Hexagonal boron nitride
(h-BN), together with other members of
the van der Waals crystal family, has been studied for over a decade,
both in terms of fundamental and applied research. Up to now, the
spectrum of h-BN-based devices has broadened significantly, and systems
containing the h-BN/III-V junctions have gained substantial interest
as building blocks in, inter alia, light emitters, photodetectors,
or transistor structures. Therefore, the understanding of electronic
phenomena at the h-BN/III-V interfaces becomes a question of high
importance regarding device engineering. In this study, we present
the investigation of electronic phenomena at the h-BN/GaN interface
by means of contactless electroreflectance (CER) spectroscopy. This
nondestructive method enables precise determination of the Fermi level
position at the h-BN/GaN interface and the investigation of carrier
transport across the interface. CER results showed that h-BN induces
an enlargement of the surface barrier height at the GaN surface. Such
an effect translates to Fermi level pinning deeper inside the GaN
band gap. As an explanation, we propose a mechanism based on electron
transfer from GaN surface states to the native acceptor states in
h-BN. We reinforced our findings by thorough structural characterization
and demonstration of the h-BN/GaN Schottky diode. The surface barriers
obtained from CER (0.60 ± 0.09 eV for GaN and 0.91 ± 0.12
eV for h-BN/GaN) and electrical measurements are consistent within
the experimental accuracy, proving that CER is an excellent tool for
interfacial studies of 2D/III–V hybrids.