On the origin of the 2.2-2.3 eV photoluminescence from chemically etched germanium

The photoluminescence (PL) at ∼2.2-2.3 eV from Ge-based nanocrystalline materials is described in the literature as nanocrystal size-independent. We have observed visible luminescence from two different types of stain-etched Ge samples, one prepared after Sendova-Vassileva et al. (Thin Solid Films 255 (1995) 282) in a solution of H₂O₂:HF at 50:1 volume ratio, and the other in a solution of HF:H₃PO₄:H₂O₂ at 34:17:1 volume ratio. Energy dispersive X-ray analysis (EDX), Raman and FTIR spectroscopy, and the near edge X-ray absorption structure (XANES), indicate that the chemically etched Ge layers of the former type of samples are composed of non-stoichometric Ge oxides, i.e. GeO_x (0<x<2), and free from any Ge nanoconstructions. It is also suggested from XANES that the latter type of chemically etched Ge samples comprise 8-9 nm nanocrystals of Ge, surface-covered with mainly oxygen. Photoluminescence occurred at ∼2.3 eV for all samples. The PL behavior of the latter type of chemically etched Ge on annealing in different chemical environments (air or H) allowed us to conclude that the PL from these materials, as well as that from those Ge-based nanocrystalline materials reported in the literature, is from GeO_xs.     

Oxidation of epitaxial Y(0 0 0 1) films

We have investigated the oxidation behavior of MBE grown epitaxial Y(0 0 0 1)/Nb(1 1 0) films on sapphire substrates at elevated temperatures under atmospheric conditions with a combination of experimental methods. At room temperature X-ray diffraction (XRD) reveals the formation of a 25 Å thick YO_xH_x layer at the surface, while simultaneously oxide growth proceeds along defect lines normal to the film plane, resulting in the formation of a single crystalline cubic Y₂O₃ (2 2 2) phase. Furthermore, nuclear resonance analysis (NRA) reveals that hydrogen penetrates into the sample and transforms the entire Y film into the hydride YH₂ phase. Additional annealing in air leads to further oxidation radially out from the already existing oxide channels. Finally material transport during oxidation results in the formation of conically shaped oxide precipitations at the surface above the oxide channels as observed by atomic force microscopy (AFM).     

Wet cleaning and surface characterization of Si1−xGex virtual substrates after a CMP step

New reactants such as ozone dissolved in ultra-pure water have been widely used the last few years instead of the original Radio Corporation of America (RCA) cleaning (which is a combination of the Standard Cleaning 1 (SC1) and the Standard Cleaning 2 (SC2)). In a first part of the study (Microelectron. Eng. 83 (2006) 1986), we had quantified the efficiency of a new cleaning sequence (that calls upon HF and H₂O/O₃ solutions) on polished Si_1−xGe_x virtual substrates (x = 0.2-0.5). We are discussing here the surface morphology and wetability together with the oxide thickness and structure typically obtained after this so-called “DDC-SiGe” wet cleaning. Flat surface morphologies are found after cleaning whatever the Ge content (from 20 to 50%). Typical root mean square roughness is around 0.4 nm. We have used X-ray Photoelectron Spectroscopy to determine the characteristics of the surface termination after this “DDC-SiGe” cleaning. An oxide mainly composed of SiO₂ is formed, with a low fraction of Ge sub-oxide and GeO₂. The distribution of chemical species is not that different from the one obtained after the use of a SC1 cleaning. However, the chemical oxide formed is slightly thicker. Such a HF/O₃ cleaning leads, when used on thick Ge layers grown on Si, to the formation of a really thin Ge sub-oxide. Our oxidation model assumes a competition in O₃ solutions between the oxidation rates of Si and Ge atoms (faster for Si) and the dissolution of the Ge oxide formed in solution. This mechanism, which implies the formation of a slightly porous oxide, is different from the one seeming to occur in SC1-based solutions. Indeed, the addition of surfactant in a SC1 solution modifies the oxidation rate compared to standard SC1 or O₃-based solutions, suggesting a diffusion of reactants towards the interface between the SiGe and the oxide in formation, assisted by the reactions of species within the cleaning solutions.     

Stability of hydrogen-terminated vicinal Si(1 1 1) surface under ambient atmosphere

In this paper a comparative study of different wet-chemical etching procedures of vicinal Si(1 1 1) surface passivation is presented. The stability against oxidation under ambient atmosphere was studied by X-ray photoelectron spectroscopy and atomic force microscopy. The best results were achieved by the buffered HF etching and the final smoothing of the surface by hot (72 °C) NH₄F. The procedures consisting of a large number of etching steps were unsatisfactory, since the probability of contamination during each step was increasing. The passivated surface was stable against oxidation for at least 3 h under ambient atmosphere.     

Structural, magnetic and electronic transport properties of MnxGe1−x/Ge(0 0 1) films grown by MBE at 350 °C

We report on the structural, magnetic and electronic transport properties of thin Mn_xGe_1−x films grown at 350 °C. Isolated Mn₅Ge₃ nanoclusters, about 100 nm in size, were formed at the top surface of the film, dominating the magnetic properties of the whole film. Electronic transport properties show Mn doping effect indicating the presence of substitutional Mn ions dispersed in the Ge host, contributing to the formation of a Mn_xGe_1−x diluted phase. Electrical behaviour indicates a saturation effect with the raise of the nominal Mn concentration in the film, above x ≅ 0.03.     

Electrical characteristics of hole resonant tunneling diodes with high Ge fraction (x > 0.4) Si/strained Si1−xGex/Si(1 0 0) heterostructure

Effectiveness of a Ge fraction modulated spacer in hole resonant tunneling diodes (RTDs) with Si/strained Si_1−xGe_x heterostructures epitaxially grown on Si(1 0 0) was investigated to improve the electrical characteristics at higher temperatures. Electrical characteristics measured for 30 RTDs, with the modulated spacer at higher Ge fraction (x = 0.48) on a single wafer, show that the deviation of the peak current and voltage at the resonant peak falls in ranges of ±25% and ±10%, respectively. For the RTDs, negative differential conductance (NDC) characteristics are obtained even at higher temperatures around 230 K than that for the RTDs with x = 0.42. The result indicates that the introduction of higher Ge fraction is effective for NDC in RTD at higher temperature.     

Surface reaction mechanism of atomic layer deposition of HfO2 on Ge(1 0 0)-2 × 1: A density functional theory study

Density functional theory is employed to investigate atomic layer deposition mechanism of HfO₂ on Ge(1 0 0)-2 × 1 surface. Both the HfCl₄ and H₂O half-reactions proceed through an analogous trapping-mediated mechanism. The neighboring hydroxyl in the reaction of HfCl₄ with two Ge-OH* sites has a major effect on the formation of HfCl₄ adsorbed complex. In addition, both the Ge and Si reaction pathways are qualitatively similar, however, adsorption of HfCl₄ is favorable on Ge than on Si surface hydroxyl sites. By comparison of the reactions of H₂O on the different surfaces, the differences in energy are negligible to alter the reaction mechanism.     

Hydrogen-induced metallization on Ge(1 1 1) c(2 × 8)

We have studied hydrogen adsorption on the Ge(1 1 1) c(2 × 8) surface using scanning tunneling microscopy (STM) and angle-resolved photoelectron spectroscopy (ARPES). We find that atomic hydrogen preferentially adsorbs on rest atom sites. The neighbouring adatoms appear higher in STM images, which clearly indicates a charge transfer from the rest atom states to the adatom states. The surface states near the Fermi-level have been followed by ARPES as function of H exposure. Initially, there is strong emission from the rest atom states but no emission at the Fermi-level which confirms the semiconducting character of the c(2 × 8) surface. With increasing H exposure a structure develops in the close vicinity of the Fermi-level. The energy position clearly indicates a metallic character of the H-adsorbed surface. Since the only change in the STM images is the increased brightness of the adatoms neighbouring a H-terminated rest atom, we identify the emission at the Fermi-level with these adatom states.     

Effect of Ge surface termination on oxidation behavior

Sulfur-termination was formed on the Ge(1 0 0) surface using (NH₄)₂S solution. Formation of Ge-S and the oxidation of the S-terminated Ge surface were monitored with multiple internal reflection Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. In the 0.5, 5, or 20% (NH₄)₂S solution, H-termination on the Ge(1 0 0) surface was substituted with S-termination in 1 min. When the S-terminated Ge(1 0 0) surface was exposed in air ambient, the oxidation was retarded for about 3600 min. The preservation time of the oxide layer up to one monolayer of S-terminated Ge(1 0 0) surface was about 120 times longer than for the H-terminated Ge(1 0 0) surface. However, the oxidation of S-terminated Ge(1 0 0) surface drastically increased after the threshold time. There was no significant difference in threshold time between S-terminations formed in 0.5, 5, and 20% (NH₄)₂S solutions. With the surface oxidation, desorption of S on the Ge surface was observed. The desorption behavior of sulfur on the S-terminated Ge(1 0 0) surface was independent of the concentration of the (NH₄)₂S solution that forms S-termination. Non-ideal S-termination on Ge surfaces may be related to drastic oxidation of the Ge surface. Finally, with the desulfurization on the S-terminated Ge(1 0 0) surface, oxide growth is accelerated.     

Scanning tunneling microscopy observation of initial growth of Sn and Ge1−xSnx layers on Ge(0 0 1) substrates

We have investigated the initial growth of Sn and Ge_1−xSn_x layers on Ge(0 0 1) surface by using scanning tunneling microscopy. After the growth of a 0.035 ML-thick Sn layer at room temperature, Sn clusters lining vertically to a dimer row was observed. In the case of the 0.035-0.018 ML-thick Sn growth at 250 °C, the characteristic surface reconstruction with the step-edge undulation like a comb was observed. In the growth of a Ge_0.994Sn_0.006 layer at 250 °C, the multilayer polynuclear growth with a lot of two-dimensional small domain was observed. These surface reconstructions should be accounted for by the large compressive stress induced in the surface layer due to the incorporation of Sn atoms.     

Modification of H-terminated Ge surface in hydrochloric acid

Various amounts of H-termination on a Ge surface were prepared by dipping a Ge wafer in differentially diluted hydrofluoric acid solutions for different periods of time. Formation of GeH_x in hydrofluoric acid and its disappearance in hydrochloric acid (HCl) were directly measured by using multiple internal reflection Fourier transform infrared spectroscopy (MIR FT-IR). Peak intensity of GeH_x vibration mode was increased with diluted hydrofluoric acid (DHF) treatment time and the concentration of HF solution. Therefore, it is suggested that microroughness of a Ge surface changes depending on the concentration of HF. Peak intensity of GeH_x vibration mode was reduced when the GeH_x surface was treated in HCl solution. With an increase in HCl treatment time, peak intensity of GeH_x vibration mode was reduced. Ge surfaces treated in a more diluted HF solution were barely modified, because it was thought to have fewer kink sites, dihydrides and trihydrides.     

Influence of Co doping content on its valence state in Zn1−xCoxO (0 ≤ x ≤ 0.15) thin films

Zn_1−xCo_xO (0 ≤ x ≤ 0.15) thin films grown on Si (1 0 0) substrates were prepared by a sol-gel technique. The effects of Co doped on the structural, optical properties and surface chemical valence states of the Zn_1−xCo_xO (0 ≤ x ≤ 0.15) films were investigated by X-ray diffraction (XRD), ultraviolet-visible spectrometer and X-ray photoelectron spectroscopy (XPS). XRD results show that the Zn_1−xCo_xO films retained a hexagonal crystal structure of ZnO with better c-axis preferred orientation compared to the undoped ZnO films. The optical absorption spectra suggest that the optical band-gap of the Zn_1−xCo_xO thin films varied from 3.26 to 2.79 eV with increasing Co content from x = 0 to x = 0.15. XPS studies show the possible oxidation states of Co in Zn_1−xCo_xO (0 ≤ x ≤ 0.05), Zn_0.90Co_0.10O and Zn_0.85Co_0.15O are CoO, Co₃O₄ and Co₂O₃, with an increase of Co content, respectively.     

Solid phase epitaxy of Ge films on CaF2/Si(1 1 1)

At room temperature deposited Ge films (thickness < 3 nm) homogeneously wet CaF₂/Si(1 1 1). The films are crystalline but exhibit granular structure. The grain size decreases with increasing film thickness. The quality of the homogeneous films is improved by annealing up to 200 °C. Ge films break up into islands if higher annealing temperatures are used as demonstrated combining spot profile analysis low energy electron diffraction (SPA-LEED) with auger electron spectroscopy (AES). Annealing up to 600 °C reduces the lateral size of the Ge islands while the surface fraction covered by Ge islands is constant. The CaF₂ film is decomposed if higher annealing temperatures are used. This effect is probably due to the formation of GeF_x complexes which desorb at these temperatures.     

Physico-chemical and electrical properties of rapid thermal oxides on Ge-rich SiGe heterolayers

Rapid thermal oxidation of high-Ge content (Ge-rich) Si_1−xGe_x (x = 0.85) layers in dry O₂ ambient has been investigated. High-resolution X-ray diffraction (HRXRD) and strain-sensitive two-dimensional reciprocal space mapping X-ray diffractometry (2D-RSM) are employed to investigate strain relaxation and composition of as-grown SiGe alloy layers. Characterizations of ultra thin oxides (∼6-8 nm) have been performed using Fourier transform infrared spectroscopy (FTIR) and high-resolution X-ray photoelectron spectroscopy (HRXPS). Formation of mixed oxide i.e., (SiO₂ + GeO₂) and pile-up of Ge at the oxide/Si_1−xGe_x interface have been observed. Enhancement in Ge segregation and reduction of oxide thickness with increasing oxidation temperature are reported. Interface properties and leakage current behavior of the rapid thermal oxides have been studied by capacitance-voltage (C-V) and current-voltage (J-V) techniques using metal-oxide-semiconductor capacitor (MOSCAP) structures and the results are reported.     

Impact of O2 exposure on surface crystallinity of clean and Ba terminated Ge(1 0 0) surfaces

In analogy with the case of Sr on Si [Y. Liang, S. Gan, M. Engelhard, Appl. Phys. Lett. 79 (2001) 3591], we studied surface crystallinity and oxidation behaviour of clean and Ba terminated Ge(1 0 0) surfaces as a function of oxygen pressure and temperature. The structural and chemical changes in the Ge surface layer were monitored by LEED, XPS and real-time RHEED. In contrast to the oxidation retarding effect, observed for 1/2 monolayer of Sr on Si, the presence of a Ba termination layer leads to a pronounced increase in Ge oxidation rate with respect to clean Ge. In fact, while the Ge(1 0 0) surface terminated with 1/2 ML Ba amorphizes for a pO₂ of 10⁻² Torr, LEED indicates that clean Ge forms a thin (4.5 Å), 1 × 1 ordered oxide upon aggressive O₂ exposure (150 Torr, 200 °C, 30 min). We briefly discuss the origins for the difference in behaviour between Ba on Ge and Sr on Si.     

Photoemission studies of initial oxidation for ultra-thin zinc film on 6H-SiC(0 0 0 1) surface with synchrotron radiation

The thermal oxidation process of metallic zinc on 6H-SiC(0 0 0 1) surface has been investigated by using atomic force microscopy (AFM), synchrotron radiation photoelectron spectroscopy (SRPES) and XPS methods. The AFM images characterize the surface morphology of ZnO film formed during the thermal oxidation and SRPES record the valence band, Si 2p and Zn 3d spectra at different stages. The O 1s peak is recorded by XPS because of the energy limit of the synchrotron radiation. Our results reveal that the silicon oxides layer of SiC substrate can be reduce by hot metallic zinc atom deposition. The oxygen atoms in the silicon oxides are captured by the zinc atoms to form ZnO_x at the initial stage and as a result, the oxidized SiC surface are deoxidized. After the zinc deposition with the final thickness of 2.5 nm, the sample is exposed in oxygen atmosphere and annealed at different temperatures. According to the evolution of peaks integrated intensities, it is considered that the Zn/SiC system will lose zinc atoms during the annealing in oxygen flux at high temperature due to the low evaporation temperature of pure zinc. After further annealing in oxygen flux at higher temperature, the substrate is also oxidized and finally the interface becomes a stable SiC-SiO_x-ZnO sandwich structure.     

On the short-range order of the SiOx (0 ≤ x ≤ 2) surface

Fine (oscillating) structure (FS) in the elastically scattered electron spectra (ESES) [O. Bondarchuk, S. Goysa, I. Koval, P. Melnik, M. Nakhodkin, Surf. Sci. 258 (1991) 239; O. Bondarchuk, S. Goysa, I. Koval, P. Melnik, M. Nakhodkin, Surf. Rev. Lett. 4 (1997) 965] was used to investigate surface structure of the SiO_x (0 ≤ x ≤ 2). SiO_x surface with different stoichiometry was prepared by implantation of 500 eV oxygen ions into a silicon wafer. Fourier transformation of the FS ESES contains one peak at 2.32 Å for Si, two peaks at 1.62 Å and 2.65 Å for a-SiO₂ and three peaks centered at 1.6-1.7 Å, 2.1-2.2 Å and 2.65-3.04 Å for SiO_x. Peaks at 1.62 Å and 2.65 Å are assigned to Si-O and O-O nearest distances correspondently. Ratio of the area under the peak at 2.65 Å to the area under the peak at 1.62 Å turned out to be not constant but grows linearly with the composition parameter x. The latter is considered to prove validity of the Random Bond Model to describe short-range order on the surface of non-stoichiometric silicon oxide.     

Effect of chemical surface treatments on interfacial and electrical characteristics of atomic-layer-deposited Al2O3 films on Ge substrates

The Ge surfaces were cleaned and passivated by two kinds of chemical pretreatments: conventional combination of HF + (NH₄)₂S, and new one of HBr + (NH₄)₂S. The chemical states and stability at passivated Ge surfaces were carefully characterized. The influence of chemical surface treatments on the interface and electrical properties of Al₂O₃ gate dielectric films on Ge grown by atomic layer deposition (ALD) has been investigated deeply. It is found that the combination of HBr and (NH₄)₂S can remove more Ge-O bonds on the Ge surface compared to that of conventional HF and (NH₄)₂S with excellent stability. X-ray photoelectron spectroscopy (XPS) reveals that HBr and (NH₄)₂S treated Ge surface has a mixture states of GeO_x (9.25%) and GeS (7.40%) while HF and (NH₄)₂S treated Ge surface has a mixture states of GeO_x (16.45%) and GeS (3.37%). And the Ge-S peak from the surface of Ge substrates decreases a little after the HBr and (NH₄)₂S treated Ge surface was exposed in the ambient for 300 min, which suggests the Ge surface is stable to oxidants. The Al₂O₃ films on HBr and (NH₄)₂S treated Ge substrates exhibits better electrical properties such as large capacitance, decreased leakage current density by ∼two orders of magnitude, and less C-V hysteresis. This indicates that a reduction in charge traps possibly at the interface and more interface traps are terminated by sulfur. The surface treatment of HBr and (NH₄)₂S seems to be very promising in improving the quality of high-k gate stack on Ge substrates.     

Ruthenium adsorption and diffusion on the GaN(0 0 0 1) surface

We report first principles calculations to analyze the ruthenium adsorption and diffusion on GaN(0 0 0 1) surface in a 2×2geometry. The calculations were performed using the generalized gradient approximation (GGA) with ultrasoft pseudopotential within the density functional theory (DFT). The surface is modeled using the repeated slabs approach. To study the most favorable ruthenium adsorption model we considered T₁, T₄ and H₃ special sites. We find that the most energetically favorable structure corresponds to the Ru- T₄ model or the ruthenium adatom located at the T₄ site, while the ruthenium adsorption on top of a gallium atom (T₁ position) is totally unfavorable. The ruthenium diffusion on surface shows an energy barrier of 0.612 eV. The resultant reconstruction of the ruthenium adsorption on GaN(0 0 0 1)- 2×2 surface presents a lateral relaxation of some hundredth of Å in the most stable site. The comparison of the density of states and band structure of the GaN(0 0 0 1) surface without ruthenium adatom and with ruthenium adatom is analyzed in detail.     

Oxygen-induced p(3 × 1) reconstruction of the W(1 0 0) surface

The oxidation of the W(1 0 0) surface at elevated temperatures has been studied using room temperature STM and LEED. High exposure of the clean surface to O₂ at 1500 K followed by flash-annealing to 2300 K in UHV results in the formation of a novel p(3 × 1) reconstruction, which is imaged by STM as a missing-row structure on the surface. Upon further annealing in UHV, this surface develops a floreted LEED pattern characteristic of twinned microdomains of monoclinic WO_x, while maintaining the p(3 × 1) missing-row structure. Atomically resolved STM images of this surface show a complex domain structure with single and double W〈0 1 0〉 rows coexisting on the surface in different domains.