Interfacial reaction and adhesion between SiC and thin sputtered cobalt films

Thin sputtered cobalt films on SiC were annealed in an Ar/4 vol% H₂ atmosphere at temperatures between 500 and 1450 °C for various times. The reaction process and the reaction-product morphology were characterized using optical microscopy, surface profilometry, X-ray diffraction, scanning electron microscopy and electron probe microanalysis. The relative adhesive strength between the film and substrate was determined by the scratch test method. Below 850 °C sputtered cobalt with a thickness of 2 m on SiC showed no detectable reaction products. Cobalt initially reacted with SiC at 850 °C producing Co₂Si and unreacted cobalt in the reaction zone. At 1050 °C the first-formed Co₂Si layer reacted to CoSi, and carbon precipitates were formed in the reaction zones. Sputtered thin cobalt layers reacted completely with SiC after annealing at 1050 °C for 2 h. Above 1250°C only CoSi was observed with carbon precipitates having an oriented structure in the reaction zone. Above 1450°C, a significant amount of graphitic carbon in the reaction zone was detected.     

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     

Thermal aging of 16Cr – 5Ni – 1Mo stainless steel Part 1 – Microstructural analysis

Abstract

Specimens of 16Cr - 5Ni - 1Mo stainless steel were solution treated at 1050 ° C for 1 h followed by heating in the temperature range 400 - 750 ° C for different holding times (1 - 16 h). After heat treatment, optical microscopy, scanning (SEM) and transmission (TEM) electron microscopy, and X-ray diffraction examinations were conducted. The microstructure of all aged specimens was found to consist of martensite with variable fractions of δ ferrite and reversed austenite. Very fine precipitates of Mo carbides were revealed in the specimens aged at 475 ° C. The specimens aged at 625 ° C showed a decrease in the dislocation density and a high volume fraction of austenite and precipitation of Fe₂Mo Laves phase was detected by X-ray analysis. Above 625 ° C, Cr₂₃C₆ and TiC became the predominate carbides heterogeneously precipitated in the martensitic matrix. Partial transformation of reversed austenite to unaged martensite was observed at temperatures above 625 ° C.     

Effect of re-melting on particle distribution and interface formation in SiC reinforced 2124Al matrix composite

The interface between metal matrix and ceramic reinforcement particles plays an important role in improving properties of the metal matrix composites. Hence, it is important to find out the interface structure of composite after re-melting. In the present investigation, the 2124Al matrix with 10 wt.% SiC particle reinforced composite was re-melted at 800 °C and 900 °C for 10 min followed by pouring into a permanent mould. The microstructures reveal that the SiC particles are distributed throughout the Al-matrix. The volume fraction of SiC particles varies from top to bottom of the composite plate and the difference increases with the decrease of re-melting temperature. The interfacial structure of re-melted 2124Al–10 wt.%SiC composite was investigated using scanning electron microscopy, an electron probe micro-analyzer, a scanning transmission electron detector fitted with scanning electron microscopy and an X-ray energy dispersive spectrometer. It is found that a thick layer of reaction product is formed at the interface of composite after re-melting. The experimental results show that the reaction products at the interface are associated with high concentration of Cu, Mg, Si and C. At re-melting temperature, liquid Al reacts with SiC to form Al₄C₃ and Al–Si eutectic phase or elemental Si at the interface. High concentration of Si at the interface indicates that SiC is dissociated during re-melting. The X-ray energy dispersive spectrometer analyses confirm that Mg- and Cu-enrich phases are formed at the interface region. The Mg is segregated at the interface region and formed MgAl₂O₄ in the presence of oxygen. The several elements identified at the interface region indicate that different types of interfaces are formed in between Al matrix and SiC particles. The Al–Si eutectic phase is formed around SiC particles during re-melting which restricts the SiC dissolution.     

Silicide formation with nickel and platinum double layers on silicon

Diffusion effects and silicide formation in double layers of electron-gun-evaporated thin films of nickel and platinum on 〈100〉 and 〈111〉 silicon substrates were studied by megaelectronvolt backscattering spectrometry, transmission electron microscopy and glancing angle X-ray diffraction as a function of heat treatment (200–900 °C) for both sequences of thin films. It was found for the Si/Ni/Pt(Si/Pt/Ni) system that Ni₂Si(Pt₂Si) starts growing first. When all the nickel (platinum) has been consumed by this compound growth, platinum (nickel) diffuses through the Ni₂Si(Pt₂Si) layer and accumulates at the SiNi₂Si(SiPt₂Si) interface. This platinum (nickel) diffusion seems to be a grain boundary diffusion.For 〈100〉 Si/Ni/Pt samples with thin platinum layers it has been shown that platinum acts as a marker for the moving species in the transition from Ni₂Si to NiSi. For thick platinum layers it was observed that similar processes occur, leading to essentially a four-layered silicide where the layers are alternately rich in nickel and rich in platinum (450 °C, 20 min). In the silicide for the 〈100〉 Si/Pt/Ni system the distribution of nickel and platinum is approximately the reverse of the asdeposited distribution (about 450 °C, 20 min). In the further evolution of the profiles the elemental distribution becomes smooth and flat for both sequences of the layers (750 °C, 20 min). We suggest the existence of a ternary of the type SiNi_1?xPt_x.     

Chemische Zusammensetzung und Mikrostruktur polymerabgeleiteter Gläser und Keramiken im System Si–C–O. Teil 2: Charakterisierung der Gefügeausbildung mittels hochauflösender Durchstrahlungselektronenmikroskopie und Feinbereichsbeugung

Chemical Composition and Microstructure of Polymer‐Derived Glasses and Ceramics in the Si–C–O System. Part 2: Characterization of microstructure formation by means of high‐resolution transmission electron microscopy and selected area diffraction Liquid or solid silicone resins represent the economically most interesting class of organic precursors for the pyrolytic production of glass and ceramics materials on silicon basis. As dense, dimensionally stable components can be cost‐effectively achieved by admixing reactive filler powders, chemical composition and microstructure development of the polymer‐derived residues must be exactly known during thermal decomposition. Thus, in the present work, glasses and ceramics produced by pyrolysis of the model precursor polymethylsiloxane at temperatures from 525 to 1550 °C are investigated. In part 1, by means of analytical electron microscopy, the bonding state of silicon was determined on a nanometre scale and the phase separation of the metastable Si–C–O matrix into SiO₂, C and SiC was proved. The in‐situ crystallization could be considerably accelerated by adding fine‐grained powder of inert fillers, such as Al₂O₃ or SiC, which permits effective process control. In part 2, the microstructure is characterized by high‐resolution transmission electron microscopy and selected area diffraction. Turbostratic carbon and cubic β‐SiC precipitate as crystallization products. Theses phases are embedded in an amorphous matrix. Inert fillers reduce the crystallization temperature by several hundred °C. In this case, the polymer‐derived Si–C–O material acts as a binding agent between the powder particles. Reaction layer formation does not occur. On the investigated pyrolysis conditions, no crystallization of SiO₂ was observed.     

Alloying reaction in thin nickel films deposited on GaAs

The alloying reaction in a thin nickel film deposited on a GaAs substrate was investigated using microprobe Auger spectroscopy, reflection high energy electron diffraction and transmission electron diffraction. A nickel film reacts with the substrate above 200°C to form a metastable hexagonal reaction product with the composition Ni:Ga:As = 2:1:1, which is monocrystalline with the orientation relation 〈0001〉 hexagonal // 〈111〉 GaAs and 〈11$\text{2}$0〉 hexagonal // 〈110〉 GaAs. Above 400°C the metastable reaction product decomposes into NiAs and β-NiGa, both of which are also monocrystalline with the same orientation relation as the metastable reaction product. The role of nickel in GaAs contact systems is explained by the high reactivity of nickel with GaAs in the solid-solid phase.     

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.     

SiC／Ni3Al界面固相反应区的相组成与显微结构

使用光学显微镜、扫描电子显微镜和能谱仪等对1000℃×5h加热处理的SiC／Ni3Al界面固相反应区显微结构、相组成以及反应区中元素分布等进行观察、分析和测试。研究表明,SiC／Ni3Al界面固相反应形成Ni2Si、石墨态碳沉积物和Ni5.4AlSi2。SiC／Ni3Al界面固相反应形成两层结构的反应区,其厚度大约是16μm。其中,靠近SiC侧的反应区由Ni2Si,Ni5．4AlSi2和分布在其中的颗粒状的石墨颗粒构成,而靠近Ni3Al侧的反应区则由Ni2Si和Ni5．4AlSi2构成。     

Effect of Ni loading and reaction temperature on the formation of carbon nanotubes from methane catalytic decomposition over Ni/SiO<Subscript>2</Subscript>

Since their discovery carbon nanotubes (CNT) have attracted much attention due to their singular physical, mechanical and chemical properties. Catalytic chemical vapor deposition (CCVD) of hydrocarbons over metal catalysts is the most promising method for the synthesis of CNT, because of the advantages of low cost and large-scale production and the relatively low temperature used in the process, compared to the other methods (laser ablation and discharge between graphite electrodes). In this study, CNT were synthesized by CCVD using Ni supported on SiO₂ as a catalyst. The carbon deposited in the reaction was analyzed by Raman spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The effects of reaction temperature and Ni loading on the carbon nanotube formation were evaluated. The catalyst with 5% Ni favored high yield of CNT at lower temperature, with abundant “multi-walled carbon nanotubes” (MWNTs) at 625 °C, while single-walled carbon nanotubes (SWNTs) and MWNTs were obtained at 650 °C. With an increase in the reaction temperature a marked decrease in the yield of CNT was observed, probably due to the sintering of the catalyst. The catalyst with 1% Ni gave SWNTs with a high degree of order at all reaction temperatures, but in low quantity.     

Preparation and characterization of SiC nanowires and nanoparticles from filter paper by sol–gel and carbothermal reduction processing

The carbothermal reduction of SiO₂ gel containing filter paper (as carbon precursors) in argon was used to prepare SiC nanowires and nanoparticles. The resulting SiC ceramic, as well as the conversion mechanism of carbon/silica composites to SiC nanowires and nanoparticles, have been investigated by scanning electron microscopy (SEM), Transmission electron microscopy (TEM), x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TG) techniques. XRD and IR studies show that the materials, obtained from reaction at 1550 °C for 1 h in static argon atmosphere, are β-SiC. SEM and TEM reveal that SiC nanowires is single crystal wires with diameters ranging from 50–200 nm and their lengths over several tens of microns. According to thermodynamic analysis, SiC nanowires and SiC nanoparticles in the resulting SiC ceramic are formed by gas-gas reaction of SiO (g) and CO (g).     

Dynamics of dysprosium silicide nanostructures on Si(001) and (111) surfaces

The growth and coarsening dynamics of dysprosium silicide nanostructures are observed in real-time using photoelectron emission microscopy. The annealing of a thin Dy film to temperatures in the range of 700–1050 °C results in the formation of epitaxial rectangular silicide islands and nanowires on Si(001) and triangular and hexagonal silicide islands on Si(111). During continuous annealing, individual islands are observed to coarsen via Ostwald ripening at different rates as a consequence of local variations in the size and relative location of the surrounding islands on the surface. A subsequent deposition of Dy onto the Si(001) surface at 1050 °C leads to the growth of the preexisting islands and to the formation of silicide nanowires at temperatures above where nanowire growth typically occurs. Immediately after the deposition is terminated, the nanowires begin to decay from the ends, apparently transferring atoms to the more stable rectangular islands. On Si(111), a low continuous flux of Dy at 1050 °C leads to the growth of kinked and jagged island structures, which ultimately form into nearly equilateral triangular shapes.     

Auger electron spectroscopy analysis of SiC layers formed by carbon ion implantation into silicon

Analysis of Si LVV and CKLL Auger spectra combined with Auger in-depth profiles were carried out for SiC layers formed by the implantation of carbon into silicon. It was found that in layers which were implanted with carbon ions to appropriate doses SiC-like bonds were formed at room temperature, although the crystal perfection was not pronounced. When these layers were annealed above 1100°C, their Auger spectra were in good agreement with those of β-SiC. In layers which were implanted with carbon ions much above a critical dose and annealed at 1200°C, however, CKLL Auger spectra showed the presence of graphite-like carbon. This result was consistent with the IR analysis and the transmission electron microscopy or electron diffraction observations reported in our previous papers, and it suggested the formation of carbon clusters. The Auger spectra also showed the advantages of hot implantation over room temperature implantation.     

Interface structure and reaction kinetics between SiC and thick cobalt foils

Reaction couples of SiC with thick cobalt foils were annealed in an Ar-4 vol% H₂ atmosphere at temperatures between 950 and 1250 °C for times between 4 and 100 h. At temperatures above 950 °C, solid-state reactions lead to the formation of various silicides with carbon precipitates. The typical layer sequence in the reaction zone was determined by quantitative microanalysis to be SiC/CoSi+C/Co₂Si+C/Co₂Si/Co₂Si+C/ ... /Co₂Si/Co(Si)/Co. The mechanism of the periodic band structure formation with the carbon precipitation behaviour was discussed in terms of reaction kinetics and thermodynamic considerations. Two ternary phases, CoSiC₂ and Co₂SiC₃, unstable at room temperature, may exist in the system Co-Si-C. The growth of the reaction zone is dependent on the square root of time. The reaction kinetics are proposed to estimate the effective reaction constant from the parabolic growth of the reaction zone. The mechanical properties of the reaction zones were determined by the microhardness test.     

Analysis of tensile strength and microstructure of Ni–SiC composites prepared by electroforming

Ni–SiC metal matrix composites with two kinds of SiC content were prepared by electroforming in a nickel sulphamate bath. Tensile strength and microstructure of the composites before and after heat treatment were investigated. The maximum of tensile strength was obtained after heat treatment at 300 °C × 24 h. The values were 641 N/mm² and 701 N/mm² respectively. The complete reaction between nickel and SiC particles can produce shrinkage pores in the interface. The volume of shrinkage pores was equal to 8% of the volume of SiC particles in the composites. The interfacial reaction products were composed of Ni₃Si and a little amount of Ni₃₁Si₁₂ after heat treatment at 600 °C × 24 h. The fracture evolution went though microcracks initiation, growth and coalescence. Cracking of the matrix, debonding of Ni–SiC interfaces and cracking of particles were three types of cracking modes for Ni–SiC composites.     

High temperature reactions between SiC and platinum

Solid state reactions between SiC and platinum have been studied at temperatures between 900 and 1100 °C. In the reaction zones, alternating layers of Pt₃Si and carbon, and Pt₂Si and carbon were formed at 900 and 1000 °C, respectively. Both the Pt₃Si and Pt₂Si phases were stable at respective temperatures. Annealings at 1100 °C, however, produced alternating layers of mixed Pt-silicides and carbon. The formation of platinum silicides gave rise to interfacial melting between SiC and platinum at all the temperature regimes. Laser Raman microprobe indicates that SiC decomposes into carbon and silicon at all the temperatures. The silicon reacts with platinum and forms platinum silicides, while the carbon forms clusters and stays unreacted. Based on the Raman results, the carbon exists in two different crystalline states depending upon its location from the SiC reaction interface. The reaction kinetics between SiC and platinum and the formation of periodic structure, respectively, are discussed based on the decomposition of the SiC and the phase separation of carbon from platinum silicides.     

Diffusion of nickel in silicon below 475 °C

Nickel films were deposited on (100) and (111) surfaces of single-crystal silicon and were then annealed. The conditions under which the nickel is deposited determine whether or not an NiSi compound forms on annealing. It is postulated that defects are necessary for the formation of an NiSi compound at annealing temperatures below at least 475 °C, although the presence of defects may not necessarily cause the formation of a silicide. For substrate temperatures below 70 °C, defects are created during the vapor deposition of nickel on silicon. These defects always result in the formation of nickel silicide when the sample is annealed at higher temperatures. When nickel is deposited on defect-free silicon at temperatures of about 250 °C no defects are generated and, although interdiffusion of nickel and silicon occurs, silicide formation does not take place upon subsequent annealing below 475 °C. The activation energies for the diffusion of nickel into (100) silicon and (111) silicon were determined.     

Diffusion bonding of Ti coated Zircaloy-4 and 316-L stainless steel

Diffusion bonding of Zircaloy-4 and Type 316-L stainless steel was carried out by coating the joining surfaces with Ti to minimize the interlayer effect. Bonding heat treatments were carried out in vacuum at 1000 °C for 4 h and 1050 °C for 1 h. The microstructure of the diffusion zone was investigated by scanning electron microscopy and the phases in the diffusion zone were analyzed by energy dispersive spectroscopy. It is observed that Ti coating at the interface produced a dendritic structure in the diffusion zone formed in the Zircaloy-4. The concentration of the dendrites increases with an increase in bonding temperature.     

Raman study of Ni and Ni silicide contacts on 4H- and 6H-SiC

Ni₂Si, NiSi and NiSi₂ contacts were prepared on n-type 4H- and 6H-SiC(0001) by deposition of Ni and Si multilayers in the respective stoichiometry after high-temperature annealing, as well as pure Ni contacts. After annealing, the individual contacts were analyzed by Raman spectroscopy and electrical property measurements. Contact structures were then etched-off and subsequently observed by means of AFM (Atomic Force Microscopy). Ni reacted with SiC, forming Ni₂Si and carbon. At Ni_xSi_y/SiC contact structures the respective silicides were already formed at low annealing temperatures, when only Schottky behavior of the structures was observed. The intended silicides, once formed, did not change any further with increasing annealing temperature. All contact structures provided good ohmic behavior after being annealed at 960 °C. By means of combined AFM and Raman analysis of the etched-off contacts we found that the silicide contact structures very probably did not react with SiC which is in accordance with the thermodynamic assumptions. After annealing the silicide contact structures at such temperature, when Schottky behavior changed to ohmic, a certain form of interaction between the SiC substrate and the silicide contact structures must have occurred.     

A novel method for massive fabrication of β-SiC nanowires

Silicon carbide nanowires (NWs), that were over 200 μm in length and 20–200 nm in diameter, were prepared by high-pressure reaction from SiBONC powder tablets. Annealing temperatures between 1,500 °C and 1,600 °C and Si/B molar ratios between 70:30 and 60:40 were suitable for the growth of the nanowires. The nanowires were fabricated by in situ chemical vapor growth process on the tablets. The SiC nanowires were identified as single crystal β-SiC. The analysis of X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed the single crystalline nature of nanowires with a growth direction of <111>. Massive growth of single crystalline SiC nanowires is important to meet the requirements of the fabrication of SiC nanowire-based nanodevices.