Competition Effects during Femtosecond Laser Induced Element Redistribution in Ba- and La-Migration Based Laser Written Waveguides.

Fs-laser induced element redistribution (FLIER) has been a subject of intensive research in recent years. Its application to various types of glasses has already resulted in the production of efficient optical waveguides, tappers, amplifiers and lasers. Most of the work reported on FLIER-based waveguides refers to structures produced by the cross-migration of alkali (Na, K) and lanthanides (mostly La). The latter elements act as refractive index carrying elements. Herein, we report the production of Ba-based, FLIER-waveguides in phosphate glass with an index contrast > 10-2. Phosphate glasses modified with the same amount of Na2O and K2O, and variable amounts of BaO and/or La2O3 were used to produce the FLIER-waveguides with Ba and or La acting as index carriers. Ba-only modified glasses show a waveguide writing threshold and light guiding performance comparable to that of La-based structures. However, mixed Ba-La glasses show a much higher element migration threshold, and much smaller compositionally modified regions. This behavior is consistent with a competition effect in the cross-migration of both elements (Ba and La) against the alkalis. Such an effect can be applied to inhibit undesired element redistribution effects in fs-laser processing applications in multicomponent glasses.

Carrier extraction from metallic perovskite oxide nanoparticles.

We observe the extraction of carriers excited between two types of bands in the perovskite oxide, Sr-deficient strontium niobate (Sr0.9NbO3). Sr0.9NbO3 exhibits metallic behaviour and high conductivity, whilst also displaying broad absorption across the ultraviolet, visible, and near-infrared spectral regions, making it an attractive material for solar energy conversion. Furthermore, the optoelectronic properties of strontium niobate can easily be tuned by varying the Sr fraction or through doping. Sr-deficient strontium niobate exhibits a split conduction band, which enables two types of optical transitions: intraband and interband. However, whether such carriers can be extracted from an unusual material as such remains unproven. In this report, we have overcome the immense challenge of photocarrier extraction by fabricating an extremely thin absorber layer of Sr0.9NbO3 nanoparticles. These findings open up great opportunities to harvest a very broad solar spectral absorption range with reduced recombination losses.

Femtosecond laser induced thermophoretic writing of waveguides in silicate glass.

Here in, the fs-laser induced thermophoretic writing of microstructures in ad-hoc compositionally designed silicate glasses and their application as infrared optical waveguides is reported. The glass modification mechanism mimics the elemental thermal diffusion occurring in basaltic liquids at the Earth's mantle, but in a much shorter time scale (108 times faster) and over a well-defined micrometric volume. The precise addition of BaO, Na2O and K2O to the silicate glass enables the creation of positive refractive index contrast upon fs-laser irradiation. The influence of the focal volume and the induced temperature gradient is thoroughly analyzed, leading to a variety of structures with refractive index contrasts as high as 2.5 × 10-2. Two independent methods, namely near field measurements and electronic polarizability analysis, confirm the magnitude of the refractive index on the modified regions. Additionally, the functionality of the microstructures as waveguides is further optimized by lowering their propagation losses, enabling their implementation in a wide range of photonic devices.

Supported Porous Nanostructures Developed by Plasma Processing of Metal Phthalocyanines and Porphyrins.

The large area scalable fabrication of supported porous metal and metal oxide nanomaterials is acknowledged as one of the greatest challenges for their eventual implementation in on-device applications. In this work, we will present a comprehensive revision and the latest results regarding the pioneering use of commercially available metal phthalocyanines and porphyrins as solid precursors for the plasma-assisted deposition of porous metal and metal oxide films and three-dimensional nanostructures (hierarchical nanowires and nanotubes). The most advanced features of this method relay on its ample general character from the point of view of the porous material composition and microstructure, mild deposition and processing temperature and energy constrictions and, finally, its straightforward compatibility with the direct deposition of the porous nanomaterials on processable substrates and device-architectures. Thus, taking advantage of the variety in the composition of commercially available metal porphyrins and phthalocyanines, we present the development of metal and metal oxides layers including Pt, CuO, Fe2O3, TiO2, and ZnO with morphologies ranging from nanoparticles to nanocolumnar films. In addition, we combine this method with the fabrication by low-pressure vapor transport of single-crystalline organic nanowires for the formation of hierarchical hybrid organic@metal/metal-oxide and @metal/metal-oxide nanotubes. We carry out a thorough characterization of the films and nanowires using SEM, TEM, FIB 3D, and electron tomography. The latest two techniques are revealed as critical for the elucidation of the inner porosity of the layers.

Bridging energy bands to the crystalline and amorphous states of Si QDs.

The relationship between the crystallization process and opto-electronic properties of silicon quantum dots (Si QDs) synthesized by atmospheric pressure plasmas (APPs) is studied in this work. The synthesis of Si QDs is carried out by flowing silane as a gas precursor in a plasma confined to a submillimeter space. Experimental conditions are adjusted to propitiate the crystallization of the Si QDs and produce QDs with both amorphous and crystalline character. In all cases, the Si QDs present a well-defined mean particle size in the range of 1.5-5.5 nm. Si QDs present optical bandgaps between 2.3 eV and 2.5 eV, which are affected by quantum confinement. Plasma parameters evaluated using optical emission spectroscopy are then used as inputs for a collisional plasma model, whose calculations yield the surface temperature of the Si QDs within the plasma, justifying the crystallization behavior under certain experimental conditions. We measure the ultraviolet-visible optical properties and electronic properties through various techniques, build an energy level diagram for the valence electrons region as a function of the crystallinity of the QDs, and finally discuss the integration of these as active layers of all-inorganic solar cells.

Role of the La/K Compositional Ratio in the Properties of Waveguides Written by Fs-Laser Induced Element Redistribution in Phosphate-Based Glasses.

The local modification of the composition of glasses by high repetition femtosecond laser irradiation is an attractive method for producing photonic devices. Recently, the successful production of waveguides with a refractive index contrast (Δn) above 10-2 by fs-laser writing has been demonstrated in phosphate glasses containing La2O3 and K2O modifiers. This large index contrast has been related to a local enrichment in lanthanum in the light guiding region accompanied by a depletion in potassium. In this work, we have studied the influence of the initial glass composition on the performance of waveguides that are produced by fs-laser induced element redistribution (FLIER) in phosphate-based samples with different La and K concentrations. We have analyzed the contribution to the electronic polarizability of the different glass constituents based on refractive index measurements of the untreated samples, and used it to estimate the expected index contrast caused by the experimentally measured local compositional changes in laser written guiding structures. These estimated values have been compared to experimental ones that are derived from near field images of the guided modes with an excellent agreement. Therefore, we have developed a method to estimate before-hand the expected index contrast in fs-laser written waveguides via FLIER for a given glass composition. The obtained results stress the importance of considering the contribution to the polarizability of all the moving species when computing the expected refractive index changes that are caused by FLIER processes.

One-reactor plasma assisted fabrication of ZnO@TiO 2 multishell nanotubes: assessing the impact of a full coverage on the photovoltaic performance.

This paper addresses the fabrication of vertically aligned ZnO@TiO2 multishell nanotubes by a combined full vacuum-plasma approach at mild temperatures. The growth is carried out within the premises of a one-reactor approach, i.e. minimizing the number of vacuum chambers and sample transferences. In this way, the interface between ZnO and TiO2 is fully preserved from humidity thus increasing ZnO durability and stability. These nanostructures are studied by scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy in STEM (EDX-STEM). High density one-dimensional arrays of these nanotubes formed on FTO substrates are applied as photoanode in a dye-sensitized solar cell (DSC). The evolution of the dye adsorption capacity and solar cells parameters are explored as a function of the crystallinity and thickness of the TiO2 shell. The results show the critical effect of a full coverage by TiO2 of ZnO core to explain the mixed results found in the literature.

In Situ Determination of the Water Condensation Mechanisms on Superhydrophobic and Superhydrophilic Titanium Dioxide Nanotubes.

One-dimensional (1D) nanostructured surfaces based on high-density arrays of nanowires and nanotubes of photoactive titanium dioxide (TiO2) present a tunable wetting behavior from superhydrophobic to superhydrophilic states. These situations are depicted in a reversible way by simply irradiating with ultraviolet light (superhydrophobic to superhydrophilic) and storage in dark. In this article, we combine in situ environmental scanning electron microscopy (ESEM) and near ambient pressure photoemission analysis (NAPP) to understand this transition. These experiments reveal complementary information at microscopic and atomic level reflecting the surface wettability and chemical state modifications experienced by these 1D surfaces upon irradiation. We pay special attention to the role of the water condensation mechanisms and try to elucidate the relationship between apparent water contact angles of sessile drops under ambient conditions at the macroscale with the formation of droplets by water condensation at low temperature and increasing humidity on the nanotubes' surfaces. Thus, for the as-grown nanotubes, we reveal a metastable and superhydrophobic Cassie state for sessile drops that tunes toward water dropwise condensation at the microscale compatible with a partial hydrophobic Wenzel state. For the UV-irradiated surfaces, a filmwise wetting behavior is observed for both condensed water and sessile droplets. NAPP analyses show a hydroxyl accumulation on the as-grown nanotubes surfaces during the exposure to water condensation conditions, whereas the water filmwise condensation on a previously hydroxyl enriched surface is proved for the superhydrophilic counterpart.

Peptide functionalized gold nanoparticles: the influence of pH on binding efficiency.

We report herein on the synthesis of mixed monolayer gold nanoparticles (AuNPs) capped with both polyethylene glycol (PEG) and one of three peptides. Either a receptor-mediated endocytosis peptide, an endosomal escape pathway (H5WYG) peptide or the Nrp-1 targeting RGD peptide (CRGDK) labeled with FITC. All three peptides have a thiol containing cysteine residue which can be used to bind the peptides to the AuNPs. In order to investigate the influence of pH on peptide attachment, PEGylated AuNPs were centrifuged, the supernatant removed, and the nanoparticles were then re-suspended in a range of pH buffer solutions above, below and at the respective isoelectric points of the peptides before co-functionalization. Peptide attachment was investigated using dynamic light scattering, Ultra-violet visible spectroscopy (UV/Vis), FTIR and photo luminescence spectroscopy. UV/Vis analysis coupled with protein assay results and photoluminescence of the FITC tagged RGD peptide concluded that a pH of ∼8 optimized the cysteine binding and stability, irrespective of the peptide used.

Gold nanoparticle-polymer nanocomposites synthesized by room temperature atmospheric pressure plasma and their potential for fuel cell electrocatalytic application.

Conductive polymers have been increasingly used as fuel cell catalyst support due to their electrical conductivity, large surface areas and stability. The incorporation of metal nanoparticles into a polymer matrix can effectively increase the specific surface area of these materials and hence improve the catalytic efficiency. In this work, a nanoparticle loaded conductive polymer nanocomposite was obtained by a one-step synthesis approach based on room temperature direct current plasma-liquid interaction. Gold nanoparticles were directly synthesized from HAuCl4 precursor in poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). The resulting AuNPs/PEDOT:PSS nanocomposites were subsequently characterized under a practical alkaline direct ethanol fuel cell operation condition for its potential application as an electrocatalyst. Results show that AuNPs sizes within the PEDOT:PSS matrix are dependent on the plasma treatment time and precursor concentration, which in turn affect the nanocomposites electrical conductivity and their catalytic performance. Under certain synthesis conditions, unique nanoscale AuNPs/PEDOT:PSS core-shell structures could also be produced, indicating the interaction at the AuNPs/polymer interface. The enhanced catalytic activity shown by AuNPs/PEDOT:PSS has been attributed to the effective electron transfer and reactive species diffusion through the porous polymer network, as well as the synergistic interfacial interaction at the metal/polymer and metal/metal interfaces.

Continuous In-Flight Synthesis for On-Demand Delivery of Ligand-Free Colloidal Gold Nanoparticles.

We demonstrate an entirely new method of nanoparticle chemical synthesis based on liquid droplet irradiation with ultralow (<0.1 eV) energy electrons. While nanoparticle formation via high energy radiolysis or transmission electron microscopy-based electron bombardment is well-understood, we have developed a source of electrons with energies close to thermal which leads to a number of important and unique benefits. The charged species, including the growing nanoparticles, are held in an ultrathin surface reaction zone which enables extremely rapid precursor reduction. In a proof-of-principle demonstration, we obtain small-diameter Au nanoparticles (∼4 nm) with tight control of polydispersity, in under 150 µs. The precursor was almost completely reduced in this period, and the resultant nanoparticles were water-soluble and free of surfactant or additional ligand chemistry. Nanoparticle synthesis rates within the droplets were many orders of magnitude greater than equivalent rates reported for radiolysis, electron beam irradiation, or colloidal chemical synthesis where reaction times vary from seconds to hours. In our device, a stream of precursor loaded microdroplets, ∼15 µm in diameter, were transported rapidly through a cold atmospheric pressure plasma with a high charge concentration. A high electron flux, electron and nanoparticle confinement at the surface of the droplet, and the picoliter reactor volume are thought to be responsible for the remarkable enhancement in nanoparticle synthesis rates. While this approach exhibits considerable potential for scale-up of synthesis rates, it also offers the more immediate prospect of continuous on-demand delivery of high-quality nanomaterials directly to their point of use by avoiding the necessity of collection, recovery, and purification. A range of new applications can be envisaged, from theranostics and biomedical imaging in tissue to inline catalyst production for pollution remediation in automobiles.

Ultra-small photoluminescent silicon-carbide nanocrystals by atmospheric-pressure plasmas.

Highly size-controllable synthesis of free-standing perfectly crystalline silicon carbide nanocrystals has been achieved for the first time through a plasma-based bottom-up process. This low-cost, scalable, ligand-free atmospheric pressure technique allows fabrication of ultra-small (down to 1.5 nm) nanocrystals with very low level of surface contamination, leading to fundamental insights into optical properties of the nanocrystals. This is also confirmed by their exceptional photoluminescence emission yield enhanced by more than 5 times by reducing the nanocrystals sizes in the range of 1-5 nm, which is attributed to quantum confinement in ultra-small nanocrystals. This method is potentially scalable and readily extendable to a wide range of other classes of materials. Moreover, this ligand-free process can produce colloidal nanocrystals by direct deposition into liquid, onto biological materials or onto the substrate of choice to form nanocrystal films. Our simple but efficient approach based on non-equilibrium plasma environment is a response to the need of most efficient bottom-up processes in nanosynthesis and nanotechnology.

Impact of Silicon Nanocrystal Oxidation on the Nonmetallic Growth of Carbon Nanotubes.

Carbon nanotube (CNT) growth has been demonstrated recently using a number of nonmetallic semiconducting and metal oxide nanoparticles, opening up pathways for direct CNT synthesis from a number of more desirable templates without the need for metallic catalysts. However, CNT growth mechanisms using these nonconventional catalysts has been shown to largely differ and reamins a challenging synthesis route. In this contribution we show CNT growth from partially oxidized silicon nanocrystals (Si NCs) that exhibit quantum confinement effects using a microwave plasma enhanced chemical vapor deposition (PECVD) method. On the basis of solvent and a postsynthesis frgamentation process, we show that oxidation of our Si NCs can be easily controlled. We determine experimentally and explain with theoretical simulations that the Si NCs morphology together with a necessary shell oxide of ∼1 nm is vital to allow for the nonmetallic growth of CNTs. On the basis of chemical analysis post-CNT-growth, we give insight into possible mechanisms for CNT nucleation and growth from our partially oxidized Si NCs. This contribution is of significant importance to the improvement of nonmetallic catalysts for CNT growth and the development of Si NC/CNT interfaces.

Microplasma Processed Ultrathin Boron Nitride Nanosheets for Polymer Nanocomposites with Enhanced Thermal Transport Performance.

This Research Article reports on the enhancement of the thermal transport properties of nanocomposite materials containing hexagonal boron nitride in poly(vinyl alcohol) through room-temperature atmospheric pressure direct-current microplasma processing. Results show that the microplasma treatment leads to exfoliation of the hexagonal boron nitride in isopropyl alcohol, reducing the number of stacks from >30 to a few or single layers. The thermal diffusivity of the resulting nanocomposites reaches 8.5 mm(2) s(-1), 50 times greater than blank poly(vinyl alcohol) and twice that of nanocomposites containing nonplasma treated boron nitride nanosheets. From TEM analysis, we observe much less aggregation of the nanosheets after plasma processing along with indications of an amorphous carbon interfacial layer, which may contribute to stable dispersion of boron nitride nanosheets in the resulting plasma treated colloids.

A comparison of gold nanoparticle surface co-functionalization approaches using Polyethylene Glycol (PEG) and the effect on stability, non-specific protein adsorption and internalization.

To create clinically useful gold nanoparticle (AuNP) based cancer therapeutics it is necessary to co-functionalize the AuNP surface with a range of moieties; e.g. Polyethylene Glycol (PEG), peptides and drugs. AuNPs can be functionalized by creating either a mixed monolayer by attaching all the moieties directly to the surface using thiol chemistry, or by binding groups to the surface by means of a bifunctional polyethylene glycol (PEG) linker. The linker methodology has the potential to enhance bioavailability and the amount of functional agent that can be attached. While there is a large body of published work using both surface arrangements independently, the impact of attachment methodology on stability, non-specific protein adsorption and cellular uptake is not well understood, with no published studies directly comparing the two most frequently employed approaches. This paper compares the two methodologies by synthesizing and characterizing PEG and Receptor Mediated Endocytosis (RME) peptide co-functionalized AuNPs prepared using both the mixed monolayer and linker approaches. Successful attachment of both PEG and RME peptide using the two methods was confirmed using Dynamic Light Scattering, Fourier Transform Infrared Spectroscopy and gel electrophoresis. It was observed that while the 'as synthesized' citrate capped AuNPs agglomerated under physiological salt conditions, all the mixed monolayer and PEG linker capped samples remained stable at 1M NaCl, and were stable in PBS over extended periods. While it was noted that both functionalization methods inhibited non-specific protein attachment, the mixed monolayer samples did show some changes in gel electrophoresis migration profile after incubation with fetal calf serum. PEG renders the AuNP stable in-vivo however, studies with MDA-MB-231 and MCF 10A cell lines indicated that functionalization with PEG, blocks cellular uptake. It was observed that co-functionalization with RME peptide using both the mixed monolayer and PEG linker methods greatly enhanced cellular internalization compared to PEG capped AuNPs.

Vacuum template synthesis of multifunctional nanotubes with tailored nanostructured walls.

A three-step vacuum procedure for the fabrication of vertical TiO2 and ZnO nanotubes with three dimensional walls is presented. The method combines physical vapor deposition of small-molecules, plasma enhanced chemical vapor deposition of inorganic functional thin films and layers and a post-annealing process in vacuum in order to remove the organic template. As a result, an ample variety of inorganic nanotubes are made with tunable length, hole dimensions and shapes and tailored wall composition, microstructure, porosity and structure. The fabrication of multishell nanotubes combining different semiconducting oxides and metal nanoparticles is as well explored. This method provides a feasible and reproducible route for the fabrication of high density arrays of vertically alligned nanotubes on processable substrates. The emptying mechanism and microstructure of the nanotubes have been elucidated through SEM, STEM, HAADF-STEM tomography and energy dispersive X-ray spectroscopy. In this article, as a proof of concept, it is presented the straightforward integration of ZnO nanotubes as photoanode in a photovoltaic cell and as a photonic oxygen gas sensor.

Varying Surface Chemistries for p-Doped and n-Doped Silicon Nanocrystals and Impact on Photovoltaic Devices.

Doping of quantum confined nanocrystals offers unique opportunities to control the bandgap and the Fermi energy level. In this contribution, boron-doped (p-doped) and phosphorus-doped (n-doped) quantum confined silicon nanocrystals (SiNCs) are surface-engineered in ethanol by an atmospheric pressure radio frequency microplasma. We reveal that surface chemistries induced on the nanocrystals strongly depend on the type of dopants and result in considerable diverse optoelectronic properties (e.g., photoluminescence quantum yield is enhanced more than 6 times for n-type SiNCs). Changes in the position of the SiNCs Fermi levels are also studied and implications for photovoltaic application are discussed.

Enhanced Dispersion of TiO2 Nanoparticles in a TiO2/PEDOT:PSS Hybrid Nanocomposite via Plasma-Liquid Interactions.

A facile method to synthesize a TiO2/PEDOT:PSS hybrid nanocomposite material in aqueous solution through direct current (DC) plasma processing at atmospheric pressure and room temperature has been demonstrated. The dispersion of the TiO2 nanoparticles is enhanced and TiO2/polymer hybrid nanoparticles with a distinct core shell structure have been obtained. Increased electrical conductivity was observed for the plasma treated TiO2/PEDOT:PSS nanocomposite. The improvement in nanocomposite properties is due to the enhanced dispersion and stability in liquid polymer of microplasma treated TiO2 nanoparticles. Both plasma induced surface charge and nanoparticle surface termination with specific plasma chemical species are proposed to provide an enhanced barrier to nanoparticle agglomeration and promote nanoparticle-polymer binding.

Laser treatment of Ag@ZnO nanorods as long-life-span SERS surfaces.

UV nanosecond laser pulses have been used to produce a unique surface nanostructuration of Ag@ZnO supported nanorods (NRs). The NRs were fabricated by plasma enhanced chemical vapor deposition (PECVD) at low temperature applying a silver layer as promoter. The irradiation of these structures with single nanosecond pulses of an ArF laser produces the melting and reshaping of the end of the NRs that aggregate in the form of bundles terminated by melted ZnO spherical particles. Well-defined silver nanoparticles (NPs), formed by phase separation at the surface of these melted ZnO particles, give rise to a broad plasmonic response consistent with their anisotropic shape. Surface enhanced Raman scattering (SERS) in the as-prepared Ag@ZnO NRs arrays was proved by using a Rhodamine 6G (Rh6G) chromophore as standard analyte. The surface modifications induced by laser treatment improve the stability of this system as SERS substrate while preserving its activity.

Bending induced self-organized switchable gratings on polymeric substrates.

We present a straightforward procedure of self-surface patterning with potential applications as large area gratings, invisible labeling, optomechanical transducers, or smart windows. The methodology is based in the formation of parallel micrometric crack patterns when polydimethylsiloxane foils coated with tilted nanocolumnar SiO2 thin films are manually bent. The SiO2 thin films are grown by glancing angle deposition at room temperature. The results indicate that crack spacing is controlled by the film nanostructure independently of the film thickness and bending curvature. They also show that the in-plane microstructural anisotropy of the SiO2 films due to column association perpendicular to the growth direction determines the anisotropic formation of parallel cracks along two main axes. These self-organized patterned foils are completely transparent and work as customized reversible diffraction gratings under mechanical activation.