Hidden polymorphism of FAPbI<sub>3</sub> discovered by Raman spectroscopy

Ibaceta-Jaña, Josefa; Muydinov, Ruslan; Kumar, Sri Hari Bharath Vinoth; Gunder, René; Hoffmann, A.; Szyszka, Bernd; Wagner, Markus R.

doi:10.1039/d1cp00102g

Cited by 9 publications

(5 citation statements)

References 26 publications

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“…Moreover, in FAI, the molecules are directly connected to each other, and due to the spatial position of the molecule, they can rotate without affecting the bonds. We have previously shown that the structural instability of FAPbI 3 is likely a consequence of the out-of-plane rotation of FA + around its N–N axis . The interaction between the molecule and the inorganic frame is weak ionic by nature, as discussed above.…”

Section: Discussionmentioning

confidence: 81%

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Do Lead Halide Hybrid Perovskites Have Hydrogen Bonds?

et al. 2022

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Hydrogen bonds impact many material properties due to the bond directionality and collective strength. For them to exist, the atoms connected to hydrogen should possess high electronegativity, the distance between the interacting atoms should be less than their van der Waals radii, and there should be a charge transfer between them. In hybrid perovskites, the impact of hydrogen bonds is ascribed to several phenomena. Among them are the effect of passivation at the surface, structural stability of the mixed cation compounds, structural instability of FAPbI3, and ferroelectric behavior. In this paper, we applied a deterministic method to prove the existence of hydrogen bonds using Raman spectroscopy. This approach was successfully applied to water and is based on the emergence of a Raman mode as a result of the intermolecular charge transfer, which is not measured for the isolated molecule. With the help of DFT calculations, we attributed the Raman modes detected at room temperature (RT) for MAI and FAI and compared them with the Raman spectra of MAPbX3 and FAPbX3. This comparison has shown that there are no hydrogen bonds in hybrid lead halide perovskites at RT.

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Section: Discussionmentioning

confidence: 81%

“…High frequency range of the experimental Raman spectra measured for FAPbI 3 (α δ and δ) and FAPbBr 3 at RT.…”

Section: Resultsmentioning

confidence: 99%

Do Lead Halide Hybrid Perovskites Have Hydrogen Bonds?

et al. 2022

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“…This result shows an effective band gap modulation due to the alteration of the alkylation groups on btz derivative counter cations in the inorganic lead iodine system . The band gaps of 1a–3 are larger than that of the PbI 3 -type hybrid materials with aliphatic organic counter cations, such as MAPbI 3 (1.53 eV, MA = CH 3 NH 3 + ), FAPbI 3 [1.5 eV, FA = NH 2 (CH) NH 2 + ], and (C 4 H 9 FN) 2 PbI 4 (2.44 eV) . This finding about aromatic and aliphatic moieties to modulate the band gap of hybrid haloplumbates is consistent with our previous study in hybrid iodoargentates .…”

Section: Resultsmentioning

confidence: 91%

Crystal Structure and Thermophosphorochromic Property of One-Dimensional Hybrid Haloplumbates with Alkylated Benzothiazole Counter Cations

Tang,

Gao,

Guo

et al. 2023

Crystal Growth & Design

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Low-dimensional hybrid haloplumbates have shown unique optical properties, e.g., solid state emission and temperature-dependent photoluminescence (PL). Herein, by introducing alkylated benzothiazole (btz) as counter cations into the inorganic lead halide system, five hybrid haloplumbates were afforded, namely, (Mebtz) PbI 3 (1a, Me = methyl), (Mebtz) PbBr 3 (1b), (Etbtz) PbI 3 (2, Et = ethyl), (Isbtz) PbI 3 (3, Is = isopropyl), and (Bubtz) 2 Pb 3 I 8 (4, Bu = n-butyl). The structures, optical absorptions, and PL properties of the five hybrids are regulated by changing the alkylation group on the btz molecule. Compounds 1a−3 are composed of (PbX 3 ) − (X = I or Br) single chains with methylated, ethylated, or isopropylated btz as counter cations. However, 4 contains a (Pb 3 I 8 ) 2− ribbon-like structure charge compensated by an n-butylated btz cation. The detailed crystal structure analyses reveal that the inorganic haloplumbate moieties in 1a and 3 interact with btz derivative cations mainly through Coulomb interaction, while they interact mainly through hydrogen bonds in 1b, 2, and 4. Importantly, 3 and 4 show thermophosphorochromic behaviors, which involve multiple color changes when temperature changes, namely, from white through reddish orange to orange for 3 and from greenish yellow through yellow to white for 4. Theoretical calculations and physical property measurements suggest that the thermophosphorochromic behaviors arise from two emission peaks in the visible light region. The high energy emission corresponds to the organic cation-centered charge transitions, while the lower energy emission arises from the charge transition between the inorganic and organic moieties.

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“…13 This assignment has been used in numerous studies 24–26 since, even though the cubic Pm 3̄ m symmetry of the α-phase is predicted to be Raman inactive by group theory. Two recent reports by Driscoll et al 27 and Ibaceta-Jana et al 28 dissent from these previous assignments and provide experimental data supporting the assignment of the α-phase as Raman inactive.…”

Section: Introductionmentioning

confidence: 76%

Direct observation of phase transitions between delta- and alpha-phase FAPbI₃via defocused Raman spectroscopy

Sturdza,

Gallant,

Holzhey

et al. 2024

J. Mater. Chem. A

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Hidden polymorphism of FAPbI₃ discovered by Raman spectroscopy

Abstract: Formamidinium lead iodide (FAPbI3) can exhibit polymorphism at ambient conductions. Three different structural configurations and their thermally activated phase transitions are identified by temperature dependent micro-Raman spectroscopy.

Cited by 9 publications

References 26 publications

Do Lead Halide Hybrid Perovskites Have Hydrogen Bonds?

Do Lead Halide Hybrid Perovskites Have Hydrogen Bonds?

Crystal Structure and Thermophosphorochromic Property of One-Dimensional Hybrid Haloplumbates with Alkylated Benzothiazole Counter Cations

Direct observation of phase transitions between delta- and alpha-phase FAPbI₃via defocused Raman spectroscopy

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Hidden polymorphism of FAPbI3 discovered by Raman spectroscopy

Abstract: Formamidinium lead iodide (FAPbI3) can exhibit polymorphism at ambient conductions. Three different structural configurations and their thermally activated phase transitions are identified by temperature dependent micro-Raman spectroscopy.

Cited by 9 publications

References 26 publications

Do Lead Halide Hybrid Perovskites Have Hydrogen Bonds?

Do Lead Halide Hybrid Perovskites Have Hydrogen Bonds?

Crystal Structure and Thermophosphorochromic Property of One-Dimensional Hybrid Haloplumbates with Alkylated Benzothiazole Counter Cations

Direct observation of phase transitions between delta- and alpha-phase FAPbI3via defocused Raman spectroscopy

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Product

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Hidden polymorphism of FAPbI₃ discovered by Raman spectroscopy

Direct observation of phase transitions between delta- and alpha-phase FAPbI₃via defocused Raman spectroscopy