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Light–matter interaction in hybrid systems made of fluorophores embedded into a microcavity (MC) attracts much attention. Depending on the coupling strength between the components, either photoluminescence (PL) enhancement or hybridization of the luminophore energy levels with the MC eigenmode resulting in two hybrid energy states occurs in these systems. This effect can be used in various practical applications: enhancing Raman scattering, increasing conductivity, obtaining Bose–Einstein condensates at room temperature, etc. Hybrid structures emitting in the near-infrared (NIR) range can be used in biomedical applications for exciting and detecting radiation within the transparency window of biological tissues. Here, we have developed hybrid photoluminescent structures based on porous silicon photonic crystals (PhCs) and PbS quantum dots (QDs) emitting in the NIR range. The freestanding PhC-based MCs were obtained by electrochemical etching of monocrystalline Si. Comparison of the PhC reflectance spectra before and after exfoliation from the substrate, as well as after thermal oxidation, showed a 100-nm blue shift, other parameters being almost unchanged. After embedding QDs, we observed narrowing of their PL spectrum compared to the QD solution. We attribute this to the Purcell effect and weak coupling between the QD exciton and MC eigenmode. Thus, our hybrid structures exhibit weak light–matter coupling in the NIR range, which provides the basis for new nanophotonic biosensor systems. In addition, they are freestanding, thus offering prospects for designing sensors with the option of pumping analytes through the porous structure.

The development of optical and, in particular, photoluminescent sensors is currently becoming more and more significant because of their universality, selectivity, and high sensitivity ensuring their wide applications in practice. The efficiency of existing photoluminescent sensors can be increased by using photoluminescent nanomaterials and hybrid nanostructures. For biological applications of photoluminescent sensors, it is extremely relevant to excite photoluminescence in the near infrared spectral range, which allows excluding the effect of autofluorescence of biomolecules and ensuring a deeper penetration of radiation into biological tissues. In this work, it has been studied how the spectral and kinetic parameters of photoluminescence change under two-photon excitation of semiconductor quantum dots incorporated into a one-dimensional photonic crystal, a porous silicon microcavity. It has been shown that the formation of a weak coupling between an exciton transition in quantum dots and an eigenmode of the microcavity enhances the photoluminescence of quantum dots. It is important that quantum dots placed in the porous silicon matrix hold a sufficiently large cross section for two-photon absorption, which makes it possible to efficiently excite their exciton states up to saturation without reaching powers leading to the photothermic destruction of the structure of porous silicon and to the disappearance of the weak coupling effect. It has been demonstrated that the radiative recombination rate under the two-photon excitation of the system consisting of quantum dots and the microcavity increases by a factor of 4.3; it has been shown that this increase is due to the Purcell effect. Thus, fabricated microcavities based on 1D porous silicon crystals allow controlling the quantum yield of photoluminescence of quantum dots under two-photon excitation, which opens prospects for the development of new photoluminescent sensors based on quantum dots operating in the near infrared spectral range.

Photoluminescent quantum dots (QDs), due to their unique optical properties and capacity for conjugation with biomolecules, are widely used in biomedicine. However, numerous byproducts of bioconjug...

Conventional approaches to the determination of the two-photon absorption cross-section (TPACS) of fluorescent semiconductor nanocrystals, including quantum dots (QDs) and nanoplatelets (NPLs), can...

Hybrid fluorescent liquid crystalline (LC) composites containing inorganic quantum dots (QDs) are promising materials for many applications in optics, nanophotonics and display technology, combining the superior emission capability of QDs with the externally controllable optical properties of LCs. In this work, we propose the hybrid LC composites that were obtained by embedding CdSe/ZnS QDs into a series of host LC block copolymers of different architectures by means of a two-stage ligand exchange procedure. The ABA/BAB triblock copolymers and AB diblock copolymers with different polymerization degrees are composed of nematogenic phenyl benzoate acrylic monomer units and poly(4-vinylpyridine) blocks, which are capable of binding to the QD surface. Our results clearly show that the spatial distribution of QDs within composite films as well as the formation of QD aggregates can be programed by varying the structure of the host block copolymer. The obtained composites form a nematic LC phase, with isotropization temperatures being close to those of the initial host block copolymers. In addition, the influence of the molecular architecture of the host block copolymers on fluorescence properties of the obtained composites is considered. The described strategy for the QD assembly should provide a robust and conventional route for the design of highly ordered hierarchical hybrid materials for many practical applications.

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, Rn, 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 Rn 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., Funding from the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Financing UID/FIS/04650/2020 is acknowledged. V.K. acknowledges funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement 101025664 (QESPEM). Y.P.R. acknowledges funding from the Basque Government for Consolidated groups of the Basque University (Grant IT 1526-22) and Basic and/or Applied Research Projects (Grant PIBA-2021-0026). Part of this work dealing with the synthesis of CdSe/ZnS and CdSe/ZnS/CdS/ZnS quantum dots was supported by the Russian Science Foundation (Grant 18-19-00588).

International audience; The production of enantiopure chemicals is an essential part of modern chemical industry. Hence, the emergence of asymmetric catalysis led to dramatic changes in the procedures of chemical synthesis, and now it provides the most advantageous and economically executable solution for large-scale production of chiral chemicals. In recent years, nanostructures have emerged as potential materials for asymmetric synthesis. Indeed, on the one hand, nanomaterials offer great opportunities as catalysts in asymmetric catalysis, due to their tunable absorption, chirality, and unique energy transfer properties; on the other hand, the advantages of the larger surface area, increased number of unsaturated coordination centres, and more accessible active sites open prospects for catalyst encapsulation, partial or complete, in a nanoscale cavity, pore, pocket, or channel leading to alteration of the chemical reactivity through spatial confinement. This review focuses on anisotropic nanomaterials and considers the state-of-the-art progress in asymmetric synthesis catalysed by 1D, 2D and 3D nanomaterials. The discussion comprises three main sections according to the nanostructure dimensionality. We analyze recent advances in materials and structure development, discuss the functional role of the nanomaterials in asymmetric synthesis, chirality, confinement effects, and reported enantioselectivity . Finally, the new opportunities and challenges of anisotropic 1D, 2D, and 3D nanomaterials in asymmetric synthesis, as well as the future prospects and current trends of the design and applications of these materials are analyzed in the Summary and Outlook section.

International audience; Designing nanoprobes in which quantum dots (QDs) are used as photoluminescent labels is an especially promising line of research due to their possible medical applications ranging from disease diagnosis to drug delivery. In spite of the significant progress made in designing such nanoprobes, the properties of their individual components, i.e., photoluminescent QDs, vectorization moieties, and pharmacological agents, still require further optimization to enhance the efficiency of diagnostic or therapeutic procedures. Here, we have developed a method of engineering compact multifunctional nanoprobes based on functional components with optimized properties: bright photoluminescence of CdSe/ZnS (core/shell) QDs, a compact and effective antitumor agent (an acridine derivative), and direct conjugation of the components via electrostatic interaction, which provides a final hydrodynamic diameter of nanoprobes smaller than 15 nm. Due to the possibility of conjugating various biomolecules with hydroxyl and carboxyl moieties to QDs, the method represents a versatile approach to the biomarker-recognizing molecule imaging of the delivery of the active substance as part of compact nanoprobes.

Quantum dots (QDs) are promising candidates for producing bright, color-pure, cost-efficient, and long-lasting QD-based light-emitting diodes (QDLEDs). However, one of the significant problems in achieving high efficiency of QDLEDs is the imbalance between the rates of charge-carrier injection into the emissive QD layer and their transport through the device components. Here we investigated the effect of the parameters of the deposition of a poly (methyl methacrylate) (PMMA) electron-blocking layer (EBL), such as PMMA solution concentration, on the characteristics of EBL-enhanced QDLEDs. A series of devices was fabricated with the PMMA layer formed from acetone solutions with concentrations ranging from 0.05 to 1.2 mg/mL. The addition of the PMMA layer allowed for an increase of the maximum luminance of QDLED by a factor of four compared to the control device without EBL, that is, to 18,671 cd/m2, with the current efficiency increased by an order of magnitude and the turn-on voltage decreased by ~1 V. At the same time, we have demonstrated that each particular QDLED characteristic has a maximum at a specific PMMA layer thickness, therefore, variation of the EBL deposition conditions could serve as an additional parameter space when other QDLED optimization approaches are being developed or implied in future solid-state lighting and display devices.

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

Fluorescent hybrid systems based on quantum dots (QDs) and liquid crystals (LCs) are promising materials for a high number of applications in photonics and display technology. However, it is a big challenge to achieve compatibility between inorganic QDs and organic LCs. In this work, we employ an ABA triblock copolymer with a side-chain LC central block and outer poly(4-vinylpyridine) blocks capable of complexing QDs. This approach allows the preparation of polymer–inorganic nanocomposites forming a nematic LC phase and containing a large amount of non-aggregated QDs (10 wt%). In addition, the resulting composites can be dissolved in a cholesteric LC mixture to obtain an LC system with uniformly distributed QDs where the triblock copolymer acts as a highly efficient compatibilizer. This new approach paves the way for constructing a broad range of hybrid functional materials for various applications.

International audience; Purple membrane (PMs), in which the photosensitive protein bacteriorhodopsin (bR) naturally occurs, have photovoltaic properties and are promising for optoelectronic applications. However, PMs cannot effectively absorb light in the NIR spectral region. Semiconductor quantum dots (QDs), which have high two-photon absorption cross-sections in the NIR region, can significantly improve the light sensitivity of PMs by means of Förster resonance energy transfer (FRET) from QDs to bR inside PMs. The purpose of this study was to improve the photovoltaic properties of PMs by means of FRET from QDs to bR under NIR two-photon excitation. We made the QD-PM complexes and showed high FRET efficiency in them. Finally, we found that the current signal from the QD-PM material was higher than that in the case of PMs alone under NIR excitation. The obtained results clearly demonstrate improvement of the photovoltaic properties of PMs under NIR two-photon excitation due to the FRET from QDs to bR and show the prospect of designing new photosensitive bio-nanohybrid devices.

International audience; At present, fluorescent spectroscopy is a powerful tool that is used in many biology applications. In practice, fluorescent labels based on organic dyes and semiconductor quantum dots are used. It is noteworthy that the semiconductor quantum dots have distinct advantages over organic dyes. At the same time, the efficiency parameters and modes of detection and excitation have not been investigated sufficiently. The results of theoretical study on the optimization of the excitation and detections modes for detecting ultra-small amounts of CdSe/ZnS core/shell semiconductor quantum dots are presented at this paper.

International audience; Semiconductor quantum dots (QDs) feature high values of the two-photon absorption (TPA) cross-sections, enabling their applications in biosensing and nonlinear optoelectronics. However, the efficient QD photoluminescence (PL) intensity caused by TPA requires high-intensity laser excitation which hinders these applications. Placing the QDs in the micro- or nanocavities leads to a change in their PL properties. Particularly, near plasmon nanoparticles (open nanocavities) the local field may be enhanced by the localized plasmons, which will lead to an increase of the TPA efficiency. Alternatively, placing QDs in a photonic crystal may boost an increase of their PL quantum yield due to the Purcell effect and also increase their PL intensity at the photonic mode wavelength due to the redistribution of the density of photonic states. In this study, we have fabricated thin-film hybrid materials based on QDs placed near plasmonic nanoparticles or in the photonic crystal. We have demonstrated a 4.3-fold increase of the radiative recombination rate of QDs in the photonic crystal cavity under the two-photon excitation, resulting in the increase of the PL quantum yield. In turn, the coating of the QDs films with the gold nanorods led to the 12-fold increase in TPA at the maximum of the plasmon spectrum. Our results pave the way to a strong increase of the PL efficiency of the QDs under two-photon excitation for their applications in biosensing and nonlinear optoelectronics.

Semiconductor quantum dots (QDs) are known for their high two-photon absorption (TPA) capacity. This allows them to efficiently absorb infrared photons with energies lower than the bandgap energy. Moreover, TPA in QDs can be further enhanced by the interaction of excitons of the QDs with plasmons of a metal nanoparticle. We fabricated nonlinear plasmon–exciton photodetectors based on QDs and silver nanoplates (SNPs) to demonstrate the optoelectronic application of these effects. A thin layer of CdSe QDs was used as a source of charge carriers for a photoresistor-type photodetector. SNPs with near-infrared plasmon modes were introduced into the layer of QDs to increase the light absorption efficiency. Under near-infrared irradiation, the power of the dependence of the photocurrent on the excitation intensity was twice the power of the corresponding dependence under one-photon excitation with visible light. This proved that the new photodetector efficiently operated under two-photon excitation. Although the SNP light absorption was linear, energy was transferred from plasmons to excitons in the two-quantum mode, which led to a nonlinear dependence. Moreover, we found that the photocurrent from the designed photodetector containing the QD–SNP composite was an order of magnitude higher than that from a photodetector containing QDs alone. This can be explained by the plasmon-induced increase in the TPA efficiency., This study was supported by the Russian Science Foundation, grant no. 18-72-10143. The part of this study dealing with the synthesis and characterization of nanomaterials was supported by the Russian Science Foundation, grant no. 18-19-00588. V. K. has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie, grant agreement no. 101025664 (QESPEM). I. N. acknowledges support of the French National Research Agency (ANR-20-CE19-009-02) and co-funding by the European Union via the European Regional Development Fund (FreeBioWave project).

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.

Fast, sensitive, high-throughput detection of coronavirus antigens at physiologically relevant levels is essential for population screening that could prevent epidemics such as the current COVID-19 global pandemic. Optical methods based on surface-enhanced Raman scattering (SERS) spectroscopy are promising for this purpose because they ensure quick detection of even single biological molecules in a sample. For achieving such a high sensitivity, it is crucial to design SERS-active systems concentrating incident radiation into small sample volumes. Here, metal-dielectric cavities have been obtained through interaction of protein sulfhydryl groups with a SERS-active silver surface. The concentration of light in these cavities allows the differential detection of spike glycoprotein and nucleocapsid protein of SARS-COV-2, which are its key antigens, at physiologically relevant concentrations. The cavity Q-factor can be increased by additionally covering the dielectric protein film with a silver shell to form an ultrathin cavity, which provides an at least tenfold enhancement of the detection signal. The results could be used to design high-throughput systems for specific and sensitive detection of viral antigens and quick diagnosis of viral infections.

Strong exciton–plasmon interaction enables effective control of the photonic properties of hybrid organic–inorganic nanostructures encompassing light absorption, scattering and luminescence. Whereas the manifestations of light-matter interactions in the absorption and scattering are reasonably well understood their relation to the luminescence as well as luminescence properties themselves in strongly coupled plexcitonic hybrids is still largely underexplored especially for a system with a complex mechanism of hybridisation of states. Here we report on investigation of the interaction between localized and hybridized plasmons in gold nanostars and excitons in J-aggregates under ambient conditions. Our findings demonstrate the quality performance of the formed plexciton system with multiple hybridization channels in terms of the parameters of strong coupling, such as Rabi splitting (230 meV), coupling-strength-to-transition energy ratio (0.07), and cooperativity (2.03). The results of time-resolved experiments elucidate the observed enhanced spontaneous emission rate with regard to the Purcell effect, whose value was estimated from the extinction spectra of the strongly coupled plexciton system., Financial supports from Projects PID2019-111772RB-I00 of the Spanish MINECO and the Ministry of Science and Higher Education of the Russian Federation (Grant No. 14.Y26.31.0011) are acknowledged. Y. R. acknowledges the support from the Basque Government (grant no. IT1164-19). P.S. and I.N acknowledge support from the Russian Science Foundation (grant no. 21-79-30048) of the part of this work related to nanomaterials manufacturing and functionalisation. I.N. acknowledges support from the Université de Reims Champagne-Ardenne. A.S.-I. acknowledges the Maria de Maeztu Units of Excellence Program from the Spanish State Research Agency (Grant No. MDM-2017-0720).

International audience; (IN) Received XX Month XXXX; revised XX Month, XXXX; accepted XX Month XXXX; posted XX Month XXXX (Doc. ID XXXXX); published XX Month XXXX Photoluminescence (PL)-based sensing techniques have been significantly developed in practice due to their key advantages in terms of sensitivity and versatility of the approach. Recently, various nanostructured and hybrid materials have been used to improve the PL quantum yield and spectral resolution. The near-infrared (NIR) fluorescence excitation has attracted much attention because it offers deep tissue penetration and avoiding the autofluorescence of the biological samples. In our study, we have shown both spectral and temporal PL modifications under two-photon excitation of quantum dots (QDs) placed in one-dimensional porous silicon photonic crystal (PhC) microcavities. We have demonstrated an up to 4.3-fold Purcell enhancement of the radiative relaxation rate under two-photon excitation. The data show that the use of porous silicon PhC microcavities operating in the weak coupling regime permits the enhancement of the PL quantum yield of QDs under two-photon excitation, thus extending the limits of their biosensing applications in the NIR region of optical spectrum. © 2020 Optical Society of America Light-matter resonance interaction enables control over spontaneous photoluminescence (PL) emission properties of various luminophores, including organic dyes [1,2], rare-earth ions [3], 2D metal dichalcogenides [4], and fluorescent nanocrystals [5,6]. The so-called "weak" coupling regime makes it possible to change the spectral, spatial, and temporal properties of the luminophore PL emission by varying the local electromagnetic environment [7]. The use of photonic crystals (PhCs) is one of the most promising approaches to controlling the electromagnetic field distribution and, hence, to coupling it to the emitters placed inside the PhC microcavities (MCs) [1,3,4,7]. This approach is of special interest in the field of sensing in such emerging areas as the healthcare, environmental monitoring, and food safety [8,9]. Recent studies have demonstrated significant advances of PL-based sensors employing PhC structures in order to improve the critical properties of PL labels [9,10]. Porous silicon (pSi) MCs have been shown to be promising for biosensing applications due to the simplicity and scalability of fabrication and highly developed pore structure making the sensor surface easily accessible for analytes [11-13]. However, the necessity of selective excitation of majority of conventional dyes in the visible region of optical spectrum, low photostability, brightness, and background due to the autofluorescence of biological samples remain the obstacles to wider use of PL-based biosensor techniques. Excitation of the PL probes in the near-infrared (NIR) transparency window of biological samples could resolve some of these problems, allowing one deeper tissue penetration, higher spectral resolution and avoiding the autofluorescence. The nonlinear regime of two-photon excitation is a way to obtain visible-range fluorescence using NIR light sources. Moreover, the use of semiconductor quantum dots (QDs) with uniquely high two-photon absorption cross-sections compared to conventional dyes [14,15] allows one to reach the unprecedentedly high values of fluorescence contrast [16]. In addition, QDs are the excellent probes for sensing due to their wide one-and two-photon absorption [17,18] and narrow PL spectra, high quantum yield [19], and excellent photostability [20,21]. In this study, we have investigated the spontaneous PL emission of CdSe(core)/ZnS/CdS/ZnS(multishell) QDs placed inside a porous silicon MCs under two-photon excitation. We have measured the spectral and temporal characteristics of the spontaneous PL emission of QDs under two-photon pumping, as well as their dependence on the pump power. Significant enhancement of the QD PL at the wavelength corresponding to the MC eigenmode and its suppression within the photonic bandgap were observed. The change in the QD PL spectrum inside the porous silicon microcavity depended on the excitation energy density because the relaxation rates of the PL signal in the spectral regions where it was enhanced or suppressed were different. The increase in the emission rate corresponding to the weak coupling between the exciton transition of QDs and the eigenmode of the MC has been shown, and Purcell factor was determined to be about 4.3.

The layer-by-layer (LbL) deposition approach allows combined incorporation of fluorescent, magnetic, and plasmonic nanoparticles into the shell of polyelectrolyte microcapsules to obtain stimulus-responsive systems whose imaging and drug release functions can be triggered by external stimuli. The combined use of fluorescent quantum dots (QDs) and magnetic nanoparticles (MNPs) yields magnetic-field-driven imaging tools that can be tracked and imaged even deep in tissue when the appropriate type of QDs and wavelength of their excitation are used. QDs are excellent photonic labels for microcapsule encoding due to their close-to-unity photoluminescence (PL) quantum yields, narrow PL emission bands, and tremendous one- and two-photon extinction coefficients. However, the presence of MNPs and electrically charged polyelectrolyte molecules used for the LbL fabrication of magneto-optical microcapsules provokes alterations of the QD optical properties because of the photoinduced charge and energy transfer resulting in QD photodarkening or photobrightening. These lead to variation of the microcapsule PL signal under illumination, which hampers their tracking and quantitative analysis in cells and tissues. Here, we have studied the effects of the structure and spatial arrangement of the nanoparticles within the microcapsule polyelectrolyte shell, the total shell thickness, and the shell surface charge on their PL properties under continuous illumination. The roles of the charge transfer and its main driving forces in the stability of the microcapsules PL signal have been established, and the design of the microcapsules dually encoded with QDs and MNPs providing the strongest and most stable PL has been determined. Controlling the energy transfer from the QDs and MNPs and the charge transfer from QDs to polyelectrolyte layers in the engineering of magneto-optical microcapsules with a bright and stable PL signal extends their applications to long-lasting quantitative fluorescence imaging.

Semiconductor nanocrystals (SNCs), in particular, quantum dots (QDs) and nanoplatelets (NPLs), have orders of magnitude higher two-photon absorption cross-sections (TPACS) than organic dyes, what paves the way to their advanced applications in bioimaging, sensing, and optoelectronics. Traditionally, z-scan and two-photon photoluminescence (PL) excitation spectroscopy are used to determine the TPACS values. The main disadvantage of both methods is the necessity to know the exact sample concentration. In this study, we describe an approach to the TPACS determination from the analysis of two-photon-excited (TPE) PL saturation in CdSe(core)/ZnS/CdS/ZnS(multishell) QDs and CdSe NPLs. The results obtained for NPLs using developed approach are significantly smaller than those obtained by the z-scan method and are close to the values obtained for QDs. We assume that this discrepancy occurs due to the fact, that unlike the z-scan technique, the TPE PL saturation method measures the TPACS only for single-exciton states because of the low PL quantum yields of multiexciton states. Therefore, there is no need to know the concentration, which eliminates the corresponding estimation error. Thus, the measurement of TPE PL saturation in SNCs makes it possible to determine the absolute values of the TPACS of single-exciton states, which are more informative for applications of TPE PL than the TPACS of mixed multiexciton states.

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.

Efficient biexciton (BX) photoluminescence (PL) from quantum dots (QDs) paves the way to the generation of entangled photons and related applications. However, the quantum yield (QY) of BX PL is much lower than that for single excitons (EX) due to efficient Auger-like recombination. In the vicinity of plasmon nanoparticles, the recombination rates of EX and BX may be affected by the Purcell effect, fluorescence quenching, and the excitation rate enhancement. Here, the effect of the plasmon resonance spectral position on the EX and BX PL is experimentally studied in two cases: when the plasmon band overlaps with the excitation wavelength and when it coincides with the QDs PL band. In the first case, the EX and BX excitation efficiencies are significantly increased but the EX QY reduced. As a result, the BX-to-EX QY ratio is higher than 1 at plasmon–exciton systems separations shorter than 40 nm. In the second case, the radiative recombination rates are enhanced by several orders of magnitude, which led to an increase in BX QY over distances of up to 90 nm. Finally, these two effects are obtained in the same hybrid structure, with the resultant increase in both excitation efficiency and QY of BX PL., They also acknowledge the financial support from theMinistry of Science and Higher Education of the Russian Federation (Grant Number: 14.Y26.31.0011) . Y.R. acknowledges the support from the Basque Government (IT1164‐19)

International audience; Fluorescence spectroscopy is a powerful tool used in applied biological and medical research. Colloid semi-conductor quantum dots are promising fluorescent tags for simultaneous detection of different biopathogens. The techniques employing these tags can be improved by selecting the optimal modes for signal excitation and detection. The aim of the present work was to derive a mathematical expression to describe the signal-to-noise ratios in the pulsed and modulated excitation modes. Below, we compare these two modes of fluorescence excitation in ultralow quantities of quantum dots. We demonstrate that modulated excitation should be preferred for CdSe/ZnS quantum dots given that signal accumulation time is over 100 mc and the photosensor is exposed to background light of > 1 μW.

International audience; Variation of the steady-state optical properties of quantum dots (QDs) caused by photoinduced charge transfer is a widely known phenomenon which hinders QD applications requiring long-term stability of the optical signal, for example, bioimaging, single-photon sources, molecular tracking, and lasing. Intense light irradiation may provoke QD photodarkening, when their photoluminescence (PL) quantum yield (QY) is reduced, or photobrightening, when the QY increases and QD PL becomes brighter. In order to understand the nature of these processes and to determine the optimal operating conditions for QDs with different core sizes and shell thicknesses, we have systematically studied the photodarkening and photobrightening phenomena for different wavelengths and intensities of irradiation. The results have shown that changes in the core size only slightly alter the effect of light irradiation on the QD optical properties, whereas the irradiation wavelength and shell thickness are the major factors that determine the variation of the QD PL QY. We have found that the observed photoinduced processes are independent of the irradiation intensity, which proves the single-photon origin of these processes. We have also used comparative data on irradiation of QD solution and QDs embedded in polymer matrices to develop a general model describing the mechanism of the QD sensitivity to intense irradiation and elucidating the role of surface ligands in this mechanism. Our findings determine the strategy for increasing QD optical stability and optimization of operational conditions for QD-based devices.

Hybrid fluorescent cholesteric liquid crystalline (CLC) materials are representatives of “smart” soft matter, and are characterized by light emission that can be flexibly controlled by various external stimuli. This fact is due to the many possibilities for potential applications in the fields of photonics and optics stimulating design, and study of this type of hybrid materials. Here, we report on the optical and fluorescence properties of the hybrid CLC material based on a low-molecular-weight CLC matrix and CdSe/ZnS quantum dots (QDs) stabilized by LC diblock copolymers. The hybrid CLC material is characterized by the cholesteric phase in a wide temperature range, the high loading of QDs, and no QD aggregation. We demonstrate that the cholesteric stop band alters characteristics of the QD emission due to the resonance effect. This makes the polarization state and wavelength of the QD emission thermo- and angle-dependent. This work provides a way for the design of a wide range of field-controllable photonic devices for various applications.

International audience; Organic light-emitting diodes (OLEDs) are attracting great interest of the scientific community and industry because they can be grown on flexible substrates using relatively simple and inexpensive technologies (solution processes). However, a problem in the fabrication of white OLEDs is that it is difficult to achieve a balance between the intensities of individual emission components in the blue, green, and red spectral regions. In this work, we try to solve this problem by creating a two-component light-emitting diode based on modified polyfluorene (PF-BT), which efficiently emits in the blue–green region, and CdSe/ZnS/CdS/ZnS semiconductor quantum dots emitting in the orange–red region with a fluorescence quantum yield exceeding 90%. By changing the mass ratio of components in the active light-emitting composite within 40–50%, it is possible to transform the diode emission spectrum from cold to warm white light without loss of the diode efficiency. It is very likely that optimization of the morphology of multilayer light-emitting diodes will lead to further improvement of their characteristics.

We report on the effects of surface organic ligands on the properties of CdSe/ZnS/CdS/ZnS quantum dot (QD) solutions and condensed films. Hexadecylamine, octylamine, hexadecanethiol, octanethiol, thiophenol and inorganic ZnCl2 were used as the QD surface ligands affecting their properties. Here, we analyze optical and electrical properties as well as surface quality of thin films fabricated from the QDs bearing different ligands on their surfaces. We have found that the use of thiol ligands results in QD-films with a uniform surface, sufficient quantum yield and resistance, thus approving their relevance for the use as electroluminescent layers in light emitting diodes.

Semiconductor quantum dots (QDs) are characterized by orders of magnitude higher multiphoton linear absorption cross-sections compared with conventional organic dyes. Combined with the QD photoluminescence quantum yield approaching 100%, this fact opens great prospects for the twophoton functional tumor imaging with QDs tagged with highly specific recognition molecules. Single-domain antibodies (sdAbs) or “nanobodies” derived from lamas are the smallest high-affinity recognition molecules, which may be tagged with the QDs thus permitting not only solid tumors multiphoton imaging but also rare disseminated cancer cells and micrometastases in the depth of the tissue to be detected. Additionally, unique photostability of QDs enables signal accumulation and significant enhancement of the sensitivity of routine biochemical and immunohistochemical assays to be obtained when the conjugates of QDs, instead of organic dyes, are used.

Plasmonic nanoparticles have become a popularly accepted research tool in optoelectronics, photonics, and biomedical applications. The relatively recently appearing semiconductor plasmonic nanoparticles, as opposed to metal ones, are characterized by infrared plasmonic optical transitions and their application has a great future. In this work, the possibility of conversion of semiconductor (excitonic) fluorescence nanocrystals, i.e., quantum dots of the CuInS2 composition, to plasmonic nanoparticles by postsynthetic treatment without changes in the chemical composition of inorganic part of the nanocrystals was demonstrated for the first time ever.

Semiconductor quantum dots (QDs) are known for their ability to exhibit multiphoton emission caused by recombination of biexcitons (BX). However, the quantum yield (QY) of BX emission is low due to the fast Auger process. Plasmonic nanoparticles (PNPs) provide an attractive opportunity to accelerate BX radiative recombination. Here, we demonstrate the PNPs induced distance-controlled enhancement of BX emission of single QDs. Studying the same single QD before and after its integration with the PNPs, we observed a plasmon-mediated increase in the QY of BX emission. Remarkably, the enhancement of BX emission remains pronounced even at distances of 170 nm. We attribute this effect to efficient coupling, which results in the trade-off between resonance energy transfer from QD to gold nanorods and the Purcell effect at small QD-PNP separations and the predominant influence of the Purcell effect at longer distances. Our findings constitute a reliable approach to managing the efficiency of multiexciton emission over a wide span of distances, thus paving the way for new applications., The authors acknowledge the financial support from the Ministry of Education and Science of the Russian Federation (Grant 14.Y26.31.0011). Y.R. acknowledges support from MINECO (Ministerio de Economiá y Competitividad, Spain), Project Fis2016.80174-P (PLASMOQUANTA).

The photosensitive protein bacteriorhodopsin (bR) has been shown to be a promising material for optoelectronic and photovoltaic applications, but it cannot effectively absorb and utilize light energy in the near-infrared (NIR) region of the optical spectrum. Semiconductor quantum dots (QDs) have two-photon absorption cross-sections two orders of magnitude larger than those of bR and can effectively transfer the up-converted energy of two NIR photons to bR via the Forster resonance energy transfer (FRET). In this study we fabricated a hybrid material in the form of an aqueous solution of electrostatically bound complexes of QDs and purple membranes (PMs) containing bR. Efficient FRET from QDs to bR was observed in these complexes under selective two-photon excitation of QDs. Then, we fabricated a photoelectrochemical cell operating in the NIR spectral region. Measurement of the photoelectrical signals from the cell containing pure PMs, or QD–PM hybrid material has shown that the light conversion in the QD-PM hybrid material with 3:1 bR-to-QD molar ratio is more efficient than in the material with 20:1 bR-to-QD molar ratio. The results of this study may extend the use of bioinspired hybrid materials in optoelectronics, holography, and bioenergetics under the conditions of nonlinear excitation.

Semiconductor quantum dots (QDs) have high two-photon absorption cross-sections and long photoluminescence (PL) lifetimes, which make them a promising photosensitive part for fabrication of QD-based hybrid materials for two-photon bio-imaging, bio- and optoelectronics. In these areas, mode-locked femtosecond lasers are often used for two-photon excitation of QDs because of the high peak intensity of the laser pulse. However, the QD radiative lifetime usually exceeds the period between the laser pulses of such laser systems, which can affect the absorption and PL properties of QDs. In this work, we investigated the PL properties of CdSe/ZnS QDs under two-photon excitation. We have shown that using femtosecond laser excitation at a wavelength of 790 nm with a pulse repetition rate of 80 MHz and a peak intensity of more than 10 GW/cm2, the two-photon absorption in QD is saturated. However if QDs were in complexes with purple membranes (PM) containing the photosensitive protein bacteriorhodopsin (bR), saturation was not observed up to an intensity of about 27 GW/cm2. It was concluded that the difference in the saturation of two-photon absorption between QDs and QD-PM material is associated with the Forster resonance energy transfer from QD to bR and the corresponding shortening of the PL lifetime. The results obtained will allow to optimize the two-photon excitation regime of QD-PM nano-bio hybrid material which will expand the possible areas of its application in bio-imaging, bioand optoelectronics.

State-of-the-art research related to increasing the efficiency and reducing the cost of solar energy converters is analyzed. An approach to solving these issues is to introduce graphene and its derivatives into the photoactive layer of solar cells. These materials have record high charge carrier mobility at normal temperatures and low absorption cross-sections of solar radiation. The review considers chemical materials science methods and nanotechnology approaches to the design of 2D hybrid structures based on graphene and quantum dots. Examples of their most successful use in solar cells are given and promising areas of research and development in this field are formulated. The bibliography includes 173 references.

Semiconductor quantum dots (QDs) are known for their unique photophysical properties and, in particular, their ability to multiphoton emission caused by recombination of biexcitons. However, the luminescence quantum yield of biexciton states is relatively low due to the fast Auger non-radiative process. Plasmonic nanoparticles can significantly accelerate the radiative rate of QDs. In this study we demonstrate the distance-controlled enhancement of the biexciton emission of single CdSe/ZnS/CdS/ZnS QDs due to their coupling with gold nanorods. We explain this enhancement as the distancedependent trade-off between the energy transfer and the Purcell effect. Our findings constitute a reliable approach to managing the efficiency of multiphoton emission over a wide span of distances.

International audience; The photosensitive protein bacteriorhodopsin (bR) has been shown to be a promising material for optoelectronic applications, but it cannot effectively absorb and utilize light energy in the near-infrared (NIR) region of the optical spectrum. Semiconductor quantum dots (QDs) have two-photon absorption cross-sections two orders of magnitude larger than those of bR and can effectively transfer the up-converted energy of two NIR photons to bR via the Förster resonance energy transfer (FRET). In this study, we have engineered a photoelectrochemical cell based on a hybrid material consisting of QDs and bR-containing purple membranes (PMs) of Halobacterium salinarum and demonstrated that this cell can generate an electrical signal under the two-photon laser excitation. We have shown that the efficiency of light conversion by the PM–QD hybrid material under two-photon excitation is up to 4.3 times higher than the efficiency of conversion by PMs alone. The QD integration into the bR-containing PMs significantly improves the bR capacity for utilizing light upon two-photon laser excitation, thus paving the way to the engineering of biologically inspired hybrid NIR nonlinear optoelectronic elements. The nonlinear nature of two-photon excitation may provide considerable advantages, such as a sharp sensitivity threshold and the possibility of precise three-dimensional location of excitation in holography and optical computing.