Atomistic modeling of metal–ligand chirality transfer and chiroptical properties of lead and tin hybrid perovskites

Fortino, Mariagrazia; Mattoni, Alessandro; Pietropaolo, Adriana

doi:10.1039/d3tc00507k

Cited by 9 publications

(5 citation statements)

References 60 publications

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“…While most of the reports exploring chiral perovskites are focused on device applications ,− or attempt to understand chirality transfer mechanisms, − fewer are devoted to understanding their photophysics and structure–function relationships. In the context of the latter, the control over phase purity in regular nonchiral 2D perovskites has been extensively documented, with a focus either on the solvent used for deposition or on the organic cation. − However, introducing a chiral cation alters the formation dynamics of the low-dimensional perovskite and the obtained products.…”

Section: Introductionmentioning

confidence: 99%

Understanding and Controlling the Photoluminescence Line Shapes of 2D Perovskites with Chiral Methylbenzylammonium-Based Cations

Scalon,

New,

et al. 2024

Chem. Mater.

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Chiral two-dimensional (2D) perovskites are a promising material class for the next generation of spintronic and chiroptical devices. Despite their promise, many aspects related to film formation and crystallization remain elusive. When chiral ammonium-based organic cations such as methylbenzylammonium (MBA) are employed in the preparation of chiral 2D perovskites, their interaction with the halide species in the inorganic perovskite network often introduces substantial steric hindrance, leading to the formation of one-dimensional (1D) phase impurities within the 2D matrix. Here, we demonstrate that this 1D phase manifests itself in the photoluminescence (PL) spectra of the 2D perovskite film as an additional weakly emissive, thermally activated state with a self-trapped excitonic character, leading to an asymmetric PL response. We demonstrate that the strategic introduction of a methoxy (OMe) group on the para position of the MBA cations can mitigate the formation of the 1D phase. As a result, the emission band becomes narrower and more symmetric and the 2D perovskite film has a higher PL quantum yield at room temperature. Our findings elucidate the origins of asymmetry and broadband emission of MBA-based chiral 2D perovskites and highlight the indispensable role of molecular design in chiral organic cations in controlling phase purity and attaining the desired optical properties.

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Section: Introductionmentioning

confidence: 99%

Understanding and Controlling the Photoluminescence Line Shapes of 2D Perovskites with Chiral Methylbenzylammonium-Based Cations

Scalon,

New,

et al. 2024

Chem. Mater.

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“…Previous studies suggest that the chiral activity of the CHMHs is related to the chiral organic cations, metal-halide components, and crystal dimensionalities. [34][35][36][37][38][39][40][41] Among them, halogens (X = Cl À , Br À , and I À ) play an important role in regulating many properties, including structures, [42][43][44][45][46] mechanical properties, 42,47,48 piezoelectricity, 47 phase transition temperatures, 49,50 quadratic nonlinear optical properties, 50,51 semiconductor properties, 42,[49][50][51][52][53][54] emission mechanisms, 45,55 and optical properties. 43,44,[54][55][56][57] Therefore, it is reasonable to use halogens to enhance and tune the chiral activity of the CHMHs.…”

Section: Introductionmentioning

confidence: 99%

The role of halogens in structural diversity and chirality enhancement of 1D chiral hybrid metal halides

Zhang,

Han,

Wang

et al. 2024

J. Mater. Chem. C

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“…4 It consists of a three-dimensional (3D) corner sharing network of octahedra formed by six-coordinated lead atoms. Given the large combination of molecules, metals and halogen atoms and the existence of several low dimensional phases, the class of hybrid perovskites shows great design flexibility and a huge potential ranging from energy and optoelectronic devices (such as light-emitting diodes, fieldeffect transistors, and photodetectors) up to chiroptics, 9 spin− orbitronics 10−12 and thermoelectricity. 13 Atomistic simulations based on ab initio methods are key in understanding and designing these materials, providing accurate predictions on structural and electronic properties.…”

Section: Introductionmentioning

confidence: 99%

Many-Body MYP2 Force-Field: Toward the Crystal Growth Modeling of Hybrid Perovskites

Mattoni,

Argiolas,

Cozzolino

et al. 2024

J. Chem. Theory Comput.

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Hybrid perovskites are well-known for their optoelectronic and photovoltaic properties. Molecular dynamics simulations allow the study of these soft and ionic crystals by including dynamical effects (e.g., molecular rotations, octahedra tilting, ionic diffusion and hysteresis), yet the high computational cost restricts the use of accurate ab initio forces for bulk or small atomic systems. Hence, great interest exists in the development of classical force-fields for hybrid perovskites of low and linear scaling computational cost, via both empirical methods and machine-learning. This work aims at extending the transferability of our MYP0 model, which has been successfully tailored to methylammonium lead iodide (MAPI) and applied to the study of molecular rotations, vibrations, diffusion of defects, and many other properties. The extended model, named MYP2, improves the description of inorganic or hybrid fragments and the processes of crystal formation while preserving a good description of bulk properties. More importantly, it allows for the direct simulation of the crystal growth of cubic MAPI from deposition of PbI and MAI precursors on the surfaces. Our findings pave the way toward classical force-fields able to model the microstructure evolution of hybrid perovskites and the crystalline synthesis from deposition in vacuo.

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Atomistic modeling of metal–ligand chirality transfer and chiroptical properties of lead and tin hybrid perovskites

Abstract: Hybrid organic–inorganic perovskites have emerged as excellent material for solar cell implementations. Indeed, their extreme tunability and facile synthesis open the door to many new applications. Chiral hybrid perovskites are...

Cited by 9 publications

References 60 publications

Understanding and Controlling the Photoluminescence Line Shapes of 2D Perovskites with Chiral Methylbenzylammonium-Based Cations

Understanding and Controlling the Photoluminescence Line Shapes of 2D Perovskites with Chiral Methylbenzylammonium-Based Cations

The role of halogens in structural diversity and chirality enhancement of 1D chiral hybrid metal halides

Many-Body MYP2 Force-Field: Toward the Crystal Growth Modeling of Hybrid Perovskites

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