Experimental and theoretical investigation of defects at (1 0 0) Si1−xGex/oxide interfaces

The identification of a nontrigonal Ge dangling bond at SiO₂/Si_1−xGe_x/SiO₂ heterostructures and its electrical activity are discussed, both from experimental and theoretical points of view. This dangling bond is observed from multifrequency electron-spin resonance experiments performed at 4.2 K, for typical Ge concentrations in the range 0.4 ≤ x ≤ 0.85. The electrical activity of this defect is revealed from capacitance-voltage characteristics measured at 300 and 77 K, and is found to behave like an acceptor defect. First-principles calculations of the electronic properties of this Ge dangling bond indicate that its energy level approaches the valence band edge of the Si_1−xGe_x layer as the Ge content increases, confirming its acceptor-like nature.     

Epitaxial growth of Dy2O3 thin films on epitaxial Dy-germanide films on Ge(0 0 1) substrates

Ultra-thin films of Dy are grown on Ge(0 0 1) substrates by molecular beam deposition near room temperature and immediately annealed for solid phase epitaxy at higher temperatures, leading to the formation of DyGe_x films. Thin films of Dy₂O₃ are grown on the DyGe_x film on Ge(0 0 1) substrates by molecular beam epitaxy. Streaky reflection high energy electron diffraction (RHEED) patterns reveal that epitaxial DyGe_x films grow on Ge(0 0 1) substrates with flat surfaces. X-ray diffraction (XRD) spectrum suggests the growth of an orthorhombic phase of DyGe_x films with (0 0 1) orientations. After the growth of Dy₂O₃ films, there is a change in RHEED patterns to spotty features, revealing the growth of 3D crystalline islands. XRD spectrum shows the presence of a cubic phase with (1 0 0) and (1 1 1) orientations. Atomic force microscopy image shows that the surface morphology of Dy₂O₃ films is smooth with a root mean square roughness of 10 Å.     

Band offsets at the (1 0 0)GaSb/Al2O3 interface from internal electron photoemission study

From electron internal photoemission and photoconductivity measurements at the (1 0 0)GaSb/Al₂O₃ interface, the top of the GaSb valence band is found to be 3.05 ± 0.10 eV below the bottom of the Al₂O₃ conduction band. This interface band alignment corresponds to conduction and valence band offsets of 2.3 ± 0.10 eV and 3.05 ± 0.15 eV, respectively, indicating that the valence band in GaSb lies energetically well above the valence band of In_xGa_1−xAs (0 ? x ? 0.53) or InP.     

In0.53Ga0.47As(1 0 0) native oxide removal by liquid and gas phase HF/H2O chemistries

The native oxide removal, surface termination, and stoichiometry of InGaAs(1 0 0) surfaces using liquid and gas phase HF/H₂O etching were studied using X-ray photoelectron spectroscopy. Oxide removal in liquid phase HF stopped at the As layer, producing either elemental or H-terminated As. The surface oxidized upon air exposure, forming a 4.8 Å As₂O₃ layer on an As rich InGaAs sub-surface (17% In, 16% Ga, 66% As). A sub atmospheric gas phase HF/H₂O process (100 Torr, 29 °C, 0.5 min) completely removed As₂O₃ and produced mainly In and Ga fluorides, since As fluoride is volatile at these experimental conditions. Once enough F accumulated on the surface, the water sticking probability decreased and the etching reaction proceeded at a much lower rate. The highest oxide removal (4.2 Å residual oxide) was achieved after 5 min of etching. As₂O₃ and As₂O₅ were completely removed and considerably more InF₃ and GaF₃ were produced. The surface contained a group III-fluoride rich overlayer (34% In, 36% Ga) on a slightly As rich bulk (21% In, 21% Ga, and 58% As). The As rich InGaAs sub-surface produced with both liquid and the longer gas phase HF treatments is intrinsic to HF-InGaAs chemistry, although the oxide removal mechanism is likely different.     

Crystalline orientation dependence of electrical properties of Mn Germanide/Ge(1 1 1) and (0 0 1) Schottky contacts

We have investigated the crystalline orientation dependence of the electrical properties of Mn germanide/Ge(1 1 1) and (0 0 1) Schottky contacts. We prepared epitaxial and polycrystalline Mn₅Ge₃ layers on Ge(1 1 1) and (0 0 1) substrates, respectively. The Schottky barrier height (SBH) estimated from the current density-voltage characteristics for epitaxial Mn₅Ge₃/Ge(1 1 1) is as low as 0.30 eV, while the SBH of polycrystalline Mn₅Ge₃/Ge(0 0 1) is higher than 0.56 eV. On the other hand, the SBH estimated from capacitance-voltage characteristics are higher than 0.6 eV for both samples. The difference of these SBHs can be explained by the local carrier conduction through the small area with the low SBH regions in the epitaxial Mn₅Ge₃/Ge(1 1 1) contact. This result suggests the possibility that the lowering SBH takes place due to Fermi level depinning in epitaxial germanide/Ge(1 1 1) contacts.     

H2S molecular beam passivation of Ge(0 0 1)

A fundamental issue regarding the introduction of high-mobility Ge channels in CMOS circuits is the electrical passivation of the interface with the high-k gate dielectric. In this paper, we investigate the passivation of p-Ge(0 0 1) using molecular H₂S. The modification of the semiconductor surface is monitored in situ by RHEED and the interface is characterized by XPS analyses. MOS capacitors are fabricated to extract interface state density, and finally we demonstrate the efficiency of the passivation scheme using a combination with an ultra thin Al interlayer.     

In situ atomic layer deposition and synchrotron-radiation photoemission study of Al2O3 on pristine n-GaAs(0 0 1)-4 × 6 surface

This work presents the in situ reflection high-energy electron diffraction (RHEED), scanning tunneling microscopy (STM) and synchrotron-radiation photoemission studies for the morphological and interfacial chemical characterization of in situ atomic layer deposited (ALD) Al₂O₃ on pristine molecular beam epitaxy (MBE) grown Ga-rich n-GaAs (1 0 0)-4 × 6 surface. Both the RHEED pattern and STM image demonstrated that the first cycle of ALD-Al₂O₃ process reacted immediately with the GaAs surface. As revealed by in situ synchrotron-radiation photoemission studies, two types of surface As atoms that have excess in charge in the clean surface served as reaction sites with TMA. Two oxidized states were then induced in the As 3d core-level spectra with chemical shifts of +660 meV and +1.03 eV, respectively.     

N2 effect on GaAs etching at 150 mTorr capacitively-coupled Cl2/N2 plasma

The role of N₂ on GaAs etching at 150 mTorr capacitively-coupled Cl₂/N₂ plasma is reported. A catalytic effect of N₂ was found at 20-25% N₂ composition in the Cl₂/N₂ discharges. The peak intensities of the Cl₂/N₂ plasma were monitored with optical emission spectroscopy (OES). Both atomic Cl (725.66 nm) and atomic N (367.05 nm) were detected during the Cl₂/N₂ plasma etching. With the etch rate and OES results, we developed a simple model in order to explain the etch mechanism of GaAs in the high pressure capacitively-coupled Cl₂/N₂ plasma as a function of N₂ ratio. If the plasma chemistry condition became positive ion-deficient at low % N₂ or reactive chlorine-deficient at high % N₂ in the Cl₂/N₂ plasma, the GaAs etch rate is reduced. However, if the plasma had a more balanced ratio of Cl₂/N₂ (i.e. 20-25% N₂) in the plasma, much higher etch rates (up to 150 nm/min) than that in pure Cl₂ (50 nm/min) were produced due to synergetic effect of neutral chlorine adsorption and reaction, and positive ion bombardment. Pure Cl₂ etching produced 14 nm of RMS surface roughness of GaAs. Introduction of ?20% N₂ gas in Cl₂/N₂ discharges significantly reduced the surface roughness to 2-4 nm. SEM photos showed that the morphology of photoresist mask was strongly degraded. Etch rate of GaAs slightly increased from 10 to 40 nm/min when RIE chuck power changed from 10 to 150 W at 12 sccm Cl₂/8 sccm N₂ plasma condition. The surface roughness of GaAs etched at 12 sccm Cl₂/8 sccm N₂ plasma was 2-3 nm.     

Chemical nature of the passivation layer depending on the oxidizing agent in Gd2O3/GeO2/Ge stacks grown by molecular beam deposition

In Ge-based metal oxide semiconductor technology, the insertion of a passivation layer seems to be crucial in unpinning the Fermi level at the interface and in reducing the amount of interface defects. GeO₂ was obtained by atomic oxygen (AO), molecular oxygen or ozone chemisorption. Atomic or molecular oxygen was used in the deposition of Gd₂O₃. Gd₂O₃ thin films were grown by molecular beam deposition directly on (1 0 0) Ge or on a GeO₂ interlayer. The chemical nature of the Gd₂O₃/Ge interface was characterized by time-of-flight secondary ion mass spectrometry depth profiles. Without GeO₂ layer Gd and Ge interdiffusion is observed and the concomitant formation of GeOGd bonds is also supported by X-ray photoelectron spectroscopy energy shift at the Ge 3d peak and by a singularity in the interface defect energy distribution at ∼0.48 eV. Further, depending on the GeO₂ formation process, the profile shape of Ge and O related secondary ions at the GeO₂/Ge interface can be related with a defective Ge region close to the GeO₂/Ge. In particular, considering the ratio between Ge and GeO₂ related secondary ion signals, the interlayer passivated using AO turns out to be comparatively enriched in Ge, while the use of ozone for GeO₂ formation leads to a Ge deficient layer.     

Epitaxial growth of Fe/MgO/Ge(0 0 1) heterostructures

We report on the growth of epitaxial Fe/MgO heterostructures on Ge(0 0 1) by Molecular Beam Epitaxy. The better crystal quality and interfacial chemical sharpness at the oxide-semiconductor interface have been obtained by growing MgO at room temperature, followed by a post-annealing at 773 K, on top of a p(2 × 1)-Ge(0 0 1) clean surface. The growth of Fe at room temperature followed by annealing at 473 K gives the best epitaxial structure with optimized crystallinity of each layer compatible with limited chemical interdiffusion. Tunneling devices based on the epitaxial Fe/MgO/Ge heterostructure have been micro-fabricated and tested in order to probe the electrical properties of the MgO barrier. The current-voltage characteristics clearly show that tunneling is the dominant phenomenon, thus indicating that this system is very promising for practical applications in electronics and spintronics.     

Influence of activated polymer on the etching rate of SiO2 in CF4 + H2 plasma

The reactive ion etching (RIE) of SiO₂ in CF₄ + H₂ plasma is considered. The influence of activated polymer on the RIE rate of SiO₂ in CF₄ + H₂ plasma is determined by extrapolation of experimentally measured kinetics of the etching rate. It is found that the increased surface coverage by CF₂ radicals suppresses the RIE rate of SiO₂ in CF₄ + H₂ plasma during the initial stages of the etching process. The formation of activated polymer becomes pronounced when adsorbed CF₂ radicals are slowly activated. The activated polymer intensifies the etching reaction and enhances the etching rate. At the same time, the activated polymer intensifies the polymerization reactions. The increased surface coverage by the polymer suppresses the RIE rate of SiO₂ in CF₄ + H₂ plasma at later stages of the etching process.     

MOS devices with tetragonal ZrO2 as gate dielectric formed by annealing ZrO2/Ge/ZrO2 laminate

A Ge-stabilized tetragonal ZrO₂ (t-ZrO₂) film with permittivity (κ) of 36.2 was formed by depositing a ZrO₂/Ge/ZrO₂ laminate and a subsequent annealing at 600 °C, which is a more reliable approach to control the incorporated amount of Ge in ZrO₂. On Si substrates, with thin SiON as an interfacial layer, the SiON/t-ZrO₂ gate stack with equivalent oxide thickness (EOT) of 1.75 nm shows tiny amount of hysteresis and negligible frequency dispersion in capacitance-voltage (C-V) characteristics. By passivating leaky channels derived from grain boundaries with NH₃ plasma, good leakage current of 4.8 × 10⁻⁸ A/cm² at V_g = V_fb − 1 V is achieved and desirable reliability confirmed by positive bias temperature instability (PBTI) test is also obtained.     

Structural and electrical properties of Er-doped HfO2 and of its interface with Ge (0 0 1)

Er-doped HfO₂ thin films with Er content ranging from 0% to 15% are deposited by atomic layer deposition on native oxide free Ge(001). The crystallographic phase is investigated by X-ray diffraction and is found to depend on the Er%. The cubic fluorite structure develops on Ge for Er% as low as 4% and is stable after annealing at 400 °C in N₂. Microstrain increases with increasing the Er content within the fluorite structure. Time of flight secondary ion mass and electron energy loss spectroscopy evidence a Ge diffusion from the substrate that results in the formation of a Ge-rich interfacial region which does not present a structural discontinuity with the oxide. The diffusion of Ge is enhanced by the annealing and causes a reordering of the crystal lattice. In annealed films the interface defect density measured by low temperature conductance measurements is found to decrease with decreasing the Er content.     

Direct measurement of interfacial structure in epitaxial Gd2O3 on GaAs (0 0 1) using scanning tunneling microscopy

The epitaxial growth of Gd₂O₃ on GaAs (0 0 1) has given a low interfacial density of states, resulting in the demonstration of the first inversion-channel GaAs metal-oxide-semiconductor field-effect transistor. Motivated by the significance of this discovery, in this work, cross-sectional scanning tunneling microscopy is employed herein to obtain precise structural and electronic information on these epitaxial films and interfaces. At the interface, the interfacial stacking of Gd₂O₃ films is directly correlated with the stacking sequence of the substrate GaAs. Additionally, from the local electronic states across the gate oxides, the spatial extent of the GaAs wavefunctions into the oxide dielectric may suggest a minimum Gd₂O₃ thickness to be of bulk properties.     

Studies of Ti- and Ni-germanide Schottky contacts on n-Ge(1 0 0) substrates

In this study, we investigated fabrication and characteristics of germanides Schottky contacts on germanium. Ti- and Ni-germanides were fabricated on n-Ge(1 0 0) substrates by sputtering metal Ti or Ni on Ge followed by a furnace annealing. The influence of annealing temperature on the electrical properties of Ti- and Ni-germanide on n-Ge(1 0 0) substrates was investigated. The low temperature ∼300 °C annealing helped to obtain the optimized Schottky contact characteristics in both Ti-germanide/Ge and Ni-germanide/Ge substrates contacts. The well-behaved Ti-germanides/n-Ge Schottky contact with 0.34 eV barrier height was obtained by using a 300 °C annealing process.     

Epitaxy of BaTiO3 thin film on Si(0 0 1) using a SrTiO3 buffer layer for non-volatile memory application

In this study we report the epitaxial growth of BaTiO₃ films on Si(0 0 1) substrate buffered by 5 nm-thick SrTiO₃ layer using both MBE and PLD techniques. The BaTiO₃ films demonstrate single crystalline, (0 0 1)-oriented texture and atomically flat surface on SrTiO₃/Si template. The electrical characterizations of the BaTiO₃ films using MFIS structures show that samples grown by MBE with limited oxygen pressure during the growth exhibit typical dielectric behavior despite post deposition annealing process employed. A ferroelectric BaTiO₃ layer is obtained using PLD method, which permits much higher oxygen pressure. The C-V curve shows a memory window of 0.75 V which thus enable BaTiO₃ possibly being applied to the non-volatile memory application.     

Yttrium silicide formation and its contact properties on Si(1 0 0)

Yttrium silicide formation and its contact properties on Si(1 0 0) have been studied in this paper. By evaporating a yttrium metal layer onto Si(1 0 0) wafer in conventional vacuum condition and rapid thermal annealing, we found that YSi_2-x begins to form at 350 °C, and is stable to 950 °C. Atomic force microscopy characterization shows the pinholes formation in the formed YSi_2-x film. By current-voltage measurement, the Schottky barrier height (SBH) of YSi_2-x diode on p-type Si(1 0 0) was shown to be between 0.63 and 0.69 eV for annealing temperature from 500 to 900 °C. By low temperature current-voltage measurement, the SBH of YSi_2-x diode on n-type Si(1 0 0) was directly measured and shown to be 0.46, 0.37, 0.32 eV for annealing temperature of 500, 600, and 900 °C, respectively, and possibly even lower for annealing at 700 or 800 °C.     

Effective formation of interface controlled Y2O3 thin film on Si(1 0 0) in a metal-(ferroelectric)-insulator-semiconductor structure

Yttrium was deposited on the chemical oxide of Si and annealed under vacuum to control the interface for the formation of Y₂O₃ as an insulating barrier to construct a metal-ferroelectric-insulator-semiconductor structure. Two different pre-annealing temperatures of 600 and 700 °C were chosen to investigate the effect of the interface state formed after the pre-annealing step on the successive formation of Y₂O₃ insulator and Nd₂Ti₂O₇ (NTO) ferroelectric layer through annealing under an oxygen atmosphere at 800 °C. Pre-anneal treatments of Y-metal/chemical-SiO₂/Si at 600 and 700 °C induced a formation of Y₂O₃ and Y-silicate, respectively. The difference in the pre-anneal temperature induced almost no change in the electrical properties of the Y₂O₃/interface/Si system, but degraded properties were observed in the NTO/Y₂O₃/interface/Si system pre-annealed at 600 °C when compared with the sample pre-annealed at 700 °C. C-V characteristics of the NTO/Y₂O₃/Si structured system showed a clockwise direction of hysteresis, and this gap could be used as a memory window for a ferroelectric-gate. A smaller hysteric gap and electrical breakdown values were observed in the NTO/Y₂O₃/Si system pre-annealed at 600 °C, and this was due to an unintentional distribution of the applied field from the presence of an interfacial layer containing Y-silicate and SiO₂ phases.     

An efficient wet-cleaning of SiGe virtual substrates and of thick, pure Ge layers on Si(0 0 1) after a chemical mechanical planarization step

The aim of this study is to propose an efficient wet cleaning of the surfaces of the SiGe virtual substrates just after a chemical mechanical polishing step. We have first of all studied the chemical compatibility of miscellaneous solutions, such as the standard cleaning 1 (SC1), the Standard Cleaning 2 (SC2), the CARO one etc with SiGe. A definite, logarithmic-like increase of the etch rate with the Ge content has been obtained for the SC1, the SC2 and the CARO solutions (with values 1000-10,000 those of Si evidenced for pure Ge), making them unsuitable for Ge contents above 30%. We have thus investigated the efficiency of new cleaning sequences (named “DDC-SiGe” for SiGe and “HF/O₃” for pure Ge) that call upon diluted HF and ozone solutions spiked with HCl, on SiGe and pure Ge. The overall material consumption of those cleaning sequences, which increases from 10 Å for pure Si up to 130 Å for pure Ge, is quite low. The particle removal efficiency of such cleanings is around 99% for Si_0.8Ge_0.2 and Si_0.7Ge_0.3. It drops down to 83% for Si_0.5Ge_0.5 and to 65% for pure Ge. This is most probably due to pre-existing epitaxy defects which are revealed during the wet cleaning then wrongly assimilated to particles by our surface inspection tool. The metallic contaminants present on the surface after the use of our wet cleaning sequences have a surface density lower than 10¹⁰ atoms cm⁻², this whatever the Ge content of the underlying layer.