journal article·2023-04-03Open access

Covalent bonded bilayers from germanene and stanene with topological giant capacitance effects

Binglei Zhang, Davide Grassano, Olivia Pulci, Yang Liu, Yi Luo, Adriano Mosca Conte, Fedor Vasilievich Kusmartsev, Anna Kusmartseva

Abstract

Abstract The discovery of twisted bilayer graphene with tunable superconductivity has diverted great focus at the world of twisted van der Waals heterostructures. Here we propose a paradigm for bilayer materials, where covalent bonding replaces the van der Waals interaction between the layers. On the example of germanene-stanene bilayer, we show that such systems demonstrate fascinating topological properties and manifest giant capacitance effects of the order of C = 102μ F as well as dipole-like charge densities of q = 1 − 2 × 10−4μ C cm−2, showing promise for 2D ferroelectricity. The observed unique behaviour is closely linked to transverse strain-induced buckling deformations at the bilayer/substrate interface. In alternative GeSn bilayer structures with low twist angles the strain distortions trigger rich topological defect physics. We propose that the GeSn bilayer topology may be switched locally by a substrate-strain-induced electric fields. We demonstrate an approach to fabricate covalent bilayer materials, holding vast possibilities to transform applications technologies across solar, energy and optoelectronic sectors.
Source: crossref · Quality: baseline

Research context

OpenAlex topics: Graphene research and applications · Topological Materials and Phenomena · 2D Materials and Applications

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

References (83)

Show source-provided references
1. Geim, A. K. Graphene: status and prospects. Science 324, 1530–1534 (2009).10.1126/science.1158877 ↗
2. Geim, A. K. & Novoselov, K. S. The rise of graphene. Nat. Mater. 6, 183–191 (2007).10.1038/nmat1849 ↗
3. Li, L. et al. Black phosphorus field-effect transistors. Nat. Nanotechnol. 9, 372 (2014).10.1038/nnano.2014.35 ↗
4. Koenig, S. P., Doganov, R. A., Schmidt, H., Castro Neto, A. H. & Oezyilmaz, B. Electric field effect in ultrathin black phosphorus. Appl. Phys. Lett. 104, 103106 (2014).10.1063/1.4868132 ↗
5. Liu, H. et al. Phosphorene: an unexplored 2d semiconductor with a high hole mobility. ACS Nano 8, 4033–4041 (2014).10.1021/nn501226z ↗
6. Vogt, P. et al. Silicene: compelling experimental evidence for graphenelike two-dimensional silicon. Phys. Rev. Lett. 108, 155501 (2012).10.1103/PhysRevLett.108.155501 ↗
7. Bechstedt, F., Matthes, L., Gori, P. & Pulci, O. In: Vogt, P. & Guy L. L. (eds). Silicene: Prediction, Synthesis, Application 73–98 (Springer, 2018).10.1007/978-3-319-99964-7_4 ↗
8. Das, S., Robinson, J. A., Dubey, M., Terrones, H. & Terrones, M. Beyond graphene: progress in novel two-dimensional materials and van der Waals solids. Annu. Rev. Mater. Sci. 45, 1–27 (2015).10.1146/annurev-matsci-070214-021034 ↗
9. Manzeli, S., Ovchinnikov, D., Pasquier, D., Yazyev, O. V. & Kis, A. 2D transition metal dichalcogenides. Nat. Rev. Mater. 2, 1–15 (2017).10.1038/natrevmats.2017.33 ↗
10. Bonaccorso, F., Sun, Z., Hasan, T. A. & Ferrari, A. C. Graphene photonics and optoelectronics. Nat. Photon. 4, 611 (2010).10.1038/nphoton.2010.186 ↗
11. Tao, L. et al. Silicene field-effect transistors operating at room temperature. Nat. Nanotechnol. 10, 227–231 (2015).10.1038/nnano.2014.325 ↗
12. Kusmartsev, F.V. & Tsvelik, A.M. Semimetallic properties of a heterojunction. JETP Lett. 42, 257–260 (1985).
13. Bechstedt, F., Gori, P. & Pulci, O. Beyond graphene: clean, hydrogenated and halogenated silicene, germanene, stanene, and plumbene. Prog. Surf. Sci. 96, 100615 (2021).10.1016/j.progsurf.2021.100615 ↗
14. Gong, Y. et al. Vertical and in-plane heterostructures from Ws2/MoS2 monolayers. Nat. Mater. 13, 1135–1142 (2014).10.1038/nmat4091 ↗
15. Prete, M. S., Mosca Conte, A., Gori, P., Bechstedt, F. & Pulci, O. Tunable electronic properties of two-dimensional nitrides for light harvesting heterostructures. Appl. Phys. Lett. 110, 012103 (2017).10.1063/1.4973753 ↗
16. Cao, Y. et al. Unconventional superconductivity in magic-angle graphene superlattices. Nature 556, 43 (2018).10.1038/nature26160 ↗
17. Cao, Y. et al. Correlated insulator behaviour at half-filling in magic-angle graphene superlattices. Nature 556, 80 (2018).10.1038/nature26154 ↗
18. Yankowitz, M. et al. Tuning superconductivity in twisted bilayer graphene. Science 363, 1059–1064 (2019).10.1126/science.aav1910 ↗
19. Shen, C. et al. Correlated states in twisted double bilayer graphene. Nat. Phys. 16, 520–525 (2020).10.1038/s41567-020-0825-9 ↗
20. Moriyama, S. et al. Observation of superconductivity in bilayer graphene/hexagonal boron nitride superlattices. Preprint at https://arxiv.org/abs/1901.09356 (2019)
21. Zheliuk, O. et al. Josephson coupled ising pairing induced in suspended MoS2 bilayers by double-side ionic gating. Nat. Nanotechnol. 14, 1123–1128 (2019).10.1038/s41565-019-0564-1 ↗
22. Zhang, X. et al. Transition metal dichalcogenides bilayer single crystals by reverse-flow chemical vapor epitaxy. Nat. Commun. 10, 598 (2019).10.1038/s41467-019-08468-8 ↗
23. Arcudia, J., Emrem, B., Heine, T. & Merino, G. The structural and electronic richness of buckled honeycomb asp bilayers. Nanoscale 14, 10136–10142 (2022).10.1039/D1NR08433J ↗
24. Arcudia, J., Kempt, R., Eduardo Cifuentes-Quintal, M., Heine, T. & Merino, G. Blue phosphorene bilayer is a two-dimensional metal and an unambiguous classification scheme for buckled hexagonal bilayers. Phys. Rev. Lett. 125, 196401 (2020).10.1103/PhysRevLett.125.196401 ↗
25. Huang, C. et al. Quantum phase transition in germanene and stanene bilayer: from normal metal to topological insulator. J. Phys. Chem. Lett. 7, 1919–1924 (2016).10.1021/acs.jpclett.6b00651 ↗
26. Matthes, L., Pulci, O. & Bechstedt, F. Massive dirac quasiparticles in the optical absorbance of graphene, silicene, germanene, and tinene. J. Condens. Matter Phys. 25, 395305 (2013).10.1088/0953-8984/25/39/395305 ↗
27. Matthes, L., Pulci, O. & Bechstedt, F. Optical properties of two-dimensional honeycomb crystals graphene, silicene, germanene, and tinene from first principles. New J. Phys. 16, 105007 (2014).10.1088/1367-2630/16/10/105007 ↗
28. Zhu, F.-F. et al. Epitaxial growth of two-dimensional stanene. Nat. Mater. 14, 1020–1025 (2015).10.1038/nmat4384 ↗
29. Hartman, T. & Sofer, Z. Beyond graphene: chemistry of group 14 graphene analogues: silicene, germanene, and stanene. ACS nano 13, 8566–8576 (2019).10.1021/acsnano.9b04466 ↗
30. Qihang, K. N. et al. Tunable bandgap in silicene and germanene. Sci. Rep. 12, 113–118 (2012).
31. Yang, J., Goh, K. E. J., Yu, Z. G., Wong, R. E. & Zhang, Y.-W. A first-principles study on strain engineering of monolayer stanene for enhanced catalysis of CO2 reduction. Chemosphere 268, 129317 (2021).10.1016/j.chemosphere.2020.129317 ↗
32. Thouless, D. J., Kohmoto, M., Nightingale, M. P. & den Nijs, M. D. Quantized Hall conductance in a two-dimensional periodic potential. Phys. Rev. Lett. 49, 405 (1982).10.1103/PhysRevLett.49.405 ↗
33. Kane, C. L. & Mele, E. J. Quantum spin hall effect in graphene. Phys. Rev. Lett. 95, 226801 (2005).10.1103/PhysRevLett.95.226801 ↗
34. Kane, C. L. & Mele, E. J. Z2 topological order and the quantum spin Hall effect. Phys. Rev. Lett. 95, 146802 (2005).10.1103/PhysRevLett.95.146802 ↗
35. Liu, C.-C., Jiang, H. & Yao, Y. Low-energy effective hamiltonian involving spin-orbit coupling in silicene and two-dimensional germanium and tin. Phys. Rev. B 84, 195430 (2011).10.1103/PhysRevB.84.195430 ↗
36. Xu, Y. et al. Large-gap quantum spin hall insulators in tin films. Phys. Rev. Lett. 111, 136804 (2013).10.1103/PhysRevLett.111.136804 ↗
37. Zhang, G. & Zhang, Y.-W. Exploring ag(111) substrate for epitaxially growing monolayer stanene: a first-principles study. Sci. Rep. 6, 2910 (2016).
38. Yuhara, J. et al. Large area planar stanene epitaxially grown on ag(1 1 1). 2D Mater. 5, 025002 (2018).10.1088/2053-1583/aa9ea0 ↗
39. O’Hare, A., Kusmartsev, F. V. & Kugel, K. I. A stable “flat" form of two-dimensional crystals: could graphene, silicene, germanene be minigap semiconductors? Nano Lett. 12, 1045–1052 (2012).10.1021/nl204283q ↗
40. Grassano, D. et al. Detection of topological phase transitions through entropy measurements: the case of germanene. Phys. Rev. B 97, 205442 (2018).10.1103/PhysRevB.97.205442 ↗
41. Houssa, M. et al. Topological to trivial insulating phase transition in stanene. Nano Res. 9, 774–778 (2016).10.1007/s12274-015-0956-y ↗
42. Tang, P. et al. Stable two-dimensional dumbbell stanene: a quantum spin hall insulator. Phys. Rev. B 90, 121408 (2014).10.1103/PhysRevB.90.121408 ↗
43. Ezawa, M. Monolayer topological insulators: Silicene, germanene, and stanene. J. Phys. Soc. Japan 84, 121003 (2015).10.7566/JPSJ.84.121003 ↗
44. Ma, Y., Kou, L., Du, A. & Heine, T. Group 14 element-basd non-centrosymmetric quantum spin hall insulators with large bulk gap. Nano Res. 8, 3412–3420 (2015).10.1007/s12274-015-0842-7 ↗
45. Koda, D. S., Friedhelm, B., Marques, M. & Teles, L. K. Coincidence lattices and interlayer twist in van der Waals heterostructures: application of the coincidence lattice method on hBN/MoSe2hBN/MoSe2 heterobilayer systems. J. Electron. Mater. 46, 3910–3916 (2017).10.1007/s11664-016-5037-9 ↗
46. Ezawa, M. A topological insulator and helical zero mode in silicene under an inhomogeneous electric field. New J. Phys. 14, 033003 (2012).10.1088/1367-2630/14/3/033003 ↗
47. Volkov, B. A. & Pankratov, O. A. Two-dimensional massless electrons in an inverted contact. JETP 42, 178 (1985).
48. Grazianetti, C. et al. Optical conductivity of two-dimensional silicon: evidence of Dirac electrodynamics. Nano Lett. 18, 7124–7132 (2018).10.1021/acs.nanolett.8b03169 ↗
49. Gori, P., Kupchak, I., Bechstedt, F., Grassano, D. & Pulci, O. Honeycomb silicon on alumina: massless dirac fermions in silicene on substrate. Phys. Rev. B 100, 245413 (2019).10.1103/PhysRevB.100.245413 ↗
50. Zhang, B., Liu, Y., Luo, Y., Kusmartsev, F. V. & Kusmartseva, A. Perfect impedance matching with meta-surfaces made of ultra-thin metal films: a phenomenological approach to the ideal THz sensors. Mater. 13, 5417 (2020).10.3390/ma13235417 ↗
51. Arguilla, M. Q., Jiang, S., Chitara, B. & Goldberger, J. E. Synthesis and stability of two-dimensional Ge/Sn graphane alloys. Chem. Mater. 26, 6941–6946 (2014).10.1021/cm502755q ↗
52. Gassenq, A. et al. Raman spectral shift versus strain and composition in GeSn layers with 6%–15% sn content. Appl. Phys. Lett. 110, 112101 (2017).10.1063/1.4978512 ↗
53. Prucnal, S. et al. Strain and band-gap engineering in Ge-Sn alloys via p doping. Phys. Rev. Appl. 10, 064055 (2018).10.1103/PhysRevApplied.10.064055 ↗
54. Zidi, N., Chaouchi, A., D’Astorg, S., Rguiti, M. & Courtois, C. Impedance spectroscopy study on lead-free piezoelectric ceramics. Bull. Mater. Sci. 38, 731–737 (2015).10.1007/s12034-015-0888-x ↗
55. Behera, B., Nayak, P. & Choudhary, R. N. P. Impedance spectroscopy study of NaBa2V5O15 ceramic. J. Alloys Compd. 436, 226–232 (2007).10.1016/j.jallcom.2006.07.028 ↗
56. Sinclair, D. C., Adams, T. B., Morrison, F. D. & West, A. R. CaCu2Ti4O12: one-step internal barrier layer capacitor. Appl. Phys. Lett. 80, 2153–2155 (2002).10.1063/1.1463211 ↗
57. You, Y.-H. et al. Impedance spectroscopy characterization of resistance switching NiO thin films prepared through atomic layer deposition. Appl. Phys. Lett. 89, 222105 (2006).10.1063/1.2392991 ↗
58. Kovaleva, N. N. et al. Bismuth layer properties in the ultrathin Bi–FeNi multilayer films probed by spectroscopic ellipsometry. Appl. Phys. Lett. 119, 183101 (2021).10.1063/5.0069691 ↗
59. Kusmartsev, F. V. Application of catastrophe theory to molecules and solitons. Phys. Rep. 183, 1–35 (1989).10.1016/0370-1573(89)90152-X ↗
60. Miao, M. S. et al. Polarization-driven topological insulator transition in a GaN/InN/GaN quantum well. Phys. Rev. Lett. 109, 186803 (2012).10.1103/PhysRevLett.109.186803 ↗
61. Novoselov, K. S. et al. Electric field effect in atomically thin carbon films. Science 306, 666–669 (2004).10.1126/science.1102896 ↗
62. Trabelsi, A. B. G. et al. Charged nano-domes and bubbles in epitaxial graphene. Nanotechnology 25, 165704 (2014).10.1088/0957-4484/25/16/165704 ↗
63. Trabelsi, A. B. G. et al. The emergence of quantum capacitance in epitaxial graphene. J. Mater. Chem. C . 4, 5829–5838 (2016).10.1039/C6TC02048H ↗
64. Trabelsi, A. B. G. et al. Morphological imperfections of epitaxial graphene: from a hindrance to the generation of new photo-responses in the visible domain. Nanoscale 9, 11463–11474 (2017).10.1039/C6NR08999B ↗
65. Trabelsi, A. B. G., Ouerghi, A., Kusmartseva, O. E., Kusmartsev, F. V. & Oueslati, M. Raman spectroscopy of four epitaxial graphene layers: macro-island grown on 4H-SiC 0001¯ substrate and an associated strain distribution. Thin Solid Films 539, 377–383 (2013).10.1016/j.tsf.2013.05.093 ↗
66. Ben Gouider Trabelsi, A. et al. Raman spectroscopy imaging of exceptional electronic properties in epitaxial graphene grown on sic. Nanomaterials 10, 2234 (2020).10.3390/nano10112234 ↗
67. Bkakri, R., Kusmartseva, O. E., Kusmartsev, F. V., Song, M. O. & Bouazizi, A. Degree of phase separation effects on the charge transfer properties of P3HT: graphene nanocomposites. J. Lumin. 161, 264–270 (2015).10.1016/j.jlumin.2015.01.014 ↗
68. Bkakri, R. et al. Effects of the graphene content on the conversion efficiency of P3HT: graphene based organic solar cells. J. Phys. Chem. Solids 85, 206–211 (2015).10.1016/j.jpcs.2015.05.020 ↗
69. Tan, S. et al. Interface-induced superconductivity and strain-dependent spin density waves in FeSe/SrTiO3 thin films. Nat. Mater. 12, 634–640 (2013).10.1038/nmat3654 ↗
70. Liu, D. et al. Electronic origin of high-temperature superconductivity in single-layer FeSe superconductor. Nat. Commun. 3, 1–6 (2012).10.1038/ncomms1946 ↗
71. He, S. et al. Phase diagram and electronic indication of high-temperature superconductivity at 65 K in single-layer FeSe films. Nat. Mater. 12, 605–610 (2013).10.1038/nmat3648 ↗
72. Mermin, N. D. & Wagner, H. Absence of ferromagnetism or antiferromagnetism in one-or two-dimensional isotropic Heisenberg models. Phys. Rev. Lett. 17, 1133 (1966).10.1103/PhysRevLett.17.1133 ↗
73. Liu, Y. et al. Snake states and their symmetries in graphene. Phys. Rev. B 92, 235438 (2015).10.1103/PhysRevB.92.235438 ↗
74. Kopnin, N. B., Heikkilä, T. T. & Volovik, G. E. High-temperature surface superconductivity in topological flat-band systems. Phys. Rev. B 83, 220503 (2011).10.1103/PhysRevB.83.220503 ↗
75. Giannozzi, P. et al. Quantum espresso: a modular and open-source software project for quantum simulations of materials. J. Phys.: Condens. matter 21, 395502 (2009).
76. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865 (1996).10.1103/PhysRevLett.77.3865 ↗
77. Dal Corso, A. & Mosca Conte, A. Spin-orbit coupling with ultrasoft pseudopotentials: application to Au and Pt. Phys. Rev. B 71, 115106 (2015).10.1103/PhysRevB.71.115106 ↗
78. Mosca Conte, A., Fabris, S. & Baroni, S. Properties of Pt-supported Co nanomagnets from relativistic density functional theory calculations. Phys. Rev. B 78, 014416 (2008).10.1103/PhysRevB.78.014416 ↗
79. Fu, L. & Kane, C. L. Time reversal polarization and a Z2 adiabatic spin pump. Phys. Rev. B 74, 195312 (2006).10.1103/PhysRevB.74.195312 ↗
80. Gresch, D. et al. Z2Pack: numerical implementation of hybrid Wannier centers for identifying topological materials. Phys. Rev. B 95, 075146 (2017).10.1103/PhysRevB.95.075146 ↗
81. Soluyanov, A. A. & Vanderbilt, D. Computing topological invariants without inversion symmetry. Phys. Rev. B 83, 235401 (2011).10.1103/PhysRevB.83.235401 ↗
82. Djawad, Y. A., Kiely, J., Wraith, P. & Luxton, R. Lock-in amplifier as a sensitive instrument for biomedical measurement: analysis and implementation. Indones. J. Electr. Eng. Comput. Sci. 12, 7214–7222 (2014).
83. Fafilek, G. & Breiter, M. W. Instrumentation for AC four-probe measurements of large impedances. J. Electroanal. Chem. 430, 269–278 (1997).10.1016/S0022-0728(97)00263-5 ↗