Rafael Abargues

High-resolution electron-beam patternable nanocomposite containing metal nanoparticles for plasmonics

Polymer nanocomposites containing noble metal nanoparticles are promising materials for plasmonic applications. In this paper, we report on a high-resolution negative-tone nanocomposite resist based on poly(vinyl alcohol) where silver nanoparticles and nanopatterns are simultaneously generated by electron-beam lithography. Our results indicate nanostructures with a relatively high concentration of nanoparticles and, consequently, an electromagnetic coupling among the nanoparticles. Therefore, the patternable nanocomposite described in this work may be a suitable material for future plasmonic circuitry.

Nanotexturing To Enhance Photoluminescent Response of Atomically Thin Indium Selenide with Highly Tunable Band Gap.

Manipulating properties of matter at the nanoscale is the essence of nanotechnology, which has enabled the realization of quantum dots, nanotubes, metamaterials, and two-dimensional materials with tailored electronic and optical properties. Two-dimensional semiconductors have revealed promising perspectives in nanotechnology. However, the tunability of their physical properties is challenging for semiconductors studied until now. Here we show the ability of morphological manipulation strategies, such as nanotexturing or, at the limit, important surface roughness, to enhance light absorption and the luminescent response of atomically thin indium selenide nanosheets. Besides, quantum-size confinement effects make this two-dimensional semiconductor to exhibit one of the largest band gap tunability ranges observed in a two-dimensional semiconductor: from infrared, in bulk material, to visible wavelengths, at the single layer. These results are relevant for the design of new optoelectronic devices, including heterostructures of two-dimensional materials with optimized band gap functionalities and in-plane heterojunctions with minimal junction defect density.

Localized surface plasmon resonance sensor based on Ag-PVA nanocomposite thin films

In this work we demonstrate the use of nanocomposite thin films of poly(vinyl alcohol) with embedded silver NPs for chemosensing purposes. Silver NPs are in situ synthesized inside polyvinyl alcohol during the bake step of the formation of a nanocomposite thin film. The polymer in the nanocomposite provides an appropriate chemical and electromagnetic environment for metal NPs in order to interact with and hence detect the chemical species. A limit of detection below 20 nM is found when detecting 2-mercaptoethanol as the analyte, when measuring spectral changes (peak wavelength, linewidth and intensity) in the Localized Surface Plasmon Resonance. Potential qualitative and semi-quantitative sensors based on such nanocomposites would be easy-to-prepare, easy-to-use and low-cost, which are the basis of a fully disposable sensing platform technology.

Optical properties of different polymer thin films containing in situ synthesized Ag and Au nanoparticles

Here we report on the in situ synthesis of Ag and Au nanoparticles inside several polymer matrixes by solid-state chemical reduction of a metallic salt. Poly(ethyleneimine) (PEI), poly(hydroxyethyl methacrylate) (PHEMA), poly(vinylpyrrolidone) (PVP), novolak, poly(4-vinylphenol) (P4VP), poly(4-vinylphenol)-co-(methyl methacrylate) (P4VP-co-MMA) and poly(styrene-co-allyl alcohol) (PS-co-AA) were able to reduce Ag(I) and Au(III) to the corresponding nanoparticles during the baking process. The nanoparticle diameters of Ag and Au were found to range from 2 to 25 nm. TEM also indicated a uniform distribution of nanoparticles embedded in the thin film. This approach is suitable for controlling the size of the nanoparticles and its homogeneous distribution in the polymer matrix.

Scalable heterogeneous synthesis of metallic nanoparticles and aggregates with polyvinyl alcohol

Here we report on a new route to synthesize colloidal silver and gold nanoparticles, potentially scalable for massive nanoparticle-production. This method is based on the microwave-assisted heterogeneous reduction of the metal salts with polyvinylalcohol. The reaction is carried out in alcohols, which are non-solvents for polyvinylalcohol. Nanoparticles can be very easily separated by filtration. The reaction kinetics are extremely fast. Size-controlled formation of nanoparticle agglomerates is accomplished with a seed-mediated synthesis of nanoparticles upon MW exposure.

Polymer/QDs nanocomposites for waveguiding applications

In this paper we review our recent progress in a still young type of active waveguides based on hybrid organic (polymer)-- inorganic (semiconductor quantum dots) materials. They can be useful for the implementation of new photonic devices, because combining the properties of the semiconductor nanostructures (quantum size carrier confinement and temperature independent emission) with the technological capabilities of polymers. These optical waveguides can be easily fabricated by spin-coating and UV photolithography on many substrates (SiO2/Si, in the present work). We demonstrate that it is possible to control the active wavelength in a broad range (400-1100 nm), just by changing the base quantum dotmaterial (CdS, CdSe, CdTe and PbS, but other are possible), without the necessity of changing fabrication conditions. Particularly, we have determined the optimum conditions to produce multi-color photoluminescence waveguiding by embedding CdS, CdSe and CdTe quantum dots into Poly(methyl methacrylate). Finally, we show new results regarding the incorporation of CdSe nanocrystals into a SU-8 resist, in order to extrapolate the study to a photolithographic and technologically more important polymer. In this case ridge waveguides are able to confine in 2D the light emitted by the quantum dots.

The effect of quantum size confinement on the optical properties of PbSe nanocrystals as a function of temperature and hydrostatic pressure

A study based on photoluminescence and absorption measurements as a function of temperature and pressure for PbSe nanocrystals with sizes in the range 3-13 nm reveals the influence of size quantum confinement on the observed variation. In the case of the temperature variation, the effective bandgap changes from showing a positive rate of change to showing a negative one (for a quantum dot 3 nm in diameter), which can be accounted for by incorporating a linear variation of the carrier effective masses into a simple calculation of the exciton ground state in the quantum dot. In the case of the pressure variation, we observe a clear inverse correlation between the absolute value of the pressure coefficient and the nanocrystal size, a signature of quantum size confinement, with values changing from -76 to -41 meV GPa⁻¹ for quantum dots ranging from 13 to 3 nm in diameter, respectively, clearly smaller in absolute value than the rate for bulk PbSe (-84 meV GPa⁻¹). We used again the hypothesis of a linear variation of the carrier effective masses with pressure in order to fit this experimental variation quantitatively.

Quantum-Dot Double Layer Polymer Waveguides by Evanescent Light Coupling

In this work we analyze numerically and experimentally new active waveguides based on a bilayer structure composed by a passive polymer and an active poly(mehtyl methacrylate) (PMMA) film doped with CdSe colloidal quantum dots (QDs), namely a nancomposite. In a first bilayer structure a planar PMMA layer is deposited on top of the nanocomposite, where the signal beam intensity is enhanced because this cladding layer is able to collect radiated emission of QDs. Moreover, the pump beam is also propagating through the cladding without limitation by QD absorption. These results are extended to a second bilayer structure, where ridge patterns of a commercially available resist (SU-8) are deposited on the top of the nanocomposite active layer. These SU-8 patterns are also able to guide with low absorption losses both pump and signal beams. The optimum geometrical parameters of the bilayer structures were properly designed to optimize the light waveguiding, previous to their fabrication and optical characterization. For this purpose, a spontaneous emission model has been developed and programmed into an active beam propagation method. This technology can be the base for developing integrated photonics on silicon at visible and telecom wavelengths.

Ag and Au/DNQ-novolac nanocomposites patternable by ultraviolet lithography: a fast route to plasmonic sensor microfabrication

In this work we report on a method to synthesize Ag–Au nanoparticles/polymer nanocomposite patterns by UV lithography. The photoresists are based on DNQ-novolac as the polymer matrix, and Ag(I) and Au(III) salts as the nanoparticle precursors. After UV lithography, silver and gold nanoparticles are in situ synthesized inside the polymer patterns during a post bake. The resulting structured nanocomposite shows a characteristic absorbance spectrum related to the plasmon frequency of the synthesized noble metal NPs. This method represents a fast, simple and low-cost approach to the formation of extended polymer patterns with embedded silver or gold NPs. Moreover, it is a mechanism to position nanometric particles with micrometric resolution, which represents a useful tool for nanoscience. Furthermore, even with the polymeric cover, NPs plasmon resonance is affected by the binding of some organic molecules. This concept has been proven with 2-mercaptoethanol molecules, which demonstrates the feasibility of localized surface plasmon resonance chemo/biosensors by using the proposed technology.

Plasmonic optical sensors printed from Ag–PVA nanoinks

In this paper we report on the use of a nanocomposite based on silver nanoparticles embedded in PVA as a plasmonic optical sensor to detect and quantify trace amounts of amines in gas and water, respectively. The transduction mechanism of the sensor is based on the changes of the LSPR band of Ag NPs when analyte molecules are chemisorbed on their surface. The Ag–PVA sensors are fabricated by means of a high-precision microplotter, a direct-write technology developed for printing materials from solution. The nanoink is formulated with a metal precursor (AgNO3) and a polymer (PVA) using an adequate mixture of solvents to meet the rheological requirements for the fluid dispensing process. The LSPR intensity is the most sensitive magnitude to follow the interaction between Ag NPs embedded in PVA and amines. Ag–PVA patterns are tested as a plasmonic optical sensor for the detection of ethylenediamine in solution showing a limit of detection as low as 0.1 nM. Moreover Ag nanocomposite patterns are also used for sensing vapours of several biogenic (cadaverine and putrescine) and synthetic (ethylenediamine and methylenediamine) amines, where shorter amines exhibit the largest sensor response. This plasmonic optical sensor is also tested in real-time monitoring of chicken meat spoilage at room temperature. We believe that the Ag–PVA nanocomposite can be the basis for the development of sensor spots, bar-codes and other labels for smart packaging technology, among other sensing applications.