CVD-SiC纤维的拉曼光谱研究

采用激光拉曼光谱对单根CVD-SiC纤维进行了研究,并与SiCf/Ti-6A1-4V复合材料中SiC纤维的拉曼光谱进行对比分析.发现SiC纤维的第一沉积层的TO峰峰形尖锐,表明SiC晶粒较大,第二沉积层的晶粒较小,在二个沉积层中分别检测到碳和硅的拉曼峰.在复合材料中,SiC纤维的TO峰向高波数偏移,表明复合材料在制备过...     

Micro‐Raman analysis and finite‐element modeling of 3 C‐SiC microstructures

Micro‐ and nano‐electromechanical systems (MEMS and NEMS) fabricated in 3 C‐SiC are receiving particular attention thanks to the material physical properties: its wide band gap (2.3 eV), its ability to operate at high temperatures, its mechanical strength and its inertness to the exposure in corrosive environments. However, high residual stress (which is normally generated during the hetero‐epitaxial growth process) makes the use of 3 C‐SiC in Si‐based MEMS fabrication techniques very limited leading to a failure of micro‐machined/sensor structures. In this paper, micro‐Raman characterizations and finite‐element modeling (FEM) of microstructures realized on poly and single‐crystal (100) 3 C‐SiC/Si films are performed. Transverse optical (TO) Raman mode analysis reveals the stress relaxation on the free standing structure (796.5 cm⁻¹) respect to the stressed unreleased region (795.7 cm⁻¹). Also, microstructures as cantilever, bridge and planar rotating probe show an intense stress field located around the undercut region. Here, the TO Raman mode undergoes an intense shift, up to 2 cm⁻¹, ascribed to the modification of the Raman stress tensor. Indeed, the generalized axial regime, described by diagonal components of the Raman stress tensor, cannot be applied in this region. Raman maps analysis and FEM simulations show the ‘activation’ of the shear stress, i.e. non‐diagonal components of the stress tensor. The stress‐Raman modes shift correlation, in the case of fully non‐diagonal stress tensors, has been investigated. The aim of future works will be to minimize the stress field generation and the defects density within the epitaxial layer. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

SiC缓冲层对Si表面生长的 ZnO薄膜结构和光电性能的改善

用脉冲激光沉积(PLD)技术制备了ZnO/SiC/Si和 ZnO/Si薄膜并制成了紫外探测器。利用X射线衍射(XRD),光致发光(PL)谱,I-V曲线和光电响应谱对薄膜的结构和光电性能进行了研究。实验结果表明:SiC缓冲层改善了ZnO薄膜的结晶质量和光电性能,其原因可能是SiC作为柔性衬底能够减少ZnO与Si 之间大的晶格失配和热失配导致的界面缺陷和界面态。     

SiC纤维增强Ti17合金复合材料轴向残余应力的拉曼光谱和X射线衍射法对比研究

准确测量和分析SiC纤维增强Ti合金复合材料(SiC_f/Ti)中残余应力状态对优化复合材料的成型工艺和理解其失效模式具有重要意义,但其残余应力的实验测量和分析仍是一个挑战.石墨C涂层作为SiC纤维与Ti17基体合金之间必需的扩散障涂层,承载了由纤维与基体之间热不匹配引入的残余应力.本文采用显微拉曼光谱法对比测量纤维表面C涂层在复合材料中和去掉基体无应力态下G峰的峰位,通过石墨C涂层应力态下峰位移动计算出SiCf/C/Ti17复合材料中SiC纤维受到～705.0 MPa的残余压应力.采用X射线衍射方法测量了不同方向上该复合材料中基体钛合金的晶面间距以获取其空间应变,根据三轴应力模型分析了复合材料中基体钛合金沿轴向方向的残余应力为～701.3 MPa的张应力,并通过线性弹性理论转化为SiC纤维的残余压应力为～759.4 MPa.两种测试方法都确定了SiC纤维在成型过程中受到残余压应力,且获得的应力值较为接近,都可以用于对SiC_f/Ti复合材料的残余应力测量.     

Spatially resolved Raman spectroscopy evaluation of residual stresses in 3C-SiC layer deposited on Si substrates with different crystallographic orientations

Raman scattering studies were performed on hot-wall chemical vapor deposited (heteroepitaxial) silicon carbide (SiC) films grown on Si substrates with orientations of (1 0 0), (1 1 1), (1 1 0) and (2 1 1), respectively. Raman spectra suggested that good quality cubic SiC single crystals could be obtained on the Si substrate, independent of its crystallographic orientation. Average residual stresses in the epitaxially grown 3C-SiC films were measured with the laser waist focused on the epilayer surface. Tensile and compressive residual stresses were found to be stored within the SiC film and in the Si substrate, respectively. The residual stress exhibited a marked dependence on the orientation of the substrate. The measured stresses were comparable to the thermal stress deduced from elastic deformation theory, which demonstrates that the large lattice mismatch between cubic SiC and Si is effectively relieved by initial carbonization. The confocal configuration of the optical probe enabled a stress evaluation along the cross-section of the sample, which showed maximum tensile stress magnitude at the SiC/Si interface from the SiC side, decreasing away from the interface in varied rate for different crystallographic orientations. Defocusing experiments were used to precisely characterize the geometry of the laser probe in 3C-SiC single crystal. Based on this knowledge, a theoretical convolution of the in-depth stress distribution could be obtained, which showed a satisfactory agreement with stress values obtained by experiments performed on the 3C-SiC surface.     

Raman investigation of chemical reaction product in thermal‐treated SiCf/C/Mo/Ti6Al4V composite

SiC fiber‐reinforced titanium matrix composite (TMC) is an interesting material for aerospace industry because of its excellent properties. Characterization of their interfacial reaction product is principal to further optimization of the TMCs. Here we report application of Raman spectroscopy to identify reaction products and their microstructural details in thermal‐treated SiC_f/C/Mo/Ti6Al4V composite. Meanwhile TEM is performed to help explain phenomena in Raman result. Raman line scanning along interface indicates thickness of two sublayers (Ti₅Si₃(C_x) layer next to SiC fiber and TiC_x layer next to matrix). The main Raman result of phase distribution is confirmed by TEM. While a 300‐nm Ti₃SiC₂ layer whose Raman features are similar with nearby Ti₅Si₃(C_x) layer is also detected. Raman peakshift in Ti₅Si₃(C_x) layer possibly results from residual stress or/and microstructural evolution caused by carbon solution. No evidence indicates Mo participation of interfacial reactions. However, Mo diffusion changes phase distribution of matrix alloy and affects interfacial reaction indirectly. Meanwhile, TEM and Raman results indicate that particles are TiC_x and defective Ti₃AlC₂. Raman features of Ti₃AlC₂ particles differ from that of bulk material, which is attributed to defects. Although Ti₃AlC₂ formation mechanism is ambiguous, it possibly relates to TiC_x formation nearby. Copyright © 2014 John Wiley & Sons, Ltd.     

溅射工艺参数对硅薄膜微结构影响的Raman分析

为了解决碳化硅难以进行光学加工的问题,该文采用射频磁控溅射方法,在碳化硅反射镜坯体上沉积与碳化硅具有相近热膨胀系数且易于进行光学加工的硅薄膜。利用拉曼光谱(Raman)对衬底温度、射频功率、衬底偏压等溅射工艺条件对硅膜微结构的影响进行了分析。研究发现：随着衬底温度的升高,薄膜的晶化率先增大后减小;衬底偏压的增加不利于薄膜有序结构的形成;射频功率对薄膜微结构的影响比较复杂,随着功率的升高,薄膜晶粒尺寸减小,晶化率降低,当射频功率进一步升高时,薄膜中有序团簇尺寸和晶化率逐渐升高。但过高的射频功率反而不利于薄膜的晶化。     

Mechanism for crystalline Si surface passivation by the combination of SiO2 tunnel oxide and µc‐SiC:H thin film

This work demonstrates that the combination of a wet‐chemically grown SiO₂ tunnel oxide with a highly‐doped microcrystalline silicon carbide layer grown by hot‐wire chemical vapor deposition yields an excellent surface passivation for phosphorous‐doped crystalline silicon (c‐Si) wafers. We find effective minority carrier lifetimes of well above 6 ms by introducing this stack. We investigated its c‐Si surface passivation mechanism in a systematic study combined with the comparison to a phosphorous‐doped polycrystalline‐Si (pc‐Si)/SiO₂ stack. In both cases, field effect passivation by the n‐doping of either the µc‐SiC:H or the pc‐Si is effective. Hydrogen passivation during µc‐SiC:H growth plays an important role for the µc‐SiC:H/SiO₂ combination, whereas phosphorous in‐diffusion into the SiO₂ and the c‐Si is operative for the surface passivation via the Pc‐Si/SiO₂ stack. The high transparency and conductivity of the µc‐SiC:H layer, a low thermal budget and number of processes needed to form the stack, and the excellent c‐Si surface passivation quality are advantageous features of µc‐SiC:H/SiO₂ that can be beneficial for c‐Si solar cells. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Low-temperature formation of nanocrystalline SiC particles and composite from three-layer Si/C/Si film for the novel enhanced white photoluminescence

In this article, nanocrystalline silicon carbide (nc-SiC) and composite have been synthesized at an annealing temperature as low as 750 °C through the thermal reaction of Si/C/Si multilayers deposited on the Si(100) substrate by ultra-high-vacuum ion beam sputtering (UHV IBS) compared with the conventional thermal formation of crystalline SiC (c-SiC) nanostructures above 1,000 °C. The evolution of microstructure and reaction between C and Si was examined by Raman spectroscopy, Fourier transform infrared spectrometer (FTIR), high-resolution field emission scanning electron microscope (HR-FESEM), and high-resolution transmission electron microscopy. The c-SiC nanoparticles (np-SiC) of around 20–120 nm in diameter appeared on the top and bottom of the three-layer film with a particle density of around 2.63 × 10¹⁰ cm⁻² after 750 °C annealing. The composite of nc-SiC and Si nanocrystals (nc-Si) size below 5 nm embedded in an amorphous SiC (a-SiC) matrix appeared at the interface between the Si and C layers. Efficient thermal energy is the driving force for the formation of nc-SiC and composite through interdiffusion between C and Si. The broad visible photoluminescence (PL) spectrum of 350–750 nm can be obtained from the annealed composite Si/C/Si multilayer and deconvoluted into four bands of blue (~430 nm), green (~500 nm), green–yellow (~550 nm), and orange (~640 nm) emission, corresponding to the emission origins from nc-SiC, sp² carbon clusters, np-SiC, and nc-Si, respectively.     

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.     

Micromechanical Behavior of Carbon Nanotube-Covered SiC Fibers in Polymer Matrix Composites

The incorporation of nanotube-covered fibers in continuous fiber/epoxy composites has been shown to influence the mechanical, electrical, and thermal properties of the composite. Increased interlaminar shear stress, flexural strength and modulus have been reported in such composites over composites containing bare fibers. In this study, the microstructure and interfacial shear strength (ISS) of continuous silicon carbide fiber/epoxy composites with and without nanotubes grown from the SiC fiber surface were investigated with micro-Raman spectroscopy (MRS) and microscopy. The fibers with nanotubes grown from the surface were found to have a reduced ISS compared with the bare fibers. Electron microscopy showed good wetting of epoxy in the nanotube forests, but poor attachment of the nanotube forests to the fibers. These results suggest that the mechanism leading to improvements in bulk composite properties is not due to an improvement in the fiber/matrix ISS.     

Monitoring of the microstructure of ion‐irradiated nuclear ceramics by in situ Raman spectroscopy

Raman spectroscopy is an efficient technique for studying the evolution of microstructure of materials under irradiation. For that purpose, a Raman spectrometer has been recently installed at the JANNUS‐Saclay platform. In this paper, we describe the new setup for in situ experiments. These in situ experiments allowed following the microstructural evolution of different materials (SiC, ZrO₂ and B₄C) as a function of ion fluence on a single sample (either single crystal or polycrystalline ceramics) under the same irradiation conditions. Our results show that Raman spectroscopy is a versatile non‐contact technique for studying on‐line crystalline phase changes or amorphization of irradiated iono‐covalent solids. A detailed analysis of Raman spectra is provided for the three materials (SiC, ZrO₂ and B₄C) investigated in this study, revealing quite different behaviors upon irradiation. Basically, Raman spectroscopy gives insight on these evolutions at the level of bonds given by specific phonon modes, in good agreement with Rutherford backscattering channeling (RBS/C), X‐ray diffraction (XRD) or transmission electron microscopy (TEM) data, which provide information at a long‐range scale. Copyright © 2015 John Wiley & Sons, Ltd.     

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利用化学气相反应法对掺杂石墨材料进行了SiC梯度涂层,研究了SiC梯度涂层对掺杂石墨材料热力学性能以及微观结构的影响。获得了约100μm的SiC涂层,涂层后的材料导热性能下降,而机械强度有所增加。对涂层表面的物相成分分析表明,除了SiC之外,还有少量的单质Si。厚膜SiC梯度涂层的掺杂石墨材料在HT-7托卡马克装置中经等离子体放电实验后,SiC的颗粒形貌发生了明显的变化,涂层厚度下降到约30μm。     

聚合物前驱体制备层状SiC纳米棒的光学性质

采用聚硅氮烷前驱体在高温常压下热裂解方法制备了SiC纳米棒。透射电镜图表明SiC纳米棒中包含有独特的层状结构,电子能谱表明SiC纳米棒中的C ∶ Si组分比接近1 ∶ 1。用X射线衍射和喇曼光谱表征了SiC纳米棒的结构和成分,层状结构为6H-SiC和3C-SiC交替形成所致。利用光致发光谱在该层状结构中观察到强的紫外发射,认为强而锐的紫外发射峰是来源于厚度比较均一的6H-SiC层。     

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.     

复合材料残余应力的拉曼测定

本文报道在拉曼光谱仪中用拉曼光谱术和荧光光谱术测定复合材料残余应力(应变)的方法和结果。复合材料组分中Al2O3的荧光R1峰、Si晶体和SiC纤维拉曼峰的位置(波数)随应变的偏移与应变值都有近似的线性关系。这种关系可用于确定复合材料中由外负荷力学作用或热学作用引起的残余应变。在显微拉曼系统中测定了ZrO2-Al2O3层状复合材料,Al-Si共晶体和SiC纤维增强玻璃复合材料的残余应变及其空间分布。     

Raman investigation of defective SiC nanocrystals

Phonon confinement effect and surface optical mode in SiC nanocrystal have been investigated through Raman spectroscopy. Considering high density of stacking faults in SiC grains, the correlation length of RWL (proposed by Richter, Wang, Li to explain phonon confinement in nano silicon) model is determined as a distance between nearby stacking faults. Thus, homogeneous region becomes thin slices in cylindrical SiC grains, which redefines weighting function. Effect of anisotropy of phonon dispersion curve is also analyzed during calculation. The additional 875‐cm⁻¹ band is attributed to defects and amorphous SiC, which is confirmed by transmission electron microscopy. SiC grains are approximated as column array with grain boundary substances regarded as surrounding medium, which explains surface optical phonon mode at 915 cm⁻¹. Copyright © 2015 John Wiley & Sons, Ltd.     

3D Raman mapping of uniaxially loaded 6H‐SiC crystals

Raman spectroscopy is used to investigate the three‐dimensional stress distribution in 6H‐silicon carbide (SiC) specimens subjected to stresses up to 3.7 GPa along the c‐axis. Specifically, the relative Raman shift of the longitudinal optic phonon of 6H‐SiC is used to evaluate the local stress across the bulk crystal. For this purpose, an anvil device with opposed 6H‐SiC and sapphire specimens was used. After subjecting the anvils to uniaxial load, several series of two‐dimensional Raman maps were registered at different depths in the 6H‐SiC anvil. The analysis of the Raman spectra reveals an exponential decay of the stress as a function of the depth. A novel phenomenological Grüneisen‐like model is introduced here to account for such observation. On the contrary, the in‐plane stress analysis shows a radial Gaussian‐like distribution regardless the depth, a distinct behavior that is attributed to the appearance of shear stress components. The suitability of both models and their applicability to other materials are discussed, along with some future directions. Copyright © 2013 John Wiley & Sons, Ltd.     

不同退火方式对Ni/SiC接触界面性质的影响

采用快速热退火(rapid thermal annealing, RTA)法和脉冲激光辐照退火(laser spark annealing, LSA)法, 在n型4H-SiC的Si面制备出Ni电极欧姆接触. 经传输线法测得RTA样品与LSA样品的比接触电阻分别为5.2×10^-4 Ω·cm², 1.8× 10^-4 Ω·cm². 使用扫描电子显微镜、原子力显微镜、透射电子显微镜、拉曼光谱等表征手段, 比较了两种退火方式对电极表面形貌、电极/衬底截面形貌和元素成分分布、SiC衬底近表层碳团簇微结构的影响. 结果表明, 相比于RTA, LSA法制备出的欧姆接触在电极表面形貌、界面形貌、电极层组分均匀性等方面都具有明显优势, 有望使LSA成为一种非常有潜力的制备欧姆接触的退火处理方法.