Size-Induced Ferroelectricity in Antiferroelectric Oxide Membranes

Ruijuan Xu; Kevin J Crust; Varun Harbola; Rémi Arras; Kinnary Y Patel; Sergey Prosandeev; Hui Cao; Yu-Tsun Shao; Piush Behera; Lucas Caretta; Woo Jin Kim; Aarushi Khandelwal; Megha Acharya; Melody M Wang; Yin Liu; Edward S Barnard; Archana Raja; Lane W Martin; X Wendy Gu; Hua Zhou; Ramamoorthy Ramesh; David A Muller; Laurent Bellaiche; Harold Y Hwang

doi:10.1002/adma.202210562

Size-Induced Ferroelectricity in Antiferroelectric Oxide Membranes

Adv Mater. 2023 Apr;35(17):e2210562. doi: 10.1002/adma.202210562. Epub 2023 Mar 19.

Authors

Ruijuan Xu^{1

2

3}, Kevin J Crust^{2

4}, Varun Harbola^{2

4}, Rémi Arras⁵, Kinnary Y Patel⁶, Sergey Prosandeev⁶, Hui Cao⁷, Yu-Tsun Shao^{8

9}, Piush Behera¹⁰, Lucas Caretta^{10

11}, Woo Jin Kim^{1

2}, Aarushi Khandelwal^{1

2}, Megha Acharya^{10

12}, Melody M Wang¹³, Yin Liu³, Edward S Barnard¹⁴, Archana Raja¹⁴, Lane W Martin^{10

12}, X Wendy Gu¹⁵, Hua Zhou¹⁶, Ramamoorthy Ramesh¹⁷, David A Muller⁸, Laurent Bellaiche⁶, Harold Y Hwang^{1

2}

Affiliations

¹ Department of Applied Physics, Stanford University, Stanford, CA, 94305, USA.
² Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, 94025, USA.
³ Department of Materials Science and Engineering, North Carolina State University, Raleigh, NC, 27606, USA.
⁴ Department of Physics, Stanford University, Stanford, CA, 94305, USA.
⁵ CEMES, Université de Toulouse, CNRS, UPS, 29 rue Jeanne Marvig, F-31055, Toulouse, France.
⁶ Physics Department and Institute for Nanoscience and Engineering, University of Arkansas, Fayetteville, AR, 72701, USA.
⁷ Materials Science Division, Argonne National Laboratory, Lemont, IL, 60439, USA.
⁸ Department of Applied and Engineering Physics, Cornell University, Ithaca, NY, 14853, USA.
⁹ Mork Family Department of Chemical Engineering and Materials Science, University of Southern California, Los Angeles, CA, 90089, USA.
¹⁰ Department of Materials Science and Engineering, University of California, Berkeley, Berkeley, CA, 94720, USA.
¹¹ School of Engineering, Brown University, Providence, RI, 02912, USA.
¹² Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
¹³ Department of Materials Science and Engineering, Stanford University, Stanford, CA, 94305, USA.
¹⁴ The Molecular Foundry, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA, 94720, USA.
¹⁵ Department of Mechanical Engineering, Stanford University, Stanford, CA, 94305, USA.
¹⁶ X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Lemont, IL, 60439, USA.
¹⁷ Department of Materials Science and Nanoengineering, Department of Physics and Astronomy, Rice University, Houston, TX, 77251, USA.

PMID: 36739113
DOI: 10.1002/adma.202210562

Abstract

Despite extensive studies on size effects in ferroelectrics, how structures and properties evolve in antiferroelectrics with reduced dimensions still remains elusive. Given the enormous potential of utilizing antiferroelectrics for high-energy-density storage applications, understanding their size effects will provide key information for optimizing device performances at small scales. Here, the fundamental intrinsic size dependence of antiferroelectricity in lead-free NaNbO₃ membranes is investigated. Via a wide range of experimental and theoretical approaches, an intriguing antiferroelectric-to-ferroelectric transition upon reducing membrane thickness is probed. This size effect leads to a ferroelectric single-phase below 40 nm, as well as a mixed-phase state with ferroelectric and antiferroelectric orders coexisting above this critical thickness. Furthermore, it is shown that the antiferroelectric and ferroelectric orders are electrically switchable. First-principle calculations further reveal that the observed transition is driven by the structural distortion arising from the membrane surface. This work provides direct experimental evidence for intrinsic size-driven scaling in antiferroelectrics and demonstrates enormous potential of utilizing size effects to drive emergent properties in environmentally benign lead-free oxides with the membrane platform.

Keywords: antiferroelectric materials; membranes; phase transition; size effects; sodium niobate.

Abstract

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