Tuning optical properties of CsPbBr3by mixing Nd3+trivalent lanthanide halide cations for blue light emitting devices.

In recent years, significant progress has been made in the red and green perovskite quantum dots (PQDs) based light-emitting devices. However, a scarcity of blue-emitting devices that are extremely efficient precludes their research and development for optoelectronic applications. Taking advantage of tunable bandgaps of PQDs over the entire visible spectrum, herein we tune optical properties of CSPbBr3by mixing Nd3+trivalent lanthanide halide cations for blue light-emitting devices. The CsPbBr3PQDs doped with Nd3+trivalent lanthanide halide cations emitted strong photoemission from green into the blue region. By adjusting their doping concentration, a tunable wavelength from (515 nm) to (450 nm) was achieved with FWHM from (37.83 nm) to (16.6 nm). We simultaneously observed PL linewidth broadening thermal quenching of PL and the blue shift of the optical bandgap from temperature-dependent PL studies. The Nd3+cations into CsPbBr3PQDs more efficiently reduced non-radiative recombination. As a result of the efficient removal of defects from PQDs, the photoluminescence quantum yield (PLQY) has been significantly increased to 91% in the blue-emitting region. Significantly, Nd3+PQDs exhibit excellent long-term stability against the external environment, including water, temperature, and ultraviolet light irradiation. Moreover, we successfully transformed Nd3+doped PQDs into highly fluorescent nanocomposites. Incorporating these findings, we fabricate and test a stable blue light-emitting LED with EL emission at (462 nm), (475 nm), and successfully produce white light emission from Nd3+doped nanocomposites with a CIE at (0.32, 0.34), respectively. The findings imply that low-cost Nd3+doped perovskites may be attractive as light converters in LCDs with a broad color gamut.

The adverse role of excess negative ions in reducing the photoluminescence from water soluble MAA-CdSe/ZnS quantum dots in various phosphate buffers.

The use of CdSe/ZnS quantum dots in making biosensors or biomarkers requires them to be water soluble, which can be achieved by conjugating with MAA. We report observation of modulation in the photoluminescence intensities of MAA conjugated CdSe/ZnS QDs (MAA-QDs) that depended strongly on the types and quantity of negative ions present in various kinds of phosphate buffers. The deterioration of PL was attributed to the presence of excess ions in the media that altered the energy and occupation of HOMO and LUMO levels of MAA. Instantaneously, strong reduction in the PL intensity with pH was observed. MAA-QDs incubated for more than 24 hours in the phosphate buffer at pH ∼ 7.0-8.0 showed recovery and enhanced PL intensity, which was attributed to the presence of excess positive ions and a small amount of OH-. Saline buffers showed no significant recovery due to the presence of additional Cl- ions. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were successfully employed to determine the band edges of the MAA-QD system in the presence of excess positive or negative ions (Na+, H+, Cl-, and OH-) in the media. Thus, it is very important to have complete knowledge of the ions present in the buffer when using MAA-QDs for biomarking or biosensing applications.

One-Step Preparation of High-Stability CsPbX3/CsPb2X5 Composite Microplates with Tunable Emission.

The core-shell structure is an effective means to improve the stability and optoelectronic properties of cesium lead halide (CsPbX3 (X = Cl, Br, I)) perovskite quantum dots (QDs). However, confined by the ionic radius differences, developing a core-shell packaging strategy suitable for the entire CsPbX3 system remains a challenge. In this study, we introduce an optimized hot-injection method for the epitaxial growth of the CsPb2X5 substrate on CsPbX3 surfaces, achieved by precisely controlling the reaction time and the ratio of lead halide precursors. The synthesized CsPbX3/CsPb2X5 composite microplates exhibit an emission light spectrum that covers the entire visible range. Crystallographic analyses and density functional theory (DFT) calculations reveal a minimal lattice mismatch between the (002) plane of CsPb2X5 and the (11¯0) plane of CsPbX3, facilitating the formation of high-quality type-I heterojunctions. Furthermore, introducing Cl- and I- significantly alters the surface energy of CsPb2X5's (110) plane, leading to an evolutionary morphological shift of grains from circular to square microplates. Benefiting from the passivation of CsPb2X5, the composites exhibit enhanced optical properties and stability. Subsequently, the white light-emitting diode prepared using the CsPbX3/CsPb2X5 composite microplates has a high luminescence efficiency of 136.76 lm/W and the PL intensity decays by only 3.6% after 24 h of continuous operation.

In Situ Fabrication of Lead-Free Double Perovskite/Polymer Composite Films for Optoelectronic Devices and Anticounterfeit Printing.

Lead-free double perovskites (DP) have the potential to become a rising star in the next generation of lighting markets by addressing the toxicity and instability issues associated with traditional lead-based perovskites. However, high concentrations of hydrochloric acid (HCl) were often employed as a solvent in the preparation of most DPs, accompanied by slow crystallization at high temperatures, which not only raised the risk and cost in the preparation process, but also had a potential threat to the environment. Here, an in situ fabrication strategy was proposed to realize the crystallization of DP in the polymer at low temperature with a mild dimethyl sulfoxide (DMSO) solvent, and subsequently obtained optically well-behaved Cs2Na0.8Ag0.2BiCl6/PMMA composite films (CFs) by doping with Ag+, generating bright orange luminescence with a photoluminescence quantum yield (PLQY) of up to 21.52%. Moreover, the growth dynamics of Cs2Na0.8Ag0.2BiCl6/PMMA CFs was further investigated by in situ optical transformation, which was extended to other DP-based polymer CFs. Finally, these CFs exhibited excellent performance in optoelectronic devices and anticounterfeit printing, the results of which provide a new pathway to advance the development of lead-free DP materials in the optical field.

Ultrastable CsPbBr3@CsPb2Br5@TiO2 Composites for Photocatalytic and White Light-Emitting Diodes.

Although cesium halide lead (CsPbX3, X = Cl, Br, I) perovskite quantum dots (QDs) have excellent photovoltaic properties, their unstable characteristics are major limitations to application. Previous research has demonstrated that the core-shell structure can significantly improve the stability of CsPbX3 QDs and form heterojunctions at interfaces, enabling multifunctionalization of perovskite materials. In this article, we propose a convenient method to construct core-shell-structured perovskite materials, in which CsPbBr3@CsPb2Br5 core-shell micrometer crystals can be prepared by controlling the ratio of Cs+/Pb2+ in the precursor and the reaction time. The materials exhibited enhanced optical properties and stability that provided for further postprocessing. Subsequently, CsPbBr3@CsPb2Br5@TiO2 composites were obtained by coating a layer of dense TiO2 nanoparticles on the surfaces of micrometer crystals through hydrolysis of titanium precursors. According to density functional theory (DFT) calculations and experimental results, the presence of surface TiO2 promoted delocalization of photogenerated electrons and holes, enabling the CsPbBr3@CsPb2Br5@TiO2 composites to exhibit excellent performance in the field of photocatalysis. In addition, due to passivation of surface defects by CsPb2Br5 and TiO2 shells, the luminous intensity of white light-emitting diodes prepared with the materials only decayed by 2%-3% at high temperatures (>100 °C) when working for 24 h.

Preparation of CsPb(Cl/Br)3/TiO2:Eu3+ composites for white light emitting diodes.

The inherent single narrow emission peak and fast anion exchange process of cesium lead halide perovskite CsPbX3 (X = Cl, Br, I) nanocrystals severely limited its application in white light-emitting diodes. Previous studies have shown that composite structures can passivate surface defects of NCs and improve the stability of perovskite materials, but complex post-treatment processes commonly lead to dissolution of NCs. In this study, CsPb(Cl/Br)3 NCs was in-situ grown in TiO2 hollow shells doped with Eu3+ ions by a modified thermal injection method to prepare CsPb(Cl/Br)3/TiO2:Eu3+ composites with direct excitation of white light without additional treatment. Among them, the well-crystalline TiO2 shells acted as both a substrate for the dopant, avoiding the direct doping of Eu3+ into the interior of NCs to affect the crystal structure of the perovskite materials, and also as a protection layer to isolate the contact between PL quenching molecules and NCs, which significantly improves the stability. Further, the WLED prepared using the composites had bright white light emission, luminous efficiency of 87.39 lm/W, and long-time operating stability, which provided new options for the development of perovskite devices.

Synthesis of ZnO nanostructures for low temperature CO and UV sensing.

In this paper, synthesis and results of the low temperature sensing of carbon monoxide (CO) gas and room temperature UV sensors using one dimensional (1-D) ZnO nanostructures are presented. Comb-like structures, belts and rods, and needle-shaped nanobelts were synthesized by varying synthesis temperature using a vapor transport method. Needle-like ZnO nanobelts are unique as, according to our knowledge, there is no evidence of such morphology in previous literature. The structural, morphological and optical characterization was carried out using X-ray diffraction, scanning electron microscopy and diffused reflectance spectroscopy techniques. It was observed that the sensing response of comb-like structures for UV light was greater as compared to the other grown structures. Comb-like structure based gas sensors successfully detect CO at 75 °C while other structures did not show any response.

Strong violet emission from ultra-stable strontium-doped CsPbCl3 superlattices.

Among the lead halide perovskites, the photoluminescence quantum yields (PLQYs) of perovskite quantum dots (PQDs) in the violet region are the very lowest. This is an obstacle to the optical applications across the entire visible area based on perovskite materials. Herein, we report a novel strontium (Sr)-substitution along with chlorine passivation strategy to enhance the PLQYs of CsPbCl3 PQDs. We surprisingly found that when the molar ratio of Sr2+/Pb2+ = 0.1/0.9, CsSr0.1Pb0.9Cl3 PQDs exhibit strong single-color violet emission, which is attributed to the effective passivation of chlorine defects. We further found spontaneous self-assembly of PQDs into highly emissive PSCs from the precursor in a highly concentrated solution. Moreover, by dilution of these PSCs, a few small PQD aggregates can be regained, which is similar to the PQDs formed at lower concentrations. Benefiting from the superior collective properties of individual PQDs, these highly fluorescent CsSr0.1Pb0.9Cl3 PSCs can maintain good stability even when directly immersed in water or exposed to illumination.

Electrochemically driven optical and SERS immunosensor for the detection of a therapeutic cardiac drug.

Cardiovascular diseases pose a serious health risk and have a high mortality rate of 31% worldwide. Digoxin is the most commonly prescribed pharmaceutical preparation to cardiovascular patients particularly in developing countries. The effectiveness of the drug critically depends on its presence in the therapeutic range (0.8-2.0 ng mL-1) in the patient's serum. We fabricated immunoassay chips based on QD photoluminescence (QDs-ELISA) and AuNP Surface Enhanced Raman Scattering (SERS-ELISA) phenomena to detect digoxin in the therapeutic range. Digoxin levels were monitored using digoxin antibodies conjugated to QDs and AuNPs employing the sandwich immunoassay format in both the chips. The limit of detection (LOD) achieved through QDs-ELISA and SERS-ELISA was 0.5 ng mL-1 and 0.4 ng mL-1, respectively. It is demonstrated that the sensitivity of QDs-ELISA was dependent on the charge transfer mechanism from the QDs to the antibody through ionic media, which was further explored using electrochemical impedance spectroscopy. We demonstrate that QDs-ELISA was relatively easy to fabricate compared to SERS-ELISA. The current study envisages replacement of conventional methodologies with small immunoassay chips using QDs and/or SERS-based tags with fast turnaround detection time as compared to conventional ELISA.

Preparation of ultra-stable and environmentally friendly CsPbBr3@ZrO2/PS composite films for white light-emitting diodes.

The working stability of perovskite light-emitting diodes (LEDs) has become an urgent bottleneck to be solved in the process of commercialization. Although lead halide perovskite CsPbX3 (X = Br, I, Cl) quantum dots (QDs) are considered rising stars in the lighting market owing to their excellent optoelectronic properties, they suffer from fluorescence quenching under thermal conditions. Unfortunately, the surfaces of electronic devices inevitably warm up under long-term energization, which is extremely detrimental to the appropriate functioning of CsPbX3 QDs. Based on the above discussion, the relationship function between the energization time and surface temperature of electronic devices was analyzed, after which a strategy for the preparation of dual-encapsulating perovskites using organic (polystyrene (PS)) and inorganic (ZrO2) materials was proposed, and the change in optical stability before and after encapsulation was investigated. The results show that the thermal stability of CsPbBr3@ZrO2/PS composite films (CFs) after the dual encapsulation was remarkably enhanced, and the assembled white LEDs still retain the initial emission intensity under prolonged high-power operation. In addition, the double encapsulation layer completely suppresses the ion leakage in CsPbBr3 and avoids damage to the ecosystem. It can be seen that this encapsulation strategy was capable of imparting excellent working stability to the perovskite material, which would clear the obstacles to commercial conversion.

Trioctylphosphine-Assisted Pre-protection Low-Temperature Solvothermal Synthesis of Highly Stable CsPbBr3/TiO2 Nanocomposites.

Lead halide perovskite quantum dots (PQDs) are reported as a promising branch of perovskites, which have recently emerged as a field in luminescent materials research. However, before the practical applications of PQDs can be realized, the problem of poor stability has not yet been solved. Herein, we propose a trioctylphosphine (TOP)-assisted pre-protection low-temperature solvothermal synthesis of highly stable CsPbBr3/TiO2 nanocomposites. Due to the protection of branched ligands and the lower temperature of shell formation, these TOP-modified CsPbBr3 PQDs are successfully incorporated into a TiO2 monolith without a loss of fluorescence intensity. Because the excellent nature of both parent materials is preserved in CsPbBr3/TiO2 nanocomposites, it is found that the as-prepared CsPbBr3/TiO2 nanocomposites not only display excellent photocatalytic activity but also yield improved PL stability, enabling us to build highly stable white light-emitting diodes and to photodegrade rhodamine B.

A versatile approach for shape-controlled synthesis of ultrathin perovskite nanostructures.

Very recently, ultrathin perovskite nanostructures, with the advantages of perovskite and ultrathin properties, have received an enormous level of interest due to their many fascinating properties, such as a strong quantum confinement effect and a large specific surface area. In spite of this incredible success of perovskite nanocrystals (NCs), the development of perovskite NCs is still in its infancy, and the production of high-quality ultrathin perovskite nanostructures has been a hot topic in the fields of nanoscience and nanotechnology. Herein, we demonstrate that ultrathin CsPbBr3 perovskite nanosheets (NSs) can be obtained by a simple mixing of precursor-ligand complexes under ambient conditions. It was found that the formation of NSs is ascribed to the stepwise self-assembly of the initially formed different types of ultrathin nanostructures. Due to the disappearance of grain boundaries and protection of branched ligands, these NSs exhibit enhanced optical properties compared to other types of samples. This direct synthesis method opens up a promising road for the synthesis of ultrathin NSs and guides the fabrication of other ultrathin nanostructures.

Measurement of soil radioactivity levels and radiation hazard assessment in southern Rechna interfluvial region, Pakistan.

Rechna interfluvial region is one of the main regions of Punjab, Pakistan. It is the area which is lying between River Ravi and River Chenab, alluvial-filled. Radioactivity levels in soil samples, collected from southern Rechna interfluvial region, Pakistan, have been estimated by using gamma-ray spectrometric technique. (226)Ra, (232)Th, the primordial radionuclide (40)K, and the artificial radionuclide (137)Cs have been measured in the soil of the study area. The mean radioactivity levels of (226)Ra, (232)Th, (40)K, and (137)Cs were found to be 50.6 +/- 1.7, 62.3 +/- 3.2, 662.2 +/- 32.1, and 3.1 +/- 0.3 Bq kg(-1), respectively. The mean radium equivalent activity (Ra(eq)), outdoor radiation hazard index (H(out)), indoor radiation hazard index (H(in)), and terrestrial absorbed dose rate for the area under study were determined as 190.8 +/- 8.7 Bq kg(-1), 0.52, 0.65, and 69.8 nGy h(-1), respectively. The annual effective dose to the general public was found to be 0.43 mSv. This value lies well below the limit of 1 mSv for general public as recommended by the International Commission on Radiological Protection. The measured values are comparable with other global radioactivity measurements and are found to be safe for the public and the environment.

Pressure-Driven Transformation of CsPbBrI2 Nanoparticles into Stable Nanosheets in Solution through Self-Assembly.

Very recently, two-dimensional (2D) perovskite nanosheets (PNSs), taking the advantages of perovskite as well as the 2D structure properties, have received an enormous level of interest throughout the scientific community. In spite of this incredible success in perovskite nanocrystals (NCs), self-assembly of many nanostructures in metal halide perovskites has not yet been realized, and producing highly efficient red-emitting PNSs remains challenging. In this Letter, we show that by using CsPbBrI2 perovskite nanoparticles (NPs) as a building block, PNSs can emerge spontaneously under high ambient pressure via template-free self-assembly without additional complicated operation. It is found that the formation of PNSs is ascribed to the high pressure that provides the driving force for the alignment of NPs in solution. Because of the disappearance of the grain boundaries between the adjacent NPs and increased crystallinity, these PNSs self-assembled from NPs exhibit enhanced properties compared to the initial NPs, including higher PL intensity and remarkable chemical stability toward light and water.

Efficient seed-mediated method for the large-scale synthesis of Au nanorods.

Seed-mediated methods are widely followed for the synthesis of Au nanorods (NRs). However, mostly dilute concentrations of the Au precursor (HAuCl4) are used in the growth solution, which leads to a low final concentration of NRs. Attempts of increasing the concentration of NRs by simply increasing the concentration of HAuCl4, other reagents in the growth solution and seeds lead to a faster growth kinetics which is not favourable for NR growth. Herein, we demonstrate that the increase in growth kinetics for high concentrations of reagents in growth solution can be neutralised by decreasing the pH of the solution. The synthesis of the NRs can be scaled up by using higher concentrations of reagents and adding an optimum concentration of HCl in the growth solution. The concentration of HAuCl4 in the growth solution can be increased up to 5 mM, and 10-20 times more NRs can be synthesised for the same reaction volume compared to that of the conventional seed-mediated method. We have also noticed that a cetyltrimethylammonium bromide (CTAB)-to-HAuCl4 molar ratio of 50 is sufficient for obtaining high yield of NRs.