Confinement-Induced Isosymmetric Metal-Insulator Transition in Ultrathin Epitaxial V2O3 Films.

Dimensional confinement has shown to be an effective strategy to tune competing degrees of freedom in complex oxides. Here, we achieved atomic layered growth of trigonal vanadium sesquioxide (V2O3) by means of oxygen-assisted molecular beam epitaxy. This led to a series of high-quality epitaxial ultrathin V2O3 films down to unit cell thickness, enabling the study of the intrinsic electron correlations upon confinement. By electrical and optical measurements, we demonstrate a dimensional confinement-induced metal-insulator transition in these ultrathin films. We shed light on the Mott-Hubbard nature of this transition, revealing a vanishing quasiparticle weight as demonstrated by photoemission spectroscopy. Furthermore, we prove that dimensional confinement acts as an effective out-of-plane stress. This highlights the structural component of correlated oxides in a confined architecture, while opening an avenue to control both in-plane and out-of-plane lattice components by epitaxial strain and confinement, respectively.

Growth and Characterization of Ultrathin Vanadium Oxide Films on HOPG.

Integration of graphene into various electronic devices requires an ultrathin oxide layer on top of graphene. However, direct thin film growth of oxide on graphene is not evident because of the low surface energy of graphene promoting three-dimensional island growth. In this study, we demonstrate the growth of ultrathin vanadium oxide films on a highly oriented pyrolytic graphite (HOPG) surface, which mimics the graphene surface, using (oxygen-assisted) molecular beam epitaxy, followed by a post-annealing. The structural properties, surface morphology, and chemical composition of the films have been systematically investigated by in situ reflection high-energy electron diffraction during the growth and by ex situ techniques, such as atomic force microscopy, scanning tunneling microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy (XPS). Crystalline monolayer vanadium oxide can be achieved on HOPG by systematically tuning the deposition time of V atoms and by subsequent annealing at 450 °C in controlled atmospheres. Increasing the partial pressure of O2 during the deposition seems to decrease the mobility of V atoms on the graphitic surface of HOPG and promote the formation of a two-dimensional (2D) vanadium oxide. The obtained oxide layers are found to be polycrystalline with an average grain size of 15 nm and to have a mixed-valence state with mainly V5+ and V4+. Moreover, XPS valence band measurements indicate that the vanadium oxide is insulating. These results demonstrate that a 2D insulating vanadium oxide can be grown directly on HOPG and suggest vanadium oxide as a promising candidate for graphene/oxide heterostructures.

Nanoscale self-organization and metastable non-thermal metallicity in Mott insulators.

Mott transitions in real materials are first order and almost always associated with lattice distortions, both features promoting the emergence of nanotextured phases. This nanoscale self-organization creates spatially inhomogeneous regions, which can host and protect transient non-thermal electronic and lattice states triggered by light excitation. Here, we combine time-resolved X-ray microscopy with a Landau-Ginzburg functional approach for calculating the strain and electronic real-space configurations. We investigate V2O3, the archetypal Mott insulator in which nanoscale self-organization already exists in the low-temperature monoclinic phase and strongly affects the transition towards the high-temperature corundum metallic phase. Our joint experimental-theoretical approach uncovers a remarkable out-of-equilibrium phenomenon: the photo-induced stabilisation of the long sought monoclinic metal phase, which is absent at equilibrium and in homogeneous materials, but emerges as a metastable state solely when light excitation is combined with the underlying nanotexture of the monoclinic lattice.

Carbon Nanotube Fibers Decorated with MnO2 for Wire-Shaped Supercapacitor.

Fibers made from CNTs (CNT fibers) have the potential to form high-strength, lightweight materials with superior electrical conductivity. CNT fibers have attracted great attention in relation to various applications, in particular as conductive electrodes in energy applications, such as capacitors, lithium-ion batteries, and solar cells. Among these, wire-shaped supercapacitors demonstrate various advantages for use in lightweight and wearable electronics. However, making electrodes with uniform structures and desirable electrochemical performances still remains a challenge. In this study, dry-spun CNT fibers from CNT carpets were homogeneously loaded with MnO2 nanoflakes through the treatment of KMnO4. These functionalized fibers were systematically characterized in terms of their morphology, surface and mechanical properties, and electrochemical performance. The resulting MnO2-CNT fiber electrode showed high specific capacitance (231.3 F/g) in a Na2SO4 electrolyte, 23 times higher than the specific capacitance of the bare CNT fibers. The symmetric wire-shaped supercapacitor composed of CNT-MnO2 fiber electrodes and a PVA/H3PO4 electrolyte possesses an energy density of 86 nWh/cm and good cycling performance. Combined with its light weight and high flexibility, this CNT-based wire-shaped supercapacitor shows promise for applications in flexible and wearable energy storage devices.

Efficient Direct Band-Gap Transition in Germanium by Three-Dimensional Strain.

Complementary to the development of highly three-dimensional (3D) integrated circuits in the continuation of Moore's law, there has been a growing interest in new 3D deformation strategies to improve the device performance. To continue this search for new 3D deformation techniques, it is essential to explore beforehand, using computational predictive methods, which strain tensor leads to the desired properties. In this work, we study germanium (Ge) under an isotropic 3D strain on the basis of first-principles methods. The transport and optical properties are studied by a fully ab initio Boltzmann transport equation and many-body Bethe-Salpeter equation (BSE) approach, respectively. Our findings show that a direct band gap in Ge could be realized with only 0.70% triaxial tensile strain (negative pressure) and without the challenges associated with Sn doping. At the same time, a significant increase in the refractive index and carrier mobility, particularly for electrons, is observed. These results demonstrate that there is a huge potential in exploring the 3D deformation space for semiconductors, and potentially many other materials, to optimize their properties.

Simultaneous growth of three-dimensional carbon nanotubes and ultrathin graphite networks on copper.

A new way to simultaneously grow carbon nanotubes (CNTs) and ultrathin graphite on copper (Cu) foils has been investigated. This one-step growth process yields three-dimensional networks of CNTs on graphitic layers (3D CNTs/G) on Cu foils. Their synthesis conditions and growth mechanism are discussed in detail taking their structural properties into account. Individual CNTs and the 3D CNTs/G networks by means of an in-situ conductive atomic force microscope inside a scanning electron microscope are electrically characterized. Time-resolved photoluminescence demonstrated fast charge transfer and high carrier collection efficiency superior to two-dimensional ultrathin graphite only. Their facile and tunable growth and excellent electrical properties show that the 3D CNTs/G are strongly attractive for various applications such as solar cells, sensors, supercapacitors, photovoltaics, power generation, and optoelectronics.

Magnetic orders and origin of exchange bias in Co clusters embedded oxide nanocomposite films.

Magnetic nanoparticles embedded oxide semiconductors are interesting candidates for spintronics in view of combining ferromagnetic (FM) and semiconducting properties. In this work, Co-ZnO and Co-V2O3 nanocomposite thin films are synthesized by Co ion implantation in crystalline thin films. Magnetic orders vary with the implantation fluence in Co-ZnO, where superparamagnetic (SPM) order appears in the low-fluence films (2 × 1016 and 4 × 1016 ions cm-2) and FM order co-exists with the SPM phase in high-fluence films (1 × 1017 ions cm-2). Exchange bias (EB) appears in the high-fluence films, with an EB field of about 100 Oe at 2 K and a blocking temperature of around 100 K. On the other hand, Co-V2O3 thin films with an implantation fluence of 3.5 × 1016 ions cm-2 exhibit a clear antiferromagnetic (AFM) coupling at low temperatures without the EB effect. The different magnetic behavior of the Co-implanted films with different Co content leads us to conclude that the observed EB effect in the Co-ZnO films results from the FM/AFM coupling between sizable Co nanoparticles and their CoO/Co3O4 surroundings in the (Zn,Co)O matrix. On the other hand, the absence of EB effect in Co-V2O3 appears to be due to the small size of the FM Co nanoparticles in spite of an AFM magnetic order. Detailed studies of magnetic orders and EB effect in magnetic nanocomposite semiconductors can pave the way for their application in spintronics.

Characterization and Photocatalytic Performance of Potassium-Doped Titanium Oxide Nanostructures Prepared via Wet Corrosion of Titanium Microspheres.

Potassium doped titanium oxide (KTiOx) nanowires were prepared by the wet corrosion process (WCP) and their photocatalytic effects were systematically characterized. For the synthesis of KTiOx, the potassium hydroxide concentration of the WCP was varied in order to obtain nanostructures with different surface area and surface charge. Structural and crystalline properties of KTiOx were studied by means of X-ray diffraction, scanning and transmission electron microscopy. Chemical composition was determined by X-ray fluorescence and energy-dispersive X-ray analysis. Photocatalytic performance was investigated as a function of the surface area, pH, and crystalline structures by studying the degradation of methylene blue, cardiogreen, and azorubine red dyes upon UV irradiation. The negatively charged crystalline KTiOx nanostructures with high surface area showed significantly higher photocatalytic degradation compared to their TiOx counterpart. They also showed high efficiency for recovery and re-use. Annealing KTiOx nanostructures improved structural properties leading to well-ordered layered structures and improved photocatalysis. However, annealing at temperatures higher than 600 °C yielded formation of rutile grains at the surface of nanowires, significantly affecting the photocatalytic performance. We believe that KTiOx nanostructures produced by WCP are very promising for photocatalysis, especially due to their high photocatalytic efficiency as well as their potential for re-use and durability.

Experimental demonstration of a tunable transverse electric pass polarizer based on hybrid VO2/silicon technology.

A tunable transverse electric (TE) pass polarizer is demonstrated based on hybrid vanadium dioxide/silicon (VO2/Si) technology. The 20-µm-long TE pass polarizer exploits the phase transition of the active VO2 material to control the rejection of the unwanted transverse magnetic (TM) polarization. The device features insertion losses below 1 dB at static conditions and insertion losses of 5.5 dB and an attenuation of TM polarization of 19 dB in the active state for a wavelength range between 1540 nm and 1570 nm. To the best of our knowledge, this is the first time that tunable polarizers compatible with Si photonics are demonstrated.

Optical switching in hybrid VO2/Si waveguides thermally triggered by lateral microheaters.

The performance of optical devices relying in vanadium dioxide (VO2) technology compatible with the silicon platform depends on the polarization of light and VO2 properties. In this work, optical switching in hybrid VO2/Si waveguides thermally triggered by lateral microheaters is achieved with insertion losses below 1 dB and extinction ratios above 20 dB in a broad bandwidth larger than 30 nm. The optical switching response has been optimized for TE and TM polarizations by using a homogeneous and a granular VO2 layer, respectively, with a small impact on the electrical power consumption. The stability and reversibility between switching states showing the possibility of bistable performance is also demonstrated.

Solvation Structure of Sodium Bis(fluorosulfonyl)imide-Glyme Solvate Ionic Liquids and Its Influence on Cycling of Na-MNC Cathodes.

Electrolytes consisting of sodium bis(fluorosulfonyl)imide (NaFSI) dissolved in glymes (monoglyme, diglyme, and triglyme) were characterized by FT-Raman spectroscopy and 13C, 17O, and 23Na NMR spectroscopy. The glyme:NaFSI molar ratio was varied from 50:1 to 1:1, and it was observed that, in the dilute electrolytes, the sodium salt is completely dissociated into solvent separated ion pairs (SSIPs). However, contact ion pairs (CIPs) and aggregates (AGGs) become the predominant species in more concentrated solutions. Some of the electrolytes with the highest concentrations can be classified as solvate ionic liquids (SILs), where all of the solvent molecules are coordinated to sodium cations. Therefore, these electrolytes are fundamentally different from more dilute electrolytes which are typically used in commercially available secondary batteries. The melting point or glass transition temperature, dynamic viscosity, density, sodium concentration, and ionic conductivity of these solvate ionic liquids are reported as well as the crystal structures of [Na(G3)][FSI] and [Na(G3)2][FSI]. Galvanostatic cycling experiments were performed in coin-type cells with a Na2/3[Mn0.55Ni0.30Co0.15]O2 cathode to study the influence of these electrolytes on the electrochemical stability and charge/discharge behavior.

Case Study III: The Construction of a Nanotoxicity Database - The MOD-ENP-TOX Experience.

The amount of experimental studies on the toxicity of nanomaterials is growing fast. Interpretation and comparison of these studies is a complex issue due to the high amount of variables possibly determining the toxicity of nanomaterials.Qualitative databases providing a structured combination, integration and quality evaluation of the existing data could reveal insights that cannot be seen from different studies alone. A few database initiatives are under development but in practice very little data is publicly available and collaboration between physicists, toxicologists, computer scientists and modellers is needed to further develop databases, standards and analysis tools.In this case study the process of building a database on the in vitro toxicity of amorphous silica nanoparticles (NPs) is described in detail. Experimental data were systematically collected from peer reviewed papers, manually curated and stored in a standardised format. The result is a database in ISA-Tab-Nano including 68 peer reviewed papers on the toxicity of 148 amorphous silica NPs. Both the physicochemical characterization of the particles and their biological effect (described in 230 in vitro assays) were stored in the database. A scoring system was elaborated in order to evaluate the reliability of the stored data.

Use of Zebrafish Larvae as a Multi-Endpoint Platform to Characterize the Toxicity Profile of Silica Nanoparticles.

Nanomaterials are being extensively produced and applied in society. Human and environmental exposures are, therefore, inevitable and so increased attention is being given to nanotoxicity. While silica nanoparticles (NP) are one of the top five nanomaterials found in consumer and biomedical products, their toxicity profile is poorly characterized. In this study, we investigated the toxicity of silica nanoparticles with diameters 20, 50 and 80 nm using an in vivo zebrafish platform that analyzes multiple endpoints related to developmental, cardio-, hepato-, and neurotoxicity. Results show that except for an acceleration in hatching time and alterations in the behavior of zebrafish embryos/larvae, silica NPs did not elicit any developmental defects, nor any cardio- and hepatotoxicity. The behavioral alterations were consistent for both embryonic photomotor and larval locomotor response and were dependent on the concentration and the size of silica NPs. As embryos and larvae exhibited a normal touch response and early hatching did not affect larval locomotor response, the behavior changes observed are most likely the consequence of modified neuroactivity. Overall, our results suggest that silica NPs do not cause any developmental, cardio- or hepatotoxicity, but they pose a potential risk for the neurobehavioral system.

Development of a fluorescence based flux sensor for thin film growth and nanoparticle deposition.

An optical flux sensor, based on the fluorescence properties of materials and nanoparticles, has been developed to control the deposition rate in thin film deposition systems. Using a simple diode laser and a photomultiplier tube with a light filter, we report the detection of gallium atoms and CdSe-ZnS quantum dots. This setup has a high sensitivity and reproducibility.

Development of a new direct liquid injection system for nanoparticle deposition by chemical vapor deposition using nanoparticle solutions.

Nanoparticles of different materials are already in use for many applications. In some applications, these nanoparticles need to be deposited on a substrate in a fast and reproducible way. We have developed a new direct liquid injection system for nanoparticle deposition by chemical vapor deposition using a liquid nanoparticle precursor. The system was designed to deposit nanoparticles in a controlled and reproducible way by using two direct liquid injectors to deliver nanoparticles to the system. The nanoparticle solution is first evaporated and then the nanoparticles flow onto a substrate inside the vacuum chamber. To allow injection and evaporation of the liquid, a direct liquid injection and vaporization system are mounted on top of the process chamber. The deposition of the nanoparticles is controlled by parameters such as deposition temperature, partial pressure of the gases, and flow rate of the nanoparticle suspension. The concentration of the deposited nanoparticles can be varied simply by changing the flow rate and deposition time. We demonstrate the capabilities of this system using gold nanoparticles. The selected suspension flow rates were varied between 0.25 and 1 g/min. AFM analysis of the deposited samples showed that the aggregation of gold nanoparticles is well controlled by the flow and deposition parameters.

Dependence of Gold Nanoparticle Radiosensitization on Functionalizing Layer Thickness.

Gold nanoparticles functionalized with polyethylene glycol of different chain lengths are used to determine the influence of the capping layer thickness on the radiosensitizing effect of the particles. The size variations in organic coating, built up with polyethylene glycol polymers of molecular weight 1-20 kDa, allow an evaluation of the decrease in dose enhancement percentages caused by the gold nanoparticles at different radial distances from their surface. With localized eradication of malignant cells as a primary focus, radiosensitization is most effective after internalization in the nucleus. For this reason, we performed controlled radiation experiments, with doses up to 20 Gy and particle diameters in a range of 5-30 nm, and studied the relaxation pattern of supercoiled DNA. Subsequent gel electrophoresis of the suspensions was performed to evaluate the molecular damage and consecutively quantify the gold nanoparticle sensitization. In conclusion, on average up to 58.4% of the radiosensitizing efficiency was lost when the radial dimensions of the functionalizing layer were increased from 4.1 to 15.3 nm. These results serve as an experimental supplement for biophysical simulations and demonstrate the influence of an important parameter in the development of nanomaterials for targeted therapies in cancer radiotherapy.

Formation of crystalline InGaO3(ZnO)n nanowires via the solid-phase diffusion process using a solution-based precursor.

One-dimensional single crystalline InGaO3(ZnO)n (IGZO) nanostructures have great potential for various electrical and optical applications. This paper demonstrates for the first time, to our knowledge, a non-vacuum route for the synthesis of IGZO nanowires by annealing ZnO nanowires covered with solution-based IGZO precursor. This method results in nanowires with highly periodic IGZO superlattice structure. The phase transition of IGZO precursor during thermal treatment was systematically studied. Transmission electron microscopy studies reveal that the formation of the IGZO structure is driven by anisotropic inter-diffusion of In, Ga, and Zn atoms, and also by the crystallization of the IGZO precursor. Optical measurements using cathodoluminescence and UV-vis spectroscopy confirm that the nanowires consist of the IGZO compound with wide optical band gap and suppressed luminescence.

The pH-dependent photoluminescence of colloidal CdSe/ZnS quantum dots with different organic coatings.

The photoluminescence (PL) of colloidal quantum dots (QDs) is known to be sensitive to the solution pH. In this work we investigate the role played by the organic coating in determining the pH-dependent PL. We compare two types of CdSe/ZnS QDs equipped with different organic coatings, namely dihydrolipoic acid (DHLA)-capped QDs and phospholipid micelle-encapsulated QDs. Both QD types have their PL intensity quenched at acidic pH values, but they differ in terms of the reversibility of the quenching process. For DHLA-capped QDs, the quenching is nearly irreversible, with a small reversible component visible only on short time scales. For phospholipid micelle-encapsulated QDs the quenching is notably almost fully reversible. We suggest that the surface passivation by the organic ligands is reversible for the micelle-encapsulated QDs. Additionally, both coatings display pH-dependent spectral shifts. These shifts can be explained by a combination of irreversible processes, such as photo-oxidation and acid etching, and reversible charging of the QD surface, leading to the quantum-confined Stark effect (QCSE), the extent of each effect being coating-dependent. At high ionic strengths, the aggregation of QDs also leads to a spectral (red) shift, which is attributable to the QCSE and/or electronic energy transfer.

Preparation and Photocatalytic Activity of Potassium- Incorporated Titanium Oxide Nanostructures Produced by the Wet Corrosion Process Using Various Titanium Alloys.

Nanostructured potassium-incorporated Ti-based oxides have attracted much attention because the incorporated potassium can influence their structural and physico-chemical properties. With the aim of tuning the structural and physical properties, we have demonstrated the wet corrosion process (WCP) as a simple method for nanostructure fabrication using various Ti-based materials, namely Ti-6Al-4V alloy (TAV), Ti-Ni (TN) alloy and pure Ti, which have 90%, 50% and 100% initial Ti content, respectively. We have systematically investigated the relationship between the Ti content in the initial metal and the precise condition of WCP to control the structural and physical properties of the resulting nanostructures. The WCP treatment involved various concentrations of KOH solutions. The precise conditions for producing K-incorporated nanostructured titanium oxide films (nTOFs) were strongly dependent on the Ti content of the initial metal. Ti and TAV yielded one-dimensional nanowires of K-incorporated nTOFs after treatment with 10 mol/L-KOH solution, whereas TN required a higher concentration (20 mol/L-KOH solution) to produce comparable nanostructures. The obtained nanostructures revealed a blue-shift in UV absorption spectra due to the quantum confinement effects. A significant enhancement of the photocatalytic activity was observed via the chromomeric change and the intermediate formation of methylene blue molecules under UV irradiation. This study demonstrates the WCP as a simple, versatile and scalable method for the production of nanostructured K-incorporated nTOFs to be used as high-performance photocatalysts for environmental and energy applications.

Vibrational spectroscopic study of pure and silica-doped sulfonated poly(ether ether ketone) membranes.

We report the vibrational properties of sulfonated poly(ether ether ketone) (SPEEK) membranes, used as electrolytes in proton exchange membrane (PEM) fuel cells, studied by Fourier transform infrared (FTIR) spectroscopy. We discuss the changes in the vibrational modes of the functional groups present in the polymer arising due to the sulfonation process and the subsequent incorporation of silica particles functionalized with sulfonic acid group. From the infrared spectra, we confirm the incorporation of sulfonic acid group in the polymer chain as well as in the functionalized silica particles. We have also measured the variations in the peak area ratio of the characteristic out-of-plane vibrations of the aromatic rings in the PEEK polymer at 1280cm(-1) with respect to a reference peak at 1305cm(-1). These values were correlated to the crystallinity (XC) values experimentally determined by DSC technique, providing a non-destructive means to calculate the crystallinity of polymer membranes. The calculated XC values were in good agreement with the experimental values. The crystallinity was observed to decrease with increasing degree of sulfonation (DS), indicating the crystalline-to-amorphous phase modification of the polymer by sulfonation, which along with the enhanced ion-exchange capacity and water uptake, is responsible for the improved ionic conductivity at higher DS values.