Synthesis, physico-chemical characterization and structure of the elusive hydroxylammonium lead iodide perovskite NH<sub>3</sub>OHPbI<sub>3</sub>

D’Annibale, Andrea; Panetta, Riccardo; Tarquini, Ombretta; Colapietro, Marcello; Quaranta, Simone; Cassetta, Alberto; Barba, Luisa; Chita, Giuseppe; Latini, Alessandro

doi:10.1039/c9dt00690g

Cited by 13 publications

(14 citation statements)

References 34 publications

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“…In contrast, a recent study indicates that FM was not successfully embedded in the perovskite structure, but rather it was included as an additive [36], despite the similarity with the FA cation. The pure usage of HA cations yields structures with face-sharing octahedra that differ from the standard, corner-sharing perovskites [37]. This is despite the fact that the Goldsmith factor would indicate a typical 3D structure is possible and the anomaly was explained by the formation of hydrogen bonds.…”

Section: Mixed-cation Mixed-halide Perovskitesmentioning

confidence: 93%

Investigation of Opto-Electronic Properties and Stability of Mixed-Cation Mixed-Halide Perovskite Materials with Machine-Learning Implementation

et al. 2021

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The feasibility of mixed-cation mixed-halogen perovskites of formula AxA’1−xPbXyX’zX”3−y−z is analyzed from the perspective of structural stability, opto-electronic properties and possible degradation mechanisms. Using density functional theory (DFT) calculations aided by machine-learning (ML) methods, the structurally stable compositions are further evaluated for the highest absorption and optimal stability. Here, the role of the halogen mixtures is demonstrated in tuning the contrasting trends of optical absorption and stability. Similarly, binary organic cation mixtures are found to significantly influence the degradation, while they have a lesser, but still visible effect on the opto-electronic properties. The combined framework of high-throughput calculations and ML techniques such as the linear regression methods, random forests and artificial neural networks offers the necessary grounds for an efficient exploration of multi-dimensional compositional spaces.

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Section: Mixed-cation Mixed-halide Perovskitesmentioning

confidence: 93%

Investigation of Opto-Electronic Properties and Stability of Mixed-Cation Mixed-Halide Perovskite Materials with Machine-Learning Implementation

et al. 2021

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“…Thus, the 3D structure is predicted to be stable when the tolerance factor is between 0.8 and 1.0, and this condition is satisfied only for cesium, methylammonium (MA + ), hydroxylammonium (NH 3 OH + ), hydrazinium (NH 2 NH 3 + ), azetidinium ((CH 2 ) 3 NH 2 + ), formamidinium (FA + ), and imidazolium (C 3 N 2 H 5 + ) cations . Experimental studies show that the real situation is even worse because 3D perovskites containing corner-sharing PbX 6 octahedra thus far comprised only MA + , FA + , or Cs + as cations, while for the remaining small organic cations, a nonperovskite or layered perovskite structure were formed. − It is worth adding that, most recently, a new 3D lead halide perovskite-related ferroelectric [2-trimethylammonioethylammonium]Pb 2 Cl 6 was reported that, however, has a different lead chloride framework of both corner- and edge-sharing PbCl 6 octahedra …”

Section: Introductionmentioning

confidence: 99%

Three-Dimensional Perovskite Methylhydrazinium Lead Chloride with Two Polar Phases and Unusual Second-Harmonic Generation Bistability above Room Temperature

et al. 2020

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Formation of noncentrosymmetric three-dimensional (3D) lead halide perovskites has been a widely sought after goal because the polar structure opens up new vistas to properties of these materials, e.g., improved charge separation for photovoltaics arising from ferroelectric order. Here, we report growth and unique properties of a new highly distorted 3D perovskite, methylhydrazinium lead chloride (CH3NH2NH2PbCl3, MHyPbCl 3 ). This perovskite crystallizes in polar P21 structure at room temperature, which consists of two types of PbCl6 octahedra: one weakly and another strongly deformed. The unusual deformation of every second perovskite layer is forced by the large size of methylhydrazinium cations and the ability of NH2 + terminal groups of methylhydrazinium cations to form coordination bonds with Pb2+ metal centers. On heating, MHyPbCl 3 undergoes a phase transition at 342 K into another polar Pb21 m phase with ordered organic cations. Temperature-resolved second-harmonic generation (TR-SHG) measurements confirm acentricity of both phases and show that second-harmonic response is enhanced for the high-temperature Pb21 m phase. This intriguing property of MHyPbCl 3 has been employed to demonstrate an unprecedented kind of quadratic nonlinear optical switching in which a second-harmonic response is switched between a room-temperature, low-SHG state and a high-temperature, high-SHG state. X-ray diffraction shows that enhancement of polar properties is due to rearrangement of the perovskite’s organic substructure. There is a clear pyrocurrent peak, but switching of the electric polarization could not be observed. Optical studies showed that MHyPbCl 3 is a wide-bandgap material with a bandgap of 3.4 eV (365 nm). At low temperatures, it exhibits weak UV emissions at 362 and 369 nm as well as a strong broadband white emission.

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“…However, interestingly, the successful synthesis of the corresponding perovskite has not been reported for some amines with a similar radius as MA + , such as hydrazinium and fluoroammonium ions [30] . Although NH 3 OHPbI 3 with an A‐site cation of 216 pm can be synthesized, it is unsuitable for photovoltaic applications because of its low melting and decomposition temperatures (80 °C and 103 °C, respectively) [31] . This indicates that, in addition to the ion size effect, coordination effects, including hydrogen bonds, dipole moments, etc., may also play important roles in the structural stability of FAPbI 3 [32] …”

Section: Functional Construction Of Different Structural Aminesmentioning

confidence: 99%

From Structural Design to Functional Construction: Amine Molecules in High‐Performance Formamidinium‐Based Perovskite Solar Cells

Tang

et al. 2022

Angew Chem Int Ed

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Formamidinium (FA) based perovskites are considered as one of the most promising light-absorbing perovskite materials owing to their narrower band gap and better thermal stability compared to conventional methylammonium-based perovskites. Constant improvement by using various additives stimulates the potential application of these perovskites. Amine molecules with different structures have been widely used as typical additives in FA-based perovskite solar cells, and decent performances have been achieved. Thus, a systematic review focusing on structural regulation and functional construction of amines in FA-based perovskites is of significance. Herein, we analyze the construction mechanism of different structural amines on the functional perovskite crystals. The influence of amine molecules on specific perovskite properties including defect conditions, charge transfer, and moisture resistance are evaluated. Finally, we summarize the design rules of amine molecules for the application in high-performance FA-based perovskites and propose directions for the future development of additive molecules.

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Synthesis, physico-chemical characterization and structure of the elusive hydroxylammonium lead iodide perovskite NH₃OHPbI₃

Abstract: The elusive hydroxylammonium lead iodide NH3OHPbI3 has been successfully synthesized and characterized for the first time.

Cited by 13 publications

References 34 publications

Investigation of Opto-Electronic Properties and Stability of Mixed-Cation Mixed-Halide Perovskite Materials with Machine-Learning Implementation

Investigation of Opto-Electronic Properties and Stability of Mixed-Cation Mixed-Halide Perovskite Materials with Machine-Learning Implementation

Three-Dimensional Perovskite Methylhydrazinium Lead Chloride with Two Polar Phases and Unusual Second-Harmonic Generation Bistability above Room Temperature

From Structural Design to Functional Construction: Amine Molecules in High‐Performance Formamidinium‐Based Perovskite Solar Cells

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Synthesis, physico-chemical characterization and structure of the elusive hydroxylammonium lead iodide perovskite NH3OHPbI3

Abstract: The elusive hydroxylammonium lead iodide NH3OHPbI3 has been successfully synthesized and characterized for the first time.

Cited by 13 publications

References 34 publications

Investigation of Opto-Electronic Properties and Stability of Mixed-Cation Mixed-Halide Perovskite Materials with Machine-Learning Implementation

Investigation of Opto-Electronic Properties and Stability of Mixed-Cation Mixed-Halide Perovskite Materials with Machine-Learning Implementation

Three-Dimensional Perovskite Methylhydrazinium Lead Chloride with Two Polar Phases and Unusual Second-Harmonic Generation Bistability above Room Temperature

From Structural Design to Functional Construction: Amine Molecules in High‐Performance Formamidinium‐Based Perovskite Solar Cells

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Synthesis, physico-chemical characterization and structure of the elusive hydroxylammonium lead iodide perovskite NH₃OHPbI₃