Densification of silicon dioxide formed by plasma-enhanced atomic layer deposition on 4H-silicon carbide using argon post-deposition annealing

Post-deposition annealing (PDA) was used to improve gate oxide physical and electrical properties. Deposition was accomplished by plasma-enhanced atomic layer deposition (PEALD). We investigated the densification silicon dioxide (SiO₂) formed by PEALD on 4H-silicon carbide (SiC) using PDA without oxidation and nitridation. PDA was conducted at 400–1200?°C in argon (Ar) ambient. The thickness of the SiO₂ was reduced by up to 13.5% after Ar PDA at 1000?°C. As the temperature of the Ar PDA increased, the etching rate of SiO₂ decreased. At temperatures greater than 1000?°C, the SiO₂ etching rate was low compared with that of thermal SiO₂. After PDA, the SiO₂/4H-SiC interface was smoother than that of thermal SiO₂/4H-SiC. The current density versus oxide field and capacitance versus voltage of the SiO₂/4H-SiC metal oxide semiconductor (MOS) capacitors were measured. Sufficient densification of SiO₂ formed by PEALD on 4H-SiC was obtained using Ar PDA at 1200?°C.     

Carbon Interlayer Between CVD SiC and SiO2 in High‐Temperature Passive Oxidation

The oxidation behavior of high‐purity silicon carbide (SiC) prepared by chemical vapor deposition was investigated by thermogravimetry, transmission electron microscopy, and Raman spectroscopy in the temperature range 1534–1902 K in pure O₂. The carbon layer formed at the SiC/SiO₂ interface upon oxidation above 1784 K. Raman peaks corresponding to D‐ and G‐bands could be identified from the carbon layer. Bubbles were observed in the SiO₂ scale after the oxidation at 1873 K. This could be attributed to the accumulation of CO gas at the SiC/SiO₂ interface, resulting in the formation of the carbon layer and bubbles. These suggest that the oxidation rate of SiC is limited by the outward diffusion of CO in the SiO₂ scale in this temperature range.     

Synthesis of SiC/SiO2 core–shell powder by rotary chemical vapor deposition and its consolidation by spark plasma sintering

SiC (core) and SiO₂ (shell) powders were synthesized via rotary chemical vapor deposition (RCVD). The SiC particles (3C, <1 μm in diameter) were coated with a layer of SiO₂ (10–15 nm in thickness). Using spark plasma sintering, the SiC/SiO₂ nanopowders were then synthesized into SiC/SiO₂ composite bodies. Although a phase transformation from 3C to 6H was observed at above 2123 K in the sintered monolithic SiC bodies, sintered SiC/SiO₂ bodies did not display such phase transformation. In addition, SiC/SiO₂ bodies did not exhibited grain growth until the sintering temperature reached 2223 K. The density and Vickers hardness of the sintered SiC/SiO₂ bodies increased with increasing sintering temperature. The highest density and hardness of SiC/SiO₂ composite bodies were 98.1% and 24.4 GPa at 2223 K, respectively, which were higher than the corresponding values of 90% and 14 GPa for monolithic SiC bodies.     

Phase evolution of a novel silicon-alumina-fused mullite-containing Ti2O3 refractory at 1300 °C in N2

A novel silicon-alumina-fused mullite-containing Ti₂O₃ composite refractory is prepared and sintered in the presence of solid carbon at 1300 °C in N₂. The sintered samples exhibit a functional gradient characteristic. The phase evolution can be described as follows: Passive and active oxidation of Si to form SiO₂ and SiO to reduce the partial pressure of oxygen. SiO(g) and Si react with N₂ to form Si₃N₄ respectively. As the temperature increases and the partial pressure of oxygen decreases, Ti₂O₃ reacts with CO and N₂ to form Ti(C,N)ss, which is accompanied by the release of O₂. Si₃N₄ fixes the O₂ and reacts to form Si₂N₂O, and Si₂N₂O reacts with Al₂O₃ to form O′-Sialon, thereby realizing the transformation from Si₃N₄ to Sialon. CO and residual carbon from the pyrolysis of phenolic resin react with SiO(s) and Si to form SiC. The dense layer formed by SiC and SiO₂ blocks the diffusion of external gas to the central parts of the samples, there is still free Si which can continue to react and transform into a non-oxide reinforcing phase. In this paper, the reaction models are presented.     

Effect of SiC nanowires on the thermal shock resistance of joint between carbon/carbon composites and Li2O–Al2O3–SiO2 glass ceramics

In order to improve the bonding property of joint between SiC modified carbon/carbon (C/C) composites and Li₂O–Al₂O₃–SiO₂ (LAS) glass ceramics, SiC nanowires were attempted as the reinforcement materials in the interface region of SiC transition layer and Li₂O–MgO–Al₂O₃–SiO₂ (LMAS) gradient joining interlayer. The C/C–LAS joint with SiC nanowire-reinforced interface layer was prepared by a three-step technique of pack cementation, in situ reaction and hot-pressing. The microstructure and thermal shock resistance of the as-prepared joints were examined. The average shear strength of the joined samples with SiC nanowires increased from 24.9 MPa to 31.6 MPa after 40 thermal cycles between 1000 °C and room temperature, while that of the joined samples without SiC nanowires dropped from 21.4 MPa to 8.3 MPa. The increase of thermal shock resistance of the C/C–LAS joints was mainly attributed to the toughening mechanism of SiC nanowires by pullout, bridging and crack deflection.     

High-temperature oxidation resistance of spent MoSi2 modified ZrB2–SiC–MoSi2 coatings prepared by spark plasma sintering

The spent MoSi₂ modified ZrB₂–SiC–MoSi₂ coatings were prepared on carbon matrixes by spark plasma sintering. A continuous metallurgical bonding was formed at the interface between the coating and matrix, and no obvious defects such as pores and cracks were observed inside. The effects of spent MoSi₂ content and trace doping in the spent powder on the oxidation behavior of the coatings in air at 1700 °C were investigated. During the active oxidation stage, the spent MoSi₂ promoted the densification of the coating and enhanced the structural oxygen barrier properties. With the increase of service time, during the inert oxidation stage, doping an appropriate amount of spent MoSi₂ helped to increase the fluidity of the rich-SiO₂ protective layer so that the Zr oxides fully dispersed in the generated Zr–B–Si–O–Al multiphase glass layer, which could impede the penetration of oxygen and enhance the oxidation protection efficiency. However, excessive spent MoSi₂ exacerbated the volatilization of gas by-products, forming pores and cracks in the glass layer and rising the oxidation loss. When the content of spent MoSi₂ was 20 vol%, the glass layer is dense and uniform, with few defects and the best oxygen resistance property. Moreover, compared with commercial powders, spent MoSi₂ contained Al₂O₃ and SiO₂. Al₂O₃ had an excellent modification effect, while SiO₂ glass can promote liquid phase sintering and seal the defects in the coatings. By adding spent MoSi₂, the modified ZrB₂–SiC–MoSi₂ composite coatings could inhibit the formation of defects and improve the dynamic stability of the coatings effectively.     

Electrical characterisation of MNOS devices on p-type 6H-SiC

Metal–nitride–oxide semiconductor (MNOS), metal–oxide semiconductor (MOS) and metal–nitride semiconductor (MNS) devices have been fabricated on p-type 6H-SiC substrates without epitaxial layers. They have been characterised using high frequency capacitance–voltage (CV), conductance–voltage (GV) and current–voltage (IV) measurements. High frequency CV characteristics of SiC MNOS structures exhibit a capacitance–voltage behaviour that is very similar to high frequency CV characteristics of SiC MOS capacitors. Similar leakage current characteristics compared with p-type 6H-SiC MNS structures have been found for p-type 6H-SiC MNOS devices, but the SiO₂/Si₃N₄ insulator current is lower, particularly for positive electric fields.     

Thermal shock resistance of tri‐layer Yb2SiO5/Yb2Si2O7/Si coating for SiC and SiC‐matrix composites

A new tri‐layer Yb₂SiO₅/Yb₂Si₂O₇/Si coating was fabricated on SiC, C/SiC, and SiC/SiC substrates, respectively, using atmospheric plasma spray (APS) technique. All coated samples were subjected to thermal shock test at 1350°C. The evolution of phase composition and microstructure and thermo‐mechanical properties of those samples before and after thermal shock test were characterized. Results showed that adhesion between all the 3 layers and substrates appeared good. After thermal shock tests, through microcracks which penetrated the Yb₂SiO₅ top layer were mostly halted at the Yb₂SiO₅‐Yb₂Si₂O₇ interface and no thermal growth oxide (TGO) was formed after 40‐50 quenching cycles, implying the excellent crack propagation resistance of the environmental barrier coating (EBC) system. Transmission electron microscopy analysis confirmed that twinnings and dislocations were the main mechanisms of plastic deformation of the Yb₂Si₂O₇ coating, which might have positive effects on crack propagation resistance. The thermal shock behaviors were clarified based on thermal stresses combined with thermal expansion behaviors and elastic modulus analysis. This study provides a strategy for designing EBC systems with excellent crack propagation resistance.     

Thermal cycle test performances of environmental barrier coatings of HfO2-SiO2/Yb2Si2O7 in the steam environment at 1475 °C

The novel bi-layer environmental barrier coatings (EBCs) with HfO₂-SiO₂/Yb₂Si₂O₇ structure (70HfO₂-30SiO₂/Yb₂Si₂O₇: 70HS/YbDS, 50HfO₂-50SiO₂/Yb₂Si₂O₇: 50HS/YbDS, molar ratios) was tested in 90%H₂O–10%O₂ conditions between room temperature and 1475 °C in an Al₂O₃ tube furnace, then its performance was evaluated. The YbDS layer was contaminated by alumina impurities under steam conditions. After 22 cycles, the 70HS/YbDS completely separated from the SiC substrate, while the 50HS/YbDS and SiC did not separate, even though cracks formed at the 50HS/SiC interface and the TGO layer. Furthermore, the thermally grown oxide (TGO) layer formed at the HfO₂-SiO₂/SiC interface. Formation and growth of the TGO led to the formation and propagation of cracks at the HfO₂-SiO₂/TGO interface and TGO interior, which was the culprit leading to the failure of EBCs. These results demonstrated that the 50HS/YbDS EBCs have the potential to protect SiC in steam conditions at 1475 °C.     

Single-crystalline SiC integrated onto Si-based substrates via plasma-activated direct bonding

We propose a plasma-activated direct bonding process at low temperatures (≤200 °C) to form heterostructures between single-crystalline SiC and conventional Si-based substrates (SiO₂, Si, and glass) without any interlayers. Surface activation was performed via an inductively coupled O₂ plasma for 60 s with a lower bombardment damage position. The SiC surfaces were much more hydrophilic after activation, and the generation of defect states was suppressed. Consequently, void-free and robust bonding interfaces of SiC/SiO₂, SiC/Si and SiC/glass were successfully achieved. There were no carbon-enriched layers across the bonding interfaces, which could improve the electrical properties of SiC-based devices. Additionally, the bonding interface of SiC/glass exhibited excellent optical transparency, and interfacial corrosion resistance was confirmed via immersion tests in biological solutions. This bonding method provides a feasible route towards industry-compatible heterogeneous integration of single-crystalline bulk SiC onto Si-based platforms for electronic, optical, mechanical, and biomedical applications.     

Enhanced electromagnetic wave absorption properties of a novel SiC nanowires reinforced SiO2/3Al2O3·2SiO2 porous ceramic

To realize the broad-bandwidth and high-efficiency absorption characteristics, a novel SiC nanowires reinforced SiO₂/3Al₂O₃·2SiO₂ porous ceramic was successfully fabricated by method of precursor infiltration pyrolysis (PIP). Polycarbosilane (PCS) and ferrocene (Fe(C₅H₅)₂) were used as the precursor and catalyst to incorporate SiC nanowires into the SiO₂/3Al₂O₃·2SiO₂ porous ceramic. The curvy SiC nanowires formed three-dimensional (3D) networks with a proper nanometer heterostructure, thereby consuming the microwave energies. The influence of SiC nanowires contents on the microwave absorption properties was investigated. The results indicate that the SiC nanowires contents can be tuned by controlling the PIP cycles, thereby modifying the dielectric properties of as-prepared composite ceramics. The dielectric and electromagnetic wave absorption performances are gradually enhanced with an increasing of SiC nanowires contents. The SiC nanowires reinforced SiO₂/3Al₂O₃·2SiO₂ composite ceramic exhibits excellent electromagnetic wave absorption abilities when the SiC nanowires content is 23.9% (PIP5). The minimum reflection coefficient (RC_min) of the composite ceramic is −30 dB at 10.0 GHz, corresponding to more than 99.9% of the electromagnetic wave consumption. The effective absorption bandwidth (EAB) can cover the frequency ranges of 8.2–12.4 GHz (the entire X-band) at the thickness of 5.0 mm. In general, the novel SiC nanowires reinforced SiO₂/3Al₂O₃·2SiO₂ composite ceramic can be considered as a promising electromagnetic wave absorbing material.     

Fabrication of mullite-bonded porous silicon carbide ceramics by in situ reaction bonding

An in situ reaction bonding technique was developed to fabricate mullite-bonded porous silicon carbide (SiC) ceramics in air from SiC and α-Al₂O₃, using graphite as the pore-former. Graphite is burned out to produce pores and the surface of SiC is oxidized to SiO₂ at high temperature. With further increasing the temperature, the amorphous SiO₂ converts into cristobalite and reacts with α-Al₂O₃ to form mullite (3Al₂O₃·2SiO₂). SiC particles are bonded by the mullite and oxidation-derived SiO₂ to obtain porous SiC ceramics. The reaction bonding behavior, open porosity, pore size distribution and mechanical strength of porous SiC ceramics were investigated as a function of the sintering temperature, forming pressure and graphite content. In addition, the phase composition and microstructure were also studied.     

Characterization of Yb2Si2O7–Yb2SiO5 composite environmental barrier coatings resultant from in situ plasma spray processing

Plasma spraying of multicomponent materials produces shifts in coating composition associated with differential vaporization of constituent elements within the strong thermal gradients of the process. This effect is quite noticeable in rare-earth silicates which are now widely being employed as Environmental Barrier Coatings (EBCs) for SiC based ceramic components of turbine engines. Of particular interest is the preferential volatilization of SiO₂ during thermal plasma spraying Yb₂Si₂O₇ (ytterbium disilicate) coatings which leads to the deviation from stoichiometry of the desired disilicate composition resulting in a mixed phase coating consisting of Yb₂Si₂O₇ plus Yb₂SiO₅ (ytterbium monosilicate). Recent work has shown that presence of monosilicate can be beneficial as its evolution from amorphous, metastable to stable crystalline phase can lead to crack healing during high temperature exposure, however, careful control of the chemistry and architecture may be needed. In this work a 50/50 mol% Yb₂Si₂O₇–Yb₂SiO₅ composite coating has been targeted through in situ decomposition during plasma spray from stoichiometric Yb₂Si₂O₇ powder. The as sprayed amorphous coating reverts to crystalline upon thermal treatment passing through a metastable state identified by XRD and Raman spectroscopy. The transition to the final stable phases results in a mixed phase coating comprising of 46/54 mol% Yb₂Si₂O₇–Yb₂SiO₅ composite that is thermo-mechanically stable with the underlying bond coated silicon coated SiC substrate.     

Ablation behavior of (TiZrHfNbTa)C high-entropy ceramics with the addition of SiC secondary under an oxyacetylene flame

The ablation behavior of high-entropy ceramics (HECs) was investigated in this study using an oxyacetylene flame at 2000 °C. Spark plasma sintering was used to construct a dense HEC (TiZrHfNbTa)C with a 20 vol% of SiC addition (HEC-20SiC). The densification of HEC-20SiC can be improved to a certain extent by adding SiC particles, increasing the hardness of HEC-20SiC to up to 24.6 GPa, and the crack deflection observed through the addition of SiC particles were considered to be the strengthening and toughening mechanisms. After ablation, Hf₆Ta₂O₁₇, Ti_5.1Ta_4.9O₂₀, Nb₂Zr₆O₁₇, TaZr_2.75O₈, and SiO₂ can be detected on an ablated surface and HEC-20SiC possesses the minimum mass ablation rate (?1.9 mg s^?1) and line ablation rate (2.1 μm s^?1) among the comparative ceramics. On the one hand, the SiC phase forms gaseous CO, CO₂, and SiO as well as viscous SiO₂ during ablation and some part of the heat can be dissipated by the evaporation of gaseous CO, CO₂, and SiO; further, pore defects can be healed by viscous SiO₂, thus inhibiting the diffusion of reactive oxygen species. On the other hand, the HEC phase with a lattice-distortion caused by single-phase solid-solution can effectively inhibit the invasion of reactive oxygen species and the outward migration of metal atoms. The invasion rate of reactive oxygen is considered to be the main step during HEC-20SiC ablation, and it is believed that higher principal component HECs can improve ablation performance even further.     

Low thermal conductivity in porous SiC–SiO2–Al2O3–TiO2 ceramics induced by multiphase thermal resistance

The introduction of multiple heterogeneous interfaces in a ceramic is an efficient way to increase its thermal resistance. Novel porous SiC–SiO₂–Al₂O₃–TiO₂ (SSAT) ceramics were fabricated to achieve multiple heterogeneous interfaces by sintering equal volumes of SiC, SiO₂, Al₂O₃, and TiO₂ compacted powders with polysiloxane as a bonding phase and carbon as a template at 600 °C in air. The porosity could be controlled between 66% and 74% by adjusting the amounts of polysiloxane and the carbon template. The lowest thermal conductivity (0.059 W/(m·K) at 74% porosity) obtained in this study is an order of magnitude lower than those (0.2–1.3 W/(m·K)) of porous monolithic SiC, SiO₂, Al₂O₃, and TiO₂ ceramics at an equivalent porosity. The typical specific compressive strength value of the porous SSAT ceramics at 74% porosity was 3.2 MPa cm³/g.     

Towards chrome-free of high-temperature solid waste gasifier through in-situ SiC whisker enhanced silica sol bonded SiC castable

Refractory containing Cr₂O₃ was widely used in solid waste gasifier due to its excellent slag resistance. However, hexavalent chrome compounds (formed during the preparation and the use of refractory containing Cr₂O₃) will give rise to detrimental effect on environment and human's health. In addition, the Al₂O₃-Cr₂O₃ materials acted as the lining materials. Serious exfoliation occurred after about twenty days. For the purpose of chrome-free and service longevity of lining materials for solid waste gasifier, in-situ SiC whisker enhanced SiC castable and spinel castable containing 20%wt of Cr₂O₃ were prepared. The mechanical properties and corrosion resistance after heat treatment in different temperature of the castables were determined. The strength of SiC castable rised with the increasing of the temperature. And the nano SiC/SiO₂ core-shell whiskers was formed at 1500 °C. In comparison to the spinel castable containing 20 wt% of Cr₂O₃, the better volume stability and the reinforcement of the nano whiskers led to excellent resistance to crack propagation at high temperature. In addition, SiC castable showed lower apparent porosity because of the forming of SiO₂ through the oxidation of SiC over 1300 °C, the viscosity of slag increased since that the SiO₂ dissolve into the slag, which caused excellent penetration resistance of SiC castable compared with spinel-Cr₂O₃ castable. Excellent mechanical properties and slag resistance at high temperature indicated that SiC castable had the application prospect for high-temperature solid waste gasifier.     

Interface evolution of Si/Mullite/Yb2SiO5 PS-PVD environmental barrier coatings under high temperature

Plasma spray-physical vapor deposition (PS-PVD) was used to prepare tri-layer environmental barrier coatings (EBCs) Si/mullite/Yb₂SiO₅ on SiC_f/SiC substrate. Isothermal oxidation tests of EBCs were performed at 1300 ℃ for 1000 h. The thermochemical and thermomechanical interface interaction among EBCs were investigated. The results show that more dense EBCs can be obtained through PS-PVD process, which is attributed to the mixed deposition of liquid/gas states. After isothermal oxidation, many pores were observed in the Yb₂SiO₅ coating near the interface of Yb₂SiO₅/mullite coating, which results from the diffusion of Yb₂O₃ phase dissociated from Yb₂SiO₅ into mullite coating at high temperature. In the mullite coating, the Yb₂O₃ reacted with Al₂O₃ generating rod-like Yb₃Al₅O₁₂ phase. Additionally, due to the thermal expansion mismatch and high temperature oxidation, cracks were formed at the interfaces of mullite/Si coating. Those interface cracks resulted in buckling in the mullite coating.     

Enhancement of bonding network for silica sol bonded SiC castables by reactive micropowder

Silica sol bonded castables have obvious advantages over low cement or hydratable alumina bonded castables in drying performance and sintering properties for SiC castables. However, they are not widely used due to their weak strength at low temperature. The efficiency of bonding network for silica sol bonded SiC castable in the presence of different reactive micropowder such as SiO₂ micropowder and α-Al₂O₃ micropowder was evaluated through oscillatory tests, sintered properties and microstructural analysis. Results show that the polymerization reaction between SiO₂ micropowders enhanced the siloxane network and reinforced the bonding strength, furthermore, the addition of α-Al₂O₃ micropowder contributed to accelerating the formation of the siloxane network and hardening of the silica sol at lower temperatures and shorter time. Silica sol performed well as a binder agent for SiC castables with an addition content of 3 wt% SiO₂ micropowder and 2 wt% α-Al₂O₃ micropowder, which showed high strength and good workability at room temperature. And Silica sol bonded SiC castable with the above micropowder contents possessed the best mechanical behavior after heat treatment due to combined binding of SiC whiskers and mullite.     

Deposition of graded SiO2/SiC coatings using high-velocity solution plasma spray

Carbon/carbon (C/C) composites are widely used in structural components, particularly in the aerospace and aeronautics sectors. However, the application of C/C composites is limited by low oxidation resistance at high temperatures. In order to overcome this problem, graded SiO₂/SiC coatings were deposited on C/C composites by a high-velocity solution plasma spray (HVSPS) process. Graded coatings were formed by reactions between the Si(OH)₄ sprayed liquid precursor and the C/C substrate; these reactions were promoted by the high temperature of the plasma torch. The morphologies, microstructures, and chemical compositions of the coatings were investigated by X-ray diffraction, Raman spectroscopy, Fourier-transform infrared spectroscopy, and scanning electron microscopy/energy-dispersive X-ray spectroscopy. By altering the deposition time, the coating thickness was controlled, therefore demonstrating SiC formation and realizing graded SiO₂/SiC coatings.     

Cyclic oxidation performances of new environmental barrier coatings of HfO2-SiO2/Yb2Si2O7 coated SiC at 1375 °C and 1475 °C in the air environment

The objective of this work is to study the cyclic oxidation performances of the environmental barrier coatings (EBCs) containing the novel HfO₂-SiO₂ bond coats in the air environment. Bi-layer HfO₂-SiO₂/Yb₂Si₂O₇ (50HfO₂-50SiO₂, 70HfO₂-30SiO₂ bond coats) and conventional Si/Yb₂Si₂O₇ EBCs were deposited on SiC substrate using atmospheric plasma spray. The effect of the pre-mixing ratios of HfO₂/SiO₂ on the cyclic oxidation behavior of HfO₂-SiO₂/Yb₂Si₂O₇ EBCs was examined. The results showed that the higher content of the HfSiO₄ formed from the 50HfO₂-50SiO₂ bond coats, and it remained intact. A thermally grown oxide (TGO) SiO₂ layer was formed at the bond coat/SiC interface. The parabolic oxidation rate constant (k_p, μm²/h) of the TGO has been reduced 2 orders of magnitude in 50HfO₂-50SiO₂/Yb₂Si₂O₇ EBCs coated SiC compared to the bare SiC at 1475 °C, indicating that the 50HfO₂-50SiO₂/Yb₂Si₂O₇ EBCs effectively protected the SiC substrate at 1475 °C.