You can use spectroscopic ellipsometry which gives you thickness with high accuracy. But for some materials, this measure is difficult or even impossible.
Also cross-sectional view by Scanning Electron Microscopy (SEM) can be used.
Abdulhadi.... XPS (X-ray Photoelectron Spectroscopy) as a surface analytical technique has been used successfully in characterization of a variety of thin films (Non-destructive depth profiling and Destructive depth profiling with Imaging )