Letter | Published:

Electric-field control of tri-state phase transformation with a selective dual-ion switch

Nature volume 546, pages 124128 (01 June 2017) | Download Citation

Abstract

Materials can be transformed from one crystalline phase to another by using an electric field to control ion transfer, in a process that can be harnessed in applications such as batteries1, smart windows2 and fuel cells3. Increasing the number of transferrable ion species and of accessible crystalline phases could in principle greatly enrich material functionality. However, studies have so far focused mainly on the evolution and control of single ionic species (for example, oxygen, hydrogen or lithium ions4,5,6,7,8,9,10). Here we describe the reversible and non-volatile electric-field control of dual-ion (oxygen and hydrogen) phase transformations, with associated electrochromic2 and magnetoelectric11 effects. We show that controlling the insertion and extraction of oxygen and hydrogen ions independently of each other can direct reversible phase transformations among three different material phases: the perovskite SrCoO3−δ (ref. 12), the brownmillerite SrCoO2.5 (ref. 13), and a hitherto-unexplored phase, HSrCoO2.5. By analysing the distinct optical absorption properties of these phases, we demonstrate selective manipulation of spectral transparency in the visible-light and infrared regions, revealing a dual-band electrochromic effect that could see application in smart windows2,9. Moreover, the starkly different magnetic and electric properties of the three phases—HSrCoO2.5 is a weakly ferromagnetic insulator, SrCoO3−δ is a ferromagnetic metal12, and SrCoO2.5 is an antiferromagnetic insulator13—enable an unusual form of magnetoelectric coupling, allowing electric-field control of three different magnetic ground states. These findings open up opportunities for the electric-field control of multistate phase transformations with rich functionalities.

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References

  1. 1.

    & Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001)

  2. 2.

    Electrochromics for smart windows: oxide-based thin films and devices. Thin Solid Films 564, 1–38 (2014)

  3. 3.

    & Materials for fuel-cell technologies. Nature 414, 345–352 (2001)

  4. 4.

    et al. Suppression of metal-insulator transition in VO2 by electric field-induced oxygen vacancy formation. Science 339, 1402–1405 (2013)

  5. 5.

    , & Reversibly switchable electromagnetic device with leakage-free electrolyte. Adv. Electron. Mater. 2, 1600044 (2016)

  6. 6.

    , , , & Reversible oxygen scavenging at room temperature using electrochemically reduced titanium oxide nanotubes. Nat. Nanotechnol. 10, 418–422 (2015)

  7. 7.

    , & Modulation of the electrical properties of VO2 nanobeams using an ionic liquid as a gating medium. Nano Lett. 12, 2988–2992 (2012)

  8. 8.

    & Modulation of metal–insulator transition in VO2 by electrolyte gating-induced protonation. Adv. Electron. Mater. 2, 1500131 (2016)

  9. 9.

    , , & Tunable near-infrared and visible-light transmittance in nanocrystal-in-glass composites. Nature 500, 323–326 (2013)

  10. 10.

    & Voltage-controlled topotactic phase transition in thin-film SrCoOx monitored by in situ X-ray diffraction. Nano Lett. 16, 1186–1193 (2016)

  11. 11.

    Multi-ferroic magnetoelectrics. Ferroelectrics 162, 317–338 (1994)

  12. 12.

    et al. Reversible redox reactions in an epitaxially stabilized SrCoOx oxygen sponge. Nat. Mater. 12, 1057–1063 (2013)

  13. 13.

    et al. Crystallographic and magnetic structure of SrCoO2.5 brownmillerite: neutron study coupled with band-structure calculations. Phys. Rev. B 78, 054404 (2008)

  14. 14.

    et al. Infinite-layer iron oxide with a square-planar coordination. Nature 450, 1062–1065 (2007)

  15. 15.

    et al. Strongly correlated perovskite fuel cells. Nature 534, 231–234 (2016)

  16. 16.

    et al. The hydride anion in an extended transition metal oxide array: LaSrCoO3H0.7. Science 295, 1882–1884 (2002)

  17. 17.

    et al. An oxyhydride of BaTiO3 exhibiting hydride exchange and electronic conductivity. Nat. Mater. 11, 507–511 (2012)

  18. 18.

    et al. Reversible phase modulation and hydrogen storage in multivalent VO2 epitaxial thin films. Nat. Mater. 15, 1113–1119 (2016)

  19. 19.

    & Materials for electrochemical capacitors. Nat. Mater. 7, 845–854 (2008)

  20. 20.

    et al. Electric-field-induced superconductivity in an insulator. Nat. Mater. 7, 855–858 (2008)

  21. 21.

    et al. Electrically induced ferromagnetism at room temperature in cobalt-doped titanium dioxide. Science 332, 1065–1067 (2011)

  22. 22.

    et al. Electrostatic and electrochemical nature of liquid-gated electric-double-layer transistors based on oxide semiconductors. J. Am. Chem. Soc. 132, 18402–18407 (2010)

  23. 23.

    , , & Oxygen diffusion pathways in brownmillerite SrCoO2.5: influence of structure and chemical potential. J. Chem. Phys. 141, 084710 (2014)

  24. 24.

    et al. O-K and Co-L XANES study on oxygen intercalation in perovskite SrCoO3-δ. Chem. Mater. 22, 70–76 (2010)

  25. 25.

    et al. Influence of crystal structure, ligand environment and morphology on Co L-edge XAS spectral characteristics in cobalt compounds. J. Synchrotron Radiat. 22, 1450–1458 (2015)

  26. 26.

    et al. Why LiFePO4 is a safe battery electrode: Coulomb repulsion induced electron-state reshuffling upon lithiation. Phys. Chem. Chem. Phys. 17, 26369–26377 (2015)

  27. 27.

    et al. Bivalence Mn5O8 with hydroxylated interphase for high-voltage aqueous sodium-ion storage. Nat. Commun. 7, 13370 (2016)

  28. 28.

    et al. Topotactic synthesis of strontium cobalt oxyhydride thin film with perovskite structure. AIP Adv. 5, 107147 (2015)

  29. 29.

    et al. Experimental confirmation of the x-ray magnetic circular dichroism sum rules for iron and cobalt. Phys. Rev. Lett. 75, 152–155 (1995)

  30. 30.

    et al. Electrical control of antiferromagnetic domains in multiferroic BiFeO3 films at room temperature. Nat. Mater. 5, 823–829 (2006)

  31. 31.

    & Relaxation dynamics of ionic liquid-VO2 interfaces and influence in electric double-layer transistors. J. Appl. Phys. 111, 084508 (2012)

  32. 32.

    et al. Collective bulk carrier delocalization driven by electrostatic surface charge accumulation. Nature 487, 459–462 (2012)

  33. 33.

    et al. Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy. J. Phys. D 49, 413003 (2016)

  34. 34.

    . et al. The structure of the first coordination shell in liquid water. Science 304, 995–999 (2004)

  35. 35.

    et al. Energetics of hydrogen bond network rearrangements in liquid water. Science 306, 851–853 (2004)

  36. 36.

    et al. Oxygen 1s x-ray-absorption edges of transition metal oxides. Phys. Rev. B 40, 5715 (1989)

  37. 37.

    et al. Probing oxygen vacancy concentration and homogeneity in solid-oxide fuel-cell cathode materials on the subunit-cell level. Nat. Mater. 11, 888–894 (2012)

  38. 38.

    et al. Understanding chemical expansion in non-stoichiometric oxides: ceria and zirconia case studies. Adv. Funct. Mater. 22, 1958–1965 (2012)

  39. 39.

    et al. Field-induced water electrolysis switches an oxide semiconductor from an insulator to a metal. Nat. Commun. 1, 118 (2010)

  40. 40.

    , , & A ToF-SIMS study of the deuterium-hydrogen exchange induced by ammonia plasma treatment of polyolefins. J. Anal. At. Spectrom. 26, 1157–1165 (2011)

  41. 41.

    et al. Electrical properties of epitaxial thin films of oxyhydrides ATiO3-xHx (A = Ba and Sr). Chem. Mater. 27, 6354–6359 (2015)

  42. 42.

    et al. Strontium vanadium oxide-hydrides: “square-planar” two-electron phases. Angew. Chem. Int. Ed. 53, 7556–7559 (2014)

  43. 43.

    et al. Direct synthesis of chromium perovskite oxyhydride with a high magnetic-transition temperature. Angew. Chem. Int. Ed. 53, 10377–10380 (2014)

  44. 44.

    et al. Reduction and oxidation of SrCoO2.5 thin films at low temperatures. Dalton Trans. 41, 10507–10510 (2012)

  45. 45.

    et al. Infrared-sensitive electrochromic device based on VO2. Appl. Phys. Lett. 103, 153503 (2013)

  46. 46.

    & Toward solid-state switchable mirrors using a zirconium oxide proton conductor. Solid State Ion. 145, 17–24 (2001)

  47. 47.

    et al. Electrochemically induced transformations of vanadium dioxide nanocrystals. Nano Lett. 16, 6021–6027 (2016)

  48. 48.

    et al. Correlated perovskites as a new platform for super-broadband-tunable photonics. Adv. Mater. 28, 9117–9125 (2016)

  49. 49.

    et al. Vacancy induced semiconductor-insulator-metal transitions in nonstoichiometric nickel and tungsten oxides. Nano Lett. 16, 7067–7077 (2016)

  50. 50.

    et al. Electrochemical properties of novel ionic liquids for electric double layer capacitor applications. Electrochim. Acta 49, 3603–3611 (2004)

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Acknowledgements

This study was financially supported by the National Basic Research Program of China (grants 2015CB921700, 2016YFA0301004 and 2015CB921002); the National Natural Science Foundation of China (grants 11274194, 51561145005, 51332001 and 11334006); the Initiative Research Projects of Tsinghua University (grant 20141081116); and the Beijing Advanced Innovation Center for Future Chip (ICFC). L.G. acknowledges support from the National Program on Key Basic Research Project (2014CB921002) and the Strategic Priority Research Program of Chinese Academy of Sciences (XDB07030200) and National Natural Science Foundation of China (grants 51522212, 51421002 and 51672307). The Advanced Light Source is supported by the US Department of Energy under contract no. DE-AC02-05CH11231.

Author information

Affiliations

  1. State Key Laboratory of Low Dimensional Quantum Physics and Department of Physics, Tsinghua University, Beijing 100084, China

    • Nianpeng Lu
    • , Pengfei Zhang
    • , Hao-Bo Li
    • , Yujia Wang
    • , Jingwen Guo
    • , Ding Zhang
    • , Zheng Duan
    • , Zhuolu Li
    • , Meng Wang
    • , Shuzhen Yang
    • , Mingzhe Yan
    • , Shuyun Zhou
    • , Jian Wu
    •  & Pu Yu
  2. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Science, Beijing 100190, China

    • Qinghua Zhang
    •  & Lin Gu
  3. State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China

    • Qinghua Zhang
    •  & Ce-Wen Nan
  4. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    • Ruimin Qiao
    • , Elke Arenholz
    •  & Wanli Yang
  5. Department of Physics, Durham University, Durham DH1 3LE, UK

    • Qing He
  6. Collaborative Innovation Center of Quantum Matter, Beijing 100084, China

    • Shuyun Zhou
    • , Lin Gu
    • , Jian Wu
    •  & Pu Yu
  7. RIKEN Center for Emergent Matter Science (CEMS), Wako 351-198, Japan

    • Yoshinori Tokura
    •  & Pu Yu

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Contributions

P.Y. conceived the project and designed the experiments. N.L., Y.W., Z.D. and Z.L. fabricated the thin films. N.L. performed the ILG, X-ray diffraction, magnetic and optical measurements, with H.-B.L. Y.W., S.Y. and M.W. P.Z. performed the theoretical analysis and calculations, under the supervision of J.W. Q.Z. performed the scanning transmission electron microscopy measurements, under the supervision of L.G. and C.-W.N. R.Q., J.G. and M.Y. performed the room-temperature soft X-ray absorption measurements, under the supervision of S.Z. and W.Y. Q.H., J.G. and E.A. performed the low-temperature soft X-ray magnetic circular dichroism measurements. D.Z., H.-B.L. and N.L. performed the electrical transport measurements. Y.T. discussed the results. N.L. and P.Y. wrote the manuscript. All authors discussed the results and commented on the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Jian Wu or Pu Yu.

Reviewer Information Nature thanks D. Milliron, S. Ramanathan and the other anonymous reviewer(s) for their contribution to the peer review of this work.

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DOI

https://doi.org/10.1038/nature22389

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