Magnetic dipole emission in resonant metal-dielectric-metal structures.

We explore a possibility to control magnetic dipole emission with plasmonic cavities, placing Eu3+ emitters inside profile-modulated metal-dielectric-metal structures. Significant variations in the branching ratio of the magnetic and electric dipole transitions are observed as the function of the thickness of the intermediate layer. The experimental results are confirmed with numerical simulations which account for cavity and gap plasmon resonances and predict modifications in the spontaneous emission spectrum as the function of the gap size and a strong directionality of the emission for small thicknesses of the intermediate layer. The implications of having a competition between electric and magnetic dipole relaxation channels in Eu3+ are discussed.

Hydrothermal synthesis of chiral carbon dots.

Nanocolloids that are cumulatively referred to as nanocarbons, attracted significant attention during the last decade because of facile synthesis methods, water solubility, tunable photoluminescence, easy surface modification, and high biocompatibility. Among the latest development in this reserach area are chiral nanocarbons exemplified by chiral carbon dots (CDots). They are expected to have applications in sensing, catalysis, imaging, and nanomedicine. However, the current methods of CDots synthesis show often contradictory chemical/optical properties and structural information that required a systematic study with careful structural evaluation. Here, we investigate and optimize chiroptical activity and photoluminescence of L- and D-CDots obtained by hydrothermal carbonization of L- and D-cysteine, respectively. Nuclear magnetic resonance spectroscopy demonstrates that they are formed via gradual dehydrogenation and condensation reactions of the starting amino acid leading to particles with a wide spectrum of functional groups including aromatic cycles. We found that the chiroptical activity of CDots has an inverse correlation with the synthesis duration and temperature, whereas the photoluminescence intensity has a direct one, which is associated with degree of carbonization. Also, our studies show that the hydrothermal synthesis of cysteine in the presence of boric acid leads to the formation of CDots rather than boron nitride nanoparticles as was previously proposed in several reports. These results can be used to design chiral carbon-based nanoparticles with optimal chemical, chiroptical, and photoluminescent properties.

Manipulation of Magnetic Dipole Emission from Eu3+ with Mie-Resonant Dielectric Metasurfaces.

Mie-resonant high-index dielectric nanoparticles and metasurfaces have been suggested as a viable platform for enhancing both electric and magnetic dipole transitions of fluorescent emitters. While the enhancement of the electric dipole transitions by such dielectric nanoparticles has been demonstrated experimentally, the case of magnetic-dipole transitions remains largely unexplored. Here, we study the enhancement of spontaneous emission of Eu3+ ions, featuring both electric and magnetic-dominated dipole transitions, by dielectric metasurfaces composed of Mie-resonant silicon nanocylinders. By coating the metasurfaces with a layer of an Eu3+ doped polymer, we observe an enhancement of the Eu3+ emission associated with the electric (at 610 nm) and magnetic-dominated (at 590 nm) dipole transitions. The enhancement factor depends systematically on the spectral proximity of the atomic transitions to the Mie resonances as well as their multipolar order, both controlled by the nanocylinder size. Importantly, the branching ratio of emission via the electric or magnetic transition channel can be modified by carefully designing the metasurface, where the magnetic dipole transition is enhanced more than the electric transition for cylinders with radii of about 130 nm. We confirm our observations by numerical simulations based on the reciprocity principle. Our results open new opportunities for bright nanoscale light sources based on magnetic transitions.

Enhancing Eu(3+) magnetic dipole emission by resonant plasmonic nanostructures.

We demonstrate the enhancement of magnetic dipole spontaneous emission from Eu3+ ions by an engineered plasmonic nanostructure that controls the electromagnetic environment of the emitter. Using an optical microscope setup, an enhancement in the intensity of the Eu3+ magnetic dipole emission was observed for emitters located in close vicinity to a gold nanohole array designed to support plasmonic resonances overlapping with the emission spectrum of the ions.

Effect of the Growth Conditions on Organic Crystals with Rare Earth Ions and 1,10-Phenanthroline.

Using a simple solution growth technique, we grow crystals with phenanthroline as a ligand and various rare earth ions: thulium (Tm), ytterbium (Yb), gadolinium (Gd), lanthanum (La), neodymium (Nd), europium (Eu), and erbium (Er). We then selected the composition that forms thin plates with well-defined shapes, Er(NO3)Phen2, and explored the effects of various conditions on crystal formation and growth, including temperature regime, light illumination, and substrates where the crystals are formed and grown. The composition and local environment strongly affect the size and shape of microcrystals and substrate coverage. The use of gold substrates significantly enhances the crystal growing process. Elevated temperatures negatively affect the crystal growth.

Anomalous Dispersion in Reflection and Emission of Dye Molecules Strongly Coupled to Surface Plasmon Polaritons.

We have studied dispersion of surface plasmon polaritons (SPPs) in the Kretschmann geometry (prism/Ag/dye-doped polymer) in weak, intermediate, and ultra-strong exciton-plasmon coupling regimes. The dispersion curves obtained in the reflection experiment were in good agreement with the simple model predictions at small concentrations of dye (Rhodamine 590, Rh590) in the polymer (Poly(methyl methacrylate), PMMA). At the same time, highly unusual multi-segment "staircase-like" dispersion curves were observed at extra-large dye concentrations, also in agreement with the simple theoretical model predicting large, small, and negative group velocities featured by different polariton branches. In a separate experiment, we measured angular dependent emission of Rh590 dye and obtained the dispersion curves consisting of two branches, one nearly resembling the SPP dispersion found in reflection and the second one almost horizontal. The results of our study pave the road to unparalleled fundamental science and future applications of weak and strong light-matter interactions.

Probing Charge Transport Kinetics in a Plasmonic Environment with Cyclic Voltammetry.

Possible modifications in electrochemical reaction kinetics are explored in a nanostructured plasmonic environment with and without additional light illumination using a cyclic voltammetry (CV) method. In nanostructured gold, the effect of light on anodic and cathodic currents is much pronounced than that in a flat system. The electron-transfer rate shows a 3-fold increase under photoexcitation. The findings indicate a possibility of using plasmonic excitations for controlling electrochemical reactions.

Nanoporous gold nanoleaf as tunable metamaterial.

We have studied optical properties of single-layer and multi-fold nanoporous gold leaf (NPGL) metamaterials and observed highly unusual transmission spectra composed of two well-resolved peaks. We explain this phenomenon in terms of a surface plasmon absorption band positioned on the top of a broader transmission band, the latter being characteristic of both homogeneous "solid" and inhomogeneous "diluted" Au films. The transmission spectra of NPGL metamaterials were shown to be controlled by external dielectric environments, e.g. water and applied voltage in an electrochemical cell. This paves the road to numerous functionalities of the studied tunable and active metamaterials, including control of spontaneous emission, energy transfer and many others.

Study of absorption and reflection in solid-state random laser media.

Comparing the absorption spectrum of a single-crystalline material and the reflection spectrum of its powder, we have derived a simple empirical formula for the reflection coefficient of absorbing powder. The proposed equation, which slightly resembles the Lambert-Beer law for transmission, does not correspond to the equation derived in the approximation of a simple one-dimensional diffusion model.