Whispering Gallery Mode (WGM) microlasers were obtained by impregnating polystyrene microspheres in an aqueous solution of plasmonic nanoparticles and Rhodamine 6G. The emission spectra of Rhodamine-doped microspheres with diameters of 1 μm and 5-7 μm exhibited peaks corresponding to WGM, with a low Q-factor for 1-μm and a higher Q-factor for 5-7-μm spheres. The embedding of gold nanoparticles into microlasers results in a 40% decrease in the WGM intensity, while doping with silver nanoparticles increases it by 10%.
Nanoscale molecular clusters are fascinating fluorescent nanomaterials formed by highly ordered assembly of organic dyes with the optical properties strongly different from those of monomolecules. Hybrid films formed by pseudoisocyanine dye coated metal nanoparticles on a sapphire substrate or nanoporous alumina on an aluminum substrate were studied with steady‐state and time-resolved spectroscopy. On-surface reaction caused isomerization of cyanine molecules as well as self-assembly into molecular nanoclusters, so called J‐aggregates. The excitonic band of clusters had been strongly coupled to plasmonic response of metal nanoparticles. The dynamics of the strong coupling regime was directly analyzed depending on environmental conditions (temperature and presence of gas analyte). The energy transfer of the optical excitation from oxygen vacancies of alumina to the molecular clusters was observed depending on the anodization conditions of the aluminum substrate. Such unique feature should provide a new approach to develop new sensors.
The hybrid systems consisting of noble metal nanoparticles with plasmon resonances and organic cyanine dye, which are able to delocalize and migrate the energy of excitons on a large number of aggregated molecules of the structure, can be used to study the plasmon-exciton interaction. The position as well as the region of overlap of the absorption of the exciton band and the plasmon resonance of the nanoparticles in the form of island film allows observing both weak and strong coupling. The influence of overlap between the J-aggregate band of cyanine dyes with different length of the conjugation chain and nanoparticle plasmon resonance on the optical properties of hybrid structures was studied. Inhomogeneous ensembles of noble nanoparticles were obtained as an island films on the sapphire substrates by thermal deposition in vacuum. The homologous series of dicarbocyanine, monocarbocyanine and pseudoisocyanine dyes was used for forming J-aggregates in ethanol solution without adding salt by the original technique. Dye solution was spincoated on the island film to obtained hybrid structure. The plasmon resonance of the island film was broadened due to the large dispersion of the nanoparticles in size. So strong and weak plasmon-exciton coupling can be observed in hybrid structures due to overlap of the absorption bands of island film and exciton-transition in J-aggregates. The influence of near field of noble nanoparticles on enhancement of dye molecule absorption is observed in hybrid films with dicarbocyanine and monocarbocyanine. The surface molecular concentration was monitored, in the experiment there was no significant increase of the number of adsorbed molecules on island film in comparison with clean dielectric substrate. Spectral dip at the wavelength of the maximum absorption of the J-aggregate was observed for hybrid films with pseudoisocyanine.
Optical properties of layered composite materials consisting of plasmonic nanostructures and semiconductor quantum dots (QDs) have been investigated both experimentally and theoretically. It was demonstrated that in the case of spectrally overlapping bands of plasmonic absorption and fluorescence of alloyed QDs placed directly onto silver island film, the fluorescent intensity increases. While in other samples with alloyed QDs the fluorescence was not sensitive to silver nanoparticles or even quenched by silver nanoparticles for core-shell QDs. That was explained by resonant and non-resonant interaction of QDs with the near fields of plasmonic structures. Measuring the fluorescence decay time, we observed a clear correlation between the fluorescence intensity of alloyed QDs and reducing fluorescent lifetime in the case of resonant interaction or the Purcell effect. The interaction between excitons in semiconductor material and plasmons in metal nanoparticle was explored also in the Zn-ZnO system via numerical modeling. This system is interesting because metal films may be easily created via magnetron sputtering on silica glass substrates and then fully or partially oxidized in the course of thermal annealing in air. Thus a core-shell nanostructure consisting of a semiconductor shell with promising chemical sensor properties (ZnO) and metallic core with the plasmon resonance in the same spectral region (Zn) will be created.
The new manufacturing method for fabrication of Surface Nanoscale Axial Photonics (SNAP) structures has been developed. We showed experimentally that the bent fiber can achieve the nanometer-scale variation in the effective fiber radius sufficient for fabrication of SNAP microresonators. The advantage of the demonstrated method is in its simplicity, robustness, and mechanical tunability of the fabricated devices.
Several coherent light sources with dimensions less than the diffraction limit were proposed and demonstrated in the last decade. One of the most popular of them is a spaser. Since its theoretical proposal, there were a number of experimental realizations based on metal nanoparticle colloids and laser dyes. However, the disaffection with these realizations grows as the conditions of the performed experiments were too close to that of the random-lasing phenomena. Hence, an experiment with a refined setup that greatly reduces an unintended feedback due to the multiple scattering events is in order. In this work, we achieved this goal by creating a monolayer of metal nanoparticles on the solid surface and cover them with a thin layer of dye molecules.
A method for preparation silver nanoparticles supporting plasmon oscillations is proposed. Using a seed-mediated growth approach in a rod-like micellar media, silver nanorods of varied aspect ratio were prepared from nearly spherical silver nanoparticles. The concentrations of synthesis reagents were determined to obtain nanorods whose plasmon resonances are shifted toward larger wavelengths relative to resonances of spherical particles.
Alexander Kosarev, Vladimir Chaldyshev, Nikita Toropov, Igor Gladskikh, Polina Gladskikh, Kseniia Baryshnikova, Valeriy Preobrazhenskiy, Michael Putyato, Boris Semyagin, Tigran Vartanyan
A stack of five layers of epitaxial InAs QDs with GaAs barriers was grown by molecular-beam epitaxy. The upper layer of QDs was capped by 3nm-GaAs/3nm-AlAs/4nm-GaAs layer sequence. Then, a thin silver layer was added via physical vapor deposition. After annealing isolated silver nanoparticles were formed above the layer of buried InAs quantum dots. We studied interplay of the exciton resonance in InAs QDs and plasmon resonance in Ag nanoparticles. In particular, we observed more than twofold enhancement of the exciton photoluminescence intensity from the InAs QDs when they were coupled to the silver nanoparticles.
The optical properties of hybrid film based on plasmon Ag nanoparticles of different size and cyanine dyes with different
length of conjugation chain depending on the relative position of the plasmon resonance and the absorption of organic
molecules were studied. The absorption spectra of the films revealed several molecular forms, such as all-trans- and cisisomers,
dimers and J-aggregate, which also exist in pure organic films without Ag nanoparticles. It’s shown that the
absorption of aggregate bands increased after exposure by nanosecond laser on the hybrid films due to photo-induced
additional self-organization of aggregates. In the presence of Ag nanoparticles, laser radiation leads to the change of
molecular forms at a comparatively low threshold.
Optical properties of composite structures comprised of the island films of silver nanoparticles with a thin molecular layer of a dye rhodamine 6G were obtained and studied in this paper. In the near field of plasmonic nanoparticles enhancement and shifting of the maximums of the absorption and fluorescence spectra were observed. In the absorption and fluorescence spectra of thin molecular films with nanoparticles the new red-shifted band in comparison with spectra of thin films without nanoparticles was found. This band was associated with the formation of aggregates. Thus, the silver nanoparticles can contribute to fluorescence enhancement and formation of the aggregates in the rhodamine thin films.
Self-assembled silver, gold, and copper nanostructures on the monocrystalline GaAs (100) wafer surface were obtained
via physical vapor deposition and characterized by optical reflection spectroscopy, scanning electron microscopy, and
current-voltage curve measurements. Reflection spectra of the samples with Ag equivalent thicknesses of 2, 5, 7.5, and
10 nm demonstrated wide plasmonic bands in the visible range of spectra. Thermal annealing of the nanostructures led to
narrowing of the plasmonic bands of Au and Ag nanostructures caused by major transformations of the film morphology.
While the as prepared films predominantly had a small scale labyrinth structure, after annealing well-separated
nanoislands are formed on the gallium arsenide surface. A clear correlation between films morphology and their optical
and electrical properties is elucidated. Annealing of the GaAs substrate with Ag nanostructures at 100 °C under control
of the resistivity allowed us to obtain and fix the structure at the percolation threshold. It is established that the samples
at the percolation threshold possess the properties of resistance switching and hysteresis.
In this paper we investigated the optical properties of a composite material consisting of a thin film of polymer doped by
CdSe/ZnS quantum dots and silver nanoparticles on a transparent insulating substrate. It is found that in the presence of
silver nanoparticles the quantum dots absorption is increased fivefold, the luminescence intensity is increased twelvefold
while the luminescence lifetime is reduced.
We strive to obtain highly fluorescent planar materials that may be used for the development of nanolasers based on localized plasmons. The promissing candidates for this purpose are materials consisting of mixtures of organic molecules, polymer, and silver nanoparticles. Silver nanoparticles were preliminary deposited on the quartz substrates. These samples were characterized by SEM and absorption spectroscopy. Then, they were covered by the polymer/rhodamine and polymer/coumarin layers using either spin-coating or evaporation techniques and characterized by confocal luminescent microscopy and spectroscopy. As a result of the localized surface plasmon excitation, we observed the enhancement of the rhodamine and coumarine absorption in the near fields of silver nanoparticles. The fluorescence of the thin films of polymer activated by dyes molecules with silver nanoparticles was almost 20-fold more intense than that on the bare dielectric surfaces without silver nanoparticles. In the presence Ag nanoparticles and at increased intensities of excitation we found also slight narrowing of the luminescence spectrum of polymer/coumarin layers.
Photonic properties and photoinduced transformations of hybrid materials comprising silver nanoparticles and
polymethine dye layers were studied. Granular films were obtained via thermal evaporation of Ag on transparent
substrates in a vacuum. Polymethine dye was spin-coated over the Ag films. The samples were characterized by optical
spectroscopy, confocal fluorescent and scanning electron microscopy. Transformations of polymethine dye molecules
were studied under the action of pulsed and cw laser irradiation. The threshold of laser induced transformations of dye
molecules in hybrid films was found to be much lower than that for the bare dielectric substrate under the action of
Nd:YAG laser second harmonic pulses. In the case of a hybrid film, transformations lead to the increased absorption in
the J-aggregate band while the dye layers on a bare substrate experience, albeit 3.5 times smaller, decrease of absorption.
Enhancement of absorption and fluorescence of dyes in the fields of Ag nanoparticles was observed.
Optical properties of supported silver nanoparticles with cyanine dyes overlayers were investigated. The spectrum of the hybrid material was treated as a result of mutual interactions between the plasmon oscillations in the metal nanoparticles and resonance absorption and refraction of dye molecules. The spectral positions of the plasmon resonances are shifted due to the anomalous refraction of dye molecules while the absorption of dye molecules is enhanced due to the incident field amplification in the near field of metal nanoparticles. The photoinduced transformations of hybrid material were also observed.
We study the component composition of cyanine dye layers on different substrates (glass, mica, and sapphire) by the
absorption spectroscopy. We found that the molecular layer contains isomers of the molecules being coated and
aggregated components (dimers and J-aggregates). The relative concentrations of the components depend on the
structure of dye and its surface concentration.
The single laser pulses of several nanosecond length lead to irreversible changes in the structure of molecular nanolayers
and result in the change of the relative concentrations of the layer components.
Two types of the spatial orientation of the nanocomponents with different orientations with respect to the surface are
formed. One of these types of the orientation transforms into another type under the action of pulsed laser radiation.
The above changes were found for all the dielectric substrates studied.
Granular films of alkali and coinage metals are the most popular objects for exploring plasmonic effects. They are easy to obtain via physical vapor deposition and to study via optical means. In this contribution we show several ways not only to record but also to modify the granular metal films using thermal and nonthermal optical effects.
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