Origin of suppressed ferroelectricity in κ-Ga2O3: interplay between polarization and lattice domain walls
Source abstract
Abstract
Abstract Remanent polarization and coercive field in ferroelectrics are often predicted to be high, yet experimentally observed to be much lower-an inconsistency that hinders the rational design of functional materials and devices. We identify a hidden mechanism underlying this discrepancy: the interaction between polarization domain walls (PDWs) and lattice domain walls (LDWs) that standard models omit. Using κ-Ga 2 O 3 as a representative ferroelectric, we develop a machine-learning potential trained on ab initio molecular-dynamics data to capture realistic polarization switching. Our simulations reveal that PDWs become topologically blocked at 120° LDWs, stabilizing residual domain-wall networks that suppress remanent polarization while enabling rapid, low-field switching by bypassing slow nucleation. The blocking strengthens as lattice domains shrink, offering a new strategy for tuning ferroelectric performance through lattice-domain engineering. The mechanism not only reconciles theoretical with experimental results but also provides a practical approach for improving ferroelectric performance.
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Research context
OpenAlex topics: Ga2O3 and related materials · Ferroelectric and Negative Capacitance Devices · Ferroelectric and Piezoelectric Materials
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (73)
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1. Wen, J., Luo, Z. -r, Fang, L. -c, Chen, W. -x & Zhuang, G. -l Photoinduced ferroelectric phase transition triggering photocatalytic water splitting. npj Comput. Mater. 11, 112 (2025).10.1038/s41524-025-01601-w ↗
2. Cui, B. et al. Ferroelectric photosensor network: an advanced hardware solution to real-time machine vision. Nat. Commun. 13, 1707 (2022).10.1038/s41467-022-29364-8 ↗
3. Zhang, T. et al. Tunable Schottky barriers and magnetoelectric coupling driven by ferroelectric polarization reversal of MnI3/In2Se3 multiferroic heterostructures. npj Comput. Mater. 10, 238 (2024).10.1038/s41524-024-01429-w ↗
4. Zhou, S. & Rappe, A. M. Nucleation mechanism of multiple-order parameter ferroelectric domain wall motion in hafnia. Proc. Natl. Acad. Sci. USA 122, e2406316122 (2025).10.1073/pnas.2406316122 ↗
5. Katayama, T., Yasui, S., Hamasaki, Y., Osakabe, T. & Itoh, M. Chemical tuning of room-temperature ferrimagnetism and ferroelectricity in ε-Fe2O3-type multiferroic oxide thin films. J. Mater. Chem. C 5, 12597–12601 (2017).10.1039/C7TC04363E ↗
6. Cho, S. B. & Mishra, R. Epitaxial engineering of polar ε-Ga2O3 for tunable two-dimensional electron gas at the heterointerface. Appl. Phys. Lett. 112, 162101 (2018).10.1063/1.5019721 ↗
7. Maccioni, M. B. & Fiorentini, V. Phase diagram and polarization of stable phases of (Ga1−xInx)2O3. Appl. Phys. Express 9, 041102 (2016).10.7567/APEX.9.041102 ↗
8. Shimada, K. First-principles study of crystal structure, elastic stiffness constants, piezoelectric constants, and spontaneous polarization of orthorhombic Pna21-M2O3 (M = Al, Ga, In, Sc, Y). Mater. Res. Express 5, 036502 (2018).10.1088/2053-1591/aab118 ↗
9. Mukherjee, B., Fedorova, N. S. & Íñiguez-González, J. First-principles predictions of HfO2-based ferroelectric superlattices. npj Comput. Mater. 10, 153 (2024).10.1038/s41524-024-01344-0 ↗
10. Rao, B. N. et al. Investigation of ferrimagnetism and ferroelectricity in AlxFe2−xO3 thin films. J. Mater. Chem. C 8, 706–714 (2020).10.1039/C9TC05390E ↗
11. Ducharme, S. et al. Intrinsic ferroelectric coercive field. Phys. Rev. Lett. 84, 175–178 (2000).10.1103/PhysRevLett.84.175 ↗
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. 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 ↗
14. Wang, Z. & Dong, S. Polarization switching in sliding ferroelectrics: Roles of fluctuation and domain wall. Phys. Rev. B 111, L201406 (2025).10.1103/PhysRevB.111.L201406 ↗
15. Vizner Stern, M. et al. Interfacial ferroelectricity by van der Waals sliding. Science 372, 1462–1466 (2021).10.1126/science.abe8177 ↗
16. Janzen, B. M. et al. Comprehensive Raman study of orthorhombic κ/ε-Ga2O3 and the impact of rotational domains. J. Mater. Chem. C 9, 14175–14189 (2021).10.1039/D1TC03500B ↗
17. 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 ↗
18. King-Smith, R. D. & Vanderbilt, D. Theory of polarization of crystalline solids. Phys. Rev. B 47, 1651–1654 (1993).10.1103/PhysRevB.47.1651 ↗
19. Tao, A. et al. Ferroelectric polarization and magnetic structure at domain walls in a multiferroic film. Nat. Commun. 15, 6099 (2024).10.1038/s41467-024-50431-9 ↗
20. Xu, K., Feng, J. S., Liu, Z. P. & Xiang, H. J. Origin of ferrimagnetism and ferroelectricity in room-temperature multiferroic ε-Fe2O3. Phys. Rev. Appl. 9, 044011 (2018).10.1103/PhysRevApplied.9.044011 ↗
21. Momma, K. & Izumi, F. VESTA3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272–1276 (2011).10.1107/S0021889811038970 ↗
22. Liu, S., Grinberg, I. & Rappe, A. M. Intrinsic ferroelectric switching from first principles. Nature 534, 360–363 (2016).10.1038/nature18286 ↗
23. Shin, Y.-H., Grinberg, I., Chen, I. W. & Rappe, A. M. Nucleation and growth mechanism of ferroelectric domain-wall motion. Nature 449, 881–884 (2007).10.1038/nature06165 ↗
24. Unke, O. T. et al. Machine learning force fields. Chem. Rev. 121, 10142–10186 (2021).10.1021/acs.chemrev.0c01111 ↗
25. Zhang, L. et al. A deep potential model with long-range electrostatic interactions. J. Chem. Phys. 156, 124107 (2022).10.1063/5.0083669 ↗
26. Staacke, C. G. et al. On the role of long-range electrostatics in machine-learned interatomic potentials for complex battery materials. ACS Appl. Energy Mater. 4, 12562–12569 (2021).10.1021/acsaem.1c02363 ↗
27. Deng, Y., Fu, S., Guo, J., Xu, X. & Li, H. Anisotropic collective variables with machine learning potential for ab initio crystallization of complex ceramics. ACS Nano 17, 14099–14113 (2023).10.1021/acsnano.3c04602 ↗
28. Gigli, L. et al. Thermodynamics and dielectric response of BaTiO3 by data-driven modeling. npj Comput. Mater. 8, 209 (2022).10.1038/s41524-022-00845-0 ↗
29. Myung, C. W. et al. Challenges, opportunities, and prospects in metal halide perovskites from theoretical and machine learning perspectives. Adv. Energy Mater. 12, 2202279 (2022).10.1002/aenm.202202279 ↗
30. Zhong, W., Vanderbilt, D. & Rabe, K. M. First-principles theory of ferroelectric phase transitions for perovskites: The case of BaTiO3. Phys. Rev. B 52, 6301–6312 (1995).10.1103/PhysRevB.52.6301 ↗
31. Wu, J., Zhang, Y., Zhang, L. & Liu, S. Deep learning of accurate force field of ferroelectric HfO2. Phys. Rev. B 103, 024108 (2021).10.1103/PhysRevB.103.024108 ↗
32. He, R. et al. Unconventional ferroelectric domain switching dynamics in CuInP2S6 from first principles. Phys. Rev. B 108, 024305 (2023).10.1103/PhysRevB.108.024305 ↗
33. Gong, Z., Liu, J. Z., Ding, X., Sun, J. & Deng, J. Strain-aided room-temperature second-order ferroelectric phase transition in monolayer PbTe: Deep potential molecular dynamics simulations. Phys. Rev. B 108, 134112 (2023).10.1103/PhysRevB.108.134112 ↗
34. Wang, H., Zhang, L. & Han, J. E W. DeePMD-kit: A deep learning package for many-body potential energy representation and molecular dynamics. Comput. Phys. Commun. 228, 178–184 (2018).10.1016/j.cpc.2018.03.016 ↗
35. Zeng, J. et al. DeePMD-kit v2: A software package for deep potential models. J. Chem. Phys. 159, 054801 (2023).10.1063/5.0155600 ↗
36. Gao, A. & Remsing, R. C. Self-consistent determination of long-range electrostatics in neural network potentials. Nat. Commun. 13, 1572 (2022).10.1038/s41467-022-29243-2 ↗
37. Behler, J. & Parrinello, M. Generalized neural-network representation of high-dimensional potential-energy surfaces. Phys. Rev. Lett. 98, 146401 (2007).10.1103/PhysRevLett.98.146401 ↗
38. Zhang, L. et al. Deep neural network for the dielectric response of insulators. Phys. Rev. B 102, 041121 (2020).10.1103/PhysRevB.102.041121 ↗
39. Umari, P. & Pasquarello, A. Ab initio molecular dynamics in a finite homogeneous electric field. Phys. Rev. Lett. 89, 157602 (2002).10.1103/PhysRevLett.89.157602 ↗
40. Souza, I., Íñiguez, J. & Vanderbilt, D. First-principles approach to insulators in finite electric fields. Phys. Rev. Lett. 89, 117602 (2002).10.1103/PhysRevLett.89.117602 ↗
41. Spaldin, N. A. A beginner’s guide to the modern theory of polarization. J. Solid State Chem. 195, 2–10 (2012).10.1016/j.jssc.2012.05.010 ↗
42. Tagantsev, A. K., Stolichnov, I., Setter, N., Cross, J. S. & Tsukada, M. Non-Kolmogorov-Avrami switching kinetics in ferroelectric thin films. Phys. Rev. B 66, 214109 (2002).10.1103/PhysRevB.66.214109 ↗
43. Ishibashi, Y. & Takagi, Y. Note on ferroelectric domain switching. J. Phys. Soc. Jpn. 31, 506–510 (1971).10.1143/JPSJ.31.506 ↗
44. Yang, J. et al. Theoretical lower limit of coercive field in ferroelectric hafnia. Phys. Rev. X 15, 021042 (2025).
45. Jo, J. Y. et al. Nonlinear dynamics of domain-wall propagation in epitaxial ferroelectric thin films. Phys. Rev. Lett. 102, 045701 (2009).10.1103/PhysRevLett.102.045701 ↗
46. Tybell, T., Paruch, P., Giamarchi, T. & Triscone, J. M. Domain wall creep in epitaxial ferroelectric Pb(Zr0.2Ti0.8)O3 thin films. Phys. Rev. Lett. 89, 097601 (2002).10.1103/PhysRevLett.89.097601 ↗
47. Merz, W. J. Domain formation and domain wall motions in ferroelectric BaTiO3 single crystals. Phys. Rev. 95, 690–698 (1954).10.1103/PhysRev.95.690 ↗
48. Miller, R. C. & Weinreich, G. Mechanism for the sidewise motion of 180° domain walls in barium titanate. Phys. Rev. 117, 1460–1466 (1960).10.1103/PhysRev.117.1460 ↗
49. Ke, C., Liu, F. & Liu, S. Superlubric motion of wavelike domain walls in sliding ferroelectrics. Phys. Rev. Lett. 135, 046201 (2025).10.1103/jhlq-2dd7 ↗
50. Cora, I. et al. The real structure of ε-Ga2O3 and its relation to κ-phase. CrystEngComm 19, 1509–1516 (2017).10.1039/C7CE00123A ↗
51. Hrubišák, F. et al. Heteroepitaxial growth of Ga2O3 on 4H-SiC by liquid-injection MOCVD for improved thermal management of Ga2O3 power devices. J. Vac. Sci. Technol. A 41, 042708 (2023).10.1116/6.0002649 ↗
52. Cora, I. et al. In situ TEM study of κ→β and κ→γ phase transformations in Ga2O3. Acta Mater 183, 216–227 (2020).10.1016/j.actamat.2019.11.019 ↗
53. Nishinaka, H. et al. Plan-view TEM observation of a single-domain κ-Ga2O3 thin film grown on ε-GaFeO3 substrate using GaCl3 precursor by mist chemical vapor deposition. Jpn. J. Appl. Phys. 61, 018002 (2022).10.35848/1347-4065/ac3e17 ↗
54. Katayama, T., Yasui, S., Hamasaki, Y. & Itoh, M. Control of crystal-domain orientation in multiferroic Ga0.6Fe1.4O3 epitaxial thin films. Appl. Phys. Lett. 110, 212905 (2017).10.1063/1.4984211 ↗
55. Hamasaki, Y. et al. Ferroelectric and magnetic properties in ε-Fe2O3 epitaxial film. Appl. Phys. Lett. 119, 182904 (2021).10.1063/5.0063021 ↗
56. Huang, F. T. et al. Domain topology and domain switching kinetics in a hybrid improper ferroelectric. Nat. Commun. 7, 11602 (2016).10.1038/ncomms11602 ↗
57. Han, M.-G. et al. Ferroelectric switching dynamics of topological vortex domains in a hexagonal manganite. Adv. Mater. 25, 2415–2421 (2013).10.1002/adma.201204766 ↗
58. Mazzolini, P. et al. Silane-mediated expansion of domains in Si-doped κ-Ga2O3 epitaxy and its impact on the in-plane electronic conduction. Adv. Funct. Mater. 33, 2207821 (2023).10.1002/adfm.202207821 ↗
59. Bian, R. et al. Developing fatigue-resistant ferroelectrics using interlayer sliding switching. Science 385, 57–62 (2024).10.1126/science.ado1744 ↗
60. 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 ↗
61. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).10.1103/PhysRevB.54.11169 ↗
62. Kühne, T. D. et al. CP2K: An electronic structure and molecular dynamics software package - Quickstep: Efficient and accurate electronic structure calculations. J. Chem. Phys. 152, 194103 (2020).10.1063/5.0007045 ↗
63. Jia, W. et al. Fast plane wave density functional theory molecular dynamics calculations on multi-GPU machines. J. Comput. Phys. 251, 102–115 (2013).10.1016/j.jcp.2013.05.005 ↗
64. Jia, W. et al. The analysis of a plane wave pseudopotential density functional theory code on a GPU machine. Comput. Phys. Commun. 184, 9–18 (2013).10.1016/j.cpc.2012.08.002 ↗
65. Perdew, J. P. et al. Restoring the density-gradient expansion for exchange in solids and surfaces. Phys. Rev. Lett. 100, 136406 (2008).10.1103/PhysRevLett.100.136406 ↗
66. Goedecker, S., Teter, M. & Hutter, J. Separable dual-space Gaussian pseudopotentials. Phys. Rev. B 54, 1703–1710 (1996).10.1103/PhysRevB.54.1703 ↗
67. VandeVondele, J. & Hutter, J. Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases. J. Chem. Phys. 127, 114105 (2007).10.1063/1.2770708 ↗
68. Marzari, N., Mostofi, A. A., Yates, J. R., Souza, I. & Vanderbilt, D. Maximally localized Wannier functions: Theory and applications. Rev. Mod. Phys. 84, 1419–1475 (2012).10.1103/RevModPhys.84.1419 ↗
69. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).10.1103/PhysRevB.50.17953 ↗
70. Hamann, D. R. Optimized norm-conserving Vanderbilt pseudopotentials. Phys. Rev. B 88, 085117 (2013).10.1103/PhysRevB.88.085117 ↗
71. Thompson, A. P. et al. LAMMPS - a flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scales. Comput. Phys. Commun. 271, 108171 (2022).10.1016/j.cpc.2021.108171 ↗
72. Zhang L, Han J, Wang H, Car R E. W. Deep potential molecular dynamics: A scalable model with the accuracy of quantum mechanics. Phys. Rev. Lett. 120, 143001 (2018).10.1103/PhysRevLett.120.143001 ↗
73. Nunes, R. W. & Gonze, X. Berry-phase treatment of the homogeneous electric field perturbation in insulators. Phys. Rev. B 63, 155107 (2001).10.1103/PhysRevB.63.155107 ↗