Epitaxial AlN thin films have been grown on 6H–SiC substrates by ultra-high-vacuum (UHV) ion-assisted reactive dc magnetron sputtering. The low-energy ion-assisted growth (Ei=17–27 eV) results in an increasing surface mobility, promoting domain-boundary annihilation and epitaxial growth. Domain widths increased from 42 to 135 nm and strained-layer epitaxy was observed in this energy range. For Ei≫52 eV, an amorphous interfacial layer of AlN was formed on the SiC, which inhibited epitaxial growth. Using UHV condition and very pure nitrogen sputtering gas yielded reduced impurity levels in the films (O: 3.5×1018 cm-3). Analysis techniques used in this study are in situ reflection high-energy electron diffraction, secondary-ion-mass spectroscopy, atomic-force microscopy, x-ray diffraction, and cross-section high-resolution electron microscopy. © 2000 American Institute of Physics.