The hydride vapor phase epitaxy (HVPE) of {0 0 0 1} AlN films on {1 1 1} Si substrates covered with epitaxial {1 1 1} cubic SiC (3C-SiC intermediate layers) was carried out. 3C-SiC intermediate layers are essential to obtAlN high-quality AlN films on Si substrates, because specular AlN films are obtAlNed with 3C-SiC intermediate layers, whereas rough AlN films are obtAlNed without 3C-SiC intermediate layers. We determined the polarities of AlN films and the underlying 3C-SiC intermediate layers by convergent beam electron diffraction (CBED) using transmission electron microscopy. For the first time, the polarities of the AlN films and the 3C-SiC intermediate layers were determined as At and Si polarities, respectively. The AlN films were hardly etched by aqueous KOH solution, thereby indicating Al polarity. This supports the results obtAlNed by CBED. The result is also consistent with electrostatic arguments. An interfacial structure was proposed. The 3C-SiC intermediate layers are promising for the HVPE of AlN films on Si substrates. (C) 2007 Elsevier B.V. All rights reserved.