Metal oxide hybridization enhances room temperature phosphorescence of carbon dots-SiO2 matrix for information encryption and anti-counterfeiting.

Room temperature phosphorescent (RTP) carbon dot (CD) materials have been widely used in various fields, but it is difficult to achieve a long lifetime, high stability and easy synthesis. In particular, realizing the phosphorescence emission of CDs using a metal oxide (MO) matrix is a challenge. Here, solid gels are synthesized via in situ hydrolysis, and then RTP CDs are synthesized based on a SiO2 matrix (CDs@SiO2) and hybridized with a MO matrix (CDs@SiO2-MO) by high-temperature calcination. Among the materials synthesized, Al2O3 matrix RTP CDs (CDs@SiO2-Al2O3) have a long phosphorescence lifetime of 689 ms and can exhibit yellow-green light visible to the naked eye for 9 s after the UV light (365 nm) is turned off. Compared with the green phosphorescence of CDs@SiO2, the yellow-green phosphorescence lifetime of CDs@SiO2-Al2O3 is enhanced by 420 ms. In addition, CDs@SiO2-Al2O3 maintains good stability of phosphorescence emission in water, strongly oxidizing solutions and organic solvents. As a result, CDs@SiO2-Al2O3 can be applied to the field of information encryption and security anti-counterfeiting, and this work provides a new, easy and efficient synthesis method for MO as an RTP CD matrix.

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.

Stability Enhancement in All-Inorganic Perovskite Light Emitting Diodes via Dual Encapsulation.

Addressing the challenge of lighting stability in perovskite white light emitting diodes (WLEDs) is crucial for their commercial viability. CsPbX3 (X = Cl, Br, I, or mixed) nanocrystals (NCs) are promising for next-generation lighting due to their superior optical and electronic properties. However, the inherent soft material structure of CsPbX3 NCs is particularly susceptible to the elevated temperatures associated with prolonged WLED operation. Additionally, these NCs face stability challenges in high humidity environments, leading to reduced lighting performance. This study introduces a two-step dual encapsulation method, resulting in CsPbBr3@SiO2/Al2SiO5 composite fibers (CFs) with enhanced optical stability under extreme conditions. In testing, WLEDs incorporating these CFs, even under prolonged operation at high power (100 mA for 9 h), maintain consistent electroluminescence (EL) intensity and optoelectronic parameters, with surface temperatures reaching 84.2 °C. Crucially, when subjected to 85 °C and 85% relative humidity for 200 h, the WLEDs preserve 97% of their initial fluorescence efficiency. These findings underscore the efficacy of the dual encapsulation strategy in significantly improving perovskite material stability, marking a significant step toward their commercial application in optoelectronic lighting.

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.

Studies on the optical stability of CsPbBr3 with different dimensions (0D, 1D, 2D, 3D) under thermal environments.

The thermal stability of phosphor materials had long been a bottleneck in their commercialization. Nowadays, cesium lead halide perovskite CsPbBr3 has been considered a potential replacement for the next generation of optoelectronic devices due to its excellent optical and electronic properties, however, the devices inevitably generate high temperatures on the surface under prolonged energization conditions in practical applications, which can be fatal to CsPbBr3. Despite the various strategies that have been employed to improve the thermal stability of CsPbBr3, systematic studies of the thermal stability of the basis CsPbBr3 are lacking. In this study, CsPbBr3 with different dimensions (0D quantum dots (QDs), 1D nanowires (NWs), 2D nanoplate (NPs), 3D micron crystals (MCs)) was prepared by traditional high-temperature thermal injection, and a systematic study was carried out on their optical properties and thermal stability. The results revealed that the dimensional change will directly influence the optical properties as well as the thermal stability of CsPbBr3. In particular, 3D CsPbBr3 MCs maintained relatively high thermal stability under high-temperature environments, which will bring interest for the commercialization of next-generation perovskite optoelectronic devices.

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.

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.

Optical Properties and Upconversion Luminescence of BaTiO3 Xerogel Structures Doped with Erbium and Ytterbium.

Erbium upconversion (UC) photoluminescence (PL) from sol-gel derived barium titanate (BaTiO3:Er) xerogel structures fabricated on silicon, glass or fused silica substrates has been studied. Under continuous-wave excitation at 980 nm and nanosecond pulsed excitation at 980 and 1540 nm, the fabricated structures demonstrate room temperature PL with several bands at 410, 523, 546, 658, 800 and 830 nm, corresponding to the 2H9/2 → 4I15/2, 2H11/2 → 4I15/2, 4S3/2 → 4I15/2, 4F9/2→ 4I15/2 and 4I9/2→ 4I15/2 transitions of Er3+ ions. The intensity of erbium UC PL increases when an additional macroporous layer of strontium titanate is used beneath the BaTiO3 xerogel layer. It is also enhanced in BaTiO3 xerogel films codoped with erbium and ytterbium (BaTiO3:(Er,Yb)). For the latter, a redistribution of the intensity of the PL bands is observed depending on the excitation conditions. A multilayer BaTiO3:(Er,Yb)/SiO2 microcavity structure was formed on a fused silica substrate with a cavity mode in the range of 650-680 nm corresponding to one of the UC PL bands of Er3+ ions. The obtained cavity structure annealed at 450 °C provides tuning of the cavity mode by 10 nm in the temperature range from 20 °C to 130 °C. Photonic application of BaTiO3 xerogel structures doped with lanthanides is discussed.

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.

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.

Highly stable Na: CsPb(Br,I)3@Al2O3 nanocomposites prepared by a pre-protection strategy.

Among the leading energy materials, metal tri-halide perovskite quantum dots (PQDs) with outstanding optoelectronic properties are at the forefront of current research. However, enormous challenges remain to be addressed, including hazardous components and poor stability, before achieving practical applications of PQDs. Although there are diverse methods to improve the stability of PQDs, it is of central importance to avoid damage during operation. Herein, we develop a pre-protected strategy in which the coating combines the advantages of doping with sodium ions to jointly improve stability. Because the stable Na-rich surface acts as a defence, it protects the PQDs from damage during the coating process; therefore, they retain their initial fluorescence. When employing these Na-rich PQDs as core materials of a coating, the highly fluorescent Na: CsPb(Br,I)3@Al2O3 nanocomposites can maintain good stability even when directly immersed in water or exposed to illumination. Clearly, the combination of these features sheds light on the stabilization and applications of PQDs.

Reversible transformation between CsPbBr3 nanowires and nanoparticles.

We show that CsPbBr3 nanowires (NWs) are formed by the hierarchical arrangement of individual nanoparticles (NPs), and reversible transformation from NWs to NPs is also achieved by anion exchange.