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

Баранов, Д. А.; Caputo, Gianvito; Goldoni, Luca; Dang, Zhiya; Scarfiello, Riccardo; Trizio, Luca De; Portone, Alberto; Fabbri, Filippo; Camposeo, Andrea; Pisignano, Dario; Manna, Liberato

doi:10.1039/d0sc00738b

Cited by 68 publications

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“… 12 , 13 Examples include metal–perovskite (Au–CsPbBr 3 ), 14 metal chalcogenide–perovskite (PbS–CsPbX 3 , 15 ZnS–CsPbX 3 , 16 , 17 and PbSe–CsPbX 3 18 ), metal dichalcogenide–perovskite (Cs 2 SnI 6 /SnS 2 ), 19 CsPbX 3 /metal oxide Janus (TiO 2 –CsPbBr 3 , 20 CsPbX 3 /SiO 2 , 21 CsPbX 3 /ZrO 2 , 22 and CsPbBr 3 /TiO 2 23 ), CsBr–CsPbBr 3 , 24 and Cs 4 PbBr 6 –CsPbBr 3 NCs. 25 The latter case is a particularly revealing example of an epitaxial heterointerface (recently disclosed by our group), in which it is possible to observe a continuity of the sublattice of Cs + cations across the interface between the two domains, a common theme underlying the various heterostructures involving metal halide NCs. 26 Many of these nano-heterostructures may find applications in various fields, such as solar cells, LEDs, and photocatalysis.…”

Section: Introductionmentioning

confidence: 79%

Halide Perovskite–Lead Chalcohalide Nanocrystal Heterostructures

et al. 2021

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We report the synthesis of colloidal CsPbX3–Pb4S3Br2 (X = Cl, Br, I) nanocrystal heterostructures, providing an example of a sharp and atomically resolved epitaxial interface between a metal halide perovskite and a non-perovskite lattice. The CsPbBr3–Pb4S3Br2 nanocrystals are prepared by a two-step direct synthesis using preformed subnanometer CsPbBr3 clusters. Density functional theory calculations indicate the creation of a quasi-type II alignment at the heterointerface as well as the formation of localized trap states, promoting ultrafast separation of photogenerated excitons and carrier trapping, as confirmed by spectroscopic experiments. Postsynthesis reaction with either Cl– or I– ions delivers the corresponding CsPbCl3–Pb4S3Br2 and CsPbI3–Pb4S3Br2 heterostructures, thus enabling anion exchange only in the perovskite domain. An increased structural rigidity is conferred to the perovskite lattice when it is interfaced with the chalcohalide lattice. This is attested by the improved stability of the metastable γ phase (or “black” phase) of CsPbI3 in the CsPbI3–Pb4S3Br2 heterostructure.

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Section: Introductionmentioning

confidence: 79%

Halide Perovskite–Lead Chalcohalide Nanocrystal Heterostructures

et al. 2021

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“… 2020 11 3986 3995 . 1 Change of Structure: The capture of Cs 4 PbBr 6 –CsPbBr 3 heterostructures during the conversion between Pb-poor and Pb-rich cesium lead halide serves as an elegant illustration of the preservation of Cs + substructure principle directing transformations between various Cs–Pb–X compounds. Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions Akkerman Q.…”

Section: Key Referencesmentioning

confidence: 99%

“…One example is the templated conversion of a film of CsPbBr 3 emissive nanocrystals into nonemissive Cs 4 PbBr 6 nanocrystals upon exposure to butylamine vapors, which can be reverted by mild heating (d). Reprinted with permission from refs ( 1 , 10 , 13 , 15 , 18 , and 20 ). Copyright 2020 Royal Society of Chemistry (ref ( 1 )) and 2017–2020 American Chemical Society.…”

Section: Changing Structure By Ion Trade Reactionsmentioning

confidence: 99%

“…However, it appeared from the beginning that these materials, particularly in the form of colloidal nanocrystals, suffer from poor stability as they are very reactive toward their surroundings. While this aspect is detrimental for many practical applications, from a chemist’s viewpoint it offers the opportunity to investigate, master, and exploit their various possible transformations: these can be structural 1 or compositional, 2 and they can affect the surface 4 or shape, 3 or they can combine all these aspects together. The last 30 years of research on colloidal nanomaterials have provided chemists with an advanced array of tools, and it is no wonder so much has been disclosed since the first report of colloidal perovskite nanocrystals in 2015.…”

Section: Introductionmentioning

confidence: 99%

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Metamorphoses of Cesium Lead Halide Nanocrystals

2021

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Conspectus Following the impressive development of bulk lead-based perovskite photovoltaics, the “perovskite fever” did not spare nanochemistry. In just a few years, colloidal cesium lead halide perovskite nanocrystals have conquered researchers worldwide with their easy synthesis and color-pure photoluminescence. These nanomaterials promise cheap solution-processed lasers, scintillators, and light-emitting diodes of record brightness and efficiency. However, that promise is threatened by poor stability and unwanted reactivity issues, throwing down the gauntlet to chemists. More generally, Cs–Pb–X nanocrystals have opened an exciting chapter in the chemistry of colloidal nanocrystals, because their ionic nature and broad diversity have challenged many paradigms established by nanocrystals of long-studied metal chalcogenides, pnictides, and oxides. The chemistry of colloidal Cs–Pb–X nanocrystals is synonymous with change: these materials demonstrate an intricate pattern of shapes and compositions and readily transform under physical stimuli or the action of chemical agents. In this Account, we walk through four types of Cs–Pb–X nanocrystal metamorphoses: change of structure, color, shape, and surface. These transformations are often interconnected; for example, a change in shape may also entail a change of color. The ionic bonding, high anion mobility due to vacancies, and preservation of cationic substructure in the Cs–Pb–X compounds enable fast anion exchange reactions, allowing the precise control of the halide composition of nanocrystals of perovskites and related compounds (e.g., CsPbCl 3 ⇄ CsPbBr 3 ⇄ CsPbI 3 and Cs 4 PbCl 6 ⇄ Cs 4 PbBr 6 ⇄ Cs 4 PbI 6 ) and tuning of their absorption edge and bright photoluminescence across the visible spectrum. Ion exchanges, however, are just one aspect of a richer chemistry. Cs–Pb–X nanocrystals are able to capture or release (in short, trade) ions or even neutral species from or to the surrounding environment, causing major changes to their structure and properties. The trade of neutral PbX 2 units allows Cs–Pb–X nanocrystals to cross the boundaries among four different types of compounds: 4CsX + PbX 2 ⇄ Cs 4 PbBr 6 + 3PbX 2 ⇄ 4CsPbBr 3 + PbX 2 ⇄ 4CsPb 2 X 5 . These reactions do not occur at random, because the reactant and product nanocrystals are connected by the Cs + cation substructure preservation principle, stating that ion trade reactions can transform one compound into another by means of distorting, expanding, or contracting their shared Cs + cation substructu...

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“…The increased stability of CsPbX 3 /PMAO QDs is attributed to the ring‐opening addition of oleylamine (OAm) to anhydride groups of the polymer and subsequent wrapping of the formed polysuccinamic acid around the QDs surface. [ 36,37 ] Figure a is a schematic diagram of the structure of the WLED, where the blue GaN‐LED chip was used to excite the green CsPbBr 3 /PMAO layer and red CsPbBr 0.6 I 2.4 /PMAO QDs layer. Figure 5b shows the electroluminescence (EL) spectrum of a WLED device at an injection current of 30 mA.…”

Section: Figurementioning

confidence: 99%

Transient Optical Properties of CsPbX₃/Poly(maleic anhydride‐alt‐1‐octadecene) Perovskite Quantum Dots for White Light‐Emitting Diodes

Zhu

Chen³

et al. 2020

Physica Rapid Research Ltrs

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Poly(maleic anhydride‐alt‐1‐octadecene) (PMAO)‐coated green CsPbBr3 and red CsPbBr0.6I2.4 quantum dots (QDs), as the phosphor materials for white light‐emitting diodes (WLEDs), are reported. The anhydride groups of PMAO can be bound to the surface ligands of perovskite QDs and act as a protective layer. The results show that CsPbX3/PMAO (X = Cl, Br, I) presents good crystallinity and excellent luminescence properties. Time‐resolved photoluminescence (TRPL) shows that the PL lifetime of CsPbX3/PMAO is prolonged, and the transient absorption (TA) results show that intraband hot‐exciton relaxation and exciton recombination can be slowed down when the CsPbX3 QDs are coated with PMAO. However, the PL quantum yields (PLQYs) increase for both the green‐emitting QDs and the red‐emitting QDs after PMAO coating. WLED devices are fabricated by integrating the green CsPbBr3/PMAO QDs and red CsPbBr0.6I2.4/PMAO QDs on the blue GaN chips. The devices show stable white light emission with Commission Internationale de L'Eclairage (CIE) color coordinates of (0.314, 0.291). The results indicate that CsPbX3/PMAO QDs can be an ideal downconversion fluorescent material for WLED devices.

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

Abstract:
The challenge of making strongly emissive CsPbBr₃ perovskite nanocrystals with a robust surface passivation is solved via Cs₄PbBr₆ → CsPbBr₃ transformation triggered by a reaction of oleylamine ligand with poly(maleic anhydride-1-alt-octadecene).

Cited by 68 publications

References 63 publications

Halide Perovskite–Lead Chalcohalide Nanocrystal Heterostructures

Halide Perovskite–Lead Chalcohalide Nanocrystal Heterostructures

Metamorphoses of Cesium Lead Halide Nanocrystals

Transient Optical Properties of CsPbX₃/Poly(maleic anhydride‐alt‐1‐octadecene) Perovskite Quantum Dots for White Light‐Emitting Diodes

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

Abstract: The challenge of making strongly emissive CsPbBr3 perovskite nanocrystals with a robust surface passivation is solved via Cs4PbBr6 → CsPbBr3 transformation triggered by a reaction of oleylamine ligand with poly(maleic anhydride-1-alt-octadecene).

Cited by 68 publications

References 63 publications

Halide Perovskite–Lead Chalcohalide Nanocrystal Heterostructures

Halide Perovskite–Lead Chalcohalide Nanocrystal Heterostructures

Metamorphoses of Cesium Lead Halide Nanocrystals

Transient Optical Properties of CsPbX3/Poly(maleic anhydride‐alt‐1‐octadecene) Perovskite Quantum Dots for White Light‐Emitting Diodes

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Product

Resources

About

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

Abstract:
The challenge of making strongly emissive CsPbBr₃ perovskite nanocrystals with a robust surface passivation is solved via Cs₄PbBr₆ → CsPbBr₃ transformation triggered by a reaction of oleylamine ligand with poly(maleic anhydride-1-alt-octadecene).

Transient Optical Properties of CsPbX₃/Poly(maleic anhydride‐alt‐1‐octadecene) Perovskite Quantum Dots for White Light‐Emitting Diodes