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Direct visualization of the Jahn–Teller effect coupled to Na ordering in Na5/8MnO2

Nature Materials volume 13, pages 586–592 (2014)Cite this article

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Abstract

The cooperative Jahn–Teller effect (CJTE) refers to the correlation of distortions arising from individual Jahn–Teller centres in complex compounds1,2. The effect usually induces strong coupling between the static or dynamic charge, orbital and magnetic ordering, which has been related to many important phenomena such as colossal magnetoresistance1,3 and superconductivity1,4. Here we report a Na5/8MnO2 superstructure with a pronounced static CJTE that is coupled to an unusual Na vacancy ordering. We visualize this coupled distortion and Na ordering down to the atomic scale. The Mn planes are periodically distorted by a charge modulation on the Mn stripes, which in turn drives an unusually large displacement of some Na ions through long-ranged Na–O–Mn3+–O–Na interactions into a highly distorted octahedral site. At lower temperatures, magnetic order appears, in which Mn atomic stripes with different magnetic couplings are interwoven with each other. Our work demonstrates the strong interaction between alkali ordering, displacement, and electronic and magnetic structure, and underlines the important role that structural details play in determining electronic behaviour.

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Figure 1: Superstructure hkl spots in electron diffraction patterns show the ordering of Na+ in NaxMnO2.
Figure 2: Atomic-resolution STEM image visualizes CJTE and STEM-EELS shows Mn charge ordering.
Figure 3: Na5/8MnO2 superstructure shows VNa ordering, Mn charge and magnetic stripe orderings.
Figure 4: The Na ordering in Na5/8MnO2 is visualized by STEM ABF and ADF images.
Figure 5: Neutron diffraction and magnetic susceptibility measurement indicates magnetic stripe ordering.

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Acknowledgements

This work was supported by the Samsung Advanced Institute of Technology. The STEM work carried out at the Center for Functional Nanomaterials, Brookhaven National Laboratory (BNL), was supported by the US Department of Energy (DOE), Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886. The neutron scattering activities by Y.S.L. were supported by DOE under Grant No. DE-FG02-07ER46134. Use of the National Synchrotron Light Source, BNL, was supported by the DOE, Office of Science, Office of Basic Energy Sciences, and by DOE-EERE under the Batteries for Advanced Transportation Technologies (BATT) Program, under Contract No. DE-AC02-98CH10886. The identification of commercial product or trade name does not imply recommendation by the National Institute of Standards and Technology. This work made use of the Shared Experimental Facilities supported in part by the MRSEC Program of the National Science Foundation under award number DMR-0819762. This work was also supported by a user project of ORNL’s Center for Nanophase Materials Sciences (CNMS), which is sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, US Department of Energy. We appreciate the assistance with magnetic SQUID measurements from S. Chu at MIT.

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Author notes

  1. Shyue Ping Ong & Hailong Chen

    Present address: Present addresses: Department of NanoEngineering, University of California, San Diego, La Jolla, California, USA (S.P.O.); School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia, USA (H.C.).,

Authors and Affiliations

  1. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    Xin Li, Xiaohua Ma, Lei Liu, Shyue Ping Ong, Hailong Chen, Alexandra Toumar, Yuechuan Lei & Gerbrand Ceder

  2. Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, USA

    Dong Su

  3. Department of Physics, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    Robin Chisnell & Young S. Lee

  4. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA

    Juan-Carlos Idrobo

  5. National Synchrotron Light Source, Brookhaven National Laboratory, Upton, New York 11973, USA

    Jianming Bai

  6. Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton, New York 11973, USA

    Feng Wang

  7. NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA

    Jeffrey W. Lynn

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Contributions

G.C. planned the study and supervised all aspects of the research. X.L. and G.C. wrote the manuscript. X.L. performed the electron diffraction measurement and DFT calculation, and solved the Na vacancy superstructure. X.L. calculated the spin exchange parameters by DFT and predicted the magnetic structure. X.M. and Y.L. synthesized the pristine compound. X.M. and X.L. obtained the superstructure phase by electrochemistry. X.L. and D.S. performed the STEM measurement and analysed together with J.C.I. the STEM results. L.L. and X.L. synthesized the superstructure phase by chemical de-intercalation. J.W.L. took the magnetic neutron diffraction data and order parameter, and R.C. and Y.S.L. solved the magnetic structure. X.L. took the magnetic susceptibility data. S.P.O. and A.T. calculated the phase diagram by DFT. J.B. and F.W. took the synchrotron XRD data. H.C., J.B. and X.L. performed the synchrotron XRD refinement. All authors discussed the results and commented on the manuscript.

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Correspondence to Gerbrand Ceder.

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Li, X., Ma, X., Su, D. et al. Direct visualization of the Jahn–Teller effect coupled to Na ordering in Na5/8MnO2. Nature Mater 13, 586–592 (2014). https://doi.org/10.1038/nmat3964

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