Bornite (Cu5FeS4) nanocrystals as an ultrasmall biocompatible NIR-II contrast agent for photoacoustic imaging.

In this study, we demonstrate the potential of the bornite crystal structure (Cu5FeS4) of copper iron sulfide as a second near infrared (NIR-II) photoacoustic (PA) contrast agent. Bornite exhibits comparable dose-dependent biocompatibility to copper sulfide nanoparticles in a cell viability study with HepG2 cells, while exhibiting a 10-fold increase in PA amplitude. In comparison to other benchmark contrast agents at similar mass concentrations, bornite demonstrated a 10× increase in PA amplitude compared to indocyanine green (ICG) and a 5× increase compared to gold nanorods (AuNRs). PA signal was detectable with a light pathlength greater than 5 cm in porcine tissue phantoms at bornite concentrations where in vitro cell viability was maintained. In vivo imaging of mice vasculature resulted in a 2× increase in PA amplitude compared to AuNRs. In summary, bornite is a promising NIR-II contrast agent for deep tissue PA imaging.

Synthesis of Cs3Cu2I5 Nanocrystals in a Continuous Flow System.

Achieving the goal of generating all of the world's energy via renewable sources and significantly reducing the energy usage will require the development of novel, abundant, nontoxic energy conversion materials. Here, a cost-efficient and scalable continuous flow synthesis of Cs3Cu2I5 nanocrystals is developed as a basis for the rapid advancement of novel nanomaterials. Ideal precursor solutions are obtained through a novel batch synthesis, whose product served as a benchmark for the subsequent flow synthesis. Realizing this setup enabled a reproducible fabrication of Cs3Cu2I5 nanocrystals. The effect of volumetric flow rate and temperature on the final product's morphology and optical properties are determined, obtaining 21% quantum yield with the optimal configuration. Consequently, the size and morphology of the nanocrystals can be tuned with far more precision and in a much broader range than previously achievable. The flow setup is readily applicable to other relevant nanomaterials. It should enable a rapid determination of a material's potential and subsequently optimize its desired properties for renewable energy generation or efficient optoelectronics.

NC Meets CN: Porous Photoanodes with Polymeric Carbon Nitride/ZnSe Nanocrystal Heterojunctions for Photoelectrochemical Applications.

The utilization of photoelectrochemical cells (PEC) for converting solar energy into fuels (e.g., hydrogen) is a promising method for sustainable energy generation. We demonstrate a strategy to enhance the performance of PEC devices by integrating surface-functionalized zinc selenide (ZnSe) semiconductor nanocrystals (NCs) into porous polymeric carbon nitride (CN) matrices to form a uniformly distributed blend of NCs within the CN layer via electrophoretic deposition (EPD). The achieved type II heterojunction at the CN/NC interface exhibits intimate contact between the NCs and the CN backbone since it does not contain insulating binders. This configuration promotes efficient charge separation and suppresses carrier recombination. The reported CN/NC composite structure serves as a photoanode, demonstrating a photocurrent density of 160 ± 8 µA cm-2 at 1.23 V vs a reversible hydrogen electrode (RHE), 75% higher compared with a CN-based photoelectrode, for approximately 12 h. Spectral and photoelectrochemical analyses reveal extended photoresponse, reduced charge recombination, and successful charge transfer at the formed heterojunction; these properties result in enhanced PEC oxygen production activity with a Faradaic efficiency of 87%. The methodology allows the integration of high-quality colloidal NCs within porous CN-based photoelectrodes and provides numerous knobs for tuning the functionality of the composite systems, thus showing promise for achieving enhanced solar fuel production using PEC.

Direct Excitation Transfer in Plasmonic Metal-Chalcopyrite-Hybrids: Insights from Single Particle Line Shape Analysis.

Hybrid nanomaterials containing both noble metal and semiconductor building blocks provide an engineerable platform for realizing direct or indirect charge and energy transfer for enhanced plasmonic photoconversion and photocatalysis. In this work, silver nanoparticles (AgNPs) and chalcopyrite (CuFeS2) nanocrystals (NCs) are combined into a AgNP@CuFeS2 hybrid structure comprising NCs embedded in a self-assembled lipid coating around the AgNP core. In AgNP@CuFeS2 hybrid structures, both metallic and semiconductor NCs support quasistatic resonances. To characterize the interactions between these resonances and their effect on potential charge and energy transfer, direct interfacial excitation transfer between the AgNP core and surrounding CuFeS2 NCs is probed through single particle line shape analysis and supporting electromagnetic simulations. These studies reveal that CuFeS2 NCs localized in the evanescent field of the central AgNP induce a broadening of the metal NP line shape that peaks when an energetic match between the AgNP and CuFeS2 NC resonances maximizes direct energy transfer. Dimers of AgNPs whose resonances exhibit poor energetic overlap with the CuFeS2 NC quasistatic resonance yield much weaker line shape broadening in a control experiment, corroborating the existence of resonant energy transfer in the AgNP@CuFeS2 hybrid. Resonant coupling between the metallic and semiconductor building blocks in the investigated hybrid architecture provides a mechanism for utilizing the large optical cross-section of the central AgNP to enhance the generation of reactive charge carriers in the surrounding semiconductor NCs for potential applications in photocatalysis.

Identification of Semiconductor Nanocrystals with Bright Ground-State Excitons.

While semiconductor nanocrystals provide versatile fluorescent materials for light-emitting devices, their brightness suffers from the "dark exciton"─an optically inactive electronic state into which nanocrystals relax before emitting. Recently, a theoretical mechanism, the Rashba effect, was discovered that can overcome this limitation by inverting the lowest-lying levels and creating a bright excitonic ground state. However, no methodology is available to systematically identify materials that exhibit this inversion, hindering the development of superbright nanocrystals and their devices. Here, based on a detailed understanding of the Rashba mechanism, we demonstrate a procedure that reveals previously unknown "bright-exciton" nanocrystals. We first define physical criteria to reduce over 500,000 known solids to 173 targets. Higher-level first-principles calculations then refine this list to 28 candidates. From these, we select five with high oscillator strength and develop effective-mass models to determine the nature of their lowest excitonic state. We confirm that four of the five solids yield bright ground-state excitons in nanocrystals. Thus, our results provide a badly needed roadmap for experimental investigation of bright-exciton nanomaterials.

Multiphoton-Driven Photocatalytic Defluorination of Persistent Perfluoroalkyl Substances and Polymers by Visible Light.

Perfluoroalkyl substances (PFASs) and fluorinated polymers (FPs) have been extensively utilized in various industries, whereas their extremely high stability poses environmental persistence and difficulty in waste treatment. Current decomposition approaches of PFASs and FPs typically require harsh conditions such as heating over 400 °C. Thus, there is a pressing need to develop a new technique capable of decomposing them under mild conditions. Here, we demonstrated that perfluorooctanesulfonate (PFOS), known as a "persistent chemical," and Nafion, a widely utilized sulfonated FP for ion-exchange membranes, can be efficiently decomposed into fluorine ions under ambient conditions via the irradiation of visible LED light onto semiconductor nanocrystals (NCs). PFOS was completely defluorinated within 8-h irradiation of 405-nm LED light, and the turnover number of the C-F bond dissociation per NC was 17200. Furthermore, 81 % defluorination of Nafion was achieved for 24-h light irradiation, demonstrating the efficient photocatalytic properties under visible light. We revealed that this decomposition is driven by cooperative mechanisms involving light-induced ligand displacements and Auger-induced electron injections via hydrated electrons and higher excited states. This study not only demonstrates the feasibility of efficiently breaking down various PFASs and FPs under mild conditions but also paves the way for advancing toward a sustainable fluorine-recycling society.

Development of Fluorescent Sensors for Biorelevant Anions in Aqueous Media Using Positively Charged Quantum Dots.

Quantum dots (QDs) have captured the attention of the scientific community due to their unique optical and electronic properties, leading to extensive research for different applications. They have also been employed as sensors for ionic species owing to their sensing properties. Detecting anionic species in an aqueous medium is a challenge because the polar nature of water weakens the interactions between sensors and ions. The anions bicarbonate (HCO3-), carbonate (CO32-), sulfate (SO42-), and bisulfate (HSO4-) play a crucial role in various physiological, environmental, and industrial processes, influencing the regulation of biological fluids, ocean acidification, and corrosion processes. Therefore, it is necessary to develop approaches capable of detecting these anions with high sensitivity. This study utilized CdTe QDs stabilized with cysteamine (CdTe-CYA) as a fluorescent sensor for these anions. The QDs exhibited favorable optical properties and high photostability. The results revealed a gradual increase in the QDs' emission intensity with successive anion additions, indicating the sensitivity of CdTe-CYA to the anions. The sensor also exhibited selectivity toward the target ions, with good limits of detection (LODs) and quantification (LOQs). Thus, CdTe-CYA QDs show potential as fluorescent sensors for monitoring the target anions in water sources.

Revealing Two Distinct Formation Pathways of 2D Wurtzite-CdSe Nanocrystals Using In Situ X-Ray Scattering.

Understanding the mechanism underlying the formation of quantum-sized semiconductor nanocrystals is crucial for controlling their synthesis for a wide array of applications. However, most studies of 2D CdSe nanocrystals have relied predominantly on ex situ analyses, obscuring key intermediate stages and raising fundamental questions regarding their lateral shapes. Herein, the formation pathways of two distinct quantum-sized 2D wurtzite-CdSe nanocrystals - nanoribbons and nanosheets - by employing a comprehensive approach, combining in situ small-angle X-ray scattering techniques with various ex situ characterization methods is studied. Although both nanostructures share the same thickness of ≈1.4 nm, they display contrasting lateral dimensions. The findings reveal the pivotal role of Se precursor reactivity in determining two distinct synthesis pathways. Specifically, highly reactive precursors promote the formation of the nanocluster-lamellar assemblies, leading to the synthesis of 2D nanoribbons with elongated shapes. In contrast, mild precursors produce nanosheets from a tiny seed of 2D nuclei, and the lateral growth is regulated by chloride ions, rather than relying on nanocluster-lamellar assemblies or Cd(halide)2 -alkylamine templates, resulting in 2D nanocrystals with relatively shorter lengths. These findings significantly advance the understanding of the growth mechanism governing quantum-sized 2D semiconductor nanocrystals and offer valuable guidelines for their rational synthesis.

UV Light as an Efficient Tool for Reducing Surface Defects of ZnSe-MSA Quantum Dots.

Defects in ZnSe quantum dots are responsible for increasing the trap states, which can lead to the drastic reduction of their fluorescence output, being one of the major drawbacks of these materials. As surface atoms become more relevant in these nanoscale structures, energy traps due to surface vacancies, play a very definite role in the final emission quantum yield. In the present study, we report the use of photoactivation procedures to decrease surface defects of ZnSe QDs stabilized with mercaptosuccinic acid (MSA), in order to improve the radiative pathways. We applied the colloidal precipitation procedure in a hydrophilic medium and evaluated the role of Zn/Se molar ratios as well as the Zn2+ precursors (nitrate and chloride salts) on their optical properties. Best results (i.e. increment of 400% of the final fluorescence intensity) were obtained for nitrate precursor and a Zn/Se = 1.2 ratio. Thus, we suggest that the chloride ions may compete more efficiently than nitrate ions with MSA molecules decreasing the passivation capability of this molecule. The improvement in ZnSe QDs fluorescence can potentialize their use for biomedical applications.

Nanocrystal Materials for Resistive Memory and Artificial Synapses: Progress and Prospects.

BACKGROUND: Resistive random-access memory (RRAM) is considered to be the most promising next-generation non-volatile memory because of its low cost, low energy consumption, and excellent data storage characteristics. However, the on/off (SET/RESET) voltages of RRAM are too random to replace the traditional memory. Nanocrystals (NCs) offer an appealing option for these applications since they combine excellent electronic/optical properties and structural stability and can address the requirements of low-cost, large-area, and solution-processed technologies. Therefore, the doping NCs in the function layer of RRAM are proposed to localize the electric field and guide conductance filaments (CFs) growth. OBJECTIVE: The purpose of this article is to focus on a comprehensive and systematical survey of the NC materials, which are used to improve the performance of resistive memory (RM) and optoelectronic synaptic devices and review recent experimental advances in NC-based neuromorphic devices from artificial synapses to light-sensory synaptic platforms. METHODS: Extensive information related to NCs for RRAM and artificial synapses and their associated patents were collected. This review aimed to highlight the unique electrical and optical features of metal and semiconductor NCs for designing future RRAM and artificial synapses. RESULTS: It was demonstrated that doping NCs in the function layer of RRAM could not only improve the homogeneity of SET/RESET voltage but also reduce the threshold voltage. At the same time, it could still increase the retention time and provide the probability of mimicking the bio-synapse. CONCLUSION: NC doping can significantly enhance the overall performance of RM devices, but there are still many problems to be solved. This review highlights the relevance of NCs for RM and artificial synapses and also provides a perspective on the opportunities, challenges, and potential future directions.

Efficient Hole Transfer from CdSe Quantum Dots Enabled by Oxygen-Deficient Polyoxovanadate-Alkoxide Clusters.

A limitation of the implementation of cadmium chalcogenide quantum dots (QDs) in charge transfer systems is the efficient removal of photogenerated holes. Rapid hole transfer has typically required the ex situ functionalization of hole acceptors with groups that can coordinate to the surface of the QD. In addition to being synthetically limiting, this strategy also necessitates a competitive binding equilibrium between the hole acceptor and native, solubilizing ligands on the nanocrystal. Here we show that the incorporation of oxygen vacancies into polyoxovanadate-alkoxide clusters improves hole transfer kinetics by promoting surface interactions between the metal oxide assembly and the QD. Investigating the reactivity of oxygen-deficient clusters with phosphonate-capped QDs reveals reversible complexation of the POV-alkoxide with a phosphonate ligand at the nanocrystal surface. These findings reveal a new method of facilitating QD-hole acceptor association that bypasses the restrictions of exchange interactions.

Isolation of cubic Si3P4 in the form of nanocrystals.

This article describes an approach for synthesizing silicon phosphide nanoparticles with a defective zinc blende structure under mild conditions through thermal annealing of hydrogenated silicon nanoparticles with red phosphorus. The synthesized Si3P4 nanoparticles were analyzed using FTIR, XRD, electron diffraction, EDX, TEM, Raman spectroscopy, X-ray fluorescence spectrometry, and UV-vis spectrophotometry. For the isolated cubic Si3P4 phase, a cell parameter of a = 5.04 Å was determined, and the bandgap was estimated to be equal to 1.25 eV. Because of the nanoscale dimensions of the obtained Si3P4 nanoparticles, the product may exhibit several exceptional properties as a precursor for diffusion doping of wafers and as anode material for Li-ion batteries. A similar method with a hydrogenation step offers the possibility to obtain other compounds, such as silicon selenides, arsenides, and sulfides.

Moisture-Induced Degradation of Quantum-Sized Semiconductor Nanocrystals through Amorphous Intermediates.

Elucidating the water-induced degradation mechanism of quantum-sized semiconductor nanocrystals is an important prerequisite for their practical application because they are vulnerable to moisture compared to their bulk counterparts. In-situ liquid-phase transmission electron microscopy is a desired method for studying nanocrystal degradation, and it has recently gained technical advancement. Herein, the moisture-induced degradation of semiconductor nanocrystals is investigated using graphene double-liquid-layer cells that can control the initiation of reactions. Crystalline and noncrystalline domains of quantum-sized CdS nanorods are clearly distinguished during their decomposition with atomic-scale imaging capability of the developed liquid cells. The results reveal that the decomposition process is mediated by the involvement of the amorphous-phase formation, which is different from conventional nanocrystal etching. The reaction can proceed without the electron beam, suggesting that the amorphous-phase-mediated decomposition is induced by water. Our study discloses unexplored aspects of moisture-induced deformation pathways of semiconductor nanocrystals, involving amorphous intermediates.

Raman study of colloidal Cu2ZnSnS4 nanocrystals obtained by "green" synthesis modified by seed nanocrystals or extra cations in the solution.

The method of affordable colloidal synthesis of nanocrystalline Cu2ZnSnS4 (CZTS) is developed, which is suitable for obtaining bare CZTS nanocrystals (NCs), cation substituted CZTS NCs, and CZTS-based hetero-NCs. For the hetero-NCs, the synthesized in advance NCs of another material are introduced into the reaction solution so that the formation of CZTS takes place preferably on these "seed" NCs. Raman spectroscopy is used as the primary method of structural characterization of the NCs in this work because it is very sensitive to the CZTS structure and allows to probe NCs both in solutions and films. Raman data are corroborated by optical absorption measurements and transmission electron microscopy on selected samples. The CdTe and Ag NCs are found to be good seed NCs, resulting in a comparable or even better quality of the CZTS compound compared to bare CZTS NCs. For Au NCs, on the contrary, no hetero-NCs could be obtained under the given condition. Partial substitution of Zn for Ba during the synthesis of bare CZTS NCs results in a superior structural quality of NCs, while the introduction of Ag for partial substitution of Cu deteriorates the structural quality of the NCs.

Threonine functionalized colloidal cadmium sulfide (CdS) quantum dots: The role of solvent and counterion in ligand induced chiroptical properties.

The functionalization of semiconductor nanocrystals, quantum dots (QDs), with small organic molecules has been studied extensively to gain better knowledge on how to tune the electronic, optical and chiroptical properties of QDs. Chiral QDs have progressively emerged as key materials in a vast range of applications including biosensing and biorecognition, imaging, asymmetric catalysis, optoelectronic devices, and spintronics. To engage the full potential of the unique properties of chiral nanomaterials and be able to prepare them with tailorable chiroptical characteristics, it is essential to understand how chirality is rendered from chiral molecular ligands at the surface of nanocrystals to the electronic states of QDs. Using a series of polar protic and aprotic solvents together with ammonium (NH4+), tetramethylammonium (TMA+), and tetrabutylammonium (TBA+) countercations in the preparation of threonine-functionalized cadmium sulfide (Thr-CdS) QDs by phase transfer ligand exchange approach, we demonstrated the significance of the role both the solvent and the countercations play in the transfer of chirality from chiral molecular ligand to achiral semiconductor QDs as apparent by the modulations of the signatures and anisotropy of the circular dichroism (CD) spectra. Moreover, we have utilized tetrabutylammonium countercation to successfully synthesize chiral QDs in nonpolar cyclohexane solvent for the first time. This study provides further insights into the origin of the ligand induced chirality of colloidal nanomaterials and facilitates the synthesis of tailormade chiral QDs.

Copper indium sulfide quantum dots in photocatalysis.

Since the advent of photocatalytic technology, scientists have been searching for semiconductor materials with high efficiency in solar energy utilization and conversion to chemical energy. Recently, the development of quantum dot (QD) photocatalysts has attracted much attention because of their unique characteristics: small size, quantum effects, strong surface activity, and wide photoresponse range. Among ternary chalcogenide semiconductors, CuInS2 QDs are increasingly examined in the field of photocatalysis due to their high absorption coefficients, good matching of the absorption range with sunlight spectrum, long lifetimes of photogenerated electron-hole pairs and environmental sustainability. In this review paper, the structural and electronic properties, synthesis methods and various photocatalytic applications of CuInS2 QDs are systematically expounded. The current research status on the photocatalytic properties of materials based on CuInS2 QD is discussed combined with the existing modification approaches for the enhancement of their performances. Future challenges and new development opportunities of CuInS2 QDs in the field of photocatalysis are then prospected.

Quantum Dot Patterning and Encapsulation by Maskless Lithography for Display Technologies.

For their unique optical properties, quantum dots (QDs) have been extensively used as light emitters in a number of photonic and optoelectronic applications. They even met commercialization success through their implementation in high-end displays with unmatched brightness and color rendering. For such applications, however, QDs must be shielded from oxygen and water vapor, which are known to degrade their optical properties over time. Even with highly qualitative QDs, this can only be achieved through their encapsulation between barrier layers. With the emergence of mini- and microLED for higher contrast and miniaturized displays, new strategies must be found for the concomitant patterning and encapsulation of QDs, with sub-millimeter resolution. To this end, we developed a new approach for the direct patterning of QDs through maskless lithography. By combining QDs in photopolymerizable resins with digital light processing (DLP) projectors, we developed a versatile and massively parallel fabrication process for the additive manufacturing of functional structures that we refer to as QD pockets. These 3D heterostructures are designed to provide isotropic encapsulation of the QDs, and hence prevent edge ingress from the lateral sides of QD films, which remains a shortcoming of the current technologies.

Lead-Free Cesium Manganese Halide Nanocrystals Embedded Glasses for X-Ray Imaging.

The toxicity of heavy-metal Pb and instability of lead-based halide perovskite nanomaterials are main factors to impede their practical applications in the fields of solar cells, LEDs and scintillators. In this paper, all inorganic lead-free cesium manganese halide nanocrystals are synthesized in glass for the first time. Red photoluminescence with broad PL band, negligible self-absorption and a high photoluminescence quantum yield of 41.8% is obtained. In addition, modulating halide component can change the Mn2+ ions coordination environment to obtain tunable photoluminescence from red to green. More importantly, cesium manganese halide nanocrystals embedded glasses exhibit outstanding long-term stabilities. Theses cesium manganese halide nanocrystals embedded glasses are also highly stable against high energy irradiation and exhibit highly efficient radioluminescence, making them promising for high-resolution X-ray imaging. These results demonstrate that cesium manganese halide nanocrystals embedded glasses are promising eco-friendly candidates for applications in light-emitting diodes and scintillators.

Charging and Charged Species in Quantum Dot Light-Emitting Diodes.

Despite recent rapid advances in improving quantum dot light-emitting diodes, many fundamental aspects of the device operating mechanism remain unresolved. Through transient electroluminescence and time-resolved photoluminescence measurements, the effects of offset voltage on charging and charge transport are examined. First, capacitive charging occurs with a time constant of ∼500 ns, followed by electron transport through quantum dots with a mobility of ∼10-5 cm2 V-1 s-1. Hole injection then initiates an electroluminescence rise that is independent of offset voltage. The photoluminescence lifetime is also unaffected by the offset voltage, indicating no injection of charges into the quantum dots or on their surfaces prior to the voltage pulse. A slower equilibration to steady-state electroluminescence is dependent on the offset voltage, indicative of another charging process. Elemental mapping shows that ZnO deposition from solution can lead to the diffusion of charged species into the quantum dot layer, which may cause the slower process.

Tunable Circularly Polarized Luminescence via Chirality Induction and Energy Transfer from Organic Films to Semiconductor Nanocrystals.

Circularly polarized luminescent (CPL) films with high dissymmetry factors hold great potential for optoelectronic applications. Herein, we propose a strategy for achieving strongly dissymetric CPL in nanocomposite films based on chirality induction and energy transfer to semiconductor nanocrystals. First, focusing on a purely organic system, aggregation-induced emission (AIE) and CPL activity of organic liquid crystals (LCs) forming helical nanofilaments was detected, featuring green emission with high dissymmetry factors glum ∼ 10-2. The handedness of helical filaments, and thus the sign of CPL, was controlled via minute amounts of a small chiral organic dopant. Second, nanocomposite films were fabricated by incorporating InP/ZnS semiconductor quantum dots (QDs) into the LC matrix, which induced the chiral assembly of QDs and endowed them with chiroptical properties. Due to the spectral matching of the components, energy transfer (ET) from LC to QDs was possible enabling a convenient way of tuning CPL wavelengths by varying the LC/QD ratio. As obtained, composite films exhibited absolute glum values up to ∼10-2 and thermally on/off switchable luminescence. Overall, we demonstrate the induction of chiroptical properties by the assembly of nonchiral building QDs on the chiral organic template and energy transfer from organic films to QDs, representing a simple and versatile approach to tune the CPL activity of organic materials.