Polar metal

A polar metal, metallic ferroelectric,[1] or ferroelectric metal[2] is a metal that contains an electric dipole moment. Its components have an ordered electric dipole. Such metals should be unexpected, because the charge should conduct by way of the free electrons in the metal and neutralize the polarized charge. However they do exist. Probably the first report of a polar metal was in single crystals of the cuprate superconductors YBa2Cu3O7-δ,.[3][4] A polarization was observed along one (001) axis by pyroelectric effect measurements, and the sign of the polarization was shown to be reversible, while its magnitude could be increased by poling by an electric field.[5] The polarization was found to disappear in the superconducting state.[6] The lattice distortions responsible were considered to be a result of oxygen ion displacements induced by doped charges that break inversion symmetry.[7][8] The effect was utilized for fabrication of pyroelectric detectors for space applications, having the advantage of large pyroelectric coefficient and low intrinsic resistance.[9] Another substance family that can produce a polar metal is the nickelate perovskites. One example interpreted to show polar metallic behavior is lanthanum nickelate, LaNiO3.[10][11] A thin film of LaNiO3 grown on the (111) crystal face of lanthanum aluminate, (LaAlO3) was interpreted to be both conductor and a polar material at room temperature.[10] The resistivity of this system, however, shows an upturn with decreasing temperature, hence does not strictly adhere to the definition of a metal. Also, when grown 3 or 4 unit cells thick (1-2 nm) on the (100) crystal face of LaAlO3, the LaNiO3 can be a polar insulator or polar metal depending on the atomic termination of the surface.[11] Lithium osmate,[12] LiOsO3 also undergoes a ferrorelectric transition when it is cooled below 140K. The point group changes from R3c to R3c losing its centrosymmetry.[13][14] At room temperature and below, lithium osmate is an electric conductor, in single crystal, polycrystalline or powder forms, and the ferroelectric form only appears below 140K. Above 140K the material behaves like a normal metal.[15]

Native metallicity and ferroelectricity has been observed at room temperature in bulk single-crystalline tungsten ditelluride (WTe2); a transition metal dichalcogenide (TMDC). It has bistable and electrically switchable spontaneous polarization states indicating ferroelectricity.[16] Coexistence of metallic behavior and switchable electric polarization in WTe2, which is a layered material, has been observed in the low-thickness limit of two- and three-layers.[17] Calculations suggest this originates from vertical charge transfer between the layers, which is switched by interlayer sliding.[18]

P. W. Anderson and E. I. Blount predicted that a ferroelectric metal could exist in 1965.[13] They were inspired to make this prediction based on superconducting transitions, and the ferroelectric transition in barium titanate. The prediction was that atoms do not move far and only a slight crystal non-symmetrical deformation occurs, say from cubic to tetragonal. This transition they called martensitic. They suggested looking at sodium tungsten bronze and InTl alloy. They realised that the free electrons in the metal would neutralise the effect of the polarization at a global level, but that the conduction electrons do not strongly affect transverse optical phonons, or the local electric field inherent in ferroelectricity.[19]

References
  1. Drexel University (2 April 2014). "Researchers open path to finding rare, polarized metals". phys.org. Retrieved 23 April 2016.
  2. Benedek, Nicole A.; Birol, Turan (2016). "'Ferroelectric' metals reexamined: fundamental mechanisms and design considerations for new materials". Journal of Materials Chemistry C. 4 (18): 4000–4015. arXiv:1511.06187. doi:10.1039/C5TC03856A.
  3. Mihailovic, Dragan; Heeger, Alan J. (1990). "Pyroelectric and piezoelectric effects in single crystals of YBa2Cu3O7-d". Solid State Communications. 75: 319. doi:10.1016/0038-1098(90)90904-P.|https://doi.org/10.1016/0038-1098(90)90904-P
  4. Poberaj, Igor; Mihailovic, Dragan (1992). "Pyroelectric effect measurements in YBa2Cu3O6+y and La2CuO4 materials". Ferroelectrics. 128: 197. doi:10.1080/00150199208015091.| https://doi.org/10.1016/0921-4534(91)91614-A
  5. Mihailovic, Dragan; Poberaj, Igor (1991). "Ferroelectricity in YBa2Cu3O7−δ and La2CuO4+δ single crystals". Physica C: Superconductivity. 185-189: 781. doi:10.1016/0921-4534(91)91614-A.
  6. Mihailovic, Dragan; Poberaj, Igor; Mertelj, Alenka (1993). "Characterization of the pyroelectric effect in YBa2Cu3O7-d". Physical Review B. 48 (22): 16634–16640. doi:10.1103/PhysRevB.48.16634. PMID 10008248.| https://doi.org/10.1103/PhysRevB.48.16634
  7. Mihailovic, Dragan; Heeger, Alan J. (1990). "Pyroelectric and piezoelectric effects in single crystals of YBa2Cu3O7-d". Solid State Communications. 75: 319. doi:10.1016/0038-1098(90)90904-P.
  8. Viskadourakis, Z. (2015). "Ferroelectricity in underdoped La-based cuprates". Sci. Rep. 5: 15268. doi:10.1038/srep15268. PMC 4614081. PMID 26486276.
  9. Butler, D.; Celik-Butler, Z.; Jahanzeb, A.; Gray, J.; Travers, C. (1998). "Micromachined YBaCuO capacitor structures as uncooled pyroelectric infrared detectors". J. Appl. Phys. 84 (3): 1680. Bibcode:1998JAP....84.1680B. doi:10.1063/1.368257.
  10. Kim, T. H.; Puggioni, D.; Yuan, Y.; Xie, L.; Zhou, H.; Campbell, N.; Ryan, P. J.; Choi, Y.; Kim, J.-W.; Patzner, J. R.; et al. (20 April 2016). "Polar metals by geometric design". Nature. 533 (7601): 68–72. Bibcode:2016Natur.533...68K. doi:10.1038/nature17628. PMID 27096369.
  11. Kumah, D.P.; Malashevich, A.; Disa, A.S.; Arena, D.A.; Walker, F.J.; Ismail-Beigi, S.; Ahn, C.H. (6 November 2015). "Effect of Surface Termination on the Electronic Properties of LaNiO3 Films". Physical Review Applied. 2 (5): 054004. Bibcode:2014PhRvP...2e4004K. doi:10.1103/PhysRevApplied.2.054004.
  12. "When is a ferroelectric not a ferroelectric?". www.isis.stfc.ac.uk. 2013. Retrieved 21 April 2016.
  13. Shi, Youguo; Guo, Yanfeng; Wang, Xia; Princep, Andrew J.; Khalyavin, Dmitry; Manuel, Pascal; Michiue, Yuichi; Sato, Akira; Tsuda, Kenji; Yu, Shan; et al. (2013). "A ferroelectric-like structural transition in a metal". Nature Materials. 12 (11): 1024–1027. arXiv:1509.01849. Bibcode:2013NatMa..12.1024S. doi:10.1038/nmat3754. PMID 24056805.
  14. Paredes Aulestia, Esteban I.; Cheung, Yiu Wing; Fang, Yue-Wen; He, Jianfeng; Yamaura, Kazunari; Lai, Kwing To; Goh, Swee K.; Chen, Hanghui (2018-07-02). "Pressure-induced enhancement of non-polar to polar transition temperature in metallic LiOsO3". Applied Physics Letters. 113 (1): 012902. arXiv:1806.00639. Bibcode:2018ApPhL.113a2902P. doi:10.1063/1.5035133. ISSN 0003-6951.
  15. Shi, Youguo; Guo, Yanfeng; Wang, Xia; Princep, Andrew J.; Khalyavin, Dmitry; Manuel, Pascal; Michiue, Yuichi; Sato, Akira; Tsuda, Kenji; Yu, Shan; et al. (22 September 2013). "A ferroelectric-like structural transition in a metal" (PDF). Nature Materials. 12 (11). Supplementary information. arXiv:1509.01849. Bibcode:2013NatMa..12.1024S. doi:10.1038/nmat3754. PMID 24056805.
  16. Sharma, Pankaj; Xiang, Fei-Xiang; Shao, Ding-Fu; Zhang, Dawei; Tsymbal, Evgeny Y.; Hamilton, Alex R.; Seidel, Jan (2019). "A room-temperature ferroelectric semimetal". Science Advances. 5 (7): eaax5080. Bibcode:2019SciA....5.5080S. doi:10.1126/sciadv.aax5080. PMC 6611688. PMID 31281902.
  17. Fei, Zaiyao; Zhao, Wenjin; Palomaki, Tauno A.; Sun, Bosong; Miller, Moira K.; Zhao, Zhiying; Yan, Jiaqiang; Xu, Xiaodong; Cobden, David H. (August 2018). "Ferroelectric switching of a two-dimensional metal". Nature. 560 (7718): 336–339. arXiv:1809.04575. doi:10.1038/s41586-018-0336-3. ISSN 1476-4687. PMID 30038286.
  18. Yang, Qing; Wu, Menghao; Li, Ju (2018-12-20). "Origin of Two-Dimensional Vertical Ferroelectricity in WTe2 Bilayer and Multilayer". The Journal of Physical Chemistry Letters. 9 (24): 7160–7164. doi:10.1021/acs.jpclett.8b03654. PMID 30540485.
  19. Anderson, P. W.; Blount, E. I. (15 February 1965). "Symmetry Considerations on Martensitic Transformations: "Ferroelectric" Metals?". Physical Review Letters. 14 (7): 217–219. Bibcode:1965PhRvL..14..217A. doi:10.1103/PhysRevLett.14.217.
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