Fluorescent imaging is widely used in the diagnosis and tracking of the distribution, interaction, and transformation processes at molecular, cellular, and tissue levels. To be detectable, delivery systems should exhibit a strong and bright fluorescence. Quantum dots (QDs) are highly photostable fluorescent semiconductor nanocrystals with wide absorption spectra and narrow, size-tunable emission spectra, which make them suitable fluorescent nanolabels to be embedded into microparticles used as bioimaging and theranostic agents. The layer-by-layer deposition approach allows the entrapping of QDs, resulting in bright fluorescent microcapsules with tunable surface charge, size, rigidity, and functional properties. Here, we report on the engineering and validation of the structural and photoluminescent characteristics of nanoparticle-doped hybrid microcapsules assembled by the deposition of alternating oppositely charged polyelectrolytes, water-soluble PEGylated core/shell QDs with a cadmium selenide core and a zinc sulfide shell (CdSe/ZnS), and carboxylated magnetic nanoparticles (MNPs) onto calcium carbonate microtemplates. The results demonstrate the efficiency of the layer-by-layer approach to designing QD-, MNP-doped microcapsules with controlled photoluminescence properties, and pave the way for the further development of next-generation bioimaging agents based on hybrid materials for continuous fluorescence imaging.

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 nanostructures. 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 Conclusions and outlook section.

In photovoltaic cells based on PbS colloidal quantum dot (CQD) solids, the photoconductivity and efficiency for PbS CQDs with inorganic atomic ligands of tetrabutylammonium iodide (TBAI) are reasonably larger than those for PbS CQDs with molecular ligands of the same length. The TBAI ligands can act as electron-transporting sites and contribute to the increase in mobility. The developed simple model allows the maximum efficiency of a CQD solar cell to be determined, which can be achieved by eliminating the recombination losses of charge carriers. Both experimental data and theoretical modeling testify in favor of the hopping nature of the electron transport in CQD-solids.

Colloidal quantum dots (QDs) are a promising luminescent material for the development of next generation hybrid light-emitting diodes (QDLEDs). In particular, QDs are of great interest in terms of the development of solid-state light sources with an emission spectrum that mimics daylight. In this study, we used CdSe(core)/ZnS/CdS/ZnS(shell) QDs with organic ligands mimicking polyfluorene and its modified derivatives to obtain QD–polymer composites emitting white light. We found that the emission of the composites obtained by spin-coating, being strongly dependent on the chemical structure of the polymer matrix and the QD-to-polymer mass ratio, can be accurately controlled and adjusted to bring its emission spectrum close to the spectrum of daylight (CIE coordinates: 1931 0.307; 0.376). Moreover, the light emission of these composites has been found to be temporally stable, which is due to the minimal structural instability and volume-uniform charge and energy transfer properties. Thus, the use of the synthesized polyfluorene-based organic ligands with controllable chemical structures adaptable to the structure of the polymer matrix can significantly increase the stability of white light emission from QD composites, which can be considered promising electroluminescent materials for fabrication of white QDLEDs.

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.

Colloidal quantum dots and other semiconductor nanocrystals are essential components of next-generation lighting and display devices. Due to their easily tunable and narrow emission band and near-unity fluorescence quantum yield, they allow cost-efficient fabrication of bright, pure-color and wide-gamut light emitting diodes (LEDs) and displays. A critical improvement in the quantum dot LED (QLED) technology was achieved when zinc oxide nanoparticles (NPs) were first introduced as an electron transport layer (ETL) material, which tremendously enhanced the device brightness and current efficiency due to the high mobility of electrons in ZnO and favorable alignment of its energy bands. During the next decade, the strategy of ZnO NP doping allowed the fabrication of QLEDs with a brightness of about 200 000 cd/m2 and current efficiency over 60 cd/A. On the other hand, the known ZnO doping approaches rely on a very fine tuning of the energy levels of the ZnO NP conduction band minimum; hence, selection of the appropriate dopant that would ensure the best device characteristics is often ambiguous. Here we address this problem via detailed comparison of QLEDs whose ETLs are formed by a set of ZnO NPs doped with Al, Ga, Mg, or Li. Although magnesium-doped ZnO NPs are the most common ETL material used in recently designed QLEDs, our experiments have shown that their aluminum-doped counterparts ensure better device performance in terms of brightness, current efficiency and turn-on voltage. These findings allow us to suggest ZnO NPs doped with Al as the best ETL material to be used in future QLEDs.

A study is made of the effect a surface ligand’s molecules have on the photoconductivity and photovoltaic effect in thin solid layers of structures based on PbS quantum dots. Thin solid layers are prepared of both quantum dots and bulk heterojunctions of a blend of quantum dots and fullerene derivative ([6,6]-phenyl-C(61)butyric acid ester (PCBM)). An exponential dependence of photoconductivity on the length of ligands is obtained for the quantum dot films, and the photovoltaic effect displays a strong dependence on the length of a ligand. In contrast, the effect the length of a ligand has on current–voltage characteristics and charge carrier mobility was not observed in bulk heterojunction structures with quantum dots. Physical reasons for the observed phenomena are discussed.

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 CuInS 2 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.

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.

AbstractPlasmonic 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 CuInS_2 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.

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.

The quantum dot (QD) solids are promising materials for use in electronics. We studied the effect of variations in the length of organic ligands on the optical properties of PbS QD solids from the measurements of photoluminescence spectra and decay kinetics. The decay is becoming exponentially faster along with the decrease of the length of ligand molecules, which is consistent with the decay of excitons by hopping of charge carriers.

We study the influence of various organic molecules of ligands on the optical properties of the condensates of lead sulfide quantum dots (QD) and photoconductivity of diode structures made on their basis. It is shown that the decrease of the molecule length of surface ligands by a factor of 4 leads to the significant increase in the conductivity, and the emergence of photocurrent. We also demonstrate that the thickness of the photoactive QD layer plays an important role in the performances of photovoltaic cells.

In the last decade, colloidal semiconductor nanocrystals (quantum dots) have been not only studied fundamentally but also applied in photovoltaics, optoelectronics, and biomedicine. Beginning with simple approaches to the deposition of protective shells, e.g., ZnS on CdSe cores, searches for ways to increase the quantum yield of photoluminescence of quantum dots have resulted now in the development of new types of quantum dots characterized not only by record high extinction coefficients but also by high photoluminescence quantum yields. In this work, the optical properties of core–multishell quantum dots have been analyzed. These quantum dots have been specially designed to reach the maximum possible localization of excited charge carriers inside luminescent cores, which makes it possible to reach a photoluminescence quantum yield close to 100%. Core–multishell quantum dot samples with a shell thickness of 3–7 monolayers have been fabricated. Changes in the characteristics of optical transitions in such quantum dots with an increase in the number of layers of the shell have been studied. The effect of the thickness of the shell on the optical properties of prepared quantum dots has been analyzed. In particular, analysis of photoluminescence lifetimes of such quantum dots has revealed a possible alternative mechanism of radiation of core–multishell quantum dots based on the slow charge carrier transfer from the excited outer layer of the CdS shell to the CdSe core.

AbstractThe photoconductivity of condensates of lead-sulfide quantum dots (QDs)—QD solids—with various organic ligands is studied. It is demonstrated that the QD solid photoconductivity increases exponentially with a reduction in length of ligand molecules and does not depend on their chemical structures, since it is governed by hopping transport of charge carriers. In contrast, the photocurrent in photovoltaic ITO/PEDOT: PSS/PbS/ZnO/Al elements depends on the ligand structure, since this structure sets the positions of QD energy levels and thus affects the efficiency of charge carrier transfer to electrodes. The difference between mechanisms of generation of photoconductivity and photovoltaic currents is discussed.

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.

The photoconductivity of condensates of lead-sulfide quantum dots (QDs)QD solidswith various organic ligands is studied. It is demonstrated that the QD solid photoconductivity increases exponentially with a reduction in length of ligand molecules and does not depend on their chemical structures, since it is governed by hopping transport of charge carriers. In contrast, the photocurrent in photovoltaic ITO/PEDOT: PSS/PbS/ZnO/Al elements depends on the ligand structure, since this structure sets the positions of QD energy levels and thus affects the efficiency of charge carrier transfer to electrodes. The difference between mechanisms of generation of photoconductivity and photovoltaic currents is discussed.