Luminescence enhancement effects on nanostructured perovskite thin films for Er/Yb-doped solar cells.

Recent attempts to improve solar cell performance by increasing their spectral absorption interval incorporate up-converting fluorescent nanocrystals on the structure. These nanocrystals absorb low energy light and emit higher energy photons that can then be captured by the solar cell active layer. However, this process is very inefficient and it needs to be enhanced by different strategies. In this work, we have studied the effect of nanostructuration of perovskite thin films used in the fabrication of hybrid solar cells on their local optical properties. The perovskite surface was engraved with a focused ion beam to form gratings of one-dimensional grooves. We characterized the surfaces with a fluorescence scanning near-field optical microscope, and obtained maps showing a fringe pattern oriented in a direction parallel to the grooves. By scanning structures as a function of the groove depth, ranging from 100 nm to 200 nm, we observed that a 3-fold luminescence enhancement could be obtained for the deeper ones. Near-field luminescence was found to be enhanced between the grooves, not inside them, independent of the groove depth and the incident polarization direction. This indicates that the ideal position of the nanocrystals is between the grooves. In addition, we also studied the influence of the inhomogeneities of the perovskite layer and we observed that roughness tends to locally modify the intensity of the fringes and distort their alignment. All the experimental results are in good agreement with numerical simulations.

Spatially Resolved Temperature Distribution in a Rare-Earth-Doped Transparent Glass-Ceramic.

Knowing the temperature distribution within the conducting walls of various multilayer-type materials is crucial for a better understanding of heat-transfer processes. This applies to many engineering fields, good examples being photovoltaics and microelectronics. In this work we present a novel fluorescence technique that makes possible the non-invasive imaging of local temperature distributions within a transparent, temperature-sensitive, co-doped Er:GPF1Yb0.5Er glass-ceramic with micrometer spatial resolution. The thermal imaging was performed with a high-resolution fluorescence microscopy system, measuring different focal planes along the z-axis. This ultimately enabled a precise axial reconstruction of the temperature distribution across a 500-µm-thick glass-ceramic sample. The experimental measurements showed good agreement with computer-modeled heat simulations and suggest that the technique could be adopted for the spatial analyses of local thermal processes within optically transparent materials. For instance, the technique could be used to measure the temperature distribution of intermediate, transparent layers of novel ultra-high-efficiency solar cells at the micron and sub-micron levels.

Mapping plasmon-enhanced upconversion fluorescence of Er/Yb-doped nanocrystals near gold nanodisks.

Fluorescence enhancement effects have many potential applications in the domain of biochemical sensors and optoelectronic devices. Here, the emission properties of up-converting nanocrystals near nanostructures that support surface plasmon resonances have been investigated. Gold nanodisks of various diameters were illuminated in the near-infrared (λ = 975 nm) and a single fluorescent nanocrystal glued at the end of an atomic force microscope tip was scanned around them. By detecting its visible fluorescence around each structure, it is found that the highest fluorescence enhancement occurs in a zone that forms a two-lobe pattern near the nanodisks and which corresponds to the map of the near-field intensity calculated at the excitation wavelength. In agreement with numerical simulations, it is also observed that the maximum fluorescence enhancement takes place when the disk diameter is around 200 nm. Surprisingly, this disk size is small when compared to that yielding the highest far-field scattering resonance, which occurs for disks with a diameter of 300-350 nm at the same excitation wavelength. This shift between the near and far-field resonances should be taken into account in the design of structures in systems that use plasmon enhanced fluorescence effects.

Exploring the Magnetic and Electric Side of Light through Plasmonic Nanocavities.

Light-matter interactions are often considered to be mediated by the electric component of light only, neglecting the magnetic contribution. However, the electromagnetic energy density is equally distributed between both parts of the optical fields. Within this scope, we experimentally demonstrate here, in excellent agreement with numerical simulations, that plasmonic nanostructures can selectively manipulate and tune the magnetic versus electric emission of luminescent nanocrystals. In particular, we show selective enhancement or decay of magnetic and electric emission from trivalent europium-doped nanoparticles in the vicinity of plasmonic nanocavities, designed to efficiently couple to either the electric or magnetic emission of the quantum emitter. Specifically, by precisely controlling the spatial position of the emitter with respect to our plasmonic nanostructures, by means of a near-field optical microscope, we record local distributions of both magnetic and electric radiative local densities of states (LDOS) with nanoscale precision. The distribution of the radiative LDOS reveals the modification of both the magnetic and electric optical quantum environments induced by the presence of the metallic nanocavities. This manipulation and enhancement of magnetic light-matter interaction by means of plasmonic nanostructures opens up new possibilities for the research fields of optoelectronics, chiral optics, nonlinear and nano-optics, spintronics, and metamaterials, among others.

Time-gated luminescence bioimaging with new luminescent nanocolloids based on [Mo6I8(C2F5COO)6]2- metal atom clusters.

Bioimaging and cell labeling using red or near infrared phosphors emitting in the "therapeutic window" of biological tissues have recently become some of the most active research fields in modern medical diagnostics. However, because organic and inorganic autofluorophores are omnipresent in nature, very often the background signal from fluorochromes other than targeted probes has to be eliminated. This discrimination could be available using a time-gated luminescence microscopy (TGLM) technique associated with long lifetime phosphorescent nanocomposites. Here, we report new SiO2 nanostructured particle (50 nm in diameter) embedded luminescent nanosized [Mo6I8(C2F5COO)6]2- metal atom clusters (1 nm in diameter), successfully prepared by the microemulsion technique. This combination provides new physical insight and displays red emission in biological based solution under UV-Vis excitation with long lifetimes of around 17 and 84 µs. Moreover, the nanoparticles can be internalized by cancer cells after surface functionalization by transferrin protein and clearly imaged by TGLM under excitation at 365 nm. The nanocomposites have been mainly characterized by scanning and transmission electron microscopies (SEM and HAADF-STEM), UV-Vis and photoluminescence (PL) spectroscopies.

Multifunctional hybrid silica nanoparticles based on [Mo6Br14]²â» phosphorescent nanosized clusters, magnetic γ-Fe2O3 and plasmonic gold nanoparticles.

We report on the synthesis, characterization and photophysical study of new luminescent and magnetic hybrid silica nanoparticles. Our method is based on the co-encapsulation of single maghemite γ-Fe2O3 nanoparticles and luminescent molybdenum cluster units [Mo6Br(i)8Br(a)6](2-) through a water-in-oil (W/O) microemulsion technique. The as-prepared core-shell [Cs2Mo6Br14-γFe2O3]@SiO2 nanoparticles (45-53 nm) possess a single magnetic core (6, 10.5 or 15 nm) and the cluster units are dispersed in the entire volume of the silica sphere. The [Cs2Mo6Br14-γFe2O3]@SiO2 nanoparticles have a perfect spherical shape with a good monodispersity and they display red and near-infrared (NIR) emission in water under UV excitation, whose intensity depends on the magnetic core size. The hybrid nanoparticles have been characterized by transmission electron microscopy (TEM), high annular angular dark field scanning transmission electron microscopy (HAADF-STEM), energy-dispersive X-ray spectroscopy (EDX), UV-Vis-NIR spectroscopy and magnetometer SQUID analysis. Small gold nanoparticles were successfully nucleated at the surface of the hybrid silica nanoparticles in order to add plasmonic properties.

Note: A scanning thermal probe microscope that operates in liquids.

We have developed a scanning thermal probe microscope that operates in liquid environments. The thermal sensor is a fluorescent particle glued at the end of a sharp tungsten tip. Since light emission is a strongly thermally sensitive effect, the measurement of the particle fluorescence variations allows the determination of the temperature. No electrical wiring of the probe is needed. As a demonstrative example, we have measured the temperature map of a Joule-heated microheater immersed in a water∕glycerol solution. Both topographical and thermal images are obtained with a good sensitivity.

Tuning temperature and size of hot spots and hot-spot arrays.

By using scanning thermal microscopy, it is shown that nanoscale constrictions in metallic microwires deposited on an oxidized silicon substrate can be tuned in terms of temperature and confinement size. High-resolution temperature maps indeed show that submicrometer hot spots and hot-spot arrays are obtained when the SiO(2) layer thickness decreases below 100 nm. When the SiO(2) thickness becomes larger, heat is less confined in the vicinity of the constrictions and laterally spreads all along the microwire. These results are in good agreement with numerical simulations, which provide dependences between silica-layer thickness and nanodot shape and temperature.

Functional silica nanoparticles synthesized by water-in-oil microemulsion processes.

Water-in-oil (W/O) microemulsion is a well-suitable confined reacting medium for the synthesis of structured functional nanoparticles of controlled size and shape. During the last decade, it allowed the synthesis of multi-functional silica nanoparticles with morphologies as various as core-shell, homogenous dispersion or both together. The morphology and properties of the different intermediates and final materials obtained through this route are discussed in the light of UV-Vis-NIR spectroscopy, dynamic light scattering (DLS) and X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and magnetometer SQUID analysis.

Scanning thermal imaging by near-field fluorescence spectroscopy.

A scanning thermal microscope that uses a fluorescent particle as a temperature probe has been developed. The particle, made of a rare-earth ion-doped fluoride glass, is glued at the extremity of a sharp tungsten tip and scanned on the surface of an electronic device. The temperature of the device is determined by measuring the fluorescence spectrum of the particle at every point on the surface and by comparing the intensity variations of two emission lines. As an example, we will show some images obtained on a nickel stripe 1 microm wide, heated by an electrical current. A good agreement is observed with a simulation of the temperature field on the device.

Er(3+)-doped nanoparticles for optical detection of magnetic field.

A bright persistent photoluminescence has been observed in Er(3+)-doped nanoparticles prepared by selective dissolution of bulk oxyfluoride nano-glass-ceramics. A 2 orders of magnitude decrease of intensity of the (4)S(3/2)-->(4)I(15/2) green emission band of Er(3+) in these nanoparticles is observed in magnetic fields up to 50 T. This strong luminescence sensitivity to magnetic field can be used for localization and distant optical detection of magnetic field in nanovolumes with a field-resolution of 0.01 T.

Local order around rare earth ions during the devitrification of oxyfluoride glasses.

Erbium L(3)-edge extended x-ray absorption fine structure (EXAFS) measurements were performed on rare earth doped fluorosilicate and fluoroborate glasses and glass ceramics. The well known nucleating effects of erbium ions for the crystallization of cubic lead fluoride (based on x-ray diffraction measurements) and the fact that the rare earth ions are present in the crystalline phase (as indicated by Er(3+) emission spectra) seem in contradiction with the present EXAFS analysis, which indicates a lack of medium range structural ordering around the Er(3+) ions and suggests that the lead fluoride crystallization does not occur in the nearest neighbor distance of the rare earth ion. Molecular dynamics simulations of the devitrification process of a lead fluoride glass doped with Er(3+) ions were performed, and results indicate that Er(3+) ions lower the devitrification temperature of PbF(2), in good agreement with the experimental results. The genuine role of Er(3+) ions in the devitrification process of PbF(2) has been investigated. Although Er(3+) ions could indeed act as seeds for crystallization, as experiments suggest, molecular dynamics simulation results corroborate the experimental EXAFS observation that the devitrification does not occur at its nearest neighbor distance.

Near-field scattered by a single nanoslit in a metal film.

Using a scanning near-field optical microscope, we visualize, in three dimensions, the electromagnetic field distribution near an isolated slit aperture in a thin gold film. At the metal-air interface and for a TM incident polarization, we confirm some recently observed results and show that the slit generates two kinds of surface waves: a slowly decaying surface plasmon polariton and a quasi-cylindrical wave that decreases more rapidly when moving away from the slit. These waves are not generated for a TE incident polarization. In a noncontact mode, we also observe how the transmitted light diverges in free space. At a small distance from the slit (< 2 microm), we find that the emerging light spreads in all directions for TM, forming an electromagnetic cloud, whereas it is concentrated above the slit for TE, forming a more directive light jet. The experimental images are in good agreement with the numerical simulations.

EPR and optical studies of erbium-doped beta-PbF2 single-crystals and nanocrystals in transparent glass-ceramics.

beta-PbF(2) single-crystals and nanocrystals in transparent glass-ceramics doped with ErF(3) have been synthesized and studied with two complementary techniques: electron paramagnetic resonance (EPR) and optical spectroscopy (absorption, selective excitation, fluorescence). A comparative study shows that, in both single-crystals and glass-ceramics, Er(3+) ions occupy the same types of sites, leading to similar optical properties. An EPR investigation demonstrates that, in these materials, part of the Er(3+) ions occupy cubic symmetry sites. For these ions, we determine the crystal field splitting of the ground state (4)I(15/2) and the symmetry of its sublevels. We also provide evidence for the presence of another type of Er(3+) ions, not detectable by EPR but evidenced by optical spectroscopy. We clearly show that this Er(3+), which gives rise to up-conversion luminescence, corresponds to clusters associating Er(3+) and F(-) ions. In the single-crystals, the proportion of these two types of erbium ions is estimated. It strongly depends on the doping rate of the beta-PbF(2) crystals.

Molecular dynamics simulation study of erbium induced devitrification in vitreous PbF2.

Molecular dynamics simulations of the devitrification process of a lead fluoride glass doped with Er(3+) ions were carried out. This technique appears to be a relevant way to perform systematic analysis of the system structure and to study the influence of defects on PbF2 crystallization. We modeled the total enthalpy, the radial distribution functions, and the diffracted intensities of systems containing different amounts of Er(3+) ions. We demonstrated by means of different simulations that Er(3+) ions lowered the devitrification temperature of PbF2, in good agreement with the experimental results. The genuine role of Er(3+) ions in the devitrification process of PbF2 has been investigated. Er(3+) ions have an unquestionable influence of the crystallization of PbF2. Although the latter does not start in the nearest neighborhood of Er(3+) ions, the presence of Er(3+) ions in a close environment may favor the lead fluoride crystallization.

Fabrication and characterization of fluorescent rare-earth-doped glass-particle-based tips for near-field optical imaging applications.

Fluorescent rare-earth-doped glass particles glued to the end of an atomic force microscope tip have been used to perform scanning near-field optical measurements on nanostructured samples. The fixation procedure of the fluorescent fragment at the end of the tip is described in detail. The procedure consists of depositing a thin adhesive layer on the tip. Then a tip approach is performed on a fragment that remains stuck near the tip extremity. To displace the particle and position it at the very end of the tip, a nanomanipulation is achieved by use of a second tip mounted on piezoelectric scanners. Afterward, the particle size is reduced by focused ion beam milling. These particles exhibit a strong green luminescence where excited in the near infrared by an upconversion mechanism. Images obtained near a metallic edge show a lateral resolution in the 180-200-nm range. Images we obtained by measuring the light scattered by 250-nm holes show a resolution well below 100 nm. This phenomenon can be explained by a local excitation of the particle and by the nonlinear nature of the excitation.