Dong-Ick Lee

Surface Termination and Roughness of Ge(100) Cleaned by HF and HCl Solutions

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 atomic force microscopy which shows that HF treatment leaves a rougher surface than HCl.

Chemical states and electronic structure of a HfO2∕Ge(001) interface

We report the chemical bonding structure and valence band alignment at the HfO{sub 2}/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 HfO{sub 2} film using a dilute HF-solution. We found that a very non-stoichiometric GeO{sub x} layer exists at the HfO{sub 2}/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 GeO{sub x} was determined to be {Delta}E{sub v} (Ge-GeO{sub x}) = 2.2 {+-} 0.15 eV, and that between Ge and HfO{sub 2}, {Delta}E{sub v} (Ge-HfO{sub 2}) = 2.7 {+-} 0.15 eV.

Chemical states and electrical properties of a high-k metal oxide/silicon interface with oxygen-gettering titanium-metal-overlayer

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 ∼6.5A thick, which is significantly less than the initial SiO2 IL thickness of ∼15A, 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.

Zirconia-germanium interface photoemission spectroscopy using synchrotron radiation

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 presence of any interfacial germanium suboxide layer. By taking progressive core-level spectra during the layer-by-layer removal of the zirconia film, an oxidized germanium layer with submonolayer 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.

Nitrogen doping and thermal stability in HfSiOxNy studied by photoemission and x-ray absorption spectroscopy

We have investigated nitrogen-doping effects into HfSiO{sub x} films on Si and their thermal stability using synchrotron-radiation photoemission and x-ray absorption spectroscopy. N 1s core-level photoemission and N K-edge absorption spectra have revealed that chemical-bonding states of N-Si{sub 3-x}O{sub x} and interstitial N{sub 2}-gas-like features are clearly observed in as-grown HfSiO{sub x}N{sub y} film and they decrease upon ultrahigh vacuum (UHV) annealing due to a thermal instability, which can be related to the device performance. Annealing-temperature dependence in Hf 4f and Si 2p photoemission spectra suggests that the Hf-silicidation temperature is effectively increased by nitrogen doping into the HfSiO{sub x} although the interfacial SiO{sub 2} layer is selectively reduced. No change in valence-band spectra upon UHV annealing suggests that crystallization of the HfSiO{sub x}N{sub y} films is also hindered by nitrogen doping into the HfSiO{sub x}.

Formation of cesium peroxide and cesium superoxide on InP photocathode activated by cesium and oxygen

Activation of p-type III-V semiconductors with cesium and oxygen has been widely used to prepare negative electron affinity (NEA) photocathodes. However, the nature of the chemical species on the surface after the activation is not well understood. In this study, InP NEA photocathodes activated with cesium and oxygen are studied using synchrotron radiation photoelectron spectroscopy, also called photoemission. Based on the O 1s core level as well as the valence band spectra, Cs peroxide and Cs superoxide are identified on the InP surface. Transformation from Cs peroxide to Cs superoxide is observed after the activation, and is probably the major reason for the decay of the quantum yield of the photocathode. The oxidation of the InP substrate is also observed with elapse of time, adding to the decay of the quantum yield.

Roles of oxygen and water vapor in the oxidation of halogen terminated Ge(111) surfaces

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.

Angular Dependence of the Photoelectron Energy Distribution of InP(100) and GaAs(100) Negative Electron Affinity Photocathodes

Energy distribution of the photoelectrons from InP(100) photocathodes are investigated with a photon energy range from 0.62eV to 2.76eV. When the photon energy is less than 1.8eV, only electrons emitted from the Gamma valley are observed in the energy distribution curves (EDC). At higher photon energies, electrons from the L valley are observed. The angular dependence of the electron energy distributions of InP and GaAs photocathodes are studied and compared. The electrons emitted from the L valley have a larger angular spread than the ones from the Gamma valley due to the larger effective mass of the L valley minimum.

Study on mechanism of crystallization in HfO2 films on Si substrates by in-depth profile analysis using photoemission spectroscopy

We have investigated the effect of HfO2 layer thickness on crystallization in thin HfO2 films using photoemission spectroscopy and x-ray absorption spectroscopy (XAS). O K-edge XAS spectra depending on annealing temperature indicate that crystallization in thin HfO2 films is suppressed upon annealing for thin HfO2 film, which in turn has a beneficial effect on the performance of devices. The annealing-temperature dependence of the depth profile of HfO2 films suggests that diffusion of Si atoms into the HfO2 layer plays only a minor role in the suppression of crystallization, indicating that HfO2 films can restrain a decrease in dielectric constant.

The distribution of oxide species in the Cs/O activation layer on InP(100) negative electron affinity photocathodes

The atomic arrangement of Cs oxides in the activation layer of an InP photocathode is investigated using angle dependent photoemission spectroscopy. Two distinct peaks in the O1s core level and in valence band spectra have led to the discovery of two molecular oxygen species incorporated in the thin activation layer: Cs peroxide (Cs2O2) and Cs superoxide (CsO2). The different angular dependences of these oxides observed in the photoemission spectra are caused by different vertical locations of the oxygen molecules in each Cs oxide in the activation layer. The thickness of the activation layer, which is about 7A, suggests lateral distribution of Cs peroxide and Cs superoxide. The quantum efficiency of InP photocathodes in our ultra high vacuum system decreases with time due to the chemical transformation of the Cs oxides and subsequent substrate oxidation, as deduced from an observation of the peak evolution in the photoemission spectra, and supported by the thermodynamic stability of Cs superoxide as comp...