Screening of metal flux for SiC solution growth by a thin-film combinatorial method

4H-SiC is a wide-bandgap semiconductor with potential applications in power devices. The lack of a liquid phase in SiC hinders conventional crystal growth from the melt; consequently, SiC wafers still have low quality and are nearly 100 times more expensive than Si wafers. To take advantage of the solution growth for improving the quality and reducing the cost of SiC, Ni addition to Si–Ti flux has been investigated. A combinatorial approach was employed to accelerate the screening of metal flux for the SiC solution growth.     

Growth and characterisation of SiC films deposited on a-SiO2/Si (100) substrates

Abstract

The growth of polycrystalline SiC films has been carried out by low pressure chemical vapour deposition in a horizontal quartz reaction chamber using tetramethylsilane and H2 as the precursor gas mixture. Silicon (100) wafers were used as substrates. A thin Si O₂ amorphous layer of ~6 nm was formed before SiC deposition to reduce the strain induced by the 8% difference in thermal expansion coefficients between SiC and Si. Samples were. analysed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and infrared reflectivity. The structure of films grown at temperatures between 950 and 1150°C varies from amorphous to polycrystalline SiC. Preferential [111] orientation and columnar growth of polycrystalline films develops with increasing temperature.

MST/3317     

Epitaxial silicon carbide on a 6″ silicon wafer

The results of the growth of silicon-carbide films on silicon wafers with a large diameter of 150 mm (6″) by using a new method of solid-phase epitaxy are presented. A SiC film growing on Si wafers was studied by means of spectral ellipsometry, SEM, X-ray diffraction, and Raman scattering. As follows from the studies, SiC layers are epitaxial over the entire surface of a 150-mm wafer. The wafers have no mechanical stresses, are smooth, and do not have bends. The half-width of the X-ray rocking curve (FWHM_ω?θ) of the wafers varies in the range from 0.7° to 0.8° across the thickness layer of 80–100 nm. The wafers are suitable as templates for the growth of SiC, AlN, GaN, ZnO, and other wide-gap semiconductors on its surface using standard CVD, HVPE, and MBE methods.     

Synthesis and growth mechanism of NbC–SiC micro/nanowire by carbothermal reduction

Abstract

NbC–SiC micro/nanowires (MNWs) with NbC content varying from 5 to 20 mol.-% were synthesised at 1600–1800°C via carbothermal reduction utilising silica sol, niobium pentoxide powder and carbon black as starting materials. The synthesis process and growth mechanism of NbC–SiC system were investigated. Results show that the morphology of the synthesised products mainly appears as curve shaped microwires or nanowires. The crystalline consists of both SiC and NbC phases which doped with each other by substitution and interstitial reactions in solid solution. NbC–SiC MNWs were developed by vapour–liquid–solid mechanism according to the existence of liquid droplet phase in the tip at reaction temperature. β-SiC twin crystal growing along [112] direction was formed in the stem, and NbC polycrystal was dissociated from Nb–Si liquid phase. The varied concentration of Nb and Si in the Nb–Si liquid phase could be a significant reason for the curved growth of NbC–SiC MNWs.     

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.     

Surface nano-structured silicon carbide thin film produced using hot filament decomposition of ethylene at low temperature on silicon wafer

The structure and spectroscopic properties of nano-structured silicon carbide (SiC) thin films were studied for films obtained through deposition of decomposed ethylene (C₂H₄) on silicon wafers via hot filament chemical vapor deposition method at low temperature followed by annealing at various temperatures in the range 300-700 °C. The prepared films were analyzed with focus on the early deposition stage and the initial growth layers. The analysis of the film's physics and structural characteristics was performed with Fourier transform infrared spectroscopy and Raman spectroscopy, scanning electron microscopy with energy dispersive X-ray spectroscopy, and X-ray diffraction. The conditions for forming thin layer of cubic SiC phase (3C-SiC) are found. X-ray diffraction and Raman spectroscopy confirmed the presence of 3C-SiC phase in the sample. The formation conditions and structure of intermediate SiC layer, which reduces the crystal lattice mismatch between Si and diamond, are essential for the alignment of diamond growth. This finding provides an easy way of forming SiC intermediate layer using the Si from the substrate.     

Progress in the industrial production of SiC substrates for semiconductor devices

The production of large diameter, high quality SiC substrates is essential to realize the full potential of this important semiconductor material. The current status of SiC bulk sublimation growth for the production of these substrates is reviewed from an industrial point of view. Specific efforts towards larger diameter high quality substrates have led to the production of 50 and 75 mm diameter 4H and 6H wafers and the demonstration of high quality 100-mm wafers. We present thermal conductivity data for material of different doping levels, relevant for device applications. In SiC, micropipes are the most harmful defects for SiC device production. By continuous optimization of the growth process we were able to steadily decrease the micropipe density over the past several years, down to densities as low as 1.1 cm⁻² for an entire 50-mm wafer, indicating that micropipes may be totally eliminated in the next few years. In order to achieve this goal for SiC substrates of increasing diameter, a thorough understanding of the growth process is essential. We will summarize results of modeling the growth process and its experimental verification. The effect of micropipe densities and their characteristic lateral distribution in SiC wafers on achievable device yields will be discussed, using large area Schottky diodes as an example.     

硅碳比对Si(111)表面SSMBE异质外延SiC薄膜的影响

利用固源分子束外延(SSMBE)生长技术, 在不同的硅碳蒸发速率比(Si/C)条件下, 在Si(111)衬底上生长SiC单晶薄膜. 利用反射式高能电子衍射(RHEED)、X射线衍射(XRD)、原子力显微镜(AFM)和傅立叶变换红外光谱(FTIR)等实验技术, 对生长的样品形貌和结构进行了研究. 结果表明, 在Si/C比(1.1:1.0)下生长的薄膜样品, XRDω扫描得到半高宽为2.1°; RHEED结果表明薄膜具有微弱的衍射环, 有孪晶斑点. 在Si/C比(2.3:1.0)下生长的薄膜, XRDω扫描得到的半高宽为1.5°, RHEED显示具有Si的斑点和SiC的孪晶斑点. AFM显示在这两个Si/C比下生长的样品表面都有孔洞或者凹坑, 表面比较粗糙. 从红外光谱得出 薄膜存在着比较大的应力. 但在Si/C比(1.5:1.0)下生长的薄膜样品, XRDω 扫描得到的半高宽仅为1.1°; RHEED显示出清晰的SiC的衍射条纹, 并可看到SiC的3×3表面重构, 无孪晶斑点; AFM图像表明, 没有明显的空洞, 表面比较平整. FTIR谱的位置显示, 在此Si/C比下生长的薄膜内应力比较小. 因此可以认为, 存在着一个优化的Si/C比(1.5:1.0), 在这个Si/C比下, 生长的薄膜质量较好.     

Radially non-uniform interaction of nitrogen with silicon wafers

Reproducible and pronounced ring-like structures have been revealed on both sides of commercial grade wafers after certain regimes of annealing in pure nitrogen atmosphere at 1200 °C. To minimize residual oxygen concentration during the annealing procedure, a furnace with a Si₃N₄ coated SiC reactor tube and high purity N₂ flow were employed. Single-side polished Cz–Si wafers with a diameter of 200 mm, used in the experiments, were manufactured from silicon crystals free of oxidation-induced stacking fault rings.It was established that the ramp rate plays a key role in the formation of the ring-like structures. The ring-like images, visible in both, reflection and scattering geometry were located at approximately half-radius of all wafers subjected to fast temperature ramping. For the wafers annealed under slow ramping conditions the ring-like contrasts were not detected. Dendrite-like islands containing N, O, Si, and traces of C were revealed by scanning electron microscope (SEM) equipped with energy dispersive X-ray spectroscopy (EDXS). Fourier transform infrared (FTIR) spectroscopy with enhanced sensitivity detected phases of SiO₂ and Si₃N₄ at the ring position as well as NN- and NNO-point defect complexes in the underlying bulk Si. Possible origins of the observed structures are discussed.     

Reaction products and growth kinetics during diffusion bonding of SiC ceramic to Ni–Cr alloy

Abstract

Vacuum diffusion bonding of SiC ceramic to Ni–25 at.-%Cr alloy was carried out at 1223–1323 K for 0.9–3.6 ks under a pressure of 7.2 MPa. The kinds of the reaction products and the interface structures of the joints were investigated by scanning electron microscopy (SEM), electron probe microanalysis (EPMA), and X-ray diffraction (XRD), and the kinetic parameters describing the growth of reaction layers were calculated. The experiment and analysis identify that four kinds of reaction products, namely Ni₂Si, graphite (G), Ni₅Cr₃Si₂ and Cr₃Ni₂SiC, have formed during the diffusion bonding of SiC ceramic to Ni–25 at.-%Cr alloy. The interface structure of the SiC/Ni–Cr joints is SiC/(Ni₂Si+G)/(Cr₃Ni₂SiC + Ni₅Cr₃Si₂)/Ni₅Cr₃Si₂/Ni- Cr, and each reaction layer in this structure grows according to a parabolic law. The activation energies for growth of (Ni₂Si+G), (Cr₃Ni₂SiC+Ni₅Cr₃Si₂), and Ni₅Cr₃Si₂ are 217, 248, and 233 kJ mol ­ 1, respectively.     

Vertically bent single crystal silicon wafers as a neutron monochromator

A simple technique to construct monochromators for neutron beams is presented. The monochromator consists of a set of Si wafers stacked together and elastically bent to focus in the vertical geometry. The apparatus is described. It is shown that the peak reflectivity of the set is mainly governed by the number of wafers, while symmetry and smoothness of the rocking curve is achieved by the bending process. A prototype monochromator based on the (220) reflection of Si wafers has been tested and has successfully performed as a fixed monochromator selecting a flux of 3 × 10⁶ n/(s cm²) (at 45 meV) at the sample position (with 20′ collimation in the white beam and 10′ after the reflection from the monochromator). We conjecture that such a technique could be applied to any kind of material provided the wafers are cut from a single crystal with the surface parallel to the reflecting planes.     

Role of preplaced silicon on a TIG processed SiC incorporated microalloyed steel

ABSTRACT

Research aimed at enhancing the surface properties of carbon steels by incorporating fine silicon carbide particulates has had limited success because the dissolution of the ceramic occurred. This research considers a method of reducing SiC dissolution by generating a high Fe–Si liquid which protects the ceramic. Three particulate groups were investigated, (1) ～ 5?µm SiC, (2) ～45?µm Si +～ 5?µm SiC, and (3) ～45?µm Si, all incorporated into a microalloyed steel using a tungsten inert gas process. Detailed microhardness of the melt zones together with microstructural analysis showed that the addition of Si resulted in a cracked hard layer containing SiC. However, in Specimen 1, a thicker, hardcrack-free layer resulted from the microstructure developed by the dissolution of SiC.     

Low-temperature epitaxy of silicon by electron beam evaporation

In this paper we report on homoepitaxial growth of thin Si films at substrate temperatures T_s = 500-650 °C under non-ultra-high vacuum conditions by using electron beam evaporation. Si films were grown at high deposition rates on monocrystalline Si wafers with (100), (110) and (111) orientations. The ultra-violet visible reflectance spectra of the films show a dependence on T_s and on the substrate orientation. To determine the structural quality of the films in more detail Secco etch experiments were carried out. No etch pits were found on the films grown on (100) oriented wafers. However, on films grown on (110) and (111) oriented wafers different types of etch pits could be detected. Films were also grown on polycrystalline silicon (poly-Si) seed layers prepared by an Aluminum-Induced Crystallisation (AIC) process on glass substrates. Electron Backscattering Diffraction (EBSD) shows that the film growth proceeds epitaxially on the grains of the seed layer. But a considerably higher density of extended defects is revealed by Secco etch experiments.     

Continuous wafer-scale graphene on cubic-SiC（O01）

The atomic and electronic structure of graphene synthesized on commercially available cubic-SiC（001）/Si（001） wafers have been studied by low energy electron microscopy （LEEM）, scanning tunneling microscopy （STM）, low energy electron diffraction （LEED）, and angle resolved photoelectron spectroscopy （ARPES）. LEEM and STM data prove the wafer-scale continuity and uniform thickness of the graphene overlayer on SIC（001）. LEEM, STM and ARPES studies reveal that the graphene overlayer on SIC（001） consists of only a few monolayers with physical properties of quasi-freestanding graphene. Atomically resolved STM and micro-LEED data show that the top graphene layer consists of nanometer-sized domains with four different lattice orientations connected through the 〈110〉-directed boundaries. ARPES studies reveal the typical electron spectrum of graphene with the Dirac points close to the Fermi level. Thus, the use of technologically relevant SiC（001）/Si（001） wafers for graphene fabrication repre-sents a realistic way of bridging the gap between the outstanding properties of graphene and their applications.     

Reaction–formation mechanisms and microstructure evolution of biomorphic SiC

Biomorphic SiC is fabricated by liquid Si infiltration of a carbon preform obtained from pyrolized wood that can be selected for tailored properties. The microstructure and reaction kinetics of biomorphic SiC have been investigated by means of TEM, SEM, EBSD, and partial infiltration experiments. The microstructure of the material consists of SiC and Si and a small fraction of unreacted C. The SiC follows a bimodal size distribution of grains in the micrometer and the nanometer range with no preferential orientation. The infiltration-reaction constant has been determined as 18 × 10⁻³ s⁻¹. These observations suggest that the main mechanism for SiC formation is solution–precipitation in the first stage of growth. If the pores in the wood are small enough they can be choked by SiC grains that act as a diffusion barrier between Si and C. If that is the case, Si will diffuse through SiC forming SiC grains in the nanometer range.     

Superconductivity in carrier-doped silicon carbide

Abstract

We report growth and characterization of heavily boron-doped 3C-SiC and 6H-SiC and Al-doped 3C-SiC. Both 3C-SiC:B and 6H-SiC:B reveal type-I superconductivity with a critical temperature T_c=1.5 K. On the other hand, Al-doped 3C-SiC (3C-SiC:Al) shows type-II superconductivity with T_c=1.4 K. Both SiC:Al and SiC:B exhibit zero resistivity and diamagnetic susceptibility below T_c with effective hole-carrier concentration n higher than 10²⁰ cm^?3. We interpret the different superconducting behavior in carrier-doped p-type semiconductors SiC:Al, SiC:B, Si:B and C:B in terms of the different ionization energies of their acceptors.     

A new single-component low-cost emitter etch-back process for silicon wafer solar cells

A way of achieving lightly doped emitter is a combination of a heavy emitter diffusion and emitter etch back, which has an added advantage of phosphorous diffusion gettering. However, this chemical emitter etch-back process must fulfil some critical requirements, e.g. cost-effectiveness, near-conformal Si etching even after deep emitter etch back, controlled Si etch rate, post-etch clean Si surface and lowest safety issues in chemical handling and drainage. In this work, we report a new low-cost (less than 1 US Cents/wafer), single-chemical, non-acidic, high-throughput emitter etch-back process for tube-diffused emitters for crystalline Si wafers. This process uses only sodium hypochlorite solution at 80 °C as the Si etchant. This process is versatile with its applications on phosphorous and boron tube-diffused monocrystalline Si and phosphorous tube-diffused multicrystalline Si wafers. The preparation, usage and drainage of this highly diluted solution are easy and safe. The Si etching process leads to excellent spatial uniformity over large-area Si wafers (243 cm²). With deep etch back resulting in a change of sheet resistance by ~60 Ω/sq, the standard deviation value changes by only 2.7%. High surface conformity in the etch-back surface is evident from reflectance studies. Quasi-steady-state photoconductance and photoluminescence imaging are used to demonstrate improved electrical parameters of the etch-back wafers.     

High-temperature thermal conductivity of biomorphic SiC/Si ceramics

Thermal conductivity of biomorphic SiC/Si, a silicon carbide + silicon containing two phase material, was evaluated using the laser steady-state heat flux method. These materials were processed via silicon melt infiltration of wood-derived carbon scaffolds. In this approach, heat flux was measured through the thickness when one side of the specimen was heated with a 10.6-µm CO₂ laser. A thin mullite layer was applied to the heated surface to ensure absorption and minimize reflection losses, as well as to ensure a consistent emissivity to facilitate radiative loss corrections. The influence of the mullite layer was accounted for in the thermal conductivity calculations. The effect of microstructure and composition (inherited from the wood carbonaceous performs) on measured conductivity was evaluated. To establish a baseline for comparison, a dense, commercially available sintered SiC ceramic was also evaluated. It was observed that at a given temperature, thermal conductivity falls between that of single-crystal silicon and fine-grained polycrystalline SiC and can be rationalized in terms of the SiC volume fraction in biomorphic SiC/Si material.     

Microstructure of interfacial reaction zone in SCS-6 SiC fibre reinforced super α2 composites

Abstract

The microstructure of the interfacial reaction zone in SCS-6 SiC/super α2 composites heat treated at 700°C for 3000 h was investigated by means of analytical transmission electron microscopy. The very fine grained reaction layer adjacent to the carbon coating of the SiC fibre was found to consist of two sub layers, determined to be (Ti, V)C and (Ti, V,Nb)₅Si₃. The second layer is (Ti,Nb)C with large equiaxed grainsfollowed by the third layer consisting of the (Ti,Nb)₃(Al,Si)C phase. This layer is separated from the matrix by a fourth layer with the phase composition (Ti,Nb)₅(Si,Al)₃. At some interface positions, the two layers of(Ti,Nb)C and (Ti,Nb)₃(Al,Si)C are separated by an additional layer of the (Ti,Nb)₃(Si,Al) phase. The thickening of the interfacial reaction zone at 700°C is mainly due to the layers of (Ti, Nb)₃(Al,Si)C and (Ti,Nb)₃(Si,Al). The growth of these two layers is probably responsible for the degradation of the mechanical properties of the composites.     

Catalyst-free synthesis of silicon nanowires by oxidation and reduction process

A new process has been developed to grow silicon (Si) nanowires (NWs), and their growth mechanisms were explored and discussed. In this process, SiNWs were synthesized by simply oxidizing and then reducing Si wafers in a high temperature furnace. The process involves H₂, in an inert atmosphere, reacts with thermally grown SiO₂ on Si at 1100 °C enhancing the growth of SiNWs directly on Si wafers. High-resolution transmission electron microscopy studies show that the NWs consists of a crystalline core of ~25 nm in diameter and an amorphous oxide shell of ~2 nm in thickness, which was also supported by selected area electron diffraction patterns. The NWs synthesized exhibit a high aspect ratio of ~167 and room temperature phonon confinement effect. This simple and economical process to synthesize crystalline SiNWs opens up a new way for large scale applications.