Abrupt, epitaxial silicide/silicon heterostructures may be grown so that, for the first time, the physics of electron transport across near perfect, single crystal, metal/semiconductor interfaces may be probed experimentally. Transport measurements through type-A and -B oriented NiSi2 layers on Si(111) substrates have revealed Schottky barrier heights differing by 140 meV. In this paper we present results of experiments designed to explore the possible role of bulk and interface defects in determining the potential barrier at these near ideal epitaxial metal-semiconductor contacts. We have found little evidence for the presence of defects and the Schottky barrier is insensitive to details of the microscopic interfacial perfection. By contrast we find that both the electrical quality and magnitude of the barrier occurring at the NiSi2 /Si(100) heterojunction are dependent upon details of the microscopic interfacial perfection.