Ta based films are important building blocks for modern microelectronic applications. To meet the requirements of miniaturization, atomic layer deposition appears to be an alternative technology in comparison to PVD and CVD. In the present paper investigations of a thermal TBTDET ALD process will be presented with emphasis to the first ALD reaction cycles on native silicon oxide and HF etched silicon surfaces. The investigations show that the substrate chemistry is a crucial parameter for the film growth and appears to be a key to control the ALD deposition. The investigations were done by XPS without any vacuum break between the deposition and the surface analysis.