Effect of growth parameters on the heteroepitaxy of 3C-SiC on 6H-SiC substrate by chemical vapor deposition

Epitaxial 3C-SiC(1 1 1) films were grown on 6H-SiC(0 0 0 1) Si face on axis substrates by chemical vapor deposition under H₂, SiH₄ and C₃H₈ in a cold wall vertical reactor. Two temperatures were studied (1450 and 1700 °C) with various C/Si ratio and deposition time. It was found that under conditions giving high lateral growth (low C/Si and/or high temperature), homoepitaxial growth occurred even at temperatures as low as 1450 °C. For other conditions, the 3C-SiC polytype was detected and always together with the formation of double positioning boundaries whose density was found to depend on the growth conditions but not on the initial surface reconstruction. Single domain enlargement was observed when growth was performed at 1700 °C over a nucleation layer grown at 1450 °C.     

Boron phosphide films prepared by co-evaporation technique: Synthesis and characterization

We report the physical and electronic properties of BP films of 1:1, 1:1.15 and 1.25:1 stoichiometry prepared by co-evaporating B and P onto glass and Si (100) substrates. Compositional information was obtained from X-ray photoelectron spectroscopy measurements. Optical studies indicated allowed indirect transition at  2.08 eV. The room temperature photoluminescence peak at  2.01 eV was due to band gap transitions which shifted to higher energy value when recorded at lower temperature. Fourier transformed infrared (FTIR) spectra were dominated by the characteristic peak of the B–P located at  810 cm^− 1 which could be identified as arising due to transverse optical vibration mode (k  0) while the shoulder at  850 cm^− 1 may be due to longitudinal optical (k  0) vibration mode. Other characteristic peaks for B–O, P–O and B–H vibration modes were also present in the FTIR spectra. Characteristic Raman peaks for BP located at  415 cm^− 1 and 806 cm^− 1 were observed in these films.     

Observation of metal on Si(0 0 1) by STM/STS and its consideration based on the first principles calculations

Local density of states (LDOS) is obtained by the first principles calculation based on the density functional theory on the Si(0 0 1)2 × 1 surface and on the surface with an Al dimer. At an Al dimer, LDOS has a high intensity in the conduction band region, which cannot be seen on the Si(0 0 1)2 × 1 surface. This tendency is observed in STS measurements as well. The possibility for a microelementary analysis is presented by applying this method to other metal atoms on the Si surface. Furthermore, it is pointed out that STS measurements should be always performed at the same tip-sample separation to obtain reproducible STS spectrums.     

Boron segregation on a vicinal Si(1 0 0) surface

Energetics of boron on a Si(1 0 0) stepped surface has been studied quantum mechanically at semi-empirical level. The step is represented by a cluster of silicon atoms and the boron impurity is moved in the step in substitutional and interstitial positions. The optimal configuration of the step with the impurity is evaluated from the minimization of the total energy. It has been found that, similarly to the known behavior in the flat surface, the boron impurity segregates below the surface. However the preferred adsorption sites have also a remarkable dependence on the distance from the step-edge. We illustrate the dependence of these sites on the step geometry.     

Microwave-hydrothermal synthesis of nanostructured Na-birnessites and phase transformation by arsenic(III) oxidation

Microwave-hydrothermal synthesis was employed to produce Na-birnessites. Crystalline, single-phase materials were obtained at temperatures as low as 120 °C and times as short as 1 min. X-ray diffraction and Raman spectroscopy were used to characterize the structural features of the nanostructured powders. Birnessites possessed a monoclinic structure in space group C2/m with nine Raman-active bands, all of which were observed for the first time due to optimized acquisition of the spectroscopic data. The highly reactive materials produced were submitted to sorption experiments with As(III). An oxidative precipitation occurred with the production of Mn(II) arsenate at higher arsenic concentrations. In addition, the formation of hausmannite (Mn₃O₄) was confirmed by X-ray diffraction and Raman analyses of the reacted solid phase. The observed 14 Raman-active modes were adjusted according to the tetragonal I4₁/amd space group for hausmannite. An additional band related to the breathing mode of the arsenate was observed, leading to the conclusion that adsorption onto hausmannite takes place in addition to the oxidative precipitation of manganese arsenate.     

Adsorption/desorption kinetics of Na atoms on reconstructed Si (111)-7 × 7 surface

Self-assembled nanostructures on a periodic template are fundamentally and technologically important as they put forward the possibility to fabricate and pattern micro/nano-electronics for sensors, ultra high-density memories and nanocatalysts. Alkali-metal (AM) nanostructure grown on a semiconductor surface has received considerable attention because of their simple hydrogen like electronic structure. However, little efforts have been made to understand the fundamental aspects of the growth mechanism of self-assembled nanostructures of AM on semiconductor surfaces. In this paper, we report organized investigation of kinetically controlled room-temperature (RT) adsorption/desorption of sodium (Na) metal atoms on clean reconstructed Si (111)-7 × 7 surface, by X-ray photoelectron spectroscopy (XPS). The RT uptake curve shows a layer-by-layer growth (Frank-vander Merve growth) mode of Na on Si (111)-7 × 7 surfaces and a shift is observed in the binding energy position of Na (1s) spectra. The thermal stability of the Na/Si (111) system was inspected by annealing the system to higher substrate temperatures. Within a temperature range from RT to 350 °C, the temperature induced mobility to the excess Na atoms sitting on top of the bilayer, allowing to arrange themselves. Na atoms desorbed over a wide temperature range of 370 °C, before depleting the Si (111) surface at temperature 720 °C. The acquired valence-band (VB) spectra during Na growth revealed the development of new electronic-states near the Fermi level and desorption leads the termination of these. For Na adsorption up to 2 monolayers, decrease in work function (−1.35 eV) was observed, whereas work function of the system monotonically increases with Na desorption from the Si surface as observed by other studies also. This kinetic and thermodynamic study of Na adsorbed Si (111)-7 × 7 system can be utilized in fabrication of sensors used in night vision devices.     

Raman scattering studies of Mn-doped ZnO thin films deposited under pure Ar or Ar + N2 sputtering atmosphere

This paper investigates the anomalous and specific Raman modes present in Mn-doped ZnO thin films deposited using the magnetron co-sputtering method. To trace these peaks, we prepared Mn-doped ZnO films with different Mn concentrations by altering the sputtering power of the Mn target in a pure Ar or Ar + N₂ sputtering atmosphere. A broad band observed in the Raman spectra of heavily Mn-doped ZnO films ranges from 500 to 590 cm^− 1. This band involves the enhanced A₁ longitudinal mode and activated silent modes of ZnO, as well as a characteristic mode of Mn₂O₃. Four anomalous Raman peaks at approximately 276, 510, 645 and 585 cm^− 1 are present in pure and Mn-doped ZnO films deposited under the Ar + N₂ sputtering atmosphere. The peaks at 276 cm^− 1 and 510 cm^− 1 may originate from the complex defects of Zn_i-N_O and Zn_i-O_i, respectively, while the peak at approximately 645 cm^− 1 could be due to a complex defect of Zn_i coupled with both the N and Mn dopants. The results of this study suggest classifying the origins of anomalous and specific Raman peaks in Mn-doped ZnO films into three major types: structural disorder and morphological changes caused by the Mn dopant, Mn-related oxides and intrinsic host-lattice defects coupled with/without the N dopant.     

Influence of Si doping level on the Raman and IR reflectivity spectra and optical absorption spectrum of GaN

The optical absorption (hν) and Raman and Infra Red (IR) spectra of Si doped GaN layers deposited on sapphire through buffer layers have been recorded for electron concentrations from 5×10¹⁷ to 5×10¹⁹ cm⁻³. The (hν) values deduced from photothermal deflection spectroscopy (0.5–3.5 eV) and IR absorption (0.15–0.5 eV) vary between 50 and 10⁴ cm⁻¹ showing doping dependant free electron absorption at low energy, doping independant band gap at high energy, and slowly doping dependant defect absorption in the medium energy range. In our micro Raman geometry, maxima appear or can be deduced near the frequency expected for either the A₁(LO⁻) or the A₁(LO⁺) modes split from the A₁(LO) mode by plasmon phonon interaction. There is a large systematic evolution in the expected way for the IR reflectivity.     

Growth of 3C-SiC on Si(111) using the four-step non-cooling process

A modified four-step method was applied to grow a 3C-SiC thin film of high quality on the off-axis 1.5° Si(111) substrate in a mixed gas of C₃H₈, SiH₄ and H₂ using low pressure chemical vapor deposition. The modified four-step method adds a diffusion step after the carburization step and removes the cooling from the traditional three-step method (clean, carburization, and growth). The X-ray intensity of the 3C-SiC(111) peak is enhanced from 5 × 10⁴ counts/s (the modified three steps) to 1.1 × 10⁵ counts/s (the modified four steps). The better crystal quality of 3C-SiC is confirmed by the X-ray rocking curves of 3C-SiC(111). 3C-SiC is epitaxially grown on Si(111) supported by the selected area electron diffraction patterns taken at the 3C-SiC/Si(111) interface. Some {111} stacking faults and twins appear inside the 3C-SiC, which may result from the stress induced in the 3C-SiC thin film due to lattice mismatch. The diffusion step plays roles in enhancing the formation of Si-C bonds and in reducing the void density at the 3C-SiC/Si(111) interface.     

Characterization of fluorine-doped silicon dioxide films by Raman spectroscopy and Electron-spin resonance

We have measured Raman and Electron-spin resonance (ESR) spectra of fluorine-doped SiO₂ films deposited by two different methods. In high-density plasma (HDP) films, the Raman band at about 490 cm^− 1 becomes drastically stronger as the F/Si ratio increases, whereas the Raman band from threefold ring defect is independent of the F/Si ratio. The unusual increase of the intensity of the 490 cm^− 1 band in HDP films has been interpreted in terms of the existence of Si-Si clusters. From a comparison between Raman spectra of HDP film and plasma chemical vapor deposition using tetraethoxysilane (p-TEOS) film with the same F/Si ratios it has been found that HDP film has more Si-Si bonds and threefold ring defects than p-TEOS film. Furthermore, the polarized Raman spectra in the 810 cm^− 1 bands indicate that inhomogeneous SiO₂ clusters of various sizes should exist in the network structure of HDP film. The result of the ESR measurement shows that HDP films have fewer dangling bonds than p-TEOS films. It is considered that many Si-Si clusters, threefold ring defects, and inhomogeneous SiO₂ cluster sizes, and the few dangling bonds in HDP films give rise to the film properties of low stress, good adhesion with Si substrate, and low water permeation.     

Electronic structure of bulk and (0 0 1) surface layers of pyrite FeS2

The electronic structure of bulk and (0 0 1) surface layers of iron pyrite FeS₂ have been calculated using a modern ab initio pseudo-potential method. For the bulk pyrite the calculated lattice constant, position parameter of sulfur, and band gap are in agreement with experimental values. For the (0 0 1) surface it is found that surface states form a conducting band. The conducting band and the conducting band tail of the bulk conduction manifold overlap and the width of the band gap is not influenced by the surface state. The surface states arise mainly from the iron 3d orbitals in the topmost layer with a smaller contribution from the sulfur 3p states. The relaxation of iron and sulfur atoms is found to be greatest in the top most layer. The surface energy is calculated to be equal to 1.063 J/m².     

Energetics of Ge addimers on the Si(1 0 0) and Ge(1 0 0) surfaces: a comparative study

The adsorption energetics of Ge dimers on the (1 0 0) surfaces of Ge and Si has been investigated using the first-principles molecular dynamics method. Four high-symmetry configurations have been considered and fully relaxed. The most stable configuration for Ge dimers on Si(1 0 0) is found to be in the trough between two surface dimer rows, oriented parallel to the substrate Si dimers. These results are consistent with recent experimental studies of the system using the scanning tunneling microscopy (STM), and help to clarify some existing controversies on the interpretation of the STM images. In contrast, for Ge dimers on Ge(1 0 0), the most stable configuration is on top of the substrate dimer row.     

Synthesis of hexagonal and cubic GaN thin film on Si (111) using a low-cost electrochemical deposition technique

Gallium nitride GaN thin films were deposited on Si (111) substrates using electrochemical deposition technique at 20 °C. SEM images and EDX results indicated that the growth of GaN films varies with the current density. XRD and Raman analyses showed the presence of hexagonal wurtzite and cubic zinc blende GaN phases with the crystallite size around 18-19 nm. Photoluminescence spectrum showed that the energy gaps of h-GaN/Si (111) and c-GaN/Si (111) were near 3.39 eV and 3.2 eV respectively at 300 K. Raman spectrum indicated the presence of mixed phonon modes of hexagonal and cubic GaN.     

Theoretical investigation of atomic structure and electronic properties of Ca/Si(110)-(2 × 1) reconstruction

We have presented first-principles total-energy calculations for the adsorption of Ca metals onto a Si(110) surface. The density functional method was employed within its local density approximation to study the atomic and electronic properties of the Ca/Si(110) structure. We considered the (1 × 1) and (2 × 1) structural models for Ca coverages of 0.5 monolayer (ML) and 0.25 ML, respectively. Our total-energy calculations indicate that the (1 × 1) phase is not expected to occur. It was found that Ca adatoms are adsorbed on top of the surface and form a bridge with the uppermost Si atoms. The Ca/Si(110)-(2 × 1) produces a semiconducting surface band structure with a direct band gap that is slightly smaller than that of the clean surface. One filled and two empty surface states were observed in the gap; these empty surface states originate from the uppermost Si dangling bond states and the Ca 4 s states. It is found that the Ca-Si bonds have an ionic nature and complete charge being transferred from Ca to the surface Si atoms. Finally, the key structural parameters of the equilibrium geometry are detailed and compared with the available results for metal-adsorbed Si(110) surface, Ca/Si(001), and Ca/Si(111) structures.     

Characterization of 3C-SiC micro-pillars on Si(100) substrate grown by vapor-liquid-solid process

Cubic silicon carbide (3C-SiC) micro-pillars were fabricated on Si (100) substrate by vapor-liquid-solid (VLS) process. The microstructure and residual stress of the micro-pillars were investigated by electron microscopy and micro-Raman spectroscopy, respectively. The selected area diffraction pattern of the SiC micro-pillar indicated that the micro-pillar was 3C-SiC single crystal. The residual stress of about 0.3 GPa in the micro-pillar calculated from Raman spectrum indicated that the VLS grown 3C-SiC micro-pillars had good crystalline quality.     

Effects of SiC buffer layer growth temperature on the residual strain of GaN/SiC/Si thin films

Effects of SiC buffer layers were studied on the residual strain of GaN films grown on 3C-SiC/Si (111) substrates. It was clearly observed by Raman scattering measurement that the residual strain of the GaN/Si is reduced by inserting the SiC intermediate layer. Furthermore, residual strain within the GaN/SiC/Si films decreased when the growth temperature of the SiC buffer layer decreased. It was proposed that the irreversible creep phenomenon occurs during the high temperature growth of SiC, affecting nature of the residual strain within the SiC and the GaN layers.     

Ab initio study on the lattice instability of silicon and aluminum under [0 0 1] tension

Two different single crystals, Si with the diamond structure and Al with face-centered-cubic, are subjected to [0 0 1] tension in ab initio molecular dynamics (static) simulations based on Bachelet–Hammann–Schlüter (BHS) pseudopotential. Not only the ideal tensile strength under isotropic Poisson contraction, but also the crystal stability and bifurcation to anisotropic contraction are discussed in terms of the elastic stiffness matrix and the change in the charge density. The ideal tensile strengths are overestimated to as high as =0.18, σ=18.7 GPa for Si and =0.25, σ=23.5 GPa for Al, respectively. These values are inconsistent with the experimentally observed characteristics such as the hardness of Al being lower than that of Si. The elastic stiffness matrix reveals that the crystals become unstable at far lower strain and stress, =0.094, σ=10.7 GPa for Si and =0.055, σ=5.65 GPa for Al, and bifurcate to the lower energy pass of the anisotropic contraction. The change in the electronic structure suggests that nucleation/passage of a partial dislocation would take place in the bifurcated anisotropic contraction. Thus the instability point indicates the onset of the nonelastic deformation and is much more important than the ideal tensile strength.     

CVI-GSI工艺制备C/C-SiC复合材料的组成结构与力学性能

采用密度为1.0g/cm~3的C/C素坯,联合化学气相渗透(CVI)和气相渗硅(GSI)2种工艺制备C/C-SiC复合材料,研究CVI C/C-SiC复合材料中间体的密度对CVI-GSI C/C-SiC复合材料物相组成、微观结构及力学性能的影响。结果表明:随着CVI C/C-SiC复合材料中间体密度的增大,CVI-GSI C/C-SiC复合材料C含量增多,残余Si含量减少,SiC含量先增多后减少,CVI-GSI C/C-SiC复合材料的密度先增大后减小;随着CVI C/C-SiC复合材料中间体的密度由1.27g/cm~3增加到1.63g/cm~3时,得到的CVI-GSI C/C-SiC复合材料的力学性能先升高后降低。当CVI C/C-SiC复合材料密度为1.42g/cm~3时,制得的CVI-GSI C/C-SiC复合材料力学性能最好,其弯曲强度为247.50MPa,弯曲模量为25.63GPa,断裂韧度为10.08MPa·m~(1/2)。     

Growth of 3C-SiC on 150-mm Si(100) substrates by alternating supply epitaxy at 1000 °C

To lower deposition temperature and reduce thermal mismatch induced stress, heteroepitaxial growth of single-crystalline 3C-SiC on 150 mm Si wafers was investigated at 1000 °C using alternating supply epitaxy. The growth was performed in a hot-wall low-pressure chemical vapor deposition reactor, with silane and acetylene being employed as precursors. To avoid contamination of Si substrate, the reactor was filled in with oxygen to grow silicon dioxide, and then this thin oxide layer was etched away by silane, followed by a carbonization step performed at 750 °C before the temperature was ramped up to 1000 °C to start the growth of SiC. Microstructure analyses demonstrated that single-crystalline 3C-SiC is epitaxially grown on Si substrate and the film quality is improved as thickness increases. The growth rate varied from 0.44 to 0.76 ± 0.02 nm/cycle by adjusting the supply volume of SiH₄ and C₂H₂. The thickness nonuniformity across wafer was controlled with ± 1%. For a prime grade 150 mm virgin Si(100) wafer, the bow increased from 2.1 to 3.1 μm after 960 nm SiC film was deposited. The SiC films are naturally n type conductivity as characterized by the hot-probe technique.     

Relaxing layers of silicon carbide grown on a silicon substrate by magnetron sputtering

Epitaxial layers of silicon carbide of the 3C-polytype are prepared by magnetron sputtering on Si(111) substrates of structural perfection with ω_θ = 1.4°. The crystalline structure and surface morphology of the 3C-SiC/Si(111) heterostructures depending on film thickness are studied by X-ray diffraction, Raman scattering, and atomic-force microscopy. It is found that the additional energy of ionized particles that is imparted to the Si(111) substrate during magnetron sputtering contributes the formation of strong C-C and β-SiC bonds, which hinders the crossing of the grain boundary by dislocations with increasing growth time.