Polarization reversal by intramolecular disordering in organic ferroelectrics: trichloroacetamide

Saito, Kazuya; Yamamura, Yuichi; Kikuchi, Naoya; Nakao, Akiko; Yasuzuka, Syuma; Akishige, Y.; Murakami, Youichi

doi:10.1039/c0ce00751j

Cited by 14 publications

(7 citation statements)

References 40 publications

(56 reference statements)

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“…Similar molecular motions have been observed in other molecular IC ferroelectrics, such as trichloroacetamide. 28 Based on this study, it is deduced that the unique structural modulations of 1 are driven and dominated by the occupational and positional disordering of anions. In detail, for this rotator−stator assembly, anionic moieties are highly disordered at PEP, acting as dynamic rotor-like units.…”

Section: ■ Results and Discussionmentioning

confidence: 96%

Unusual Long-Range Ordering Incommensurate Structural Modulations in an Organic Molecular Ferroelectric

Sun

et al. 2017

J. Am. Chem. Soc.

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The incommensurate (IC) behaviors of ferroelectrics have been widely investigated in inorganic oxides as an exciting branch for aperiodic materials, whereas it still remains a great challenge to achieve such intriguing effects in organic systems. Here, we present that successive ordering of dynamic dipoles in an organic molecular ferroelectric, N-isopropylbenzylaminium trichloroacetate (1), enables unusual incommensurately modulated structures between its paraelectric phase and ferroelectric phase. In particular, 1 exhibits three distinct IC states coupling with a long-range ordering modulation. That is, the incommensurately modulated lattice is ∼7 times as large as its periodic prototype, and the IC structure is well solved using a (3 + 1)D superspace group with the modulated wavevector q = (0, 0, 0.1589). To the best of our knowledge, 1 is the first organic ferroelectric showing such a long-range ordering IC structural modulation. In addition, structural analyses reveal that slowing down dynamic motions of anionic moieties accounts for its modulation behaviors, which also results in dramatic reorientation of dipolar moments and concrete ferroelectric polarization of 1 (∼0.65 μC/cm). The combination of unique IC structural modulations and ferroelectricity makes 1 a potential candidate for the assembly of an artificially modulated lattice, which will allow for a deep understanding of the underlying chemistry and physics of aperiodic materials.

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Section: ■ Results and Discussionmentioning

confidence: 96%

Unusual Long-Range Ordering Incommensurate Structural Modulations in an Organic Molecular Ferroelectric

Sun

et al. 2017

J. Am. Chem. Soc.

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“…For 1 , it exhibits the well‐rectangle P ‐ E loops with the P s value of approximately 3.2 μC cm −2 at 298 K. This value is larger than that of some organic ferroelectrics, such as trichloroacetamide (ca. 0.2 μC cm −2 ), Rochelle salt (ca. 0.5 μC cm −2 ), and N ‐isopropylbenzylaminium trichloroacetate (ca.…”

Section: Figurementioning

confidence: 99%

A Molecular Ferroelectric Showing Room‐Temperature Record‐Fast Switching of Spontaneous Polarization

Sun

Tao

et al. 2018

Angewandte Chemie

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Fast switching of spontaneous polarization (Ps) is one of the most essential requirements for ferroelectrics used in the field of data storage. However, in contrast to inorganic counterparts, the low operating frequency (<500 Hz) for molecular ferroelectrics severely hinders their large‐scale applications. Herein, for the first time, we achieved the room‐temperature fastest switching of the Ps in a new molecular ferroelectric, N‐methylmorpholinium trinitrophenolate (1), which displays notable ferroelectricity (Ps=3.2 μc cm−2). Strikingly, electric polarizations of 1 have been switched under a record‐high frequency of 263 kHz, and this performance remains stable without any obvious fatigue after ca. 2×105 switching cycles. To our knowledge, 1 is the first organic ferroelectric to switch polarization at such a high operating frequency, exceeding the majority of organic ferroelectrics, which opens up new possibilities for its potential in the field of non‐volatile memory.

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“…29 Comparing with this isomer, the molecule of croconic acid with hydroxyl groups orienting in the same direction has a larger dimerization binding energy via hydrogen bonds, which makes itself has some advantages during the crystallization. Some organic ferroelectrics, such as TCAA, 30 also have considerable molecular dipole, however, unlike croconic acid, their opposing orientations of molecules in crystal make most of the dipole moments counterbalanced. That is one of reasons why organic ferroelectrics are rare.…”

Section: Polarization and Ferroelectric Phase Transitionmentioning

confidence: 99%

Ferroelectric mechanism of croconic acid: A first-principles and Monte Carlo study

Cai

Luo

Zhu

et al. 2013

The Journal of Chemical Physics

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The ferroelectric mechanism of croconic acid in terms of the electronic structure and the molecular structure was studied by first principles using the density functional theory with the generalized gradient approximation. The spontaneous polarization (Ps) was simulated by the Berry phase method. It is found that the large polarization originates from charge transfer due to the strong "push-pull" effect of electron-releasing and -withdrawing groups along the hydrogen bond. According to the characteristics of polarization of croconic acid, we constructed a one-dimensional ferroelectric Hamiltonian model to describe the ferroelectric properties of croconic acid. Based on the Hamiltonian model, the thermal properties of the ferroelectricity of croconic acid were studied by Monte Carlo method. The simulated Curie temperature is 756 K, and the spontaneous polarization keeps well temperature range stability up to 400 K. These results are in good agreement with the experimental data.

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Polarization reversal by intramolecular disordering in organic ferroelectrics: trichloroacetamide

Cited by 14 publications

References 40 publications

Unusual Long-Range Ordering Incommensurate Structural Modulations in an Organic Molecular Ferroelectric

Unusual Long-Range Ordering Incommensurate Structural Modulations in an Organic Molecular Ferroelectric

A Molecular Ferroelectric Showing Room‐Temperature Record‐Fast Switching of Spontaneous Polarization

Ferroelectric mechanism of croconic acid: A first-principles and Monte Carlo study

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