In this work, the atomic layer deposition (ALD) of an ultra-thin AlN film on the surface of monolayer EG grown on-axis 4H-SiC(0001) substrates has been investigated as a function of the number of ALD cycles. The formation of a homogeneous film with a 10 nm thickness and crystalline wurtzite structure was obtained after 320 cycles, as demonstrated by atomic force microscopy (AFM) mapping, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction. Raman mapping revealed a significant reduction in the native compressive strain of as-grown EG (ε ≈ -0.36%) with increasing ALD cycles, down to a value of -0.16% after full coverage. Finally, Kelvin Probe Force Microscopy (KPFM) surface potential mapping allowed the evaluation of energy band alignment of the AlN/EG heterojunction, with a conduction band offset of ~2.6 eV between the crystalline AlN film and the underlying EG. Such a large offset confirms AlN as a promising gate dielectric for EG-based devices.