polymer supported NHC-PdII complexes and these polymers were applied as heterogeneous catalysts in directed C-H halogenation of arenes with a pyridine-type directing group. The catalysts demonstrated medium-high catalytic activity with up to 90 % conversion and 100 % selectivity in chlorination. They are heterogeneous and recyclable (at least six times) with no significant leaching of palladium in batch mode catalysis. The best catalyst was also applied under continuous flow conditions where it disclosed an exceptional activity (90 % conversion) and 100 % selectivity for the mono-halogenated product for at least six days, with no leaching of palladium, no loss of activity and an ability to maintain the original oxidation state of PdII .

Kinetic Engineering of Wurtzite and Zinc-Blende AlSb Shells on InAs Nanowires.

Using AlSb as the model system, we demonstrate that kinetic limitations can lead to the preferential growth of wurtzite (WZ) AlSb shells rather than the thermodynamically stable zinc-blende (ZB) AlSb and that the WZ and ZB relative thickness can be tuned by a careful control of the deposition parameters. We report selective heteroepitaxial radial growth of AlSb deposited by metal-organic vapor phase epitaxy (MOVPE) on InAs nanowire core templates with engineered lengths of axial WZ and ZB segments. AlSb shell thickness, crystal phase, nanostructure, and composition are investigated as a function of the shell growth temperature, Ts, using scanning electron microscopy, transmission electron microscopy, electron tomography, and energy-dispersive X-ray spectroscopy. We find that ZB- and WZ-structured AlSb shells grow heteroepitaxially around the ZB and WZ segments of the InAs core, respectively. Surprisingly, at 390 < Ts < 450 °C, the WZ-AlSb shells are thicker than the ZB-AlSb shells, and their thickness increases with decreasing Ts. In comparison, the ZB-AlSb shell thicknesses increase slightly with increasing Ts. We find that the increased thickness of the WZ-AlSb shells is due to the formation and enhanced deposition on {112̅0} facets rather than on the more commonly grown {101̅0} sidewall facets. Overall, these results, which are in direct contrast with previous reports suggesting that heteroepitaxial radial growth of III-antimonides is always favored on the ZB-structure facets, indicate that the growth of WZ-AlSb is preferred over the thermodynamically stable ZB-AlSb at lower growth temperatures. We attribute this behavior to kinetic limitations of MOVPE of AlSb on ZB and WZ phases of InAs.

n-type doping and morphology of GaAs nanowires in Aerotaxy.

Controlled doping in semiconductor nanowires modifies their electrical and optical properties, which are important for high efficiency optoelectronic devices. We have grown n-type (Sn) doped GaAs nanowires in Aerotaxy, a new continuous gas phase mass production technique. The morphology of Sn doped nanowires is found to be a strong function of dopant, tetraethyltin to trimethylgallium flow ratio, Au-Ga-Sn alloying, and nanowire growth temperatures. High temperature and high flow ratios result in low morphological quality nanowires and in parasitic growth on the wire base and surface. Alloying and growth temperatures of 400 °C and 530 °C, respectively, resulted in good morphological quality nanowires for a flow ratio of TESn to TMGa up to 2.25 × 10-3. The wires are pure zinc-blende for all investigated growth conditions, whereas nanowires grown by metal-organic vapor phase epitaxy with the same growth conditions are usually mainly Wurtzite. The growth rate of the doped wires is found to be dependent more on the TESn flow fraction than on alloying and nanowire growth temperatures. Our photoluminescence measurements, supported by four-point probe resistivity measurements, reveal that the carrier concentration in the doped wires varies only slightly (1-3) × 1019 cm-3 with TESn flow fraction and both alloying and growth temperatures, indicating that good morphological quality wires with high carrier density can be grown with low TESn flow. Carrier concentrations lower than 1019 cm-3 can be grown by further reducing the flow fraction of TESn, which may give better morphology wires.

Continuous gas-phase synthesis of nanowires with tunable properties.

Semiconductor nanowires are key building blocks for the next generation of light-emitting diodes, solar cells and batteries. To fabricate functional nanowire-based devices on an industrial scale requires an efficient methodology that enables the mass production of nanowires with perfect crystallinity, reproducible and controlled dimensions and material composition, and low cost. So far there have been no reports of reliable methods that can satisfy all of these requirements. Here we show how aerotaxy, an aerosol-based growth method, can be used to grow nanowires continuously with controlled nanoscale dimensions, a high degree of crystallinity and at a remarkable growth rate. In our aerotaxy approach, catalytic size-selected Au aerosol particles induce nucleation and growth of GaAs nanowires with a growth rate of about 1 micrometre per second, which is 20 to 1,000 times higher than previously reported for traditional, substrate-based growth of nanowires made of group III-V materials. We demonstrate that the method allows sensitive and reproducible control of the nanowire dimensions and shape--and, thus, controlled optical and electronic properties--through the variation of growth temperature, time and Au particle size. Photoluminescence measurements reveal that even as-grown nanowires have good optical properties and excellent spectral uniformity. Detailed transmission electron microscopy investigations show that our aerotaxy-grown nanowires form along one of the four equivalent〈111〉B crystallographic directions in the zincblende unit cell, which is also the preferred growth direction for III-V nanowires seeded by Au particles on a single-crystal substrate. The reported continuous and potentially high-throughput method can be expected substantially to reduce the cost of producing high-quality nanowires and may enable the low-cost fabrication of nanowire-based devices on an industrial scale.

Polymer-Supported Palladium(II) Carbene Complexes: Catalytic Activity, Recyclability, and Selectivity in C-H Acetoxylation of Arenes.

Heterogeneous catalysts for selective oxidation of C-H bonds were synthesized by co-polymerization of new N-heterocyclic carbene-palladium(II) (NHC-PdII ) monomers with divinylbenzene. The polymer-supported NHC-PdII -catalysed undirected C-H acetoxylation of simple and methylated arenes as well as polyarenes, with similar or superior efficiency compared to their homogeneous analogues. In particular, the regioselectivity has been improved in the acetoxylation of biphenyl and naphthalene compared to the best homogeneous catalysts. The new polymer-supported catalysts maintain the original oxidation state of PdII after repeated catalytic reactions, and exhibit no significant leaching of palladium. In addition, the new catalysts have been successfully recovered and reused without loss of activity over several cycles of reactions.

Growth parameter design for homogeneous material composition in ternary Ga(x)In(1-x)P nanowires.

Ternary nanowires (NWs) often exhibit varying material composition along the NW growth axis because of different diffusion properties of the precursor molecules. This constitutes a problem for optoelectronic devices for which a homogeneous material composition is most often of importance. Especially, ternary GaInP NWs grown under a constant Ga-In precursor ratio typically show inhomogeneous material composition along the length of the NW due to the complexity of low temperature precursor pyrolysis and relative rates of growth species from gas phase diffusion and surface diffusion that contribute to synthesis of particle-assisted growth. Here, we present the results of a method to overcome this challenge by in situ tuning of the trimethylindium molar fraction during growth of ternary Zn-doped GaInP NWs. The NW material compositions were determined by use of x-ray diffraction, scanning transmission electron microscopy and energy dispersive x-ray spectroscopy and the optical properties by photoluminescence spectroscopy.

FIB plan and side view cross-sectional TEM sample preparation of nanostructures.

Focused ion beam is a powerful method for cross-sectional transmission electron microscope sample preparation due to being site specific and not limited to certain materials. It has, however, been difficult to apply to many nanostructured materials as they are prone to damage due to extending from the surface. Here we show methods for focused ion beam sample preparation for transmission electron microscopy analysis of such materials, demonstrated on GaAs-GaInP core shell nanowires. We use polymer resin as support and protection and are able to produce cross-sections both perpendicular to and parallel with the substrate surface with minimal damage. Consequently, nanowires grown perpendicular to the substrates could be imaged both in plan and side view, including the nanowire-substrate interface in the latter case. Using the methods presented here we could analyze the faceting and homogeneity of hundreds of adjacent nanowires in a single lamella.

Electron trapping in InP nanowire FETs with stacking faults.

Semiconductor III-V nanowires are promising components of future electronic and optoelectronic devices, but they typically show a mixed wurtzite-zinc blende crystal structure. Here we show, theoretically and experimentally, that the crystal structure dominates the conductivity in such InP nanowires. Undoped devices show very low conductivities and mobilities. The zincblende segments are quantum wells orthogonal to the current path and our calculations indicate that an electron concentration of up to 4.6 × 10(18) cm(-3) can be trapped in these. The calculations also show that the room temperature conductivity is controlled by the longest zincblende segment, and that stochastic variations in this length lead to an order of magnitude variation in conductivity. The mobility shows an unexpected decrease for low doping levels, as well as an unusual temperature dependence that bear resemblance with polycrystalline semiconductors.

Electron transfer in quantum-dot-sensitized ZnO nanowires: ultrafast time-resolved absorption and terahertz study.

Photoinduced electron injection dynamics from CdSe quantum dots to ZnO nanowires is studied by transient absorption and time-resolved terahertz spectroscopy measurements. Ultrafast electron transfer from the CdSe quantum dots to ZnO is proven to be efficient already on a picoseconds time scale (τ = 3-12 ps). The measured kinetics was found to have a two-component character, whose origin is discussed in detail. The obtained results suggest that electrons are injected into ZnO via an intermediate charge transfer state.

Probing the wurtzite conduction band structure using state filling in highly doped InP nanowires.

We have grown InP nanowires doped with hydrogen sulfide, which exhibit sulfur concentrations of up to 1.4%. The highest doped nanowires show a pure wurtzite crystal structure, in contrast to bulk InP which has the zinc blende structure. The nanowires display photoluminescence which is strongly blue shifted compared with the band gap, well into the visible range. We find evidence of a second conduction band minimum at the gamma point about 0.23 eV above the band edge, in excellent agreement with recent theoretical predictions. Electrical measurements show high conductivity and breakdown currents of 10(7) A/cm(2).

Growth of straight InAs-on-GaAs nanowire heterostructures.

One of the main motivations for the great interest in semiconductor nanowires is the possibility of easily growing advanced heterostructures that might be difficult or even impossible to achieve in thin films. For III-V semiconductor nanowires, axial heterostructures with an interchange of the group III element typically grow straight in only one interface direction. In the case of InAs-GaAs heterostructures, straight nanowire growth has been demonstrated for growth of GaAs on top of InAs, but so far never in the other direction. In this article, we demonstrate the growth of straight axial heterostructures of InAs on top of GaAs. The heterostructure interface is sharp and we observe a dependence on growth parameters closely related to crystal structure as well as a diameter dependence on straight nanowire growth. The results are discussed by means of accurate first principles calculations of the interfacial energies. In addition, the role of the gold seed particle, the effect of its composition at different stages during growth, and its size are discussed in relation to the results observed.

Electron image series reconstruction of twin interfaces in InP superlattice nanowires.

The twin interface structure in twinning superlattice InP nanowires with zincblende structure has been investigated using electron exit wavefunction restoration from focal series images recorded on an aberration-corrected transmission electron microscope. By comparing the exit wavefunction phase with simulations from model structures, it was possible to determine the twin structure to be the ortho type with preserved In-P bonding order across the interface. The bending of the thin nanowires away from the intended 110 axis could be estimated locally from the calculated diffraction pattern, and this parameter was successfully taken into account in the simulations.

Changes in contact angle of seed particle correlated with increased zincblende formation in doped InP nanowires.

Nanowires grown with the vapor-liquid-solid method commonly exhibit polytypism, showing both zincblende and wurtzite crystal structure. We have grown p-type InP nanowires using DEZn as a dopant precursor and studied the wetting of the seed particle and the nanowire crystal structure. The nanowires grown with high DEZn molar fractions exhibit deformed seed particles after growth. We observe 20% smaller nanowire diameter at the highest DEZn molar fraction, indicating a significant increase in contact angle of the seed particle during growth. The decrease in diameter correlates with an increase in zincblende segment length as measured by TEM. We explain the results with a modified nucleation model.

XEDS-mapping for explaining release patterns from single pellets.

A common way to formulate controlled-release (CR) pharmaceuticals is to coat pellets of active substance with a polymer film, decrease the size of the pellets and distribute them as multiple-unit dosages in capsules. To increase the understanding of the release mechanism, the pellet shape and surface structure of pellets, before and after release in microtitre plates, have been studied by scanning electron microscope and X-ray energy-dispersive spectrometry. By performing these studies we associate release profiles during the first few hours to the microscopic structure. Pellets were divided into three classes (spherical pellets, dumbbell shaped pellets and twin-pellets) according to pellet form. Cases of burst release occurred for all three shape classes due to "open-window-defects" at the surface. Areas of thinner polymer film in the neck-region of dumbbell shaped pellets broaden the range of intermediate release rates for this pellet shape. The surface of twin pellets and dumbbell shaped pellets showed more defects, which increases the release rates in comparison to spherical pellets. All pellets with high release rates revealed ruptures in the polymer film, whereas only small cracks could be traced for pellets with slow release rates. The information gained is necessary for the development of future formulations and mathematical modelling of release patterns. The pharmaceutical used as model was remoxipride coated with a polymer film of ethyl cellulose and 10 wt.% triethyl citrate.

Phase Transformation in Radially Merged Wurtzite GaAs Nanowires.

III-V Nanowires (NWs) grown with metal-organic chemical vapor deposition commonly show a polytypic crystal structure, allowing growth of structures not found in the bulk counterpart. In this paper we studied the radial overgrowth of pure wurtzite (WZ) GaAs nanowires and characterized the samples with high resolution X-ray diffraction (XRD) to reveal the crystal structure of the grown material. In particular, we investigated what happens when adjacent WZ NWs radially merge with each other by analyzing the evolution of XRD peaks for different amounts of radial overgrowth and merging. By preparing cross-sectional lamella samples we also analyzed the local crystal structure of partly merged NWs by transmission electron microscopy. Once individual NWs start to merge, the crystal structure of the merged segments is transformed progressively from initial pure WZ to a mixed WZ/ZB structure. The merging process is then modeled using a simple combinatorial approach, which predicts that merging of two or more WZ NWs will result in a mixed crystal structure containing WZ, ZB, and 4H. The existence large and relaxed segments of 4H structure within the merged NWs was confirmed by XRD, allowing us to accurately determine the lattice parameters of GaAs 4H. We compare the measured WZ and 4H unit cells with an ideal tetrahedron and find that both the polytypes are elongated in the c-axis and compressed in the a-axis compared to the geometrically converted cubic ZB unit cell.

Simulation of the release from a multiparticulate system validated by single pellet and dose release experiments.

A previously described single-pellet release model has been simplified and modified to give predictions of the release from multiple-pellet systems, besides describing the release from single pellets. The simplified single-pellet model has been verified using single-pellet data and has been used to estimate three release-controlling parameters, namely the pellet core radius, the overall mass transfer coefficient, and the lag time. Single-pellet release experiments showed that the release from the individual film-coated drug cores resulted in a wide distribution of release profiles, a phenomenon not observed on the dose level. Therefore, the parameter estimations resulted in distributions of these parameter values. The core radius and the lag times compared well with the experimental data. The distributions were used as input data for the multiple pellet model, in order to predict the release profiles on the dose level, showing results consistent with the measured dose release. The dose-predictive ability of the model was demonstrated in simulations by studying the effect of a change in the size of the single subunits (of constant total dose), showing that smaller pellets give an increased release rate with less variation. The model for predicting dose-release profiles could be of great value in optimising the performance of an existing formulation, as well as in the development of a new controlled-release pharmaceutical.

Multiple exciton generation in nano-crystals revisited: consistent calculation of the yield based on pump-probe spectroscopy.

Multiple exciton generation (MEG) is a process in which more than one exciton is generated upon the absorption of a high energy photon, typically higher than two times the band gap, in semiconductor nanocrystals. It can be observed experimentally using time resolved spectroscopy such as the transient absorption measurements. Quantification of the MEG yield is usually done by assuming that the bi-exciton signal is twice the signal from a single exciton. Herein we show that this assumption is not always justified and may lead to significant errors in the estimated MEG yields. We develop a methodology to determine proper scaling factors to the signals from the transient absorption experiments. Using the methodology we find modest MEG yields in lead chalcogenide nanocrystals including the nanorods.

High-resolution fluorescence diffuse optical tomography developed with nonlinear upconverting nanoparticles.

Fluorescence diffuse optical tomography (FDOT) is an emerging biomedical imaging technique that can be used to localize and quantify deeply situated fluorescent molecules within tissues. However, the potential of this technique is currently limited by its poor spatial resolution. In this work, we demonstrate that the current resolution limit of FDOT can be breached by exploiting the nonlinear power-dependent optical emission property of upconverting nanoparticles doped with rare-earth elements. The rare-earth-doped core-shell nanoparticles, NaYF(4):Yb(3+)/Tm(3+)@NaYF(4) of hexagonal phase, are synthesized through a stoichiometric method, and optical characterization shows that the upconverting emission of the nanoparticles in tissues depends quadratically on the power of excitation. In addition, quantum-yield measurements of the emission from the synthesized nanoparticles are performed over a large range of excitation intensities, for both core and core-shell particles. The measurements show that the quantum yield of the 800 nm emission band of core-shell upconverting nanoparticles is 3.5% under an excitation intensity of 78 W/cm(2). The FDOT reconstruction experiments are carried out in a controlled environment using liquid tissue phantoms. The experiments show that the spatial resolution of the FDOT reconstruction images can be significantly improved by the use of the synthesized upconverting nanoparticles and break the current spatial resolution limits of FDOT images obtained from using conventional linear fluorophores as contrast agents.

Vertical "III-V" V-shaped nanomembranes epitaxially grown on a patterned Si[001] substrate and their enhanced light scattering.

We report on a new form of III-V compound semiconductor nanostructures growing epitaxially as vertical V-shaped nanomembranes on Si(001) and study their light-scattering properties. Precise position control of the InAs nanostructures in regular arrays is demonstrated by bottom-up synthesis using molecular beam epitaxy in nanoscale apertures on a SiO(2) mask. The InAs V-shaped nanomembranes are found to originate from the two opposite facets of a rectangular pyramidal island nucleus and extend along two opposite <111> B directions, forming flat {110} walls. Dark-field scattering experiments, in combination with light-scattering theory, show the presence of distinctive shape-dependent optical resonances significantly enhancing the local intensity of incident electromagnetic fields over tunable spectral regions. These new nanostructures could have interesting potential in nanosensors, infrared light emitters, and nonlinear optical elements.