Probing ultrafast energy transfer between excitons and plasmons in the ultrastrong coupling regime

Cataloged from PDF version of article.We investigate ultrafast energy transfer between excitons and plasmons in ensembles of core-shell type nanoparticles consisting of metal core covered with a concentric thin J-aggregate (JA) shell. The high electric field localization by the Ag nanoprisms and the high oscillator strength of the JAs allow us to probe this interaction in the ultrastrong plasmon-exciton coupling regime. Linear and nonlinear optical properties of the coupled system have been measured using transient absorption spectroscopy revealing that the hybrid system shows half-plasmonic and half-excitonic properties. The tunability of the nanoprism plasmon resonance provides a flexible platform to study the dynamics of the hybrid state in a broad range of wavelengths. (C) 2014 AIP Publishing LLC

Tunable Plexcitonic Nanoparticles: A Model System for Studying Plasmon-Exciton Interaction from the Weak to the Ultrastrong Coupling Regime

Controlling the number of dye molecules on metallic nanoparticles, which in turn affects the magnitude of Rabi splitting energy, is crucial for obtaining hybrid metal core-organic shell nanoparticles with tunable optical properties in the visible spectrum since the magnitude of the Rabi splitting energy directly determines the strength of the coupling between plasmonic nanoparticles and dye molecules. In this work, we present a new method for the synthesis of plexcitonic nanoparticles, and thus we are able to control the number of dye molecules self-assembled on Ag nanoprisms (Ag NPs) by adjusting the concentration of dye molecules used in the synthesis. Indeed, individual dye molecules self-assemble into J-aggregates on Ag NPs. Thus, in the finite-element simulations and experimental data of the hybrid metal organic nanoparticles, we observed a transition from weak coupling to the ultrastrong coupling regime. Besides, ultrafast energy transfer between plasmonic nanoparticles and excitonic aggregated dye molecules has been extensively studied as a function of Rabi splitting energy. We observe that the lifetime of the polariton states increases with the coupling strength and the upper polaritons are short-lived, whereas the lower polaritons are long-lived. Hybrid metal-organic nanoparticles presented in this study (i) have tunable Rabi splitting energies, (ii) are easy to prepare in large quantities in aqueous medium, (iii) can be uniformly assembled on solid substrates, (iv) have resonance frequencies in the visible spectrum, and (v) have small mode volume, thus making them an excellent model system for studying light-matter interaction at nanoscale dimensions from the weak to ultrastrong coupling regime. © 2016 American Chemical Society

Ultrafast transient optical loss dynamics in exciton-plasmon nano-assemblies

We study the exciton-plasmon dynamics that lead to optical loss mitigation via ultrafast transient absorption spectroscopy (UTAS) on hybrid aggregates of core-shell quantum dots (QDs) and Au nanoparticles (NPs). We highlight that generating hot electrons in plasmonic NPs contributes to the transient differential absorption spectrum under optical excitation. The results suggest modifying the method of analyzing the transient absorption spectra of loss mitigated systems. Additionally, we investigate the effect of Electron Oscillation frequency-Phonon Resonance Detuning (EOPRD) on loss mitigation efficiency. Moreover, power dependent UTAS reveal a frequency pulling like effect in the transient bleach maximum towards the gain emission. We show that the appropriate choice of the pump wavelength and by changing the pump power we can conclusively prove the existence of loss mitigation using UTAS. Finally, we study the transient kinetics of hybrid gain-plasmon systems and report interesting hybrid transient kinetics. © 2017 The Royal Society of Chemistry

Fabrication of Supramolecular n/p-Nanowires via Coassembly of Oppositely Charged Peptide-Chromophore Systems in Aqueous Media

Fabrication of supramolecular electroactive materials at the nanoscale with well-defined size, shape, composition, and organization in aqueous medium is a current challenge. Herein we report construction of supramolecular charge-transfer complex one-dimensional (1D) nanowires consisting of highly ordered mixed-stack π-electron donor-acceptor (D-A) domains. We synthesized n-type and p-type β-sheet forming short peptide-chromophore conjugates, which assemble separately into well-ordered nanofibers in aqueous media. These complementary p-type and n-type nanofibers coassemble via hydrogen bonding, charge-transfer complex, and electrostatic interactions to generate highly uniform supramolecular n/p-coassembled 1D nanowires. This molecular design ensures highly ordered arrangement of D-A stacks within n/p-coassembled supramolecular nanowires. The supramolecular n/p-coassembled nanowires were found to be formed by A-D-A unit cells having an association constant (KA) of 5.18 × 105 M-1. In addition, electrical measurements revealed that supramolecular n/p-coassembled nanowires are approximately 2400 and 10 times more conductive than individual n-type and p-type nanofibers, respectively. This facile strategy allows fabrication of well-defined supramolecular electroactive nanomaterials in aqueous media, which can find a variety of applications in optoelectronics, photovoltaics, organic chromophore arrays, and bioelectronics. © 2017 American Chemical Society

Tunable Plexcitonic Nanoparticles: A Model System for Studying Plasmon-Exciton Interaction from the Weak to the Ultrastrong Coupling Regime

Controlling the number of dye molecules on metallic nanoparticles, which in turn affects the magnitude of Rabi splitting energy, is crucial for obtaining hybrid metal core-organic shell nanoparticles with tunable optical properties in the visible spectrum since the magnitude of the Rabi splitting energy directly determines the strength of the coupling between plasmonic nanoparticles and dye molecules. In this work, we present a new method for the synthesis of plexcitonic nanoparticles, and thus we are able to control the number of dye molecules self-assembled on Ag nanoprisms (Ag NPs) by adjusting the concentration of dye molecules used in the synthesis. Indeed, individual dye molecules self-assemble into J-aggregates on Ag NPs. Thus, in the finite-element simulations and experimental data of the hybrid metal organic nanoparticles, we observed a transition from weak coupling to the ultrastrong coupling regime. Besides, ultrafast energy transfer between plasmonic nanoparticles and excitonic aggregated dye molecules has been extensively studied as a function of Rabi splitting energy. We observe that the lifetime of the polariton states increases with the coupling strength and the upper polaritons are short-lived, whereas the lower polaritons are long-lived. Hybrid metal-organic nanoparticles presented in this study (i) have tunable Rabi splitting energies, (ii) are easy to prepare in large quantities in aqueous medium, (iii) can be uniformly assembled on solid substrates, (iv) have resonance frequencies in the visible spectrum, and (v) have small mode volume, thus making them an excellent model system for studying light-matter interaction at nanoscale dimensions from the weak to ultrastrong coupling regime

Enhancement of two photon absorption properties and intersystem crossing by charge transfer in pentaaryl boron-dipyrromethene (BODIPY) derivatives

Novel BODIPY derivatives containing N,N-diphenylamine, 4-methoxyphenyl, 2,4-dimethoxyphenyl, triphenylamine, and 1-pyrene moieties were designed and synthesized for the first time by employing the palladium-catalyzed Suzuki-Miyaura coupling on pentaaryl boron dipyrromethene compounds. The effect of various moieties and charge transfer on linear and nonlinear optical absorption was investigated. It was found that moieties with strong electron donor properties and long conjugation lengths increase charge transfer and enhance intersystem crossing in the investigated compounds. Besides, the investigated compounds showed strong two photon absorption properties at near infrared wavelengths (800 nm and 900 nm), which is required for two photon photodynamic therapy. Two photon absorption cross section values were found to be 83, 454, 331, 472 and 413 GM for B1, B2, B3, B4 and B5 compounds at 800 nm wavelength, respectively. The highest two-photon absorption cross-section value was obtained for the B4 compound containing a triphenylamine moiety due to its more efficient charge transfer characteristics. Strong two-photon absorption properties in the near infrared region, efficient intersystem crossing and heavy atom free nature of the investigated compounds make them good candidates for two photon photodynamic therapy applications. We believe that this work will be one of the leading studies for two-photon photodynamic therapy applications of pentaaryl BODIPY derivatives