- Open Access
Host-Atom-Driven Transformation of a Honeycomb Oxide into a Dodecagonal Quasicrystal
Phys. Rev. Lett. 136, 156201 – Published 17 April, 2026
DOI: https://doi.org/10.1103/ws7j-tvty
Abstract
Dodecagonal oxide quasicrystals (OQCs) have so far been limited to a few elemental systems, with no general formation mechanism established. Here, we demonstrate a versatile approach to OQC formation via a host-atom-induced transformation of a metal-oxide honeycomb network. Adsorption of Ba, Sr, or Eu onto the honeycomb layer triggers its reorganization into a dodecagonal tiling, as revealed by low-energy electron diffraction and scanning tunneling microscopy. Full conversion occurs when 73% of the honeycomb rings are occupied. Kelvin probe and UV photoelectron spectroscopy show a linear decrease in work function with increasing host coverage, followed by a sharp increase upon quasicrystal formation due to reduced host dipoles. This transformation mechanism enables the fabrication of structurally precise OQCs, including a new Eu-Ti-O phase that extends the field to lanthanide quasicrystals, forming a 2D grid of localized magnetic moments. The method might offer a more general route to explore lattice-matched substrates for epitaxial growth and may be adapted to other 2D honeycomb materials such as graphene, hexagonal ice, and silica, paving the way for engineered aperiodic systems beyond transition metal oxides.
Physics Subject Headings (PhySH)
Article Text
References (34)
- D. Shechtman, I. Blech, D. Gratias, and J. W. Cahn, Metallic phase with long-range orientational order and no translational symmetry, Phys. Rev. Lett. 53, 1951 (1984).
- X. Zeng, B. Glettner, U. Baumeister, B. Chen, G. Ungar, F. Liu, and C. Tschierske, A columnar liquid quasicrystal with a honeycomb structure that consists of triangular, square and trapezoidal cells, Nat. Chem. 15, 625 (2023).
- C. Xiao, N. Fujita, K. Miyasaka, Y. Sakamoto, and O. Terasaki, Dodecagonal tiling in mesoporous silica, Nature (London) 487, 349 (2012).
- A. Plati, R. Maire, E. Fayen, F. Boulogne, F. Restagno, F. Smallenburg, and G. Foffi, Quasi-crystalline order in vibrating granular matter, Nat. Phys. 20, 465 (2024).
- A. Jagannathan, B. Douçot, A. Szallas, and S. Wessel, Geometric fluctuations in a two-dimensional quantum antiferromagnet, Phys. Rev. B 85, 094434 (2012).
- A. Szallas, A. Jagannathan, and S. Wessel, Phason-disordered two-dimensional quantum antiferromagnets, Phys. Rev. B 79, 172406 (2009).
- M. De Boissieu, Phonons, phasons and atomic dynamics in quasicrystals, Chem. Soc. Rev. 41, 6778 (2012).
- R. Tamura, A. Ishikawa, S. Suzuki, T. Kotajima, Y. Tanaka, T. Seki, N. Shibata, T. Yamada, T. Fujii, C.-W. Wang, M. Avdeev, K. Nawa, D. Okuyama, and T. J. Sato, Experimental observation of long-range magnetic order in icosahedral quasicrystals, J. Am. Chem. Soc. 143, 19938 (2021).
- S. Förster, K. Meinel, R. Hammer, M. Trautmann, and W. Widdra, Quasicrystalline structure formation in a classical crystalline thin-film system, Nature (London) 502, 215 (2013).
- S. Schenk, O. Krahn, E. Cockayne, H. Meyerheim, M. De Boissieu, S. Förster, and W. Widdra, 2D honeycomb transformation into dodecagonal quasicrystals driven by electrostatic forces, Nat. Commun. 13, 7542 (2022).
- E. Cockayne, M. Mihalkovič, and C. L. Henley, Structure of periodic crystals and quasicrystals in ultrathin films of Ba-Ti-O, Phys. Rev. B 93, 020101(R) (2016).
- N. Niizeki and H. Mitani, Two-dimensional dodecagonal quasilattices, J. Phys. A 20, L405 (1987).
- F. Gähler, Proceedings of the ILL/CODEST Workshop, (World Scientific, Singapore, 1988).
- S. Schenk, E. M. Zollner, O. Krahn, B. Schreck, R. Hammer, S. Förster, and W. Widdra, Full real-space analysis of a dodecagonal quasicrystal, Acta Crystallogr. Sect. A 75, 307 (2019).
- A. Stone and D. Wales, Theoretical studies of icosahedral C60 and some related species, Chem. Phys. Lett. 128, 501 (1986).
- U. Müller, Anorganische Strukturchemie (Vieweg+Teubner, Wiesbaden, 2008).
- C. Wu, M. R. Castell, J. Goniakowski, and C. Noguera, Stoichiometry engineering of ternary oxide ultrathin films: on Au(111), Phys. Rev. B 91, 155424 (2015).
- T. T. Dorini, F. Brix, C. Chatelier, A. Kokalj, and E. Gaudry, Two-dimensional oxide quasicrystal approximants with tunable electronic and magnetic properties, Nanoscale 13, 10771 (2021).
- F. Sedona, G. A. Rizzi, S. Agnoli, F. X. Llabrés i Xamena, A. Papageorgiou, D. Ostermann, M. Sambi, P. Finetti, K. Schierbaum, and G. Granozzi, Ultrathin films on Pt(111): A LEED, XPS, and STM investigation, J. Phys. Chem. B 109, 24411 (2005).
- M. Farstad, D. Ragazzon, H. Grönbeck, M. Strømsheim, C. Stavrakas, J. Gustafson, A. Sandell, and A. Borg, TiOx thin films grown on Pd(100) and Pd(111) by chemical vapor deposition, Surf. Sci. 649, 80 (2016).
- S. Schenk, S. Förster, K. Meinel, R. Hammer, B. Leibundgut, M. Paleschke, J. Pantzer, C. Dresler, F. O. Schumann, and W. Widdra, Observation of a dodecagonal oxide quasicrystal and its complex approximant in the system, J. Phys. Condens. Matter 29, 134002 (2017).
- F. Silly and M. R. Castell, Encapsulated Pd nanocrystals supported by nanoline-structured , J. Phys. Chem. B 109, 12316 (2005).
- M. Imperor-Clerc, P. Kalugin, S. Schenk, W. Widdra, and S. Förster, Higher-dimensional geometrical approach for the characterization of two-dimensional square-triangle-rhombus tilings, Phys. Rev. B 110, 144106 (2024).
- A. W. Robertson, C. S. Allen, Y. A. Wu, K. He, J. Olivier, J. Neethling, A. I. Kirkland, and J. H. Warner, Spatial control of defect creation in graphene at the nanoscale, Nat. Commun. 3, 1144 (2012).
- S. Kurasch, J. Kotakoski, O. Lehtinen, V. Skákalová, J. Smet, C. E. Krill, A. V. Krasheninnikov, and U. Kaiser, Atom-by-atom observation of grain boundary migration in graphene, Nano Lett. 12, 3168 (2012).
- R. Ma, D. Cao, C. Zhu, Y. Tian, J. Peng, J. Guo, J. Chen, X.-Z. Li, J. S. Francisco, X. C. Zeng, L.-M. Xu, E.-G. Wang, and Y. Jiang, Atomic imaging of the edge structure and growth of a two-dimensional hexagonal ice, Nature (London) 577, 60 (2020).
- J. Hong, Y. Tian, T. Liang, X. Liu, Y. Song, D. Guan, Z. Yan, J. Guo, B. Tang, D. Cao, J. Guo, J. Chen, D. Pan, L.-M. Xu, E.-G. Wang, and Y. Jiang, Imaging surface structure and premelting of ice Ih with atomic resolution, Nature (London) 63, 375 (2024).
- H. Sahin, J. Sivek, S. Li, B. Partoens, and F. M. Peeters, Stone-Wales defects in silicene: Formation, stability, and reactivity of defect sites, Phys. Rev. B 88, 045434 (2013).
- J.-Q. Zhong and H.-J. Freund, Two-dimensional ultrathin silica films, Chem. Rev. 122, 11172 (2022).
- P. I. Wemhoff, C. Noguera, J. Goniakowski, and N. Nilius, Structure and stoichiometry self-organization in a mixed vanadium–iron oxide honeycomb film on Ru(0001), J. Phys. Chem. C 126, 19947 (2022).
- M. Haller, J. Hewelt, V. Y. M. R. Chirala, L. V. Tran, A. Bhide, M. Wegner, S. Förster, and W. Widdra, Workfunction data and LEED images corresponding to Fig. 2, Zenodo, 10.5281/zenodo.16286368 (2026).
- M. Haller, J. Hewelt, V. Y. M. R. Chirala, L. V. Tran, A. Bhide, M. Wegner, S. Förster, and W. Widdra, STM and LEED data corresponding to Fig. 3, Zenodo, 10.5281/zenodo.16287446 (2026).
- M. Haller, J. Hewelt, V. Y. M. R. Chirala, L. V. Tran, A. Bhide, M. Wegner, S. Förster, and W. Widdra, XPS data corresponding to Fig. 4, Zenodo, 10.5281/zenodo.16358426 (2026).
- M. Haller, J. Hewelt, V. Y. M. R. Chirala, L. V. Tran, A. Bhide, M. Wegner, S. Förster, and W. Widdra, STM and LEED data corresponding to Fig. 5, Zenodo, 10.5281/zenodo.16358669 (2026).