Mechanochemical synthesis of 0D and 3D cesium lead mixed halide perovskites

Karmakar, Abhoy; Dodd, Mya S.; Zhang, Xiaoyue; Oakley, Meagan S.; Kłobukowski, Mariusz; Michaelis, Vladimir K.

doi:10.1039/c8cc09622h

Cited by 86 publications

(163 citation statements)

References 41 publications

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“…As we have previously seen, this has been used to make brightly emissive quantum dots over the whole visible range (see Figure ) . Mixed‐halide bulk perovskites have also been investigated by MCS . Generally, it is found that Br‐I and Br‐Cl mixed compositions can be formed with any ratio of both halides.…”

Section: Mcs As a Way To Investigate Mixed‐composition Halide Perovskmentioning

confidence: 90%

Making by Grinding: Mechanochemistry Boosts the Development of Halide Perovskites and Other Multinary Metal Halides

Palazón

Ajjouri

Bolink

2019

Advanced Energy Materials

101

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Mechanochemical synthesis has recently emerged as a promising route for the synthesis of functional lead halide perovskites as well as other (lead‐free) metal halides. Mechanochemical synthesis presents several advantages with regards to more commonly used solution‐based processes such as an inherent lower toxicity by avoiding organic solvents and a finer control over stoichiometry of the final products. The ease of implementation, either through the use of a simple mortar and pestle or with an electrically powered ball‐mill, and low amount of side products make mechanochemical synthesis appealing for upscaling the production of halide perovskites. Due to the defect tolerance of lead halide perovskites, they are ideally suited to be prepared by this solvent‐free method. However, the implementation of these semiconductors in high‐efficiency optoelectronic devices requires the transformation of synthesized powder into smooth thin films where still some hurdles remain to be cleared.

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Section: Mcs As a Way To Investigate Mixed‐composition Halide Perovskmentioning

confidence: 90%

Making by Grinding: Mechanochemistry Boosts the Development of Halide Perovskites and Other Multinary Metal Halides

Palazón

Ajjouri

Bolink

2019

Advanced Energy Materials

101

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“…[24][25][26][27][28][29] Indeed, solid-state NMR spectroscopy has proven to be a valuable tool to study cation dynamics [30][31][32][33][34][35] and the structure of bulk lead halide perovskites. 31,[36][37][38][39][40][41][42] To the best of our knowledge, solid-state NMR spectroscopy has only been applied to study lead halide perovskite QDs in a handful of cases. Piveteau et al 43 recorded DNP enhanced spectra of 133 Cs from perovskite CsPbBr3 QDs.…”

Section: Introductionmentioning

confidence: 99%

Surface Termination of CsPbBr₃ Perovskite Quantum Dots Determined by Solid-State NMR Spectroscopy

et al. 2020

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Cesium lead halide perovskite quantum dots (QDs) have gained significant attention as next-generation optoelectronic materials; however, their properties are highly dependent on their surface chemistry. The surfaces of cuboidal CsPbBr3 QDs have been intensively studied by both theoretical and experimental techniques, but fundamental questions still remain about the atomic termination of the QDs. The binding sites and modes of ligands at the surface remain unproven. Herein, we demonstrate that solid-state NMR spectroscopy allows the unambiguous assignments of organic surface ligands via 1H, 13C, and 31P NMR. Surface-selective 133Cs solid-state NMR spectra show the presence of an additional 133Cs NMR signal with a unique chemical shift that is attributed to Cs atoms terminating the surface of the particle and which are likely coordinated by carboxylate ligands. Dipolar dephasing curves that report on the distance between the surface ammonium ligands and Cs and Pb were recorded using double resonance 1H{133Cs} and 1H{207Pb} RESPDOR experiments. Model QD surface slabs with different possible surface terminations were generated from the CsPbBr3 crystal structure and theoretical RESPDOR dipolar dephasing curves considering all possible 1H-133Cs/207Pb spin pairs were then calculated. Comparison of the calculated and experimental RESPDOR curves indicates the particles are CsBr terminated (not PbBr2 terminated), with alkylammonium ligands situated within surface Cs vacancies, consistent with the surface-selective 133Cs NMR experiments. These results highlight the utility of high-resolution solid-state NMR spectroscopy for studying ligand binding and the surface structure of nanomaterials.

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“…Most of the subsequent studies concentrated on 1 H, 2 H, 13 C, 14 N, 15 N nuclei to characterize and understand the dynamics and mobility of the organic cations (MA or FA) [22][23][24][25][26][27][43][44][45] . Only a few studies concerned 133 Cs NMR 29,31,[46][47][48][49][50][51] . As to the halides, NMR spectroscopy had thus far been hampered by their large quadrupolar constants, leading to massively broadened signals and distorted line shapes 52,53 .…”

mentioning

confidence: 99%

Lead-Halide Scalar Couplings in 207Pb NMR of APbX3 Perovskites (A = Cs, Methylammonium, Formamidinium; X = Cl, Br, I)

Aebli

Piveteau

Nazarenko

et al. 2020

Sci Rep

110

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Understanding the structure and dynamics of newcomer optoelectronic materials-lead halide perovskites ApbX 3 [A = cs, methylammonium (cH 3 nH 3 + , MA), formamidinium (cH(nH 2) 2 + , fA); X = cl, Br, i]-has been a major research thrust. in this work, new insights could be gained by using 207 pb solid-state nuclear magnetic resonance (nMR) spectroscopy at variable temperatures between 100 and 300 K. The existence of scalar couplings 1 J pb-cl of ca. 400 Hz and 1 J pb-Br of ca. 2.3 kHz could be confirmed for MAPbX 3 and cspbX 3. Diverse and fast structure dynamics, including rotations of A-cations, harmonic and anharmonic vibrations of the lead-halide framework and ionic mobility, affect the resolution of the coupling pattern. 207 pb nMR can therefore be used to detect the structural disorder and phase transitions. furthermore, by comparing bulk and nanocrystalline cspbBr 3 a greater structural disorder of the pbBr 6-octahedra had been confirmed in a nanoscale counterpart, not readily captured by diffraction-based techniques. Semiconducting lead halide perovskite materials, foremost of APbX 3-type [A = Cs, methylammonium (CH 3 NH 3 + , MA), formamidinium (CH(NH 2) 2 + , FA); X = Cl, Br, I], have raised tremendous interest over the past years due to their outstanding optoelectronic properties, which find application in solar cells 1,2 , X-ray 3 and gamma detectors 4-6 and light-emitting devices 7-14. These semiconductors exhibit unusually high defect-tolerance, which is the nearly intrinsic semiconducting behaviour in spite of the high abundance of structural imperfections. Such defect-tolerance had been attributed to the specifics of the electronic structure, crystal structure and structural dynamics 15-21. It is therefore fundamental to develop an experimental toolset and a related mind-set for studying the local structure and structural dynamics as well as their relationship to the electronic and physical properties of these semiconductors. Solid-state nuclear magnetic resonance (NMR) is a powerful technique for characterizing solid materials. It is complementary to X-ray diffraction, as it is particularly sensitive to the local environment of nuclei. Chemical composition of APbX 3 makes these compounds very well suited for NMR, owing to the range of NMR-active nuclei (1

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Mechanochemical synthesis of 0D and 3D cesium lead mixed halide perovskites

Abstract: A simplified mechanochemical synthesis approach for Cs-containing mixed halide perovskite materials of lower and higher dimensionality (0D and 3D, respectively) is presented with stoichiometric control from their halide salts, CsX and PbX2 (X = Cl, Br, I).

Cited by 86 publications

References 41 publications

Making by Grinding: Mechanochemistry Boosts the Development of Halide Perovskites and Other Multinary Metal Halides

Making by Grinding: Mechanochemistry Boosts the Development of Halide Perovskites and Other Multinary Metal Halides

Surface Termination of CsPbBr₃ Perovskite Quantum Dots Determined by Solid-State NMR Spectroscopy

Lead-Halide Scalar Couplings in 207Pb NMR of APbX3 Perovskites (A = Cs, Methylammonium, Formamidinium; X = Cl, Br, I)

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Mechanochemical synthesis of 0D and 3D cesium lead mixed halide perovskites

Abstract: A simplified mechanochemical synthesis approach for Cs-containing mixed halide perovskite materials of lower and higher dimensionality (0D and 3D, respectively) is presented with stoichiometric control from their halide salts, CsX and PbX2 (X = Cl, Br, I).

Cited by 86 publications

References 41 publications

Making by Grinding: Mechanochemistry Boosts the Development of Halide Perovskites and Other Multinary Metal Halides

Making by Grinding: Mechanochemistry Boosts the Development of Halide Perovskites and Other Multinary Metal Halides

Surface Termination of CsPbBr3 Perovskite Quantum Dots Determined by Solid-State NMR Spectroscopy

Lead-Halide Scalar Couplings in 207Pb NMR of APbX3 Perovskites (A = Cs, Methylammonium, Formamidinium; X = Cl, Br, I)

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Surface Termination of CsPbBr₃ Perovskite Quantum Dots Determined by Solid-State NMR Spectroscopy