The formation of thin AlN films on NiAl(001) has been studied by means of high resolution electron energy loss spectroscopy (HREELS), low‐energy electron diffraction (LEED), and Auger electron spectroscopy. The AlN films were grown by the adsorption of NH3on NiAl(001) atT=80 K and subsequent thermal decomposition at elevated temperatures. After annealing toT=1250 K, a distinct LEED pattern appears which exhibits pseudo‐twelvefold symmetry. This indicates the formation of two hexagonal domains of AlN which are rotated by 90° with respect to each other. HREEL spectra of the ordered AlN film show a Fuchs–Kliewer phonon mode at 865 cm−1in good agreement with theoretical spectra calculated on the base of the dielectric theory. The electronic energy gap of the thin AlN films is determined to beEg&bartil;6.1 eV. ©1995 American Institute of Physics.