Statistical Analysis of Photoluminescence Decay Kinetics in Quantum Dot Ensembles: Effects of Inorganic Shell Composition and Environment.

Discerning the kinetics of photoluminescence (PL) decay of packed quantum dots (QDs) and QD-based hybrid materials is of crucial importance for achieving their promising potential. However, the interpretation of the decay kinetics of QD-based systems, which usually are not single-exponential, remains challenging. Here, we present a method for analyzing photoluminescence (PL) decay curves of fluorophores by studying their statistical moments. A certain combination of such moments, named as the n-th order moments' ratio, R n , is studied for several theoretical decay curves and experimental PL kinetics of CdSe quantum dots (QDs) acquired by time-correlated single photon counting (TCSPC). For the latter, three different case studies using the R n ratio analysis are presented, namely, (i) the effect of the inorganic shell composition and thickness of the core-shell QDs, (ii) QD systems with Förster resonance energy transfer (FRET) decay channels, and (iii) system of QDs near a layer of plasmonic nanoparticles. The proposed method is shown to be efficient for the detection of slight changes in the PL kinetics, being time-efficient and requiring low computing power for performing the analysis. It can also be a powerful tool to identify the most appropriate physically meaningful theoretical decay function, which best describes the systems under study.

Metal-Polymer Heterojunction in Colloidal-Phase Plasmonic Catalysis.

Plasmonic catalysis in the colloidal phase requires robust surface ligands that prevent particles from aggregation in adverse chemical environments and allow carrier flow from reagents to nanoparticles. This work describes the use of a water-soluble conjugated polymer comprising a thiophene moiety as a surface ligand for gold nanoparticles to create a hybrid system that, under the action of visible light, drives the conversion of the biorelevant NAD+ to its highly energetic reduced form NADH. A combination of advanced microscopy techniques and numerical simulations revealed that the robust metal-polymer heterojunction, rich in sulfonate functional groups, directs the interaction of electron-donor molecules with the plasmonic photocatalyst. The tight binding of polymer to the gold surface precludes the need for conventional transition-metal surface cocatalysts, which were previously shown to be essential for photocatalytic NAD+ reduction but are known to hinder the optical properties of plasmonic nanocrystals. Moreover, computational studies indicated that the coating polymer fosters a closer interaction between the sacrificial electron-donor triethanolamine and the nanoparticles, thus enhancing the reactivity.

Synergy of Excitation Enhancement and the Purcell Effect for Strong Photoluminescence Enhancement in a Thin-Film Hybrid Structure Based on Quantum Dots and Plasmon Nanoparticles.

Reliable control of spontaneous radiation from quantum emitters, such as quantum dots (QDs), is an extremely important problem in quantum science, nanophotonics, and engineering. The QD photoluminescence (PL) may be enhanced near plasmon nanoparticles because of excitation field enhancement or the Purcell effect. However, both of these effects have their specific limitations. The excitation enhancement is usually accompanied by a decrease in the PL quantum yield (QY) due to the plasmon-induced energy transfer, and the Purcell effect cannot significantly enhance the PL of QDs with an initially high QY because of the obvious limitation of the QY by the value of 100%. Here, we have shown that the synergistic combination of excitation enhancement caused by silver nanospheres and the Purcell effect caused by silver nanoplates in the same QD-in-polymer hybrid thin-film nanostructure permits simultaneous increases in the radiative and excitation rates to be obtained. This overcomes the limitations of each individual effect and yields a synergistic PL increase (+1320%) greater than the sum of the PL enhancements determined by each effect alone (+70% and +360%).

Strongly coupled exciton-plasmon nanohybrids reveal extraordinary resistance to harsh environmental stressors: temperature, pH and irradiation.

Hybridized plexcitonic states have unique properties which have been widely studied in recent decades in many research fields targeted at both fundamental science and innovative applications. However, to make these applications come true one needs to ensure the stabilization and preservation of electronic states and optical transitions in hybrid nanostructures, especially under the influence of external stressors, in regimes, that have not yet been comprehensively investigated. The present work shows that the nanohybrid system, composed of plasmonic nanoparticles and J-aggregates of organic molecules, displays outstanding resistance to harsh environmental stressors such as temperature, pH and strong light irradiation as well as demonstrates long-term stability and processability of the nanostructures both in weak and strong coupling regimes. These findings contribute to a deeper understanding of the physicochemical properties of plexcitonic nanoparticles and may find important implications for the development of potential applications in optoelectronics, optical imaging and chemo-bio-sensing and, in general, in the field of optical materials science.

Double Rabi Splitting in a Strongly Coupled System of Core-Shell Au@Ag Nanorods and J-Aggregates of Multiple Fluorophores.

The interaction of several components in the strong coupling regime yielding multiple Rabi splittings opens up remarkable possibilities for studies of multimode hybridization and energy transfer, which is of considerable interest in both fundamental and applied science. Here we demonstrate that three different components, such as core-shell Au@Ag nanorods and J-aggregates of two different dyes, can be integrated into a single hybrid structure, which leads to strong collective exciton-plasmon coupling and double-mode Rabi splitting totaling 338 meV. We demonstrate strong coupling in these multicomponent plexitonic nanostructures by means of magnetic circular dichroism spectroscopy and demonstrate strong magneto-optical activity for the three hybridized states resulting from this coupling. The J-aggregates of two different nonmagnetic dyes interact with metal nanoparticles effectively, achieving magnetic properties due to the hybridization of electronic excitations in the three-component system.

A versatile tunable microcavity for investigation of light-matter interaction.

Light-matter interaction between a molecular ensemble and a confined electromagnetic field is a promising area of research, as it allows light-control of the properties of coupled matter. The common way to achieve coupling is to place an ensemble of molecules or quantum emitters into a cavity. In this approach, light-matter coupling is evidenced by modification of the spectral response of the emitter, which depends on the strength of interaction between emitter and cavity modes. However, there is not yet a user-friendly approach that allows the study of a large number of different and replaceable samples in a wide optical range using the same resonator. Here, we present the design of such a device that can speed up and facilitate investigation of light-matter interaction ranging from weak to strong coupling regimes in ultraviolet-visible and infrared (IR) spectral regions. The device is based on a tunable unstable λ/2 Fabry-Pérot microcavity consisting of plane and convex mirrors that satisfy the plane-parallelism condition at least at one point of the curved mirror and minimize the mode volume. Fine tuning of the microcavity length is provided by a Z-piezopositioner in a range up to 10 µm with a step of several nm. This design makes a device a versatile instrument that ensures easy finding of optimal conditions for light-matter interaction for almost any sample in both visible and IR areas, enabling observation of both electronic and vibrational couplings with microcavity modes thus paving the way to investigation of various coupling effects including Raman scattering enhancement, modification of chemical reactivity rate, lasing, and long-distance nonradiative energy transfer.

Strong Magneto-Optical Response of Nonmagnetic Organic Materials Coupled to Plasmonic Nanostructures.

Plasmonic nanoparticles (PNPs) can significantly modify the optical properties of nearby organic molecules and thus present an attractive opportunity for sensing applications. However, the utilization of PNPs in conventional absorption, fluorescence, or Raman spectroscopy techniques is often ineffective due to strong absorption background and light scattering, particularly in the case of turbid solutions, cell suspensions, and biological tissues. Here we show that nonmagnetic organic molecules may exhibit magneto-optical response due to binding to a PNP. Specifically, we detect strong magnetic circular dichroism signal from supramolecular J-aggregates, a representative organic dye, upon binding to silver-coated gold nanorods. We explain this effect by strong coupling between the J-aggregate exciton and the nanoparticle plasmon, leading to the formation of a hybrid state in which the exciton effectively acquires magnetic properties from the plasmon. Our findings are fully corroborated by theoretical modeling and constitute a novel magnetic method for chemo- and biosensing, which (upon adequate PNP functionalization) is intrinsically insensitive to the organic background and thus offers a significant advantage over conventional spectroscopy techniques.

Chiroptical activity in colloidal quantum dots coated with achiral ligands.

We studied the chiroptical properties of colloidal solution of CdSe and CdSe/ZnS quantum dots (QDs) with a cubic lattice structure which were initially prepared without use of any chiral molecules and coated with achiral ligands. We demonstrate circular dichroism (CD) activity around first and second excitonic transition of these CdSe based nanocrystals. We consider that this chiroptical activity is caused by imbalance in racemic mixtures of QDs between the left and right handed nanoparticles, which appears as a result of the formation of various defects or incorporation of impurities into crystallographic structure during their synthesis. We demonstrate that optical activity of colloidal solution of CdSe QDs with achiral ligands weakly depends on the QDs size and number of ZnS monolayers, but does not depend on the nature of achiral ligands or polarity of the solution.

Rabi Splitting in Photoluminescence Spectra of Hybrid Systems of Gold Nanorods and J-Aggregates.

We experimentally and theoretically investigate the interactions between localized plasmons in gold nanorods and excitons in J-aggregates under ambient conditions. Thanks to our sample preparation procedure we are able to track a clear anticrossing behavior of the hybridized modes not only in the extinction but also in the photoluminescence (PL) spectra of this hybrid system. Notably, while previous studies often found the PL signal to be dominated by a single mode (emission from so-called lower polariton branch), here we follow the evolution of the two PL peaks as the plasmon energy is detuned from the excitonic resonance. Both the extinction and PL results are in good agreement with the theoretical predictions obtained for a model that assumes two interacting modes with a ratio between the coupling strength and the plasmonic losses close to 0.4, indicative of the strong coupling regime with a significant Rabi splitting estimated to be ∼200 meV. The evolution of the PL line shape as the plasmon is detuned depends on the illumination wavelength, which we attribute to an incoherent excitation given by decay processes in either the metallic rods or the J-aggregates.

Tunable plasmon modes in single silver nanowire optical antennas characterized by far-field microscope polarization spectroscopy.

Performing far-field microscope polarization spectroscopy and finite element method simulations, we investigated experimentally and theoretically the surface plasmon modes in single Ag nanowire antennas. Our results show that the surface plasmon resonances in the single Ag nanowire antenna can be tuned from the dipole plasmon mode to a higher order plasmon mode, which would result in the emission with different intensities and polarization states, for the semiconductor quantum dots coupled to the nanowire antenna. The fluorescence polarization is changed with different polarized excitation of the 800 nm light beam, while it remains parallel to the Ag nanowire axis at the 400 nm excitation. The 800 nm incident light interacts nonresonantly with the dipole plasmon mode with the polarized excitation parallel to the Ag nanowire axis, while it excites a higher order plasmon mode with the perpendicular excitation. Under excitation of 400 nm, either the parallel or perpendicular excitation can only result in a dipole plasmon mode. In addition, we demonstrate that the single Ag nanowire antenna can work as an energy concentrator for enhancing the two-photon excited fluorescence of semiconductor quantum dots.

Strong plasmon-exciton coupling in a hybrid system of gold nanostars and J-aggregates.

Hybrid materials formed by plasmonic nanostructures and J-aggregates provide a unique combination of highly localized and enhanced electromagnetic field in metal constituent with large oscillator strength and extremely narrow exciton band of the organic component. The coherent coupling of localized plasmons of the multispiked gold nanoparticles (nanostars) and excitons of JC1 dye J-aggregates results in a Rabi splitting reaching 260 meV. Importantly, broad absorption features of nanostars extending over a visible and near-infrared spectral range allowed us to demonstrate double Rabi splitting resulting from the simultaneous coherent coupling between plasmons of the nanostars and excitons of J-aggregates of two different cyanine dyes.

Large enhancement of nonlinear optical response in a hybrid nanobiomaterial consisting of bacteriorhodopsin and cadmium telluride quantum dots.

We report wavelength-dependent enormous enhancement of the nonlinear refractive index of wild-type bacteriorhodopsin in the presence of semiconductor quantum dots. The effect is strongest in the region just below the absorption edge of both constituents of this hybrid material and in samples that show strong Förster resonance energy transfer. We show that enhancements of up to 4000% can be achieved by controlled engineering of the hybrid structure involving variations of the molar ratio of the constituents. This new hybrid material with exceptional nonlinear properties will have numerous photonic and optoelectronic applications employing its photochromic, energy transfer, and conversion properties.

Whispering gallery mode resonators with J-aggregates.

We have studied the optical properties of a hybrid system consisting of cyanine dye J-aggregates attached to a spherical microcavity. A periodic structure of narrow peaks was observed in the photoluminescence spectrum of the J-aggregates, arising from the coupling between the emission of J-aggregates and the whispering gallery modes (WGMs) of the microcavity. The most striking result of our study is the observation of polarization sensitive mode damping caused by re-absorption of J-aggregate emission. This effect manifests itself in dominating emission from TM modes in the spectral region of J-aggregates absorption band where the TE modes are strongly suppressed. In contrast, the TE modes totally dominate emission spectrum in the region where absorption is negligible. We also demonstrate that the emission intensity can be further enhanced by depositing a hybrid layer of J-aggregates and Ag nanoparticles onto the spherical microcavity. Owing to the concerted action of WGMs and plasmonic hot spots in the Ag aggregates, we observe an enhanced Raman signal from the J-aggregates. Microcavities covered by J-aggregates and plasmonic nanoparticles could be thus useful for a variety of photonic applications in basic science and technology.

Pterin detection using surface-enhanced Raman spectroscopy incorporating a straightforward silver colloid-based synthesis technique.

Optical techniques toward the realization of sensitive and selective biosensing platforms have received considerable attention in recent times. Techniques based on interferometry, surface plasmon resonance, and waveguides have all proved popular, while spectroscopy in particular offers much potential. Raman spectroscopy is an information-rich technique in which the vibrational frequencies reveal much about the structure of a compound, but it is a weak process and offers poor sensitivity. In response to this problem, surface-enhanced Raman scattering (SERS) has received much attention, due to significant increases in sensitivity instigated by bringing the sample into contact with an enhancing substrate. Here we discuss a facile and rapid technique for the detection of pterins using SERS-active colloidal silver suspensions. Pterins are a family of biological compounds that are employed in nature in color pigmentation and as facilitators in metabolic pathways. In this work, small volumes of xanthopterin, isoxanthopterin, and 7,8-dihydrobiopterin have been examined while adsorbed to silver colloids. Limits of detection have been examined for both xanthopterin and isoxanthopterin using a 10-s exposure to a 12 mW 532 nm laser, which, while showing a trade-off between scan time and signal intensity, still provides the opportunity for the investigation of simultaneous detection of both pterins in solution.

CdTe Quantum Dot/Dye Hybrid System as Photosensitizer for Photodynamic Therapy.

We have studied the photodynamic properties of novel CdTe quantum dots-methylene blue hybrid photosensitizer. Absorption spectroscopy, photoluminescence spectroscopy, and fluorescence lifetime imaging of this system reveal efficient charge transfer between nanocrystals and the methylene blue dye. Near-infrared photoluminescence measurements provide evidence for an increased efficiency of singlet oxygen production by the methylene blue dye. In vitro studies on the growth of HepG2 and HeLa cancerous cells were also performed, they point toward an improvement in the cell kill efficiency for the methylene blue-semiconductor nanocrystals hybrid system.

Resonance energy transfer improves the biological function of bacteriorhodopsin within a hybrid material built from purple membranes and semiconductor quantum dots.

Purple membrane (PM) from bacteria Halobacterium salinarum contains a photochromic protein bacteriorhodopsin (bR) arranged in a 2D hexagonal nanocrystalline lattice (Figure 1 ). Absorption of light by the protein-bound chromophore retinal results in pumping the protons through the PM creating an electrochemical gradient which is then used by the ATPases to energize the cellular processes. Energy conversion, photochromism, and photoelectrism are the inherent effects which are employed in many bR technical applications. bR, along with the other photosensitive proteins, is not able to deal with the excess energy of photons in UV and blue spectral region and utilizes less than 0.5% of the energy from the available incident solar light for its biological function. Here, we proceed with optimization of bR functions through the engineering of a "nanoconverter" of solar energy based on semiconductor quantum dots (QDs) tagged with the PM. These nanoconverters are able to harvest light from deep-UV to the visible region and to transfer this additionally collected energy to bR via Förster resonance energy transfer (FRET). We show that specific nanobio-optical and spatial coupling of QDs (donor) and bR retinal (acceptor) provide a means to achieve FRET with efficiency approaching 100%. We have finally demonstrated that the integration of QDs within PM significantly increases the efficiency of light-driven transmembrane proton pumping, which is the main bR biological function. This new QD-PM hybrid material will have numerous optoelectronic, photonic, and photovoltaic applications based on its energy conversion, photochromism, and photoelectrism properties.

Photosensitizer methylene blue-semiconductor nanocrystals hybrid system for photodynamic therapy.

In this work we report on the development of novel hybrid material with enhanced photodynamic properties based on methylene blue and CdTe nanocrystals. Absorption spectroscopy, visible photoluminescence spectroscopy and fluorescence lifetime imaging of this system reveal efficient charge transfer between nanocrystals and the methylene blue dye. Near infra-red photoluminescence measurements provide evidence for an increased efficiency of singlet oxygen production by the methylene blue dye. In vitro studies on the growth of HepG2 and HeLa cancerous cells were also performed, they point towards an improvement in the cell kill efficiency for the methylene blue-semiconductor nanocrystals hybrid system.

Emerging applications of fluorescent nanocrystals quantum dots for micrometastases detection.

The occurrence of metastases is one of the main causes of death in many cancers and the main cause of death for breast cancer patients. Micrometastases of disseminated tumour cells and circulating tumour cells are present in more than 30% of breast cancer patients without any clinical or even histopathological signs of metastasis. Low abundance of these cell types in clinical diagnostic material dictates the necessity of their enrichment prior to reliable detection. Current micrometastases detection techniques are based on immunocytochemical and molecular methods suffering from low efficiency of tumour cells enrichment and observer-dependent interpretation. The use of highly fluorescent semiconductor nanocrystals, also known as "quantum dots" and nanocrystal-encoded microbeads tagged with a wide panel of antibodies against specific tumour markers offers unique possibilities for ultra-sensitive micrometastases detection in patients' serum and tissues. The nanoparticle-based diagnostics provides an opportunity for highly sensitive parallel quantification of specific proteins in a rapid and low-cost method, thereby providing a link between the primary tumour and the micrometastases for early diagnosis.

The photoluminescent lifetime of polyelectrolytes in thin films formed via layer by layer self-assembly.

We present results on luminescence lifetime studies of thin multilayer films of polyelectrolyte molecules produced via layer by layer (LbL) electrostatic assembly. We found that, in contrast to common assumptions, LbL films show measurable photoluminescent lifetimes with an average value of 6 ns. Scanning fluorescence lifetime imaging microscopy studies combined with steady-state photoluminescence measurements imply that this lifetime may be due to aggregation of polyelectrolyte molecules during preparation of LbL films. This conclusion has been further confirmed by atomic force microscopy (AFM). AFM images clearly show the presence of 100-200 nm high aggregates on the surface of these films. This aggregation of polyelectrolyte molecules contributes significantly to the experimentally detected luminescence decays of any light-emitting samples attached to LbL film, especially in a single molecule detection regime. To demonstrate this effect we compare photoluminescence lifetime results for CdTe quantum dots deposited on the surface of LbL polyelectrolyte films.