Luiz Fernando Zagonel

Nanometer Scale Spectral Imaging of Quantum Emitters in Nanowires and Its Correlation to Their Atomically Resolved Structure

We report the spectral imaging in the UV to visible range with nanometer scale resolution of closely packed GaN/AlN quantum disks in individual nanowires using an improved custom-made cathodoluminescence system. We demonstrate the possibility to measure full spectral features of individual quantum emitters as small as 1 nm and separated from each other by only a few nanometers and the ability to correlate their optical properties to their size, measured with atomic resolution. The direct correlation between the quantum disk size and emission wavelength provides evidence of the quantum confined Stark effect leading to an emission below the bulk GaN band gap for disks thicker than 2.6 nm. With the help of simulations, we show that the internal electric field in the studied quantum disks is smaller than what is expected in the quantum well case. We show evidence of a clear dispersion of the emission wavelengths of different quantum disks of identical size but different positions along the wire. This dispersion is systematically correlated to a change of the diameter of the AlN shell coating the wire and is thus attributed to the related strain variations along the wire. The present work opens the way both to fundamental studies of quantum confinement in closely packed quantum emitters and to characterizations of optoelectronic devices presenting carrier localization on the nanometer scale.

Ultraviolet Photodetector Based on GaN/AlN Quantum Disks in a Single Nanowire

We report the demonstration of single-nanowire photodetectors relying on carrier generation in GaN/AlN QDiscs. Two nanowire samples containing QDiscs of different thicknesses are analyzed and compared to a reference binary n-i-n GaN nanowire sample. The responsivity of a single wire QDisc detector is as high as 2 x 10(3) A/W at lambda = 300 nm at room temperature. We show that the insertion of an axial heterostructure drastically reduces the dark current with respect to the binary nanowires and enhances the photosensitivity factor (i.e., the ratio between the photocurrent and the dark current) up to 5 x 10(2) for an incoming light intensity of 5 mW/cm(2). Photocurrent spectroscopy allows identification of the spectral contribution related to carriers generated within large QDiscs, which lies below the GaN band gap due to the quantum confined Stark effect.

Imaging and quantifying the morphology of an organic-inorganic nanoparticle at the sub-nanometre level

The development of hybrid organic-inorganic nanoparticles is of interest for applications such as drug delivery, DNA and protein recognition, and medical diagnostics. However, the characterization of such nanoparticles remains a significant challenge due to the heterogeneous nature of these particles. Here, we report the direct visualization and quantification of the organic and inorganic components of a lipid-coated silica particle that contains a smaller semiconductor quantum dot. High-angle annular dark-field scanning transmission electron microscopy combined with electron energy loss spectroscopy was used to determine the thickness and chemical signature of molecular coating layers, the element atomic ratios, and the exact positions of different elements in single nanoparticles. Moreover, the lipid ratio and lipid phase segregation were also quantified.

Unveiling Nanometer Scale Extinction and Scattering Phenomena through Combined Electron Energy Loss Spectroscopy and Cathodoluminescence Measurements

Plasmon modes of the exact same individual gold nanoprisms are investigated through combined nanometer-resolved electron energy-loss spectroscopy (EELS) and cathodoluminescence (CL) measurements. We show that CL only probes the radiative modes, in contrast to EELS, which additionally reveals dark modes. The combination of both techniques on the same particles thus provides complementary information and also demonstrates that although the radiative modes give rise to very similar spatial distributions when probed by EELS or CL, their resonant energies appear to be different. We trace this phenomenon back to plasmon dissipation, which affects in different ways the plasmon signatures probed by these techniques. Our experiments are in agreement with electromagnetic numerical simulations and can be further interpreted within the framework of a quasistatic analytical model. We therefore demonstrate that CL and EELS are closely related to optical scattering and extinction, respectively, with the addition of nanometer spatial resolution.

Growth mechanism and properties of InGaN insertions in GaN nanowires.

We demonstrate the strong influence of strain on the morphology and In content of InGaN insertions in GaN nanowires, in agreement with theoretical predictions which establish that InGaN island nucleation on GaN nanowires may be energetically favorable, depending on In content and nanowire diameter. EDX analyses reveal In inhomogeneities between the successive dots but also along the growth direction within each dot, which is attributed to compositional pulling. Nanometer-resolved cathodoluminescence on single nanowires allowed us to probe the luminescence of single dots, revealing enhanced luminescence from the high In content top part with respect to the lower In content dot base.

Single-Wire Light-Emitting Diodes Based on GaN Wires Containing Both Polar and Nonpolar InGaN/GaN Quantum Wells

Single-wire light-emitting diodes based on radial p–i–n multi quantum well (QW) junctions have been realized from GaN wires grown by catalyst-free metal organic vapor phase epitaxy. The InxGa1-xN/GaN undoped QW system is coated over both the nonpolar lateral sidewalls and on the polar upper surface. Cathodo- and electroluminescence (EL) experiments provide evidence that the polar QWs emit in the visible spectral range at systematically lower energy than the nonpolar QWs. The EL of the polar or nonpolar QWs can be selectively activated by varying the sample temperature and current injection level.

Direct quantification of gold along a single Si nanowire.

The presence of gold on the sidewall of a tapered, single silicon nanowire is directly quantified from core-level nanospectra using energy-filtered photoelectron emission microscopy. The uniform island-type partial coverage of gold determined as 0.42+/-0.06 (approximately 1.8 ML) is in quantitative agreement with the diameter reduction of the gold catalyst observed by scanning electron microscopy and is confirmed by a splitting of the photothresholds collected from the sidewall, from which characteristic local work functions are extracted using a model of the full secondary electron distributions.

Photocatalytic hydrogen production of Co(OH)2 nanoparticle-coated α-Fe2O3 nanorings

The production of hydrogen from water using only a catalyst and solar energy is one of the most challenging and promising outlets for the generation of clean and renewable energy. Semiconductor photocatalysts for solar hydrogen production by water photolysis must employ stable, non-toxic, abundant and inexpensive visible-light absorbers capable of harvesting light photons with adequate potential to reduce water. Here, we show that α-Fe₂O₃ can meet these requirements by means of using hydrothermally prepared nanorings. These iron oxide nanoring photocatalysts proved capable of producing hydrogen efficiently without application of an external bias. In addition, Co(OH)₂ nanoparticles were shown to be efficient co-catalysts on the nanoring surface by improving the efficiency of hydrogen generation. Both nanoparticle-coated and uncoated nanorings displayed superior photocatalytic activity for hydrogen evolution when compared with TiO₂ nanoparticles, showing themselves to be promising materials for water-splitting using only solar light.

Orientation-dependent work function of in situ annealed strontium titanate.

We have used energy-filtered x-ray photoelectron emission microscopy (XPEEM) and synchrotron radiation to measure the grain orientation dependence of the work function of a sintered niobium-doped strontium titanate ceramic. A significant spread in work function values is found. Grain orientation and surface reducing/oxidizing conditions are the main factors in determining the work function. Energy-filtered XPEEM looks ideally suited for analysis of other technologically interesting polycrystalline samples.

Visualizing highly localized luminescence in GaN/AlN heterostructures in nanowires.

The optical properties of a stack of GaN/AlN quantum discs (QDiscs) in a GaN nanowire have been studied by spatially resolved cathodoluminescence (CL) at the nanoscale (nanoCL) using a scanning transmission electron microscope (STEM) operating in spectrum imaging mode. For the electron beam excitation in the QDisc region, the luminescence signal is highly localized, with spatial extent as low as 5 nm, due to the high band gap difference between GaN and AlN. This allows the discrimination between the emission of neighbouring QDiscs and evidencing the presence of lateral inclusions, about 3 nm thick and 20 nm long rods (quantum rods, QRods), grown unintentionally on the nanowire sidewalls. These structures, also observed by STEM dark-field imaging, are proved to be optically active in nanoCL, emitting at similar, but usually shorter, wavelengths with respect to most QDiscs.