Mechanochemical synthesis of inorganic halide perovskites: evolution of phase-purity, morphology, and photoluminescence

Palazón, Francisco; Ajjouri, Yousra El; Sebastiá-Luna, Paz; Lauciello, Simone; Manna, Liberato; Bolink, Henk J.

doi:10.1039/c9tc03778k

Cited by 62 publications

(71 citation statements)

References 37 publications

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“…The resulting powder particles are in the size range of micrometers ( Fig. S7(d) in the ESM), which is expected and consistent with literature reports [38,39]. In its own turn, the nano-sized perovskite NPs can be prepared in the presence of h-PMMA as shown in Fig.…”

Section: Formation and Phase Conversion Of The Nanoparticlessupporting

confidence: 89%

Mechanosynthesis of polymer-stabilized lead bromide perovskites: insight into the formation and phase conversion of nanoparticles

et al. 2020

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The application of polymers to replace oleylamine (OLA) and oleic acid (OA) as ligands for perovskite nanocrystals is an effective strategy to improve their stability and durability especially for the solution-based processing. Herein, we report a mechanosynthesis of lead bromide perovskite nanoparticles (NPs) stabilized by partially hydrolyzed poly(methyl methacrylate) (h-PMMA) and high-molecular-weight highly-branched poly(ethylenimine) (PEI-25K). The as-synthesized NP solutions exhibited green emission centered at 516 nm, possessing a narrow full-width at half-maximum of 17 nm and as high photoluminescence quantum yield (PL QY) as 85%, while showing excellent durability and resistance to polar solvents, e.g., methanol. The colloids of polymer-stabilized NPs were directly processable to form stable and strongly-emitting thin films and solids, making them attractive as gain media. Furthermore, the roles of h-PMMA and PEI-25K in the grinding process were studied in depth. The h-PMMA can form micelles in the grinding solvent of dichloromethane to act as size-regulating templates for the growth of NPs. The PEI-25K with large amounts of amino groups induced significant enrichment of PbBr2 in the reaction mixture, which in turn caused the formation of CsPb2Br5-mPbBr2 and CsPbBr3-Cs4PbBr6-nCsBr NPs. The presence of CsPbBr3-Cs4PbBr6-nCsBr NPs was responsible for the high PL QY, as the Cs4PbBr6 phase with a wide energy bandgap can passivate the surface defects of the CsPbBr3 phase. This work describes a direct and facile mechanosynthesis of polymer-coordinated perovskite NPs and promotes in-depth understanding of the formation and phase conversion for perovskite NPs in the grinding process.

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Section: Formation and Phase Conversion Of The Nanoparticlessupporting

confidence: 89%

Mechanosynthesis of polymer-stabilized lead bromide perovskites: insight into the formation and phase conversion of nanoparticles

et al. 2020

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“…It was shown that Cs and MA‐containing lead halides as well as various mixed cation and anion compositions can be relatively easily prepared in a matter of minutes by manual grinding or milling the mixtures of corresponding binary halides . Since no solvent is used, the procedure is often claimed to be ‘solvent free’ . However, in most cases the raw materials, AX (A‐MA, Cs) and PbX 2 , are used for the synthesis ‘as received’, without any preliminary purification, and since both methylammonium and cesium halides are hygroscopic compounds, the starting mixture AX+PbX 2 may contain some unknown amount of water even if weighing and subsequent grinding or milling are carried out in the dry atmosphere.…”

Section: Results Of 15 Min Mechanochemical Activation Of Stoichiometrmentioning

confidence: 99%

“…If synthesis is done under ambient atmosphere, then water impact may be even stronger. This may, at least partially, explain the huge scatter, from about 5 min to several hours, in the reported mechanochemical reaction times necessary for obtaining single‐phase APbX 3 perovskite halides . Moreover, the mechanism of the mechanochemical formation of APbX 3 halides still has not received adequate attention, although this is obviously the key to optimization of the synthesis procedure in order to produce high‐quality single‐phase perovskite halides within the shortest possible time.…”

Section: Results Of 15 Min Mechanochemical Activation Of Stoichiometrmentioning

confidence: 99%

Crucial Role of Water in the Mechanosynthesis of CsPbI₃ and Other ABX₃ Halides

Цветков

Mazurin

Ivanov

et al. 2020

Chemistry A European J

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Mechanochemical synthesis of CsPbI 3 ,a sa model system for ABX 3 halides, was studied.W ater was shown to strongly promote the kinetics of formation of CsPbI 3 from the CsI + PbI 2 mixture through increased mobility of the constituting ionic species.S ince many binary and ternary halides are hygroscopic, it was concluded that the presence of small, uncontrollable and unintentional additions of water should often occur in both precursor mixtures and synthesized complex halides boostingthe kinetics of formation of many,i fn ot all,t ernaryo rganic-inorganich ybrid halides such as, for example, MAPbX 3 (X = Cl, Br,I). In addition, trace amounts of water should influence the transport characteristics of complex halides. Thus, the presence of water explains, at least partially,t he huge scatter in both the reported mechanochemical reaction times necessary for obtaining single-phaseAPbX 3 perovskite halidesa nd the activation energies of ionic diffusion in APbX 3 .

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“…This is in agreement with previous reports. [21,30] When increasing amounts of SnBr 2 are added as replacement of PbBr 2 , we do not observe significant changes in the diffraction pattern, except a gradual shift toward higher angles (see Figure S1a for a better visualization, Supporting Information). This is ascribed to a shrinkage of the unit cell which is expected as Sn 2+ has a lower ionic radius than Pb 2+ .…”

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confidence: 83%

Tunable Wide‐Bandgap Monohalide Perovskites

Ajjouri

Igual‐Muñoz

Sessolo

et al. 2020

Advanced Optical Materials

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Herein the mechanochemical synthesis of inorganic as well as hybrid organic–inorganic monohalide perovskites with tunable bandgaps is reported. It is shown that the bandgap bowing known for iodide mixed Sn–Pb perovskites is also present in the pure bromide analogous. This results in technologically very interesting materials with bandgaps in the range of 1.7–1.9 eV. Similar bandgap perovskites are typically achieved by mixing two halides that are prone to segregate over time. This limits the achievable open circuit voltage. For monohalide perovskites this problem is eliminated, making these materials especially promising wide bandgap absorbers for tandem solar cells.

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Mechanochemical synthesis of inorganic halide perovskites: evolution of phase-purity, morphology, and photoluminescence

Abstract: Solvent-free mechanochemical synthesis of phase-pure inorganic halide perovskites is investigated in depth revealing several beneficial and detrimental effects of ball-milling.

Cited by 62 publications

References 37 publications

Mechanosynthesis of polymer-stabilized lead bromide perovskites: insight into the formation and phase conversion of nanoparticles

Mechanosynthesis of polymer-stabilized lead bromide perovskites: insight into the formation and phase conversion of nanoparticles

Crucial Role of Water in the Mechanosynthesis of CsPbI₃ and Other ABX₃ Halides

Tunable Wide‐Bandgap Monohalide Perovskites

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Mechanochemical synthesis of inorganic halide perovskites: evolution of phase-purity, morphology, and photoluminescence

Abstract: Solvent-free mechanochemical synthesis of phase-pure inorganic halide perovskites is investigated in depth revealing several beneficial and detrimental effects of ball-milling.

Cited by 62 publications

References 37 publications

Mechanosynthesis of polymer-stabilized lead bromide perovskites: insight into the formation and phase conversion of nanoparticles

Mechanosynthesis of polymer-stabilized lead bromide perovskites: insight into the formation and phase conversion of nanoparticles

Crucial Role of Water in the Mechanosynthesis of CsPbI3 and Other ABX3 Halides

Tunable Wide‐Bandgap Monohalide Perovskites

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Crucial Role of Water in the Mechanosynthesis of CsPbI₃ and Other ABX₃ Halides