Thermodynamics of a phase transition of silicon nanoparticles at the annealing and carbonization of porous silicon

The formation of SiC nanocrystals of the cubic modification in the process of high-temperature carbonization of porous silicon has been analyzed. A thermodynamic model has been proposed to describe the experimental data obtained by atomic-force microscopy, Raman scattering, spectral analysis, Auger spectroscopy, and X-ray diffraction spectroscopy. It has been shown that the surface energy of silicon nanoparticles and quantum filaments is released in the process of annealing and carbonization. The Monte Carlo simulation has shown that the released energy makes it possible to overcome the nucleation barrier and to form SiC nanocrystals. The processes of laser annealing and electron irradiation of carbonized porous silicon have been analyzed.     

Exciton related photoluminescence stimulation in SiC nanocrystals

The paper presents the results of porous SiC characterization using scanning electron microscopy (SEM), X-ray diffraction (XRD) and photoluminescence spectroscopy techniques. XRD study shows the investigated porous 6H-SiC layers contain inclusions of 4H-SiC and 15R-SiC polytypes as well as the amorphous graphite phase. Photoluminescence study of PSiC layers with different thicknesses and SiC NC sizes reveals the intensity stimulation for exciton and defect-related PL bands. The intensity stimulation of defect-related PL bands is due to the increase, at the etching process, of the concentration of surface defects, apparently to deal with carbon. The intensity enhancement for exciton-related PL bands is attributed to the exciton recombination rate increasing due to the realization of exciton confinement and exciton–polariton effects in big size SiC NCs of different polytypes (6H-PSiC with inclusions of 15R- and 4H-PSiC).     

Comparative study of porous amorphous a-Si1−xCx films and a-Si1−xCx membranes on structural and luminescence properties

Electrochemical etching of amorphous SiC in fluoride solution was studied. Anodic dissolution and passivation are observed for p-type electrodes under dark illumination. The dissolution of p-type a-Si_1−xC_x is found to be under mixed transport/kinetic control; the diffusion current is of first order in fluoride concentration. Porous etching was not observed in this case. The surface finish of 6H-SiC depends on the experimental conditions; both uniform and porous etching is observed. In this paper, we report the formation of porous p-type amorphous SiC (a-Si_1−xC_x) films, elaborated previously by DC magnetron sputtering and analyze the porous layers (PSC) using scanning electron microscopy, spectrophotometer and photoluminescence. The crystal structures and the preparation conditions of porous SiC are shown to have an effect on the structural and electrical properties of the material obtained. SEM observation indicates that the porous a-Si_1−xC_x layers have shown some specific feature; a semi-cylindrical structure of the porous network has been observed.     

Investigation of porous silicon carbide as a new material for environmental and optoelectronic applications

In this paper, we present an experimental study on the chemical and electrochemical etching of silicon carbide (SiC) in different HF-based solutions and its application in different fields, such as optoelectronics (photodiode) and environment (gas sensors). The thin SiC films have been grown by pulsed laser deposition method. Different oxidant reagents have been explored. It has been shown that the morphology of the surface evolves with the etching conditions (oxidant, concentration, temperature, etc.). A new chemical polishing solution of polycrystalline 6H-SiC based on HF:Na₂O₂ solution has been developed. Moreover, an electrochemical etching method has been carried out to form a porous SiC layer on both polycrystalline and thin SiC films. The PL results show that the porous polycrystalline 6H-SiC and porous thin SiC films exhibited an intense blue luminescence and a green-blue luminescence centred at 2.82 eV (430 nm) and 2.20 eV (560 nm), respectively. Different device structures based on both prepared samples have been investigated as photodiode and gas sensors.     

包覆燃料颗粒碳化硅层的Raman光谱研究

本文研究了球床高温气冷堆燃料元件中包覆颗粒碳化硅层的Raman光谱. 通过分析不同制备条件下的碳化硅层断面的Raman光谱的峰位、半高全宽与强度, 明确了包覆颗粒中碳化硅层的晶相特征、密度变化和剩余应力等物性.通过分析不同密度碳化硅层一级Raman峰的同步、异步二维相关谱, 发现其LO模较TO模对于密度变化的响应更敏感. 这些结论为研究球床高温气冷堆燃料元件包覆颗粒中碳化硅层的结构及其物性有指导意义.     

一维纳米材料的拉曼光谱学研究

本文将报告对硅纳米线、多孔硅、Si C纳米棒和碳纳米管等一维纳米体系的本征拉曼光谱及其特征的研究结果 ,并讨论拉曼光谱在上述材料的几何和物理特性研究中的应用。     

无紫外光照射下n型15R-SiC及6H-SiC晶体的电化学腐蚀

本文在无紫外光照射下通过电化学腐蚀法制备了多孔n型15R-及6H-SiC,并用扫描电子显微镜(SEM),拉曼散射及X射线衍射仪(XRD)对多孔层的结构进行了分析。结果表明:晶体的晶型及氧化条件等因素对多孔结构有较大影响。首次观察到多孔n型15-SiC的半圆管状结构,其孔隙率约是66%。     

Diamond-like and graphite-like carbon states in short-period superlattices

The Raman and luminescence spectra are studied in superlattices consisting of carbon layers separated by thin SiC barrier layers. It is shown experimentally that, upon the avalanche annealing of an initially amorphous superlattice, the carbon layers can crystallize into either a diamond-like or graphite-like structure, depending on the geometrical parameters of the superlattice. A method is proposed for obtaining carbon films with a specified crystal modification within a unified technology.     

Investigation of Porous Silicon Wetting by Raman Scattering

Wetting phenomena in porous silicon layers are experimentally investigated by Raman scattering. The experimental results show a reversible blue-shift of Raman spectra of wetted porous silicon layers with respect to the unperturbed layers. We ascribe the shift to a compressive stress due to the increased lattice mismatch between the porous silicon layer and the bulk silicon substrate in wetting conditions.     

SiC过渡层制备温度对碳化硅/氟化类金刚石复合薄膜血液相容性的影响

以316L不锈钢为基底,SiC晶体为靶材,Ar为源气体,采用磁控溅射法在不同温度下制备出系列SiC过渡层.然后以高纯石墨作靶,Ar和CHF_3为源气体,在同一工艺条件下再续镀一层氟化类金刚石(F-DLC)薄膜,形成SiC/F-DLC复合薄膜.研究表明,相比于F-DLC薄膜,复合薄膜的附着力显著增加,血液相容性明显改善.通过样品的拉曼和红外光谱分析了不同温度下制备的SiC过渡层以及复合薄膜结构的演变.结果表明,控制SiC过渡层制备温度可以有效调制过渡层中C=C键的比例以及—C—C—不饱和键的密度,复合薄膜中保留较高比例的芳香环式结构以及合适的F/C比是薄膜的血液相容性得以进一步改善的原因,SiC过渡层制备温度控制在500℃左右效果尤为明显.SiC薄膜和F-DLC两种薄膜的界面处形成一定比例的Si—C键和C=C键是导致复合薄膜附着力显著上升的直接原因.适当条件下在316L不锈钢和F-DLC薄膜之间增加SiC过渡层对于增强薄膜的附着力、改善其血液相容性是可行、有效的.     

Raman Spectrum of Epitaxial Graphene on SiC （0001） by Pulsed Electron Irradiation

We report new Raman features of epitaxial graphene （EG） on Si-face 4H-SiC prepared by pulsed electron irradiation （PEI）. With increasing graphene layers, frequencies of G and 2D peaks show blue-shifts and approach those of bulk highly-oriented pyrolytic graphite. It is indicated that the EG is slightly tension strained and tends to be strain-free. Meanwhile, single Lorentzian line shapes are well fitted to the 2D peaks of EG on SiC（O001） and their full widths at half maximum decrease with the increasing graphene layers, which indicates that the multilayer EG on Si-face can also contain turbostratic stacking by our PEI route instead of only AB Bernal stacking by a traditional thermal annealing method. It is worth noting that the stacking style plays an important role on the charge carrier mobility. Therefore our findings will be a candidate for growing quality graphene with high carrier mobility both on the Si- and C-terminated SiC substrate. Mechanisms behind the features are studied and discussed.     

Structural and optical properties of thin films porous amorphous silicon carbide formed by Ag-assisted photochemical etching

In this work, we present the formation of porous layers on hydrogenated amorphous SiC (a-SiC: H) by Ag-assisted photochemical etching using HF/K₂S₂O₈ solution under UV illumination at 254 nm wavelength. The amorphous films a-SiC: H were elaborated by d.c. magnetron sputtering using a hot pressed polycrystalline 6H-SiC target. Because of the high resistivity of the SiC layer, around 1.6 MΩ cm and in order to facilitate the chemical etching, a thin metallic film of high purity silver (Ag) has been deposited under vacuum onto the thin a-SiC: H layer. The etched surface was characterized by scanning electron microscopy, secondary ion mass spectroscopy, infrared spectroscopy and photoluminescence. The results show that the morphology of etched a-SiC: H surface evolves with etching time. For an etching time of 20 min the surface presents a hemispherical crater, indicating that the porous SiC layer is perforated. Photoluminescence characterization of etched a-SiC: H samples for 20 min shows a high and an intense blue PL, whereas it has been shown that the PL decreases for higher etching time. Finally, a dissolution mechanism of the silicon carbide in 1HF/1K₂S₂O₈ solution has been proposed.     

Inelastic light scattering and X-ray diffraction from thick free-standing porous silicon films

The results of Raman scattering and X-ray diffraction studies of thick, free-standing, porous Si layers with thickness up to 500 μm are presented. The Raman scattering spectra have a distinctive difference from previous data for porous Si films on Si substrate and for thin, free-standing, porous Si layers. The experimental data can be explained by a modified phonon confinement model that accounts for a comprehensive strained Si nanocrystal. The comprehensive strain is a tensile one, and the value of stress can be up to 3 GPa. This interpretation is supported by data of X-ray diffraction measurements.     

On the correction of errors in quantum cryptography systems

The Raman and photoluminescence spectra of short-period C/SiC superlattices produced by RF magnetron sputtering are investigated. The Raman data indicate that, in 35-period Sitall/Ni/[C/SiC] superlattices with the C and SiC effective thicknesses of 3.5 and 3 Å, respectively, subjected to postgrowth avalanche annealing, the carbon layers assume the structure of multilayer graphene with 3–5 graphene sheets per superlattice period. A method for the fabrication of graphene-like carbon structures on the basis of short-period superlattices grown by RF sputtering is suggested and implemented.     

Biomorphous SiC ceramics prepared from cork oak as precursor

Porous ceramic materials of SiC were synthesized from carbon matrices obtained via pyrolysis of natural cork as precursor. We propose a method for the fabrication of complex-shaped porous ceramic hardware consisting of separate parts prepared from natural cork. It is demonstrated that the thickness of the carbon-matrix walls can be increased through their impregnation with Bakelite phenolic glue solution followed by pyrolysis. This decreases the material’s porosity and can be used as a way to modify its mechanical and thermal characteristics. Both the carbon matrices (resulted from the pyrolysis step) and the resultant SiC ceramics are shown to be pseudomorphous to the structure of initial cork. Depending on the synthesis temperature, 3C-SiC, 6H-SiC, or a mixture of these polytypes, could be obtained. By varying the mass ratio of initial carbon and silicon components, stoichiometric SiC or SiC:С:Si, SiC:С, and SiC:Si ceramics could be produced. The structure, as well as chemical and phase composition of the prepared materials were studied by means of Raman spectroscopy and scanning electron microscopy.     

Effect of changing incident wavelength on Raman features of optical phonons in SiC nanorods and TaC nanowires

Novel Raman scattering in polar semiconductor SiC and TaC one-dimensional materials have been carried out. With increasing incident laser wavelength from 488 to 633 nm there is a huge difference in Raman intensity enhancement for the LO/IF peaks and the TO peak. This has been interpreted as due to Fröhlich interaction and abundant defects in polar nano-scale semiconductor materials.     

Isotopic heterogeneity in synthetic and natural silicon carbide

The distribution of both carbon and silicon isotopes in synthetic sublimation growth SiC wafers and in natural SiC grains was studied using secondary ion mass-spectrometry (SIMS). Significant variations in both isotopic ratios were observed which were broadly correlated with the crystalline perfection as documented by Raman microspectroscopy. Domains consisting of 15R (or with its admixture) are, on average, enriched in ¹²C isotope relative to 6H domains, and they also show larger scatter in their observed silicon isotope ratios. We ascribe such heterogeneity to fluctuations of Si/C ratio in the growth medium and it is possible to model the spatial extent of such fluctuations. For the natural SiC grains the isotopic data suggest that they grew under relatively stable conditions, although some of them show significant isotopic zoning.     

High-dose carbon implantations into silicon: fundamental studies for new technological tricks

Depending on the implantation temperature, the implantation of carbon ions into silicon at high doses results in the formation of either amorphous SiC_x or crystalline 3C-SiC precipitates. Various aspects of the precipitation behaviour observed, such as the impeded nucleation, the limited growth and the resulting sensitivity to ballistic destruction are attributed to the large interfacial energy between crystalline silicon and 3C-SiC. Periodically arranged amorphous SiC_x nanoclusters, which are formed at lower temperatures, are shown to promote amorphisation by their surrounding stress field and to represent sinks for silicon self-interstitials, which can be activated by annealing at 900 °C. By control of the depth distribution of equally sized, oriented 3C-SiC precipitates formed at higher implantation temperatures, it is possible to establish suitable starting conditions for the formation of buried homogeneous, single-crystalline 3C-SiC layers during a post-implantation anneal. The properties of these ion-beam-synthesised SiC layers are described and attempts to combine them with insulating and metallic layers are reviewed. A survey is given of the emerging applications of ion-beam-synthesised buried SiC layers and microstructures in electronic, optical and micromechanical devices and as large-area SiC pseudosubstrates. Received: 11 November 2002 / Accepted: 12 November 2002 / Published online: 4 April 2003 RID="*" ID="*"Corresponding author. Fax: +49-821/598-3425, E-mail: lindner@physik.uni-augsburg.de     

Raman scattering in mosaic silicon carbide films

The Raman spectra of mosaic silicon carbide films grown on silicon substrates by solid-state epitaxy have been studied. The main polytypes forming the film material have been determined. It has been experimentally revealed that the properties of the silicon carbide film are changed after an aluminum nitride film is deposited on the former film. This has been interpreted as a manifestation of good damping properties of the SiC film when layers of other semiconductors are grown on it.     

Effect of Al Doping on Properties of SiC Films

Undoped and Al-doped 3C-SiC films are deposited on Si（100） substrates by low-pressure chemical vapour deposition. Effects of aluminium incorporation on crystallinity, strain stress, surface morphology and growth rate of SiC films have been investigated. The x-ray diffraction patterns and rocking curves indicate that the crystallinity is improved with aluminium doping. Raman scatting patterns also demonstrate that the strain stress in SiC films is released due to the incorporation of Al ions and the increase of film thickness. Furthermore, due to the catalysis of surface reaction which is induced by trimethylaluminium, the growth rate is increased greatly and the growth process varies from three-dimensional island-growth mode to step-flow growth mode.