While convenient solution-based procedures have been realized for the synthesis of colloidal perovskite nanocrystals, the impact of surfactant ligands on the shape, size, and surface properties still remains poorly understood, which calls for a more detailed structure-morphology study. Herein we have systematically varied the hydrocarbon chain composition of carboxylic acids and amines to investigate the surface chemistry and the independent impact of acid and amine on the size and shape of perovskite nanocrystals. Solution phase studies on purified nanocrystal samples by (1)H NMR and IR spectroscopies have confirmed the presence of both carboxylate and alkylammonium ligands on surfaces, with the alkylammonium ligand being much more mobile and susceptible to detachment from the nanocrystal surfaces during polar solvent washes. Moreover, the chain length variation of carboxylic acids and amines, ranging from 18 carbons down to two carbons, has shown independent correlation to the size and shape of nanocrystals in addition to the temperature effect. We have additionally demonstrated that employing a more soluble cesium acetate precursor in place of the universally used Cs2CO3 results in enhanced processability without sacrificing optical properties, thus offering a more versatile recipe for perovskite nanocrystal synthesis that allows the use of organic acids and amines bearing chains shorter than eight carbon atoms. Overall our studies have shed light on the influence of ligand chemistry on crystal growth and stabilization of the nanocrystals, which opens the door to functionalizable perovskite nanocrsytals through surface ligand manipulation.
All-inorganic CsPbX3 (X = Cl, Br or I) perovskite nanocrystals have attracted extensive interest recently due to their exceptional optoelectronic properties. In an effort to improve the charge separation and transfer following efficient exciton generation in such nanocrystals, novel functional nanocomposites were synthesized by the in situ growth of CsPbBr3 perovskite nanocrystals on two-dimensional MXene nanosheets. Efficient excited state charge transfer occurs between CsPbBr3 NCs and MXene nanosheets, as indicated by significant photoluminescence (PL) quenching and much shorter PL decay lifetimes compared with pure CsPbBr3 NCs. The as-obtained CsPbBr3/MXene nanocomposites demonstrated increased photocurrent generation in response to visible light and X-ray illumination, attesting to the potential application of these heterostructure nanocomposites for photoelectric detection. The efficient charge transfer also renders the CsPbBr3/MXene nanocomposite an active photocatalyst for the reduction of CO2 to CO and CH4. This work provides a guide for exploration of perovskite materials in next-generation optoelectronics, such as photoelectric detectors or photocatalyst.
Despite the exceptional optoelectronic characteristics of the emergent perovskite nanocrystals, the ionic nature greatly limits their stability, and thus restricts their potential applications. Here we have adapted a self-assembly strategy to access a rarely reported nanorod suprastructure that provide excellent encapsulation of perovskite nanocrystals by polymer-grafted graphene oxide layers. Polyacrylic acid-grafted graphene oxide (GO-g-PAA) was used as a surface ligand during the synthesis of the CsPbX perovskite nanocrystals (NCs), yielding particles (5-12 nm) with tunable halide compositions that were homogeneously embedded in the GO-g-PAA matrix. The resulting NC-GO-g-PAA exhibits a higher photoluminescence quantum yield than previously reported encapsulated NCs while maintaining an easily tunable bandgap, allowing for emission spanning the visible spectrum. The NC-GO-g-PAA hybrid further self-assembles into well-defined nanorods upon solvent treatment. The resulting nanorod morphology imparts extraordinary chemical stability toward protic solvents such as methanol and water and much enhanced thermal stability. The introduction of barrier layers by embedding the perovskite NCs in the GO-g-PAA matrix, together with its unique assembly into nanorods, provides a novel strategy to afford robust perovskite emissive materials with environmental stability that may meet or exceed the requirement for optoelectronic applications.
The potential optoelectronic applications of perovskite nanocrystals (NCs) are primarily limited by major material instability arising from the ionic nature of the NC lattice. Herein, we introduce a facile and effective strategy to prepare extremely stable CsPbX3 NC-polymer composites. NC surfaces are passivated with reactive methacrylic acid (MA) ligands, resulting in the formation of homogenous nanocubes (abbreviated as MA-NCs) with a size of 14-17 nm and a photoluminescence quantum yield (PLQY) above 80%. The free double bonds on the surface then serve as chemically addressable synthetic handles, enabling UV-induced radical polymerization. Critically, a bromide-rich environment is developed to prevent NC sintering. The composites obtained from copolymerizing MA-NCs with hydrophobic methyl methacrylate (MMA) and methacrylisobutyl polyhedral oligomeric silsesquioxane (MA-POSS) monomers exhibit enhanced properties compared to previously reported encapsulated NCs, including higher QYs, remarkable chemical stability towards water, and much enhanced thermal stability. The good solubility of the composite in organic solvent further enables its use as a solution processable luminescent ink, used here for fabrication of white light-emitting diodes (WLED) with high luminous effciency and excellent color rendering index. The resulting fluorescent and stable NC ink opens the door to potential scalable and robust optoelectronic applications.
All-inorganic cesium lead halide perovskite nanocrystals (CsPbX3, X = Cl, Br, or I) present broad applications in the field of optoelectronics due to their excellent photoluminescence (PL), narrow spectral bandwidth, and wide spectral tunability. However, their poor stability limits their practical application. In this work, we successfully use an in situ crystallization strategy for growing and cladding CsPbBr3 perovskite nanocrystals in poly(vinylidene difluoride) (PVDF). The CsPbBr3 nanocrystals in the as-fabricated CsPbBr3@PVDF composites have an average diameter of 16–18 nm and a strong PL emission (537 nm), with a photoluminescence quantum yield exceeding 30%. In addition, the fabricated CsPbBr3@PVDF composites present improved resistance to heat and water preserving with remarkable optical performance, owing to the effective protection of PVDF. Moreover, the CsPbBr3 nanocrystals generated in PVDF can withstand temperatures up to 170 °C and can be completely immersed in water for 60 days while still retaining high PL intensity, which facilitate the practical application of CsPbBr3 perovskite nanocrystals. These CsPbBr3@PVDF composite films with remarkable optical performances and superior anti-interference ability have broad application prospects in optoelectronics as well as good potential as temperature sensors in mechanical engineering.
Creating highly stable inorganic perovskite nanocrystals (CsPbX 3 , X=Cl, Br and I) with excellent optical performance is challenging because their optical properties depend on their ionic structure and its inherent defects. Here, we present a facile and effective synthesis using a nano confinement strategy to grow Mn 2+ doped CsPbCl 3 nanocrystals embedded in dendritic mesoporous silica nanospheres (MSNs). The resulting nanocomposite is abbreviated as Cs(Pb x /Mn 1x)Cl 3 @MSNs and can serve as the orange emitter for white lightemitting diodes (WLED). The MSN matrix was prepared via a templated solgel technique as monodispersed centerradial dendritic porous particles, with a diamater of around 105 nm and an inner pore size of around 13 nm. The MSN was then utilized as the matrix to initiate the growth of Mndoped perovskite nanocrystals (NCs). The NCs in the resulting composite have an average diameter of 8 nm and a photoluminescence quantum yield (PLQY) exceeding 30%. In addition, the optical properties of the Cs(Pb x /Mn 1x)Cl 3 @MSNs composite can be tuned by varying the Mn 2+ doping level. The resulting composites presented a significantly improved resistance to UV light, temperature, and moisture compared to the bare Cs(Pb 0.72 /Mn 0.28)Cl 3. Finally, we fabricated downconverting white light emitting diodes (WLEDs) by using Cs(Pb x /Mn 1x)Cl 3 @MSNs composite as the orangeemitting phosphor deposited onto UV emitting chips, demonstrating their promising applications in solidstate lighting. This work provides a valuable approach to fabricate stable orange luminophores as replacements for traditional emitters in LED devices.
Graphene quantum dot (GQD) encapsulated melamine‐formaldehyde (MF) polymer microspheres with uniform particle size and tunable high‐quality white‐light emissions are prepared via a polymer‐mediated GQD assembly and encapsulation strategy. In solution, GQDs are first aggregated with MF prepolymer through electrostatic interaction and further encapsulated inside the microspheres formed by polymerization of MF prepolymer under acid catalysis and heating. During this process, the aggregated GQDs are fixed in the MF polymer matrix with their emission extended from blue to full visible range, presenting bright white luminescence under ultraviolet excitation. The prepared white‐light‐emitting GQD‐MF microspheres exhibit uniform morphology with an average particle size of 2.0 ± 0.08 µm and their luminescence properties are effectively regulated by the doping concentration of GQDs in the MF polymer matrix. A series of white‐light‐emitting GQD‐MF microspheres with quantum yields from 0.83 to 0.43, Commission Internationale de L'Eclairage coordinates from (0.28, 0.28) to (0.33, 0.32), and color rendering index from 0.75 to 0.88 are obtained with excellent photostability and thermal stability. By dispersing the GQD‐MF microspheres in cross‐linked polydimethylsiloxane matrix, flexible film with dual functions of high‐quality white‐light‐emitting and light diffusion is obtained and successfully applied for white light‐emitting diode fabrication.
Ordered self-assembled arrays or superstructures of nanocrystals (NCs) have attracted intense research interest due to their ability to translate valuable nanoscale properties to larger length scales. Numerous techniques have been explored to induce self-assembly into various superstructures. Here we investigated a simple kinetic approach to form self-assembled one-dimensional perovskite CsPbX (X: halides) nanocrystal arrays templated inside a pod shaped inert lead sulfate (PbSO) scaffold. Both the solvent effects, and the self-assembly process and mechanism, are systematically studied based on a uniform procedure developed to generate CsPbX nanocrystal superlattices with different sizes and compositions. The formation of one-dimensional (1D) chains of NCs within a half-cylindrical pod of PbSO reflects a balance between solvophobicity and solvophilicity of the components. By reducing the size of NCs, we successfully realized 2D superlattices with two or three rows of close-packed CsPbBr NCs, in addition to single string-of-pearl type 1D assemblies. The superlattices can be assembled both inside and outside of the half-cylindrical shells by regulating the reaction conditions. The self-assembly behavior is reminiscent of the host-guest systems of organic molecular species where supramolecular recognition rules apply to give well-defined complexes. The current study opens a door for controlling self-assembled nanostructures of CsPbX NCs, and provides an attainable platform for future optoelectronic devices.
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