Electronic structures of Ga203(Gd203) gate dielectric on n-Ge(001) as grown and after CF4 plasma treatment: A synchrotron-radiation photoemission study

The interfacial electronic structure of Ga2O3(Gd2O3) (GGO) on n-Ge(001) is determined using high-resolution synchrotron radiation photoemission. The excitation photon energy was specifically chosen to observe the interaction at the GGO/Ge interface (hv = 463 eV) as well as the possible diffusion of Ge up to the GGO surface (hν = 120 eV). The Ge 3d core-level spectra were fit to extract the contributing components. Photoemission measurements were done for four samples, as deposited, N2annealed, CF4plasmatreated, and the combined CF4plasmatreated and N2annealed. No surface passivation was employed prior to the dielectric deposition. SRPES data clearly showed that the elemental Ge in the as-deposited sample was effectively kept in the wafer. Prevention of Gediffusion was attributed to formation of a thin germanatelike oxide layer. Other than contributions from bulk Ge, an analytical fit to the Ge 3d cores gives two components that are associated with bonding to Gd2O3 (GdGe*) and to Ga2O3 (GaGe*), which had chemical shifts of 3.46 and 1.80 eV, respectively. We hereby label them as MGe*, where M stands for either Gd2O3 or Ga2O3. Area occupations of the GdGe* and GaGe* oxides are ∼87% and ∼10%, respectively. A CF4plasma treatment disturbs the film itself as well as the interfacial oxide so that the GGO surface begins to show both elemental Ge and Ga. Nevertheless, the follow-up N2annealing produces the GdGe*+GaGe* layer with characteristics similar to those at the GGO/Ge interface. Both GdGe* and GaGe* states in the CN-treated sample show simultaneously a smaller chemical shift by 0.31 ± 0.02 eV than those in the as-deposited sample. The treatments also induce upward band bending on both the high κ and the Ge sides, which causes the valence band offset at the GGO/Ge interface to be 2.95 eV.