A computational elucidation of the structure-property relationships in graphene-organic 2D crystal heterostructures
Source abstract
Abstract
Abstract The integration of graphene with porous organic 2D crystals (O2DCs) represents an emerging class of van der Waals heterostructures in which the periodic pore structure of the O2DC can impose a well-defined structural superlattice on graphene. In this work, we investigate the structure-property relationships in graphene-O2DC (G-O2DC) heterostructures and the role of substrate interactions through computational studies. We demonstrate how O2DCs impose well-defined corrugation on graphene. The corrugation amplitude and superlattice periodicity are directly governed by O2DC pore dimensions and substrate, with larger pores and substrate interactions significantly enhancing the corrugation effect. Across all investigated configurations, the linear Dirac dispersion of graphene is preserved with no band flattening, while corrugation-induced band gaps of up to ~12 meV emerge at the Dirac point. Although these gap openings are below k B T at room temperature, they are of comparable magnitude to the remote-band gaps of magic-angle twisted bilayer graphene (TBG) and become significant at cryogenic temperatures. The underlying mechanism is corrugation-induced sublattice symmetry breaking together with a weak electrostatic perturbation from the O2DC layer, qualitatively distinct from the interlayer-hybridization mechanism responsible for the flat-band regime of magic-angle TBG. These findings establish G-O2DC heterostructures as a controllable platform for structural superlattice engineering of graphene and quantify the magnitude of the resulting electronic modification across a systematic series of pore geometries, laying the foundation for future studies exploiting chemical functionalization or through-pore interactions to enhance the electronic response.
Source: crossref · Quality: baseline
Research context
OpenAlex topics: 2D Materials and Applications · Covalent Organic Framework Applications · Graphene research and applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (43)
Show source-provided references
1. Novoselov, K. S., Mishchenko, A., Carvalho, A. & Castro Neto, A. H. 2D materials and van der Waals heterostructures. Science 353, aac9439 (2016).10.1126/science.aac9439 ↗
2. Balandin, A. A. et al. Superior thermal conductivity of single-layer graphene. Nano Lett. 8, 902–907 (2008).10.1021/nl0731872 ↗
3. Bonaccorso, F., Sun, Z., Hasan, T. & Ferrari, A. C. Graphene photonics and optoelectronics. Nat. Photonics 4, 611–622 (2010).10.1038/nphoton.2010.186 ↗
4. Castro Neto, A. H., Guinea, F., Peres, N. M. R., Novoselov, K. S. & Geim, A. K. The electronic properties of graphene. Rev. Mod. Phys. 81, 109–162 (2009).10.1103/RevModPhys.81.109 ↗
5. Lee, C., Wei, X., Kysar, J. W. & Hone, J. Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321, 385–388 (2008).10.1126/science.1157996 ↗
6. Park, J.-S. & Choi, H. J. Band-gap opening in graphene: a reverse-engineering approach. Phys. Rev. B 92, 045402 (2015).10.1103/PhysRevB.92.045402 ↗
7. Cao, Y. et al. Unconventional superconductivity in magic-angle graphene superlattices. Nature 556, 43–50 (2018).10.1038/nature26160 ↗
8. Cao, Y. et al. Correlated insulator behaviour at half-filling in magic-angle graphene superlattices. Nature 556, 80–84, https://doi.org/10.1038/nature26154 (2018).10.1038/nature26154 ↗
9. Bistritzer, R. & MacDonald, A. H. Moiré bands in twisted double-layer graphene. Proc. Natl. Acad. Sci. USA 108, 12233–12237 (2011).10.1073/pnas.1108174108 ↗
10. Falorsi, F. et al. Interlayer charge transfer in graphene–2D polyimide heterostructures. 2D Mater. 12, 025011 (2025).10.1088/2053-1583/adac6e ↗
11. Woods, C. R. et al. Commensurate–incommensurate transition in graphene on hexagonal boron nitride. Nat. Phys. 10, 451–456 (2014).10.1038/nphys2954 ↗
12. Kennes, D. M. et al. Moiré heterostructures as a condensed-matter quantum simulator. Nat. Phys. 17, 155–163 (2021).10.1038/s41567-020-01154-3 ↗
13. Zhang, Y. et al. Molecularly soldered covalent organic frameworks for ultrafast precision sieving. Sci. Adv. 7, eabe8706 (2021).10.1126/sciadv.abe8706 ↗
14. Mu, Z. et al. Covalent organic frameworks with record pore apertures. J. Am. Chem. Soc. 144, 5145–5154 (2022).10.1021/jacs.2c00584 ↗
15. Colson, J. W. & Dichtel, W. R. Rationally synthesized two-dimensional polymers. Nat. Chem. 5, 453–465 (2013).10.1038/nchem.1628 ↗
16. Payamyar, P., King, B. T., Öttinger, H. C. & Schlüter, A. D. Two-dimensional polymers: concepts and perspectives. Chem. Commun. 52, 18–34 (2016).10.1039/C5CC07381B ↗
17. Arnold, F. M., Ghasemifard, A., Kuc, A., Kunstmann, J. & Heine, T. Relaxation effects in twisted bilayer molybdenum disulfide: structure, stability, and electronic properties. 2D Mater. 10, 045010 (2023).10.1088/2053-1583/aceb75 ↗
18. Waller, P. J. et al. Chemical conversion of linkages in covalent organic frameworks. J. Am. Chem. Soc. 138, 15519–15522 (2016).10.1021/jacs.6b08377 ↗
19. Sahabudeen, H. et al. Highly crystalline and semiconducting imine-based two-dimensional polymers enabled by interfacial synthesis. Angew. Chem. Int. Ed. 59, 6028–6036 (2020).10.1002/anie.201915217 ↗
20. Carr, S. et al. Relaxation and domain formation in incommensurate two-dimensional heterostructures. Phys. Rev. B 98, 224102 (2018).10.1103/PhysRevB.98.224102 ↗
21. Lu, X. et al. Superconductors, orbital magnets and correlated states in magic-angle bilayer graphene. Nature 574, 653–657 (2019).10.1038/s41586-019-1695-0 ↗
22. Côté, A. P. et al. Porous, crystalline, covalent organic frameworks. Science 310, 1166–1170 (2005).10.1126/science.1120411 ↗
23. romankempt/hetbuilder v. Zenodo Release (v0.5.1-alpha) (Zenodo, 2021).
24. Koda, D. S., Bechstedt, F., Marques, M. & Teles, L. K. Coincidence lattices of 2D crystals: heterostructure predictions and applications. J. Phys. Chem. C. 120, 10895–10908 (2016).10.1021/acs.jpcc.6b01496 ↗
25. Sahabudeen, H. et al. Wafer-sized multifunctional polyimine-based two-dimensional conjugated polymers with high mechanical stiffness. Nat. Commun. 7, 13461 (2016).10.1038/ncomms13461 ↗
26. Löffler, D. et al. Growth and structure of crystalline silica sheet on Ru(0001). Phys. Rev. Lett. 105, 146104 (2010).10.1103/PhysRevLett.105.146104 ↗
27. Ishigami, M., Chen, J. H., Cullen, W. G., Fuhrer, M. S. & Williams, E. D. Atomic structure of graphene on SiO2. Nano Lett. 7, 1643–1648 (2007).10.1021/nl070613a ↗
28. Telychko, M., Berger, J., Majzik, Z., Jelínek, P. & Švec, M. Graphene on SiC(0001) inspected by dynamic atomic force microscopy at room temperature. Beilstein J. Nanotechnol. 6, 901–906 (2015).10.3762/bjnano.6.93 ↗
29. Li, W., Brumme, T. & Heine, T. Relaxation effects in transition metal dichalcogenide bilayer heterostructures. npj 2D Mater. Appl. 8, 43 (2024).10.1038/s41699-024-00477-6 ↗
30. Porezag, D., Frauenheim, T., Köhler, T., Seifert, G. & Kaschner, R. Construction of tight-binding-like potentials on the basis of density-functional theory: application to carbon. Phys. Rev. B 51, 12947–12957 (1995).10.1103/PhysRevB.51.12947 ↗
31. Hourahine, B. et al. DFTB+, a software package for efficient approximate density functional theory based atomistic simulations. J. Chem. Phys.s 152 (2020)
32. AMS 2025.1, SCM (Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands).
33. Zhechkov, L., Heine, T., Patchkovskii, S., Seifert, G. & Duarte, H. A. An efficient a posteriori treatment for dispersion interaction in density-functional-based tight binding. J. Chem. Theory Comput. 1, 841–847 (2005).10.1021/ct050065y ↗
34. Elstner, M. et al. Self-consistent-charge density-functional tight-binding method for simulations of complex materials properties. Phys. Rev. B 58, 7260–7268 (1998).10.1103/PhysRevB.58.7260 ↗
35. Rappe, A. K., Casewit, C. J., Colwell, K. S., Goddard, W. A. III & Skiff, W. M. UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations. J. Am. Chem. Soc. 114, 10024–10035 (1992).10.1021/ja00051a040 ↗
36. Oliveira, A. F., Philipsen, P. & Heine, T. DFTB parameters for the periodic table, part 2: energies and energy gradients from hydrogen to calcium. J. Chem. Theory Comput. 11, 5209–5218 (2015).10.1021/acs.jctc.5b00702 ↗
37. Frenzel, J., Oliveira, A., Jardillier, N., Heine, T. & Seifert, G. Semi-relativistic, self-consistent charge Slater-Koster tables for density-functional based tight-binding (DFTB) for materials science simulations. Zeolites 2, 7 (2004).
38. Sakhraoui, T. Effect of vacancy defect and strain on the structural, electronic and magnetic properties of carbon nitride 2D monolayers by DFTB method. J. Phys. Condens. Matter 35, 324003 (2023).10.1088/1361-648X/acd293 ↗
39. Raptakis, A., Dianat, A., Croy, A. & Cuniberti, G. Predicting the bulk modulus of single-layer covalent organic frameworks with square-lattice topology from molecular building-block properties. Nanoscale 13, 1077–1085 (2021).10.1039/D0NR07666J ↗
40. Klontzas, E., Tylianakis, E., Varshney, V., Roy, A. K. & Froudakis, G. E. Organically interconnected graphene flakes: A flexible 3-D material with tunable electronic bandgap. Sci. Rep. 9, 13676. https://doi.org/10.1038/s41598-019-50037-y (2019).10.1038/s41598-019-50037-y ↗
41. Blum, V. et al. Ab initio molecular simulations with numeric atom-centered orbitals. Computer Phys. Commun. 180, 2175–2196 (2009).10.1016/j.cpc.2009.06.022 ↗
42. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).10.1103/PhysRevLett.77.3865 ↗
43. Hjorth Larsen, A. et al. The atomic simulation environment—a Python library for working with atoms. J. Phys. Condens. Matter 29, 273002 (2017).10.1088/1361-648X/aa680e ↗