Comprehensive Model for the Transformation of Zinc Nitride Metastable Layers.

In this work, we performed systematic studies on the oxidation of zinc nitride metastable layers using a climate chamber with controlled temperature and relative humidity. The electrical properties of the samples were in situ analyzed using a programmable microprocessor with a voltage divider, while the structural and optical properties were ex situ measured by scanning electron microscopy, elastic recoil detection analysis, and spectroscopic ellipsometry. Our results show that zinc nitride transformation proceeds in a top-down way, with a progressive substitution of N by O, which leads to the formation of pores and a remarkable swelling effect. The overall behavior is well explained by a universal logistic growth model. Considering this model, we successfully fabricated and tested a zinc nitride-based dehydration sensor for biomedical applications.

Breast cancer biomarker detection through the photoluminescence of epitaxial monolayer MoS2 flakes.

In this work we report on the characterization and biological functionalization of 2D MoS2 flakes, epitaxially grown on sapphire, to develop an optical biosensor for the breast cancer biomarker miRNA21. The MoS2 flakes were modified with a thiolated DNA probe complementary to the target biomarker. Based on the photoluminescence of MoS2, the hybridization events were analyzed for the target (miRNA21c) and the control non-complementary sequence (miRNA21nc). A specific redshift was observed for the hybridization with miRNA21c, but not for the control, demonstrating the biomarker recognition via PL. The homogeneity of these MoS2 platforms was verified with microscopic maps. The detailed spectroscopic analysis of the spectra reveals changes in the trion to excitation ratio, being the redshift after the hybridization ascribed to both peaks. The results demonstrate the benefits of optical biosensors based on MoS2 monolayer for future commercial devices.

Enhanced electrochemiluminescence by ZnO nanowires for taurine determination.

A novel electrochemiluminescence (ECL) sensor for the sensitive detection of taurine was developed. Taurine contains an aliphatic amine that gives it co-reactant properties. The ECL response of the taurine/[Ru(bpy)3]2+ system was analyzed on two different electrodes surfaces, screen-printed graphene and gold electrodes, before and after modification with ZnO nanowires (ZnO NWs). The ZnO NWs modified electrode yielded an enhanced ECL signal, allowing rapid detection of taurine at 5.5 × 10-6 mol L-1 detection limit. The ECL signal is stable and reproducible. The sensor has been applied to the determination of taurine in a commercial taurine supplement.

Energy Transfer and Interference by Collective Electromagnetic Coupling.

The physics of collective optical response of molecular assemblies, pioneered by Dicke in 1954, has long been at the center of theoretical and experimental scrutiny. The influence of the environment on such phenomena is also of great interest due to various important applications in, e.g., energy conversion devices. In this Letter, we demonstrate both experimentally and theoretically the spatial modulations of the collective decay rates of molecules placed in proximity to a metal interface. We show in a very simple framework how the cooperative optical response can be analyzed in terms of intermolecular correlations causing interference between the response of different molecules and the polarization induced on a nearby metallic boundary and predict similar collective interference phenomena in excitation energy transfer between molecular aggregates.

Photoluminescence enhancement of monolayer MoS2 using plasmonic gallium nanoparticles.

2D monolayer molybdenum disulphide (MoS2) has been the focus of intense research due to its direct bandgap compared with the indirect bandgap of its bulk counterpart; however its photoluminescence (PL) intensity is limited due to its low absorption efficiency. Herein, we use gallium hemispherical nanoparticles (Ga NPs) deposited by thermal evaporation on top of chemical vapour deposited MoS2 monolayers in order to enhance its luminescence. The influence of the NP radius and the laser wavelength is reported in PL and Raman experiments. In addition, the physics behind the PL enhancement factor is investigated. The results indicate that the prominent enhancement is caused by the localized surface plasmon resonance of the Ga NPs induced by a charge transfer phenomenon. This work sheds light on the use of alternative metals, besides silver and gold, for the improvement of MoS2 luminescence.

High Ultraviolet Absorption in Colloidal Gallium Nanoparticles Prepared from Thermal Evaporation.

New methods for the production of colloidal Ga nanoparticles (GaNPs) are introduced based on the evaporation of gallium on expendable aluminum zinc oxide (AZO) layer. The nanoparticles can be prepared in aqueous or organic solvents such as tetrahydrofuran in order to be used in different sensing applications. The particles had a quasi mono-modal distribution with diameters ranging from 10 nm to 80 nm, and their aggregation status depended on the solvent nature. Compared to common chemical synthesis, our method assures higher yield with the possibility of tailoring particles size by adjusting the deposition time. The GaNPs have been studied by spectrophotometry to obtain the absorption spectra. The colloidal solutions exhibit strong plasmonic absorption in the ultra violet (UV) region around 280 nm, whose width and intensity mainly depend on the nanoparticles dimensions and their aggregation state. With regard to the colloidal GaNPs flocculate behavior, the water solvent case has been investigated for different pH values, showing UV-visible absorption because of the formation of NPs clusters. Using discrete dipole approximation (DDA) method simulations, a close connection between the UV absorption and NPs with a diameter smaller than ~40 nm was observed.

Gallium plasmonic nanoparticles for label-free DNA and single nucleotide polymorphism sensing.

A label-free DNA and single nucleotide polymorphism (SNP) sensing method is described. It is based on the use of the pseudodielectric function of gallium plasmonic nanoparticles (GaNPs) deposited on Si (100) substrates under reversal of the polarization handedness condition. Under this condition, the pseudodielectric function is extremely sensitive to changes in the surrounding medium of the nanoparticle surface providing an excellent sensing platform competitive to conventional surface plasmon resonance. DNA sensing has been carried out by immobilizing a thiolated capture probe sequence from Helicobacter pylori onto GaNP/Si substrates; complementary target sequences of Helicobacter pylori can be quantified over the range of 10 pM to 3.0 nM with a detection limit of 6.0 pM and a linear correlation coefficient of R(2) = 0.990. The selectivity of the device allows the detection of a single nucleotide polymorphism (SNP) in a specific sequence of Helicobacter pylori, without the need for a hybridization suppressor in solution such as formamide. Furthermore, it also allows the detection of this sequence in the presence of other pathogens, such as Escherichia coli in the sample. The broad applicability of the system was demonstrated by the detection of a specific gene mutation directly associated with cystic fibrosis in large genomic DNA isolated from blood cells.

Immunosensing platform based on gallium nanoparticle arrays on silicon substrates.

Gallium nanoparticles (GaNPs) of different sizes are deposited on Si(100) substrates by thermal evaporation. Through ellipsometric analysis, it is possible to investigate the plasmonic effects in the GaNPs and exploit them to develop biosensors. The excitation of the resonant modes for certain incidence angles leads to negative values of the imaginary part of the pseudodielectric function (<εi>) obtained in ellipsometry. Furthermore, there is an abrupt sign change when the difference between the phase shifts of p- and s-polarization components reaches 180° at an energy of around 3.15 eV. At that energy, reversal of the polarization handedness (RPH) occurs for an elliptically-polarized input beam. The energy of the RPH condition reduces as the evaporation time increases. The slope of <εi> at the RPH condition is extremely sensitive to changes in the surrounding medium of the NP surface and prompts the use of the GaNP/Si system as sensor platform. Fourier transformed infrared spectroscopy (FTIR) is used before and after functionalization with 3,3'-dithiodipropionic acid di(N-succinimidyl ester) and a glutathione-specific antibody to confirm the chemical modification of the sample surface. The developed immunosensor is exposed to different concentrations of glutathione (GSH) showing a linear relationship between the slope of the pseudodielectric function at the RPH condition and the GSH concentration. The immunosensor shows a limit of detection of 10nM enabling its use for the detection of low GSH levels in different medical conditions.

Optical sensors based on III-nitride photodetectors for flame sensing and combustion monitoring.

Combustion control requires visible photodetectors to sense the CH* CL emission at 430 nm that combined with a visible-blind UV photodetector allows us to obtain the OH*/CH* ratio. UV-visible P-InGaN/GaN multiple quantum well-N photodiodes with 15-18 mm2 areas were fabricated to conduct OH* (308 nm) and CH* CL detection without external filters. Bandpass detectors at 230-390 nm and 360-450 nm presented linear responses over five decades and rejection ratios >10(3) at 430 and 308 nm, respectively. A full optical sensor system was built and detectors operated at 120 degrees C in a combustion chamber, showing linear responses within the dynamic range, maximum signal-to-noise ratios of 103 and response times of <1 s. An exponential association dependence between the optical OH*/CH* CL signals and the gas/air ratios was found.