Two-dimensional ferroelasticity in van der Waals β’-In2Se3
10.1038/s41467-021-23882-7
Crossref journal-article
Springer Science and Business Media LLC
Nature Communications (297)
Abstract

AbstractTwo-dimensional (2D) materials exhibit remarkable mechanical properties, enabling their applications as flexible and stretchable ultrathin devices. As the origin of several extraordinary mechanical behaviors, ferroelasticity has also been predicted theoretically in 2D materials, but so far lacks experimental validation and investigation. Here, we present the experimental demonstration of 2D ferroelasticity in both exfoliated and chemical-vapor-deposited β’-In2Se3 down to few-layer thickness. We identify quantitatively 2D spontaneous strain originating from in-plane antiferroelectric distortion, using both atomic-resolution electron microscopy and in situ X-ray diffraction. The symmetry-equivalent strain orientations give rise to three domain variants separated by 60° and 120° domain walls (DWs). Mechanical switching between these ferroelastic domains is achieved under ≤0.5% external strain, demonstrating the feasibility to tailor the antiferroelectric polar structure as well as DW patterns through mechanical stimuli. The detailed domain switching mechanism through both DW propagation and domain nucleation is unraveled, and the effects of 3D stacking on such 2D ferroelasticity are also discussed. The observed 2D ferroelasticity here should be widely available in 2D materials with anisotropic lattice distortion, including the 1T’ transition metal dichalcogenides with Peierls distortion and 2D ferroelectrics such as the SnTe family, rendering tantalizing potential to tune 2D functionalities through strain or DW engineering.

Bibliography

Xu, C., Mao, J., Guo, X., Yan, S., Chen, Y., Lo, T. W., Chen, C., Lei, D., Luo, X., Hao, J., Zheng, C., & Zhu, Y. (2021). Two-dimensional ferroelasticity in van der Waals β’-In2Se3. Nature Communications, 12(1).

Authors 12
  1. Chao Xu (first)
  2. Jianfeng Mao (additional)
  3. Xuyun Guo (additional)
  4. Shanru Yan (additional)
  5. Yancong Chen (additional)
  6. Tsz Wing Lo (additional)
  7. Changsheng Chen (additional)
  8. Dangyuan Lei (additional)
  9. Xin Luo (additional)
  10. Jianhua Hao (additional)
  11. Changxi Zheng (additional)
  12. Ye Zhu (additional)
References 59 Referenced 81
  1. Yang, H., Kim, S. W., Chhowalla, M. & Lee, Y. H. Structural and quantum-state phase transitions in van der Waals layered materials. Nat. Phys. 13, 931 (2017). (10.1038/nphys4188) / Nat. Phys. by H Yang (2017)
  2. Balents, L., Dean, C. R., Efetov, D. K. & Young, A. F. Superconductivity and strong correlations in moiré flat bands. Nat. Phys. 16, 725–733 (2020). (10.1038/s41567-020-0906-9) / Nat. Phys. by L Balents (2020)
  3. Huang, B. et al. Emergent phenomena and proximity effects in two-dimensional magnets and heterostructures. Nat. Mater. 19, 1276–1289 (2020). (10.1038/s41563-020-0791-8) / Nat. Mater. by B Huang (2020)
  4. Tang, X. & Kou, L. Two-dimensional ferroics and multiferroics: Platforms for new physics and applications. J. Phys. Chem. Lett. 10, 6634–6649 (2019). (10.1021/acs.jpclett.9b01969) / J. Phys. Chem. Lett. by X Tang (2019)
  5. Nicolosi, V., Chhowalla, M., Kanatzidis, M. G., Strano, M. S. & Coleman, J. N. Liquid exfoliation of layered materials. Science 340, 1226419 (2013). (10.1126/science.1226419) / Science by V Nicolosi (2013)
  6. Chhowalla, M. et al. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 5, 263–275 (2013). (10.1038/nchem.1589) / Nat. Chem. by M Chhowalla (2013)
  7. Novoselov, K. S., Mishchenko, A., Carvalho, A. & Castro Neto, A. H. 2D materials and van der Waals heterostructures. Science 353, aac9439 (2016). (10.1126/science.aac9439) / Science by KS Novoselov (2016)
  8. Lu, J. M. et al. Evidence for two-dimensional Ising superconductivity in gated MoS2. Science 350, 1353–1357 (2015). (10.1126/science.aab2277) / Science by JM Lu (2015)
  9. Navarro-Moratalla, E. et al. Enhanced superconductivity in atomically thin TaS2. Nat. Commun. 7, 11043 (2016). (10.1038/ncomms11043) / Nat. Commun. by E Navarro-Moratalla (2016)
  10. Cao, Y. et al. Unconventional superconductivity in magic-angle graphene superlattices. Nature 556, 43–50 (2018). (10.1038/nature26160) / Nature by Y Cao (2018)
  11. Huang, B. et al. Layer-dependent ferromagnetism in a van der Waals crystal down to the monolayer limit. Nature 546, 270–273 (2017). (10.1038/nature22391) / Nature by B Huang (2017)
  12. Gong, C. et al. Discovery of intrinsic ferromagnetism in two-dimensional van der Waals crystals. Nature 546, 265–269 (2017). (10.1038/nature22060) / Nature by C Gong (2017)
  13. Chang, K. et al. Discovery of robust in-plane ferroelectricity in atomic-thick SnTe. Science 353, 274–278 (2016). (10.1126/science.aad8609) / Science by K Chang (2016)
  14. Liu, F. et al. Room-temperature ferroelectricity in CuInP2S6 ultrathin flakes. Nat. Commun. 7, 12357 (2016). (10.1038/ncomms12357) / Nat. Commun. by F Liu (2016)
  15. Zhou, Y. et al. Out-of-plane piezoelectricity and ferroelectricity in layered α-In2Se3 nanoflakes. Nano Lett. 17, 5508–5513 (2017). (10.1021/acs.nanolett.7b02198) / Nano Lett. by Y Zhou (2017)
  16. Yuan, S. et al. Room-temperature ferroelectricity in MoTe2 down to the atomic monolayer limit. Nat. Commun. 10, 1775 (2019). (10.1038/s41467-019-09669-x) / Nat. Commun. by S Yuan (2019)
  17. Fei, Z. et al. Ferroelectric switching of a two-dimensional metal. Nature 560, 336–339 (2018). (10.1038/s41586-018-0336-3) / Nature by Z Fei (2018)
  18. Xu, C. et al. Two-dimensional antiferroelectricity in nanostripe-ordered In2Se3. Phys. Rev. Lett. 125, 047601 (2020). (10.1103/PhysRevLett.125.047601) / Phys. Rev. Lett. by C Xu (2020)
  19. Dziaugys, A. et al. Piezoelectric domain walls in van der Waals antiferroelectric CuInP2Se6. Nat. Commun. 11, 3623 (2020). (10.1038/s41467-020-17137-0) / Nat. Commun. by A Dziaugys (2020)
  20. Liu, Y., Huang, Y. & Duan, X. Van der Waals integration before and beyond two-dimensional materials. Nature 567, 323–333 (2019). (10.1038/s41586-019-1013-x) / Nature by Y Liu (2019)
  21. Aizu, K. Possible species of “ferroelastic” crystals and of simultaneously ferroelectric and ferroelastic crystals. J. Phys. Soc. Jpn. 27, 387–396 (1969). (10.1143/JPSJ.27.387) / J. Phys. Soc. Jpn. by K Aizu (1969)
  22. Salje, E. K. H. Ferroelastic materials. Annu. Rev. Mater. Res. 42, 265–283 (2012). (10.1146/annurev-matsci-070511-155022) / Annu. Rev. Mater. Res. by EKH Salje (2012)
  23. Ahmed, E., Karothu, D. P., Warren, M. & Naumov, P. Shape-memory effects in molecular crystals. Nat. Commun. 10, 3723 (2019). (10.1038/s41467-019-11612-z) / Nat. Commun. by E Ahmed (2019)
  24. Ogawa, Y., Ando, D., Sutou, Y. & Koike, J. A lightweight shape-memory magnesium alloy. Science 353, 368–370 (2016). (10.1126/science.aaf6524) / Science by Y Ogawa (2016)
  25. Narayan, B. et al. Electrostrain in excess of 1% in polycrystalline piezoelectrics. Nat. Mater. 17, 427–431 (2018). (10.1038/s41563-018-0060-2) / Nat. Mater. by B Narayan (2018)
  26. Hu, Y. et al. Ferroelastic-switching-driven large shear strain and piezoelectricity in a hybrid ferroelectric. Nat. Mater. 20, 1–6, (2021). (10.1038/s41563-020-00875-3)
  27. Park, S. K. & Diao, Y. Martensitic transition in molecular crystals for dynamic functional materials. Chem. Soc. Rev. 49, 8287–8314 (2020). (10.1039/D0CS00638F) / Chem. Soc. Rev. by SK Park (2020)
  28. Li, W. & Li, J. Ferroelasticity and domain physics in two-dimensional transition metal dichalcogenide monolayers. Nat. Commun. 7, 10843 (2016). (10.1038/ncomms10843) / Nat. Commun. by W Li (2016)
  29. Zhang, C., Nie, Y., Sanvito, S. & Du, A. First-principles prediction of a room-temperature ferromagnetic Janus VSSe monolayer with piezoelectricity, ferroelasticity, and large valley polarization. Nano Lett. 19, 1366–1370 (2019). (10.1021/acs.nanolett.8b05050) / Nano Lett. by C Zhang (2019)
  30. Zhang, T. et al. Two-dimensional ferroelastic semiconductors in Nb2SiTe4 and Nb2GeTe4 with promising electronic properties. J. Phys. Chem. Lett. 11, 497–503 (2019). (10.1021/acs.jpclett.9b03433) / J. Phys. Chem. Lett. by T Zhang (2019)
  31. Zhang, L., Tang, C. & Du, A. Two-dimensional vanadium tetrafluoride with antiferromagnetic ferroelasticity and bidirectional negative Poisson’s ratio. J. Mater. Chem. C. 9, 95–100 (2021). (10.1039/D0TC04846A) / J. Mater. Chem. C. by L Zhang (2021)
  32. Xiao, X. et al. Layer number dependent ferroelasticity in 2D Ruddlesden-Popper organic-inorganic hybrid perovskites. Nat. Commun. 12, 1332 (2021). (10.1038/s41467-021-21493-w) / Nat. Commun. by X Xiao (2021)
  33. Osamura, K., Murakami, Y. & Tomiie, Y. Crystal structures of α- and β-Indium Selenide, In2Se3. J. Phys. Soc. Jpn. 12, 1848 (1966). (10.1143/JPSJ.21.1848) / J. Phys. Soc. Jpn. by K Osamura (1966)
  34. Popović, S., Čelustka, B. & Bidjin, D. X-ray diffraction measurement of lattice parameters of In2Se3. Phys. Status Solidi A 6, 301–304 (1971). (10.1002/pssa.2210060134) / Phys. Status Solidi A by S Popović (1971)
  35. van Landuyt, J., van Tendeloo, G. & Amelinckx, S. Phase transitions in In2Se3 as studied by electron microscopy and electron diffraction. Phys. Status Solidi A 30, 299–314 (1975). (10.1002/pssa.2210300131) / Phys. Status Solidi A by J van Landuyt (1975)
  36. Popovic, S., Tonejc, A., Grzeta-Plenkovic, B., Celustka, B. & Trojko, R. Revised and new crystal data for indium selenides. J. Appl. Crystallogr. 12, 416–420 (1979). (10.1107/S0021889879012863) / J. Appl. Crystallogr. by S Popovic (1979)
  37. Van Landuyt, J., Van Tendeloo, G. & Amelinckx, S. New low-temperature phase in α-In2Se3. Phys. Status Solidi A 26, K103–K104 (1974). (10.1002/pssa.2210260245) / Phys. Status Solidi A by J Van Landuyt (1974)
  38. Ding, W. J. et al. Prediction of intrinsic two-dimensional ferroelectrics in In2Se3 and other III2-VI3 van der Waals materials. Nat. Commun. 8, 14956 (2017). (10.1038/ncomms14956) / Nat. Commun. by WJ Ding (2017)
  39. Manolikas, C. New results on the phase transformations of In2Se3. J. Solid State Chem. 74, 319–328 (1988). (10.1016/0022-4596(88)90361-1) / J. Solid State Chem. by C Manolikas (1988)
  40. Tao, X. & Gu, Y. Crystalline-crystalline phase transformation in two-dimensional In2Se3 thin layers. Nano Lett. 13, 3501–3505 (2013). (10.1021/nl400888p) / Nano Lett. by X Tao (2013)
  41. Liu, L. et al. Atomically resolving polymorphs and crystal structures of In2Se3. Chem. Mater. 31, 10143–10149 (2019). (10.1021/acs.chemmater.9b03499) / Chem. Mater. by L Liu (2019)
  42. Xue, F. et al. Room-temperature ferroelectricity in hexagonally layered α-In2Se3 nanoflakes down to the monolayer limit. Adv. Funct. Mater. 28, 1803738 (2018). (10.1002/adfm.201803738) / Adv. Funct. Mater. by F Xue (2018)
  43. Si, M. et al. A ferroelectric semiconductor field-effect transistor. Nat. Electron. 2, 580–586 (2019). (10.1038/s41928-019-0338-7) / Nat. Electron. by M Si (2019)
  44. Sun, W. et al. Controlling bimerons as skyrmion analogues by ferroelectric polarization in 2D van der Waals multiferroic heterostructures. Nat. Commun. 11, 5930 (2020). (10.1038/s41467-020-19779-6) / Nat. Commun. by W Sun (2020)
  45. Wang, S. et al. Two-dimensional ferroelectric channel transistors integrating ultra-fast memory and neural computing. Nat. Commun. 12, 53 (2021). (10.1038/s41467-020-20257-2) / Nat. Commun. by S Wang (2021)
  46. Ding, J., Shao, D.-F., Li, M., Wen, L.-W. & Tsymbal, E. Y. Two-dimensional antiferroelectric tunnel junction. Phys. Rev. Lett. 126, 057601 (2021). (10.1103/PhysRevLett.126.057601) / Phys. Rev. Lett. by J Ding (2021)
  47. Wan, S. et al. Nonvolatile ferroelectric memory effect in ultrathin α-In2Se3. Adv. Funct. Mater. 29, 1808606 (2019). (10.1002/adfm.201808606) / Adv. Funct. Mater. by S Wan (2019)
  48. Choi, M. S. et al. Electrically driven reversible phase changes in layered In2Se3 crystalline film. Adv. Mater. 29, 1703568 (2017). (10.1002/adma.201703568) / Adv. Mater. by MS Choi (2017)
  49. Zheng, C. et al. Room temperature in-plane ferroelectricity in van der Waals In2Se3. Sci. Adv. 4, eaar7720 (2018). (10.1126/sciadv.aar7720) / Sci. Adv. by C Zheng (2018)
  50. Aizu, K. Determination of the state parameters and formulation of spontaneous strain for ferroelastics. J. Phys. Soc. Jpn. 28, 706–716 (1970). (10.1143/JPSJ.28.706) / J. Phys. Soc. Jpn. by K Aizu (1970)
  51. Tagantsev, A. K., Cross, L. E. & Fousek, J. Domains in ferroic crystals and thin films. (Springer, New York, 2010). (10.1007/978-1-4419-1417-0)
  52. Huang, F.-T. et al. Polar and phase domain walls with conducting interfacial states in a Weyl semimetal MoTe2. Nat. Commun. 10, 4211 (2019). (10.1038/s41467-019-11949-5) / Nat. Commun. by F-T Huang (2019)
  53. Streiffer, S. et al. Domain patterns in epitaxial rhombohedral ferroelectric films. I. Geometry and experiments. J. Appl. Phys. 83, 2742–2753 (1998). (10.1063/1.366632) / J. Appl. Phys. by S Streiffer (1998)
  54. Dai, Z., Liu, L. & Zhang, Z. Strain engineering of 2D materials: Issues and opportunities at the interface. Adv. Mater. 31, 1805417 (2019). (10.1002/adma.201805417) / Adv. Mater. by Z Dai (2019)
  55. Strelcov, E. et al. CH3NH3PbI3 perovskites: ferroelasticity revealed. Sci. Adv. 3, e1602165 (2017). (10.1126/sciadv.1602165) / Sci. Adv. by E Strelcov (2017)
  56. Pedramrazi, Z. et al. Manipulating topological domain boundaries in the single-layer quantum spin hall insulator 1T’-WSe2. Nano Lett. 19, 5634–5639 (2019). (10.1021/acs.nanolett.9b02157) / Nano Lett. by Z Pedramrazi (2019)
  57. Chang, K. et al. Microscopic manipulation of ferroelectric domains in SnSe monolayers at room temperature. Nano Lett. 20, 6590–6597 (2020). (10.1021/acs.nanolett.0c02357) / Nano Lett. by K Chang (2020)
  58. Higashitarumizu, N. et al. Purely in-plane ferroelectricity in monolayer SnS at room temperature. Nat. Commun. 11, 2428 (2020). (10.1038/s41467-020-16291-9) / Nat. Commun. by N Higashitarumizu (2020)
  59. Li, Z. et al. Efficient strain modulation of 2D materials via polymer encapsulation. Nat. Commun. 11, 1151 (2020). (10.1038/s41467-020-15023-3) / Nat. Commun. by Z Li (2020)
Dates
Type When
Created 4 years, 2 months ago (June 16, 2021, 6:03 a.m.)
Deposited 2 years, 8 months ago (Dec. 2, 2022, 7:52 a.m.)
Indexed 1 week, 1 day ago (Aug. 12, 2025, 6:08 p.m.)
Issued 4 years, 2 months ago (June 16, 2021)
Published 4 years, 2 months ago (June 16, 2021)
Published Online 4 years, 2 months ago (June 16, 2021)
Funders 4
  1. Research Grants Council, University Grants Committee 10.13039/501100002920

    Region: Asia

    pri (Universities (academic only))

    Labels5
    1. 研究資助局
    2. 研究資助局
    3. 研究資助局
    4. 研究資助局
    5. 研究資助局
    Awards3
    1. PolyU 153033/17P
    2. 15305718
    3. 15303718
  2. National Natural Science Foundation of China 10.13039/501100001809

    Region: Asia

    gov (National government)

    Labels11
    1. Chinese National Science Foundation
    2. Natural Science Foundation of China
    3. National Science Foundation of China
    4. NNSF of China
    5. NSF of China
    6. 国家自然科学基金委员会
    7. National Nature Science Foundation of China
    8. Guójiā Zìrán Kēxué Jījīn Wěiyuánhuì
    9. NSFC
    10. NNSF
    11. NNSFC
    Awards2
    1. 11832019
    2. 11804286
  3. the Fundamental Research Funds for the Central Universities
  4. The Hong Kong Polytechnic University Grant No. ZVRP

@article{Xu_2021, title={Two-dimensional ferroelasticity in van der Waals β’-In2Se3}, volume={12}, ISSN={2041-1723}, url={http://dx.doi.org/10.1038/s41467-021-23882-7}, DOI={10.1038/s41467-021-23882-7}, number={1}, journal={Nature Communications}, publisher={Springer Science and Business Media LLC}, author={Xu, Chao and Mao, Jianfeng and Guo, Xuyun and Yan, Shanru and Chen, Yancong and Lo, Tsz Wing and Chen, Changsheng and Lei, Dangyuan and Luo, Xin and Hao, Jianhua and Zheng, Changxi and Zhu, Ye}, year={2021}, month=jun }