All-Perovskite Multicomponent Nanocrystal Superlattices.

Nanocrystal superlattices (NC SLs) have long been sought as promising metamaterials, with nanoscale-engineered properties arising from collective and synergistic effects among the constituent building blocks. Lead halide perovskite (LHP) NCs come across as outstanding candidates for SL design, as they demonstrate collective light emission, known as superfluorescence, in single- and multicomponent SLs. Thus far, LHP NCs have only been assembled in single-component SLs or coassembled with dielectric NC building blocks acting solely as spacers between luminescent NCs. Here, we report the formation of multicomponent LHP NC-only SLs, i.e., using only CsPbBr3 NCs of different sizes as building blocks. The structural diversity of the obtained SLs encompasses the ABO6, ABO3, and NaCl structure types, all of which contain orientationally and positionally locked NCs. For the selected model system, the ABO6-type SL, we observed efficient NC coupling and Förster-like energy transfer from strongly confined 5.3 nm CsPbBr3 NCs to weakly confined 17.6 nm CsPbBr3 NCs, along with characteristic superfluorescence features at cryogenic temperatures. Spatiotemporal exciton dynamics measurements reveal that binary SLs exhibit enhanced exciton diffusivity compared to single-component NC assemblies across the entire temperature range (from 5 to 298 K). The observed coherent and incoherent NC coupling and controllable excitonic transport within the solid NC SLs hold promise for applications in quantum optoelectronic devices.

Strong coupling in mechanically flexible free-standing organic membranes.

Strong coupling of a confined optical field to the excitonic or vibronic transitions of a molecular material results in the formation of new hybrid states called polaritons. Such effects have been extensively studied in Fabry-Pèrot microcavity structures where an organic material is placed between two highly reflective mirrors. Recently, theoretical and experimental evidence has suggested that strong coupling can be used to modify chemical reactivity as well as molecular photophysical functionalities. However, the geometry of conventional microcavity structures limits the ability of molecules "encapsulated" in a cavity to interact with their local environment. Here, we fabricate mirrorless organic membranes that utilize the refractive index contrast between the organic active material and its surrounding medium to confine an optical field with Q-factor values up to 33. Using angle-resolved white light reflectivity measurements, we confirm that our structures operate in the strong coupling regime, with Rabi-splitting energies between 60 and 80 meV in the different structures studied. The experimental results are matched by transfer matrix and coupled oscillator models that simulate the various polariton states of the free standing membranes. Our work demonstrates that mechanically flexible and easy-to-fabricate free standing membranes can support strong light-matter coupling, making such simple and versatile structures highly promising for a range of polariton applications.

Gold Nanobipyramids for Near-Infrared Fluorescence-Enhanced Imaging and Treatment of Triple-Negative Breast Cancer.

There is an imminent need for novel strategies for the diagnosis and treatment of aggressive triple-negative breast cancer (TNBC). Cell-targeted multifunctional nanomaterials hold great potential, as they can combine precise early-stage diagnosis with local therapeutic delivery to specific cell types. In this study, we used mesoporous silica (MS)-coated gold nanobipyramids (MS-AuNBPs) for fluorescence imaging in the near-infrared (NIR) biological window, along with targeted TNBC treatment. Our MS-AuNBPs, acting partly as light amplification components, allow considerable metal-enhanced fluorescence for a NIR dye conjugated to their surfaces compared to the free dye. Fluorescence analysis confirms a significant increase in the dye's modified quantum yield, indicating that MS-AuNBPs can considerably increase the brightness of low-quantum-yield NIR dyes. Meanwhile, we tested the chemotherapeutic efficacy of MS-AuNBPs in TNBC following the loading of doxorubicin within the MS pores and functionalization to target folate receptor alpha (FRα)-positive cells. We show that functionalized particles target FRα-positive cells with significant specificity and have a higher potency than free doxorubicin. Finally, we demonstrate that FRα-targeted particles induce stronger antitumor effects and prolong overall survival compared to the clinically applied non-targeted nanotherapy, Doxil. Together with their excellent biocompatibility measured in vitro, this study shows that MS-AuNBPs are promising tools to detect and treat TNBCs.

Flexible, Free-Standing Polymer Membranes Sensitized by CsPbX3 Nanocrystals as Gain Media for Low Threshold, Multicolor Light Amplification.

Lead halide perovskite nanocrystals (NCs) are highly suitable active media for solution-processed lasers in the visible spectrum, owing to the wide tunability of their emission from blue to red via facile ion-exchange reactions. Their outstanding optical gain properties and the suppressed nonradiative recombination losses stem from their defect-tolerant nature. In this work, we demonstrate flexible waveguides combining the transparent, bioplastic, polymer cellulose acetate with green CsPbBr3 or red-emitting CsPb(Br,I)3 NCs in simple solution-processed architectures based on polymer-NC multilayers deposited on polymer micro-slabs. Experiments and simulations indicate that the employment of the thin, free-standing membranes results in confined electrical fields, enhanced by 2 orders of magnitude compared to identical multilayer stacks deposited on conventional, rigid quartz substrates. As a result, the polymer structures exhibit improved amplified emission characteristics under nanosecond excitation, with amplified spontaneous emission (ASE) thresholds down to ∼95 µJ cm-2 and ∼70 µJ cm-2 and high net modal gain up to ∼450 and ∼630 cm-1 in the green and red parts of the spectrum, respectively. The optimized gain properties are accompanied by a notable improvement of the ASE operational stability due to the low thermal resistance of the substrate-less membranes and the intimate thermal contact between the polymer and the NCs. Their application potential is further highlighted by the membrane's ability to sustain dual-color ASE in the green and red parts of the spectrum through excitation by a single UV source, activate underwater stimulated emission, and operate as efficient white light downconverters of commercial blue LEDs, producing high-quality white light emission, 115% of the NTSC color gamut.

Structural Diversity in Multicomponent Nanocrystal Superlattices Comprising Lead Halide Perovskite Nanocubes.

Nanocrystal (NC) self-assembly is a versatile platform for materials engineering at the mesoscale. The NC shape anisotropy leads to structures not observed with spherical NCs. This work presents a broad structural diversity in multicomponent, long-range ordered superlattices (SLs) comprising highly luminescent cubic CsPbBr3 NCs (and FAPbBr3 NCs) coassembled with the spherical, truncated cuboid, and disk-shaped NC building blocks. CsPbBr3 nanocubes combined with Fe3O4 or NaGdF4 spheres and truncated cuboid PbS NCs form binary SLs of six structure types with high packing density; namely, AB2, quasi-ternary ABO3, and ABO6 types as well as previously known NaCl, AlB2, and CuAu types. In these structures, nanocubes preserve orientational coherence. Combining nanocubes with large and thick NaGdF4 nanodisks results in the orthorhombic SL resembling CaC2 structure with pairs of CsPbBr3 NCs on one lattice site. Also, we implement two substrate-free methods of SL formation. Oil-in-oil templated assembly results in the formation of binary supraparticles. Self-assembly at the liquid-air interface from the drying solution cast over the glyceryl triacetate as subphase yields extended thin films of SLs. Collective electronic states arise at low temperatures from the dense, periodic packing of NCs, observed as sharp red-shifted bands at 6 K in the photoluminescence and absorption spectra and persisting up to 200 K.

High-Performance Luminescence Thermometer with Field-Induced Slow Magnetic Relaxation Based on a Heterometallic Cyanido-Bridged 3d-4f Complex.

The 1:1:1 reaction of DyCl3·6H2O, K3[Co(CN)6] and bpyO2 in H2O has provided access to a complex with formula [DyCo(CN)6(bpyO2)2(H2O)3]·4H2O (1) in a very good yield, while [DyFe(CN)6(bpyO2)2 (H2O)3]·4H2O (2) was also precipitated (also in a high yield) using K3[Fe(CN)6] instead of K3[Co(CN)6]. Their structures have been determined by single-crystal X-ray crystallography and characterized based on elemental analyses and IR spectra. Combined direct current (dc) and alternating current (ac) magnetic susceptibility revealed slow magnetic relaxation upon application of a dc field. µ-SQUID measurements and CASSCF calculations revealed high-temperature relaxation dynamics for both compounds. Low-temperature magnetic studies show the relaxation characteristics for 1, while for compound 2 the dynamics corresponds to an antiferromagnetically coupled Dy···Fe pair. High-resolution optical studies have been carried out to investigate the performance of compounds 1 and 2 as luminescence thermometers. For 1, a maximum thermal sensitivity of 1.84% K-1 at 70 K has been calculated, which is higher than the acceptable sensitivity boundary of 1% K-1 for high-performance luminescence thermometers in a broad range of temperature between 40 and 140 K. Further optical studies focused on the chromaticity diagram of compound 1 revealed a temperature shift from warm white (3200 K) at 10 K toward a more natural white color near 4000 K at room temperature.

Single-Exciton Gain and Stimulated Emission Across the Infrared Telecom Band from Robust Heavily Doped PbS Colloidal Quantum Dots.

Materials with optical gain in the infrared are of paramount importance for optical communications, medical diagnostics, and silicon photonics. The current technology is based either on costly III-V semiconductors that are not monolithic to silicon CMOS technology or Er-doped fiber technology that does not make use of the full fiber transparency window. Colloidal quantum dots (CQDs) offer a unique opportunity as an optical gain medium in view of their tunable bandgap, solution processability, and CMOS compatibility. The 8-fold degeneracy of infrared CQDs based on Pb-chalcogenides has hindered the demonstration of low-threshold optical gain and lasing, at room temperature. We demonstrate room-temperature, infrared, size-tunable, band-edge stimulated emission with a line width of ∼14 meV. Leveraging robust electronic doping and charge-exciton interactions in PbS CQD thin films, we reach a gain threshold at the single exciton regime representing a 4-fold reduction from the theoretical limit of an 8-fold degenerate system, with a net modal gain in excess of 100 cm-1.

Dual Emission in a Ligand and Metal Co-Doped Lanthanide-Organic Framework: Color Tuning and Temperature Dependent Luminescence.

In this study, we report the luminescence color tuning in the lanthanide metal-organic framework (LnMOF) ([La(bpdc)Cl(DMF)] (1); bpdc2- = [1,1'-biphenyl]-4,4'-dicarboxylate, DMF = N,N-dimethylformamide) by introducing dual emission properties in a La3+ MOF scaffold through doping with the blue fluorescent 2,2'-diamino-[1,1'-biphenyl]-4,4'-dicarboxylate (dabpdc2-) and the red emissive Eu3+. With a careful adjustment of the relative doping levels of the lanthanide ions and bridging ligands, the color of the luminescence was modulated, while at the same time the photophysical characteristics of the two chromophores were retained. In addition, the photophysical properties of the parent MOF (1) and its doped counterparts with various dabpdc2-/bpdc2- and Eu3+/La3+ ratios and the photoinduced energy transfer pathways that are possible within these materials are discussed. Finally, the temperature dependence study on the emission profile of a doped analogue containing 10% dabpdc2- and 2.5% Eu3+ (7) is presented, highlighting the potential of this family of materials to behave as temperature sensors.

Afterglow Effects as a Tool to Screen Emissive Nongeminate Charge Recombination Processes in Organic Photovoltaic Composites.

Disentangling temporally overlapping charge carrier recombination events in organic bulk heterojunctions by optical spectroscopy is challenging. Here, a new methodology for employing delayed luminescence spectroscopy is presented. The proposed method is capable of distinguishing between recombination of spatially separated charge carriers and trap-assisted charge recombination simply by monitoring the delayed luminescence (afterglow) of bulk heterojunctions with a quasi time-integrated detection scheme. Applied on the model composite of the donor poly(6,12-dihydro-6,6,12,12-tetraoctyl-indeno[1,2-b]fluorene-alt-benzothiadiazole) (PIF8BT) polymer and the acceptor ethyl-propyl perylene diimide (PDI) derivative, that is, PIF8BT:PDI, the luminescence of charge-transfer (CT) states created by nongeminate charge recombination on the ns to µs timescale is observed. Fluence-dependent, quasi time-integrated detection of the CT luminescence monitors exclusively emissive charge recombination events, while rejecting the contribution of other early-time emissive processes. Trap-assisted and bimolecular charge recombination channels are identified based on their distinct dependence on fluence. The importance of the two recombination channels is correlated with the layer's order and electrical properties of the corresponding devices. Four different microstructures of the PIF8BT:PDI composite obtained by thermal annealing are investigated. Thermal annealing of PIF8BT:PDI shrinks the PDI domains in parallel with the growth of the PIF8BT domains in the blend. Common to all states studied, the delayed CT luminescence signal is dominated by trap-assisted recombination. Yet, the minor fraction of fully separated charge recombination in the overall CT emission increases as the difference in the size of the donor and acceptor domains in the PIF8BT:PDI blend becomes larger. Electric field-induced quenching measurements on complete PIF8BT:PDI devices confirm quantitatively the dominance of emissive trap-limited charge recombination and demonstrates that only 40% of the PIF8BT/PDI CT luminescence comes from the recombination of fully-separated charges, taking place within 200 ns after photoexcitation. The method is applicable to other nonfullerene acceptor blends beyond the system discussed here, if their CT state luminescence can be monitored.

Temperature-dependent interchromophoric interaction in a fluorescent pyrene-based metal-organic framework.

Compounds exhibiting tuneable fluorescence emission upon heating or cooling are considered smart materials as their optical properties can be exquisitely controlled by adjusting the external temperature. Herein, we report such a material, which is a porous pyrene-based metal-organic framework with a chemical formula of [Mg1.5(HTBAPy)(H2O)2]·3DMF (H4TBAPy = 1,3,6,8-tetrakis(p-benzoic acid)pyrene), named SION-7. The bulk solid material of SION-7 can display either monomer or excimer fluorescence emission due to the temperature-dependent extent of interchromophoric interactions between the HTBAPy3- ligands within the framework. Consequently, the fluorescence emission colours gradually change from blue at low temperature (80 K) to yellow-green at high temperature (450 K). Interestingly, while kept in a relatively wide temperature range of 80-200 K, SION-7 displays a structured monomer-like spectrum and its colour changes reversibly from deep to light blue. Ex situ variable-temperature (100-350 K) single-crystal X-ray diffractometry studies revealed the impact of solvent content on the optical properties of SION-7, and illustrated the correlation between the position of the phenylene groups of the HTBAPy3- ligands at different temperatures and the interchromophoric interaction. Our study demonstrates a step forward towards the design of tuneable thermofluorochromic materials sought by optoelectronics.

Unraveling the Radiative Pathways of Hot Carriers upon Intense Photoexcitation of Lead Halide Perovskite Nanocrystals.

The slowdown of carrier cooling in lead halide perovskites (LHP) may allow the realization of efficient hot carrier solar cells. Much of the current effort focuses on the understanding of the mechanisms that retard the carrier relaxation, while proof-of-principle demonstrations of hot carrier harvesting have started to emerge. Less attention has been placed on the impact that the energy and momentum relaxation slowdown imparts on the spontaneous and stimulated light-emission process. LHP nanocrystals (NCs) provide an ideal testing ground for such studies as they exhibit bright emission and high optical gain, while the carrier cooling bottleneck is further pronounced compared to their bulk analogues due to confinement. Herein, the luminescent properties of CsPbBr3, FAPbBr3, and FAPbI3 NCs in the strong photoexcitation regime are investigated. In the former two NC systems, amplified spontaneous emission is found to dominate over the radiative recombination at average carrier occupancy per nanocrystal larger than 5-10. On the other hand, under the same photoexcitation conditions in the FAPbI3 NCs, a longer lived population of hot carriers results in a competition between hot luminescence, stimulated emission, and defect recombination. The dynamic interplay between the aforementioned three emissive channels appears to be influenced by various experimental and material parameters that include temperature, material purity, film morphology, and excitation pulse width and wavelength.

Robust Hydrophobic and Hydrophilic Polymer Fibers Sensitized by Inorganic and Hybrid Lead Halide Perovskite Nanocrystal Emitters.

Advances in the technology and processing of flexible optical materials have paved the way toward the integration of semiconductor emitters and polymers into functional light emitting fabrics. Lead halide perovskite nanocrystals appear as highly suitable optical sensitizers for such polymer fiber emitters due to their ease of fabrication, versatile solution-processing and highly efficient, tunable, and narrow emission across the visible spectrum. A beneficial byproduct of the nanocrystal incorporation into the polymer matrix is that it provides a facile and low-cost method to chemically and structurally stabilize the perovskite nanocrystals under ambient conditions. Herein, we demonstrate two types of robust fiber composites based on electrospun hydrophobic poly(methyl methacrylate) (PMMA) or hydrophilic polyvinylpyrrolidone (PVP) fibrous membranes sensitized by green-emitting all-inorganic CsPbBr3 or hybrid organic-inorganic FAPbBr3 nanocrystals. We perform a systematic investigation on the influence of the nanocrystal-polymer relative content on the structural and optical properties of the fiber nanocomposites and we find that within a wide content range, the nanocrystals retain their narrow and high quantum yield emission upon incorporation into the polymer fibers. Quenching of the radiative recombination at the higher/lower bound of the nanocrystal:polymer mass ratio probed is discussed in terms of nanocrystal clustering/ligand desorption due to dilution effects, respectively. The nanocomposite's optical stability over an extended exposure in air and upon immersion in water is also discussed. The studies confirm the demonstration of robust and bright polymer-fiber emitters with promising applications in backlighting for LCD displays and textile-based light emitting devices.

Selective, Fast-Response, and Regenerable Metal-Organic Framework for Sampling Excess Fluoride Levels in Drinking Water.

Prolonged consumption of water contaminated with fluoride ions (F-) at concentrations exceeding 1.5 ppm can lead to considerable health implications, particularly in children and developing embryos. With irreversible and potentially severe forms of fluoride (F-) toxicity such as skeletal fluorosis being endemic in at least 25 countries, constructing affordable, remote-access, reliable water-sampling methods for F- contamination is an important goal. In this work, we present a novel lanthanide-based luminescent metal-organic framework, named SION-105, with a boron (B) receptor site whose interactions with F- in aqueous solutions are simultaneously electrostatic and specific in nature because of its carefully designed structural environment. This allows the material to be easily regenerated and used over 10 cycles, setting it apart from most existing molecular and polymeric F- sensors. SION-105 has been combined with a portable prototype sampling device that was designed and built in-house to measure F- concentrations in natural groundwater samples taken from three different countries, with the results showing excellent agreement with ion chromatography analysis.

Lead halide perovskites and other metal halide complexes as inorganic capping ligands for colloidal nanocrystals.

Lead halide perovskites (CH3NH3PbX3, where X = I, Br) and other metal halide complexes (MX(n), where M = Pb, Cd, In, Zn, Fe, Bi, Sb) have been studied as inorganic capping ligands for colloidal nanocrystals. We present the methodology for the surface functionalization via ligand-exchange reactions and the effect on the optical properties of IV-VI, II-VI, and III-V semiconductor nanocrystals. In particular, we show that the Lewis acid-base properties of the solvents, in addition to the solvent dielectric constant, must be properly adjusted for successful ligand exchange and colloidal stability. High luminescence quantum efficiencies of 20-30% for near-infrared emitting CH3NH3PbI3-functionalized PbS nanocrystals and 50-65% for red-emitting CH3NH3CdBr3- and (NH4)2ZnCl4-capped CdSe/CdS nanocrystals point to highly efficient electronic passivation of the nanocrystal surface.

Alkaline disinfection of urban wastewater and landfill leachate by wood fly ash.

Wood fly ash is an industrial by-product of the combustion of different wood materials and is mostly disposed of as waste on landfills. In our preliminary experiments, wood ash exhibited antibacterial activity against urban wastewater bacteria and we focused on wood fly ash as a potential substrate for wastewater disinfection. The addition of ash at a concentration of 10 g L⁻¹ (1%) caused an instant increase of pH in urban wastewater and landfill leachate. High pH (10.1-12.7) inactivated bacterial populations in the wastewater and the removal of faecal coliforms and intestinal enterococci after 6 h of contact was 100% (below the detection limit; <1 CFU per mL) with the most efficient ash sample (ash from combustion of beech) both in urban wastewater and landfill leachate. Properly chosen wood fly ash, i.e. one that tends to increase the pH to the greatest extent, proved to be a very effective disinfection substrate. Considering that water treated with wood ash has a high pH and needs to be neutralised before discharge, ash would be suitable for disinfection of leachates when smaller volumes are treated.

Comparative uptake study of toxic elements from aqueous media by the different particle-size-fractions of fly ash.

The purpose of the study described in this paper was to determine the removal of Cr (total), Cr (VI), Cu, Ni, Pb, Zn and Cd from wastewater using different particle-size-fractions of highly calcareous and highly siliceous fly ashes (FAs). Three different Hellenic FAs (two calcareous and one siliceous) were tested for their capability of precipitating heavy metals from aqueous solutions. Each FA sample was separated into six different size-fractions with a grain diameter range of: [(0-25) (25-40) (40-90) (90-150) (150-400) and (>400)] µm. The different FA grain-fractions were evaluated in terms of their chemical composition, pH, Loss on Ignition (LOI) and CaO(f) (%). Batch adsorption experiments were then carried out, indicating that the various grain-fractions of the highly siliceous FA were more efficient in precipitating Cr (VI) but less capable of retaining Cd, Cu, Ni, Pb and Zn. On the other hand, the high-Ca fly ashes were proven to be more efficient in uptaking Cd, Cu, Ni, Pb and Zn, but less in hexavalent chromium. This particular tendency was also confirmed in the case of the different particle-size-fractions of same fly ashes. It was actually verified that FAs can be more effective in the field of industrial wastewater-remediation when separated into their size-fractions.

Removal of heavy metals from wastewater using CFB-coal fly ash zeolitic materials.

Polish bituminous (PB) and South African (SA) coal fly ash (FA) samples, derived from pilot-scale circulated fluidized bed (CFB) combustion facilities, were utilized as raw materials for the synthesis of zeolitic products. The two FAs underwent a hydrothermal activation with 1M NaOH solution. Two different FA/NaOH solution/ratios (50, 100g/L) were applied for each sample and several zeolitic materials were formed. The experimental products were characterized by means of X-ray diffraction (XRD) and energy dispersive X-ray coupled-scanning electron microscope (EDX/SEM), while X-ray fluorescence (XRF) was applied for the determination of their chemical composition. The zeolitic products were also evaluated in terms of their cation exchange capacity (CEC), specific surface area (SSA), specific gravity (SG), particle size distribution (PSD), pH and the range of their micro- and macroporosity. Afterwards the hybrid materials were tested for their ability of adsorbing Cr, Pb, Ni, Cu, Cd and Zn from contaminated liquids. Main parameters for the precipitation of the heavy metals, as it was concluded from the experimental results, are the mineralogical composition of the initial fly ashes, as well as the type and the amount of the produced zeolite and specifically the mechanism by which the metals ions are hold on the substrate.

Synthesis and size control of luminescent ZnSe nanocrystals by a microemulsion-gas contacting technique.

A scalable method for controlled synthesis of luminescent compound semiconductor nanocrystals (quantum dots) using microemulsion-gas contacting at room temperature is reported. The technique exploits the dispersed phase of a microemulsion to form numerous identical nanoreactors. ZnSe quantum dots were synthesized by reacting hydrogen selenide gas with diethylzinc dissolved in the heptane nanodroplets of a microemulsion formed by self-assembly of a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) amphiphilic block copolymer in formamide. A single nanocrystal is grown in each nanodroplet, thus allowing good control of particle size by manipulation of the initial diethylzinc concentration in the heptane. The ZnSe nanocrystals exhibit size-dependent luminescence and excellent photostability.