Solid–state NMR of hybrid halide perovskites

Franssen, Wouter M. J.; Kentgens, A.P.M.

doi:10.1016/j.ssnmr.2019.03.005

Cited by 78 publications

(89 citation statements)

References 55 publications

(80 reference statements)

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“…Solid-state nuclear magnetic resonance (NMR) spectroscopy is a robust analytical characterization tool to determine short-(<5 Å) and medium-(5−10 Å) range structures as well as ion dynamics in perovskites. 16,[31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] More specifically, 133 Cs (I = 7/2, Qm = −0.34 fm 2 , 100% abundance) 48 is an ideal NMR-active nucleus to identify the chemical environments around the A-site in perovskites. 36,42,47,49-52 119 Sn (I = 1/2, 8.6% abundance), the most receptive nucleus among three NMR-active tin isotopes ( 115 Sn, 117 Sn, 119 Sn) (Table S1), 48 has been used to resolve the local B-site structural environments and halogen dynamics in ABX3 perovskites and other tin-containing compounds.…”

Section: Introductionmentioning

confidence: 99%

Uncovering Halide Mixing and Octahedral Dynamics in Vacancy-Ordered Double Perovskites by Multinuclear Magnetic Resonance Spectroscopy

Karmakar¹,

Mukhopadhyay²,

Gachod³

et al. 2021

Preprint

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Vacancy-ordered double perovskites Cs2SnX6 (X = Cl, Br, I) have emerged as promising lead-free and ambient-stable materials for photovoltaic and optoelectronic applications. To advance these promising materials, it is crucial to determine the correlations between physical properties and their local structure and dynamics. Solid-state NMR spectroscopy of multiple NMR-active nuclei (133Cs, 119Sn and 35Cl) in these cesium tin(IV) halides has been used to decode the structure, which plays a key role in the materials’ optical properties. The 119Sn NMR chemical shifts span approximately 4000 ppm and the 119Sn spin-lattice relaxation times span three orders of magnitude when the halogen goes from chlorine to iodine in these diamagnetic compounds. Moreover, ultrawideline 35Cl NMR spectroscopy for Cs2SnCl6 indicates an axially symmetric chlorine electric field gradient tensor with a large quadrupolar coupling constant of ca. 32 MHz, suggesting a chlorine that is directly attached to Sn(IV) ions. Variable temperature 119Sn spin lattice relaxation time measurements uncover the presence of hidden dynamics of octahedral SnI6 units in Cs2SnI6 with a low activation energy barrier of 12.45 kJ/mol (0.129 eV). We further show that complete mixed-halide solid solutions of Cs2SnClxBr6−x and Cs2SnBrxI6−x (0 ≤ x ≤ 6) form at any halogen compositional ratio. 119Sn and 133Cs NMR spectroscopy resolve the unique local SnClnBr6−nand SnBrnI6−n (n = 0−6) octahedral and CsBrmI12−m (m = 0−12) cuboctahedral environments in the mixed-halide samples. The experimentally observed 119Sn NMR results are consistent with magnetic shielding parameters obtained by density functional theory computations to verify random halogen distribution in mixed-halide analogues. Finally, we demonstrate the difference in the local structures and optical absorption properties of Cs2SnI6 samples prepared by solvent-assisted and solvent-free synthesis routes.

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Section: Introductionmentioning

confidence: 99%

Uncovering Halide Mixing and Octahedral Dynamics in Vacancy-Ordered Double Perovskites by Multinuclear Magnetic Resonance Spectroscopy

Karmakar¹,

Mukhopadhyay²,

Gachod³

et al. 2021

Preprint

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“…Solid-state magic angle spinning (MAS) NMR has been established as the primary tool for studying the atomic-level microstructure of hybrid halide perovskites. 30 We and other groups have shown its use for determining local changes induced by composition engineering: A/B-site cation 31 − 39 and halide 29 , 40 − 44 mixing and phase segregation as well as surface interactions between perovskites and organic passivation dopants. 45 − 48 Solid-state NMR has also been used to study the degradation of hybrid halide perovskites 49 and the dynamics of their constituents: A-site cation reorientation 31 , 50 − 53 and ion diffusion.…”

Section: Introductionmentioning

confidence: 99%

Halide Mixing and Phase Segregation in Cs₂AgBiX₆ (X = Cl, Br, and I) Double Perovskites from Cesium-133 Solid-State NMR and Optical Spectroscopy

et al. 2020

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All-inorganic double perovskites (elpasolites) are a promising potential alternatives to lead halide perovskites in optoelectronic applications. Although halide mixing is a well-established strategy for band gap tuning, little is known about halide mixing and phase segregation phenomena in double perovskites. Here, we synthesize a wide range of single- and mixed-halide Cs 2 AgBiX 6 (X = Cl, Br, and I) double perovskites using mechanosynthesis and probe their atomic-level microstructure using 133 Cs solid-state MAS NMR. We show that mixed Cl/Br materials form pure phases for any Cl/Br ratio while Cl/I and Br/I mixing is only possible within a narrow range of halide ratios (<3 mol % I) and leads to a complex mixture of products for higher ratios. We characterize the optical properties of the resulting materials and show that halide mixing does not lead to an appreciable tunability of the PL emission. We find that iodide incorporation is particularly pernicious in that it quenches the PL emission intensity and radiative charge carrier lifetimes for iodide ratios as low as 0.3 mol %. Our study shows that solid-state NMR, in conjunction with optical spectroscopies, provides a comprehensive understanding of the structure–activity relationships, halide mixing, and phase segregation phenomena in Cs 2 AgBiX 6 (X = Cl, Br, and I) double perovskites.

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“…I) 34 . In this contribution, we focus on 207 Pb NMR spectroscopy of APbX 3 compounds and report on the existence of scalar lead-halide J-couplings in some of them.…”

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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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Solid–state NMR of hybrid halide perovskites

Cited by 78 publications

References 55 publications

Uncovering Halide Mixing and Octahedral Dynamics in Vacancy-Ordered Double Perovskites by Multinuclear Magnetic Resonance Spectroscopy

Uncovering Halide Mixing and Octahedral Dynamics in Vacancy-Ordered Double Perovskites by Multinuclear Magnetic Resonance Spectroscopy

Halide Mixing and Phase Segregation in Cs₂AgBiX₆ (X = Cl, Br, and I) Double Perovskites from Cesium-133 Solid-State NMR and Optical Spectroscopy

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

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Solid–state NMR of hybrid halide perovskites

Cited by 78 publications

References 55 publications

Uncovering Halide Mixing and Octahedral Dynamics in Vacancy-Ordered Double Perovskites by Multinuclear Magnetic Resonance Spectroscopy

Uncovering Halide Mixing and Octahedral Dynamics in Vacancy-Ordered Double Perovskites by Multinuclear Magnetic Resonance Spectroscopy

Halide Mixing and Phase Segregation in Cs2AgBiX6 (X = Cl, Br, and I) Double Perovskites from Cesium-133 Solid-State NMR and Optical Spectroscopy

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

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Halide Mixing and Phase Segregation in Cs₂AgBiX₆ (X = Cl, Br, and I) Double Perovskites from Cesium-133 Solid-State NMR and Optical Spectroscopy