Charge-mediated magnetoelectricity: from ferroelectric field effect to charge-ordering ferroelectrics

An Ming; Dong Shuai

doi:10.7498/aps.69.20201193

Abstract

Magnetoelectricity is an emerging topic and a frontier issue of the field of ferroelectricity. Multiferroics containing more than one ferroic order is an ideal system to pursuit intrinsic and robust magnetoelectric coupling, which holds rich physics and great potential applications. As a branch of the correlated electron family, multiferroic also has multiple degrees of freedom, including the charge, spin, orbital, and lattice. Among them, the charge degree of freedom has been mostly overlooked in the past researches and actually it may play an important role in magnetoelectricity. In this topical review, the charge-mediated magnetoelectricity is introduced, including the ferroelectric field effect in heterostructures and the charge ordering in single-phase multiferroics. The physical mechanisms will be revealed, together with several examples we given in recent years. We hope that this topical review can provide a reference for the researches in this vigorous filed.

Keywords:

Authors and contacts

An Ming,
Dong Shuai

School of Physics, Southeast University, Nanjing 211189, China

Corresponding author: Dong Shuai, sdong@seu.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 11834002, 11674055)

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References

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Cited By

图 1 铁电场效应示意图(箭头表示铁电极化的方向)　(a) 极化向上时, 界面处吸引空穴; (b) 极化向下时, 界面处吸引电子; 即极化翻转导致界面处局域电荷重新分布^[11]

Figure 1. Sketch of ferroelectric-field effect: (a) When the ferroelectric polarization (as denoted by assows) is upward, holes are attracted at the interface; (b) in contrast, electrons will gather at the interface when the polarization is reversed ^[11].

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图 2 (a) La_1–xA_xMnO₃/BaTiO₃ (001)异质结结构示意图, 界面处La_1–xA_xMnO₃ (LAMO)(虚线框区域)随着BaTiO₃ (BTO)极化方向(黑色箭头所示)翻转, 从铁磁态转变为A型反铁磁态; (b) 界面处锰氧化物的局域态密度随着BaTiO₃极化方向翻转而变化(极化指向界面时, 蓝色虚线表示; 极化背离界面时, 红色实线)^[19]

Figure 2. (a) Interfacial magnetic transition induced by charge redistribution at the La_1–xA_xMnO₃/BaTiO₃ interface. Specifically, the local moments of Mn (denoted by small arrows) close to the interface change from parallel to antiparallel as the polarization of BaTiO₃ (denoted by large arrows) is reversed; (b) the spin-resolved local density of states of the interfacial La_0.5A_0.5MnO₃ varies with the ferroelectric field direction of BaTiO₃, shifting downwards (blue dashed line) or upwards (red solid line) as the polarization pointing to or away from the interface, respectively^[19].

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图 3 (a) 100 K时PbZr_0.2Ti_0.8O₃不同极化方向下La_0.8Sr_0.2MnO₃在面内[100]方向上测得的磁滞回线; (b)异质结界面处受极化翻转调制的自旋结构示意图(黑色箭头, Mn离子自旋方向; n, 界面开始的Mn离子层数^[20]); (c) 100 K时受外电场调控的磁响应曲线^[21]; (d) BiFeO₃/La_0.5Ca_0.5MnO₃界面电荷密度及自旋结构示意图^[25]

Figure 3. (a) Magnetic hysteresis curves of La_0.8Sr_0.2MnO₃ along [100] direction taken at 100 K as the PbZr_0.2Ti_0.8O₃ polariztion points down into (black dots) or away from (red hollow diamonds) the interface; (b) sketch of the spin configurations of interfacial Mn for the two polarization states of PbZr_0.2Ti_0.8O₃. The schematic change of Mn and O orbital states are shown along with the layer-resolved magnetic moment. The spin orientation of Mn are denoted by arrows^[20]; (c) magnetoelectric hysteresis curve taken at 100 K which is obviously manipulated by the external electric field^[21]; (d) sketch of the interfacial charge distribution and spin structure of BiFeO₃/La_0.5Ca_0.5MnO₃ (denoed by arrows with different size)^[25].

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图 4 (a)铁电-锰氧化物异质结模型模拟结果: 铁电极化(灰色区域)调节界面处静电势(线)和Mn上e_g电子密度分布(点线); (b)铁电调控磁性相图: 从铁磁基态出发, 加大铁电极化(Q, 负值代表极化方向背离界面), 可以诱发界面反铁磁相(如CE1, Cx1)^[26]

Figure 4. (a) Schematic of the interfacial electrostatic potential (lines without dots) and the corresponding curve of Mns’ e_g charge density (line with dots), with the original density (dashed lines) for reference. The typical polarization cases (left: Q = –0.4, right: Q = 0.4) are shown for better illustration. The sandwiched ferroelectric gate and its polarization are also drafted. (b) Ferroelectric field dependent ground-state phase diagram for the interfacial layers. In addition to the intrinsic ferromangentic phase, there are many antiferromagnetic orders (such as CE1 and Cx1)^[26].

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图 5 (a) 锰氧化物-铁电BaTiO₃超晶格结构示意图(黄色小球代表三价稀土金属元素和二价碱土金属元素的混合; Ba, Mn, Ti, O分别用绿色、紫色、蓝绿色和红色表示; +P和–P箭头代表铁电极化方向; 绿色箭头代表(铁磁相)自旋; 紫色箭头代表(亚铁磁相)自旋); (b) 不同MnO₂层中Mn的e_g电荷密度(用紫色球体大小区分)以及相应静电势(黑色横线)示意图^[11]

Figure 5. (a) The superlattice structure composed of manganite and ferroelectric titanate. The Ba, O, Ti, Mn, and the mixture of trivalent and divalent cations are denoted by green, red, cyan, purple, and yellow balls. The n/p-type interfaces have been marked. The magnetic order of manganite can be switched from ferromagnetic to ferrimagnetic as the polarization of titanate changes from –P (left) to +P (right); (b) the layer-resolved e_g density (spheres) and electrostatic potential (bars) modulated by n/p-type interfaces (bricks) and –P/+P polarizations (arrows)^[11].

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图 6 (a), (b)沿不同方向观察的立方结构中G型反铁磁序示意图, 其中绿色和红色分别代表不同自旋方向; (c)沿[111]方向构建的BiFeO₃/SrTiO₃超晶格结构示意图; (d), (e)超晶格中BiFeO₃层中电子密度空间分布示意图, 箭头分别表示极化P的方向(绿色)和净磁矩M的方向(橘色); (f)电控磁示意图: 随着极化方向的翻转, 体系净磁矩方向也相应发生翻转^[28]

Figure 6. (a), (b) Schematic of G-type antiferromagnetic order in pseudocubic perovskite structure (as in BiFeO₃) viewed from different orientations. The antiparallel spins are distinguished by green and purple; (c) the superlattice structure of BiFeO₃/SrTiO₃ stacking along the pseudocubic [111] direction. The two Fe’s in bilayer are labeled as 1 and 2; (d), (e) spatial charge distribution for the P_up and P_down cases. The orientations of M and P are also indicated; (f) the schematic process of the electric field switch of magnetism, forming an E-M hysteresis loop^[28].

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图 7 (a)三金红石LiFe₂F₆的晶体结构(棕色球, Fe; 绿色球, Li; 银色球, F); (b), (c)在面内双轴应力(–3%)作用下LiFe₂F₆中以电荷序为媒介的磁电耦合示意图: (b) 模拟的材料铁电极化翻转过程示意图, 插图为初态、中间态和末态时Fe²⁺/Fe³⁺二聚体的示意图; (c)随铁电极化变化的净磁矩翻转过程示意图, 插图为初末态对应的价带顶部分电荷密度图(沿[110]方向)^[39]

Figure 7. (a) Crystal structure of LiFe₂F₆, in which the Fe, Li, and F are denoted by brown, green, and silver balls, respectively; (b), (c) the sketch of charge-ordering-mediated magnetoelectricity in LiFe₂F₆ with moderate compressive strain: (b) the switch of polarization. Insert: sketch of the charge redistribution within Fe²⁺/Fe³⁺ dimer; (c) the switch of local moment. Insert: the corresponding profile of partial charge density^[39].

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map

[1]	Hill N A 2000 J. Phys. Chem. B 104 6694 Google Scholar
[2]	Wang J, Neaton J B, Zheng H, et al. 2003 Science 299 1719 Google Scholar
[3]	Kimura T, Goto T, Shintani H, Ishizaka K, Arima T, Tokura Y 2003 Nature 426 55 Google Scholar
[4]	Dong S, Liu J M, Cheong S W, Ren Z F 2015 Adv. Phys. 64 519 Google Scholar
[5]	Ramesh R, Spaldin N A 2007 Nat. Mater. 6 21 Google Scholar
[6]	Dong S, Xiang H J, Dagotto E 2019 Natl. Sci. Rev. 6 629 Google Scholar
[7]	徐萌, 晏建民, 徐志学, 郭磊, 郑仁奎, 李晓光 2018 67 157506 Google Scholar Xu M, Yan J M, Xu Z X, Guo L, Zheng R K, Li X G 2018 Acta. Phys. Sin. 67 157506 Google Scholar
[8]	宋骁, 高兴森, 刘俊明 2018 67 157512 Google Scholar Song X, Gao X S, Liu J M 2018 Acta Phys. Sin. 67 157512 Google Scholar
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[14]	Rondinelli J M, Stengel M, Spaldin N A 2008 Nat. Nano. 3 46 Google Scholar
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[18]	Vaz C A F, Walker F J, Ahn C H, Ismail-Beigi S 2015 J. Phys.: Condens. Matter 27 123001 Google Scholar
[19]	Burton J D, Tsymbal E Y 2009 Phys. Rev. B 80 174406 Google Scholar
[20]	Molegraaf H J A, Hoffman J, Vaz C A F, Gariglio S, Marel D V D, Ahn C H, Triscone J M 2009 Adv. Mater. 21 3470 Google Scholar
[21]	Vaz C A F, Hoffman J, Segal Y, Reiner J W, Grober R D, Zhang Z, Ahn C H, Walker F J 2010 Phys. Rev. Lett. 104 127202 Google Scholar
[22]	Vaz C A F, Hoffman J, Segal Y, Marshall M S J, Reiner J W, Zhang Z, Grober R D, Walker F J, Ahn C H 2011 J. Appl. Phys. 109 07D905 Google Scholar
[23]	Lu H, George T A, Wang Y, Ketsman I, Burton J D, Bark C W, Ryu S, Kim D J, Wang J, Binek C, Dowben P A, Sokolov A, Eom C B, Tsymbal E Y, Gruverman A 2012 Appl. Phys. Lett. 100 232904 Google Scholar
[24]	Jiang L, Choi W S, Jeen H, Egami T, Lee H N 2012 Appl. Phys. Lett. 101 042902 Google Scholar
[25]	Yi D, Liu J, Okamoto S, Jagannatha S, Chen Y C, Yu P, Chu Y H, Arenholz E, Ramesh R 2013 Phys. Rev. Lett. 111 127601 Google Scholar
[26]	Dong S, Zhang X T, Yu R, Liu J M, Dagotto E 2011 Phys. Rev. B 84 155117 Google Scholar
[27]	Ma X, Kumar A, Dussan S, Zhai H, Fang F, Zhao H B, Scott J F, Katiyar R S, Lüpke G 2014 Appl. Phys. Lett. 104 132905 Google Scholar
[28]	Weng Y K, Lin L F, Dagotto E, Dong S 2016 Phys. Rev. Lett. 117 037601 Google Scholar
[29]	Bhattacharya A, May S J, Velthuis S G E, Warusawithana M, Zhai X, Jiang B, Zuo J M, Fitzsimmons M R, Bader S D, Eckstein J N 2008 Phys. Rev. Lett. 100 257203 Google Scholar
[30]	Dong S, Yu R, Yunoki S, Alvarez G, Liu J M, Dagotto E 2008 Phys. Rev. B 78 201102(R)Google Scholar
[31]	Gibert M, Zubko P, Scherwitzl R, Íñiguez J, Triscone J M 2012 Nature Mater. 11 195 Google Scholar
[32]	Brink J V D, Khomskii D I 2008 J. Phys.: Condens. Matter 20 434217 Google Scholar
[33]	Ikeda N, Ohsumi H, Ohwada K, Ishii K, Inami T, Kakurai K, Murakami Y, Yoshii K, Mori S, Horibe Y, Kitô H 2005 Nature 436 1136 Google Scholar
[34]	Nagano A, Naka M, Nasu J, Ishihara S 2007 Phys. Rev. Lett. 99 217202 Google Scholar
[35]	Alexe M, Ziese M, Hesse D, Esquinazi P, Yamauchi K, Fukushima T, Picozzi S, Gösel U 2009 Adv. Mater. 21 4452 Google Scholar
[36]	Efremov D V, van den Brink J, Khomskii D I 2004 Nat. Mater. 3 853 Google Scholar
[37]	Giovannetti G, Kumar S, van den Brink J, Picozzi S 2009 Phys. Rev. Lett. 103 037601 Google Scholar
[38]	Portier J, Tressaud A, De Pape R, Hagenmuller P 1970 J. Solid State Chem. 2 269 Google Scholar
[39]	Lin L F, Xu Q R, Zhang Y, Zhang J J, Liang Y P, Dong S 2017 Phys. Rev. Mater. 1 071401(R)Google Scholar
[40]	Wu S W, Cybart S A, Yu P, Rossell M D, Zhang J X, Ramesh R, Dynes R C 2010 Nat. Mater. 9 756 Google Scholar
[41]	Yu P, Lee J S, Okamoto S, Rossell M D, Huijben M, Yang C H, He Q, Zhang J X, Yang S Y, Lee M J, Ramasse Q M, Erni R, Chu Y H, Arena D A, Kao C C, Martin L, Ramesh R 2010 Phys. Rev. Lett. 105 027201 Google Scholar
[42]	Weisheit M, Fähler S, Marty A, Souche Y, Poinsignon C, Givord D 2007 Science 315 349 Google Scholar
[43]	Eerenstein W, Wiora M, Prieto J L, Scott J F, Mathur N D 2007 Nat. Mater. 6 348 Google Scholar
[44]	Lebeugle D, Mougin A, Viret M, Colson D, Ranno L 2009 Phys. Rev. Lett. 103 257601 Google Scholar
[45]	Tsymbal E Y, Kohlstedt H 2006 Science 313 181 Google Scholar
[46]	Garcia V, Bibes M 2014 Nat. Commun. 5 4289 Google Scholar
[47]	Chen A, Wen Y, Fang B, Zhao Y L, Zhang Q, Chang Y S, Li P S, Wu H, Huang H L, Lu Y L, Zeng Z M, Cai J W, Han X F, Wu T, Zhang X X, Zhao Y G 2019 Nat. Commun. 10 243 Google Scholar

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Vol. 69, Issue 21 - 2020-11-05

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