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Experimental data and data from theoretical simulations for Figures 1-5 in the main text of the submitted manuscript.

Generally adopted design strategies for enhancing the photocatalytic activity are aimed at tuning properties such as the visible light response, the exposed crystal facets, and the nanocrystal shape. Here, we present a different approach for designing efficient photocatalysts displaying a substrate-specific reactivity upon defect engineering. The defective anisotropic brookite TiO2 photocatalyst functionalized with Pt nanocrystals are tested for alcohol photoreforming showing up to an 11-fold increase in methanol oxidation rate, compared to the unreduced one, whilst presenting much lower ethanol or isopropanol specific oxidation rates. We demonstrate that the alcohol oxidation and hydrogen evolution reactions are tightly related, and when the substrate-specific alcohol oxidation ability is increased, the hydrogen evolution is significantly boosted. The reduced anisotropic brookite shows up to twenty-six-fold higher specific photoactivity with respect to anatase and brookite with isotropic nanocrystals, reflecting the different type of defective catalytic sites formed depending on the TiO2 polymorph and its crystal shape. Advanced in-situ characterizations and theoretical investigations reveal that controlled engineering over oxygen vacancies and lattice strain produces large electron polarons hosting the substrate-specific active sites for alcohol photo-oxidation.

Doping and compositional tuning of Cs(2)AInCl(6) (A = Ag, Na) double perovskite nanocrystals (PNCs) is considered a promising strategy toward the development of light-emitting sources for applications in solution-processed optoelectronic devices. Oleic acid and oleylamine are by far the most often used surface capping ligands for PNCs. However, the undesirable desorption of these ligands due to proton-exchange reaction during isolation and purification processing results in colloidal and structural instabilities. Thus, the improvement of colloidal and optical stability of PNCs represents one of the greatest challenges in the field. Here, we report a trioctylphosphine-mediated synthesis and purification method toward Sb-alloyed Cs2NaInCl6 PNCs with excellent stability and optical features. Nuclear magnetic resonance spectroscopy enabled one to explain the role of trioctylphosphine and to reveal the reaction mechanism during crystal nucleation and growth. Under the optimized reaction conditions, in situ-generated trioctylphosphonium chloride and benzoyl trioctylphosphonium chloride serve as highly reactive halide sources, while benzoyl trioctylphosphonium and oleylammonium cations together with the oleate anion serve as surface capping ligands, which are bound strongly to the PNC surface. The tightly bound ionic pair of oleylammonium oleate and benzoyl trioctylphosphonium chloride/oleate ligands allows one to obtain monodispersed bright-blue-emitting PNCs with high photoluminescence quantum yields exceeding 50% at an optimum Sb content (0.5%), which also exhibit long-term colloidal stability. The approach based on dual cationic ligand passivation of double PNCs opens the doors for applications in other systems with a potential to achieve higher stability along with superior optical properties. Web of Science 13 40 47859 47845

Luminescent solar concentrators (LSCs) are light-harvesting devices that redirect solar light to an edge-attached photovoltaic cell, and thus, they have high potential to be incorporated directly into buildings’ windows to allow for generating electricity. Perovskite nanocrystals (PNCs) are promising materials for LSCs because their enticing optical properties can be engineered to provide a high photoluminescence (PL) quantum yield (QY) and low overlap between absorption and emission spectra. Replacement of toxic, lead-containing perovskites in LSCs by lead-free PNCs, while retaining high optical efficiency of the device, remains the key challenge, which needs to be overcome to build environmentally friendly solar-harvesting platforms. In this work, we use nanocrystals of Bi-doped Cs2Ag0.4Na0.6InCl6 double perovskites with a self-trapped exciton emission to realize for the first time a transparent, low-reabsorption, lead-free perovskite-based LSC. Fabricated 100 cm2 LSCs show an internal optical quantum efficiency of 21.2% with the corresponding internal concentration factor of 2.7. Monte Carlo (MC) ray-tracing simulations identified the loss caused by nonunity PL QY to be the most significant contribution to the overall efficiency loss. The MC simulations also allowed us to estimate the efficiency of 39.4% for 2,500 cm2 LSCs with hypothetical unity PL. These results demonstrate a significant promise held by Bi-doped lead-free PNCs for LSCs.

Highly fluorescent carbon nanoparticles called carbon dots (CDs) have been the focus of intense research due to their simple chemical synthesis, nontoxic nature, and broad application potential including optoelectronics, photocatalysis, biomedicine, and energy-related technologies. Although a detailed elucidation of the mechanism of their photoluminescence (PL) remains an unmet challenge, the CDs exhibit robust, reproducible, and environment-sensitive PL signals, enabling us to monitor selected chemical phenomena including phase transitions or detection of ultralow concentrations of molecular species in solution. Herein, we report the PL turn-off/on behavior of aqueous CDs allowing the reversible monitoring of the water-ice phase transition. The bright PL attributable to molecular fluorophores present on the CD surface was quenched by changing the liquid aqueous environment to solid phase (ice). Based on light-induced electron paramagnetic resonance (LEPR) measurements and density functional theory (DFT) calculations, the proposed kinetic model assuming the presence of charge-separated trap states rationalized the observed sensitivity of PL lifetimes to the environment. Importantly, the PL quenching induced by freezing could be suppressed by adding a small amount of alcohols. This was attributed to a high tendency of alcohol to increase its concentration at the CD/solvent interface, as revealed by all-atom molecular dynamics simulations. Based on this behavior, a fluorescence "turn-on" alcohol sensor for exhaled breath condensate (EBC) analysis has been developed. This provided an easy method to detect alcohols among other common interferents in EBC with a low detection limit (100 ppm), which has a potential to become an inexpensive and noninvasive clinically useful diagnostic tool for early stage lung cancer screening.

Improving the effectiveness of cancer therapy will require tools that enable more specific cancer targeting and improved tumor visualization. Theranostics have the potential for improving cancer care because of their ability to serve as both diagnostics and therapeutics; however, their diagnostic potential is often limited by tissue-associated light absorption and scattering. Herein, we develop CuInSe

Luminescent solar concentrators (LSCs) are light-management devices and are used for harvesting and concentrating solar light from a large area to their edges. Being semitransparent devices, LSCs show great promise for future utilization in glass walls of urban buildings as environmentally friendly photovoltaic power plants. The development of cheap and eco-safe materials, the extension of the LSC operation range, and the enhancement of the optical efficiency are the key challenges, which need to be solved in order to transform energetically passive buildings into self-sustainable units. Herein, a large area (64 cm2) tandem LSC fabricated using entirely eco-friendly highly emissive blue, green, and red carbon dots is demonstrated, with an internal optical quantum efficiency of 23.6% and an external optical quantum efficiency of 2.3%, while maintaining a high transparency across the visible spectrum. This opens up a new direction for the application of carbon dots in advanced solar light harvesting technologies.

Doping and compositional tuning of Cs

Highly fluorescent carbon nanoparticles called carbon dots (CDs) have been the focus of intense research due to their simple chemical synthesis, nontoxic nature, and broad application potential including optoelectronics, photocatalysis, biomedicine, and energy-related technologies. Although a detailed elucidation of the mechanism of their photoluminescence (PL) remains an unmet challenge, the CDs exhibit robust, reproducible, and environment-sensitive PL signals, enabling us to monitor selected chemical phenomena including phase transitions or detection of ultralow concentrations of molecular species in solution. Herein, we report the PL turn-off/on behavior of aqueous CDs allowing the reversible monitoring of the water-ice phase transition. The bright PL attributable to molecular fluorophores present on the CD surface was quenched by changing the liquid aqueous environment to solid phase (ice). Based on light-induced electron paramagnetic resonance (LEPR) measurements and density functional theory (DFT) calculations, the proposed kinetic model assuming the presence of charge-separated trap states rationalized the observed sensitivity of PL lifetimes to the environment. Importantly, the PL quenching induced by freezing could be suppressed by adding a small amount of alcohols. This was attributed to a high tendency of alcohol to increase its concentration at the CD/solvent interface, as revealed by all-atom molecular dynamics simulations. Based on this behavior, a fluorescence "turn-on" alcohol sensor for exhaled breath condensate (EBC) analysis has been developed. This provided an easy method to detect alcohols among other common interferents in EBC with a low detection limit (100 ppm), which has a potential to become an inexpensive and noninvasive clinically useful diagnostic tool for early stage lung cancer screening.

Two-dimensional (2D) layered hybrid bromoplumbate perovskites are promising candidates for solution-processed light-emitting materials. Here, we report the synthesis and characterization of two novel layered bromoplumbates: (4BrPhMA)(2)PbBr4 (1) and (4BrPhA)(6)Pb3Br12 (2), where 4BrPhMA is (4-bromophenyl)methylammonium and 4BrPhA is (4-bromophenyl) ammonium. Despite similar optical absorption, these materials show remarkably different photoluminescence properties: 1 emits a narrow exciton band at ca. 395 nm with a very small bandwidth (particularly at low temperatures of 1550 K) and Stokes shift, while 2 exhibits a broad emission at ca. 560 nm with a large Stokes shift, both at low and ambient temperatures. However, under several kbar of hydrostatic pressure, the broad emission diminishes and a new band reversibly develops at ca. 395 nm, similar to that in 1. Our results emphasize organic layer flexibility as an important design factor for this class of perovskite-like materials featuring broadband emission.

Epitaxially growing a semiconductor shell on the surface of upconversion nanocrystals to form a core/shell structure is believed to be a promising strategy to improve the luminescent efficiency of lanthanide ions doped in particle cores and, meanwhile, enriches the optical properties of the resulting nanocrystals. However, liquid-phase synthesis of such core/shell-structured nanocrystals comprised of a lanthanide ion-doped core and semiconductor shell remains challenging because of the chemical incompatibilities between lanthanides and the most intermediate gap semiconductors. In this context, the successful growth of ZnS shell on a KMnF

Targeted therapies of various diseases are nowadays widely studied in many biomedical fields. Photodynamic therapy (PDT) represents a modern treatment of cancer using a locally activated light. TMPyP is an efficient synthetic water-soluble photosensitizer (PS), yet with poor absorption in the visible and the red regions. In this work, we prepared size-selected and colloidally stable graphene oxide (GO) that is appropriate for biomedical use. Thanks to the negative surface charge of GO, TMPyP was easily linked in order to create conjugates of GO/TMPyP by electrostatic force. Due to the strong ionic interactions, charge transfers between GO and TMPyP occur, as comprehensively investigated by steady-state and time-resolved fluorescence spectroscopy. Biocompatibility and an in vitro effect of GO/TMPyP were confirmed by a battery of in vitro tests including MTT, comet assay, reactive oxygen species (ROS) production, and monitoring the cellular uptake. PDT efficiency of GO/TMPyP was tested using 414 and 740 nm photoexcitation. Our newly prepared nanotherapeutics showed a higher PDT effect than in free TMPyP, and is promising for targeted therapy using clinically favorable conditions.

Carbon dots (CDs) rank among the most promising luminescent nanomaterials for anti-counterfeiting application owing to their high fluorescence quantum yield and nontoxicity. Herein, we report a novel, high-level security performance anti-counterfeiting strategy achieved by fluorescence-lifetime-encoded CD fluorescent inks. CD-inks have identical steady-state emission properties, but they have distinctive and well-separated fluorescence lifetimes, allowing authentication of security tags using exclusively fluorescence lifetime imaging. A proof-of-concept anti-counterfeiting tag using CD-based lifetime-encoded inks is demonstrated. The developed CD lifetime-based anti-counterfeit technology is awaited to be applicable to a wide spectrum of security-protecting purposes. Furthermore, the presented method can be easily extended to integrate fluorescence-lifetime-encoded CDs in multichannel bioimaging, high-throughput flow cytometry, and optical data storage.

Photocatalysts based on glutathione-protected Au clusters (1.5 ± 0.4 nm) were synthesized and assessed for the visible-light degradation of ten different endocrine-disrupting chemicals (EDCs) and related compounds. In its as-prepared form, the Au clusters undergo rapid photocharge recombination resulting in no appreciable photocatalytic activity. Coupling with non-activated TiO 2 acceptor was necessary to achieve efficient interfacial charge separation that allowed the photocharges on the Au clusters to be effectively harvested for surface redox reactions. Under visible light excitation, the Au cluster undergoes ligand-to-metal charge transfer and resulting in the accumulation of photohole on the glutathione ligand (i.e., the HOMO state). The transfer of photoholes to the hydrogen-bonded EDCs is identified as the main oxidation pathway. The hole transfer oxidation, which was probably complemented by superoxide radicals attack, was necessary since the low HOMO level of the Au clusters (+1.21 V vs. RHE, pH 0) disallowed the production of hydroxyl radicals (+2.68 V vs. RHE, pH 0). As such, the photocatalytic degradation rates of EDCs are in accordance with the trend of Langmuir adsorption capacities. Lastly, we demonstrated the high reusability of the Au cluster/TiO 2 photocatalyst, retaining 96% of the initial activity even after 5 repeated cycles or equivalent to 25 h of continuous irradiation.

Metal halide perovskite nanocrystals are promising materials for a diverse range of applications, such as light-emitting devices and photodetectors. We demonstrate the bandgap tunability of strongly emitting CH3NH3PbBr3 nanocrystals synthesized at both room and elevated (60 °C) temperature through the variation of the precursor and ligand concentrations. We discuss in detail the role of two ligands, oleylamine and oleic acid, in terms of the coordination of the lead precursors and the nanocrystal surface. The growth mechanism of nanocrystals is elucidated by combining the experimental results with the principles of nucleation/growth models. The proposed formation mechanism of perovskite nanocrystals will be helpful for further studies in this field and can be used as a guide to improve the synthetic methods in the future., The development of perovskite nanocrystals is limited by poor mechanistic understanding of their growth. Here, the authors systematically study the ligand-assisted reprecipitation synthesis of CH3NH3PbBr3 nanocrystals, revealing the effect of precursor and ligand concentrations on bandgap tunability.

We present the first bottom-up approach to synthesize Fe(III)-functionalized carbon dots (CDs) from molecular precursors without the need of conventional thermal or microwave treatment and additional reagents. Specifically, sonication of xylene in the presence of anhydrous FeCl 3 results in oxidative coupling of the aromatic substrate towards Fe(III)-functionalized CDs. The as-prepared CDs are spherical in shape with a size of 3–8 nm, highly dispersible in organic solvents and display wavelength-dependent photoluminescence (PL). The iron ions attached to the surface endow the CDs with superior catalytic activity for olefin hydrogenation with excellent conversion and selectivity (up to 100%). The Fe(III)-CDs are more effective in the hydrogenation of a series of electron donating or withdrawing olefin substrates compared to conventional homogeneous or heterogeneous Fe(III)-based catalysts. The as-prepared heterogeneous nanocatalyst can be used repeatedly without any loss of catalytic activity. Importantly, the stability of the new catalysts can be easily monitored by PL intensity or quantum yield measurements, which certainly opens the doors for real time monitoring in a range of applications. Additionally, to the best of our knowledge, for the first time, the oxidative property of Fe-CDs was also explored in decomposition of hydrogen peroxide in water with the first order rate constant of 0.7 × 10 −2 min −1 , proving the versatile catalytic properties of such hybrid systems.

Solid-state luminophores operating in the near-infrared (NIR) region may have applications in sensing, communication, and medicine. We report environmentally protected solid-state NIR-emitting luminophores fabricated by embedding CdHgTe colloidal quantum dots (QDs) into a NaCl matrix, with remarkable photo- and thermal stability and a photoluminescence quantum yield of 31% in the solid state, which is among the highest reported for solid-state NIR luminophores so far. We employed this luminophore as a down-conversion layer in a NIR-light-emitting device with a stable emission at 940 nm. Carrier recombination dynamics of the CdHgTe QDs@NaCl powders are examined as a function of temperature using steady-state and transient photoluminescence spectroscopy, and characteristic parameters such as the band gap, the temperature coefficient, the Debye temperature, the activation energy of thermal quenching, and radiative and nonradiative recombination rates are derived. Temperature-dependent changes of the spectral...

In this study, we report fluorescent organic nanoprobes with intense blue, green, and orange-red emissions prepared by self-assembling three carbazole derivatives into nanorods/nanoparticles. The three compounds consist of two or four electron-donating carbazole groups linked to a central dicyanobenzene electron acceptor. Steric hindrance from the carbazole groups leads to noncoplanar 3D molecular structures favorable to fluorescence in the solid state, while the donor-acceptor structures endow the molecules with good two-photon excited emission properties. The fluorescent organic nanoprobes exhibit good water dispersibility, low cytotoxicity, superior resistance against photodegradation and photobleaching. Both one- and two-photon fluorescent imaging were shown in the A549 cell line. Two-photon fluorescence imaging with the fluorescent probes was demonstrated to be more effective in visualizing and distinguishing cellular details compared to conventional one-photon fluorescence imaging.

We have studied light emission kinetics and analyzed carrier recombination channels in HgTe quantum dots that were initially grown in H2O. When the solvent is replaced by D2O, the nonradiative recombination rate changes highlight the role of the vibrational degrees of freedom in the medium surrounding the dots, including both solvent and ligands. The contributing energy loss mechanisms have been evaluated by developing quantitative models for the nonradiative recombination via (i) polaron states formed by strong coupling of ligand vibration modes to a surface trap state (nonresonant channel) and (ii) resonant energy transfer to vibration modes in the solvent. We conclude that channel (i) is more important than (ii) for HgTe dots in either solution. When some of these modes are removed from the relevant spectral range by the H2O to D2O replacement, the polaron effect becomes weaker and the nonradiative lifetime increases. Comparisons with CdTe quantum dots (QDs) served as a reference where the resonant energy loss (ii) a priori was not a factor, also confirmed by our experiments. The solvent exchange (H2O to D2O), however, is found to slightly increase the overall quantum yield of CdTe samples, probably by increasing the fraction of bright dots in the ensemble. The fundamental study reported here can serve as the foundation for the design and optimization principles of narrow bandgap quantum dots aimed at applications in long wavelength colloidal materials for infrared light emitting diodes and photodetectors.

There was tested a simple extraction procedure of flavonoids separation from the original corn silk (CS) material. It was found, that the total flavonoids content differs with the extraction time and extraction temperature. There were found different flavonoids contents in extracts prepared from different maturity stages of the original corn silk material (silking stage (CS-S), milky stage (CS-M)). Extracted flavonoids content was quantified by the lutin standardization method by means of colorimetry at 510 nm wavelength. Obsreved flavonoids concentration was ranging from 2×10-3 mg.mL-1 to 7 ×10-3 mg.mL-1 dependent on the extraction time period and extraction temperature. The highest flavonoids concentration of 7.5×10-3 mg.mL-1 was found for CS-M after 20 minutes extraction time and 80 °C extraction temperature. There was confirmed the presence of flavonoids by fluorescence mapping experiments. There was found a typical multistep decomposition process for both CS-S and CS-M materials by TG analysis. There was found a melting temperature of flavonoids of 54.3 °C for corn silk silking stage material exhibiting 58.9 J.g-1 heat of fusion and 60.2 °C for corn silk milky stage material with 112.9 J.g-1 heat of fusion. The optimal conditions of corn silk flavonoids extraction were 40 ℃, 50 minutes for CS-S, the optimal flavonoids extraction content was (6.8 ±2.1)×10-3 mg.mL-1, 80℃, 20 minutes for CS-M and the optimal extraction content was (7.2 ±0.3)×10-3 mg.mL-1.

Graphene derivatives are promising candidates as electrode materials in supercapacitor cells, therefore, functionalization strategies are pursued to improve their performance. A scalable approach is reported for preparing a covalently and homogenously functionalized graphene with iron tetraaminophthalocyanine (FePc-NH2) with a high degree of functionalization. This is achieved by exploiting fluorographene’s reactivity with the diethyl bromomalonate, producing graphene-dicarboxylic acid after hydrolysis, which is conjugated with FePc-NH2. The material exhibits an ultrahigh gravimetric specific capacitance of 960 F g−1 at 1 A g−1 and zero losses upon charging–discharging cycling. The energy density of 59 Wh kg−1 is eminent among supercapacitors operating in aqueous electrolytes with graphene-based electrode materials. This is attributed to the structural and functional synergy of the covalently bound components, giving rise to a zwitterionic surface with extensive π–π stacking, but not graphene restacking, all being very beneficial for charge and ionic transport. The safety of the proposed system, owing to the benign Na2SO4 aqueous electrolyte, the high capacitance, energy density, and potential of preparing the electrode material on a large-scale and at low cost make the reported strategy very attractive for development of supercapacitors based on the covalent attachment of suitable molecules onto graphene toward high synergy hybrids.

Carbon dots (CDs) are a stable and highly biocompatible fluorescent material offering great application potential in cell labeling, optical imaging, LED diodes, and optoelectronic technologies. Because their emission wavelengths provide the best tissue penetration, red-emitting CDs are of particular interest for applications in biomedical technologies. Current synthetic strategies enabling red-shifted emission include increasing the CD particle size (sp2 domain) by a proper synthetic strategy and tuning the surface chemistry of CDs with suitable functional groups (e.g., carboxyl). Here we present an elegant route for preparing full-color CDs with well-controllable fluorescence at blue, green, yellow, or red wavelengths. The two-step procedure involves the synthesis of a full-color-emitting mixture of CDs from citric acid and urea in formamide followed by separation of the individual fluorescent fractions by column chromatography based on differences in CD charge. Red-emitting CDs, which had the most negat...

Hybrid nanostructures combining semiconductor quantum dots and graphene are attracting increasing attention because of their optoelectronic properties promising for photovoltaic applications. We present a hot-injection synthesis of a colloidal nanostructure which we define as quasi core/shell PbS/graphene quantum dots due to the incomplete passivation of PbS surfaces with an ultrathin layer of graphene. Simulation by density functional theory of a prototypical model of a nonstoichiometric Pb-rich core (400 atoms) coated by graphene (20 atoms for each graphene sheet) indicates the possibility of surface passivation of (111) planes of PbS with graphene resulting in a decrease in trap states and recombination sites. The graphene coating of the PbS quantum dots decreases the exciton lifetime up to 0.78 μs as compared to 1.2 μs for the oleic acid passivated PbS quantum dots due to the fast extraction of carriers. We have employed PbS/graphene as well as Cd-doped PbS/graphene quantum dots as active layers of bu...

The effect of microwave radiation on the luminescence properties of CdS and CdTe:Cl single crystals is studied. It is established that the exposure of these semiconductors to short-term (≤30 s) microwave radiation substantially modifies their impurity and defect structure. The mechanisms of transformation of the defect subsystem of II–VI single crystals upon microwave treatment are discussed. It is shown that the experimentally observed changes are defined by the nonthermal effects of microwave radiation at a power density of 7.5 W cm–2; at 90 W cm–2, nonthermal effects are prevailing.

Graphitic carbon nitride (g-CN) films are important components of optoelectronic devices, but current techniques for their production, such as drop casting and spin coating, fail to deliver uniform and pinhole-free g-CN films on solid substrates. Here, versatile, cost-effective, and large-area growth of uniform and pinhole-free g-CN films is achieved by using a thermal vapor condensation method under atmospheric pressure. A comparison of the X-ray diffraction and Fourier transform infrared data with the calculated infrared spectrum confirmed the graphitic build-up of films composed of tri-s-triazine units. These g-CN films possess multiple active energy states including π*, π, and lone-pair states, which facilitate their efficient (6 % quantum yield in the solid state) photoluminescence, as confirmed by both experimental measurements and theoretical calculations.

The impact of strain on the optical properties of semiconductor quantum dots (QDs) is fundamentally important while still awaiting detailed investigation. CdTe/CdS core/shell QDs represent a typical strained system due to the substantial lattice mismatch between CdTe and CdS. To probe the strain-related effects, aqueous CdTe/CdS QDs were synthesized by coating different sized CdTe QD cores with CdS shells upon the thermal decomposition of glutathione as a sulfur source under reflux. The shell growth was carefully monitored by both steady-state absorption and fluorescence spectroscopy and transient fluorescence spectroscopy. In combination with structural analysis, the band alignments as a consequence of the strain were modified based on band deformation potential theory. By further taking account of these strain-induced band shifts, the effective mass approximation (EMA) model was modified to simulate the electronic structure, carrier spatial localization, and electron-hole wave function overlap for comparing with experimentally derived results. In particular, the electron/hole eigen energies were predicted for a range of structures with different CdTe core sizes and different CdS shell thicknesses. The overlap of electron and hole wave functions was further simulated to reveal the impact of strain on the electron-hole recombination kinetics as the electron wave function progressively shifts into the CdS shell region while the hole wave function remains heavily localized in CdTe core upon the shell growth. The excellent agreement between the strain-modified EMA model with the experimental data suggests that strain exhibits remarkable effects on the optical properties of mismatched core/shell QDs by altering the electronic structure of the system.

A new method for formation of the cross-linked polymer films at the solid surface as well as the thin nanocomposite films based on them with embedded CdS nanocrystals is reported in this paper. The process involves several stages, namely, (i) thin polymer film formation on glass slide by spin coating of an organic solution of reactive peroxide-containing copolymer (RC), polyethylene glycols (PEG) of various molecular weight, and cadmium acetate [Cd(Ac)2] as nanocrystal precursor; (ii) melting and cross-linking of the polymer film; and (iii) synthesis of CdS nanocrystals inside the polymer film via sol–gel technique. The X-ray diffraction analysis and UV–visible spectroscopy prove formation of the CdS nanocrystals in the thin polymer films. This method allows forming multilayered nanocomposite films with tuned properties. The obtained results reveal that size of the CdS nanocrystals and optical properties (absorption and photoluminescence spectra) of the nanocomposite films depend on the nature of polymer matrix, PEG/RC ratio, Cd(Ac)2 concentration, and the number of layers composing the films.

Nanoscale biocompatible photoluminescence (PL) thermometers that can be used to accurately and reliably monitor intracellular temperatures have many potential applications in biology and medicine. Ideally, such nanothermometers should be functional at physiological pH across a wide range of ionic strengths, probe concentrations, and local environments. Here, we show that water-soluble N,S-co-doped carbon dots (CDs) exhibit temperature-dependent photoluminescence lifetimes and can serve as highly sensitive and reliable intracellular nanothermometers. PL intensity measurements indicate that these CDs have many advantages over alternative semiconductor- and CD-based nanoscale temperature sensors. Importantly, their PL lifetimes remain constant over wide ranges of pH values (5–12), CD concentrations (1.5 × 10–5 to 0.5 mg/mL), and environmental ionic strengths (up to 0.7 mol·L–1 NaCl). Moreover, they are biocompatible and nontoxic, as demonstrated by cell viability and flow cytometry analyses using NIH/3T3 and...

A number of different composition CdxHg1-xTe alloy quantum dots have been synthesized using a modified aqueous synthesis and ion exchange method. The benefits of good stoichiometric control and high emission quantum yield were retained whilst also ensuring that the tendency to form gel-like clusters and adsorb excess cations in the stabilizing ligand shells was mitigated using a sequestering method to remove excess ionic material during and after the synthesis. This was highly desirable for ultrafast carrier dynamics measurements, avoiding strong photocharging effects which may mask fundamental carrier signals. Transient grating measurements revealed a composition dependent carrier multiplication process which competes with phonon mediated carrier cooling to deplete the initial hot carrier population. The interplay between these two mechanisms is strongly dependent on the electron effective mass which in these alloys has a marked composition dependence and may be considerably lower than the hole effective mass. For a composition x = 0.52 we measured a maximum carrier multiplication quantum yield of 199 ± 19% with pump photon energy 3 times the bandgap energy, Eg, whilst the threshold energy is calculated to be just 2.15Eg. There is some evidence to suggest an impact ionization process analogous to the inverse Auger S mechanism seen in bulk CdxHg1-xTe.

Multicolor luminescent materials are of immense importance nowadays, while it still constitutes a challenge to achieve luminescence color tunability, transparency, and flexibility at the same time. Here we show how ultrasmall carbon dots (CDs) fluorescing strongly across the visible spectrum can be surface functionalized and incorporated into highly flexible hybrid materials by combination with ionic liquids within silica gel networks to form CD-ionogels with properties promising for fabrication of flexible displays and other optical technologies without the use of any toxic materials. We demonstrate how the emission from such hybrid materials can be tuned across a large range of the Commission Internationale de l'Enclairage (CIE) display gamut giving full-color performance. We highlight how the rich ladder of emissive states attributable to organic functional groups and CD surface functionalization supports a smooth sequential multiple self-absorption tuning mechanism to red shift continuously from blue emitting n-π* transitions down through the lower energy states.

A simple optical model is presented to describe the influence of a planar luminescent down-shifting layer (LDSL) on the external quantum efficiencies of photovoltaic solar cells. By employing various visible light-emitting LDSLs based on CdTe quantum dots or CdSe/CdS core–shell quantum dots and tetrapods, we show enhancement in the quantum efficiencies of thin-film CdTe/CdS solar cells predominantly in the ultraviolet regime, the extent of which depends on the photoluminescence quantum yield (PLQY) of the quantum dots. Similarly, a broad enhancement in the quantum efficiencies of crystalline Si solar cells, from ultraviolet to visible regime, can be expected for an infrared emitting LDSL based on PbS quantum dots. A PLQY of 80% or higher is generally required to achieve a maximum possible short-circuit current increase of 16 and 50% for the CdTe/CdS and crystalline Si solar cells, respectively. As also demonstrated in this work, the model can be conveniently extended to incorporate LDSLs based on organic ...

Incorporation of fluorescein dye molecules into layered double hydroxide (LDH) nanoparticles to form nanocomposites has great potential for optical and biological applications. Herein, we report a novel highly luminescent covalently bonded LDH–sodium fluorescein dye nanohybrid. This nanocomposite shows a significantly higher quantum yield (QY) of 55.1% than the nanohybrids prepared using the previously reported anion exchange (3.0%) and coprecipitation (12.4%) approaches. Our LDH–sodium fluorescein nanohybrid is superior to the pure fluorescent dye from a number of perspectives. Firstly, the nanohybrid exhibits excellent linearity between the fluorescence intensity and the concentration in a certain range. Secondly, the nanohybrid remains fluorescent even in a dry powder form. Thirdly, the nanohybrid can self-assemble into a transparent and free-standing film which is fluorescent under UV, which will lead to important applications in optical devices.

⁡Carbon-dot based light-emitting diodes (LEDs) with driving current controlled color change are reported. These devices consist of a carbon-dot emissive layer sandwiched between an organic hole transport layer and an organic or inorganic electron transport layer fabricated by a solution-based process. By tuning the device structure and the injecting current density (by changing the applied voltage), we can obtain multicolor emission of blue, cyan, magenta, and white from the same carbon dots. Such a switchable EL behavior with white emission has not been observed thus far in single emitting layer structured nanomaterial LEDs. This interesting current density-dependent emission is useful for the development of colorful LEDs. The pure blue and white emissions are obtained by tuning the electron transport layer materials and the thickness of electrode.

We report a series of monochromatic light-emitting diodes based on monodisperse carbon dots with an emission color ranging from blue to red, which is determined by the thickness of the down-conversion layers and the carbon dot doping concentration in the polymer matrix. We further demonstrate the potential of CDs for fabrication of relief graphical patterns with anti-counterfeiting security.

Composite photoelectrodes consisting of CdS sensitizer, reduced graphene oxide (rGO) transporter, and TiO2 acceptor were synthesized in a solvothermal synthesis. Under solvothermal conditions, the dimethyl sulfoxide (DMSO) solvent medium decomposed to form free sulfides, which facilitated the formation of CdS and, at the same time, which also reduced graphene oxide sheets by forming disulfide moieties. Compared to pure CdS and TiO2, coupling of these materials either as bi- or tricomponent composites (including rGO) allowed efficient interfacial charge separation and prolonged electron lifetimes. In particular, in the CdS/rGO/TiO2 tricomposite case, the rGO plays vital roles in alleviating trapped electrons at the heterojunction and serves as a platform for shuttling electrons between CdS and TiO2. Taking into account all of the structure-related charge-transport characteristics, including interfacial contacts, the highest quantum efficiency (incident photon-to-current efficiency, IPCE, at 460 nm = 12%) w...

Core/shell CdTe/ZnS colloidal quantum dots with varying dopant levels (4.7–9.7%) of paramagnetic manganese ions spatially distributed within the thin ZnS shell are synthesized by the aqueous approach. They exhibit both strong fluorescence originating from the CdTe core (up to 45% room temperature emission quantum yield) and high ionic relaxivity in the range of 10.7–5.4 mM–1 s–1, which render them promising dual fluorescent/paramagnetic probes.

A colloidal suspension method is used to obtain CdTe nanocrystals modified with thioglycolic acid in aqueous solutions of ethylene glycol. Their photoluminescence spectrum is shifted to shorter wavelengths relative to that of CdTe nanocrystals synthesized in water. It is found that the ethylene glycol molecules participate in the stabilization of the nanocrystals and passivation of surface defects, with an optimum concentration of 10% ethylene glycol in the reactive mixture for production of stably dispersed CdTe. It is difficult to observe plasmon effects in these nanoparticles when Ag nanoparticles are present because cadmium iodide is used as a precursor salt, which leads to the appearance of I2, an oxidant for Ag nanoparticles, in the solution. When a protective polyelectrolyte intermediate layer of thickness ~11.7 nm is deposited on a colloidal silver substrate, the photoluminescence intensity of the CdTe nanoparticles increases by a factor of 1.7. The chemical features of these nanoparticle solutions cause their luminescence characteristics to be highly sensitive to the presence of Ag nanoparticles in the solution. Changes in the position and intensity of the photoluminescence peak are observed for concentrations of Ag nanoparticles in the solution as low as 10–11 mol/l.

The technology for preparing colloidal CdTe quantum dots (QDs) in an alcaline medium in the presence of passivators thioglycolic acid (TGA) and L-cysteine (L-cys) as well as the technology for preparing colloidal CdSe QDs by method of the reverse micelles is presented. The CdTe QDs were synthesized at different technologic conditions in an aqua colloidal solutions as well as in a polymeric matrix of poly(diallydimethylammonium chloride). For synthesis of CdSe QDs in microemulsion system Triton X-100 and n-hexyl alcohol were used. Cyclohexane served as a non-polar phase, water and water solutions of cadmium acetate and sodium selenide were used as polar phase. The peculiarities of photoluminescence (PL) and optical absorption spectra of CdTe QDs in the 4.2 K– 300 K temperature range were investigated. PL spectrum consist of relatively narrow exciton line with maximum at 2.1–2.4 eV for QDs synthesized at different content of thioglycolic acid (TGA) and L-cysteine (L-cys). It was shown that the Stokes shift in PL and optical absorption spectra monotonically increases from 170 meV to 200 meV at decreasing of QDs size from 3.1 nm to 1.8 nm that is caused by the increasing of the electron–phonon interaction. The dependence of the Huang-Rhys factor on QDs size was obtained.

Temperature-dependent optical studies of semiconductor quantum dots (QDs) are fundamentally important for a variety of sensing and imaging applications. The steady-state and time-resolved photoluminescence properties of CdTe QDs in the size range from 2.3 to 3.1 nm embedded into a protective matrix of NaCl are studied as a function of temperature from 80 to 360 K. The temperature coefficient is found to be strongly dependent on QD size, with the highest sensitivity obtained for the smallest size of QDs. The emission from solid-state CdTe QD-based powders is maintained with high color purity over a wide range of temperatures. Photoluminescence lifetime data suggest that temperature dependence of the intrinsic radiative lifetime in CdTe QDs is rather weak, and it is mostly the temperature-dependent nonradiative decay of CdTe QDs which is responsible for the thermal quenching of photoluminescence intensity. By virtue of the temperature-dependent photoluminescence behavior, high color purity, photostability, and high photoluminescence quantum yield (26%-37% in the solid state), CdTe QDs embedded in NaCl matrices are useful solid-state probes for thermal imaging and sensing over a wide range of temperatures within a number of detection schemes and outstanding sensitivity, such as luminescence thermochromic imaging, ratiometric luminescence, and luminescence lifetime thermal sensing.

We present a simple approach towards highly efficient solid-state luminophores with strong deep blue emission and a record high photoluminescence quantum yield of 60% by embedding water-soluble N,S-co-doped carbon dots into a polyhedral oligomeric silsesquioxane (POSS) matrix.

In a line with most recent trends in developing non-toxic fluorescent nanomaterials, we combined blue emissive carbon dots with green and red emissive zinc copper indium sulfide (ZCIS) core/shell quantum dots (QDs) to achieve white light-emitting diodes (WLEDs) with a high color rendering index of 93. This indicates that ZCIS QDs, with their broad emission bands, can be employed to effectively make up the emission of carbon dots in the yellow and red regions to produce WLEDs in the wide region of color temperature by tuning the volume ratio of these constituting luminophores. Their electroluminescence characteristics including color rendering index, Commission Internationale de l'Eclairage (CIE) color coordinates, and color temperatures were evaluated as a function of forward current. The CIE-1931 chromaticity coordinates of the as-prepared WLEDs, exhibiting good stability, were slightly shifted from (0.321, 0.312) at 10 mA to (0.351, 0.322) at 30 mA, which was mainly caused by the different thermal quenching coefficients of carbon dots and ZCIS QDs.

Direct hydrothermal growth of Sn(II)-doped SnO2 films on fluorine-doped tin oxide (FTO) substrates results in the formation of upstanding SnO2 nanosheet arrays covered by hierarchical SnO2 nanoflowers. The n-type semiconductor films show extended photoresponse in the visible spectrum arising from the coexistence of Sn(II) dopant ions and oxygen vacancies in these hierarchical SnO2 nanostructures, which leads to a narrowed bandgap. Photoluminescence spectroscopy revealed that the emission in the UV, blue and red spectral ranges is related to the evolution of Sn(II) dopants and oxygen vacancies with annealing temperature, whereas oxygen vacancies are mostly responsible for visible emission. The Sn(II)-doped SnO2 films show higher photocurrent when sensitized with narrow bandgap CdS nanoparticles, serving as efficient electron acceptors.

We report on a series of fluorescent powders based on CdTe colloidal nanocrystals embedded into a protective NaCl matrix, which provide solid-state luminophores with emission colors covering the whole green to red spectral region of visible spectrum and enhanced fluorescence quantum yields comparing to the parent CdTe nanocrystals, unravelled by UV-vis absorption and diffuse reflectance measurements as well as by steady-state and time-resolved photoluminescence spectroscopy. Prototypes of hybrid light-emitting diodes of high color quality utilizing this kind of luminophores as a down-converting layer are demonstrated.