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近年来有一系列二维范德瓦耳斯材料铁电性被实验证实, 层间滑移铁电体是其中重要的一类, 该机制是传统铁电所没有, 而很多二维材料普遍具有的. 本文回顾了相关研究, 介绍了这种铁电的起源: 不少二维材料双层中上下两层并不对等, 造成净层间垂直电荷转移, 而层间滑移使该垂直铁电极化得以翻转. 这种独特的滑移铁电可广泛存在于范德瓦耳斯双层、多层乃至体相结构中, 层间滑移势垒较传统铁电低几个数量级, 有望极大节约铁电翻转所需的能量. 目前这种滑移铁电机制已在WTe2和β-InSe双层/多层体系得到实验证实, 不少预期极化更高的滑移铁电体系(如BN)也有望在近期实现.
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关键词:
- 二维范德瓦耳斯铁电体 /
- 层间滑移 /
- 纳米发电机 /
- 铁电莫列超晶格
In recent years, the existence of ferroelectricity in a series of two-dimensional van der Waals materials has been experimentally confirmed, in which the ferroelectricity induced by interlayer sliding is an important type. This mechanism is not available in traditional ferroelectrics but can be applied to many two-dimensional materials. In this paper we review the relevant researches and introduce the origin of this type of ferroelectricity: in many two-dimensional van der Waals bilayers, the upper layer is not equivalent to the lower layer, thus giving rise to a net interlayer charge transfer and the inducing vertical polarization to be switchable via interlayer sliding. This unique sliding ferroelectricity can widely exist in many van der Waals bilayers, multilayers and even bulk structures. The interlayer sliding barrier is several orders of magnitude lower than that of traditional ferroelectric, which may greatly save the energy required by ferroelectric switching. At present, this type of interlayer sliding ferroelectricity has been experimentally confirmed in WTe2 and β-InSe bilayer/multilayer systems, and more systems predicted to be with much stronger interlayer sliding ferroelectricity (like BN) may be realized in near future.-
Keywords:
- two-dimensional van der Waals ferroelectrics /
- interlayer sliding /
- nanogenerator /
- ferroelectric Moire superlattice
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图 1 (a) BN双层的铁电翻转路径; (b)石墨烯/BN (C/BN)异质双层不同堆叠方式会产生不同的层间电势, 可被用作纳米发电; 灰色、粉色和蓝色小球分别代表C, B和N原子, 黑色和红色箭头分别表示电荷转移和电极化的方向[15]
Fig. 1. (a) Ferroelectric switching pathway of BN bilayer; (b) different stacking configurations of graphene/BN heterobilayer with distinct interlayer potentials, which can be utilized as nanogenerators. Gray, pink, and blue spheres denote C, B and N atoms, and black and red arrows denote the direction of charge transfer and polarizations, respectively[15].
图 2 (a)层间小的扭转角和(b)上层和下层之间轻微的应力差别形成的铁电莫列超晶格(黄色、绿色和红色圈住的区域分别代表AB-up, AB-down和AA畴)[15]
Fig. 2. Ferroelectric Moire superlattice upon (a) a small twist angle or (b) a slight difference in strain between upper and down layer. AB-up, AB-down and AA regions are marked in yellow, green and red circles, respectively[15].
图 4 (a)最上边的两个结构为双层WTe2的态I和相对态I的中心水平面进行镜像操作得到极化方向相反的态II, 下边的图表示滑移的过程; (b)采用层间滑移的方式使态I翻转为态II的翻转势垒; 图中天蓝色和橙色的小球分别表示W和Te原子, 红色箭头代表电极化的方向[17]
Fig. 4. (a) Geometric structure of state I of WTe2 bilayer and state II obtained by reflecting state I across the central horizontal plane, which can be also obtained by interlayer translation; (b) ferroelectricity switching pathway of WTe2 bilayer from state I to state II. Blue and orange spheres denote W and Te atoms respectively, and red arrows denote the polarization direction[17].
图 5 (a)当y = 0时, 沿着–x方向进行层间平移, 能量和电极化与滑移距离x的关系; (b)在x = –(a + b)/2时, 沿着–y方向进行层间平移, 能量和电极化与滑移距离y的关系; (c)双层WTe2被压缩时, 电极化与层间距被压缩比例的关系[17]
Fig. 5. (a) Dependence of energy and polarization on x along the –x direction at y = 0; (b) dependence of energy and polarization on y along the –y direction at x = –(a + b)/2; (c) dependence of polarization on the compression of interlayer distance of the WTe2 bilayer[17].
图 6 (a) β-InSe纳米片的晶体结构, 紫色和蓝色的箭头分别表示电荷转移和电极化的方向; 7 nm厚纳米片的(b) PFM振幅曲线和(c) PFM相滞回线[46]
Fig. 6. (a) Crystal structure of β-InSe. Purple and blue arrows denote the direction of charge transfer and polarizations, respectively; (b) PFM amplitude and (c) PFM phase hysteresis loops on a 7-nm-thick flake[46].
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[1] Wu M, Jena P 2018 WIREs Comput. Mol. Sci. 8 e1365
Google Scholar
[2] Wu M, Burton J D, Tsymbal E Y, Zeng X C, Jena P 2013 Phys. Rev. B 87 081406
Google Scholar
[3] Kou L, Ma Y, Liao T, Du A, Chen C 2018 Phys. Rev. Appl. 10 024043
Google Scholar
[4] Wu M, Dong S, Yao K, Liu J, Zeng X C 2016 Nano Lett. 16 7309
Google Scholar
[5] Wu M, Zeng X C 2016 Nano Lett. 16 3236
Google Scholar
[6] Fei R X, Kang W, Yang L 2016 Phys. Rev. Lett. 117 097601
Google Scholar
[7] Chang K, Liu J W, Lin H C, Wang N, Zhao K, Zhang A M, Jin F, Zhong Y, Hu X P, Duan W H 2016 Science 353 274
Google Scholar
[8] Bao Y, Song P, Liu Y, Chen Z, Zhu M, Abdelwahab I, Su J, Fu W, Chi X, Yu W, Liu W, Zhao X, Xu Q H, Yang M, Loh K P 2019 Nano Lett. 19 5109
Google Scholar
[9] Wu M, Zeng X C 2017 Nano Lett. 17 6309
Google Scholar
[10] Ghosh T, Samanta M, Vasdev A, Dolui K, Ghatak J, Das T, Sheet G, Biswas K 2019 Nano Lett. 19 5703
Google Scholar
[11] Belianinov A, He Q, Dziaugys A, Maksymovych P, Eliseev E, Borisevich A, Morozovska A, Banys J, Vysochanskii Y, Kalinin S V 2015 Nano Lett. 15 3808
Google Scholar
[12] Liu F, You L, Seyler K L, Li X, Yu P, Lin J, Wang X, Zhou J, Wang H, He H, Pantelides S T, Zhou W, Sharma P, Xu X, Ajayan P M, Wang J, Liu Z 2016 Nat. Commun. 7 12357
Google Scholar
[13] Ding W, Zhu J, Wang Z, Gao Y, Xiao D, Gu Y, Zhang Z, Zhu W 2017 Nat. Commun. 8 14956
Google Scholar
[14] Zheng C, Yu L, Zhu L, Collins J L, Kim D, Lou Y D, Xu C, Li M, Wei Z, Zhang Y P 2018 Sci. Adv. 4 7720
Google Scholar
[15] Li L, Wu M 2017 ACS Nano 11 6382
Google Scholar
[16] Fei Z, Zhao W, Palomaki T A, Sun B, Miller M K, Zhao Z, Yan J, Xu X, Cobden D H 2018 Nature 560 336
Google Scholar
[17] Yang Q, Wu M, Li J 2018 J. Phys. Chem. Lett. 9 7160
Google Scholar
[18] Ribeiro R M, Peres N M R 2011 Phys. Rev. B 83 235312
Google Scholar
[19] Constantinescu G, Kuc A, Heine T 2013 Phys. Rev. Lett. 111 036104
Google Scholar
[20] Henkelman G, Uberuaga B P, Jónsson H 2000 J. Chem. Phys. 113 9901
Google Scholar
[21] Shirodkar S N, Waghmare U V 2014 Phys. Rev. Lett. 112 157601
Google Scholar
[22] Fan F R, Tian Z Q, Lin Wang Z 2012 Nano Energy 1 328
Google Scholar
[23] Zhang B, Chen J, Jin L, Deng W, Zhang L, Zhang H, Zhu M, Yang W, Wang Z L 2016 ACS Nano 10 6241
Google Scholar
[24] Zhang L, Zhang B, Chen J, Jin L, Deng W, Tang J, Zhang H, Pan H, Zhu M, Yang W, Wang Z L 2016 Adv. Mater. 28 1650
Google Scholar
[25] Zhang L, Jin L, Zhang B, Deng W, Pan H, Tang J, Zhu M, Yang W 2015 Nano Energy 16 516
Google Scholar
[26] Jin L, Chen J, Zhang B, Deng W, Zhang L, Zhang H, Huang X, Zhu M, Yang W, Wang Z L 2016 ACS Nano 10 7874
Google Scholar
[27] Wang Z L, Wang X D 2015 Nano Energy 14 1
Google Scholar
[28] Duerloo K A N, Reed E J 2013 Nano Lett. 13 1681
Google Scholar
[29] Qi J S, Qian X F, Qi L, Feng J, Shi D N, Li J 2012 Nano Lett. 12 1224
Google Scholar
[30] Chen Y, Ke F, Ci P, Ko C, Park T, Saremi S, Liu H, Lee Y, Suh J, Martin L W, Ager J W, Chen B, Wu J 2017 Nano Lett. 17 194
Google Scholar
[31] Jaffe A, Lin Y, Mao W L, Karunadasa H I 2017 J. Am. Chem. Soc. 139 4330
Google Scholar
[32] Wu M, Qian X, Li J 2014 Nano Lett. 14 5350
Google Scholar
[33] Poncharal P, Ayari A, Michel T, Sauvajol J L 2008 Phys. Rev. B 78 113407
Google Scholar
[34] Freeman C L, Claeyssens F, Allan N L, Harding J H 2006 Phys. Rev. Lett. 96 066102
Google Scholar
[35] Sorokin P B, Kvashnin A G, Zhu Z, Tomanek D 2014 Nano Lett. 14 7126
Google Scholar
[36] Naguib M, Mochalin V N, Barsoum M W, Gogotsi Y 2014 Adv. Mater. 26 992
Google Scholar
[37] Ma Y, Dai Y, Guo M, Niu C, Zhu Y, Huang B 2012 ACS Nano 6 1695
Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
[41] Dawber M, Rabe K, M&Scott J F 2005 Rev. Mod. Phys. 77 1083
Google Scholar
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Google Scholar
[43] Mak K F, Lee C, Hone J, Shan J, Heinz T F 2010 Phys. Rev. Lett. 105 136805
Google Scholar
[44] Sharma P, Xiang F X, Shao D F, Zhang D, Tsymbal E Y, Hamilton A R, Seidel J 2019 Sci. Adv. 5 eaax5080
Google Scholar
[45] Xiao J, Wang Y, Wang H, Pemmaraju C D, Wang S, Muscher P, Sie E J, Nyby C M, Devereaux T P, Qian X, Zhang X, Lindenberg A M 2020 Nat. Phys. 1 7
Google Scholar
[46] Hu H, Sun Y, Chai M, Xie D, Ma J, Zhu H 2019 Appl. Phys. Lett. 114 252903
Google Scholar
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