van der Waals epitaxial growth of atomically thin Bi₂Se₃ and thickness-dependent topological phase transition.

Two-dimensional (2D) atomic-layered heterostructures stacked by van der Waals interactions recently introduced new research fields, which revealed novel phenomena and provided promising applications for electronic, optical, and optoelectronic devices. In this study, we report the van der Waals epitaxial growth of high-quality atomically thin Bi2Se3 on single crystalline hexagonal boron nitride (h-BN) by chemical vapor deposition. Although the in-plane lattice mismatch between Bi2Se3 and h-BN is approximately 65%, our transmission electron microscopy analysis revealed that Bi2Se3 single crystals epitaxially grew on h-BN with two commensurate states; that is, the (1̅21̅0) plane of Bi2Se3 was preferably parallel to the (1̅100) or (1̅21̅0) plane of h-BN. In the case of the Bi2Se3 (2̅110) ∥ h-BN (11̅00) state, the Moiré pattern wavelength in the Bi2Se3/h-BN superlattice can reach 5.47 nm. These naturally formed thin crystals facilitated the direct assembly of h-BN/Bi2Se3/h-BN sandwiched heterostructures without introducing any impurity at the interfaces for electronic property characterization. Our quantum capacitance (QC) measurements showed a compelling phenomenon of thickness-dependent topological phase transition, which was attributed to the coupling effects of two surface states from Dirac Fermions at/or above six quintuple layers (QLs) to gapped Dirac Fermions below six QLs. Moreover, in ultrathin Bi2Se3 (e.g., 3 QLs), we observed the midgap states induced by intrinsic defects at cryogenic temperatures. Our results demonstrated that QC measurements based on h-BN/Bi2Se3/h-BN sandwiched structures provided rich information regarding the density of states of Bi2Se3, such as quantum well states and Landau quantization. Our approach in fabricating h-BN/Bi2Se3/h-BN sandwiched device structures through the combination of bottom-up growth and top-down dry transferring techniques can be extended to other two-dimensional layered heterostructures.