Plasma enhanced atomic layer deposition (PEALD) TaCN deposited on HfO2 was studied by X-ray photoelectron spectroscopy (XPS) to understand the reactions taking place at the interface and connect them with C-V electrical characteristics of MOS devices. Moreover, angular resolved XPS (AR-XPS) was used for composition depth profiling of TaCN/HfO2/SiO2/Si stacks. Clear oxidation of the metal electrode through Ta-O bonding formation and migration of N in the dielectric with Hf-N are shown. These modifications of chemical bonding give an insight on the electrical results. Low equivalent oxide thicknesses (EOT), as low as 0.89 nm and current leakage improvement by more than 5 decades, are observed for deposition with low plasma power and can be related to HfN content in HfO2 layer. The increase of plasma power used for TaCN deposition results in densification of the layer and promotes the creation of TaC in TaCN material. However H-2 plasma has an impact on HfO2 with a reduction and scattering of the measured current leak gain. TaCN/HfO2 interface is also impacted with further creation of TaOx, leading to an increase of EOT when plasma power is increased. Based on these findings, reaction mechanisms with the corresponding Gibbs free energy are proposed. (C) 2014 Elsevier B. V. All rights reserved.