CsPbX3/SiOx (X = Cl, Br, I) monoliths prepared via a novel sol–gel route starting from Cs4PbX6 nanocrystals

Park, Sungwook; An, Mai Ngoc; Almeida, Guilherme; Palazón, Francisco; Spirito, Davide; Krahne, Roman; Dang, Zhiya; Trizio, Luca De; Manna, Liberato

doi:10.1039/c9nr07766a

Cited by 26 publications

(28 citation statements)

References 48 publications

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“…Surface destabilization and acidic environments are both general conditions that are known to cause the Cs 4 PbBr 6 / CsPbBr 3 transformation. 10,25,42 The stoichiometry of the transformation is balanced by a nominal removal of 3 equivalents of CsBr from 1 equivalent of Cs 4 PbBr 6 , yet we have not experimentally detected crystalline CsBr by XRD or high-resolution TEM (HRTEM). This discrepancy is tentatively rationalized by solvation of Cs + and Br À ions by oleate and polysuccinamic acid species, similar to the previously reported dissociation of CsBr in dimethylformamide in the presence of the polyacrylic acid co-polymer.…”

Section: Rationalization Of the Observed Reactivity Between Pmao And mentioning

confidence: 86%

Transforming colloidal Cs₄PbBr₆ nanocrystals with poly(maleic anhydride-alt-1-octadecene) into stable CsPbBr₃ perovskite emitters through intermediate heterostructures

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Section: Rationalization Of the Observed Reactivity Between Pmao And mentioning

confidence: 86%

Transforming colloidal Cs₄PbBr₆ nanocrystals with poly(maleic anhydride-alt-1-octadecene) into stable CsPbBr₃ perovskite emitters through intermediate heterostructures

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“…[ 152,153 ] During the reaction, a self‐organization driven by a van der Waals force occurred during the conversion from Cs 4 PbBr 6 to CsPbBr 3 , resulting in the CsPbBr 3 nanorods. Similarly, CsPbX 3 /oxide hybridized nanostructures (Figure 12f) could be prepared as well via this method, [ 154–156 ] in which CsPbX 3 was obtained through Cs 4 PbX 6 degeneration accompanied with the hydrolysis of an oxide precursor. The luminescent on→off upon water triggering have made Cs 4 PbX 6 NCs a promising candidate for use in humidity sensors and anticounterfeiting.…”

Section: Transformation Between Perovskites With Different Dimensionsmentioning

confidence: 99%

Low‐Dimensional‐Networked Cesium Lead Halide Perovskites: Properties, Fabrication, and Applications

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resistance against thermal-treatment compared to organic-inorganic hybrid lead halide perovskites (MAPbX 3 and FAPbX 3), due to the high thermal decomposition temperature of inorganic cations, thus drawing much attention. Owing to their impressive features, all-inorganic lead halide perovskites have been greatly useful in photovoltaic and optoelectronic applications, including solar cells, light-emitting diodes (LEDs), lasers, photodetectors and photocatalysis. [5-17] The conspicuous achievements in CsPbX 3 provoke the rapid development of its derivatives, Cs 4 PbX 6 and CsPb 2 X 5. These Cs x Pb y X z materials are composed of the same element compositions and [PbX 6 ] 4− unit cells. However, they possess completely different connectivity characters of [PbX 6 ] 4− octahedrons. CsPbX 3 is classified as a type of 3D perovskite, because [PbX 6 ] 4− octahedra are corner-shared along all three axes, while CsPb 2 X 5 has a sandwich-like arrangement with Cs + cations in between PbX 2 crystallographic planes, which can be regarded as a 2D phase. In Cs 4 PbX 6 , disconnected [PbBr 6 ] 4− octahedra are completely decoupled by Cs + cations. Among these three structures, CsPb 2 X 5 and Cs 4 PbX 6 , with dimensional-network less than 3 are referred to as lowdimensional-networked cesium lead halide perovskites. Besides the connectivity, these structures can be understood from a confinement perspective. CsPbX 3 is not confined in any dimension such that it can be considered as a 3D networked semiconductor. CsPb 2 X 5 and Cs 4 PbX 6 are confined in one dimension and all three dimensions, hence the name 2D and 0D structures, respectively. [18,19] In CsPb 2 X 5 and Cs 4 PbX 6 , the excitons cannot dissociate easily within all dimensions; instead, they are confined in the PbX 2 planes and individual [PbX 6 ] 4− units, respectively, resulting in larger bandgaps compared to the traditional ABX 3 phase. Figure 1 illustrates these three structures with different dimensions. Until now, comprehensive accounts of these Cs x Pb y X z materials have been made. However, most recent research focuses on CsPbX 3 , which has excellent optical properties and promising potential in various applications. Its derivatives, CsPb 2 X 5 and Cs 4 PbX 6 have achieved tremendous progress but are still far behind that of CsPbX 3. Many problems still seriously limit the rapid development of these low-dimensional-networked perovskites, a typical one being the debate on the origin of their luminescence. In this Review article, we focus on Cs 4 PbX 6 and CsPb 2 X 5 , and attempt to unveil their features, potential in All-inorganic cesium lead halide perovskites have emerged as promising optoelectronic materials with excellent photophysical properties and great potential in a variety of applications. In parallel with the most investigated CsPbX 3 , its derivates, Cs 4 PbX 6 and CsPb 2 X 5 , with low-dimensional-networked structures have also attracted great attention. In this review, recent advancements on the low-dimensional-networked cesium lead halide perovs...

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“…Surface destabilization and acidic environment are both general conditions that are known to cause the Cs4PbBr6 → CsPbBr3 transformation. 10,27,35 Eventually, our 1 H NMR analysis also revealed that the final NCs were capped solely by polysuccinamic acid, indicating the displacement of both the oleate and amine/ammonium ligands from the NC surface upon the transformation (see discussion in Section S9 and Figures S19-S21).…”

Section: Rationalization Of the Observed Reactivity Between Pmao And Cs4pbbr6mentioning

confidence: 76%

Transforming Colloidal Cs4PbBr6 Nanocrystals by Poly(maleic anhydride-alt-1-octadecene) into Stable CsPbBr3 Perovskite Emitters Through Intermediate Heterostructures

Баранов

Caputo²,

Goldoni³

et al. 2020

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The preparation of strongly emissive CsPbBr3 perovskite nanocrystals with a robust surface passivation is a challenge in the field of lead halide perovskite nanomaterials. We report an approach to prepare polymer-capped CsPbBr3 perovskite nanocrystals by reacting oleylammonium/oleate-capped Cs4PbBr6 nanocrystals with poly(maleic anhydride-alt-1-octadecene) (PMAO). PMAO contains succinic anhydride units that are reactive towards the oleylamine species present on Cs4PbBr6 nanocrystals’ surface and produces polysuccinamic acid, which, in turn, triggers the Cs4PbBr6 to CsPbBr3 conversion. The transformation occurs through the formation of Cs4PbBr6-CsPbBr3 heterostructures as intermediates, which were captured because of the mild reactivity of PMAO and were investigated by high-resolution electron microscopy. The Cs4PbBr6-CsPbBr3 heterostructures demonstrate a dual emission at cryogenic temperature with an indication of the energy transfer from Cs4PbBr6 to CsPbBr3. The fully-transformed CsPbBr3 NCs have high photoluminescence quantum yield and enhanced colloidal stability, which we attribute to the adhesion of polysuccinamic acid to the NC surface through its multiple functional groups in place of oleate and alkylammonium ligands. The PMAO-induced transformation of Cs4PbBr6 NCs opens up a strategy for the chemical modification of metal halide NCs initially passivated with nucleophilic amines.

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CsPbX₃/SiO_x (X = Cl, Br, I) monoliths prepared via a novel sol–gel route starting from Cs₄PbX₆ nanocrystals

Abstract: We developed a facile synthesis of nanocomposite powders of CsPbX3 nanocrystals (NCs) embedded in silica.

Cited by 26 publications

References 48 publications

Transforming colloidal Cs₄PbBr₆ nanocrystals with poly(maleic anhydride-alt-1-octadecene) into stable CsPbBr₃ perovskite emitters through intermediate heterostructures

Transforming colloidal Cs₄PbBr₆ nanocrystals with poly(maleic anhydride-alt-1-octadecene) into stable CsPbBr₃ perovskite emitters through intermediate heterostructures

Low‐Dimensional‐Networked Cesium Lead Halide Perovskites: Properties, Fabrication, and Applications

Transforming Colloidal Cs4PbBr6 Nanocrystals by Poly(maleic anhydride-alt-1-octadecene) into Stable CsPbBr3 Perovskite Emitters Through Intermediate Heterostructures

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CsPbX3/SiOx (X = Cl, Br, I) monoliths prepared via a novel sol–gel route starting from Cs4PbX6 nanocrystals

Abstract: We developed a facile synthesis of nanocomposite powders of CsPbX3 nanocrystals (NCs) embedded in silica.

Cited by 26 publications

References 48 publications

Transforming colloidal Cs4PbBr6 nanocrystals with poly(maleic anhydride-alt-1-octadecene) into stable CsPbBr3 perovskite emitters through intermediate heterostructures

Transforming colloidal Cs4PbBr6 nanocrystals with poly(maleic anhydride-alt-1-octadecene) into stable CsPbBr3 perovskite emitters through intermediate heterostructures

Low‐Dimensional‐Networked Cesium Lead Halide Perovskites: Properties, Fabrication, and Applications

Transforming Colloidal Cs4PbBr6 Nanocrystals by Poly(maleic anhydride-alt-1-octadecene) into Stable CsPbBr3 Perovskite Emitters Through Intermediate Heterostructures

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CsPbX₃/SiO_x (X = Cl, Br, I) monoliths prepared via a novel sol–gel route starting from Cs₄PbX₆ nanocrystals

Transforming colloidal Cs₄PbBr₆ nanocrystals with poly(maleic anhydride-alt-1-octadecene) into stable CsPbBr₃ perovskite emitters through intermediate heterostructures

Transforming colloidal Cs₄PbBr₆ nanocrystals with poly(maleic anhydride-alt-1-octadecene) into stable CsPbBr₃ perovskite emitters through intermediate heterostructures