Ferroelectric α-Bi2O3 films derived from β-Bi via ultraviolet ozone oxidation

Wei Li; Wei Zhang; Lingyuan Kong; Tianci Hu; Zeguo Lin; Yi Jiang; Fang Yang; Yang Guo; Pan Chen; Runzhang Xu; Yan Liang; Jiandi Zhang

doi:10.1088/1674-4926/26070002

J. Semicond. > Just Accepted

ARTICLES

Ferroelectric α-Bi₂O₃ films derived from β-Bi via ultraviolet ozone oxidation

Wei Li^{1, 2}, Wei Zhang^1,, Lingyuan Kong^{1, 2}, Tianci Hu², Zeguo Lin², Yi Jiang², Fang Yang², Yang Guo², Pan Chen², Runzhang Xu^3,, Yan Liang^2, and Jiandi Zhang^{2, 4,}

+ Author Affiliations

1. Hebei Key Lab of Optic-electronic Information and Materials, College of Physics Science and Technology, Hebei University, Baoding 071002, China
2. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
3. Department of Physics, The Hong Kong University of Science and Technology, Hong Kong 999077, China
4. College of Physics, University of Chinese Academy of Sciences, Beijing, 100190, China

Author Bio:

Wei Li is a master’s candidate at Hebei University. His research focuses on the molecular beam epitaxy and physical-property characterization of two-dimensional ferroelectric thin films.

Wei Zhang is an Associate Professor at Hebei University. He received his Ph.D. degree from Soochow University in 2016. His research focuses on the synthesis of novel ferroelectric/semiconductor materials and their applications for information-storage devices.

Yan Liang is an Associate Professor at the Institute of Physics, Chinese Academy of Sciences. She received her Ph.D. degree from Soochow University in 2017 and conducted postdoctoral research at Peking University from 2017 to 2021. Her research focuses on the synthesis and physical-property characterization of low-dimensional oxide thin films.

Corresponding author: Wei Zhang, zhangw@hbu.edu.cn; Runzhang Xu, xurz@ust.hk; Yan Liang, liangyan_sf6i@iphy.ac.cn; Jiandi Zhang, jiandiz@iphy.ac.cn

DOI: 10.1088/1674-4926/26070002CSTR: 32376.14.1674-4926.26070002

Abstract: Bismuth-based oxides are well known for their high Curie temperature and excellent fatigue resistance, which have attracted extensive researches and various applications. In this work, we successfully fabricated pure phase α-Bi₂O₃ films by a novel ultraviolet ozone oxidation method from β-Bi. The obtained α-Bi₂O₃ exhibits room-temperature out-of-plane ferroelectricity, as confirmed by both piezoelectric force microscopy measurements and hysteresis loops obtained from out-of-plane ferroelectric tunnel junctions. Density functional calculations predict that the ferroelectricity of α-Bi₂O₃ arises from a synergistic interplay between electric-field-induced structural deformation and charge redistribution within films. Our results demonstrate that such a thin RT ferroelectric α-Bi₂O₃ film could be a promising candidate for future multifunctional electronic devices.

References

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[32]	Pellegrino G, Mineo G, Strano V, et al. Highly efficient β-Bi₂O₃/Bi battery electrodes by reactive annealing from sol-gel precursors. Colloids Surf A Physicochem Eng Aspects, 2025, 705: 135738 doi: 10.1016/j.colsurfa.2024.135738
[33]	Kindler B, Lommel B, Celik Ayik E, et al. Comparison of Bi₂O₃-targets produced by thermal evaporation and RF magnetron sputtering. EPJ Web Conf, 2023, 285: 10001 doi: 10.1051/epjconf/202328510001
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[35]	Zhang D X, Xiang Q. Green electrophoretic deposition of Bi₂O₃ coating. J Mater Sci Mater Electron, 2016, 27(11): 11995 doi: 10.1007/s10854-016-5346-z
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Fig. 1. Preparation and physical characterization of β-Bi and α-Bi₂O₃ films. A) The crystal structures of β-Bi and α-Bi₂O₃, along with a schematic diagram of the oxidation process. B) XRD pattern of β-Bi (bottom) and α-Bi₂O₃ (top) films. The asterisks indicate the peaks of STO substrates. C) XRR data and fitting results of the β-Bi/STO heterostructure. Inset: surface topography of the sample, exhibiting an average roughness of 0.2 nm. D) XPS spectra of Bi element in β-Bi (bottom) and α- Bi₂O₃ (top) films.

DownLoad: Full-Size Img PowerPoint

Fig. 2. Out-of-plane ferroelectricity in α-Bi₂O₃ films. A) Schematic diagram of the PFM characterization setup. B) Off-field PFM amplitude loop and C) phase loop for α-Bi₂O₃ films. D) PFM characterization for bare Nb-STO substrate. E) The amplitude and F) phase images obtained after writing an opposite DC bias "box-in-box" pattern using PFM.

DownLoad: Full-Size Img PowerPoint

Fig. 3. Out-of-plane electrical measurements of FE α-Bi₂O₃. A) Schematic diagram of out-of-plane FE tunneling junction. B) I-V characteristic curve when an external voltage of 1 V is applied. The measurement repeats ten times. C) I-V curves with applied voltages of 1 V, 5 V, 10 V, 15 V and 20 V respectively.

DownLoad: Full-Size Img PowerPoint

Fig. 4. DFT calculations of the field-induced polarization in a thin α-Bi₂O₃ film. A) Crystal structure of bulk α-Bi₂O₃. The blue transparent plane and the blue dashed lines indicate the (012) plane and its lattice intersection, while a', b' and c' represent the basis vectors of the newly defined coordinate system with respect to the (012) plane. The calculated a'-, b'- and c'-parallel polarization as a function of electric field B) perpendicular to to the (012) plane.

DownLoad: Full-Size Img PowerPoint

[1]	Zhang D W, Schoenherr P, Sharma P, et al. Ferroelectric order in van der Waals layered materials. Nat Rev Mater, 2023, 8(1): 25 doi: 10.1038/s41578-022-00484-3
[2]	Li E L, He W X, Wang R X, et al. Polarity-dependent ferroelectric modulations in two-dimensional hybrid perovskite heterojunction transistors. Nat Commun, 2025, 16: 9382 doi: 10.1038/s41467-025-64387-x
[3]	Feng G D, Zhu Q X, Liu X F, et al. A ferroelectric fin diode for robust non-volatile memory. Nat Commun, 2024, 15: 513 doi: 10.1038/s41467-024-44759-5
[4]	Li Q X, Wang S W, Li Z H, et al. High-performance ferroelectric field-effect transistors with ultra-thin indium tin oxide channels for flexible and transparent electronics. Nat Commun, 2024, 15: 2686 doi: 10.1038/s41467-024-46878-5
[5]	Kim K H, Oh S, Fiagbenu M M A, et al. Scalable CMOS back-end-of-line-compatible AlScN/two-dimensional channel ferroelectric field-effect transistors. Nat Nanotechnol, 2023, 18(9): 1044 doi: 10.1038/s41565-023-01399-y
[6]	Wang R N, Li L T, Li J T, et al. Molecular ferroelectrics for highly sensitive detection toward low-frequency sound recognition. Adv Mater, 2025, 37(8): 2409251 doi: 10.1002/adma.202409251
[7]	Liu Y H, Tang W Y, Zeng J H, et al. Ferroelectric-based neuromorphic memory devices for bio-inspired computing. Nat Rev Electr Eng, 2025, 2(11): 773 doi: 10.1038/s44287-025-00222-1
[8]	Shi W, University S, Chen N, et al. Grain plastic rearrangement for fabricating textured CaBi₂Nb₂O₉-based ceramics with superior piezoelectricity. ACS Appl Mater Interfaces, 2025, 17(43): 59531 doi: 10.1021/acsami.5c13481
[9]	Zhou S, Liao L, Chen L, et al. Ferroelectricity in epitaxial perovskite oxide Bi₂WO₆ films with one-unit-cell thickness. Nano Lett, 2023, 23(17): 7838 doi: 10.1021/acs.nanolett.3c01426
[10]	Lee E, Son J Y. Growth and ferroelectric properties of SrBi₂Ta₂O₉ thin films on highly oriented pyrolytic graphite substrates with atomic structure like graphene surface. J Mater Sci, 2024, 59(32): 15399 doi: 10.1007/s10853-024-09605-5
[11]	Long C B, Chang Q, Fan H Q. Differences in nature of electrical conductions among Bi₄Ti₃O₁₂-based ferroelectric polycrystalline ceramics. Sci Rep, 2017, 7: 4193 doi: 10.1038/s41598-017-03266-y
[12]	Li L G, Boullay P, Lu P, et al. Novel layered supercell structure from Bi₂AlMnO₆ for multifunctionalities. Nano Lett, 2017, 17(11): 6575 doi: 10.1021/acs.nanolett.7b02284
[13]	Zhong W M, Liu Q X, Tang X G, et al. Ferroelectric diode effect with temperature stability of double perovskite Bi₂NiMnO6 thin films. Nanomaterials, 2019, 9(12): 1783 doi: 10.3390/nano9121783
[14]	Chen C, Wang M X, Wu J X, et al. Electronic structures and unusually robust bandgap in an ultrahigh-mobility layered oxide semiconductor, Bi₂O₂Se. Sci Adv, 2018, 4(9): eaat8355 doi: 10.1126/sciadv.aat8355
[15]	Kong L, Li W, Hu K, et al. Room-temperature ferroelectricity of Bi₂O₂Se in the two-dimensional limit. Nano Lett, 2025: 5c04402
[16]	Kong L Y, Li W, Wang Z H, et al. Room-temperature ferroelectricity in ultra-thin p-type BiCuSeO films. Adv Mater, 2025, 37(45): e10566 doi: 10.1002/adma.202510566
[17]	Han M J, Wang C, Niu K D, et al. Continuously tunable ferroelectric domain width down to the single-atomic limit in bismuth tellurite. Nat Commun, 2022, 13: 5903 doi: 10.1038/s41467-022-33617-x
[18]	Li Y F, Li A L, Wang C, et al. Buffer layer stabilized single-unit cell ferroelectric Bi₂TeO₅. Adv Funct Mater, 2025, 35(17): 2421384 doi: 10.1002/adfm.202421384
[19]	Wu Q C, Li Z R, Han B C, et al. Wafer-scale ultrathin and uniform van der Waals ferroelectric oxide. Science, 2026, 391(6784): eadz1655 doi: 10.1126/science.adz1655
[20]	Zhao T G, Duan S J, et al. Edge-dominated epitaxy of topological insulator Bi₂Se₃ with ultrabroadband response. ACS Nano, 2025, 19(28): 26055 doi: 10.1021/acsnano.5c06699
[21]	Zhao T G, Liu X, Ge X, et al. K+-free mica-assisted epitaxy of bi-based chalcogenide and oxychalcogenide single-crystals. Nat Commun, 2026, 17: 7459 doi: 10.1038/s41467-026-74341-0
[22]	Hernández-Torres J, Rivas-Silva J F, Sosa R, et al. Electronic and optical characteristics of Alfa and Delta Bi₂O₃: A DFT study. 2024 IEEE International Conference on Engineering Veracruz (ICEV). Boca del Rio, Veracruz, Mexico. IEEE, 2024: 1
[23]	Alruwaili A, El Sayed A M. Characterization and the physical properties of nano-sized Bi₂O₃/polymer for energy and high-refractive index applications. Results Phys, 2024, 61: 107746 doi: 10.1016/j.rinp.2024.107746
[24]	Karma N, Siddiqui K, Harinkhere D, et al. Structural and dielectric properties of Bi₂O₃ nanoparticles synthesized at different temperatures. Mater Today Proc, 2023, 74: 146 doi: 10.1016/j.matpr.2022.08.036
[25]	Jolley A G, Bai Q, Jayathilake R, et al. Bismuth oxide electrolytes with superior conductivity and stability. Mater Today, 2025, 86: 247 doi: 10.1016/j.mattod.2025.03.030
[26]	Lang C B, Yu X Y, Tang H, et al. High stability self-powered Bi₂O₃ based ultraviolet photodetector with p-i-n heterojunction. J Alloys Compd, 2025, 1024: 180208 doi: 10.1016/j.jallcom.2025.180208
[27]	A non-layered two-dimensional semiconductor for p-type transistors. Nat Mater, 2025, 24(5): 671
[28]	Yang Q Q, Hu J C, Fang Y W, et al. Ferroelectricity in layered bismuth oxide down to 1 nanometer. Science, 2023, 379(6638): 1218 doi: 10.1126/science.abm5134
[29]	Reuge N, Dexpert-Ghys J, Caussat B. Fluidized-bed MOCVD of Bi₂O₃ thin films from bismuth triphenyl under atmospheric pressure. Chem Vap Deposition, 2010, 16(4/5/6): 123
[30]	Shen Y D, Li Y W, Li W M, et al. Growth of Bi₂O₃ ultrathin films by atomic layer deposition. J Phys Chem C, 2012, 116(5): 3449 doi: 10.1021/jp205180p
[31]	Gao S, Lian J, Sun Z Z, et al. Study of optical properties of Bi₂O₃ and Bi₂Se₃ ultrathin films by spectroscopic ellipsometry. J Comput Theor Nanosci, 2014, 11(4): 1069
[32]	Pellegrino G, Mineo G, Strano V, et al. Highly efficient β-Bi₂O₃/Bi battery electrodes by reactive annealing from sol-gel precursors. Colloids Surf A Physicochem Eng Aspects, 2025, 705: 135738 doi: 10.1016/j.colsurfa.2024.135738
[33]	Kindler B, Lommel B, Celik Ayik E, et al. Comparison of Bi₂O₃-targets produced by thermal evaporation and RF magnetron sputtering. EPJ Web Conf, 2023, 285: 10001 doi: 10.1051/epjconf/202328510001
[34]	Koza J A, Bohannan E W, Switzer J A. Superconducting filaments formed during nonvolatile resistance switching in electrodeposited δ-Bi₂O₃. ACS Nano, 2013, 7(11): 9940 doi: 10.1021/nn4038207
[35]	Zhang D X, Xiang Q. Green electrophoretic deposition of Bi₂O₃ coating. J Mater Sci Mater Electron, 2016, 27(11): 11995 doi: 10.1007/s10854-016-5346-z
[36]	Zhao T G, Wang Z, Hu W D. Wafer-scale transfer of two-dimensional materials with UV tape. Nat Electron, 2024, 7(2): 96 doi: 10.1038/s41928-024-01117-z
[37]	Gou J, Bai H, Zhang X L, et al. Two-dimensional ferroelectricity in a single-element bismuth monolayer. Nature, 2023, 617(7959): 67 doi: 10.1038/s41586-023-05848-5
[38]	Kumar P, Vaish R. Effect of poling and excess Bi₂O₃ on piezocatalysis by BaBi₄Ti₄O₁₅. J Mater Sci Mater Electron, 2023, 34(36): 2278 doi: 10.1007/s10854-023-11614-0
[39]	Quhe R, Di Z Y, Zhang J X, et al. Asymmetric conducting route and potential redistribution determine the polarization-dependent conductivity in layered ferroelectrics. Nat Nanotechnol, 2024, 19(2): 173 doi: 10.1038/s41565-023-01539-4
[40]	Maciel García G I, Khandelwal V, et al. Lateral semiconductor–free-space gate transistors. Nano Lett, 2025, 25(43): 15579 doi: 10.1021/acs.nanolett.5c03880
[41]	Cheng Y, Tian S, Li B, et al. Unidirectional electrobending deformation in acceptor-doped piezoceramics. Adv Mater, 2025, 37(37): 2504420 doi: 10.1002/adma.202504420
[42]	Bian R J, He R, Pan E, et al. Developing fatigue-resistant ferroelectrics using interlayer sliding switching. Science, 2024, 385(6704): 57 doi: 10.1126/science.ado1744
[43]	Chai Q Z, Liu Z B, Deng Z Q, et al. Excellent energy storage properties in lead-free ferroelectric ceramics via heterogeneous structure design. Nat Commun, 2025, 16: 1633 doi: 10.1038/s41467-025-56767-0
[44]	Hao Z, et al. Observation of intrinsic and LED light-enhanced memristor performance in in-plane ferroelectric NbOI₂. ACS Nano, 2025, 19(30): 27654 doi: 10.1021/acsnano.5c07236
[45]	Zhang G, Chen Y, Zheng Z J, et al. Thin film ferroelectric photonic-electronic memory. Light Sci Appl, 2024, 13: 206 doi: 10.1038/s41377-024-01555-6
[46]	Li C L, Yu H Y, Shu T, et al. PZT optical memristors. Nat Commun, 2025, 16: 6340 doi: 10.1038/s41467-025-61536-0
[47]	Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B, 1996, 54(16): 11169 [48] [48] Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys Rev Lett, 1996, 77(18): 3865
[48]	Blöchl P E. Projector augmented-wave method. Phys Rev B, 1994, 50(24): 17953 doi: 10.1103/PhysRevB.50.17953
[49]	Wisesa P, McGill K A, Mueller T. Efficient generation of generalized Monkhorst-Pack grids through the use of informatics. Phys Rev B, 2016, 93(15): 155109 doi: 10.1103/PhysRevB.93.155109
[50]	Zhao H J, Liu X R, Wang Y C, et al. Zeeman effect in centrosymmetric antiferromagnetic semiconductors controlled by an electric field. Phys Rev Lett, 2022, 129(18): 187602 doi: 10.1103/PhysRevLett.129.187602
[51]	Resta R. Macroscopic polarization in crystalline dielectrics: The geometric phase approach. Rev Mod Phys, 1994, 66(3): 899 doi: 10.1103/RevModPhys.66.899

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Received: 01 July 2026 Revised: 09 August 2026 Online: Accepted Manuscript: 27 August 2026

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Wei Li, Wei Zhang, Lingyuan Kong, Tianci Hu, Zeguo Lin, Yi Jiang, Fang Yang, Yang Guo, Pan Chen, Runzhang Xu, Yan Liang, Jiandi Zhang. Ferroelectric α-Bi2O3 films derived from β-Bi via ultraviolet ozone oxidation[J]. Journal of Semiconductors, 2026, In Press. doi: 10.1088/1674-4926/26070002 ****W Li, W Zhang, L Y Kong, T C Hu, Z G Lin, Y Jiang, F Yang, Y Guo, P Chen, R Z Xu, Y Liang, and J D Zhang, Ferroelectric α-Bi2O3 films derived from β-Bi via ultraviolet ozone oxidation[J]. J. Semicond., 2026, accepted doi: 10.1088/1674-4926/26070002

Citation:

Wei Li, Wei Zhang, Lingyuan Kong, Tianci Hu, Zeguo Lin, Yi Jiang, Fang Yang, Yang Guo, Pan Chen, Runzhang Xu, Yan Liang, Jiandi Zhang. Ferroelectric α-Bi₂O₃ films derived from β-Bi via ultraviolet ozone oxidation[J]. Journal of Semiconductors, 2026, In Press. doi: 10.1088/1674-4926/26070002 ****

W Li, W Zhang, L Y Kong, T C Hu, Z G Lin, Y Jiang, F Yang, Y Guo, P Chen, R Z Xu, Y Liang, and J D Zhang, Ferroelectric α-Bi₂O₃ films derived from β-Bi via ultraviolet ozone oxidation[J]. J. Semicond., 2026, accepted doi: 10.1088/1674-4926/26070002

Citation:

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Ferroelectric α-Bi₂O₃ films derived from β-Bi via ultraviolet ozone oxidation

DOI: 10.1088/1674-4926/26070002

CSTR: 32376.14.1674-4926.26070002

Wei Li^{1, 2},
Wei Zhang^1,,
Lingyuan Kong^{1, 2},
Tianci Hu²,
Zeguo Lin²,
Yi Jiang²,
Fang Yang²,
Yang Guo²,
Pan Chen²,
Runzhang Xu^3,,
Yan Liang^2,,
Jiandi Zhang^{2, 4,}

1.
Hebei Key Lab of Optic-electronic Information and Materials, College of Physics Science and Technology, Hebei University, Baoding 071002, China
2.
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
3.
Department of Physics, The Hong Kong University of Science and Technology, Hong Kong 999077, China
4.
College of Physics, University of Chinese Academy of Sciences, Beijing, 100190, China

More Information

Wei Li is a master’s candidate at Hebei University. His research focuses on the molecular beam epitaxy and physical-property characterization of two-dimensional ferroelectric thin films
Wei Zhang is an Associate Professor at Hebei University. He received his Ph.D. degree from Soochow University in 2016. His research focuses on the synthesis of novel ferroelectric/semiconductor materials and their applications for information-storage devices
Yan Liang is an Associate Professor at the Institute of Physics, Chinese Academy of Sciences. She received her Ph.D. degree from Soochow University in 2017 and conducted postdoctoral research at Peking University from 2017 to 2021. Her research focuses on the synthesis and physical-property characterization of low-dimensional oxide thin films
Corresponding author: zhangw@hbu.edu.cn; xurz@ust.hk; liangyan_sf6i@iphy.ac.cn; jiandiz@iphy.ac.cn
Received Date: 2026-07-01
Revised Date: 2026-08-09

Available Online: 2026-08-27

Abstract

Abstract

Bismuth-based oxides are well known for their high Curie temperature and excellent fatigue resistance, which have attracted extensive researches and various applications. In this work, we successfully fabricated pure phase α-Bi₂O₃ films by a novel ultraviolet ozone oxidation method from β-Bi. The obtained α-Bi₂O₃ exhibits room-temperature out-of-plane ferroelectricity, as confirmed by both piezoelectric force microscopy measurements and hysteresis loops obtained from out-of-plane ferroelectric tunnel junctions. Density functional calculations predict that the ferroelectricity of α-Bi₂O₃ arises from a synergistic interplay between electric-field-induced structural deformation and charge redistribution within films. Our results demonstrate that such a thin RT ferroelectric α-Bi₂O₃ film could be a promising candidate for future multifunctional electronic devices.

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