Combining
graphene and the insulating hexagonal boron nitride (h-BN) into two-dimensional
heterostructures is promising for novel, atomically thin electronic
nanodevices. A heteroepitaxial growth, in which these materials are
grown on top of each other, will be crucial for their scalable device
integration. However, during this so-called van der Waals epitaxy,
not only the atomically thin substrate itself must be considered but
also the influences from the supporting substrate below it. Here,
we report not only a substantial difference between the formation
of h-BN on single- (SLG) and on bi-layer epitaxial graphene (BLG)
on SiC, but also vice versa, that the van der Waals epitaxy of h-BN
at growth temperatures well below 1000 °C affects the varying
number of graphene layers differently. Our results clearly demonstrate
that the additional graphene layer in BLG enhances the distance to
the corrugated, carbon-rich interface of the supporting SiC substrate
and thereby diminishes its influence on the van der Waals epitaxy,
leading to a homogeneous formation of a smooth, atomically thin heterostructure,
which will be required for a scalable device integration of 2D heterostructures.