Mechanisms for collective inversion-symmetry breaking in dabconium perovskite ferroelectrics

Allen, Dominic J. W.; Bristowe, Nicholas C.; Goodwin, Andrew L.; Yeung, Hamish H.‐M.

doi:10.1039/d1tc00619c

Cited by 24 publications

(30 citation statements)

References 38 publications

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“…In a very recent work, Allen et al have addressed the importance of hydrogen bonding, dipolar interaction, and especially the distortive strain from the framework to realize the ferroelectricity in dabconium hybrid perovskites via Monte Carlo simulation. 32 Hence, to unveil the origins of polarization in OIHPs and MOFPs, it is essential to understand both the static structure and dynamics of the A-site ligands and parent frameworks as well as the coupling between them. For this purpose, we selected three MOFPs with different A-site amines, namely, [CH 3…”

Section: ■ Introductionmentioning

confidence: 99%

Role of A-Site Molecular Ions in the Polar Functionality of Metal–Organic Framework Perovskites

Lü

Cortie

et al. 2021

Chem. Mater.

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Recent studies on organic–inorganic hybrid perovskites (OIHPs) and ferroelectric metal–organic framework perovskites (MOFPs) reveal their superb performance as highly efficient materials for photovoltaics and ferroelectrics. This has enabled the development of a new generation of optic-electronic-mechanical devices based on green chemistry. However, the fundamental understanding of these polarization-related functionalities is not yet clear, which has hindered the progress in further designing and developing materials with expected properties. In this work, we investigate three MOFPs that have the same Mg(HCOO)3 – frameworks with different molecular ions: [CH3NH3][Mg(HCOO)3] (MA-MOF), [(CH3)2NH2][Mg(HCOO)3] (DMA-MOF), and [C(NH2)3][Mg(HCOO)3] (GUA-MOF). Single-crystal and powder X-ray diffraction, inelastic neutron spectroscopy, and ab initio molecular dynamics simulations are combined to achieve a detailed description of the three MOFPs’ static and dynamic structures as a function of temperature. Intriguingly, our study reveals that the alignments and motions of the guest molecular ions are highly dependent on the directional hydrogen bonds that link N–H units to the surrounding MgO6 octahedra through the O acceptor from the frameworks. At the same time, the size, dynamic behavior, and alignments of the A-site molecular ions influence the distortive framework structures and their temperature-dependent deformation. Therefore, the mutual interaction between the guest and the framework determines the overall functionalities of the MOFPs. This study indicates that the configuration of the A-site molecular ions and the potential hydrogen bonds are critical to design the polar functionalities in both MOFPs and OIHPs.

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Section: ■ Introductionmentioning

confidence: 99%

Role of A-Site Molecular Ions in the Polar Functionality of Metal–Organic Framework Perovskites

Lü

Cortie

et al. 2021

Chem. Mater.

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“…For example, MDABCO‐NH 4 I 3 has been reported to exhibit the highest piezoelectric constant of d 15 = 179 pm V −1 due to its preferred orientation along <111>. [ 57 , 84 ] Additionally, the electromechanical coupling induced by MPB is another reason that certain piezoelectric materials possess remarkable values in d 33 (Table 1 ). However, this mostly occurs in materials with solid solution instead of pure elements.…”

Section: Properties and Applicationsmentioning

confidence: 99%

Prospects of Metal‐Free Perovskites for Piezoelectric Applications

Murti

Singh

et al. 2022

Advanced Science

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Metal‐halide perovskites have emerged as versatile materials for various electronic and optoelectronic devices such as diodes, solar cells, photodetectors, and sensors due to their interesting properties of high absorption coefficient in the visible regime, tunable bandgap, and high power conversion efficiency. Recently, metal‐free organic perovskites have also emerged as a particular class of perovskites materials for piezoelectric applications. This broadens the chemical variety of perovskite structures with good mechanical adaptability, light‐weight, and low‐cost processability. Despite these achievements, the fundamental understanding of the underlying phenomenon of piezoelectricity in metal‐free perovskites is still lacking. Therefore, this perspective emphasizes the overview of piezoelectric properties of metal‐halide, metal‐free perovskites, and their recent progress which may encourage material designs to enhance their applicability towards practical applications. Finally, challenges and outlooks of piezoelectric metal‐free perovskites are highlighted for their future developments.

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“…Off-centering necessarily creates an effective dipole in each cavity, and one might expect that, at sufficiently high A-site occupancies, the dipoles would interact in a collective way. This seems to be the case in the monoclinic structure of K 2 Mn[Fe] (a relatively common structure type for PBAs 9 ): the dipoles are large 21 and arrange themselves in precisely the manner expected for interacting dipoles on the cubic lattice 26 [Fig. 3a].…”

Section: Octahedral Tiltsmentioning

confidence: 99%

Structural complexity in Prussian blue analogues

Cattermull¹,

Pasta²,

Goodwin³

2021

Preprint

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We survey the most important kinds of structural complexity in Prussian blue analogues, their implications for materials function, and how they might be controlled through judicious choice of composition. We focus on six particular aspects: octahedral tilts, A-site 'slides', Jahn-Teller distortions, A-site species and occupancy, hexacyanometallate vacancies, and framework hydration. The promising K-ion cathode material KxMn[Fe(CN)6]y serves as a recurrent example that illustrates many of these different types of complexity. Our article concludes with a discussion of how the interplay of various distortion mechanisms might be exploited to optimise the performance of this and other related systems, so as to aid in the design of next-generation PBA materials.

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Mechanisms for collective inversion-symmetry breaking in dabconium perovskite ferroelectrics

Abstract: Dabconium hybrid perovskites include a number of recently-discovered ferroelectric phases with large spontaneous polarisations. The origin of ferroelectric response has been rationalised in general terms in the context of hydrogen...

Cited by 24 publications

References 38 publications

Role of A-Site Molecular Ions in the Polar Functionality of Metal–Organic Framework Perovskites

Role of A-Site Molecular Ions in the Polar Functionality of Metal–Organic Framework Perovskites

Prospects of Metal‐Free Perovskites for Piezoelectric Applications

Structural complexity in Prussian blue analogues

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