Ultrafast photoluminescence and multiscale light amplification in nanoplasmonic cavity glass.

Interactions between plasmons and exciton nanoemitters in plexcitonic systems lead to fast and intense luminescence, desirable in optoelectonic devices, ultrafast optical switches and quantum information science. While luminescence enhancement through exciton-plasmon coupling has thus far been mostly demonstrated in micro- and nanoscale structures, analogous demonstrations in bulk materials have been largely neglected. Here we present a bulk nanocomposite glass doped with cadmium telluride quantum dots (CdTe QDs) and silver nanoparticles, nAg, which act as exciton and plasmon sources, respectively. This glass exhibits ultranarrow, FWHM = 13 nm, and ultrafast, 90 ps, amplified photoluminescence (PL), λem≅503 nm, at room temperature under continuous-wave excitation, λexc = 405 nm. Numerical simulations confirm that the observed improvement in emission is a result of a multiscale light enhancement owing to the ensemble of QD-populated plasmonic nanocavities in the material. Power-dependent measurements indicate that >100 mW coherent light amplification occurs. These types of bulk plasmon-exciton composites could be designed comprising a plethora of components/functionalities, including emitters (QDs, rare earth and transition metal ions) and nanoplasmonic elements (Ag/Au/TCO, spherical/anisotropic/miscellaneous), to achieve targeted applications.

Spontaneous off-stoichiometry as the knob to control the dielectric properties of gapped metals.

Using first-principles calculations and La3Te4 as an example of an n-type gapped metal, we demonstrate that gapped metals can develop spontaneous defect formation resulting in off-stoichiometric compounds. Importantly, these compounds have different free carrier concentrations and can be realized by optimizing the synthesis conditions. The ability to tune the free carrier concentration allows the tailoring of the intraband and interband transitions, thus controlling the optoelectronic properties of materials in general. Specifically, by realizing different off-stoichiometric La3-xTe4 compounds, it is possible to reach specific crossings of the real part of the dielectric function with the zero line, reduce the plasma frequency contribution to the absorption spectra, or, more generally, induce metal-to-insulator transition. This is particularly important in the context of optoelectronic, plasmonic, and epsilon-near-zero materials, as it enables materials design with a target functionality. While this work is limited to the specific gapped metal, we demonstrate that the fundamental physics is transferable to other gapped metals and can be generally used to design a wide class of new optoelectronic/plasmonic materials.

In-Capillary Photodeposition of Glyphosate-Containing Polyacrylamide Nanometer-Thick Films.

The present research reports on in-water, site-specific photodeposition of glyphosate (GLP)-containing polyacrylamide (PAA-GLP) nanometer-thick films (nanofilms) on an inner surface of fused silica (fused quartz) microcapillaries presilanized with trimethoxy(octen-7-yl)silane (TMOS). TMOS was chosen because of the vinyl group presence in its structure, enabling its participation in the (UV light)-activated free-radical polymerization (UV-FRP) after its immobilization on a fused silica surface. The photodeposition was conducted in an aqueous (H2O/ACN; 3:1, v/v) solution, using UV-FRP (λ = 365 nm) of the acrylamide (AA) functional monomer, the N,N'-methylenebis(acrylamide) (BAA) cross-linking monomer, GLP, and the azobisisobutyronitrile (AIBN) UV-FRP initiator. Acetonitrile (ACN) was used as the porogen and the solvent to dissolve monomers and GLP. Because of the micrometric diameters of microcapillaries, the silanization and photodeposition procedures were first optimized on fused silica slides. The introduction of TMOS, as well as the formation of PAA and PAA-GLP nanofilms, was determined using atomic force microscopy (AFM), scanning electron microscopy with energy-dispersive X-ray (SEM-EDX) spectroscopy, and confocal micro-Raman spectroscopy. Particularly, AFM and SEM-EDX measurements determined nanofilms' thickness and GLP content, respectively, whereas in-depth confocal (micro-Raman spectroscopy)-assisted imaging of PAA- and PAA-GLP-coated microcapillary inner surfaces confirmed the successful photodeposition. Moreover, we examined the GLP impact on polymer gelation by monitoring hydration in a hydrogel and a dried powder PAA-GLP. Our study demonstrated the usefulness of the in-capillary micro-Raman spectroscopy imaging and in-depth profiling of GLP-encapsulated PAA nanofilms. In the future, our simple and inexpensive procedure will enable the fabrication of polymer-based microfluidic chemosensors or adsorptive-separating devices for GLP detection, determination, and degradation.

Optically-active metastable defects in volumetric nanoplasmonic composites.

Metastable defects in semiconductor materials have been well known for decades, but have only recently started to attract attention for their potential applications in information technology. Here, we describe active and passive nanoplasmonic materials with optically active metastable defects that can be switched on or off by cooling with or without laser illumination, respectively. To the best of our knowledge, this is the first report of metastable defects in either passive or active nanoplasmonic materials, and, more generally, in non-semiconducting materials. The nanocomposites are made of a sodium-boron-phosphate glass matrix doped with silver nanoparticles (nAg) or co-doped with nAg and Er3+ ions by NanoParticle Direct Doping method. We further show that the different origins of the two types of defect-related luminescence behaviour are attributable to either a metal-glass defect (MG1) or a metal-glass-rare-earth ion defect (MGR1). Such materials could potentially be used for data writing and erasing using laser illumination with a 'tight' focus such as direct laser writing.

Self-Phase-Matched Second-Harmonic and White-Light Generation in a Biaxial Zinc Tungstate Single Crystal.

Second-order nonlinear optical materials are used to generate new frequencies by exploiting second-harmonic generation (SHG), a phenomenon where a nonlinear material generates light at double the optical frequency of the input beam. Maximum SHG is achieved when the pump and the generated waves are in phase, for example through birefringence in uniaxial crystals. However, applying these materials usually requires a complicated cutting procedure to yield a crystal with a particular orientation. Here we demonstrate the first example of phase matching under the normal incidence of SHG in a biaxial monoclinic single crystal of zinc tungstate. The crystal was grown by the micro-pulling-down method with the (102) plane perpendicular to the growth direction. Additionally, at the same time white light was generated as a result of stimulated Raman scattering and multiphoton luminescence induced by higher-order effects such as three-photon luminescence enhanced by cascaded third-harmonic generation. The annealed crystal offers SHG intensities approximately four times larger than the as grown one; optimized growth and annealing conditions may lead to much higher SHG intensities.

Temperature and atmosphere tunability of the nanoplasmonic resonance of a volumetric eutectic-based Bi2O3-Ag metamaterial.

Nanoplasmonic materials are intensively studied due to the advantages they bring in various applied fields such as photonics, optoelectronics, photovoltaics and medicine. However, their large-scale fabrication and tunability are still a challenge. One of the promising ways of combining these two is to use the self-organization mechanism and after-growth engineering as annealing for tuning the properties. This paper reports the development of a bulk nanoplasmonic, Bi2O3-Ag eutectic-based metamaterial with a tunable plasmonic resonance between orange and green wavelengths. The material, obtained by a simple growth technique, exhibits a silver nanoparticle-related localized surface plasmon resonance (LSPR) in the visible wavelength range. We demonstrate the tunability of the LSPR (spectral position, width and intensity) as a function of the annealing temperature, time and the atmosphere. The critical role of the annealing atmosphere is underlined, annealing in vacuum being the most effective option for a broad control of the LSPR. The various potential mechanisms responsible for tuning the localized surface plasmon resonance upon annealing are discussed in relation to the nanostructures of the obtained materials.

High-pressure crystallography of rhombohedral PrAlO(3) perovskite.

The evolution of the crystal structure of rhombohedral PrAlO(3) perovskite with pressure has been investigated by single-crystal x-ray diffraction and Raman scattering experiments. The structural evolution as indicated by lattice strains, octahedral tilts, and the distortions of the octahedral AlO(6) and polyhedral PrO(12) groups with increasing pressure, is controlled by the relative compressibilities of the AlO(6) octahedra and the PrO(12) site. Because the AlO(6) octahedra are more compressible than the PrO(12) sites, up to 7.4 GPa the structure evolves towards the high-symmetry cubic phase like any other rhombohedral perovskite. The variation of volume of the rhombohedral phase with pressure can be represented by a third-order Birch-Murnaghan equation of state with bulk modulus K(0) = 193.0(1.2) GPa and K' = 6.6(4). Above 7.4 GPa the evolution towards a cubic phase is interrupted by a phase transition. Observations are consistent with the assignment of Imma symmetry to the high-pressure phase. Comparison with the low-temperature [Formula: see text] to Imma transition confirms that electronic interactions stabilize the Imma phase.