Periodic and aperiodic liquid crystal-polymer composite structures realized via spatial light modulator direct holography

In this work we present the first realization and characterization of two-dimensional periodic and aperiodic POLICRYPS (Polymer Liquid Crystal Polymer Slices) structures, obtained by means of a single-beam holographic technique exploiting a high resolution spatial light modulator (SLM). A first investigation shows that the gratings, operating in the Raman Nath regime, exhibit a morphology and a electro-optical behavior that are typical of the POLICRYPS gratings realized by two-beam interference holography

Plasmon-Exciton Resonant Energy Transfer: Across Scales Hybrid Systems

The presence of an excitonic element in close proximity of a plasmonic nanostructure, under certain conditions, may lead to a nonradiative resonant energy transfer known as Exciton Plasmon Resonant Energy Transfer (EPRET) process. The exciton-plasmon coupling and dynamics have been intensely studied in the last decade; still many relevant aspects need more in-depth studies. Understanding such phenomenon is not only important from fundamental viewpoint, but also essential to unlock many promising applications. In this review we investigate the plasmon-exciton resonant energy transfer in different hybrid systems at the nano- and mesoscales, in order to gain further understanding of such processes across scales and pave the way towards active plasmonic devices

Periodic and aperiodic structures realized by innovative soft-metter based techniques

Dottorato di Ricerca in Fisica, Ciclo XXIII, a.a. 2010Il presente lavoro di tesi `e basato sullo studio e l’utilizzo di tecniche sperimentali per la realizzazione di strutture periodiche ed a-periodiche su diverse scale di grandezza. La prima tecnica oggetto di studio rappresenta un nuovo approccio rispetto alle usuali tecniche olografiche e prevede l’utilizzo delle pi`u recenti tecnologie realizzate nell’ambito dell’olografia diffrattiva, quali i modulatori di fase spaziale. I modulatori di fase spaziale consentono la produzione di distribuzioni di intensit`a sia periodiche che a-periodiche ed in generale rendendo possibili geometrie difficilmente realizzabili con le classiche tecniche di interferenza a multi-fascio. Il sistema fotosensibile di partenza `e costituito da una miscela di pre-polimeri e cristalli liquidi nematici: la separazione di fase tra le due componenti `e indotta dalla fotopolimerizzazione. L’impiego dei cristalli liquidi consente la realizzazione di strutture dinamiche le cui propriet`a ottiche sono modificabili attraverso l’applicazione di stimoli esterni, quali campi elettrici ed ottici. Le strutture relizzate hanno una periodicit`a micrometrica che le rende applicabili nel campo dell’ottica. La seconda tecnica studiata si basa su fenomeni di auto-assemblaggio nei polimeri a blocchi e consente il raggiungimento di scale di grandezza inferiori: la periodicit`a delle strutture realizzate raggiunge infatti poche decine di nanometri. Nella tecnica di autoassemblaggio la separazione di fase tra le componenti `e regolata semplicemente dalla temperatura del sistema e le strutture risultanti hanno delle caratteristiche fortemente dipendenti dalle dimensioni dei costituenti. 3Università della Calabri

J. Opt. Soc. Am. B

Within the frame of a simple, long-wavelength, quasi-static description, we present a theoretical characterization of the optical response of metal nanoparticles doped with active gain elements in a core-shell (metallic core within an active dielectric shell) and nano-shell (active dielectric core within a metallic shell) configurations. The common feature of these structures is that, adding gain to the system produces an increase of the quality of the plasmon resonance, which becomes sharper and sharper until a singular point, after which, the system switches from absorptive to emissive (nanolaser). We use this aforementioned simple model to develop a general method allowing us to calculate both the expected singular plasmon frequency and the gain level needed to realize it and to discuss the spectral deformation occurring before and after this singular point. Finally, we propose a way to calculate if the singular behavior is reachable using realistic amounts of gain

Battling absorptive losses by plasmon-exciton coupling in multimeric nanostructures

© The Royal Society of Chemistry 2015. The strong inherent optical losses present in plasmonic nanostructures significantly limit their technological applications at optical frequencies. Here, we report on the interplay between plasmons and excitons as a potential approach to selectively reduce ohmic losses. Samples were prepared by functionalizing plasmonic core-shell nanostructures with excitonic molecules embedded in silica shells and interlocked by silica spacers to investigate the role played by the plasmon-exciton elements separation. Results obtained for different silica spacer thicknesses are evaluated by comparing dispersions of plasmonic multimers with respect to the corresponding monomers. We have observed fluorophore emission quenching by means of steady-state fluorescence spectroscopy, as well as a significant shortening of the corresponding fluorescence lifetime using TCSPC data. These results are accompanied by the simultaneous enhancement of Rayleigh scattering and transmittance, revealing more effective absorptive loss mitigation for multimeric systems. Moreover, upon decreasing the thickness of the intermediate silica layer between gold cores and the external gain functionalized silica shell, the efficiency of exciton-plasmon resonant energy transfer (EPRET) was significantly enhanced in both multimeric and monomeric samples. Simulation data along with experimental results confirm that the hybridized plasmon fields of multimers lead to more efficient optical loss compensation with respect to the corresponding monomers

Gain functionalized core-shell nanoparticles: the way to selectively compensate absorptive losses

We experimentally demonstrate that gain materials properly encapsulated into the shell surrounding metal nanoparticles (NPs) are responsible for the modification of the overall plasmon response of engineered nanostructures. A comparison between designed systems based on functionalized core-shell NPs having different encapsulated dye molecules is presented. Experimental observations of Rayleigh scattering enhancement, accompanied by an increase of transmission as a function of gain, reveal striking optical loss compensation effects. Fluorescence lifetime measurements demonstrate a quenching of dye photoluminescence in functionalized core-shell NP samples with respect to pure dye solutions, confirming the strong resonant coupling occurring between the gain medium and gold NPs. Experimental evidence of a selective modification of the gain functionalized core-shell Au NP extinction curve is found, in good agreement with the results of a simplified theoretical model. The model verifies the causality principle through Kramers-Kronig dispersion relations for the investigated gain functionalized plasmonic nanostructure

Loss-Mitigated Collective Resonances in Gain-Assisted Plasmonic Mesocapsules

Inherent optical losses of plasmonic materials represent a crucial issue for optoplasmonics, whereas the realization of hierarchical plasmonic nanostructures implemented with gain functionalities is a promising and valuable solution to the problem. Here we demonstrate that porous silica capsules embedding gold nanoparticles (Au NPs) and fabricated at a scale intermediate between the single plasmonic nanostructure and bulk materials show remarkable form–function relations. At this scale, in fact, the plasmon–gain interplay is dominated by the location of the gain medium with respect to the spatial distribution of the local field. In particular, the hollow spherical cavities of these structures allow regions of uniform plasmonic field where the energy transfer occurring between chromophoric donors and the surrounding plasmonic acceptors gives rise to a broadband attenuation of losses

Interface of Physics and Biology: Engineering Virus-Based Nanoparticles for Biophotonics

Virus-based nanoparticles (VNPs) have been used for a wide range of applications, spanning basic materials science and translational medicine. Their propensity to self-assemble into precise structures that offer a three-dimensional scaffold for functionalization has led to their use as optical contrast agents and related biophotonics applications. A number of fluorescently labeled platforms have been developed and their utility in optical imaging demonstrated, yet their optical properties have not been investigated in detail. In this study, two VNPs of varying architectures were compared side-by-side to determine the impact of dye density, dye localization, conjugation chemistry, and microenvironment on the optical properties of the probes. Dyes were attached to icosahedral cowpea mosaic virus (CPMV) and rod-shaped tobacco mosaic virus (TMV) through a range of chemistries to target particular side chains displayed at specific locations around the virus. The fluorescence intensity and lifetime of the particles were determined, first using photochemical experiments on the benchtop, and second in imaging experiments using tissue culture experiments. The virus-based optical probes were found to be extraordinarily robust under ultrashort, pulsed laser light conditions with a significant amount of excitation energy, maintaining structural and chemical stability. The most effective fluorescence output was achieved through dye placement at optimized densities coupled to the exterior surface avoiding conjugated ring systems. Lifetime measurements indicate that fluorescence output depends not only on spacing the fluorophores, but also on dimer stacking and configurational changes leading to radiationless relaxationand these processes are related to the conjugation chemistry and nanoparticle shape. For biological applications, the particles were also examined in tissue culture, from which it was found that the optical properties differed from those found on the benchtop due to effects from cellular processes and uptake kinetics. Data indicate that fluorescent cargos are released in the endolysosomal compartment of the cell targeted by the virus-based optical probes. These studies provide insight into the optical properties and fates of fluorescent proteinaceous imaging probes. The cellular release of cargo has implications not only for virus-based optical probes, but also for drug delivery and release systems