Catalytic action of gold atoms on the oxidation of Si(111) surfaces

Auger spectroscopy, electron energy loss spectroscopy and ion depth profiling techniques, under ultra high vacuum conditions, have been used in a comparative study of the oxidation of clean and gold precovered silicon (111) surfaces. Exposure of a Si surface covered by a few Au monolayers to an oxygen partial pressure induces the formation of SiO₄ tetrahedra even at room temperature. In contrast, oxidation under the same conditions of a clean Si(111) surface leads to the well known formation of a chemisorbed oxygen monolayer. In the case of the Au covered surfaces, the enhancement of the oxide growth is attributed to the presence of an AuSi alloy where the hybridization state of silicon atoms is modified as compared to bulk silicon. This Au catalytic action has been investigated with various parameters as the substrate temperature, oxygen partial pressure and Au coverage. The conclusions are two fold. At low temperature (T < 400°C), gold atoms enhance considerably the oxidation process. SiO₄ tetrahedra are readily formed even at room temperature. Nevertheless, the SiO₂ thickness saturates at about one monolayer, this effect being attributed to the lack of Si atoms alloyed with gold in the reaction area. By increasing the temperature (from 20°C to ～400°C), silicon diffusion towards the surface is promoted and a thicker SiO₂ layer can be grown on top of the substrate. In the case of the oxidation performed at temperature higher than 400°C, the results are similar to the one obtained on a clean surface. At these temperatures, the metallic film agglomerates into tridimensional crystallites on top of a very thin AuSi alloyed layer. The fact that the latter has no influence on the oxidation is attributed to the different local arrangement of atoms at the sample surface.     

Microstructure of epitaxial superconductive YBa2Cu3O7 thin films prepared at different deposition rates

A study is reported on the growth mechanism of YBa₂Cu₃O₇ with different growth speeds by high resolution transmission microscopy (HRTEM) and analysis of the interface and thin film microstructure. Two thin films were synthesized by pulse laser deposition on [100], miscut 5°, SrTiO₃ substrate at 820 °C, one with a pulse laser frequency of 1 Hz and one with 6 Hz. Cross-sections were studied by an H-9000 NAR HRTEM along the [010] direction. The growth process of the sample made at 1 Hz was as follows. First, distorted step flow growth occurred on a step-mediated substrate surface of 3–4 cells thickness. Second, about a 15 nm thickness of island shape growth becomes superimposed on the area of the step flow layer. Finally, thin film growth occurred but with growth fluctuation. The sample made at 6 Hz showed the characteristics of island growth; the growth area of island or ball shape was of small size and dense distribution, and seemed to be a confused mosaic stack. The influence of growth speed on YBCO epitaxial film microstructure was studied explicitly by HRTEM.     

Aging effect of SiO2 xerogel film on its microstructure and dielectric properties

The properties of porous SiO₂ xerogel film strongly depend on the aging process. The morphology of the surface modified SiO₂ xerogel film pre-aged for 1 hr at 70°C showed a two-dimensional structure. Aging for 12 h at 70°C and successive modification of the film induced some particle growth and a three-dimensional network structure. The microstructure of the modified SiO₂ xerogel films reflects the preformed structure during aging. The surface modification induced the changes of surface coverage from –OC₂H₅ and –OH bonds to –CH₃. However the content of surface chemical species was almost same regardless of aging time. The porosity of the modified sample pre-aged for 12 h at 70°C was 89%. The calculated/measured dielectric constants were 1.31/1.42, respectively     

Growth and characterization of silicon nitride films on various underlying materials

Characteristics of silicon nitride (SiN_x:H) films, grown by plasma enhanced chemical vapor deposition (PECVD) on various metals such as Ta, IrMn, NiFe, Cu, and CoFe at various temperatures down to 100 °C, were studied using measurements of BHF etch rate, surface roughness and Auger electron spectroscopy (AES). The results were compared with those obtained for SiN_x:H films on Si. The deposition rate of SiN_x:H films increased slightly as deposition temperature decreased, and showed a weak dependence on the underlying materials. The surface of the nitride films deposited on all underlying materials at lower temperatures (below 150 °C) became rougher. In particular, a bubble-like surface was observed on the nitride film deposited on NiFe at 100 °C. At higher deposition temperatures (above 200 °C), SiN_x:H films on all the above metals had small RMS values, except for films on Cu which cracked at 250 °C. BHF (10:1) etch rate increased dramatically for nitride films deposited below 150 °C. For different underlying films, the BHF etch rate was quite different, but exhibited the same trend with decrease in deposition temperature. AES measurements showed that Si and N concentrations in the SiN_x:H films were only slightly different for the various deposition temperatures and underlying materials. AES depth profile of nitride films indicated that both surface O content and the depth of oxygen penetrating into SiN_x:H increased for low temperature-deposited films. However, there was no observed oxygen signal from within the films, even for films deposited at 100 °C, and both Si and N concentrations were uniform throughout the film. Received: 26 October 2001 / Accepted: 2 March 2001 / Published online: 20 June 2001     

Study of the features of BaF<Subscript>2</Subscript> heteroepitaxy on CaF<Subscript>2</Subscript>/Si(100) layers obtained in the high-temperature growth mode

The surface morphology of BaF₂ epitaxial films grown by MBE (molecular beam epitaxy) in various modes on the surface of CaF₂/Si(100) is investigated by AFM. The CaF₂ layers on Si(100) are obtained in the high-temperature growth mode (Т _S = 750°C). It is shown that the epitaxy of BaF2 at a temperature of 600°C at the initial stage of growth leads to the formation of defects such as perforations in the epitaxial film, while epitaxy at a temperature of 750°C provides a defect-free film with a surface morphology suitable for the subsequent growth of semiconductors of IV–VI type and solid solutions based on them.     

Structural and phase transformations during initial stages of copper condensation on Si(001)

Auger-electron spectroscopy, electron-energy loss spectroscopy, low-energy electron diffraction, and atomic-force microscopy are employed to investigate the growth mechanism, composition, structural and phase states, and morphology of Cu films (0.1–1 nm thick) deposited on a Si(001)-2 × 1 surface at a lower temperature of Cu evaporation (900°C) and room temperature of a substrate. The Cu film phase is shown to start growing on the Si(001)⁻² × 1 surface after three Cu monolayers (MLs) are condensed. It has been revealed that atoms of Cu and Si(001) are mixed, a Cu₂Si film phase is formed, and, thereafter, Cu₃Si islands arise at a larger coating thickness. Annealing of the first Cu ML leads to reconstruction of the Si(001)-1 × 1-Cu surface layer, thereby modifying the film growth mechanism. As a consequence, the Cu₂Si film phase arises when the thickness reaches two to four MLs, and bulk Cu₃Si silicide islands begin growing at five to ten MLs. When islands continue to grow, their height and density reach, respectively, 1.5 nm and 2 × 10¹¹ cm⁻² and the island area is 70% of the substrate surface at a thickness of ten MLs.     

Stability and surface properties of GeSi alloy films on Si(111) substrate

Several GeSi alloy films with different surface properties were prepared from a 500 Å thick Ge film that had previously been grown on a Si(111)-7×7 substrate by molecular beam epitaxy. The films were prepared by combinations of sputtering, annealing and Ge deposition from an evaporator. The surface properties were studied by Auger electron spectroscopy (AES) and by low energy electron diffraction (LEED). A novel LEED system employing position-sensitive detection was used. The Ge film surface gave a superposition of 7×7 and c(2×8) LEED patterns. A 7×7 → 1×1 phase transition was observed at 425±10°C. An irreversible 7×7 → c(2×8) transition was observed when the sample was heated above 500°C. The Ge film melted at 750±30°C and formed a Ge_xSi_1−x (x = 0.85±0.05) alloy whose surface gave a 7×7 LEED pattern. A 7×7 → 1×1 phase transition was observed at 600±0.15°C. Prolonged sputtering and annealing resulted in a Ge_xSi_1−x (x = 0.53±0.05) alloy whose surface gave a 5×5 LEED pattern. An apparent 5×5 → 1×1 phase transition was observed at 870±10°C but at that temperature the film was converted irreversibly to one with a much lower Ge atom fraction (x = 0.025±0.005) whose surface gave a 7×7 LEED pattern. A surface with a 5×5 pattern identical to that for the x = 0.53 alloy was prepared by deposition or Ge on Si. A similar 5×5 surface was prepared by deposition of Ge on a facetted GeSi alloy surface originally showing a superposition of 5×5 and 7×7 patterns. The intensity distributions in all of the 7×7 LEED pattern were found to be similar to those for Si(111)-7×7 at nearly the same electron energies. The characteristics of the 7×7 → 1×1 phase transitions were discussed in direct comparison with those of the Si(111)7×7 → 1×1 and Ge(111)-c(2×8) → 1×1 transitions observed with the same LEED system.     

Structure and magnetic properties of CoPtCu:Ag nanocomposite films with (001) texture

Nanocomposite (001) textured CoPtCu:Ag films consisting of well separated L1₀ structure CoPtCu nanoparticles have been prepared using a CoPt/Cu/Ag multilayer precursor on SiO₂/Si(100) substrate by magnetron sputtering and subsequent vacuum thermal annealing. With a Cu concentration of 6–10% and Ag of 10–20% in atomic ratio, the films start ordering at an annealing temperature of 450 °C, which is roughly lower by 150 °C than that needed for most CoPt-based films especially with (001) texture. The perpendicular coercivities for the film are in the range from 5 kOe to 7 kOe after annealing at 500 °C in vacuum. The (001) texture for the film is partially due to the formation of an Ag underlayer after annealing, the decreasing of the ordering temperature is most-likely related to the formation of CoPtCu alloy nanoparticles in the film. PACS 75.30.Gw; 75.50.Kj; 75.70.Ak     

Segregation and adsorption of sulphur on Ni50Fe50(100) alloy: Studies of the surface composition and structure and of the effects on the passivation

The surface composition of Ni₅₀Fe₅₀(100) alloy was studied and the segregation and adsorption of sulphur were investigated by AES, LEED and radiotracer (³⁵S) techniques. Ion etching produces a surface composition identical to the matrix composition (Ni:Fe=1:1). In the temperature range 300–600°C iron segregates on the surface and nitrogen was detected. Heating to higher temperatures (>600°C) also causes the segregation of iron as well as the segregation of sulphur. The durface reaches a stable composition that does not depend on further changes of the temperature in the range 25–800°C. It consists of an almost complete monolayer of iron segregated on the alloy. The segregation of sulphur leads to the formation of a c(2×2) structure. A sulphur coverage of 45 ng cm^-2, consistent with the c(2×2) structure, was measured by the radiotracer method after chemisorption in gaseous H₂S/H₂ mixtures at 550° and 200 Torr. This sulphur monolayer is stable in a range of p_H2S/p_H2=7.4 × 10^-5-6×10^-4. Above this pressure, a preferential sulphidation of iron is observed. The effects of sulphur on the anodic dissolution and passivation of the alloy in acid solution were studied. Adsorbed sulphur promotes the dissolution and delays the passivation. When the alloy is doped with sulphur, bulk sulphur accumulates on the surface during the dissolution of Ni and Fe. This anodic segregation leads to the formation of an adsorbed layer of sulphur, followed by the growth of a sulphide which blocks the formation of the protective oxide film.     

Photoelectron Si 2<Emphasis Type="Italic">p</Emphasis> spectra of ultrathin CoSi<Subscript>2</Subscript> layers formed on Si(100)2×1

Solid-phase formation of ultrathin CoSi₂ layers on Si(100)2×1 was studied using high-resolution (～140 meV) photoelectron spectroscopy with synchrotron radiation (hν=130 eV). The evolution of Si 2p spectra was recorded both under deposition of cobalt on the surface of samples maintained at room temperature and in the course of their subsequent annealing. It was shown that Co adsorption on Si(100)2×1 is accompanied by a loss of reconstruction of the original silicon surface while not bringing about the formation of a stable CoSi₂-like phase. As the amount of deposited cobalt continues to increase (up to six monolayers), a discontinuous film of the Co-Si solid solution begins to grow on the silicon surface coated by chemisorbed cobalt. The solid-phase reaction of CoSi₂ formation starts at a temperature close to 250°C and ends after the samples have been annealed to ～350°C.     

Influence of ion-irradiation parameters on defect formation in silicon films

It is shown that unlike bulk silicon, for which amorphization is observed at an irradiation dose of 5 × 10¹⁶ ion/cm², thin silicon films on sapphire are amorphized at lower critical doses (10¹⁵ ion/cm²). An undamaged surface layer remains when the silicon films are irradiated with Si⁺ ion beams. Its thickness depends on the current density of the incident beam. Rutherford backscattering studies show that annealing at 950°C improves the crystallinity of the irradiated silicon film. Annealing of the films at 1100°C leads to mixing of the silicon-sapphire interface.     

Roughness simulation for thin films prepared by atomic layer deposition

The kinetic lattice Monte Carlo method for film growth simulation without taking crystallization into account was applied to study the roughness of the HfO₂ film grown by atomic layer deposition at 100–500°C from HfCl₄ and H₂O. The calculations were performed using a simplified kinetic mechanism of the growth of HfO₂ films obtained by reducing the detailed kinetic mechanism developed earlier. Ab initio quantum-chemical calculations were performed to determine the kinetic parameters of diffusion processes on the surface of hafnium oxide that could influence film roughness. Because of the special features of atomic layer deposition, the rate of film growth and film roughness were finite even if surface relaxation was ignored. It was found that, irrespective of the temperature, the diffusion of hydrogen and adsorbed HfCl₄ complexes did not change the profile of the growing film and only insignificantly increased the mean rate of growth. The results obtained were also qualitatively applicable to zirconium dioxide at fairly low (≤100°C) temperatures in the absence of crystallization.     

Epitaxial growth of cadmium telluride films on silicon with a buffer silicon carbide layer

An epitaxial 1–3-μm-thick cadmium telluride film has been grown on silicon with a buffer silicon carbide layer using the method of open thermal evaporation and condensation in vacuum for the first time. The optimum substrate temperature was 500°C at an evaporator temperature of 580°C, and the growth time was 4 s. In order to provide more qualitative growth of cadmium telluride, a high-quality ~100-nm-thick buffer silicon carbide layer was previously synthesized on the silicon surface using the method of topochemical substitution of atoms. The ellipsometric, Raman, X-ray diffraction, and electron-diffraction analyses showed a high structural perfection of the CdTe layer in the absence of a polycrystalline phase.

     

Effect of the chromium layer thickness on the morphology and optical properties of heterostructures Si(111)/(CrSi<Subscript>2</Subscript> nanocrystallites)/Si(111)

Growth and the optical properties of epitaxial heterostructures Si(111)/(CrSi₂ nanocrystallites)/Si(111) based on nanosized islands of chromium disilicide (CrSi₂) on Si(111) were studied using low-energy electron diffraction, atomic-force microscopy, and optical reflection and transmission spectroscopy. The heterostructures with thicknesses of 0.1, 0.3, 0.6, 1.0, and 1.5 nm were formed by reactive epitaxy at a temperature of 500°C followed by the epitaxial growth of silicon at 750°C. The specific features of changes in the density and sizes of CrSi₂ islands on the silicon surface were determined at T = 750°C as the chromium layer thickness was increased. It was established that, in the heterostructures with chromium layer thicknesses exceeding 0.6 nm, a small part of faceted Cr₂Si₂ nanocrystallites (NCs) emerge into near-surface region of the silicon, which is confirmed by the data from optical reflectance spectroscopy and an analysis of the spectral dependence of the absorption coefficient. A critical size of NCs is shown to exist above which their shift to the silicon surface is hampered. The decreased density of emerging NCs at chromium layer thicknesses of 1.0–1.5 nm is associated with the formation of coarser NCs within a silicon layer, which is confirmed by the data from differential reflection spectroscopy.     

Understanding the high temperature oxidation and ignition behaviour of two-phase Mg–Nd alloys and a comparison to single phase Mg–Nd

The oxidation kinetics and the mechanism of two-phase Mg–Nd alloys were investigated via isothermal heating experiments conducted in dry air at 500 °C for 12 h. The oxidation kinetic curves reveal improved oxidation resistance on neodymium (Nd)-containing alloys compared to pure Mg. A lower mass gain was detected at 2.5-%Nd than at 6-Nd%, which was related to the lower amount of intermetallic phase on the alloy surface. The intermetallic phase has a significant effect on the oxide growth stage. Nd₂O₃ formation on the intermetallic phases creates diffusion paths for oxygen to the metal/oxide interface, affecting both the oxidation kinetics and the oxidation resistance of the alloys. The formation of a Nd-depleted region at the subsurface due to extensive Nd oxidation at the oxide/intermetallic interface lowers the protective ability of the oxide scale. As increasing the Nd content of binary Mg–Nd alloys above 0.5 wt% shifts the alloys from single-phase region to two-phase region, it adversely affects the ignition resistance.     

Surfactant-mediated growth of CoSi2 on Si(100)

Thin co-deposited CoSi₂ films grown at 500–600°C on Si(100) are studied by scanning tunneling microscopy (STM). With a Si rich deposition we observe initially the formation of elongated three-dimensional CoSi₂ islands. The use of one preadsorbed atomic layer of As as a surfactant results in a drastic increase of the island density. This effect appears to be a consequence of a decreased rate of surface diffusion of Co and Si. At higher coverages the roughness of the CoSi₂ film is reduced considerably by the surfactant. The results are discussed with regard to the method of allotaxy which allows the fabrication of buried silicide layers. Here, the requirements for small precipitates and high growth temperature can possibly be met more efficiently using As as a surfactant.     

Synthesis and characterization of highly textured Pt–Bi thin films

Pt–Bi films were synthesized on glass and thermally oxidized silicon substrates by e-beam evaporation and annealing. The structures were characterized using X-ray diffraction (XRD) and transmission electron microscopy/selected area electron diffraction (TEM/SAED) techniques. Single-phase PtBi was obtained at an annealing temperature of 300°C, whereas a higher annealing temperature of 400°C was required to obtain the highly textured γ-PtBi₂ phase. TEM/SAED analysis showed that the films annealed at 400°C contain a dominant γ-PtBi₂ phase with a small amount of β-PtBi₂ and α-PtBi₂ phases. Both the PtBi and γ-PtBi₂ phases are highly textured in these two kinds of film: the c-axis of the hexagonal PtBi phase is mostly in the film plane, whereas the c-axis of the trigonal γ-PtBi₂ phase is perpendicular to the film plane. The electrical resistivity of the film with the γ-PtBi₂ phase was smaller by one order of magnitude than that of the film with the PtBi phase.     

Enhancement of the electron-stimulated desorption from amorphous aluminum oxide films on silicon during an increase in the substrate temperature

The effect of high-temperature electron-stimulated desorption (ESD) from 20-nm-thick Al₂O₃ films deposited onto silicon wafers is studied. The ESD effect is found to be significantly enhanced upon heating. The films are found to decompose during ion beam irradiation of a heated substrate resulting in pure Al appearance. This process is accompanied by the formation of islands and almost pure silicon surface regions at a certain critical irradiation dose. Outside the irradiation zone, a 20-nm-thick Al₂O₃ film remains continuous even upon heating to 700°C and holding for 90 min. The effect of the primary electron beam energy on ESD from a 20-nm-thick Al₂O₃ film on silicon is investigated, and the parameters at which ESD takes place or absent are determined.     

Photoinduced self-limited low-temperature growth of ultra-thin silicon-oxide films with water vapor

The growth of ultra-thin (<2 nm) silicon-oxide films was investigated on Si(100):H, Si(111):H, and a-Si:H surfaces in a pure water atmosphere (0.1–10 Pa) at low temperatures of 30–250 °C. Oxidation was induced photochemically by pulsed F₂-laser radiation at 157 nm. The thickness and composition of the growing oxide films were monitored in real time by spectroscopic ellipsometry in the photon energy range of 1.15–4.75 eV. The mechanism of laser-induced silicon oxidation in a H₂O atmosphere is shown to differ fundamentally from the classical Deal–Grove mechanism of thermal oxidation at 900–1200 °C, as well as from the photoinduced low-temperature oxidation in an O₂ atmosphere. In particular, the film thickness essentially does not depend on temperature below 250 °C. A kinetic model is developed for low-temperature silicon oxidation in a H₂O atmosphere. According to this model, the growth is limited at small thicknesses by the oxidation reaction and at larger thicknesses by reactions of the diffusing oxidizing species in the oxide layer. Very good agreement is established between this kinetic model and the ellipsometric measurements and the temperature and pressure dependence of the water oxidation process. PACS 82.65.+r; 07.60.Fs; 81.65.Mq; 82.50.Hp     

Features and mechanisms of growth of cubic silicon carbide films on silicon

The mechanisms and specific features of the growth of silicon carbide layers through vacuum chemical epitaxy in the range of growth temperatures from 1000 to 700°C have been considered. The structure of the heterojunction formed has been studied using the results of the performed investigations of photoluminescence spectra in the near-infrared wavelength range and the data obtained from the mass spectrometric analysis. It has been found that, in the silicon layer adjacent to the 3C-SiC/Si heterojunction, the concentration of point defects significantly increases and the dislocation structure is not pronounced. According to the morphological examinations of the surface of the growing film, by analogy with the theory of thermal oxidation of silicon, the theory of carbidization of surface silicon layers has been constructed. A distinctive feature of the model under consideration is the inclusion of the counter diffusion fluxes of silicon atoms from the substrate to the surface of the structure. The growth rate of films and the activation energy of diffusion processes have been estimated. The performed experiments in combination with the developed growth model have explained the aggregates of voids observed in practice under the silicon carbide layer formed in the silicon matrix and the possibility of forming a developed surface morphology (the island growth of films) even under conditions using only one flow of hydrocarbons in the reactor.