The crystalline AN thin film was fabricated on Si(100) substrates by plasma-enhanced atomic layer deposition. Its growth rate was illustrated by spectroscopic ellipsometer. And the surface morphology, crystal structure and composition were characterized by atomic force microscopy, X-ray diffraction, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy. Results show that the lowest temperature for deposition of the crystalline AN thin film is 200 C, and the film coverage on the substrate surface is continuous and homogeneous. The film prepared with a homogeneous concentration distribution is polycrystalline with a hexagonal wurtzite structure. High resolution Al-2p and N-1s spectra confirm the presence of AN with peaks located at 74.1 eV and 397.0 eV, respectively.