journal article·2021-12Open access

Experimental realization of strain-induced room-temperature ferroelectricity in SrMnO3 films via selective oxygen annealing

Hyunji An, Young-Gyun Choi, Yong-Ryun Jo, Hyo Jin Hong, Jeong-Kyu Kim, Owoong Kwon, Sangmo Kim, Myungwoo Son, Jiwoong Yang, Jun-Cheol Park, Hojoong Choi, Jongmin Lee, Jaesun Song, Moon-Ho Ham, Sangwoo Ryu, Yunseok Kim, Chung Wung Bark, Kyung-Tae Ko, Bong-Joong Kim, Sanghan Lee

NPG Asia Materials· Volume 13· Issue 1

Abstract

Abstract Antiferromagnetic-paraelectric SrMnO3 (SMO) has aroused interest because of the theoretical strong coupling between the ferroelectric and ferromagnetic states with increasing epitaxial strain. In strained SMO films, the <110> polarized state and polar distortions have been observed, although high leakage currents and air degradation have limited their experimental verification. We herein provide a conclusive demonstration of room-temperature ferroelectricity and a high dielectric constant (εr = 138.1) in tensile-strained SMO by securing samples with insulating properties and clean surfaces using selective oxygen annealing. Furthermore, a paraelectricity and low dielectric constant (εr = 6.7) in the strain-relaxed SMO film have been identified as properties of the bulk SMO, which directly proves that the ferroelectricity of the tensile-strained SMO film is due to strain-induced polarization. We believe that these findings not only provide a cornerstone for exploring the physical properties of multiferroic SMO but also inspire new directions for single-phase multiferroics.
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Research context

OpenAlex topics: Multiferroics and related materials · Ferroelectric and Piezoelectric Materials · Magnetic and transport properties of perovskites and related materials

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References (46)

Show source-provided references
1. Hill, N. A. Why are there so few magnetic ferroelectrics? J. Phys. Chem. B 104, 6694–6709 (2000).10.1021/jp000114x ↗
2. Martin, L. W. & Ramesh, R. Multiferroic and magnetoelectric heterostructures. Acta Mater. 60, 2449–2470 (2012).10.1016/j.actamat.2011.12.024 ↗
3. Rondinelli, J. M., Eidelson, A. S. & Spaldin, N. A. Non-d0 Mn-driven ferroelectricity in antiferromagnetic BaMnO3. Phys. Rev. B 79, 205119 (2009).10.1103/PhysRevB.79.205119 ↗
4. Maurel, L. et al. Nature of antiferromagnetic order in epitaxially strained multiferroic SrMnO3 thin films. Phys. Rev. B 92, 024419 (2015).10.1103/PhysRevB.92.024419 ↗
5. Kimura, T. et al. Distorted perovskite with e g1 configuration as a frustrated spin system. Phys. Rev. B 68, 060403 (2003). R.10.1103/PhysRevB.68.060403 ↗
6. Kimura, T. et al. Magnetic control of ferroelectric polarization. Nature 426, 55–58 (2003).10.1038/nature02018 ↗
7. Khomskii, D. Classifying multiferroics: mechanisms and effects. Physics 2, 20 (2009).10.1103/Physics.2.20 ↗
8. Ratcliff, W., Lynn, J. W., Kiryukhin, V., Jain, P. & Fitzsimmons, M. R. Magnetic structures and dynamics of multiferroic systems obtained with neutron scattering. npj Quantum Mater. 1, 16003 (2016).10.1038/npjquantmats.2016.3 ↗
9. Agrawal, P. et al. Strain-driven oxygen deficiency in multiferroic SrMnO3 thin films. Phys. Rev. B 94, 104101 (2016).10.1103/PhysRevB.94.104101 ↗
10. Ramesh, R. & Spaldin, N. A. Multiferroics: progress and prospects in thin films. Nat. Mater. 6, 21–29 (2007).10.1038/nmat1805 ↗
11. Edström, A. & Ederer, C. First-principles-based strain and temperature-dependent ferroic phase diagram of SrMnO3. Phys. Rev. Mater. 2, 104409 (2018).10.1103/PhysRevMaterials.2.104409 ↗
12. Haeni, J. H. et al. Room-temperature ferroelectricity in strained SrTiO3. Nature 430, 758–761 (2004).10.1038/nature02773 ↗
13. Antons, A., Neaton, J. B., Rabe, K. M. & Vanderbilt, D. Tunability of the dielectric response of epitaxially strained SrTiO3 from first principles. Phys. Rev. B 71, 024102 (2005).10.1103/PhysRevB.71.024102 ↗
14. Eklund, C., Fennie, C. J. & Rabe, K. M. Strain-induced ferroelectricity in orthorhombic CaTiO3 from first principles. Phys. Rev. B 79, 220101 (2009). R.10.1103/PhysRevB.79.220101 ↗
15. Lee, J. H. & Rabe, K. M. Epitaxial-strain-induced multiferroicity in SrMnO3 from first principles. Phys. Rev. Lett. 104, 207204 (2010).10.1103/PhysRevLett.104.207204 ↗
16. Lee, J. H. et al. A strong ferroelectric ferromagnet created by means of spin-lattice coupling. Nature 466, 954–958 (2010).10.1038/nature09331 ↗
17. Fennie, C. J. & Rabe, K. M. Magnetic and electric phase control in epitaxial EuTiO3 from first principles. Phys. Rev. Lett. 97, 267602 (2006).10.1103/PhysRevLett.97.267602 ↗
18. Hong, J., Stroppa, A., Íñiguez, J., Picozzi, S. & Vanderbilt, D. Spin-phonon coupling effects in transition-metal perovskites: A DFT + U and hybrid-functional study. Phys. Rev. B 85, 054417 (2012).10.1103/PhysRevB.85.054417 ↗
19. Becher, C. et al. Strain-induced coupling of electrical polarization and structural defects in SrMnO3 films. Nat. Nanotechnol. 10, 661–665 (2015).10.1038/nnano.2015.108 ↗
20. Guzmán, R. et al. Polar-graded multiferroic SrMnO3 thin films. Nano Lett. 16, 2221–2227 (2016).10.1021/acs.nanolett.5b04455 ↗
21. Wang, H. et al. Direct observation of huge flexoelectric polarization around crack tips. Nano Lett. 20, 88–94 (2020).10.1021/acs.nanolett.9b03176 ↗
22. Guo, J. W. et al. Strain-induced ferroelectricity and spin-lattice coupling in SrMnO3 thin films. Phys. Rev. B 97, 235135 (2018).10.1103/PhysRevB.97.235135 ↗
23. You, J. et al. Moisture assisted perovskite film growth for high performance solar cells. Appl. Phys. Lett. 105, 183902 (2014).10.1063/1.4901510 ↗
24. Noh, J. H. et al. Chemical management for colorful, efficient, and stable inorganic–organic hybrid nanostructured solar cells. Nano Lett. 13, 1764–1769 (2013).10.1021/nl400349b ↗
25. Mamun, A. A., Mohammed, Y., Ava, T. T., Namkoong, G. & Elmustafa, A. A. Influence of air degradation on morphology, crystal size and mechanical hardness of perovskite film. Mater. Lett. 229, 167–170 (2018).10.1016/j.matlet.2018.06.126 ↗
26. Islamov, D. R. et al. Identification of the nature of traps involved in the field cycling of Hf0.5Zr0.5O2-based ferroelectric thin films. Acta Mater. 166, 47–55 (2019).10.1016/j.actamat.2018.12.008 ↗
27. Weber, D., Vőfély, R., Chen, Y., Mourzina, Y. & Poppe, U. Variable resistor made by repeated steps of epitaxial deposition and lithographic structuring of oxide layers by using wet chemical etchants. Thin Solid Films 533, 43–47 (2013).10.1016/j.tsf.2012.11.118 ↗
28. Vorobiev, A. & Gevorgian, S. Intrinsically switchable thin film bulk acoustic wave resonators. Appl. Phys. Lett. 104, 222905 (2014).10.1063/1.4881141 ↗
29. Cai, W. et al. Significant performance improvement of oxide thin‐film transistors by a self‐assembled monolayer treatment. Adv. Electron. Mater. 6, 1901421 (2020).10.1002/aelm.201901421 ↗
30. Lien, C. et al. The demonstration of high-performance multilayer BaTiO3/BiFeO3 stack MIM capacitors. IEEE Trans. Electron Devices 65, 4834–4838 (2018).
31. Lee, B. H. et al. Issues with the electrical characterization of graphene devices. Carbon Lett. 13, 23 (2012).10.5714/CL.2012.13.1.023 ↗
32. Seo, S., Kang, H., Jang, H. & Noh, D. Effects of oxygen incorporation in tensile La0.84Sr0.16MnO3−δ thin films during ex situ annealing. Phys. Rev. B 71, 012412 (2005).10.1103/PhysRevB.71.012412 ↗
33. Park, K. W. et al. Observation and tunability of room temperature photoluminescence of GaAs/GaInAs core-multiple-quantum-well shell nanowire structure grown on Si (100) by molecular beam epitaxy. Nanoscale Res. Lett. 9, 626–636 (2014).10.1186/1556-276X-9-626 ↗
34. Gevorgian, S. S., Martinsson, T., Linner, P. L. & Kollberg, E. L. CAD models for multilayered substrate interdigital capacitors. IEEE Trans. Microw. Theory Tech. 44, 896–904 (1996).10.1109/22.506449 ↗
35. Chidambaram, N., Mazzalai, A., Balma, D. & Muralt, P. Comparison of lead zirconate titanate thin films for microelectromechanical energy harvester with interdigitated and parallel plate electrodes. IEEE Trans. Ultrason. Ferroelectr. Freq. Control 60, 1564–1571 (2013).10.1109/TUFFC.2013.2736 ↗
36. Folkman, C. et al. Study of defect-dipoles in an epitaxial ferroelectric thin film. Appl. Phys. Lett. 96, 052903 (2010).10.1063/1.3298362 ↗
37. Folkman, C. M. Spontaneous strain and ferroelectric-ferroelastic behavior in epitaxial bismuth ferrite thin films. The University of Wisconsin - Madison. ProQuest Dissertations Publishing, 3437001 (2010).
38. Kidner, N., Homrighaus, Z., Mason, T. O. & Garboczi, E. Modeling interdigital electrode structures for the dielectric characterization of electroceramic thin films. Thin Solid Films 496, 539–545 (2006).10.1016/j.tsf.2005.08.350 ↗
39. Tidrow, S. et al. New substrates for HTSC microwave devices. IEEE Trans. Appl. Supercond. 7, 1766–1768 (1997).10.1109/77.620924 ↗
40. Canedy, C. et al. Dielectric properties in heteroepitaxial Ba0.6Sr0.4TiO3 thin films: effect of internal stresses and dislocation-type defects. Appl. Phys. Lett. 77, 1695–1697 (2000).10.1063/1.1308531 ↗
41. Lee, H. N., Christen, H. M., Chisholm, M. F., Rouleau, C. M. & Lowndes, D. H. Strong polarization enhancement in asymmetric three-component ferroelectric superlattices. Nature 433, 395–399 (2005).10.1038/nature03261 ↗
42. He, B. & Wang, Z. Enhancement of the electrical properties in BaTiO3/PbZr0.52Ti0.48O3 ferroelectric superlattices. ACS Appl. Mater. Interfaces 8, 6736–6742 (2016).10.1021/acsami.5b12098 ↗
43. Song, J. et al. Enhancement of ferroelectric properties of superlattice-based epitaxial BiFeO3 thin films via substitutional doping effect. J. Phys. Chem. C 123, 11564–11571 (2019).10.1021/acs.jpcc.9b00156 ↗
44. Pintilie, L., Vrejoiu, I., Hesse, D., Le Rhun, G. & Alexe, M. Extrinsic contributions to the apparent thickness dependence of the dielectric constant in epitaxial Pb(Zr, Ti)O3 thin films. Phys. Rev. B 75, 224113 (2007).10.1103/PhysRevB.75.224113 ↗
45. Zhou, X. Y. et al. Thickness dependence of in-plane dielectric and ferroelectric properties of Ba0.7Sr0.3TiO3 thin films epitaxially grown on LaAlO3. Appl. Phys. Lett. 90, 132902 (2007).10.1063/1.2716865 ↗
46. Yang, Q., Cao, J., Zhou, Y., Sun, L. & Lou, X. Dead layer effect and its elimination in ferroelectric thin film with oxide electrodes. Acta Mater. 112, 216–223 (2016).10.1016/j.actamat.2016.04.036 ↗