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Upconverting nanoparticles (UCNPs) are well-known for their capacity to convert near-infrared light into UV/visible light, benefitting various applications where light triggering is required. At the nanoscale, loss of luminescence intensity is observed and thus, a decrease in photoluminescence quantum yield (PLQY), usually ascribed to surface quenching. We evaluate this by measuring the PLQY of NaGdF4:Er3+,Yb3+ UCNPs as a function of size (ca. 15 to 100 nm) and shape (spheres, cubes, hexagons). Our results show that the PLQY of α-phase NaGdF4 Er3+,Yb3+ surpasses that of β-NaGdF4 for sizes below 20 nm, an observation related to distortion of the crystal lattice when the UCNPs become smaller. The present study also underlines that particle shape must not be neglected as a relevant parameter for PLQY. In fact, based on a mathematical nucleus/hull volumetric model, shape was found to be particularly relevant in the 20 to 60 nm size range of the investigated UCNPs.

International audience; Adapting optical microscopy methods for nanoscale characterization of defects in two-dimensional (2D) materials is a vital step for photonic on-chip devices. To increase the analysis throughput, waveguide-based on-chip imaging platforms have been recently developed. Their inherent disadvantage, however, is the necessity to transfer the 2D material from the growth substrate to the imaging chip, which introduces nonuniform material coverage and contamination, potentially altering the characterization results. Here we present a unique approach to circumvent these shortfalls by directly growing a widely used 2D material (hexagonal boron nitride, hBN) on silicon nitride chips and optically characterizing the defects in the intact as-grown material. We compare the direct growth approach to the standard PMMA-assisted wet transfer method and confirm the clear advantages of the direct growth. While demonstrated with hBN in the current work, the method can be extended to other 2D materials.

Upconverting nanoparticles (UCNPs) are well-known for their capacity to convert near-infrared light into UV/visible light, benefitting various applications where light triggering is required. At the nanoscale, loss of luminescence intensity is observed and thus, a decrease in photoluminescence quantum yield (PLQY), usually ascribed to surface quenching. We evaluate this by measuring the PLQY of NaGdF

The electronic band structure of complex nanostructured semiconductors has a considerable effect on the final electronic and optical properties of the material and, ultimately, on the functionality of the devices incorporating them. Valence electron energy-loss spectroscopy (VEELS) in the transmission electron microscope (TEM) provides the possibility of measuring this property of semiconductors with high spatial resolution. However, it still represents a challenge for narrow-bandgap semiconductors, since an electron beam with low energy spread is required. Here we demonstrate that by means of monochromated VEELS we can study the electronic band structure of narrow-gap materials GaSb and InAs in the form of heterostructured nanowires, with bandgap values down to 0.5 eV, especially important for newly developed structures with unknown bandgaps. Using complex heterostructured InAs-GaSb nanowires, we determine a bandgap value of 0.54 eV for wurtzite InAs. Moreover, we directly compare the bandgaps of wurtzite and zinc blende polytypes of GaSb in a single nanostructure, measured here as 0.84 and 0.75 eV, respectively. This allows us to solve an existing controversy in the band alignment between these structures arising from theoretical predictions. The findings demonstrate the potential of monochromated VEELS to provide a better understanding of the band alignment at the heterointerfaces of narrow-bandgap complex nanostructured materials with high spatial resolution. This is especially important for semiconductor device applications where even the slightest variations of the electronic band structure at the nanoscale can play a crucial role in their functionality.

Zinc phosphide (Zn3P2) nanowires constitute prospective building blocks for next generation solar cells due to the combination of suitable optoelectronic properties and an abundance of the constituting elements in the Earth's crust. The generation of periodic superstructures along the nanowire axis could provide an additional mechanism to tune their functional properties. Here we present the vapour-liquid-solid growth of zinc phosphide superlattices driven by periodic heterotwins. This uncommon planar defect involves the exchange of Zn by In at the twinning boundary. We find that the zigzag superlattice formation is driven by reduction of the total surface energy of the liquid droplet. The chemical variation across the heterotwin does not affect the homogeneity of the optical properties, as measured by cathodoluminescence. The basic understanding provided here brings new propsects on the use of II-V semiconductors in nanowire technology.

Large-scale deployment of thin-film photovoltaics will be facilitated through earth-abundant components. Herein, selective area epitaxy and lateral overgrowth epitaxy are explored for the growth of zinc phosphide (Zn3P2), a promising earth-abundant absorber. The ideal growth conditions are elucidated, and the nucleation of single-crystal nanopyramids that subsequently evolve towards coalesced thin-films is demonstrated. The zinc phosphide pyramids exhibit room temperature bandgap luminescence at 1.53 eV, indicating a high-quality material. The electrical properties of zinc phosphide and the junction with the substrate are assessed by conductive atomic force microscopy on n-type, p-type and intrinsic substrates. The measurements are consistent with the p-type characteristic of zinc phosphide. Overall, this constitutes a new, and transferrable, approach for the controlled and tunable growth of high-quality zinc phosphide, a step forward in the quest for earth-abundant photovoltaics.

The use of methane as one of the cleanest energy sources has attracted significant public awareness, and methane production processes with less environmental impact than fracking are receiving considerable attention. Catalytic hydrocracking of plastic materials has been considered a potential clean alternative. However, catalysts that convert heterogeneous plastic feeds into a single product under industrially relevant conditions are lacking. Here, we describe a Ru-modified zeolite that catalytically transforms polyethylene, polypropylene, and polystyrene into grid-compatible methane (>97% purity), at 300 degrees C-350 degrees C using near-stoichiometric amounts of H-2. Mechanistic studies reveal a chain-end initiation process with limited isomerization of plastic substrates. A Ru site-dominant mechanism is proposed based on these studies and density functional theory (DFT) computations. We foresee that such a plastic-to-methane process may increase the intelligent use of plastic waste via energy recovery. There is also the potential to accommodate emerging sustainable H-2 production into existing natural gas networks, while integrating waste management, fuel production, and energy storage.

Zinc phosphide, Zn3P2, nanowires constitute prospective building blocks for next generation solar cells due to the combination of suitable optoelectronic properties and an abundance of the constituting elements in the Earths crust. The generation of periodic superstructures along the nanowire axis could provide an additional mechanism to tune their functional properties. Here we present the vapour-liquid-solid growth of zinc phosphide superlattices driven by periodic heterotwins. This uncommon planar defect involves the exchange of Zn by In at the twinning boundary. We find that the zigzag superlattice formation is driven by reduction of the total surface energy of the liquid droplet. The chemical variation across the heterotwin does not affect the homogeneity of the optical proerties, as measured by cathodoluminescence. The basic understanding provided here brings new perspectives on the use of II-V semiconductors in nanowire technology.

The integration of III–V semiconductors with Si in device fabrication is facilitated by the use of nanoscale structures such as nanowires. Nanowires are predominantly grown using Au seed particles; however, the seed material is known to affect the nanowire growth and properties. Here we present growth of GaAs nanowires using three different seed particle materials: Au, Ag, and a AgAu alloy. By comparing the results from the different seeds, we found that the growths of Au- and AgAu-seeded nanowires were in general very similar, with homogeneous and vertical nanowires observed in both cases. The Ag-seeded growths instead revealed a lower yield of vertical nanowires with large variations in lengths. Different Ga-concentrations were measured in the different seed particles, which suggested that the Au and the AgAu seed particles were liquid during growth, whereas Ag particles were solid. The chemical potential of Ga was however found to be similar for all three seed materials. We propose that the Ga concentr...

Over the past decade, III-V heterostructure nanowires have attracted a surge of attention for their application in novel semiconductor devices such as tunneling field-effect transistors (TFETs). The functionality of such devices critically depends on the specific atomic arrangement at the semiconductor heterointerfaces. However, most of the currently available characterization techniques lack sufficient spatial resolution to provide local information on the atomic structure and composition of these interfaces. Atomic-resolution spectrum imaging by means of electron energy-loss spectroscopy (EELS) in the scanning transmission electron microscope (STEM) is a powerful technique with the potential to resolve structure and chemical composition with sub-angstrom spatial resolution and to provide localized information about the physical properties of the material at the atomic scale. Here, we demonstrate the use of atomic-resolution EELS to understand the interface atomic arrangement in three-dimensional heterostructures in semiconductor nanowires. We observed that the radial interfaces of GaSb-InAs heterostructure nanowires are atomically abrupt, while the axial interface in contrast consists of an interfacial region where intermixing of the two compounds occurs over an extended spatial region. The local atomic configuration affects the band alignment at the interface and, hence, the charge transport properties of devices such as GaSb-InAs nanowire TFETs. STEM-EELS thus represents a very promising technique for understanding nanowire physical properties, such as differing electrical behavior across the radial and axial heterointerfaces of GaSb-InAs nanowires for TFET applications.

We here investigate the growth mechanism of Sn-seeded GaSb nanowires and demonstrate how the seed particle and its dynamics at the growth interface of the nanowire determine the polarity, as well as the formation of structural defects. We use aberration-corrected scanning transmission electron microscopy imaging methodologies to study the interrelationship between the structural properties, i.e. polarity, growth mechanism, and formation of inclined twin boundaries in pairs. Moreover, the optical properties of the Sn-seeded GaSb nanowires are examined. Their photoluminescence response is compared with one of their Au-seeded counterparts, suggesting the incorporation of Sn atoms from the seed particles into the nanowires.

The lack of mirror symmetry in binary semiconductor compounds turns them into polar materials, where two opposite orientations of the same crystallographic direction are possible. Interestingly, their physical properties (e.g., electronic or photonic) and morphological features (e.g., shape, growth direction, and so forth) also strongly depend on the polarity. It has been observed that nanoscale materials tend to grow with a specific polarity, which can eventually be reversed for very specific growth conditions. In addition, polar-directed growth affects the defect density and topology and might induce eventually the formation of undesirable polarity inversion domains in the nanostructure, which in turn will affect the photonic and electronic final device performance. Here, we present a review on the polarity-driven growth mechanism at the nanoscale, combining our latest investigation with an overview of the available literature highlighting suitable future possibilities of polarity engineering of semiconductor nanostructures. The present study has been extended over a wide range of semiconductor compounds, covering the most commonly synthesized III–V (GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb) and II–VI (ZnO, ZnTe, CdS, CdSe, CdTe) nanowires and other free-standing nanostructures (tripods, tetrapods, belts, and membranes). This systematic study allowed us to explore the parameters that may induce polarity-dependent and polarity-driven growth mechanisms, as well as the polarity-related consequences on the physical properties of the nanostructures., ICN2 acknowledges funding from Generalitat de Catalunya 2017 SGR 327 and the Spanish MINECO coordinated project ENE2017-85087-C3. ICN2 is supported by the Severo Ochoa program from Spanish MINECO (Grant SEV-2017-0706) and is funded by the CERCA Programme/Generalitat de Catalunya. Part of the present work has been performed in the framework of Universitat Autònoma de Barcelona Materials Science Ph.D. program. S.M.S. acknowledges funding from “Programa Internacional de Becas “la Caixa”-Severo Ochoa”. The HAADF-STEM experiments were conducted in the Laboratorio de Microscopias Avanzadas at Instituto de Nanociencia de Aragon-Universidad de Zaragoza. A.F.i.M. thanks SNSF for funding through the NCCR QSIT. This work has received funding from the European Union’s Horizon 2020 Research and Innovation Programme under grant agreement No. 654360 NFFA-Europe. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No. 823717 – ESTEEM3., We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI).

Transmission electron microscopy (TEM) offers an ample range of complementary techniques which are able to provide essential information about the physical, chemical and structural properties of materials at the atomic scale, and hence makes a vast impact on our understanding of materials science, especially in the field of semiconductor one-dimensional (1D) nanostructures. Recent advancements in TEM instrumentation, in particular aberration correction and monochromation, have enabled pioneering experiments in complex nanostructure material systems. This review aims to address these understandings through the applications of the methodology for semiconductor nanostructures. It points out various electron microscopy techniques, in particular scanning TEM (STEM) imaging and spectroscopy techniques, with their already-employed or potential applications on 1D nanostructured semiconductors. We keep the main focus of the paper on the electronic and optoelectronic properties of such semiconductors, and avoid expanding it further. In the first part of the review, we give a brief introduction to each of the STEM-based techniques, without detailed elaboration, and mention the recent technological and conceptual developments which lead to novel characterization methodologies. For further reading, we refer the audience to a handful of papers in the literature. In the second part, we highlight the recent examples of application of the STEM methodology on the 1D nanostructure semiconductor materials, especially III-V, II-V, and group IV bare and heterostructure systems. The aim is to address the research questions on various physical properties and introduce solutions by choosing the appropriate technique that can answer the questions. Potential applications will also be discussed, the ones that have already been used for bulk and 2D materials, and have shown great potential and promise for 1D nanostructure semiconductors., JA acknowledges funding from Generalitat de Catalunya 2017 SGR 327. ICN2 acknowledges support from the Severo Ochoa Programme (MINECO, Grant No. SEV-2013-0295) and is funded by the CERCA Programme/Generalitat de Catalunya.

Semiconductors made with earth abundant elements are promising as absorbers in future large-scale deployment of photovoltaic technology. This paper reports on the epitaxial synthesis of monocrystalline zinc phosphide Z n 3 P 2 films using molecular beam epitaxy with thicknesses up to 1 µm thickness on InP (100) substrates, as demonstrated by high resolution transmission electron microscopy and x-ray diffraction. We explain the mechanisms by which thick monocrystalline layers can form. We correlate the crystalline quality with the optical properties by photoluminescence at 12 K. Polycrystalline and monocrystalline films exhibit dissimilar photoluminescence below the bandgap at 1.37 and 1.30 eV, respectively. Band edge luminescence at 1.5 eV is only detected for monocrystalline samples. This work establishes a reliable method for fabricating high-quality Z n 3 P 2 thin films that can be employed in next generation photovoltaic applications.

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 inc...

We use a scanning nanometer-scale superconducting quantum interference device to map the stray magnetic field produced by individual ferromagnetic nanotubes (FNTs) as a function of applied magnetic field. The images are taken as each FNT is led through magnetic reversal and are compared with micromagnetic simulations, which correspond to specific magnetization configurations. In magnetic fields applied perpendicular to the FNT long axis, their magnetization appears to reverse through vortex states, i.e.\ configurations with vortex end domains or -- in the case of a sufficiently short FNT -- with a single global vortex. Geometrical imperfections in the samples and the resulting distortion of idealized mangetization configurations influence the measured stray-field patterns., Comment: 14 pages, 4 figures

A high speed repetition rate laser was used in an ‘eclipse’ system configuration for growing ZnO nanowires on Au patterned substrates, using vapor–liquid–solid (VLS) technique. Experimental results have shown that the nanowire length increase in the vicinity of catalyst free areas and the grown length distribution over the catalyst covered areas depend on the number of the laser pulses per train. The results suggest that the nanowire over-growth, attributed to the particle surface diffusion, is effective in the ZnO VLS growth within about 100 μm distances. ‘Glancing angle setup’ obtained for a submillimeter mask-substrate distance could provide control over VLS growing (or actually over ‘non-growing’) locations by suppressing the nanowire grow in the center of the catalyst covered areas.

The physical properties of material largely depend on their crystal structure. Nanowire growth is an important method for attaining metastable crystal structures in III-V semiconductors, giving access to advantageous electronic and surface properties. Antimonides are an exception, as growing metastable wurtzite structure has proven to be challenging. As a result, the properties of these materials remain unknown. One promising means of accessing wurtzite antimonides is to use a wurtzite template to facilitate their growth. Here, a template technique using branched nanowire growth for realizing wurtzite antimonide material is demonstrated. On wurtzite InAs trunks, InAs

III-V ternary nanowires are interesting due to the possibility of modulating their physical and material properties by tuning their material composition. Amongst them InAs

The application of the synchrotron-radiation-based coherent nanobeam X-ray diffraction method to study the type, quantity and the exact distances in between stacking faults in single GaAs nanowires is demonstrated., Coherent X-ray diffraction was used to measure the type, quantity and the relative distances between stacking faults along the growth direction of two individual wurtzite GaAs nanowires grown by metalorganic vapour epitaxy. The presented approach is based on the general property of the Patterson function, which is the autocorrelation of the electron density as well as the Fourier transformation of the diffracted intensity distribution of an object. Partial Patterson functions were extracted from the diffracted intensity measured along the direction in the vicinity of the wurtzite Bragg peak. The maxima of the Patterson function encode both the distances between the fault planes and the type of the fault planes with the sensitivity of a single atomic bilayer. The positions of the fault planes are deduced from the positions and shapes of the maxima of the Patterson function and they are in excellent agreement with the positions found with transmission electron microscopy of the same nanowire.

A high repetition rate (500 kHz) solid state laser was used for the ablation process in a Pulsed Laser Deposition (PLD)/Vapor–Liquid–Solid (VLS) growing. A ZnO target was ablated with laser powers between 0.6 W and 1.2 W, and a variable number of pulses per train and trains frequencies. ZnO structures were grown on gold patterned and unpatterned substrates surfaces. Enhanced growth of the nanostructures could be noticed on the catalyst patterned surfaces. Better nanowire morphologies were also observed for bigger number of laser pulses per train. The enhancements are more evident for low laser powers. Based on plume expansion investigations, by using a high speed camera and a Particle-In-Cell (PIC) Monte-Carlo based simulations, the nanostructure morphology variations could be understood on the basis of the plume particles diffusion process and thin film versus VLS growing competition.

We report a procedure to prepare highly monodisperse copper telluride nanocubes, nanoplates, and nanorods. The procedure is based on the reaction of a copper salt with trioctylphosphine telluride in the presence of lithium bis(trimethylsilyl)amide and oleylamine. CuTe nanocrystals display a strong near-infrared optical absorption associated with localized surface plasmon resonances. We exploit this plasmon resonance for the design of surface-enhanced Raman scattering sensors for unconventional optical probes. Furthermore, we also report here our preliminary analysis of the use of CuTe nanocrystals as cytotoxic and photothermal agents.

Dihydrogen sulphide (H2S) is a dangerous pollutant released in fossil combustion processes. Here, p-CuO (particle)/n-SnO2 (nanowire) heterostructures were evaluated as selective H2S sensors, and the working principle behind their good performance was qualitatively modelled. It was concluded that the main sensing mechanism was dissimilar to standard redox reactions typical of simple metal oxide devices, but ascribable to the sulphurization of CuO and the consequent variation of the pn-junction band structure at the CuO–SnO2 interfaces. Experimental data showed that these H2S sensors suit well for alarm applications with extremely high selectivity and sensitivity to this gas for concentrations between 1 ppm and 10 ppm.

Morphology is a key parameter in the design of novel nanocrystals and nanomaterials with controlled functional properties. Here, we demonstrate the potential of foreign metal ions to tune the morphology of colloidal semiconductor nanoparticles. We illustrate the underlying mechanism by preparing copper selenide nanocubes in the presence of Al ions. We further characterize the plasmonic properties of the obtained nanocrystals and demonstrate their potential as a platform to produce cubic nanoparticles with different composition by cation exchange.

International audience; The bottom-up assembly of nanocrystals provides access to a three-dimensional composition control at the nanoscale not attainable by any other technology. In particular, colloidal nanoheterostructures, with intrinsic multiphase organization, are especially appealing building blocks for the bottom-up production of nanocomposites. In the present work, we use PbTe-PbS as the model material system and thermoelectricity as the paradigmatic application to investigate the potential of the bottom-up assembly of core-shell nanoparticles to produce functional nanocomposites. With this goal in mind, a rapid, high-yield and scalable colloidal synthetic route to prepare grams of PbTe@PbS core-shell nanoparticles with unprecedented narrow size distributions and exceptional composition control is detailed. PbTe@PbS nanoparticles were used as building blocks for the bottom-up production of PbTe-PbS nanocomposites with tuned composition. In such PbTe-PbS nanocomposites, synergistic nanocrystal doping effects result in up to 10-fold higher electrical conductivities than in pure PbTe and PbS nanomaterials. At the same time, the acoustic impedance mismatch between PbTe and PbS phases and a partial phase alloying provide PbTe-PbS nanocomposites with strongly reduced thermal conductivities. As a result, record thermoelectric figures of merit (ZT) of ∼1.1 were obtained from undoped PbTe and PbS phases at 710 K. These high ZT values prove the potential of the proposed processes to produce efficient functional nanomaterials with programmable properties.

The particle-assisted epitaxial growth of antimonide-based nanowires has mainly been realized using gold as the seed material. However, the Au-seeded epitaxial growth of antimonide-based nanowires such as GaSb nanowires presents several challenges such as for example direct nucleation issues and crystal structure tuning. Therefore, it is of great importance to understand the role of seed material choice and properties in the growth behavior of antimonide-based nanowires to obtain a deeper understanding and a better control on their formation processes. In this report, we have investigated the epitaxial growth of GaSb and GaAs-GaSb nanowires using in situ-formed tin seeds by means of metalorganic vapor phase epitaxy technique. This comprehensive report covers the growth of in situ-formed tin seeds and Sn-seeded GaSb nanowires on both GaAs and GaSb (111)B substrates, as well as GaAs-GaSb nanowires on GaAs (111)B substrates. The growth behavior and structural properties of the obtained GaSb nanowires are further investigated and compared with the Au-seeded counterparts. The results provided by this study demonstrate that Sn is a promising seed material for the growth of GaSb nanowires.

In this work, GaN/InGaN/GaN nanocolumns (NCs) have been grown by molecular beam epitaxy. Selective area growth (SAG) and self-organized growth (SOG) were performed simultaneously in patterned and unpatterned regions of the same substrate, respectively. The resulting structures show different tip morphologies and structural properties due to the different polarity along the growth direction, namely Ga-polar with r-plane faceted tips for the SAG NCs and N-polar with c-plane top facet for the SOG ones. When growing Ga-polar GaN/InGaN NCs, no indium is incorporated at a substrate temperature of °C. Rather, indium incorporation takes place under the same growth conditions on the N-polar NCs. The In-incorporation is investigated by means of nano x-ray fluorescence and diffraction, high-angle annular dark-field scanning transmission electron microscopy and high-resolution transmission electron microscopy., The research leading to these results has received funding from the European Union Seventh Framework Programme under grant agreement no. 265073 (nanowiring).

et al., High-density arrays of uniform ZnO nanowires with a high-crystal quality have been synthesized by a catalyst-free vapor-transport method. First, a thin ZnO film was deposited on a Si substrate as nucleation layer for the ZnO nanowires. Second, spatially selective and mask-less growth of ZnO nanowires was achieved using inkjet-printed patterned islands as the nucleation sites on a SiO/Si substrate. Raman scattering and low temperature photoluminescence measurements were applied to characterize the structural and optical properties of the ZnO nanowires. The results reveal negligible amounts of strain and defects in the mask-less ZnO nanowires as compared to the ones grown on the ZnO thin film, which underlines the potential of the inkjet-printing approach for the growth of highcrystal quality ZnO nanowires.

Using a pulsed laser deposition system in a plane reflector configuration, we have grown single crystal ZnO nanowires using different gold catalyst quantities and different local particle fluxes. The number of ZnO nanowire over the square micrometer substrate surface proved to depend on both gold quantity and particle flux, in specific conditions. If for a “low particle flux” the nanowire density seems to strongly depend on the gold quantity, for a “high particle flux”, the dependence is no longer observable. The results were interpreted in terms of the catalyst absorbed particle concentration dependence on the catalyst droplet size and incident particle flux.

The ample chemical and structural freedom of quaternary compounds permits engineering materials that fulfill the requirements of a wide variety of applications. In this work, the mechanisms to achieve unprecedented size, shape, and composition control in quaternary nanocrystals are detailed. The described procedure allows obtaining tetrahedral and penta-tetrahedral quaternary nanocrystals with tuned size distributions and controlled compositions from a plethora of I2–II–IV–VI4 semiconductors.

A high-yield and upscalable colloidal synthesis route for the production of quaternary I2–II–IV–VI4 nanocrystals, particularly stannite Cu2+xCd1–xSnSe4, with narrow size distribution and precisely controlled composition is presented. It is also shown here how the diversity of valences in the constituent elements allows an effective control of their electrical conductivity through the adjustment of the cation ratios. At the same time, while the crystallographic complexity of quaternary chalcogenides is associated with intrinsically low thermal conductivities, the reduction of the lattice dimensions to the nanoscale further reduces the materials thermal conductivity. In the specific case of the stannite crystal structure, a convenient slab distribution of the valence band maximum states permits a partial decoupling of the p-type electrical conductivity from both the Seebeck coefficient and the thermal conductivity. Combining these features, we demonstrate how an initial optimization of the nanocrystals Cd/C...

Vertically aligned single-crystal and chlorine-doped ZnO nanowires (NWs) were grown by a low-cost, high-yield and seed-free electrochemical route. The effects of the applied potential and the concentration of ammonium chloride (NH4Cl) on the morphology, structural and optoelectronic properties of the ZnO:Cl NWs were comprehensively investigated. The amount of Cl ions introduced in the ZnO structure increased almost linearly with both the concentration of NH4Cl in solution, and the electrodeposition potential. As side-effects, the presence of NH4Cl in the growth solution slowed down the electrodeposition rate and resulted in closer packed and lower aspect ratio NWs, but having a higher degree of vertical alignment and less defective surfaces. The NW tip morphology also changed with the NH4Cl concentration, from pyramidal to flat tips. By changing the amount of NH4Cl in the growth solution, the carrier concentration of such ZnO:Cl NWs could be tuned in the range between 5 × 1017 and 4 × 1020 cm−3. The optical gap of the heavily doped NWs increased due to the Moss–Burstein effect. At the same time, a band gap narrowing was detected from photoluminescence measurements.

Ta2O5 thin films were prepared by spin-coating methanol solutions of Ta chloromethoxide. It was prepared by reacting TaCl5 with methanol, followed by water addition (H2O: Ta molar ratio was 16). Thin films were deposited by spin-coating onto SiO2/Si substrates, followed by drying at 90 degrees C and heat-treatment up to 700 degrees C. The films were characterized by X-ray diffraction, transmission electron microscopy and field emission scanning electron microscopy. Crystallization was obtained only after heating at 700 degrees C, in the Ta2O5 orthorhombic phase. The resulting films had a thickness of 100 nm. Their structure was constituted by porous crystals with size up to 50 nm, while the pores had a size of about 10 nm. The results demonstrated that TaCl5 is very convenient precursor for the wet chemical synthesis of Ta2O5 thin films. (C) 2013 Elsevier B.V. All rights reserved.

The crystal structure of a material has a large impact on the electronic and material properties such as band alignment, bandgap energy, and surface energies. Au-seeded III–V nanowires are promising structures for exploring these effects, since for most III–V materials they readily grow in either wurtzite or zinc blende crystal structure. In III–Sb nanowires however, wurtzite crystal structure growth has proven difficult. Therefore, other methods must be developed to achieve wurtzite antimonides. For GaSb, theoretical predictions of the band structure diverge significantly, but the absence of wurtzite GaSb material has prevented any experimental verification of the properties. Having access to this material is a critical step toward clearing the uncertainty in the electronic properties, improving the theoretical band structure models and potentially opening doors toward application of this material. This work demonstrates the use of InAs wurtzite nanowires as templates for realizing GaSb wurtzite shell layers with varying thicknesses. The properties of the axial and radial heterointerfaces are studied at the atomic scale by means of aberration-corrected scanning transmission electron microscopy, revealing their sharpness and structural quality. The transport characterizations point toward a positive offset in the valence bandedge of wurtzite compared to zinc blende.

The physical properties of material largely depend on their crystal structure. Nanowire growth is an important method for attaining metastable crystal structures in III-V semiconductors, giving access to advantageous electronic and surface properties. Antimonides are an exception, as growing metastable wurtzite structure has proven to be challenging. As a result, the properties of these materials remain unknown. One promising means of accessing wurtzite antimonides is to use a wurtzite template to facilitate their growth. Here, a template technique using branched nanowire growth for realizing wurtzite antimonide material is demonstrated. On wurtzite InAs trunks, InAs1-x Sbx branch nanowires at different Sb vapor phase compositions are grown. For comparison, branches on zinc blende nanowire trunks are also grown under identical conditions. Studying the crystal structure and the material composition of the grown branches at different xv shows that the Sb incorporation is higher in zinc blende than in wurtzite. Branches grown on wurtzite trunks are usually correlated with stacking defects in the trunk, leading to the emergence of a zinc blende segment of higher Sb content growing parallel to the wurtzite structure within a branch. However, the average amount of Sb incorporated within the branch is determined by the vapor phase composition.

Ferromagnetic MnGa(111) layers were grown on GaN(0001) by molecular beam epitaxy. MnGa/GaN Schottky diodes with a doping level of around n = 7 × 1018 cm−3 were fabricated to achieve single step tunneling across the metal/semiconductor junction. Below the GaN layer, a thin InGaN quantum well served as optical spin detector (“spin-LED”). For electron spin injection from MnGa into GaN and subsequent spin transport through a 45 nm (70 nm) thick GaN layer, we observe a circular polarization of 0.3% (0.2%) in the electroluminescence at 80 K. Interface mixing, spin polarization losses during electrical transport in the GaN layer, and spin relaxation in the InGaN quantum well are discussed in relation with the low value of the optically detected spin polarization.

Graphene-supported monometallic (Pt) and bimetallic (CuPt3) cubic nanocatalysts have been investigated as new positive electrode materials for improving the VO2+/VO2+ redox process occurring in the vanadium redox flow batteries (VRB). High-resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) have been employed to characterize the electrodes. The presence of the CuPt3 nanocubes on graphene conferred higher electrocatalytic activity due to the much higher electroactive area compared to that obtained with the Pt nanoparticles. The electrochemical surface area of the nano-(CuPt3)-decorated graphene electrode was 105% higher compared to non-decorated graphene, being then a promising alternative for improving the VRB.

III-V ternary nanowires are interesting due to the possibility of modulating their physical and material properties by tuning their material composition. Amongst them InAs1-x Sb x nanowires are good candidates for applications such as Infrared detectors. However, this material has not been grown directly from substrates, in a large range of material compositions. Since the properties of ternaries are alterable by tuning their composition, it is beneficial to gain access to a wide range of composition tunability. Here we demonstrate direct nucleation and growth of InAs1-x Sb x nanowires from Au seed particles over a broad range of compositions (x = 0.08-0.75) for different diameters and surface densities by means of metalorganic vapor phase epitaxy. We investigate how the nucleation, morphology, solid phase Sb content, and growth rate of these nanowires depend on the particle dimensions, and on growth conditions such as the vapor phase composition, V/III ratio, and temperature. We show that the solid phase Sb content of the nanowires remains invariant towards changes of the In precursor flow. We also discuss that at relatively high In flows the growth mechanism alters from Au-seeded to what is referred to as semi In-seeded growth. This change enables growth of nanowires with a high solid phase Sb content of 0.75 that are not feasible via Au-seeded growth. Independent of the growth conditions and morphology, we report that the nanowire Sb content changes over their length, from lower Sb contents at the base, increasing to higher amounts towards the tip. We correlate the axial Sb content variations to the axial growth rate measured in situ. We also report spontaneous core-shell formation for Au-seeded nanowires, where the core is Sb-rich in comparison to the Sb-poor shell.

In this work, simulations of the electronic band structure of a p-GaN/n-ZnO heterointerface are presented. In contrast to homojunctions, an additional energy barrier due to the type-II band alignment hinders the flow of majority charge carriers in this heterojunction. Spontaneous polarization and piezoelectricity are shown to additionally affect the band structure and the location of the recombination region. Proposed as potential UV-LEDs and laser diodes, p-GaN/n-ZnO heterojunction nanowires were fabricated by plasma-assisted molecular beam epitaxy (PAMBE). Atomic resolution annular bright field scanning transmission electron microscopy (STEM) studies reveal an abrupt and defect-free heterointerface with a polarity inversion from N-polar GaN to Zn-polar ZnO. Photoluminescence measurements show strong excitonic UV emission originating from the ZnO-side of the interface as well as stimulated emission in the case of optical pumping above a threshold of 55 kW/cm(2).

An appropriate way of realizing property nanoengineering in complex quaternary chalcogenide nanocrystals is presented for Cu2CdxSnSey(CCTSe) polypods. The pivotal role of the polarity in determining morphology, growth, and the polytypic branching mechanism is demonstrated. Polarity is considered to be responsible for the formation of an initial seed that takes the form of a tetrahedron with four cation-polar facets. Size and shape confinement of the intermediate pentatetrahedral seed is also attributed to polarity, as their external facets are anion-polar. The final polypod extensions also branch out as a result of a cation-polarity-driven mechanism. Aberration-corrected scanning transmission electron microscopy is used to identify stannite cation ordering, while ab initio studies are used to show the influence of cation ordering/distortion, stoichiometry, and polytypic structural change on the electronic band structure.

International audience; Herein, a colloidal synthetic route to produce highly monodisperse Cu2HgGeSe4 (CHGSe) nanoparticles (NPs) is presented in detail. The high yield of the developed procedure allowed the production of CHGSe NPs at the gram scale. A thorough analysis of their structural and optical properties is shown. CHGSe NPs displayed poly-tetrahedral morphology and narrow size distributions with average size in the range of 10-40 nm and size dispersions below 10 %. A 1.6 eV optical band gap was measured by mean of UV-Vis. By adjusting the cation ratio, an effective control of their electrical conductivity is achieved. The prepared NPs are used as building blocks for the production of CHGSe bulk nanostructured materials. The thermoelectric properties of CHGSe nanomaterials are studied in the temperature range from 300 to 730 K. CHGSe nanomaterials reached electrical conductivities up to 5 × 104 S m−1, Seebeck coefficients above 100 μV K−1, and thermal conductivities below 1.0 W m−1 K−1 which translated into thermoelectric figures of merit up to 0.34 at 730 K.

The growth of a TiO shell at the surface of TiO2 nanowires (NWs) allowed us to improve the power conversion efficiency of NW-based dye-sensitized solar cells (DSCs) by a factor 2.5. TiO2@TiO core–shell NWs were obtained by a two-step process: First, rutile-phase TiO2 NWs were hydrothermally grown. Second, a hongquiite-phase TiO shell was electrochemically deposited at the surface of the TiO2 NWs. Bare TiO2 and heterojunction TiO2@TiO NW-based DSCs were obtained using a cobalt(II/III) redox electrolyte and LEG4 as the dye. With this electrolyte/dye combination, DSCs with outstanding Voc values above 900 mV were systematically obtained. While TiO2@TiO NW-based DSCs had slightly lower Voc values than bare TiO2 NW-based DSCs, they provided 3-fold higher photocurrents, overall reaching 2.5-fold higher power conversion efficiencies. The higher photocurrents were associated with the larger surface roughness and an enhanced charge-carrier separation/transfer at the NW/dye interface.

Arrays of vertically aligned ZnO:Cl@ZnS core–shell nanowires (NWs) were grown by a facile low-cost, high-yield and seed-free two-step process. These NWs were used to demonstrate the potential of 3D electrodes based on core–shell heterostructures to enhance charge carrier separation and transfer. With this goal in mind, the photocurrent density of ZnO:Cl@ZnS NWs was characterized as a function of the shell thickness. Although no significant variations in the absorption and photoluminescence spectra were found with the presence of the shell, the photocurrent measured from the core–shell NWs was highly enhanced with respect to bare ZnO:Cl NWs. These photocurrent variations are associated with the control of the band bending in the core–shell NW surface, which modifies the efficiency of charge carrier transfer between the NW and the electrolyte.

TiO2 anatase nanocrystals were surface modified by deposition of V(V) species. The starting amorphous TiO2 nanoparticles were prepared by hydrolytic processing of TiCl4-derived solutions. A V-containing solution, prepared from methanolysis of VCl4, was added to the TiO2 suspension before a solvothermal crystallization step in oleic acid. The resulting materials were characterized by X-ray diffraction, transmission electron microscopy (TEM), Fourier transform infrared, Raman, and magic angle spinning solid-state V-51 nuclear magnetic resonance spectroscopy (MAS NMR). It was shown that in the as-prepared nanocrystals V was deposited onto the surface, forming Ti-O-V bonds. After heat treatment at 400 degrees C, TEM/electron energy loss spectroscopy and MAS NMR showed that V was partially inserted in the anatase lattice, while the surface was covered with a denser V-O-V network. After heating at 500 degrees C, V2O5 phase separation occurred, further evidenced by thermal analyses. The 400 degrees C nanocrystals had a mean size of about 5 nm, proving the successful synthesis of the colloidal counterpart of the well-known TiO2-V2O5 catalytic system. Hence, and also due to the complete elimination of organic residuals, this sample was used for processing chemoresistive devices. Ethanol was used as a test gas, and the results showed the beneficial effect of the V surface modification of anatase, with a response improvement up to almost 2 orders of magnitude with respect to pure TiO2. Moreover, simple comparison of the temperature dependence of the response clearly evidenced the catalytic effect of V addition.