Solution Synthesis and Light-Emitting Applications of One-Dimensional Lead-Free Cerium(III) Metal Halides.

Combining rare earth elements with the halide perovskite structure offers valuable insights into designing nonlead (Pb) luminescent materials. However, most of these compositions tend to form zero-dimensional (0D) networks of metal-halide polyhedra, with higher-dimensional (1D, 2D, and 3D) structures receiving relatively less exploration. Herein, we present synthesis and optical properties of Cs3CeCl6·3H2O, characterized by its unique 1D crystal structure. The conduction band minimum of Cs3CeCl6·3H2O becomes less localized as a result of the increased structural dimension, making it possible for the materials to achieve an efficient electrical injection. For both Cs3CeCl6·3H2O single crystals and nanocrystals, we also observed remarkable luminescence with near-unity photoluminescence quantum yield and exceptional phase stability. Cs3CeCl6·3H2O single crystals demonstrate an X-ray scintillation light yield of 31900 photons/MeV, higher than that of commercial LuAG:Ce (22000 photons/MeV); electrically driven light-emitting diodes fabricated with Cs3CeCl6·3H2O nanocrystals yield the characteristic emission of Ce3+, indicating their potential use in next-generation violet-light-emitting devices.

Designing a Hypoxia-Activated Sensing Platform Using an Azo Group-Triggered Reaction with the Formation of Silicon Nanoparticles.

Hypoxia is known as a specific signal of various diseases, such as liver fibrosis. We designed a hypoxia-sensitive fluorometric approach that cleaved the azo bond (N═N) in the presence of hypoxia-controlled agents (sodium dithionite and azoreductase). 4-(2-Pyridylazo) resorcinol (Py-N═N-RC) bears a desirable hypoxia-responsive linker (N═N), and its azo bond breakup can only occur in the presence of sodium dithionite and azoreductase and leads to the release of 2,4-dihydroxyaniline, which can react with 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane to generate yellow fluorescent silicon nanoparticles. This approach exhibited high selectivity and sensitivity toward both sodium dithionite and azoreductase over other potential interferences. The mouse liver microsome, which is known to contain azoreductase, was applied and confirmed the feasibility of the designed platform. Py-N═N-RC is expected to be a practical substrate for hypoxia-related biological analyses. Furthermore, silicon nanoparticles were successfully applied for Hela cell imaging owing to their negligible cytotoxicity and superb biocompatibility.

On-Off Switching of Singlet Self-Trapped Exciton Emission Endows Antimony-Doped Indium Halides with Excitation-Wavelength-Dependent Luminescence.

Excitation-wavelength-dependent (Ex-De) emitters are a fascinating category of luminescent materials whose emission properties vary with the wavelength of the light used for excitation. Antimony (Sb3+)-doped indium (In)-based metal halides are efficient light emitters; however, the peak fluorescence emission of most Sb3+-activated In-halide remains independent of the excitation wavelength. Here, the study introduces a new Sb3+-doped In-halide cluster, (BDPA)2InCl5:Sb (BDPA+ = C15H18N+, benzyldimethylphenylammonium), which demonstrates efficient Ex-De emission originating from the on-off switchable fluorescence behavior of singlet self-trapped exciton (STE) in 5-coordinate Sb3+ dopant. Interestingly, when excited within the range of 240-370 nm, photoluminescence (PL) spectra of (BDPA)2InCl5:Sb show both singlet and triplet STE emission. However, under excitation wavelengths of 370 to 420 nm, the singlet STE emission is absent, resulting in a noticeable correlated color temperature change from 1700 to 3800 K. The study provides a new approach to designing color-tunable Sb3+-based luminophores, and also presents a novel application scenario for the widely recognized Sb3+ doping strategy.

Optimizing Energy Levels and Improving Film Compactness in PbS Quantum Dot Solar Cells by Silver Doping.

PbS quantum dot (QD) solar cells harvest near-infrared solar radiation. Their conventional hole transport layer has limited hole collection efficiency due to energy level mismatch and poor film quality. Here, how to resolve these two issues by using Ag-doped PbS QDs are demonstrated. On the one hand, Ag doping relieves the compressive stress during layer deposition and thus improves film compactness and homogeneity to suppress leakage currents. On the other hand, Ag doping increases hole concentration, which aligns energy levels and increases hole mobility to boost hole collection. Increased hole concentration also broadens the depletion region of the active layer, decreasing interface charge accumulation and promoting carrier extraction efficiency. A champion power conversion efficiency of 12.42% is achieved by optimizing the hole transport layer in PbS QD solar cells, compared to 9.38% for control devices. Doping can be combined with compressive strain relief to optimize carrier concentration and energy levels in QDs, and even introduce other novel phenomena such as improved film quality.

Near-Infrared LEDs Based on Quantum Cutting-Activated Electroluminescence of Ytterbium Ions.

Cesium lead halide perovskite nanocrystals (PNCs) exhibit promising prospects for application in optoelectronic devices. However, electroactivated near-infrared (NIR) PNC light-emitting diodes (LEDs) with emission peaks over 800 nm have not been achieved. Herein, we demonstrate the electroactivated NIR PNC LEDs based on Yb3+-doped CsPb(Cl1-xBrx)3 PNCs with extraordinary high NIR photoluminescence quantum yields over 170%. The fabricated NIR LEDs possess an irradiance of 584.7 µW cm-2, an EQE of 1.2%, and a turn-on voltage of 3.1 V. The ultrafast quantum cutting process from the PNC host to Yb3+ has been revealed as the main mechanism of electroluminescence (EL)-activated Yb3+ for the first time via exploring how the trend between the EL intensity of PNC and Yb3+ varies with different voltages along with the tendency of temperature- and doping-concentration-dependent PL and EL spectra. This work will extend the application of PNCs to optical communication, night-vision devices, and biomedical imaging.

Organic-Inorganic Hybrid Cuprous-Based Metal Halides with Unique Two-Dimensional Crystal Structure for White Light-Emitting Diodes.

Ternary cuprous (Cu+)-based metal halides, represented by cesium copper iodide (e.g., CsCu2I3 and Cs3Cu2I5), are garnering increasing interest for light-emitting applications owing to their intrinsically high photoluminescence quantum yield and direct band gap. Toward electrically driven light-emitting diodes (LEDs), it is highly desirable for the light emitters to have a high structural dimensionality as it may favor efficient electrical injection. However, unlike lead-based halide perovskites whose light-emitting units can be facilely arranged in three-dimensional (3D) ways, to date, nearly all ternary Cu+-based metal halides crystallize into 0D or 1D networks of Cu-X (X=Cl, Br, I) polyhedra, whereas 3D and even 2D structures remain mostly uncharted. Here, by employing a fluorinated organic cation, we report a new kind of ternary Cu+-based metal halides, (DFPD)CuX2 (DFPD+=4,4-difluoropiperidinium), which exhibits unique 2D layered crystal structure. Theoretical calculations reveal a highly dispersive conduction band of (DFPD)CuBr2, which is beneficial for charge carrier injection. It is also of particular significance to find that the 2D (DFPD)CuBr2 crystals show appealing properties, including improved ambient stability and an efficient warm white-light emission, making it a promising candidate for single-component lighting and display applications.

Highly Enhancing CO2 Photoreduction by Metallization of an Imidazole-linked Robust Covalent Organic Framework.

Converting CO2 into value-added chemicals to solve the issues caused by carbon emission is promising but challenging. Herein, by embedding metal ions (Co2+ , Ni2+ , Cu2+ , and Zn2+ ) into an imidazole-linked robust photosensitive covalent organic framework (PyPor-COF), effective photocatalysts for CO2 conversion are rationally designed and constructed. Characterizations display that all of the metallized PyPor-COFs (M-PyPor-COFs) display remarkably high enhancement in their photochemical properties. Photocatalysis reactions reveal that the Co-metallized PyPor-COF (Co-PyPor-COF) achieves a CO production rate as high as up to 9645 µmol g-1 h-1 with a selectivity of 96.7% under light irradiation, which is more than 45 times higher than that of the metal-free PyPor-COF, while Ni-metallized PyPor-COF (Ni-PyPor-COF) can further tandem catalyze the generated CO to CH4 with a production rate of 463.2 µmol g-1 h-1 . Experimental analyses and theory calculations reveal that their remarkable performance enhancement on CO2 photoreduction should be attributed to the incorporated metal sites in the COF skeleton, which promotes the adsorption and activation of CO2 and the desorption of generated CO and even reduces the reaction energy barrier for the formation of different intermediates. This work demonstrates that by metallizing photoactive COFs, effective photocatalysts for CO2 conversion can be achieved.

Magnetic Field-Assisted Interface Embedding Strategy to Construct 2D/3D Composite Structure for Stable Perovskite Solar Cells with Efficiency Over 24.

Perovskite solar cells (PSCs) based on 2D/3D composite structure have shown enormous potential to combine high efficiency of 3D perovskite with high stability of 2D perovskite. However, there are still substantial non-radiative losses produced from trap states at grain boundaries or on the surface of conventional 2D/3D composite structure perovskite film, which limits device performance and stability. In this work, a multifunctional magnetic field-assisted interfacial embedding strategy is developed to construct 2D/3D composite structure. The composite structure not only improves crystallinity and passivates defects of perovskite layer, but also can efficiently promote vertical hole transport and provide lateral barrier effect. Meanwhile, the composite structure also forms a good surface and internal encapsulation of 3D perovskite to inhibit water diffusion. As a result, the multifunctional effect effectively improves open-circuit voltage and fill factor, reaching maximum values of 1.246 V and 81.36%, respectively, and finally achieves power conversion efficiency (PCE) of 24.21%. The unencapsulated devices also demonstrate highly improved long-term stability and humidity stability. Furthermore, an augmented performance of 21.23% is achieved, which is the highest PCE of flexible device based on 2D/3D composite perovskite films coupled with the best mechanical stability due to the 2D/3D alternating structure.

Intelligent interior atmosphere lamp system based on quantum dot LEDs for safe driving assistance.

A driver safety assisting system is essential to reduce the probability of traffic accidents. But most of the existing driver safety assisting systems are simple reminders that cannot improve the driver's driving status. This paper proposes a driver safety assisting system to reduce the driver's fatigue degree by the light with different wavelengths that affect people's moods. The system consists of a camera, an image processing chip, an algorithm processing chip, and an adjustment module based on quantum dot LEDs (QLEDs). Through this intelligent atmosphere lamp system, the experimental results show that blue light reduced the driver's fatigue degree when just turned on; but as time went on, the driver's fatigue degree rebounded rapidly. Meanwhile, red light prolonged the driver's awake time. Different from blue light alone, this effect can remain stable for a long time. Based on these observations, an algorith was designed to quantify the degree of fatigue and detect its rising trend. In the early stage, the red light is used to prolong the awake time and the blue light to suppress when the fatigue value increases, so as to maximize the awake driving time. The result showed that our device prolonged the awake driving time of the drivers by 1.95 times and reduced fatigue during driving: the quantitative value of fatigue degree generally decreased by about 0.2 times. In most experiments, the subjects were able to complete four hours of safe driving, which reached the maximum length of continuous driving at night allowed by China laws. In conclusion, our system changes the assisting system from a reminder to a helper, thus effectively reducing the driving risk.

Machine Learning Guided Discovery of Superoxide Dismutase Nanozymes for Androgenetic Alopecia.

Androgenetic alopecia (AGA) is a common form of hair loss, which is mainly caused by oxidative stress induced dysregulation of hair follicles (HF). Herein, a highly efficient manganese thiophosphite (MnPS3) based superoxide dismutase (SOD) mimic was discovered using machine learning (ML) tools. Remarkably, the IC50 of MnPS3 is 3.61 µg·mL-1, up to 12-fold lower than most reported SOD-like nanozymes. Moreover, a MnPS3 microneedle patch (MnMNP) was constructed to treat AGA that could diffuse into the deep skin where HFs exist and remove excess reactive oxygen species. Compared with the widely used minoxidil, MnMNP exhibits higher ability on hair regeneration, even at a reduced frequency of application. This study not only provides a general guideline for the accelerated discovery of SOD-like nanozymes by ML techniques, but also shows a great potential as a next generation approach for rational design of nanozymes.

Wide-coverage and Efficient NIR Emission from Single-component Nanophosphors through Shaping Multiple Metal-halide Packages.

Wide-coverage near infrared (NIR) phosphor-converted LEDs possess promising potential for practical applications, but little is developed towards the efficient and wide-coverage NIR phosphors. Here, we report the single-component lanthanide (Ln3+ ) ions doped Cs2 M(In0.95 Sb0.05 )Cl6 (M=alkali metal) nanocrystals (NCs), exhibiting emission from 850 to 1650 nm with high photoluminescence quantum yield of 20.3 %, which is accomplished by shaping the multiple metal halide octahedra of double perovskite via the simple alkali metal substitution. From Judd-Ofelt theoretical calculation and spectroscopic investigations, the shaping of metal halide octahedra in Cs2 M(In1-x Sbx )Cl6 NCs can break the forbidden of f-f transition of Ln3+ , thus increasing their radiative transition rates and simultaneously boosting the energy transfer efficiency from host to Ln3+ . Finally, the wide-coverage NIR LEDs based on Sm3+ , Nd3+ , Er3+ -tridoped Cs2 K0.5 Rb0.5 (In0.95 Sb0.05 )Cl6 NCs are fabricated and employed in the multiplex gas sensing and night-vision application.

Silver Peroxide Nanoparticles for Combined Antibacterial Sonodynamic and Photothermal Therapy.

Metal peroxide nanoparticles designed to elevate the oxidative stress are considered a promising nanotherapeutics in biomedical applications, including chemotherapy, photodynamic therapy, and bacterial disinfection. However, their lack of specificity towards the therapeutic target can cause toxic side effects to healthy tissues. Here, silver peroxide nanoparticles (Ag2 O2 NPs) capable of controlled reactive oxygen species (ROS) release are synthesized. The release of bactericidal Ag+ ions and ROS is strictly regulated by external stimuli of ultrasound (US) and near-infrared (NIR) light. In vitro and in vivo investigations show that the Ag2 O2 NPs present enhanced antibacterial and antibiofilm capabilities with a killing efficiency >99.9999% in 10 min, significantly accelerate multi-drug resistant Staphylococcus aureus infected skin wound closure with excellent cytocompatibility and hemocompatibility. This work not only provides the first paradigm for fabricating silver peroxide nanoparticle but also introduces a highly efficient noninvasive and safe therapeutic modality for combating bacterial infectious diseases.

Reversible Transformation between Cs3Cu2I5 and CsCu2I3 Perovskite Derivatives and Its Anticounterfeiting Application.

Lead halide perovskites have promising values in photoelectronic and photovoltaic applications, but the toxicity of lead is a hard barrier. Copper halide perovskite derivatives (CHPDs), as a lead-free substitution of lead halide perovskites, also exhibit excellent photoelectric properties. Here, we present a facile one-step route for the synthesis of blue-emissive Cs3Cu2I5 (emission at 440 nm) and yellow-emissive CsCu2I3 (emission at 552 nm) CHPDs in ethanol at room temperature. Triggered by ethanol or CsI, a reversible chemical transformation accompanied by emissive color change between Cs3Cu2I5 and CsCu2I3 CHPDs was achieved. The reversible transformation mechanism was discussed, and this transformation was employed for effective anticounterfeiting.

Balanced charge transport and enhanced performance of blue quantum dot light-emitting diodes via electron transport layer doping.

The unbalanced charge transport is always a key influencing factor on the device performance of quantum dot light-emitting diodes (QLEDs), particularly for the blue QLEDs due to their large optical band gap. Here, a method of electron transport layer (ETL) doping was developed to regulate the energy levels and the carrier mobility of the ETL, which resulted in more balanced charge injection, transport and recombination in the blue emitting CdZnS/ZnS core/shell QLEDs. Consequently, an enhanced performance of blue QLEDs was achieved by modulating the charge balance through ETL doping. The maximum external quantum efficiency and luminance was dramatically increased from 2.2% to 7.3% and from 3786 cd m-2to 9108 cd m-2, respectively. The results illustrate that charge transport layer doping is a simple and effective strategy to regulate the charge injection barrier and carrier mobility of QLEDs.

Bright CsPbI3 Perovskite Quantum Dot Light-Emitting Diodes with Top-Emitting Structure and a Low Efficiency Roll-Off Realized by Applying Zirconium Acetylacetonate Surface Modification.

Zirconium acetylacetonate used as a co-precursor in the synthesis of CsPbI3 quantum dots (QDs) increased their photoluminescence quantum efficiency to values over 90%. The top-emitting device structure on a Si substrate with high thermal conductivity (to better dissipate Joule heat generated at high current density) was designed to improve the light extraction efficiency making use of a strong microcavity resonance between the bottom and top electrodes. As a result of these improvements, light-emitting diodes (LEDs) utilizing Zr-modified CsPbI3 QDs with an electroluminescence at 686 nm showed external quantum efficiency (EQE) of 13.7% at a current density of 108 mA cm-2, which was combined with low efficiency roll-off (maintaining an EQE of 12.5% at a high current density of 500 mA cm-2) and a high luminance of 14 725 cd m-2, and the stability of the devices being repeatedly lit (cycled on and off at high drive current density) has been greatly enhanced.

Antibacterial Activity of Graphdiyne and Graphdiyne Oxide.

From manufacture to disposal, the interaction of graphdiyne based nanomaterials with living organisms is inevitable and crucial. However, the cytotoxic properties of this novel carbon nanomaterial are rarely investigated, and the mechanisms behind their cytotoxicity are totally unknown. In this study, the antibacterial activity of graphdiyne (GDY) and graphdiyne oxide (GDYO) is reported. GDY is capable of inhibiting broad-spectrum bacterial growth while exerting moderate cytotoxicity on mammalian cells. In comparison, GDYO exhibits lower antibacterial activity than that of GDY. Then an alterable, synergetic antibacterial mechanism of GDY, involving wrapping bacterial membrane, membrane insertion and disruption, and reactive oxygen species generation is demonstrated, while the differential gene expression analysis indicates that GDY could only alter the bacterial metabolism slightly and the oxidative stress route may be a minor bactericidal factor. The investigation of the antibacterial behaviors of GDY based nanomaterials may provide useful guidelines for the future design and application of this novel molecular allotrope of carbon.

Aqueous Precursor Induced Morphological Change and Improved Water Stability of CsPbBr3 Nanocrystals.

In the literature, lead halide perovskites are very notable for their degradation in the presence of polar solvents, such as water. In contrast, in this research, it is observed that adding a minor amount of water into the precursor solution can improve the stability and photoluminescence quantum yield of CsPbBr3 nanocrystals through a ligand-assisted reprecipitation (LARP) method. In this way, the shape and phase transformation from CsPbBr3 nanoplates to CsPbBr3 /Cs4 PbBr6 nanorods and Cs4 PbBr6 nanowires can be controlled with increasing water content in the precursor solution. Upon adding water up to an ideal amount, CsPbBr3 maintains its phase and nanoplate morphology. The key role of water amount for tuning the crystallinity, stability, morphology, optical properties, and phase transformation of cesium lead halide perovskite nanocrystals will be beneficial in the future commercialization of optoelectronics.

Room Temperature Synthesis of All Inorganic Lead-Free Zero-Dimensional Cs4SnBr6 and Cs3KSnBr6 Perovskites.

Lead halide perovskites are excellent candidates for photoelectronic and photovoltaic applications, but the toxicity from lead is extremely concerning. Recently, Sn-based zero-dimensional lead-free perovskites synthesized using solid-state reaction techniques have become a new focus in the field. Here, we report a simple room temperature antisolvent method for the synthesis of all inorganic lead-free green emissive Cs4SnBr6 (emission at 524 nm) and cyan emissive Cs3KSnBr6 (emission at 500 nm) zero-dimensional perovskites. Their photoluminescence quantum yields reach 20% and 35%, respectively. In addition, they maintain their emission for 46 and 55 h in the air, respectively, compared to only 5 min of CsSnBr3. This method provides a convenient way to do the research and apply these highly emissive perovskites.

Smart quantum dot LEDs with simulated solar spectrum for intelligent lighting.

LED light bulbs that simulate solar spectrum were fabricated using CdSe core-shell quantum dots in combination with GaN blue-light chips. They exhibited excellent optical properties such as white CIE coordinates of (0.33, 0.33), high color rendering index (CRI) of 98 and correlated color temperature (CCT) of 5352 K. Moreover, a circuit system was used to control the LEDs so that the lighting spectrum changes with the time in a day to simulate the actual solar spectrum. The results show that the sun-like spectrum smart bulbs not only have good optical properties and high electrical stability, but also can automatically adjust their spectrum according to the time, making the lighting natural. This work makes sun-like lighting conditions for some special environments to promote the application of smart bulbs in smart lighting.

Subsequent monitoring of ferric ion and ascorbic acid using graphdiyne quantum dots-based optical sensors.

Graphdiyne (GDY) as an emerging carbon nanomaterial has attracted increasing attention because of its uniformly distributed pores, highly π-conjugated, and tunable electronic properties. These excellent characteristics have been widely explored in the fields of energy storage and catalysts, yet there is no report on the development of sensors based on the outstanding optical property of GDY. In this paper, a new sensing mechanism is reported built upon the synergistic effect between inner filter effect and photoinduced electron transfer. We constructed a novel nanosensor based upon the newly-synthesized nanomaterial and demonstrated a sensitive and selective detection for both Fe3+ ion and ascorbic acid, enabling the measurements in real clinical samples. For the first time fluorescent graphdiyne oxide quantum dots (GDYO-QDs) were prepared using a facile ultrasonic protocol and they were characterized with a range of techniques, showing a strong blue-green emission with 14.6% quantum yield. The emission is quenched efficiently by Fe3+ and recovered by ascorbic acid (AA). We have fabricated an off/on fluorescent nanosensors based on this unique property. The nanosensors are able to detect Fe3+ as low as 95 nmol L-1 with a promising dynamic range from 0.25 to 200 µmol L-1. The LOD of AA was 2.5 µmol L-1, with range of 10-500 µmol L-1. It showed a promising capability to detect Fe3+ and AA in serum samples. Graphical abstract.