‘Mixed dimensional’ 2D/3D van der Waals heterostructures, where 3D metallic nanostructures are integrated with suspended two-dimensional (2D) van der Waals materials, show unique functionalities including light-matter coupling, charge transfer, and enhanced catalytic activity. To enable such integration, an understanding of how structure and defects at the 2D/3D interface affect heterostructure properties is required. Moreover, 2D/3D heterostructures display fluctuations of opto-electronic properties in nanometer spatial range; and it is advantageous to probe position-dependent properties at the same spatial scales. In this seminar, I will share work exploring the local properties of the 2D/3D interface using a combination of atomic resolution scanning transmission electron microscopy (STEM), in situ ultra-high vacuum (UHV) TEM, and monochromated high-energy resolution electron energy-loss spectroscopy (EELS). We demonstrate epitaxial, single-crystalline metallic nanoisland growth of technologically relevant metals (Au, Ti and Nb) with with ultra-low defect density interfaces and facetted morphologies on several thin suspended 2D materials. We then explore the key parameters of 2D/3D growth, including the role of temperature, defects, moiré, surface chemistry, and thermodynamic equilibrium shapes. Lastly, we fabricate more complex heterostructure stacks with defect densities controlled by the compliance of the 2D material substrate. Through fundamental understanding of the structure-property-performance relationship, we suggest that future electronic, magnetic, and optical nanodevices will utilize versatile fabrication of 2D/3D heterostructures with well-characterized interfaces and morphologies.

Heterostructures consisting of vertically stacked two-dimensional (2D) materials have recently gained large attention due to their highly controllable electronic properties. Particularly, mechanically stacked multilayered systems offer exceptional control over a stacking sequence or interlayer twist angles. On the other hand, epitaxially grown 2D materials express unprecedented quality and stability over wafer-scale lengths. In both cases controlling the interlayer coupling can generate novel electronic and topological phases and its effective implementation is commonly done with a transverse electric field. However, phases generated by high displacement fields are elusive.

Here, we introduce an exceptionally large displacement field by structural modification of a model system: AB-stacked epitaxial bilayer graphene (BLG) on a SiC(0001) surface. We show that upon intercalation of gadolinium with two specific interlayer locations, electronic states in the top two graphene layers exhibit a significant difference in the on-site potential energy (~1 eV), which effectively breaks the interlayer coupling between them. As a result, for energies close to the corresponding Dirac points, the BLG system behaves like two electronically isolated single graphene layers. We prove this fact by a comprehensive multi-technique methodology based on low-temperature scanning tunneling microscopy/spectroscopy (STM/S) and angle-resolved photoelectron spectroscopy, which are corroborated by density functional theory, tight binding, surface diffraction and multiprobe STM transport. The work presents charge transfer from intercalated metal atoms as a promising approach for the synthesis of 2D graphene heterostructures with electronic phases generated by giant displacement fields.

References

[1]M. Kolmer, B. Schrunk, M. Hupalo, J. Hall, S. Chen, J. Zhang, C.-Z. Wang, A. Kaminski, M.C. Tringides, "Highly Asymmetric Graphene Layer Doping and Band Structure Manipulation in Rare Earth–Graphene Heterostructure by Targeted Bonding of the Intercalated Gadolinium", J. Phys. Chem. C. 126, 6863 (2022). https://doi.org/10.1021/acs.jpcc.2c01332.

[2]M. Kolmer, W. Ko, J. Hall, S. Chen, J. Zhang, H. Zhao, L. Ke, C.-Z. Wang, A.-P. Li, M.C. Tringides, "Breaking of Inversion Symmetry and Interlayer Electronic Coupling in Bilayer Graphene Heterostructure by Structural Implementation of High Electric Displacement Fields", J. Phys. Chem. Lett. 13, 11571 (2022). https://doi.org/10.1021/acs.jpclett.2c02407.