Strain relaxation of epitaxial SiGe layer and Ge diffusion during Ni silicidation on cap-Si/SiGe/Si(0 0 1)

Strain relaxation of the epitaxial SiGe layer and Ge diffusion during nickel silicidation by rapid thermal annealing the structure of Ni(≅14 nm)/cap-Si(≅26 nm)/Si_0.83Ge_0.17/Si(0 0 1) at the elevated annealing temperatures, T_A, were investigated by X-ray diffraction analyses of high-resolution ω-2θ scan and reciprocal space mapping. The analyses showed a much larger strain relaxation at a lower T_A and a reduction in Ge content in the SiGe layer of Ni/SiGe/Si(0 0 1) after thermal annealing compared to the case of cap-Si/SiGe/Si(0 0 1). The results indicate that the strain relaxation of the SiGe layers in NiSi/SiGe/Si(0 0 1) is related to the phenomena of NiSi agglomeration and penetration into the SiGe layer during silicidation at elevated anneal temperatures ≥750 °C. At elevated T_A ≥ 750 °C, Ge diffused into the intact cap-Si area during silicidation.     

Femtosecond pulsed laser deposition of Ge quantum dot growth on Si(1 0 0)-(2 × 1)

Ge quantum dots were grown on Si(1 0 0)-(2 × 1) by femtosecond pulsed laser deposition at various substrate temperatures using a femtosecond Ti:sapphire laser. In situ reflection high-energy electron diffraction and ex situ atomic force microscopy were used to analyze the film structure and morphology. The morphology of germanium islands on silicon was studied at different coverages. The results show that femtosecond pulsed laser deposition reduces the minimum temperature for epitaxial growth of Ge quantum dots to ∼280 °C, which is 120 °C lower than previously observed in nanosecond pulsed laser deposition and more than 200 °C lower than that reported for molecular beam epitaxy and chemical vapor deposition.     

Effects of magnesium film thickness and annealing temperature on formation of Mg2Si films on silicon (1 1 1) substrate deposited by magnetron sputtering

Magnesium films of various thicknesses were first deposited on silicon (1 1 1) substrates by magnetron sputtering method and then annealed in annealing furnace filled with argon gas. The effects of the magnesium film thickness and the annealing temperature on the formation of Mg₂Si films were investigated by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). The Mg₂Si thin films thus obtained were found to be polycrystalline and the Mg₂Si (2 2 0) orientation is preferred regardless of the magnesium film thickness and annealing temperature. XRD results indicate that high quality magnesium silicide films are produced if the magnesium/silicon samples are annealed at 400 °C for 5 h. Otherwise, the synthesized films annealed at annealing temperatures lower than 350 °C or higher than 450 °C contain magnesium crystallites or magnesium oxide. SEM images have revealed that microstructure grains in the polycrystalline films are about 1-5 μm in dimensions, and the texture of the Mg₂Si films becomes denser and more homogeneous as the thickness of the magnesium film increases.     

Bimodal growth of manganese silicide on Si(1 0 0)

Two different growth modes of manganese silicide are observed on Si(1 0 0) with scanning tunneling microscopy. 1.0 and 1.5 monolayer Mn are deposited at room temperature on the Si(1 0 0)-(2 × 1) substrate. The as-grown Mn film is unstructured. Annealing temperatures between room temperature and 450 °C lead to small unstructured clusters of Mn or Mn_xSi_y. Upon annealing at 450 °C and 480 °C, Mn reacts chemically with the Si substrate and forms silicide islands. The dimer rows of the substrate become visible again. Two distinct island shapes are found and identified as MnSi and Mn₅Si₃.     

Epitaxial growth of Nd2Hf2O7(1 1 1) thin films on Ge(1 1 1) substrates by pulsed laser deposition

Nd₂Hf₂O₇ (NHO) thin films have been epitaxially grown by pulsed laser deposition (PLD) on Ge(1 1 1) substrates. In situ reflection high-energy electron diffraction (RHEED) evolution of the (1 1 1)-oriented NHO during the deposition has been investigated and shows that the epilayer has a twin-free character with type-B stacking. Interfacial structure of NHO/Ge has been examined by high-resolution transmission electron microscopy (HRTEM). The results indicate a highly crystalline film with a very thin interface, and the orientation relationship between NHO and Ge can be denoted as (1 1 1)_NHO//(1 1 1)_Ge and . Finally, twin-free epitaxial growth of NHO with type-B orientation displays temperature dependence and the type-B epitaxy is favored at high temperature.     

Thickness dependence on thermal stability of sputtered Ag nanolayer on Ti/Si(1 0 0)

Thermal stability of Ag layer on Ti coated Si substrate for different thicknesses of the Ag layer have been studied. To do this, after sputter-deposition of a 10 nm Ti buffer layer on the Si(1 0 0) substrate, an Ag layer with different thicknesses (150-5 nm) was sputtered on the buffer layer. Post annealing process of the samples was performed in an N₂ ambient at a flow rate of 200 ml/min in a temperature range from 500 to 700 °C for 30 min. The electrical property of the heat-treated multilayer with the different thicknesses of Ag layer was examined by four-point-probe sheet resistance measurement at the room temperature. Phase formation and crystallographic orientation of the silver layers were studied by θ-2θ X-ray diffraction analysis. The surface topography and morphology of the heat-treated films were determined by atomic force microscopy, and also, scanning electron microscopy. Four-point- probe electrical measurement showed no considerable variation of sheet resistance by reducing the thickness of the annealed Ag films down to 25 nm. Surface roughness of the Ag films with (1 1 1) preferred crystallographic orientation was much smaller than the film thickness, which is a necessary condition for nanometric contact layers. Therefore, we have shown that the Ag layers with suitable nano-thicknesses sputtered on 10 nm Ti buffer layer were thermally stable up to 700 °C.     

Growth and thermal evolution of submonolayer Pt films on Ru(0 0 0 1) studied by STM

The growth of submonolayer Pt on Ru(0 0 0 1) has been studied with scanning tunneling microscopy. We focus on the island evolution depending on Pt coverage θ_Pt, growth temperature T_G and post-growth annealing temperature T_A. Dendritic trigonal Pt islands with atomically rough borders are observed at room temperature and moderate deposition rates of about 5 × 10⁻⁴ ML/s. Two types of orientation, rotated by 180° and strongly influenced by minute amounts of oxygen are observed which is ascribed to nucleation starting at either hcp or fcc hollow sites. The preference for fcc sites changes to hcp in the presence of about one percent of oxygen. At lower growth temperatures Pt islands show a more fractal shape. Generally, atomically rough island borders smooth down at elevated growth temperatures higher than 300 K, or equivalent annealing temperatures. Dendritic Pt islands, for example, transform into compact, almost hexagonal islands, indicating similar step energies of A- and B-type of steps. Depending on the Pt coverage the thermal evolution differs somewhat: While regular islands on Ru(0 0 0 1) are formed at low coverages, vacancy islands are observed close to completion of the Pt layer.     

Alloy formation of Co/Ni/Pt(1 1 1)

The initial growth and alloy formation of ultrathin Co films deposited on 1 ML Ni/Pt(1 1 1) were investigated by Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and ultraviolet photoelectron spectroscopy (UPS). A sequence of samples of d_Co Co/1 ML Ni/Pt(1 1 1) (d_Co = 1, 2, and 3 ML) were prepared at room temperature, and then heated up to investigate the diffusion process. The Co and Ni atoms intermix at lower annealing temperature, and Co-Ni intermixing layer diffuses into the Pt substrate to form Ni-Co-Pt alloys at higher annealing temperature. The diffusion temperatures are Co coverage dependent. The evolution of UPS with annealing temperatures also shows the formation of surface alloys. Some interesting LEED patterns of 1 ML Co/1 ML Ni/Pt(1 1 1) show the formation of ordered alloys at different annealing temperature ranges. Further studies in the Curie temperature and concentration analysis, show that the ordered alloys corresponding to different LEED patterns are Ni_xCo_1−xPt and Ni_xCo_1−xPt₃. The relationship between the interface structure and magnetic properties was investigated.     

Study of Ni/Si(1 0 0) solid-state reaction with Al addition

The characteristics of Ni/Si(1 0 0) solid-state reaction with Al addition (Ni/Al/Si(1 0 0), Ni/Al/Ni/Si(1 0 0) and Al/Ni/Si(1 0 0)) is studied. Ni and Al films were deposited on Si(1 0 0) substrate by ion beam sputtering. The solid-state reaction between metal films and Si was performed by rapid thermal annealing. The sheet resistance of the formed silicide film was measured by four-point probe method. The X-ray diffraction (XRD) was employed to detect the phases in the silicide film. The Auger electron spectroscopy was applied to reveal the element profiles in depth. The influence of Al addition on the Schottky barrier heights of the formed silicide/Si diodes was investigated by current-voltage measurements. The experimental results show that NiSi forms even with the addition of Al, although the formation temperature correspondingly changes. It is revealed that Ni silicidation is accompanied with Al diffusion in Ni film toward the film top surface and Al is the dominant diffusion species in Ni/Al system. However, no Ni_xAl_y phase is detected in the films and no significant Schottky barrier height modulation by the addition of Al is observed.     

Scaling behavior of island density in submonolayer growth of CaF2 on vicinal Si(1 1 1)

We have studied the scaling behavior of two-dimensional island density during submonolayer growth of CaF₂ on vicinal Si(1 1 1) surfaces using scanning tunneling microscopy. We have analyzed the morphology of the Si(1 1 1) surfaces where CaF₂ partial monolayers with coverages of about 0.1 monolayer are deposited at ∼600 °C. The number density of terrace nucleated islands increases with substrate terrace width l as ∼l⁴ in a low island density regime. This scaling behavior is consistent with predictions for the case of the irreversible growth of islands.     

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.     

Homogeneous Si films on CaF2/Si(1 1 1) due to boron enhanced solid phase epitaxy

The structure and morphology of Si/CaF₂/Si(1 1 1) structures have been investigated by X-ray diffraction (XRD, GIXRD) and X-ray photoelectron spectroscopy (XPS). While CaF₂ films were grown via molecular beam epitaxy (MBE), Si films on CaF₂/Si(1 1 1) are fabricated by surfactant enhanced solid phase epitaxy (SE-SPE). Here Boron was used as a surfactant to obtain semiconductor films of homogeneous thickness. The Si films are entirely relaxed while the CaF₂ films have both pseudomorphic and relaxed crystallites. After exposure to ambient conditions, the Si films have a very thin native oxide film. The homogeneous Si film partially prevents the incorporation of impurities at the interface between the Si substrate and CaF₂ via migration along residual defects of the CaF₂ film.     

CoPt alloy grown on the WSe2(0 0 0 1) van der Waals surface

The structural and magnetic properties of 3-nm-thick CoPt alloys grown on WSe₂(0 0 0 1) at various temperature are investigated. Deposition at room temperature leads to the formation of a chemically disordered fcc CoPt alloy with [1 1 1] orientation. Growth at elevated temperatures induces L1₀ chemical order starting at 470 K accompanied with an increase in grain size and a change in grain morphology. As a consequence of the [1 1 1] growth direction, the CoPt grains can adopt one of the three possible variants of the L1₀ phase with tetragonal c-axis tilted from the normal to the film plane direction at 54°. The average long-range order parameter is found to be 0.35(±0.05) and does not change with the increase in the deposition temperature from 570 to 730 K. This behavior might be related to Se segregation towards the growing facets and surface disorder effects promoted by a high surface-to-volume ratio. Magnetic studies reveal a superparamagnetic behavior for the films grown at 570 and 730 K in agreement with the film morphology and degree of chemical order. The measurements at 10 K reveal the orientation of the easy axis of the magnetization lying basically in the film plane.     

Ultrathin ZrO2 films on Si-rich SiC(0 0 0 1)-(3 × 3): Growth and thermal stability

The growth and thermal stability of ultrathin ZrO₂ films on the Si-rich SiC(0 0 0 1)-(3 × 3) surface have been explored using photoelectron spectroscopy (PES) and X-ray absorption spectroscopy (XAS). The films were grown in situ by chemical vapor deposition using the zirconium tetra tert-butoxide (ZTB) precursor. The O 1s XAS results show that growth at 400 °C yields tetragonal ZrO₂. An interface is formed between the ZrO₂ film and the SiC substrate. The interface contains Si in several chemically different states. This gives evidence for an interface that is much more complex than that formed upon oxidation with O₂. Si in a 4+ oxidation state is detected in the near surface region. This shows that intermixing of SiO₂ and ZrO₂ occurs, possibly under the formation of silicate. The alignment of the ZrO₂ and SiC band edges is discussed based on core level and valence PES spectra. Subsequent annealing of a deposited film was performed in order to study the thermal stability of the system. Annealing to 800 °C does not lead to decomposition of the tetragonal ZrO₂ (t-ZrO₂) but changes are observed within the interface region. After annealing to 1000 °C a laterally heterogeneous layer has formed. The decomposition of the film leads to regions with t-ZrO₂ remnants, metallic Zr silicide and Si aggregates.     

Au/TiO2/Ru(0 0 0 1) model catalysts and their interaction with CO

Au/TiO₂/Ru(0 0 0 1) model catalysts and their interaction with CO were investigated by scanning tunneling microscopy and different surface spectroscopies. Thin titanium oxide films were prepared by Ti deposition on Ru(0 0 0 1) in an O₂ atmosphere and subsequent annealing in O₂. By optimizing the conditions for deposition and post-treatment, smooth films were obtained either as fully oxidized TiO₂ or as partly reduced TiO_x, depending on the preparation conditions. CO adsorbed molecularly on both oxidized and reduced TiO₂, with slightly stronger bonding on the reduced films. Model catalyst surfaces were prepared by depositing submonolayer quantities of Au on the films and characterized by X-ray photoelectron spectroscopy and scanning tunneling microscopy. From X-ray photoelectron spectroscopy, a weak interaction between the Au and the TiO₂ substrate was found. At 100 K CO adsorption occurred on both the TiO₂ film and on the Au nanoparticles. CO desorbed from the Au particles with activation energies between 53 and 65 kJ/mol, depending on the Au coverage. If the Au deposit was annealed to 770 K prior to CO exposure, the CO adsorption energy decreased significantly. STM measurements revealed that the Au particles grow upon annealing, but are not encapsulated by TiO_x suboxides. The higher CO adsorption energy observed for smaller Au coverages and before annealing is attributed to a significantly stronger interaction of CO with mono- and bilayer Au islands, while for higher particles, the adsorption energy becomes more bulk-like. The implications of these effects on the known particle size effects in CO oxidation over supported Au/TiO₂ catalysts are discussed.     

Surface treatments toward obtaining clean GaN(0 0 0 1) from commercial hydride vapor phase epitaxy and metal-organic chemical vapor deposition substrates in ultrahigh vacuum

We studied processes of cleaning GaN(0 0 0 1) surfaces on four different types of wafers: two types were hydride vapor phase epitaxy (HVPE) free-standing substrates and two types were metal-organic chemical vapor deposition (MOCVD) films grown on these HVPE substrates and prepared by annealing and/or Ar ion sputtering in ultra high vacuum. We observed the surfaces through treatments using in situ low-energy electron diffraction (LEED), reflection high-energy electron diffraction (RHEED), scanning tunneling microscopy (STM), and Auger electron spectroscopy, and also using ex situ temperature programmed desorption, X-ray photoelectron spectroscopy, X-ray diffraction, and secondary ion mass spectrometry. For HVPE samples, we obtained relatively clean surfaces under optimized three-step annealing conditions (200 °C for 12 h + 400 °C for 1 h + 500 °C for 5 min) without sputtering, after which the surface contamination of oxide and carbide was reduced to ∼20% of that before annealing. Clear GaN(0 0 0 1)1×1 patterns were obtained by LEED and RHEED. STM images showed flat terraces of ∼10 nm size and steps of ∼0.5 nm height. Upon annealing the HVPE-GaN samples at a much higher temperature (C), three-dimensional (3D) islands with facets were formed and the surface stoichiometry was broken down with the desorption of nitrogen in the form of ammonia, since the samples include hydrogen as an impurity. Ar⁺ sputtering was effective for removing surface contamination, however, postannealing could not recover the surface roughness but promoted the formation of 3D islands on the surface. For MOCVD/HVPE homoepitaxial samples, the surfaces are terminated by hydrogen and the as-introduced samples showed a clear 1×1 structure. Upon annealing at 500-600 °C, the surface hydrogen was removed and a 3×3 reconstruction structure partially appeared, although a 1×1 structure was dominant. We summarize the structure differences among the samples under the same treatment and clarify the effect of crystal quality, such as dislocations, the concentration of hydrogen impurities, and the residual reactant molecules in GaN films, on the surface structure.     

Band alignments at SrZrO3/Ge(0 0 1) interface: Thermal annealing effects

High-κ dielectrics SrZrO₃ were prepared on Ge(0 0 1) substrate using pulse laser deposition, and band alignments and thermal annealing effects were studied with high resolution X-ray photoemission spectroscopy. Valence and conduction band offsets at this interface were measured to be 3.26 eV and 1.77 eV, respectively. Interfacial Ge oxide layers were found at the interface. After annealing at 600 °C, the interfacial Ge oxide layers were eliminated, and the valence band offset increased to 3.50 eV, but the amorphous SrZrO₃ became polycrystalline in the meantime.     

Behavior of N atoms in atomic-order nitrided Si0.5Ge0.5(1 0 0)

Behavior of N atoms in atomic-order nitrided Si_0.5Ge_0.5(1 0 0) by heat treatment in Ar at 600 °C was investigated by X-ray photoelectron spectroscopy (XPS). For thermal nitridation by NH₃ at 400 °C, nitridation of surface Si atoms tends to proceed preferentially over nitridation of surface Ge atoms. It is also clear that, with the heat treatment, nitridation of Si atoms proceeds by transfer of N atoms from Ge atoms. Angle-resolved XPS results show that Ge fraction beneath the surface nitrided layer increases significantly at 600 °C compared to the initial surface. These results indicate that preferential nitridation of Si atoms at surface over Ge atoms induces Ge segregation beneath the surface nitrided layer at higher temperatures above 400 °C.     

Structure, dielectric and ferroelectric properties of highly (1 0 0)-oriented BaTiO3 grown under low-temperature conditions

The highly (1 0 0)-oriented BaTiO₃ thin films were fabricated on LaNiO₃(1 0 0)/Pt/Ti/SiO₂/Si substrates under low-temperature conditions. Substrate temperatures throughout the fabrication process remained at or below 400 °C, which allows this process to be compatible with many materials commonly used in integrated circuit manufacturing. X-ray diffraction data provided the evidence for single BaTiO₃ phase. Field-emission scanning electron microscopy was used to study the columnar structure of the films. The dielectric properties as a function of frequency in the range of 1 kHz to 1 MHz was obtained. The room temperature remanent polarization (2P_r) and coercive field were found to be ∼5 μC/cm² and 50 kV/cm, respectively. The BTO film maintains an excellent fatigue-free character even after 10⁹ switching cycles.     

Growth of oriented crystalline Ag nanoislands on air-exposed Si(0 0 1) surfaces

Growth of Ag islands under ultrahigh vacuum condition on air-exposed Si(0 0 1)-(2 × 1) surfaces has been investigated by in-situ reflection high energy electron diffraction (RHEED). A thin oxide is formed on Si via exposure of the clean Si(0 0 1)-(2 × 1) surface to air. Deposition of Ag on this oxidized surface was carried out at different substrate temperatures. Deposition at room temperature leads to the growth of randomly oriented Ag islands while well-oriented Ag islands, with (0 0 1)_Ag||(0 0 1)_Si, [1 1 0]_Ag||[1 1 0]_Si, have been found to grow at substrate temperatures of ≥350 °C in spite of the presence of the oxide layer between Ag islands and Si. The RHEED patterns show similarities with the case of Ag deposition on H-passivated Si(0 0 1) surfaces.