- Physical Review Journals
All JournalsPhysics Magazine

Physical Review Materials

Reuse & Permissions

It is not necessary to obtain permission to reuse this article or its components as it is available under the terms of the Creative Commons Attribution 4.0 International license. This license permits unrestricted use, distribution, and reproduction in any medium, provided attribution to the author(s) and the published article's title, journal citation, and DOI are maintained. Please note that some figures may have been included with permission from other third parties. It is your responsibility to obtain the proper permission from the rights holder directly for these figures.

Export citation

Export citation

Choose format for download:

Download Citation
  • Editors' Suggestion
  • Open Access

Rise, fall, and rebirth of an oxide: Growth and evolution of bismuth oxide on Au(111)

Alberto Turoldo1, Marco Bianchi2,*, Deborah Perco1, Andrea Berti1, Philip Hofmann3, Alessandro Baraldi1,2, and Silvano Lizzit2

  • *Contact author: marco.bianchi@elettra.eu
PDF

Phys. Rev. Materials 10, 104008 – Published 21 October, 2026

DOI: https://doi.org/10.1103/pzgn-gqz5

Abstract

We report a comprehensive, multitechnique study of bismuth oxide growth on Au(111) under different conditions such as temperature and exposure to molecular oxygen. By combining synchrotron-based x-ray photoelectron spectroscopy and diffraction with low-energy electron diffraction and scanning tunneling microscopy, we elucidate the structural evolution of the system during controlled oxidation and subsequent annealing. We find that Bi deposition induces well-defined surface reconstructions, whereas oxidation triggers the formation of a complex sequence of bismuth oxide domains. High-resolution spectroscopic and diffraction data enable us to identify an oxide structure consistent with the (201) surface of β−Bi2O3. In addition, angle-resolved photoemission experiments and work function measurements reveal substantial electronic modifications triggered by a complex interplay of segregation of Bi and Au. Notably, a work function of 3.4 eV is achieved for oxidation at 423 K. These results provide benchmark structural and electronic insights into the Bi oxide/Au(111) system and establish a framework for integrating Bi2O3 as a contact material in devices using two-dimensional semiconductors, where it can enable low contact resistance.

View figure in article

Physics Subject Headings (PhySH)

Article Text

Supplemental Material

References (60)

  1. P.-C. Shen, C. Su, Y. Lin, A.-S. Chou, C.-C. Cheng, J.-H. Park, M.-H. Chiu, A.-Y. Lu, H.-L. Tang, M. M. Tavakoli, G. Pitner, X. Ji, Z. Cai, N. Mao, J. Wang, V. Tung, J. Li, J. Bokor, A. Zettl, C.-I. Wu, et al., Ultralow contact resistance between semimetal and monolayer semiconductors, Nature (London) 593, 211 (2021).
  2. W. Li, X. Gong, Z. Yu, L. Ma, W. Sun, S. Gao, Ç. Köroğlu, W. Wang, L. Liu, T. Li, H. Ning, D. Fan, Y. Xu, X. Tu, T. Xu, L. Sun, W. Wang, J. Lu, Z. Ni, J. Li, et al., Approaching the quantum limit in two-dimensional semiconductor contacts, Nature (London) 613, 274 (2023).
  3. T. Su, Y. Li, Q. Wang, W. Zhao, L. Cao, and Y. S. Ang, Semimetal contacts to monolayer semiconductor: Weak metalization as an effective mechanism to Schottky barrier lowering, J. Phys. D: Appl. Phys. 56, 234001 (2023).
  4. A. Rai, A. Valsaraj, H. C. P. Movva, A. Roy, R. Ghosh, S. Sonde, S. Kang, J. Chang, T. Trivedi, R. Dey, S. Guchhait, S. Larentis, L. F. Register, E. Tutuc, and S. K. Banerjee, Air stable doping and intrinsic mobility enhancement in monolayer molybdenum disulfide by amorphous titanium suboxide encapsulation, Nano Lett. 15, 4329 (2015).
  5. A. Leonhardt, D. Chiappe, V. V. Afanas'ev, S. El Kazzi, I. Shlyakhov, T. Conard, A. Franquet, C. Huyghebaert, and S. de Gendt, Material-selective doping of 2D TMDC through AlxOy encapsulation, ACS Appl. Mater. Interfaces 11, 42697 (2019).
  6. C. J. McClellan, E. Yalon, K. K. H. Smithe, S. V. Suryavanshi, and E. Pop, High current density in monolayer MoS2 doped by AlOx, ACS Nano 15, 1587 (2021).
  7. L. Omiciuolo, E. R. Hernández, E. Miniussi, F. Orlando, P. Lacovig, S. Lizzit, T. O. Menteş, A. Locatelli, R. Larciprete, M. Bianchi, S. Ulstrup, P. Hofmann, D. Alfè, and A. Baraldi, Bottom-up approach for the low-cost synthesis of graphene-alumina nanosheet interfaces using bimetallic alloys, Nat. Commun. 5, 5062 (2014).
  8. T. Maeder, Review of Bi2O3 based glasses for electronics and related applications, Int. Mater. Rev. 58, 3 (2013).
  9. Y. Lou, L. Wang, Z. Zhao, Y. Zhang, Z. Zhang, G. Lu, Y. Guo, and Y. Guo, Low-temperature CO oxidation over Co3O4-based catalysts: Significant promoting effect of Bi2O3 on Co3O4 catalyst, Appl. Catal. B 146, 43 (2014).
  10. J. Chen, C. Wang, C. Zong, S. Chen, P. Wang, and Q. Chen, High catalytic performance of Au/Bi2O3 for preferential oxidation of CO in H2, ACS Appl. Mater. Interfaces 13, 29532 (2021).
  11. X. Xiao, R. Hu, C. Liu, C. Xing, C. Qian, X. Zuo, J. Nan, and L. Wang, Facile large-scale synthesis of β−Bi2O3 nanospheres as a highly efficient photocatalyst for the degradation of acetaminophen under visible light irradiation, Appl. Catal. B 140-141, 433 (2013).
  12. S. Tian, I. A. Bello, J. Peng, H. Ren, Q. Ma, M. Zhu, K. Li, H. Wang, J. Wu, and G. Zhu, Fabricating Mn3O4/β−Bi2O3 heterojunction microspheres with enhanced photocatalytic activity for organic pollutants degradation and no removal, J. Alloys Compd. 854, 157223 (2021).
  13. E. Hashemi, R. Poursalehi, and H. Delavari, Ternary Bi2O3/(BiO)2CO3/g-C3N4 multi-heterojunction nanoflakes for highly efficient photocatalytic degradation of dyes and xanthates under visible light, J. Sci.: Adv. Mater. Devices 10, 100834 (2025).
  14. Y. Xiong, D. Xu, Y. Zou, L. Xu, Y. Yan, J. Wu, C. Qian, X. Song, K. Qu, T. Zhao, J. Gao, J. Yang, K. Zhang, S. Zhang, P. Wang, X. Chen, and H. Zeng, Vapour–liquid–solid–solid growth of two-dimensional non-layered β−Bi2O3 crystals with high hole mobility, Nat. Mater. 24, 688 (2025).
  15. W. Guertler, Über Wismutoxyd, Z. Anorg. Allg. Chem. 37, 222 (1903).
  16. G. Gattow and D. Schütze, Über Wismutoxide. VI. überein wismut (III)-oxid mit höherem Sauerstoffgehalt (β-modifikation), Z. Anorg. Allg. Chem. 328, 44 (1964).
  17. C. N. R. Rao, G. V. S. Rao, and S. Ramdas, Phase transformations and electrical properties of bismuth sesquioxide, J. Phys. Chem. 73, 672 (1969).
  18. H. A. Harwig and A. G. Gerards, The polymorphism of bismuth sesquioxide, Thermochim. Acta 28, 121 (1979).
  19. A. F. Gualtieri, S. Immovilli, and M. Prudenziati, Powder x-ray diffraction data for the new polymorphic compound ω−Bi2O3, Powder Diffr. 12, 90 (1997).
  20. N. Cornei, N. Tancret, F. Abraham, and O. Mentré, New ε−Bi2O3 metastable polymorph, Inorg. Chem. 45, 4886 (2006).
  21. M. Drache, P. Roussel, and J.-P. Wignacourt, Structures and oxide mobility in Bi-Ln-O materials: Heritage of Bi2O3, Chem. Rev. 107, 80 (2007).
  22. A. Abrami, M. Barnaba, L. Battistello, A. Bianco, B. Brena, G. Cautero, Q. H. Chen, D. Cocco, G. Comelli, S. Contrino, F. DeBona, S. Di Fonzo, C. Fava, P. Finetti, P. Furlan, A. Galimberti, A. Gambitta, D. Giuressi, R. Godnig, W. Jark, et al., Super ESCA: First beamline operating at ELETTRA, Rev. Sci. Instrum. 66, 1618 (1995).
  23. S.V. Hoffmann, C. Søndergaard, C. Schultz, Z. Li, and P. Hofmann, An undulator-based spherical grating monochromator beamline for angle-resolved photoemission spectroscopy, Nucl. Instrum. Methods Phys. Res. Sect. A 523, 441 (2004).
  24. L. Bignardi, P. Lacovig, R. Larciprete, D. Alfè, S. Lizzit, and A. Baraldi, Exploring 2D materials at surfaces through synchrotron-based core-level photoelectron spectroscopy, Surf. Sci. Rep. 78, 100586 (2023).
  25. S. Lizzit, R. Larciprete, P. Lacovig, M. Dalmiglio, F. Orlando, A. Baraldi, L. Gammelgaard, L. Barreto, M. Bianchi, E. Perkins, and P. Hofmann, Transfer-free electrical insulation of epitaxial graphene from its metal substrate, Nano Lett. 12, 4503 (2012).
  26. A. P. Baddorf, Identifying the secondary electron cutoff in ultraviolet photoemission spectra for work function measurements of non-ideal surfaces, Sci. Rep. 13, 13452 (2023).
  27. F. Orlando, P. Lacovig, L. Omiciuolo, N. G. Apostol, R. Larciprete, A. Baraldi, and S. Lizzit, Epitaxial growth of a single-domain hexagonal boron nitride monolayer, ACS Nano 8, 12063 (2014).
  28. F. J. García de Abajo, M. A. Van Hove, and C. S. Fadley, Multiple scattering of electrons in solids and molecules: A cluster-model approach, Phys. Rev. B 63, 075404 (2001).
  29. A. Maeland and T. B. Flanagan, Lattice spacings of gold–palladium alloys, Can. J. Phys. 42, 2364 (1964).
  30. P. Cucka and C. S. Barrett, The crystal structure of Bi and of solid solutions of Pb, Sn, Sb and Te in Bi, Acta Crystallogr. 15, 865 (1962).
  31. D. Pérez-Mezcua, I. Bretos, R. Jiménez, J. Ricote, R. J. Jiménez-Rioboó, C. G. Silva, D. Chateigner, L. Fuentes-Cobas, R. Sirera, and M. L. Calzada, Photochemical solution processing of films of metastable phases for flexible devices: The β−Bi2O3 polymorph, Sci. Rep. 6, 39561 (2016).
  32. L. Talirz, S. Kumbhar, E. Passaro, A. V. Yakutovich, V. Granata, F. Gargiulo, M. Borelli, M. Uhrin, S. P. Huber, S. Zoupanos, C. S. Adorf, C. W. Andersen, O. Schütt, C. A. Pignedoli, D. Passerone, J. VandeVondele, T. C. Schulthess, B. Smit, G. Pizzi, and N. Marzari, Materials cloud, a platform for open computational science, Sci. Data 7, 299 (2020).
  33. D. Woodruff, Adsorbate structure determination using photoelectron diffraction: Methods and applications, Surf. Sci. Rep. 62, 1 (2007).
  34. I. Horcas, R. Fernández, J. M. Gómez-Rodríguez, J. Colchero, J. Gómez-Herrero, and A. M. Baro, wsxm: A software for scanning probe microscopy and a tool for nanotechnology, Rev. Sci. Instrum. 78, 013705 (2007).
  35. K. Momma and F. Izumi, VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data, J. Appl. Crystallogr. 44, 1272 (2011).
  36. P. Procházka, J. Čechal, ProLEED studio: Software for modeling low-energy electron diffraction patterns, J. Appl. Crystallogr. 57, 187 (2024).
  37. J. V. Barth, H. Brune, G. Ertl, and R. J. Behm, Scanning tunneling microscopy observations on the reconstructed Au(111) surface: Atomic structure, long-range superstructure, rotational domains, and surface defects, Phys. Rev. B 42, 9307 (1990).
  38. P. Li and F. Ding, Origin of the herringbone reconstruction of Au(111) surface at the atomic scale, Sci. Adv. 8, eabq2900 (2022).
  39. L. Bignardi, D. Lizzit, H. Bana, E. Travaglia, P. Lacovig, C. E. Sanders, M. Dendzik, M. Michiardi, M. Bianchi, M. Ewert, L. Buß, J. Falta, J. I. Flege, A. Baraldi, R. Larciprete, P. Hofmann, and S. Lizzit, Growth and structure of singly oriented single-layer tungsten disulfide on Au(111), Phys. Rev. Mater. 3, 014003 (2019).
  40. F. Matsui, S. Makita, H. Matsuda, T. Ueba, T. Horigome, H. Yamane, K. Tanaka, S. Kera, and N. Kosugi, Bulk and surface band dispersion mapping of the Au(111) surface by acceptance-cone tunable, e-J. Surf. Sci. Nanotechnol. 18, 18 (2020).
  41. H. Bana, E. Travaglia, L. Bignardi, P. Lacovig, C. E. Sanders, M. Dendzik, M. Michiardi, M. Bianchi, D. Lizzit, F. Presel, D. De Angelis, N. Apostol, P. Kumar Das, J. Fujii, I. Vobornik, R. Larciprete, A. Baraldi, P. Hofmann, and S. Lizzit, Epitaxial growth of single-orientation high-quality MoS2 monolayers, 2D Mater. 5, 035012 (2018).
  42. J. H. Jeon, K. H. Chung, H. Kim, and S.-J. Kahng, Corner hole adatom stacking fault structure of Bi on Au(111), Surf. Sci. 603, 145 (2009).
  43. N. Kawakami, C.-L. Lin, K. Kawahara, M. Kawai, R. Arafune, and N. Takagi, Structural evolution of Bi thin films on Au(111) revealed by scanning tunneling microscopy, Phys. Rev. B 96, 205402 (2017).
  44. B. He, G. Tian, J. Gou, B. Liu, K. Shen, Q. Tian, Z. Yu, F. Song, H. Xie, Y. Gao, Y. Lu, K. Wu, L. Chen, and H. Huang, Structural and electronic properties of atomically thin bismuth on Au(111), Surf. Sci. 679, 147 (2019).
  45. P. Vezzoni Vicente, T. Weiss, D. Meier, W. Zhao, B. S. Tömekçe, M. G. Cuxart, B. P. Klein, D. A. Duncan, T.-L. Lee, A. C. Papageorgiou, M. Muntwiler, A. P. Seitsonen, W. Auwärter, P. Feulner, J. V. Barth, and F. Allegretti, Holistic structural understanding of epitaxially-grown Bi/Au(111) moiré superstructures, Phys. Rev. Mater. 8, 104001 (2024).
  46. J. F. Moulder, W. F. Stickle, P. E. Sobol, and K. D. Bomben, Handbook of X-ray Photoelectron Spectroscopy: A Reference Book of Standard Spectra for Identification and Interpretation of XPS Data (Perkin-Elmer Corporation, Minnesota, 1995).
  47. Y. Lu, W. Xu, M. Zeng, G. Yao, L. Shen, M. Yang, Z. Luo, F. Pan, K. Wu, T. Das, P. He, J. Jiang, J. Martin, Y. P. Feng, H. Lin, and X.-s. Wang, Topological properties determined by atomic buckling in self-assembled ultrathin Bi(110), Nano Lett. 15, 80 (2015).
  48. H. Hirayama, Nucleation and growth of ultrathin Bi films, Adv. Phys.: X 6, 1845975, (2020).
  49. See Supplemental Material at http://link.aps.org/supplemental/10.1103/pzgn-gqz5 for additional information regarding the oxidation of Bi on Au(111) at pressure and temperature conditions distinct from those presented in this manuscript, and for fitting details of XPS spectra.
  50. 1L=10−6Torrs.
  51. W. E. Morgan, W. J. Stec, and J. R. Van Wazer, Inner-orbital binding-energy shifts of antimony and bismuth compounds, Inorg. Chem. 12, 953 (1973).
  52. A. Berti, M. D'Alessio, M. Bianchi, L. Bignardi, P. Lacovig, C. Sanders, S. Lizzit, P. Hofmann, A. Marrazzo, and A. Baraldi, Unraveling oxygen-driven surface segregation dynamics in platinum-gold alloys, Appl. Surf. Sci. 670, 160577 (2024).
  53. T. Saito, R. Ahmad, F. Kishimoto, T. Higashi, M. Katayama, L. Cavallo, and K. Takanabe, Identification of distinctive structural and optoelectronic properties of Bi2O3 polymorphs controlled by tantalum addition, J. Mater. Chem. C 10, 17925 (2022).
  54. M. Jiang, Y. Ding, H. Zhang, J. Ren, J. Li, C. Wan, Y. Hong, M. Qi, B. Mei, L. Deng, Y. Wu, T. Han, H. Zhang, and J. Liu, A novel ultrathin single-crystalline Bi2O3 nanosheet wrapped by reduced graphene oxide with improved electron transfer for Li storage, J. Solid State Electrochem. 24, 2487 (2020).
  55. M. Bianchi, D. Lizzit, A. Turoldo, E. Tosi, P. Lacovig, M. Schied, D. Curcio, C. E. Sanders, S. Lizzit, and P. Hofmann, Interfacial oxidation unlocks degenerate n-doping in monolayer MoS2, Nano Lett. (2026).
  56. J. B. Pendry, Reliability factors for LEED calculations, J. Phys. C 13, 937 (1980).
  57. J. Hu, X. Wang, A. C. Åsland, and J. W. Wells, Unconventional broadening of Rashba spin splitting in a Au2Sb surface alloy with periodic structural defects, npj Quantum Mater. 10, 5 (2025).
  58. M. Milun, P. Pervan, and D. P. Woodruff, Quantum well structures in thin metal films: Simple model physics in reality? Rep. Prog. Phys. 65, 99 (2002).
  59. A. Varykhalov, F. Freyse, I. Aguilera, M. Battiato, M. Krivenkov, D. Marchenko, G. Bihlmayer, S. Blügel, O. Rader, and J. Sánchez-Barriga, Effective mass enhancement and ultrafast electron dynamics of Au(111) surface state coupled to a quantum well, Phys. Rev. Res. 2, 013343 (2020).
  60. F. J. Palomares, M. Serrano, A. Ruiz, F. Soria, K. Horn, and M. Alonso, ARPES study of the surface states from Au/Ag(111): Evolution with coverage and photon energy, Surf. Sci. 513, 283 (2002).

Outline

Information

Phys. Rev. Materials 10, 104008– Published 21 October, 2026
  • Received 3 July 2026
  • Accepted 1 October 2026
Crossmark - Check for updates button
Creative Commons Logo

Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.

Published by the American Physical Society

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation