UC Riverside

Graphene, as a famous Van der Waals material, has attracted intensive attention from research group and industry all over the world after 2004, while hexagonal boron nitride (h-BN), as an excellent two-dimensional (2D) dielectric layer, has been studied intensively mainly for its compatibility with graphene and other 2D materials. To realize the technological potential of 2D system, it is essential to synthesize large-area, high-quality 2D thin films through a scalable and controllable method in order to investigate novel phenomenon in fundamental physics and promising device applications. In this thesis, the growth of graphene, h-BN and their vertical and lateral heterostructures by molecular beam epitaxy (MBE) is mainly discussed. In addition, the growth mechanism, fundamental physics and possible applications are also studied.

In-situ epitaxial growth of graphene/h-BN heterostructures on cobalt (Co) film substrate was achieved by using plasma-assisted MBE in Chapter 2. We demonstrated a solution for direct fabricating graphene/h-BN vertical stacking structures. Various characterizations, such as Raman spectroscopy, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM), were carried out to confirm and evaluate the heterostructures. Wafer-scale heterostructures consisting of single-layer/bilayer graphene and multilayer h-BN were achieved. The mismatch angle between graphene and h-BN is below 1º. Chapter 3 studied the growth of graphene/h-BN heterostructures on Co foil substrate by plasma-assisted MBE. It is found that the coverage of h-BN layers on the epitaxial thin graphite layer is growth-time dependent. Large-area, uniform-quality h-BN film was successfully deposited on thin graphite layer. Based on the as-grown h-BN (5-6 nm)/G (26-27 nm) heterostructure, without using any transferring process, we fabricated capacitor devices with Co(foil)/G/h-BN/Co(contact) configuration to evaluate the dielectric properties of h-BN film. The measured breakdown electric field showed a high value of 2.5-3.2 MV/cm. Both I-V and C-V characteristics indicated that the epitaxial h-BN film is of good insulating nature.

Following with the lateral growth of graphene on in situ epitaxial h-BN flakes by plasma-assisted MBE is discussed in Chapter 4. Single-crystal h-BN domains were grown on Co film substrates at a substrate temperature of 850~900 oC using plasma-assisted MBE. Three-point star shape h-BN domains were observed by SEM, and confirmed by Raman and XPS. The h-BN on Co template was used for in situ growth of multilayer graphene, leading to an h-BN/graphene heterostructure. Carbon atoms preferentially nucleate on Co substrate and edges of h-BN and then grow laterally to form continuous graphene. Further introduction of carbon atoms results in layer-by-layer growth of graphene on graphene and lateral growth of graphene on h-BN until it may cover entire h-BN flakes.

The final part (Chapter 5) is related to the growth of large-area and multi-layer hexagonal boron nitride film on polished Co foils by plasma-assisted MBE. The coverage of h-BN layers can be readily controlled by growth time under appropriate growth conditions. A large-area, multi-layer h-BN film is confirmed by various characterizations. Dielectric property of as-grown h-BN film is evaluated by characterization of Co(foil)/h-BN/Co(contact) capacitor devices. Breakdown electric field is in the range of 3.0-3.3 MV/cm, which indicates that the epitaxial h-BN film has good insulating characteristics. In addition, the effect of substrate morphology on h-BN growth is discussed regarding different domain density, lateral size, and thickness of the h-BN films grown on unpolished and polished Co foils.