Perovskite B‐Site Compositional Control of [110]<sub>p</sub> Polar Displacement Coupling in an Ambient‐Pressure‐Stable Bismuth‐based Ferroelectric

Dolgos, Michelle R.; Adem, Umut; Manjón-Sanz, Alicia; Wan, Xiaobing; Comyn, Tim P.; Stevenson, Timothy; Bennett, James T.; Bell, Andrew J.; Tran, T. Thao; Halasyamani, P. Shiv; Claridge, John B.; Rosseinsky, Matthew J.

doi:10.1002/ange.201203884

Cited by 10 publications

(8 citation statements)

References 33 publications

(26 reference statements)

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“…Although leaky, both the remnant polarization (P r ) and saturated polarization (P s ) increase with electric field in non-linear fashion. This behavior reflects domain wall motion associated with ferroelectricity [28]. The remnant polarization (P r ) and the coercive field (E c ) are 0.43 mC/cm 2 and 99.7 kV/cm, respectively, under the maximum electric field of 160 kV/cm.…”

Section: Resultsmentioning

confidence: 91%

Structural and multiferroic properties in double-layer Aurivillius phase Pb0.4Bi2.1La0.5Nb1.7Mn0.3O9 prepared by molten salt method

Wendari

Arief

Mufti

et al. 2020

Journal of Alloys and Compounds

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Section: Resultsmentioning

confidence: 91%

Structural and multiferroic properties in double-layer Aurivillius phase Pb0.4Bi2.1La0.5Nb1.7Mn0.3O9 prepared by molten salt method

Wendari

Arief

Mufti

et al. 2020

Journal of Alloys and Compounds

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“…Alternately, Bibased perovskite-type oxides like BiFeO 3 (BFO), have recently attracted attention because of their high Curie temperature (T c ) and its large polarization that is comparable to the Pb-based ferroelectrics. [4] The 6s 1orbital of Bi hybridizes with the adjacent oxygen 2p orbital to induce the large polar displacement of Bi. [5] Also in this case, the ferroelectricity stems from the unique property of the specific element, Bi.…”

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confidence: 99%

Ferroelectricity Driven by Twisting of Silicate Tetrahedral Chains

et al. 2013

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Conventional perovskite-type ferroelectrics are based on octahedral units of oxygen, and often comprise toxic Pb to achieve robust ferroelectricity. Here, we report the ferroelectricity in a silicate-based compound, Bi 2 SiO 5 (BSO), induced by a structural instability of the corresponding silicate tetrahedral chains. A low-energy phonon mode condenses at ~ 673 K to induce the proper ferroelectric phase transition. Polarization switching was observed in a BSO single crystal with a coercive field of 30 kV/cm and a spontaneous polarization of 0.3 μC/cm 2 along a direction normal to the cleavage plane. The in-plane polarization was estimated by first principles calculations to be 23 μC/cm 2 . The present findings provide a new guideline for designing ferroelectric materials based on SiO 4 tetrahedral units, which is ubiquitously found in natural minerals.Because of its diverse functionality, ferroelectricity is a key ingredient for electronic and optical technologies applied to non-volatile memory, actuators and sensors. (1) Ferroelectric materials are characterized by a switchable polarization caused by spontaneous displacements of cations relative to anions, which generally appears through the ferroelectric phase transition from centrosymmetric to non-centrosymmetric phases. In the case of so-called displacive-type phase transitions, the phase transition is driven by the freezing of a zone-centre optical phonon mode, "soft mode", using an eigenvector similar to the polar displacement observed in the ferroelectric phase. (2-4) Recent studies have clarified that the soft mode instability in conventional perovskite-type oxides is caused by covalency between the cations and oxygen ions in the octahedral oxygen units. (5-7) Current ferroelectric applications thus rely heavily upon toxic Pbbased compounds, because the large covalency of Pb-O is favourable for causing structural instability in these compounds to induce robust ferroelectricity. Alternately, the unconventional ferroelectricity observed in Bi-based perovskite-type oxides like BiFeO 3 (BFO), has recently attracted attention in terms of the high-T c and the large spontaneous polarization achieved without Pb. The mechanism has been understood as a lone-pair ordering, where the 6s orbital of Bi hybridizes with the 2p-orbital of an adjacent oxygen to induce the large polar displacement of Bi. (8,9) Also in this case, the ferroelectricity stems from the unique property of the specific element, Bi. Such a strong element-dependence of current ferroelectric oxides provides a demand for a new guideline principle for designing ferroelectric materials. (10,11)Here, we report for the first time the ferroelectric phase transition driven by the structural instability of the pyroxene-type one-dimensional chains of oxygen tetrahedra, which is found in the silicate-based compound Bi 2 SiO 5 (BSO). BSO has a layered structure, which comprises a single layer of one-dimensional silicate chains sandwiched between Bi 2 O 2 sheets (Fig. 1a). The proper ferroelectric phase transit...

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“…In the case of displacive-type phase transitions, the phase transition is driven by the freezing of a zone-center optical phonon mode, "soft mode", using an eigenvector similar to the polar displacement observed in the ferroelectric phase. [4] The 6s 1orbital of Bi hybridizes with the adjacent oxygen 2p orbital to induce the large polar displacement of Bi. [3] Current ferroelectric applications rely heavily upon toxic Pb-based compounds, because the strong covalency of PbÀO causes structural instability in these compounds and induces the large spontaneous polarization.…”

mentioning

confidence: 99%

Ferroelectricity Driven by Twisting of Silicate Tetrahedral Chains

et al. 2013

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Because of its diverse functionality, ferroelectricity plays a key role in electronic and optical technologies. [1] Ferroelectric materials are characterized by a switchable polarization caused by spontaneous displacements of cations relative to anions, which occurs in centrosymmetric to noncentrosymmetric ferroelectric phase transitions. In the case of displacive-type phase transitions, the phase transition is driven by the freezing of a zone-center optical phonon mode, "soft mode", using an eigenvector similar to the polar displacement observed in the ferroelectric phase. [2] Recent studies have clarified that the soft mode instability in conventional perovskite-type oxides is caused by covalency between the cations and oxygen ions in the octahedral oxygen units. [3] Current ferroelectric applications rely heavily upon toxic Pb-based compounds, because the strong covalency of PbÀO causes structural instability in these compounds and induces the large spontaneous polarization. Alternately, Bibased perovskite-type oxides like BiFeO 3 (BFO), have recently attracted attention because of their high Curie temperature (T c ) and its large polarization that is comparable to the Pb-based ferroelectrics. [4] The 6s 1orbital of Bi hybridizes with the adjacent oxygen 2p orbital to induce the large polar displacement of Bi. [5] Also in this case, the ferroelectricity stems from the unique property of the specific element, Bi. Such a strong element dependence of ferroelectric oxides demands new principle guidelines for designing ferroelectric materials. [6] Here, we report for the first time the ferroelectric phase transition driven by the structural instability of pyroxenoidtype one-dimensional chains of oxygen tetrahedra, which occur in the silicate-based compound Bi 2 SiO 5 (BSO). BSO has a layered structure, which comprises a single layer of onedimensional silicate chains sandwiched between Bi 2 O 2 sheets (Figure 1 A). The ferroelectric phase transition at 663 K is induced by the freezing of the soft mode that stems from the twisting of silicate chains. The ferroelectricity is verified by a direct observation of the P-E hysteresis loops and arises from the structural instability of the tetrahedral oxygen chains. Therefore, the present finding offers a new route for designing environmentally friendly ferroelectric oxides that are free from specific element constraints.The crystal structure of BSO has previously been reported to be an orthorhombic Cmc2 1 at room temperature. [7] Our transmission electron microscopy (TEM) observations, however, reveal that the crystallographic b angle of BSO slightly deviates from 908 at room temperature, indicating a monoclinic distortion of BSO (see Figure S1 A in the Supporting Information). X-ray powder diffraction analysis indicates that BSO has a monoclinic Cc crystal structure with lattice parameters of a = 15.1193(1) , b = 5.4435(1) , c = 5.2892(1) , and b = 90.0695(20)8 ( Figure S2 A). At 793 K, the b angle changes to 908, demonstrating a structural phase transition from the monoc...

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Perovskite B‐Site Compositional Control of [110]_p Polar Displacement Coupling in an Ambient‐Pressure‐Stable Bismuth‐based Ferroelectric

Cited by 10 publications

References 33 publications

Structural and multiferroic properties in double-layer Aurivillius phase Pb0.4Bi2.1La0.5Nb1.7Mn0.3O9 prepared by molten salt method

Structural and multiferroic properties in double-layer Aurivillius phase Pb0.4Bi2.1La0.5Nb1.7Mn0.3O9 prepared by molten salt method

Ferroelectricity Driven by Twisting of Silicate Tetrahedral Chains

Ferroelectricity Driven by Twisting of Silicate Tetrahedral Chains

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Perovskite B‐Site Compositional Control of [110]p Polar Displacement Coupling in an Ambient‐Pressure‐Stable Bismuth‐based Ferroelectric

Cited by 10 publications

References 33 publications

Structural and multiferroic properties in double-layer Aurivillius phase Pb0.4Bi2.1La0.5Nb1.7Mn0.3O9 prepared by molten salt method

Structural and multiferroic properties in double-layer Aurivillius phase Pb0.4Bi2.1La0.5Nb1.7Mn0.3O9 prepared by molten salt method

Ferroelectricity Driven by Twisting of Silicate Tetrahedral Chains

Ferroelectricity Driven by Twisting of Silicate Tetrahedral Chains

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Perovskite B‐Site Compositional Control of [110]_p Polar Displacement Coupling in an Ambient‐Pressure‐Stable Bismuth‐based Ferroelectric