journal article·2025-02-07Open access

Ferroelectricity in van der Waals multilayers via interfacial polarization engineering

Xiaokai Chen, Xiaoyu Xuan, Wanlin Guo, Zhuhua Zhang

Abstract

We report a general mechanism for building ferroelectricity in prevailing van der Waals (vdW) multilayers via interfacial engineering. Using sandwiched graphene/boron nitride (BN)/graphene multilayers as an exemplary system, we show that considerable electric polarization can arise at graphene/BN interfaces where charge redistribution enhances intralayer electric dipoles. Moreover, the electric polarization between BN layers is concertedly enhanced due to interlayer compression driven by an extraordinary cross-layer electrostatic attraction. Then, the interfacial polarization and enhanced interlayer polarization can serve as two elements for building robust ferroelectrics from vdW multilayers with cumulative, thickness-controllable polarization. We demonstrate this mechanism in generating an electric polarization of 1.0 pC/m in a nominally nonpolar BN monolayer sandwiched between graphene layers, and up to 4.2 pC/m in a sandwiched BN quadrilayer. These results underscore the previously unnoticed role of unavoidable hetero-interfaces in contributing to the observed ferroelectricity in diverse vdW devices.
Source: openalex_inverted_index · Quality: baseline

Research context

OpenAlex topics: Ferroelectric and Piezoelectric Materials · Electronic and Structural Properties of Oxides · 2D Materials and Applications

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (65)

Show source-provided references
1. Khan, A. I., Keshavarzi, A. & Datta, S. The future of ferroelectric field-effect transistor technology. Nat. Electron. 3, 588–597 (2020).10.1038/s41928-020-00492-7 ↗
2. Noheda, B., Nukala, P. & Acuautla, M. Lessons from hafnium dioxide-based ferroelectrics. Nat. Mater. 22, 562–569 (2023).10.1038/s41563-023-01507-2 ↗
3. Ding, W. 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 ↗
4. Wan, S. et al. Nonvolatile ferroelectric memory effect in ultrathin α‐In2Se3. Adv. Funct. Mater. 29, 1808606 (2019).10.1002/adfm.201808606 ↗
5. Liu, F. et al. Room-temperature ferroelectricity in CuInP2S6 ultrathin flakes. Nat. Commun. 7, 12357 (2016).10.1038/ncomms12357 ↗
6. 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 ↗
7. Li, W. et al. Emergence of ferroelectricity in a nonferroelectric monolayer. Nat. Commun. 14, 2757 (2023).10.1038/s41467-023-38445-1 ↗
8. Barraza-Lopez, S., Fregoso, B. M., Villanova, J. W., Parkin, S. S. P. & Chang, K. Colloquium: Physical properties of group-IV monochalcogenide monolayers. Rev. Mod. Phys. 93, 011001 (2021).10.1103/RevModPhys.93.011001 ↗
9. Li, L. & Wu, M. Binary compound bilayer and multilayer with vertical polarizations: Two-dimensional ferroelectrics, multiferroics, and nanogenerators. ACS Nano 11, 6382–6388 (2017).10.1021/acsnano.7b02756 ↗
10. Ji, J., Yu, G., Xu, C. & Xiang, H. J. General theory for bilayer stacking ferroelectricity. Phys. Rev. Lett. 130, 146801 (2023).10.1103/PhysRevLett.130.146801 ↗
11. Tang, P. & Bauer, G. E. W. Sliding phase transition in ferroelectric van der Waals bilayers. Phys. Rev. Lett. 130, 176801 (2023).10.1103/PhysRevLett.130.176801 ↗
12. Yasuda, K., Wang, X., Watanabe, K., Taniguchi, T. & Jarillo-Herrero, P. Stacking-engineered ferroelectricity in bilayer boron nitride. Science 372, 1458–1462 (2021).10.1126/science.abd3230 ↗
13. Vizner Stern, M. et al. Interfacial ferroelectricity by van der Waals sliding. Science 372, 1462–1466 (2021).10.1126/science.abe8177 ↗
14. Woods, C. et al. Charge-polarized interfacial superlattices in marginally twisted hexagonal boron nitride. Nat. Commun. 12, 347 (2021).10.1038/s41467-020-20667-2 ↗
15. Wang, X. et al. Interfacial ferroelectricity in rhombohedral-stacked bilayer transition metal dichalcogenides. Nat. Nanotechnol. 17, 367–371 (2022).10.1038/s41565-021-01059-z ↗
16. Weston, A. et al. Interfacial ferroelectricity in marginally twisted 2D semiconductors. Nat. Nanotechnol. 17, 390–395 (2022).10.1038/s41565-022-01072-w ↗
17. Sui, F. et al. Sliding ferroelectricity in van der Waals layered γ-InSe semiconductor. Nat. Commun. 14, 36 (2023).10.1038/s41467-022-35490-0 ↗
18. Sun, Y. et al. Mesoscopic sliding ferroelectricity enabled photovoltaic random access memory for material-level artificial vision system. Nat. Commun. 13, 5391 (2022).10.1038/s41467-022-33118-x ↗
19. Niu, Y. et al. 0D van der Waals interfacial ferroelectricity. Nat. Commun. 14, 5578 (2023).10.1038/s41467-023-41045-8 ↗
20. Liu, X., Pyatakov, A. P. & Ren, W. Magnetoelectric coupling in multiferroic bilayer VS2. Phys. Rev. Lett. 125, 247601 (2020).10.1103/PhysRevLett.125.247601 ↗
21. Wu, Y. et al. Coexisting ferroelectric and ferrovalley polarizations in bilayer stacked magnetic semiconductors. Nano Lett. 23, 6226–6232 (2023).10.1021/acs.nanolett.3c01948 ↗
22. Liang, J. et al. Optically probing the asymmetric interlayer coupling in rhombohedral-stacked MoS2 bilayer. Phys. Rev. X 12, 041005 (2022).
23. Hong, H. et al. Twist phase matching in two-dimensional materials. Phys. Rev. Lett. 131, 233801 (2023).10.1103/PhysRevLett.131.233801 ↗
24. Xiao, R.-C. et al. Non-synchronous bulk photovoltaic effect in two-dimensional interlayer-sliding ferroelectrics. npj Comput. Mater. 8, 138 (2022).10.1038/s41524-022-00828-1 ↗
25. Zhang, C., Guo, P. & Zhou, J. Tailoring bulk photovoltaic effects in magnetic sliding ferroelectric materials. Nano Lett. 22, 9297–9305 (2022).10.1021/acs.nanolett.2c02802 ↗
26. Cao, T., Shao, D.-F., Huang, K., Gurung, G. & Tsymbal, E. Y. Switchable anomalous hall effects in polar-stacked 2D antiferromagnet MnBi2Te4. Nano Lett. 23, 3781–3787 (2023).10.1021/acs.nanolett.3c00047 ↗
27. Feng, Y., Dai, Y., Huang, B., Kou, L. & Ma, Y. Layer hall effect in multiferroic two-dimensional materials. Nano Lett. 23, 5367–5372 (2023).10.1021/acs.nanolett.3c01651 ↗
28. Wu, M. & Li, J. Sliding ferroelectricity in 2D van der Waals materials: Related physics and future opportunities. Proc. Natl Acad. Sci. USA 118, e2115703118 (2021).10.1073/pnas.2115703118 ↗
29. Wang, C., You, L., Cobden, D. & Wang, J. Towards two-dimensional van der Waals ferroelectrics. Nat. Mater. 22, 542–552 (2023).10.1038/s41563-022-01422-y ↗
30. Zhang, D., Schoenherr, P., Sharma, P. & Seidel, J. Ferroelectric order in van der Waals layered materials. Nat. Rev. Mater. 8, 25–40 (2023).10.1038/s41578-022-00484-3 ↗
31. Wilson, N. P., Yao, W., Shan, J. & Xu, X. Excitons and emergent quantum phenomena in stacked 2D semiconductors. Nature 599, 383–392 (2021).10.1038/s41586-021-03979-1 ↗
32. Van Winkle, M. et al. Engineering interfacial polarization switching in van der Waals multilayers. Nat. Nanotechnol. 19, 751–757 (2024).10.1038/s41565-024-01642-0 ↗
33. Lv, M. et al. Multiresistance states in ferro- and antiferroelectric trilayer boron nitride. Nat. Commun. 15, 295 (2024).10.1038/s41467-023-44617-w ↗
34. Meng, P. et al. Sliding induced multiple polarization states in two-dimensional ferroelectrics. Nat. Commun. 13, 7696 (2022).10.1038/s41467-022-35339-6 ↗
35. Deb, S. et al. Cumulative polarization in conductive interfacial ferroelectrics. Nature 612, 465–469 (2022).10.1038/s41586-022-05341-5 ↗
36. Yang, L. & Wu, M. Across‐layer sliding ferroelectricity in 2D heterolayers. Adv. Funct. Mater. 33, 2301105 (2023).10.1002/adfm.202301105 ↗
37. Yang, L., Ding, S., Gao, J. & Wu, M. Atypical sliding and moiré ferroelectricity in pure multilayer graphene. Phys. Rev. Lett. 131, 096801 (2023).10.1103/PhysRevLett.131.096801 ↗
38. Zheng, Z. et al. Unconventional ferroelectricity in moiré heterostructures. Nature 588, 71–76 (2020).10.1038/s41586-020-2970-9 ↗
39. Niu, R. et al. Giant ferroelectric polarization in a bilayer graphene heterostructure. Nat. Commun. 13, 6241 (2022).10.1038/s41467-022-34104-z ↗
40. Zhu, Z., Carr, S., Ma, Q. & Kaxiras, E. Electric field tunable layer polarization in graphene/boron-nitride twisted quadrilayer superlattices. Phys. Rev. B 106, 205134 (2022).10.1103/PhysRevB.106.205134 ↗
41. Yan, X. et al. Moiré synaptic transistor with room-temperature neuromorphic functionality. Nature 624, 551–556 (2023).10.1038/s41586-023-06791-1 ↗
42. Van Wijk, M., Schuring, A., Katsnelson, M. & Fasolino, A. Moiré patterns as a probe of interplanar interactions for graphene on h-BN. Phys. Rev. Lett. 113, 135504 (2014).10.1103/PhysRevLett.113.135504 ↗
43. Zhou, S., Han, J., Dai, S., Sun, J. & Srolovitz, D. J. Van der Waals bilayer energetics: Generalized stacking-fault energy of graphene, boron nitride, and graphene/boron nitride bilayers. Phys. Rev. B 92, 155438 (2015).10.1103/PhysRevB.92.155438 ↗
44. Haigh, S. J. et al. Cross-sectional imaging of individual layers and buried interfaces of graphene-based heterostructures and superlattices. Nat. Mater. 11, 764–767 (2012).10.1038/nmat3386 ↗
45. King-Smith, R. & Vanderbilt, D. Theory of polarization of crystalline solids. Phys. Rev. B 47, 1651 (1993).10.1103/PhysRevB.47.1651 ↗
46. Neugebauer, J. & Scheffler, M. Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111). Phys. Rev. B 46, 16067–16080 (1992).10.1103/PhysRevB.46.16067 ↗
47. Koshino, M. Interlayer screening effect in graphene multilayers with ABA and ABC stacking. Phys. Rev. B 81, 125304 (2010).10.1103/PhysRevB.81.125304 ↗
48. Qi, Y. & Rappe, A. M. Widespread negative longitudinal piezoelectric responses in ferroelectric crystals with layered structures. Phys. Rev. Lett. 126, 217601 (2021).10.1103/PhysRevLett.126.217601 ↗
49. Cao, W. et al. Polarization saturation in multilayered interfacial ferroelectrics. Adv. Mater. 36, 2400750 (2024).10.1002/adma.202400750 ↗
50. Bučko, T., Lebègue, S., Ángyán, J. G. & Hafner, J. Extending the applicability of the Tkatchenko-Scheffler dispersion correction via iterative Hirshfeld partitioning. J. Chem. Phys. 141, 034114 (2014).10.1063/1.4890003 ↗
51. Bucko, T., Lebegue, S., Hafner, J. R. & Angyan, J. G. Improved density dependent correction for the description of London dispersion forces. J. Chem. Theory Comput. 9, 4293–4299 (2013).10.1021/ct400694h ↗
52. Sui, F. et al. Atomic-level polarization reversal in sliding ferroelectric semiconductors. Nat. Commun. 15, 3799 (2024).10.1038/s41467-024-48218-z ↗
53. Wang, H. et al. Ferroelectric polarization of graphene/h-BN bilayer of different stacking orders. Surf. Interfaces 46, 103999 (2024).10.1016/j.surfin.2024.103999 ↗
54. Mao, J. et al. Strain-engineered ferroelectricity in 2H bilayer MoS2. ACS Nano 18, 30360–30367 (2024).10.1021/acsnano.4c07397 ↗
55. He, R. et al. Ultrafast switching dynamics of the ferroelectric order in stacking-engineered ferroelectrics. Acta Mater. 262, 119416 (2024).10.1016/j.actamat.2023.119416 ↗
56. Ko, K. et al. Operando electron microscopy investigation of polar domain dynamics in twisted van der Waals homobilayers. Nat. Mater. 22, 992–998 (2023).10.1038/s41563-023-01595-0 ↗
57. Bennett, D. & Remez, B. On electrically tunable stacking domains and ferroelectricity in moiré superlattices. npj 2D Mater. Appl. 6, 7 (2022).10.1038/s41699-021-00281-6 ↗
58. Yao, P. et al. Fully hardware-implemented memristor convolutional neural network. Nature 577, 641–646 (2020).10.1038/s41586-020-1942-4 ↗
59. Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251 (1994).10.1103/PhysRevB.49.14251 ↗
60. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169 (1996).10.1103/PhysRevB.54.11169 ↗
61. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865 (1996).10.1103/PhysRevLett.77.3865 ↗
62. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953 (1994).10.1103/PhysRevB.50.17953 ↗
63. Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-d) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).10.1063/1.3382344 ↗
64. Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011).10.1002/jcc.21759 ↗
65. Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).10.1063/1.1329672 ↗