Plasmonic coupling in closed-packed ordered gallium nanoparticles.

Plasmonic gallium (Ga) nanoparticles (NPs) are well known to exhibit good performance in numerous applications such as surface enhanced fluorescence and Raman spectroscopy or biosensing. However, to reach the optimal optical performance, the strength of the localized surface plasmon resonances (LSPRs) must be enhanced particularly by suitable narrowing the NP size distribution among other factors. With this purpose, our last work demonstrated the production of hexagonal ordered arrays of Ga NPs by using templates of aluminium (Al) shallow pit arrays, whose LSPRs were observed in the VIS region. The quantitative analysis of the optical properties by spectroscopic ellipsometry confirmed an outstanding improvement of the LSPR intensity and full width at half maximum (FWHM) due to the imposed ordering. Here, by engineering the template dimensions, and therefore by tuning Ga NPs size, we expand the LSPRs of the Ga NPs to cover a wider range of the electromagnetic spectrum from the UV to the IR regions. More interestingly, the factors that cause this optical performance improvement are studied with the universal plasmon ruler equation, supported with discrete dipole approximation simulations. The results allow us to conclude that the plasmonic coupling between NPs originated in the ordered systems is the main cause for the optimized optical response.

Spectrally broad plasmonic absorption in Ga and In nanoparticle hybrids.

In this work, we use Joule-effect thermal evaporation to produce hybrid structures made of Ga and In nanoparticles (NPs) on Si (100) substrates. Taking advantage of the protective oxide shell, In NPs can be used as a template for a second deposition step without structural changes, enabling the hybridization of NPs of materials. These complex structures of mixed NPs present a spectrally broad plasmonic absorption that can be optically tuned with a wide range of photon energies from UV to IR regions with a full width at half maximum range of ∼400 to 800 nm. The results suggest that the localized surface plasmon resonance (LSPR) of the hybrid NPs is mainly due to the plasmonic coupling of the in-plane modes. Furthermore, different scenarios studied by discrete dipole approximation simulations show that the interconnection between NPs is extremely sensitive to the size and the local arrangement of the nanostructures. This kind of broadening and tunable LSPR may have interest for energy transfer applications, biosensing platforms and solar cells.

Size-selective breaking of the core-shell structure of gallium nanoparticles.

Core-shell gallium nanoparticles (Ga NPs) have recently been proposed as an ultraviolet plasmonic material for different applications but only at room temperature. Here, the thermal stability as a function of the size of the NPs is reported over a wide range of temperatures. We analyze the chemical and structural properties of the oxide shell by x-ray photoelectron spectroscopy and atomic force microscopy. We demonstrate the inverse dependence of the shell breaking temperature with the size of the NPs. Spectroscopic ellipsometry is used for tracking the rupture and its mechanism is systematically investigated by scanning electron microscopy, grazing incidence x-ray diffraction and cathodoluminescence. Taking advantage of the thermal stability of the NPs, we perform complete oxidations that lead to homogenous gallium oxide NPs. Thus, this study set the physical limits of Ga NPs to last at high temperatures, and opens up the possibility to achieve totally oxidized NPs while keeping their sphericity.

Tunable plasmonic resonance of gallium nanoparticles by thermal oxidation at low temperaturas.

The effect of the oxidation of gallium nanoparticles (Ga NPs) on their plasmonic properties is investigated. Discrete dipole approximation has been used to study the wavelength of the out-of-plane localized surface plasmon resonance in hemispherical Ga NPs, deposited on silicon substrates, with oxide shell (Ga2O3) of different thickness. Thermal oxidation treatments, varying temperature and time, were carried out in order to increase experimentally the Ga2O3 shell thickness in the NPs. The optical, structural and chemical properties of the oxidized NPs have been studied by spectroscopic ellipsometry, scanning electron microscopy, grazing incidence x-ray diffraction and x-ray photoelectron spectroscopy. A clear redshift of the peak wavelength is observed, barely affecting the intensity of the plasmon resonance. A controllable increase of the Ga2O3 thickness as a consequence of the thermal annealing is achieved. In addition, simulations together with ellipsometry results have been used to determine the oxidation rate, whose kinetics is governed by a logarithmic dependence. These results support the tunable properties of the plasmon resonance wavelength in Ga NPs by thermal oxidation at low temperatures without significant reduction of the plasmon resonance intensity.

Analysis of Zinc Nitride Resistive Indicators under Different Relative Humidity Conditions.

Zinc nitride (Zn3N2) is a metastable material in ambient conditions because of its high reactivity with water molecules. In this work we perform a systematic analysis of the oxidation of Zn3N2 layers grown by RF magnetron sputtering at room temperature. The aging and transformation of the layers toward a ZnO film is explored by means of spectroscopic ellipsometry and scanning electron microscopy for conditions with different relative humidity (RH). Accurate depth profiling by means of elastic recoil detection analysis with a time-of-flight telescope demonstrated the substitutional reaction between O and N and the important effect of the RH in this process. Because of this metastability the resistivity of the layers changes several orders of magnitude. Taking advantage of this principle, we develop electronic indicators and characterize the transformation of their electrical properties as a function of the ambient RH, finding a good correlation between the transformation time and the RH level.

Continuous-flow system and monitoring tools for the dielectrophoretic integration of nanowires in light sensor arrays.

Although nanowires (NWs) may improve the performance of many optoelectronic devices such as light emitters and photodetectors, the mass commercialization of these devices is limited by the difficult task of finding reliable and reproducible methods to integrate the NWs on foreign substrates. This work shows the fabrication of zinc oxide NWs photodetectors on conventional glass using transparent conductive electrodes to effectively integrate the NWs at specific locations by dielectrophoresis (DEP). The paper describes the careful preparation of NW dispersions by sedimentation and the dielectrophoretic alignment of NWs in a home-made system. This system includes an impedance technique for the assessment of the alignment quality in real time. Following this procedure, ultraviolet photodetectors based on the electrical contacts formed by the DEP process on the transparent electrodes are fabricated. This cost-effective mean of contacting NWs enables front-and back-illumination operation modes, the latter eliminating shadowing effects caused by the deposition of metals. The electro-optical characterization of the devices shows uniform responsivities in the order of 106 A W(-1) below 390 nm under both modes, as well as, time responses of a few seconds.

Simple diazonium chemistry to develop specific gene sensing platforms.

A simple strategy for covalent immobilizing DNA sequences, based on the formation of stable diazonized conducting platforms, is described. The electrochemical reduction of 4-nitrobenzenediazonium salt onto screen-printed carbon electrodes (SPCE) in aqueous media gives rise to terminal grafted amino groups. The presence of primary aromatic amines allows the formation of diazonium cations capable to react with the amines present at the DNA capture probe. As a comparison a second strategy based on the binding of aminated DNA capture probes to the developed diazonized conducting platforms through a crosslinking agent was also employed. The resulting DNA sensing platforms were characterized by cyclic voltammetry, electrochemical impedance spectroscopy and spectroscopic ellipsometry. The hybridization event with the complementary sequence was detected using hexaamineruthenium (III) chloride as electrochemical indicator. Finally, they were applied to the analysis of a 145-bp sequence from the human gene MRP3, reaching a detection limit of 210 pg µL(-1).

Conducting properties of nearly depleted ZnO nanowire UV sensors fabricated by dielectrophoresis.

ZnO nanowires (NWs) with different radii (rNW) have been aligned between pre-patterned electrodes using dielectrophoresis (DEP) for the fabrication of high gain UV sensors. The DEP conditions (voltage amplitude and frequency) and electrode material, geometry and size were optimized to enhance the efficiency during the DEP process. To understand the alignment mechanism of the ZnO NWs, the dielectrophoretic force (FDEP) was analyzed as a function of the DEP conditions and NW dimensions. These studies showed that the DEP alignment process tends to trap NWs with a smaller radius. The effects of NW size on device performance were analyzed by means of I-V measurements in darkness and under illumination (200 nm < λ < 600 nm). In darkness, the NW resistance increases as rNW decreases due to the reduction of the conduction volume, until saturation is reached for rNW < 65 nm. On the other hand, the NW spectral photoresponse shows high values around 10(8) A W(-1) (measured at 5 V and λ < 370 nm) and follows a linear trend as a function of the NW cross section. In addition, the cut-off wavelength depends on rNW, presenting a clear blue-shift for NWs with a lower radius (rNW < 50 nm). Transient photoresponse studies show that NWs with lower radii have longer rise times and shorter decay times mainly due to surface trapping effects. Regardless of NW size, passivation of the surface using a dielectric capping layer of SiO2 reduces the dynamic range of the photoresponse due to a strong increase of the dark current.

Gallium-assisted growth of silicon nanowires by electron cyclotron resonance plasmas.

The use of gallium droplets for growing Si nanowires (SiNWs) by electron cyclotron resonance plasmas is investigated. First, the relationship between evaporation time and resultant size of the gallium droplets is studied. Through the use of spectroscopic ellipsometry, the dependence of the surface plasmon resonance (SPR) energy on the droplet size is determined. From these gallium droplets, SiNWs were grown at 300 and 550 °C in electron cyclotron resonance plasmas containing SiH(4), Ar, and H(2). Scanning electron microscopy results show that tapered NWs are obtained for a wide range of growth conditions. Besides, it is found that H(2) plays an important role in the parasitic axial growth of the SiNWs. Namely, H(2) inhibits the radial growth and contributes dramatically to increasing the SiNW defects.