Oxide removal from Ge(100) surfaces treated by HCl and HF solutions with different concentrations are systematically studied by synchrotron radiation photoelectron spectroscopy (SR-PES). SR-PES results show that clean surfaces without any oxide can be obtained after wet chemical cleaning followed by vacuum annealing with a residual carbon contamination of less than 0.02 monolayer. HF etching leads to a hydrogen terminated Ge surface whose hydrogen coverage is a function of the HF concentration. In contrast, HCl etching yields a chlorine terminated surface. Possible etching mechanisms are discussed. Surface roughness after HF and HCl treatments is also investigated by AFM, which shows that HF treatment leaves a rougher surface than HCl. a) sysun@stanford.edu corresponding author

The initial stage of the oxidation of Cl and Br terminated Ge(111) surfaces is studied using photoelectron spectroscopy. The authors perform controlled experiments to differentiate the effects of different factors in oxidation, and find that water vapor and oxygen play different roles. Water vapor effectively replaces the halogen termination layers with the hydroxyl group, but does not oxidize the surfaces further. In contrast, little oxidation is observed for Cl and Br terminated surfaces with dry oxygen alone. However, with the help of water vapor, oxygen oxidizes the surface by breaking the Ge–Ge back bonds instead of changing the termination layer.

The authors report on the chemical bonding structure of the HfO2∕Si (001) stack after the SiO2 interfacial layer (IL) is partially removed by a reactive titanium metal overlayer. Using synchrotron photoelectron spectroscopy, they found that ultrathin SiO2-like IL ∼6.5Å thick, which is significantly less than the initial SiO2 IL thickness of ∼15Å, exists at the HfO2∕Si interface with an overlying Ti electrode. The dissociated Si from SiO2 IL is believed to go onto Si substrate where it regrows epitaxially. The interfacial trap density of the Ti-electrode sample was extracted to be ∼1.6×1011eV−1cm−2 near the midgap of Si, which was comparable to that of the control sample with W electrode.

We report the chemical bonding structure and valence band alignment at the HfO2∕Ge(001) interface by systematically probing various core level spectra as well as valence band spectra using soft x rays at the Stanford Synchrotron Radiation Laboratory. We investigated the chemical bonding changes as a function of depth through the dielectric stack by taking a series of synchrotron photoemission spectra as we etched through the HfO2 film using a dilute hydrogen fluoride solution. We found that a very nonstoichiometric GeOx layer exists at the HfO2∕Ge interface. The valence band spectra near the Fermi level in each different film structure were carefully analyzed, and as a result, the valence band offset between Ge and GeOx was determined to be ΔEv (Ge–GeOx)=2.2±0.15eV, and that between Ge and HfO2, ΔEv (Ge–HfO2)=2.7±0.15eV.

An ultrathin zirconia gate dielectric had been successfully incorporated into germanium metal-oxide-semiconductor (MOS) devices demonstrating very high permittivity gate stacks with no apparent interfacial layer. In this study, synchrotron radiation photoemission spectroscopy has been applied on the same gate stack to identify and quantify the presenc e of any interfacial germanium sub-oxide layer. By taking progressive core-level spectra during the layer-by-layer removal of the zirconia film, an oxidized germanium layer with sub-monolayer thickness was found possibly arising from an interfacial Zr-O-Ge bonding configuration. In addition, the offsets in the valence band spectra were also monitored and the energy band diagram of the zirconia-germanium heterostructure was constructed. Compared to high-κ gate stacks on Si, the thinner interfacial layer and larger conduction band offset in high-κ gate stacks on Ge suggest better scalability towards an ultimately higher MOS gate capacitance.