Doping and phase segregation in Mn2+- and Co2+-doped lead halide perovskites from133Cs and1H NMR relaxation enhancement

Kubicki, Dominik; Prochowicz, Daniel; Pinon, Arthur C.; Stevanato, Gabriele; Hofstetter, Albert; Zakeeruddin, Shaik M.; Grätzel, Michaël; Emsley, Lyndon

doi:10.1039/c8ta11457a

Cited by 60 publications

(74 citation statements)

References 78 publications

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“…The presence of paramagnetic metal ions (e.g., Fe 3+ and Cu 2+ ) usually causes extremely rapid longitudinal and transverse relaxation of the nearby nuclei due to electron spin couplings. This behavior allows us to probe a more precise distribution of the paramagnetic species in the perovskite matrix by using 133 Cs NMR T 1 relaxation measurements (31).…”

Section: Ssnmr Of Double Perovskites Cs 2 Agbibr 6 and Cs 2 Ag(bi:fe)mentioning

confidence: 99%

“…We obtain a slow T 1 relaxation time of 306 s in Cs 2 AgBiBr 6 and one slow-and one fast-relaxing phase corresponding to signals at  iso = 80.7 ± 0.5 ppm Cs T 1 relaxation times indicate that the paramagnetic ions (Fe 3+ ) are alloyed into the perovskite framework. Since we now know the amount of Fe 3+ and also the amount of Cs + , which is in close proximity to Fe 3+ , simple calculations lead us to conclude that Fe 3+ is homogenously distributed as small FeBr 6 clusters throughout the lattice (more details in the Supplementary Materials) (31).…”

Section: Ssnmr Of Double Perovskites Cs 2 Agbibr 6 and Cs 2 Ag(bi:fe)mentioning

confidence: 99%

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Magnetizing lead-free halide double perovskites

et al. 2020

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Spintronics holds great potential for next-generation high-speed and low–power consumption information technology. Recently, lead halide perovskites (LHPs), which have gained great success in optoelectronics, also show interesting magnetic properties. However, the spin-related properties in LHPs originate from the spin-orbit coupling of Pb, limiting further development of these materials in spintronics. Here, we demonstrate a new generation of halide perovskites, by alloying magnetic elements into optoelectronic double perovskites, which provide rich chemical and structural diversities to host different magnetic elements. In our iron-alloyed double perovskite, Cs2Ag(Bi:Fe)Br6, Fe3+ replaces Bi3+ and forms FeBr6 clusters that homogenously distribute throughout the double perovskite crystals. We observe a strong temperature-dependent magnetic response at temperatures below 30 K, which is tentatively attributed to a weak ferromagnetic or antiferromagnetic response from localized regions. We anticipate that this work will stimulate future efforts in exploring this simple yet efficient approach to develop new spintronic materials based on lead-free double perovskites.

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Section: Ssnmr Of Double Perovskites Cs 2 Agbibr 6 and Cs 2 Ag(bi:fe)mentioning

confidence: 99%

Section: Ssnmr Of Double Perovskites Cs 2 Agbibr 6 and Cs 2 Ag(bi:fe)mentioning

confidence: 99%

Magnetizing lead-free halide double perovskites

et al. 2020

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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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“…Using their mechanosynthesis approach, Kubicki et al [35] studied doping of perovskites with paramagnetic transition metal ions such as Mn 2þ and Co 2þ that have recently been reported to enhance the luminescence and stability of these materials. Based on a detailed 1 H and 133 Cs T 1 relaxation study, they showed that Mn 2þ readily incorporates into CsPbBr 3 and CsPbCl 3 up to at least 8 and 3 mol%, respectively.…”

Section: B Sitementioning

confidence: 99%

Solid–state NMR of hybrid halide perovskites

Franssen¹,

Kentgens²

2019

Solid State Nuclear Magnetic Resonance

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Recent advances in the development of perovskite based solar cells have increased the demand for in-depth characterisation of the perovskite structures and the dynamics of their various constituents in relation to the potential impact on the photovoltaic performance. NMR can play an important role in this respect; NMR has been used to study the incorporation of different ionic species, characterize their internal dynamics and diffusion, and monitor the chemical stability of these technologically relevant materials, including upcoming lower dimensional perovskite materials. Furthermore, the flexibility of NMR allows the study of the materials under relevant conditions e.g. under illumination. Here we present an overview of the recent literature on NMR of (hybrid) halide perovskites, focusing on the insights that NMR can provide.

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Doping and phase segregation in Mn²⁺- and Co²⁺-doped lead halide perovskites from¹³³Cs and¹H NMR relaxation enhancement

Abstract: Lead halide perovskites belong to a broad class of compounds with appealing optoelectronic and photovoltaic properties.

Cited by 60 publications

References 78 publications

Magnetizing lead-free halide double perovskites

Magnetizing lead-free halide double perovskites

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

Solid–state NMR of hybrid halide perovskites

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