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Polariton emission from optical cavities integrated with various luminophores has been extensively studied recently due to the wide variety of possible applications in photonics, particularly promising in terms of fabrication of low-threshold sources of coherent emission. Tuneable microcavities allow extensive investigation of the photophysical properties of matter placed inside the cavity by deterministically changing the coupling strength and controllable switching from weak to strong and ultra-strong coupling regimes. Here we demonstrate room temperature strong coupling of exciton transitions in CdSe/ZnS/CdS/ZnS colloidal quantum dots with the optical modes of a tuneable low-mode-volume microcavity. Strong coupling is evidenced by a large Rabi splitting of the photoluminescence spectra depending on the detuning of the microcavity. A coupling strength of 154 meV has been achieved. High quantum yields, excellent photostability, and scalability of fabrication of QDs paves the way to practical applications of coupled systems based on colloidal QDs in photonics, optoelectronics, and sensing., Comment: 14 pages, 3 figures

Excitons in semiconductor quantum dots (QDs) feature high values of the two-photon absorption cross-sections (TPACSs), enabling applications of two-photon-excited photoluminescence (TPE PL) of QDs in biosensing and nonlinear optoelectronics. However, efficient TPE PL of QDs requires high-intensity laser fields, which limits these applications. There are two possible ways to increase the TPE PL of QDs: by increasing their photoluminescence quantum yield (PLQY) or by further increasing the TPACS. Plasmonic nanoparticles (PNPs) may act as open nanocavities for increasing the PLQY via the Purcell effect, but this enhancement is strictly limited by the maximum possible PLQY value of 100%. Here we directly investigated the effect of PNPs on the effective TPACS of excitons in QDs. We have found that effective TPACS of excitons in a QD–PMMA thin film can be increased by a factor of up to 12 near the linearly excited gold nanorods (GNRs). Using gold nanospheres (GNSs), in which plasmons cannot be excited in the infrared range, as a control system, we have shown that, although both GNSs and GNRs increase the recombination rate of excitons, the TPACS is increased only in the case of GNRs. We believe that the observed effect of TPACS enhancement is a result of the nonlinear interaction of the plasmons in GNRs with excitons in QDs, which we have supported by numerical simulations. The results show the way to the rational design of the spectral features of plasmon–exciton hybrids for using them in biosensing and nonlinear optoelectronics., V. K. acknowledges support from the Russian Science Foundation (Grant No. 18-72-10143) for the part of the study related to the investigation of the effects of PNPs on the effective TPACS of excitons in QDs and numerical simulations of these effects. Support from the Ministry of Education and Science of the Russian Federation (Grant No. 14.Y26.31.0011) for the part of this study related to the synthesis and functionalisation of the QDs and engineering of hybrid QD-GNR materials is also acknowledged. Y. R. acknowledges the support from the Basque Government (grant no. IT1164-19). Y. R. and M. G. acknowledge the support from the Spanish MINECO (PID2019-111772RB-I00). I. N. acknowledges the Ministry of Higher Education, Research and Innovation of the French Republic and Université de Reims Champagne-Ardenne.

Semiconductor quantum dots (QDs) are widely used in photovoltaic and optoelectronic devices due to their unique optical properties. Photoluminescence (PL) properties of QDs can be significantly improved by their electromagnetic coupling with plasmonic nanoparticles (PNPs). The excitation of resonant localized plasmon modes leads to the enhancement of the density of photon states and increase of electromagnetic field near the surface of PNPs, what boosts the acceleration of the exciton radiative decay, known as the Purcell effect. To study the dependence of the degree of acceleration of radiative decay rate (Purcell factor) on the distance between QDs and PNPs, we fabricated thin-film hybrid structures based on CdSe(core)/ZnS/CdS/ZnS(multishell) QDs and silver or gold PNPs with a controllable distance between these components. The change in the radiative decay rate of excitons was calculated from the PL intensities and lifetimes before and after the deposition of PNPs on top of the QD thin film covered by a poly(methyl methacrylate) (PMMA) spacer. For both PNP types, the PL lifetime of underlying QDs decreased, whereas the PL intensity of the latter decreased only slightly for gold PNPs and even increased for silver PNPs. This indicates the acceleration of QDs radiative decay (Purcell effect) mediated by exciton-plasmon interaction. The Purcell factor was higher for silver PNPs than that for gold PNPs, what can be explained by the better spectral overlap between the QDs PL band and silver PNPs absorbance and the absence of interband absorption in silver at the wavelength of QDs PL. The results of this study provide better understanding of the Purcell effects in hybrid materials based on QDs and PNPs.

Enhancement of the photoluminescence signal intensity from organic and inorganic fluorophores increases the sensitivity of operation of optical sensors, detectors, and photonic diagnostic assays. Here, we have engineered and compared optical and fluorescence-enhancing properties of two types of one-dimensional porous silicon photonic crystals: a transfer-printed microcavity based on the freestanding photonic crystal and a conventional “one-piece” microcavity created on a monocrystalline silicon substrate. Comparative analysis of the eigenmodes and the photonic bandgaps of both types of microcavities demonstrated a high quality of transfer-printed microcavities and good correlation of their reflection spectra with the spectra of “one-piece” microcavities. Moreover, embedding of a highly concentrated solution of quantum dots (QDs) in the eigenmode localization region of transfer-printed microcavity was followed by three-fold reduction of the full-width-at-half-maximum of their luminescence spectrum at the microcavity eigenmode wavelength, thus confirming a weak coupling regime of QD exciton and microcavity eigenmode interaction and significant enhancement of QD luminescence within the microcavity.

Today, lots of research address the phenomenon of interaction between light and matter. In particular, it is of a special interest to investigate light–matter interaction in one-dimensional resonators based on porous materials. In this case, one can embed emitting semiconductor particles into the porous resonator, where the excitons of these particles couple to the resonator eigenmode and luminescence intensity of the emitters is enhanced, allowing an increase in the sensitivity of optical sensors, detectors, and photonic diagnostic assays. A particular challenge is to place the emitters directly in the antinode region of the resonator eigenmode in order to maximize the coupling strength, which is sometimes a problem due to the spatial distribution of emitters away from the eigenmode localization region. Here, we have shown that the transfer-printing technique can be used to obtain structures based on freestanding porous silicon photonic crystals capable of precisely controlling the emitter spatial distribution about the eigenmode localization region. This, as well as the porosity of these structures and high adsorption capacity of porous silicon, allows the light–matter interaction in these hybrid structures to be used in sensing applications. We have shown that the transfer-printing method does not worsen the optical properties of the microcavities compared to the conventional electrochemical etching of the whole microcavity at a time. Furthermore, we have observed slightly better coupling of the exciton of the emitter to the eigenmode of the transfer-printed microcavity in the weak coupling regime.

Resonance interaction between a localized electromagnetic field and excited states in molecules paves the way to control fundamental properties of a matter. In this study, we encapsulated organic molecules with relatively low unoriented dipole moments in the polymer matrix, placed them in tunable optical microcavity and realized, for the first time, controllable modification of the broad photoluminescence (PL) emission of these molecules in strong coupling regime at room temperature. Notably, while in most previous studies it was reported that the single mode dominates in the PL signal (radiation of the so-called branch of the lower polariton), here we report on the observation of two distinct PL peaks, evolution of which has been followed as the microcavity mode is detuned from the excitonic resonance. A significant Rabi splitting estimated from the modified PL spectra was as large as 225 meV. The developed approach can be used both in fundamental research of resonant light-mater coupling and its practical applications in sensing and development of coherent spontaneous emission sources using a combination of carefully designed microcavity with a wide variety of organic molecules., Ministry of Education and Science of the Russian Federation (14.Y26.31.0011); Ministerio de Economiá y Competitividad (FIS2016.80174-P, PLASMOQUANTA).

Semiconductor quantum dots (QDs) have been demonstrated to be a promising material for developing innovative optoelectronic systems and lasers. The strong and weak coupling effects between localized plasmons in noble metal nanoparticles and excitons in QDs can modulate photoluminescence properties of the latter, scaling up their applications. In particular, these effects can strongly affect the photoluminescence (PL) lifetime of QDs, opening prospects for significantly increasing the quantum yield of the biexciton emission in single QD. Here, we provide а convincing proof of the formation of many-exciton states in hybrid material based on CdSe/ZnS/CdS/ZnS core/multishell QDs and gold nanorods (NRs) embedded in thin films of PMMA. The presence of NRs causes at least an order-of-magnitude decrease in the PL lifetimes of single QD. The obtained results have demonstrated the possibility of detecting biexciton states in QDs as the main component of emission of the hybrid QD-NR material., We acknowledge the support of grant no. 14.Y26.31.0011 of the Ministry of Education and Science of the Russian Federation. Y.R. acknowledges support from project Fis2016.80174-P (PLAS-MOQUANTA) from MINECO (Ministerio de Economiá y Competitividad), Spain.

Semiconductor quantum dots (QDs) are widely used as components of hybrid materials for development of efficient light emitters and convertors. Their unique nonlinear optical properties, such as two-photon absorption and two-photon photoluminescence from biexcitons, make them promising materials for photovoltaic and optoelectronic applications. In this study, thin-film hybrid materials based on the CdSe(core)/ZnS/CdS/ZnS(multishell) QDs have been fabricated, and the two-photon photoluminescence (PL) from the generated biexcitons have been studied. The results show that fabricated thin-film hybrid materials based on the QDs are efficient fluorophores in the one- and two-photon PL regimes for applications in optoelectronics and biosensing.

Single crystal needle-like diamonds shaped as rectangular pyramids were produced by combination of chemical vapor deposition and selective oxidation with dimensions and geometrical characteristics depending on the deposition process parameters. Photoluminescence spectra and their dependencies on wavelength of excitation radiation reveal presence of nitrogen- and silicon-vacancy color centers in the diamond crystallites. Photoluminescence spectra, intensity mapping, and fluorescence lifetime imaging microscopy indicate that silicon-vacancy centers are concentrated at the crystallites apex while nitrogen-vacancy centers are distributed over the whole crystallite. Dependence of the photoluminescence on excitation radiation intensity demonstrates saturation and allows estimation of the color centers density. The combination of structural parameters, geometry and photoluminescent characteristics are prospective for advantageous applications of these diamond crystallites in quantum information processing and optical sensing., Authors are grateful for financial support from Russian Federation President Program for young scientist: Grant# МК-9230.2016.2 (for EAO and FTT) and Grant# MK-5860.2016.2 (for KGK).

Microfluidic devices present the basis of modern life sciences and chemical information processing. To control the flow and to allow optical readout, a reliable sensor material that can be easily utilized for microfluidic systems is in demand. Here, we present a new optical readout system for pH sensing based on pH sensitive, photoluminescent glutathione capped cadmium telluride quantum dots that are covalently immobilized in a poly(acrylate) hydrogel. For an applicable pH sensing the generated hybrid material is integrated in a microfluidic sensor chip setup. The hybrid material not only allows in situ readout, but also possesses valve properties due to the swelling behavior of the poly(acrylate) hydrogel. In this work, the swelling property of the hybrid material is utilized in a microfluidic valve seat, where a valve opening process is demonstrated by a fluid flow change and in situ monitored by photoluminescence quenching. This discrete photoluminescence detection (ON/OFF) of the fluid flow change (OFF/ON) enables upcoming chemical information processing., MF and SL gratefully acknowledge the cluster of Excellence “Center for Advancing Electronics Dresden (CfAED) for financial and assistant support. AD thanks the Government of the Russian Federation (Grant 074-U01) through ITMO Post-Doctoral Fellowship and the European Social Fund (ESF) for financing within the project “ChemIT”.

Mixed aerogels from semiconductor and metal nanoparticles represent an outstanding hybrid material with exceptional properties due to two striking advantages: the creation of a huge quantity of semiconductor-metal interfaces combined with a highly porous three-dimensional nanostructured network. We present a versatile synthetic pathway towards hybrid aerogels built up by joint gelation of CdTe and noble metal nanoparticles (Au, Pd and bimetallic Au/Pd). A straightforward HO treatment inducing gel formation is developed as a more elegant alternative compared to the established photooxidation approach. The use of HO allows a reproducible, simple and mild gel formation which can be easily upscaled. The tremendous influence of the HO concentration on gelation mechanism and gelation kinetics is revealed by photoluminescence quantum yield (PLQY) determinations. Resulting gels are extensively characterized via transmission electron microscopy (TEM), scanning TEM (STEM), energy dispersive X-ray analysis (EDX) as well as photoluminescence (PL) spectroscopy and PL lifetime measurements. By varying the composition of the herein presented noble metal nanoparticles in a controlled fashion the range of semiconductor-metal hybrid aerogels is widened, which demonstrates the versatility and consistency of our approach. This synthetic flexibility grants access to a variety of different mixed hybrid aerogels which are of high significance for catalytic, sensing and photonic applications., Parts of TEM investigations have been carried out at the Leibniz-Institut für Polymerforschung Dresden e.V. Access to their TEM facility is gratefully acknowledged. AD thanks the Government of the Russian Federation (Grant 074-U01) through ITMO Post-Doctoral Fellowship.

Resumen del trabajo presentado a la 19th International Conference on Transparent Optical Networks (ICTON), celebrada en Girona (España) del 2 al 6 de julio de 2017., We report our recent results of investigation of the interactions between localized plasmons in gold nanorods and excitons in J-aggregates. We were able to track an anticrossing behavior of the hybridized modes both in the extinction and in the photoluminescence spectra of this hybrid system. We identified the nonlinear optical behavior of this system by transient absorption spectroscopy. Finally using magnetic circular dichroism spectroscopy, we show that nonmagnetic organic molecules exhibit magneto-optical response due to binding to a plasmonic nanoparticles. In our experiments, we also studied the effect of detuning as well as the effect of off- and on resonance excitation on the hybrid states.

Trabajo presentado a la 3rd International Conference on Applications of Optics and Photonics, celebrado en Faro (Portugal) del 8 al 12 de mayo de 2017., We investigated the interactions between localized plasmons in gold nanorods and excitons in J-aggregates and were able to track an anticrossing behavior of the hybridized modes both in the extinction and in the photoluminescence spectra of this hybrid system. We identified the nonlinear optical behavior of this system by transient absorption spectroscopy. Finally using magnetic circular dichroism spectroscopy we showed that nonmagnetic organic molecules exhibit magneto-optical response due to binding to a plasmonic nanoparticles. In our experiments we also studied the effect of detuning as well as the effect of off- and on resonance excitation on the hybrid states., We acknowledge financial support from Project Fis2016.80174-P (PLASMOQUANTA) from MINECO (Ministerio de Economía y Competitividad). L.L.-M. acknowledges funding from the European Research Council (ERC Advanced Grant 267867, Plasmaquo). This study was supported by the Ministry of Education and Science of the Russian Federation, grant no. 14.Y26.31.0011.

The interaction between the excitonic J-band of J-aggregate molecules and localized plasmonic resonances supported by metallic structures can be large enough to reach the regime of strong coupling, giving rise to two hybridized modes [1, 2]. The new hybrid system is often characterized in extinction measurements, where the strong coupling results in an avoided crossing of the two modes as the detuning of the plasmonic mode with respect to the excitonic transition is changed. In principle, the photoluminescence (PL) signal should also exhibit a characteristic anti-crossing signature, but, so far, it has been challenging to identify it in experiments [2, 3].

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., We acknowledge financial support from Projects FIS2013-41184-P and MAT2013-46101-R of the Spanish Ministry of Economy and Competitiveness (MINECO) and ETORTEK project NANOGUNE’14. R.E. acknowledges funding as Fellow Gipuzkoa of the Gipuzkoako Foru Aldundia through Feder Funds of the European Union “Una manera de hacer Europa”.

The development of artificial photosynthetic systems that utilize solar energy is one of the most challenging goals of chemistry and material sciences. The straightforward way to construct an artificial photosynthetic device for practical solar fuel production for the practical use of solar energy is to mimic the structural and functional organization of the natural photosynthetic machinery. In photosynthetic organisms, light is initially absorbed by antenna protein–pigment complexes in which it induces an excited electronic state (exciton), and then excitons (or electron–hole pairs) are transferred by means of F rster resonance energy transfer (FRET) to specialist chlorophyll cofactors in specialized reaction centers (RCs); here, excitons dissociate into their constituent carriers which are used in chemical transformations for the synthesis of high-energy molecules that fuel the organism. An artificial device that mimics this process for solar energy conversion should include, among other components, an efficient light-harvesting antenna capable of transferring the excitation energy to the RC. Based on the principle of photosynthesis, a variety of artificial antenna systems have been developed using supramolecular chemistry in which dendrimers incorporate porphyrins or other organic fluorophores or organometallic complexes. Although efficient excitation-energy transfer was obtained in such systems, the use of organic fluorophores in light-harvesting systems is rather limited because of their narrow spectral windows for light-collecting and lack of photostability. Recently it was suggested that inorganic nanocrystals, which are able to collect light over a wide spectral window, may achieve significantly greater absorption than natural photosystems, thus enhancing and could thus be used to enhance the light-harvesting process. Simultaneously, these nanocrystals may also be very efficient in excitationenergy transfer. This has led us to contemplate the development of hybrid materials in which light energy harvested by the nanocrystals in the optical region may be transferred to the RC in order to enhance the efficiency of the photosynthetic process. The simplest and best understood photosynthetic RC is that found in purple bacteria (Rhodobacter sphaeroides, for example). Although RCs from different photosynthetic organisms vary in their structure and composition, they are always composed of complexes of pigments and proteins, and RC fromRb. sphaeroides is known to be a good model of all the photosynthetic RCs. Here, we demonstrate that photoluminescent quantum dots (QDs) of these selected photoluminescence (PL) wavelengths may be tagged with the RC of Rh. sphaeroides in such a way that FRET from the QD to the RC is realized (Figure 1). A nearly threefold increase in the rate of generation of excitons in the RC is demonstrated, and theoretical estimates predict even stronger enhancements, thus indicating that further optimization is possible. Advances in inorganic synthesis have resulted in the production of monodispersed QDs such as highly photoluminescent CdSe/ZnS core/shell and CdTe nanocrystals. The light absorption by these QDs appears as a quasicontinuous superposition of peaks with extinction coefficients orders of magnitude higher than those of organic molecules. QDs are ultrastable against photobleaching, and the quantum [*] Prof. I. Nabiev CIC NanoGUNE Consolider, 20018 San Sebastian (Spain) and EA n83798, Universit de Reims Champagne-Ardenne 51100 Reims (France) and Ikerbasque, Basque Foundation for Science 48011 Bilbao (Spain) Fax: (+34)943-574-001 E-mail: i.nabiev@nanogune.eu

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.

In this review, we discuss the feasibility of laser cooling of semiconductor nanocrystal quantum dots by phonon-assisted anti-Stokes photoluminescence. Taking into account recent experimental advances, in particular, the development of semiconductor nanocrystals with very high quantum yield, we analyze in detail how the various physical processes in nanocrystals might help or hinder the cooling process. Possible experimental approaches to achieve efficient optical cooling are also discussed.

We report on the state-of-the art synthesis and improved luminescence properties of thiol-capped CdTe nanocrystals (NCs) synthesized in water. The optimized pH (12) and molar ratio of thiol to Cd ions (1.3:1) increases the room-temperature photoluminescence quantum efficiency of as-synthesized CdTe NCs capped by thioglycolic acid (TGA) to values of 40−60%. By employing mercaptopropionic acid (MPA) as a stabilizer, we have synthesized large (up to 6.0 nm in diameter) NCs so that the spectral range of the NCs' emission currently available within this synthetic route extends from 500 to 800 nm. Sizing curve for thiol-capped CdTe NCs is provided. In contrast to CdTe NCs capped by TGA, MPA-capped CdTe NCs show up to 1 order of magnitude longer (up to 145 ns) emission decay times, which become monoexponential for larger particles. This phenomenon is explained by considering the energetics of the Te-related traps in respect to the valence-band position of CdTe NCs. The correlation between luminescence quantum ef...

The optical properties of diamond spherical-like particles, prepared by the hot-filament chemical vapor deposition technique on opal substrates, have been investigated. The particles were studied using scanning electron microscopy, micro-Raman spectroscopy and micro-photoluminescence techniques. The diamond particles, consisting of polycrystalline diamond, have a size of about 5 μm. Periodic peaks in the background of the photoluminescence spectra have been revealed. Analysis of the position of these peaks with the Lorentz–Mie theory for light scattering by single dielectric spherical particles confirms that these observed peaks can be regarded as whispering-gallery mode.

In this paper a novel technique for the production of aluminosilicate microtubes, which are shown to act as optical cylindrical microresonators, is described. The free-standing microtubes are fabricated by using vacuum-assisted wetting and filtration of silica gel through a microchannel glass matrix. The microtubes are studied using scanning electron microscopy, micro-photoluminescence spectroscopy, and fluorescence lifetime imaging confocal microscopy. In the emission spectra of the microresonators we find very narrow periodic peaks corresponding to the whispering gallery modes of two orthogonal polarizations with quality factors up to 3200. A strong enhancement in photoluminescence decay rates at high excitation power demonstrates the occurrence of amplified spontaneous emission from a single microtube. These microtubes show a large evanescent field extending many micrometers beyond the tube radius. Applications for these novel microresonators will be in the areas of microlasers and microsensors and quantum information processing.

A strategy to gate the emission efficiency of semiconductor nanocrystals in response to optical signals is proposed. Reversible modulation of the emission of CdTe nanocrystals has been studied utilizing energy transfer mechanisms in the hybrid spiropyran/CdTe system on a timescale of tens of seconds. The possibility of all-optical processing and optical control at molecular level with a nano-photonic system is demonstrated.

In this work we demonstrate the possibility to achieve efficient anti-Stokes photoluminescence emission and Raman scattering from semiconductor quantum dots deposited on spherical microcavity using excitation below the absorption edge of quantum dots. The largest spectral shift in photoluminescence spectra to shortwave region with respect to the excitation energy was found to be 380 meV, with periodic structure in optical spectra arising from the coupling between the emission from quantum dots and spherical cavity modes.

PUBLISHED, We report on the coherent coupling of whispering gallery modes (WGMs) in a photonic molecule formed from two melamine-formaldehyde spherical microcavities coated with a thin shell of light-emitting CdTe nanocrystals (NCs). Utilizing different excitation conditions, the splitting of the WGM resonances originating from bonding and antibonding branches of the photonic states is observed, and fine structure consisting of very sharp peaks resulting from lifting of the WGM degeneracy has been detected. Time-resolved measurements showed a slight increase in the spontaneous emission rate of NCs in a photonic molecule when compared to the spontaneous emission rate for NCs coating a single microsphere.

We report evidence for highly efficient F€ resonance energy transfer between CdTe nanocrystals (donors) and Rhodamine B (acceptors) in mixed solid films. Enhancement of the acceptor photoluminescence intensity and a decrease of the donor decay time are observed in the films containing nanocrystals mixed with Rhodamine B. For a wide range of films with a ratio between the amount of acceptors and the amount of donors of 0.2–5, an efficiency of energy transfer of more than 20% is estimated from time resolved measurements. � 2004 Elsevier B.V. All rights reserved.

For the first time, the anti‐Stokes luminescence in colloidal solutions of CdTe nanocrystals on excitation below the absorption edge has been discovered. The maximum spectral shift to the shortwave region relative to the excitation energy ΔEconmax = 319 meV is obtained for mean‐sized nanocrystals (2.5 nm). The conversion efficiency of the absorbed radiant energy is η ∼ 1.3·10−2%. The rise in the anti‐Stokes photoluminescence intensity with increasing temperature and the linear dependence on the exciting radiation intensity have been established. It is shown that the effect observed cannot be caused by two‐photon excitation or by Auger recombination. It is assumed that the basic mechanism of the luminescence observed is the radiative recombination through the energy levels of the states attributable to the disturbance of the crystal structure in the nanocrystals.

For the first time highly efficient photon energy up-conversion (anti-Stokes photoluminescence) has been observed in colloids of CdTe nanocrystals (NCs) and CdSe NCs covered by ZnS shell. The maximum magnitude of the up-converted blue shift ΔE max UC = 335 meV was obtained for CdSe/ ZnS NCs under excitation by a low-power He-Ne laser. The maximum efficiency for energy conversion was estimated to be about η max = 2.7 x 10 -2 % at room temperature. The intensity of the anti-Stokes photoluminescence increases with temperature and shows a linear dependence on the excitation intensity. We suggest that subgap surface states are involved as intermediate states in the up-conversion process rather than nonlinear two-photon absorption or Auger processes.

Trabajo presentado a la 16th International Conference on Transparent Optical Networks (ICTON), celebrada en Grazer Messe (Austria) del 6 al 10 de julio de 2014., In this paper, we report on fabrication and optical properties of hollow poly(methyl methacrylate) (PMMA) microspheres loaded with CdSe/CdS core-shell quantum dots. The PMMA microspheres were fabricated using a spray-drying method and investigated using scanning electron microscopy, confocal microscopy, and fluorescent lifetime imaging microscopy. Micro-photoluminescence studies of individual microspheres were also performed revealing pronounced whispering gallery modes. This result demonstrates the high optical quality of the hollow microspheres and their potential application as optical microresonators

We present the theory of the thermally activated photoluminescence upconversion, also known as anti-Stokes photoluminescence (ASPL), based on the quantum dot (QD) polaron effect and explaining all the principal features of the ASPL in colloidal solutions of chemically grown nanocrystals (NCs). The results obtained by Monte-Carlo simulations reproduce all the experimentally observed ASPL trends in colloidal NC solutions and are being extended to dense QD systems, such as films composed by layers of closely packed NCs (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

The influence of dc electric field is examined on the photoluminescence spectra of various PbI2 nanocrystals in a poly (vinyl alcohol) matrix, prepared by fast and slow cooling of a hot saturated aqueous PbI2 solution. The thin flat PbI2 nanocrystals with a thickness of less than 1 nm exhibit a strong 1D quantum confinement. The application of an electric field of up to 16 kV cm−1 causes a pronounced Stark effect in the differential absorption spectrum and enhancement of excitonic photoluminescence. The last effect results probably from the field-induced detachment of surface-trapped excitons (thermoelectronic ionization or Frenkel effect). While, the larger PbI2 nanocrystals of size 5 nm did not show an appreciable field-induced effect in the photoluminescence spectra. Such different behaviour between large and small nanocrystals demonstrates the dramatic influence of the surface on the excitonic radiative recombination in semiconductor quantum dots.

Hybrid materials formed by semiconductor quantum dots and J-aggregates of cyanine dyes provide a unique combination of enhanced absorption in inorganic constituents with large oscillator strength and extremely narrow exciton bands of the organic component. The optical properties of dendrite structures with fractal dimension 1.7-1.8, formed from J-aggregates integrated with CdTe quantum dots (QDs), have been investigated by photoluminescence spectroscopy and fluorescence lifetime imaging microscopy. Our results demonstrate that (i) J-aggregates are coupled to QDs by Förster-type resonant energy transfer and (ii) there are energy fluxes from the periphery to the centre of the structure, where the QD density is higher than in the periphery of the dendrite. Such an anisotropic energy transport can be only observed when dendrites are formed from QDs integrated with J-aggregates. These QD/J-aggregate hybrid systems can have applications in light harvesting systems and optical sensors with extended absorption spectra. © The Royal Society of Chemistry 2013., This research was supported by the ETORTEK 2011–2013 project “nanoIKER” from the Department of Industry of the Basque Government and by the Ministry of Education and Science of the Russian Federation Contract no. 8842 and 11.G34.31.0050. Financial support from the Portuguese Foundation for Science and Technology (FCT) and FEDER through Projects PTDC-FIS-113199-2009 and PEst-C/FIS/UI0607/2011 is gratefully acknowledged.

Trabajo presentado a la 15th International Conference on Transparent Optical Networks, celebrada en Cartagena (España) del 23 al 27 de Junio de 2013., Recent results on development and characterization of WGM spherical microcavities integrated with organic dye molecules in a J-aggregate state are presented. The microcavities are studied using micro-photoluminescence spectroscopy, and fluorescence lifetime imaging confocal microscopy. Directional emission of light from the microcavity is also experimentally demonstrated and attributed to the photonic jets generated in the microsphere

The structure of luminescence spectra of free excitons in CdS single crystals at T = 77 K is investigated. The dip formation is found in the top part of free A and B exciton resonant peaks of photoluminescence (PL) spectra after heating of the CdS crystals followed by fast cooling down to 77 K. Similar effects are observed when an external electric field is applied. It is shown that the structure of exciton PL spectra is due to self-absorption of resonance radiation in the near-surface layer with low exciton concentration. Our calculations demonstrate that the formation of an exciton concentration gradient may be caused by the influence of a surface electric field on the binding of electron-hole pairs to excitons. It is assumed that the increase of surface electric fields after heat treatment is caused by the thermostimulated adsorption of oxygen, which results in the formation of electron trap levels. [Russian Text Ignored].

We have studied the Raman and luminescence spectra of a microcavity–quantum dot system consisting of a melamine formaldehyde latex microsphere coated by CdTe colloidal quantum dots. The cavity-induced enhancement of the Raman scattering allows the observation of Raman spectra from only a monolayer of CdTe quantum dots. Periodic structure with very narrow peaks in the luminescence spectra of a single microsphere was detected arising from the coupling between the emission from quantum dots and spherical cavity modes. Strong anti-Stokes emission from CdTe quantum dots coupled to the cavity modes was observed using low intensity below band-gap excitation and attributed to the strong field enhancement at the microcavity resonances.

We report on the resonant modes in micro-luminescence spectra of whispering gallery microcavities combining dielectric microspheres and J-aggregates of cyanine dye. We use fluorescence lifetime imaging spectroscopy to study modification of spontaneous emission rate in J-aggregates attached to a microcavity. Directional emission of light from the integrated microcavity is experimentally shown in this work and attributed to the photonic jets generated in the microsphere. The results show that whispering gallery resonators with dye nano-aggregates can be used as micro-organic light-emitting devices.

We have studied the optical properties of a hybrid system consisting of cyanine dye J-aggregates (both PIC and TDBC) attached to a spherical microcavity. Instead of the commonly accepted chemical bonding of dye molecules to the surface of microspheres or deposition of dye-doped sol-gel film, in our experiments microspheres were coated with J-aggregate shell utilizing the layer-by-layer assembly of the ultrathin films. In this approach we aimed to take advantage of light confinement in the Whispering Gallery Modes (WGMs) microcavity by placing the emitter (shell of J-aggregates) just at the rim of the microsphere, where the resonant electromagnetic field reaches its maximum. 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 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 the transverse magnetic modes in the spectral region of J-aggregates absorption band where the transverse electric (TE) modes are strongly suppressed. Strong suppression of TE modes reflects preferential tangential orientation of transition dipole moment of J-aggregates in deposited microcavity shell. Observed polarization sensitive mode damping observed in the spectral region of high J-aggregate absorption can be used for suppression of unwanted modes in high Q optical resonators. 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 strongly enhanced Raman signal from the Jaggregates. Microcavities covered by J-aggregates and plasmonic nanoparticles could be thus useful for a variety of photonic applications in basic science and technology.

Highly luminescent semiconductor nanocrystals or quantum dots (QDs) possess a number of interesting and important properties that are tunable thanks to their size-dependent discrete electronic spectra. In this work we studied the optical properties of a novel type of hybrid structures that combine CdTe QDs with organic dye molecules (Pseudocyanine iodide) in a J-aggregate state. Due to the excitonic nature of electronic excitations, J-aggregates have the narrowest absorption and luminescence bands among organic materials, large oscillator strengths and giant third-order nonlinear susceptibility. In developed structures optical energy harvested by the quantum dots as artificial antennas then transferred to J-aggregates to enhance the photostability and efficiency of the carriers recombination. To fabricate CdTe/J-aggregates hybrid nanostructures we have used an approach based on electrostatic interaction between the positively charged dye and CdTe QDs capped with thioglycolic acid and, thus, carrying a negative charge. In order to develop an efficient hybrid material operating in the FRET regime, we carefully selected the PL colors (diameters) of the QD to be optically coupled with absorption of J-aggregates. We took advantage of extremely thin ligand shell (~0.5 nm) of CdTe QDs, which insures high efficiency of energy transfer. Formed QD/J-aggregate FRET system shows the broadband absorption in the visible and the ultraviolet part of the spectrum typical of QDs, along with the narrow emission linewidths characteristic of J-band emitters (~15 nm full width at half-maximum). We use absorption and photoluminescence spectroscopy and photoluminescence lifetime studies to conclude that efficiency of energy transfer is 95%. Also we report on development of active whispering-gallery microcavities integrated with with hybrid QDs/J-aggregate shell. Results of micro-PL spectroscopy and PL lifetime imaging confirm strong quenching of QDs emission and multifold shortening of their photoluminescence lifetime, which is consistent with highly efficient FRET in hybrid organic/inorganic semiconductor nanostructures coupled to microcavity modes.

Using electro-static assembly of complementary organic (cyanine dye) and inorganic (quantum dots) building blocks we report on formation of an advanced nanohybrid system with highly efficient nonradiative energy transfer properties. In contrast to previous approaches, formation of J-aggregates in cyanine dye solution was triggered by direct injection of as-synthesized colloidal CdTe quantum dots without any additional surface treatment. The optical properties of formed hybrid aggregates have been investigated by absorption and photoluminescence spectroscopy and fluorescence lifetime imaging microscopy. A quantum dot/J-aggregate system shows the enhanced absorption in visible and ultraviolet parts of the spectrum typical of quantum dots, along with the narrow emission linewidth and fast recombination rate characteristic of the J-band emitters. These quantum dot/J-aggregate hybrid systems may have applications in light harvesting systems with the extended spectral absorption as well as optical sensors and optoelectronic devices. © The Royal Society of Chemistry 2012., This work was in part financially supported by Ikerbasque Visiting Fellowship (NG). DS and YR acknowledge the support received from the European Science Foundation (activity PLASMON - BIONANOSENSE).

We present steady state and time-resolved photoluminescence (PL) characteristics of differently charged CdTe quantum dots (QDs) adsorbed onto a polyelectrolyte (PE) multilayer. The PE multilayer is built up using a layer-by-layer assembly technique. We find that the diffusion of the QDs into the PE multilayer is an important factor in the case of 3-mercapto-1, 2-propanediol stabilized QDs (neutral surface charge), resulting in a ∼31-fold enhancement in PL intensity accompanied by a blue shift in the PL spectra and an increase in decay lifetime from 3.74 ns to a maximum of 11.65 ns. These modified emission properties are attributed to the enhanced surface related emission resulting from the interaction of the QD's surface with the PE. We find that diffusion does not occur for thioglycolic acid (TGA) stabilized QDs (negative surface charge) or 2-mercaptoethylamine stabilized QDs (positive surface charge), indicating localization of the QDs on top of the PE multilayer. However, the PL lifetime of the TGA stabilized QDs decreases from 9.58 to 5.78 ns with increasing PE multilayer thickness. This provides evidence for increased intrinsic exciton recombination relative to surface related emission, which results in an overall reduction in the average lifetime. Our studies indicate the importance of the QD surface charge in determining the interaction with the PE multilayers and the subsequent modification of the QD emission properties.

In this paper, we report on development of active whispering-gallery microcavities integrated with shell of organic dye molecules in a J-aggregate state. Results of high-resolution micro-photoluminescence spectroscopy and photoluminescence lifetime imaging confirm strong coupling of J-aggregate emission to whispering gallery modes of spherical microcavity. Highly efficient luminescence from J-aggregate/microcavity system suggests that such photonic structures will find use as both microsensors and microlasers.

In this paper, we report on optical properties of a novel type of the hybrid nanostructures that combine CdTe colloidal quantum dots (QDs) with organic dye molecules in J-aggregate state. Formed QD/J-aggregate system shows the broadband absorption in visible and ultraviolet part of the spectrum typical of quantum dots, along with the narrow emission linewidth characteristic of J-band emitters (∼15 nm full width at a half-maximum (FWHM)). Highly efficient Forster energy transfer from an excited semiconductor quantum dot to an organic material paves the way for engineering a wide range of desired radiation rates, making these hybrid nanostructures promising for integration with whispering-gallery-mode (WGM) resonators. Photoluminescence spectroscopy and photoluminescence lifetime studies were used to conclude that the efficiency of energy transfer is ∼91%.

CdTe nanowires have been self-assembled in solution from the individual CdTe nanocrystal building blocks. Individual wires preserve the bright luminescence of CdTe nanocrystals and have been studied by photoluminescence measurements at variable temperature and by fluorescence lifetime imaging microscopy. The wires represent quantum dot solids with a strong degree of electronic coupling between the constituting semiconductor nanocrystals. Upon cooling to low temperatures the emission surprisingly red shifts in the strong coupling regime (nanowires) while for weaker coupling (closed packed and isolated nanocrystals) it blue shifts. A temperature dependent exchange interaction between the nanocrystals in the nanowires is proposed as explanation.

International audience; The potential impact of nanoscience on energy transfer processes in biomolecules was investigated on the example of a complex between fluorescent semiconductor nanocrystals and photochromic membrane protein. The interactions between colloidal CdTe quantum dots (QDs) and bacteriorhodopsin (bR) protein were studied by a variety of spectroscopic techniques, including integrated and time-resolved fluorescence spectroscopies, zeta potential and size measurement, and fluorescence correlation spectroscopy. QDs’ luminescence was found to be strongly modulated by bacteriorhodopsin, but in a controllable way. Decreasing emission lifetimes and blue shifts in QDs’ emission at increasing protein concentrations suggest that quenching occurs via Förster resonance energy transfer. On the other hand, concave Stern-Volmer plots and sigmoidal photoluminescence quenching curves imply that the self-assembling of NCs and bR exists, and the number of nanocrystals (NCs) per bacteriorhodopsin contributing to energy transfer can be determined from the inflection points of sigmoidal curves. This number was found to be highly dependent not only on the spectral overlap between NC emission and bR absorption bands, but also on nanocrystal surface charge. These results demonstrate the potential of how inorganic nanoscale materials can be employed to improve the generic molecular functions of biomolecules. The observed interactions between CdTe nanocrystals and bacteriorhodopsin can provide the basis for the development of novel functional materials with unique photonic properties and applications in areas such as all-optical switching, photovoltaics and data storage.

George Gabriel Stokes, while studying the process of light emission from solid materials, discovered that the wavelength of the emitted light is generally longer than that of the light which is exciting the emission process. This excitation-emission shift bears his name, as an observed “Stokes-shift” between the excited and emitted light [1]. In our modern quantum mechanical description of the process, the emitted photons have a lower energy than those exciting the photoluminescence, the excess energy being delivered into the material, usually by phonon excitation. Within this review, we call the process the Stokes-shifted photoluminescence (SSPL).

In this paper we describe a novel technique for the fabrication of aluminosilicate microfibres and microtubes which are shown to act as optical cylindrical microresonators. The alumosilicate microfibres and microtubes were fabricated by using vacuum-assisted wetting and filtration of silica gel through a microchannel glass matrix. The microfibres and microtubes were studied using Scanning Electron Microscopy (SEM), micro-photoluminescence spectroscopy and fluorescence lifetime imaging confocal microscopy. In the emission spectra of the micro-resonators we find very narrow periodic peaks corresponding to the whispering gallery modes of two orthogonal polarizations with quality factors up to 3200. A strong enhancement in photoluminescence decay rates at high excitation power demonstrates the occurrence of amplified spontaneous emission from a single microtube. These microtubes show a large evanescent field extending many microns beyond the tube radius. Potential applications for these novel microresonators will be in the area of optical microsensors for a single molecule detection of biological and chemical species, including anti-terrorism and defense sectors.

Fdrster resonant energy transfer (FRET) between the CdTe quantum dot (QD) acting as donors and acceptors is investigated at nanoscale proximity to gold nanoparticles (Au NPs). Photoluminescence (PL) studies of the acceptor QD emission from a mixed monolayer showed a distance dependent enhancement of the acceptor emission compared with that achieved for a donor-acceptor mixed monolayer in the absence of the Au NP layer. Time-resolved photoluminescence measurements showing a reduction in the donor lifetime, accompanied by an increase in the acceptor PL lifetime, provide further evidence for surface plasmon enhanced FRET.

We present details on the formation and optical peroperties of CdTe nanowires, which were found to grow in a standard phosphate-buffered solution, including micro-photoluminescence and fluorescence lifetime imaging.

A detailed study of the photonic modes in microtube cavity of ~ 7-8 μm outer diameter is presented. We demonstrate a new route to the fabrication of individual microtubes with the maximum length of 200 μm, using a vacuum assisted wetting and filtration through a microchannel glass matrix. The microtubes were studied using micro-photoluminescence spectroscopy and luminescence lifetime imaging confocal microscopy. In the emission spectra of the microresonators we find periodic very narrow peaks corresponding to the whispering gallery modes of two orthogonal polarizations with quality factors upto 3200 at room temperature. In order to identify the peaks in the observed mode structure, we have adopted the boundary-value solution to the problem of scattering of electromagnetic waves by a dielectric microcylinder. A strong enhancement in photoluminescence decay rates at high excitation power suggest the occurrence of amplified spontaneous emission from a single microtube. The evanescent field in these photonic structures extends a couple of micrometers into the surroundings providing the possibility for efficient coupling to an external photonic device.