Effect of the microstructure of Si3N4 on the adhesion strength of TiN film on Si3N4

The effect of the microstructure of silicon nitride, which was used as a substrate, on the adhesion strength of physical vapor deposited TiN film on Si₃N₄ was investigated. Silicon nitride substrates with different microstructures were synthesized by controlling the size (fine or coarse), the phase ( or β) of starting Si₃N₄ powder, and sintering temperature. The microstructure of Si₃N₄ was characterized in terms of grain size, aspect ratio of the elongated grain, and β-to- phase ratio. For a given chemical composition but different mechanical properties, such as toughness, elastic modulus, and hardness of Si₃N₄ were obtained from the diverse microstructures. Hertzian indentation was used to estimate the yield properties of Si₃N_4, such as critical loads for yield (P_y) and for ring cracking (P_c). The effect of the microstructure of Si₃N₄ on adhesion strength evaluated by scratch test is discussed. TiN films on Si₃N₄ showed high adhesion strengths in the range of 80–140 N. Hardness and the P_y of Si₃N₄ substrate were the primary parameters influencing the adhesion strength of TiN film. In TiN coating on Si₃N₄, substrates with finer grain sizes and higher phase ratios, which show high hardness and high P_y, were suitable for higher adhesion strength of TiN film.     

Coverage properties of silicon nitride film prepared by the Cat-CVD method

The coverage properties of silicon nitride (Si₃N₄) films prepared by the catalytic chemical vapor deposition (Cat-CVD) technique were systematically studied. By increasing the catalyzer–substrate distance, the coverage was improved from 46 to 67% on a 1.0-μm line and space pattern. The etching rate of Cat-CVD Si₃N₄ film measured using 16BHF solution was independent of the deposited position of the micro-patterns deposited, and was approximately 3 nm/min, one order of magnitude lower than that of plasma-enhanced CVD (PE-CVD) Si₃N₄ film. This means that Cat-CVD Si₃N₄ films are denser than PE-CVD Si₃N₄ films, and that the quality at the side wall is equivalent to that on the top surface. That is, Cat-CVD Si₃N₄ films show a passivation effect, which was excellent, even at the side wall of micro-patterns. These results suggest that Si₃N₄ films prepared by Cat-CVD are suitable for the passivation films in microelectronic devices having a step configuration, such as TFT-LCDs and ULSIs.     

Si3N4/FePd/Si3N4薄膜的晶体结构和磁性能研究

采用磁控溅射的方法制备了Si₃N₄/FePd/Si₃N₄三层膜, 研究了非磁性材料Si₃N₄作为插入层对磁记录FePd薄膜结构与磁性能的影响。结果表明, 热处理后Si₃N₄分布在FePd纳米颗粒之间, 抑制了FePd晶粒的生长, 与纯FePd薄膜相比, Si₃N₄/FePd/Si₃N₄薄膜的颗粒明显得到细化; 通过添加Si₃N₄层, FePd薄膜的晶体学参数c/a从0.960减小到0.946, 表明Si₃N₄可以有效促进FePd薄膜的有序化进程, 同时提升了矫顽力和剩磁比, 分别提高到249 kA/m、0.86; 随着600℃退火时间的进一步延长, 添加Si₃N₄的薄膜磁性没有迅速下降, 在较宽的热处理时间范围内磁性能保持在比较高的水平, 提高了抗热影响的能力。Si₃N₄作为插入层对FePd薄膜的磁性能具有较大的提升作用, 这对磁记录薄膜的发展具有重要意义。     

氮化硼纳米管增强氮化硅复合材料的裂纹扩展阻力行为

用氮化硼纳米管(BNNT)增强氮化硅(Si₃N₄)陶瓷制备了BNNT/Si₃N₄复合材料, 利用三点弯曲强度及单边切口梁(SENB)法测定了BNNT/Si₃N₄复合材料的弯曲强度和断裂韧性。通过SEM观察了BNNT/Si₃N₄复合材料微观形貌。基于BNNT增强Si₃N₄陶瓷复合材料的裂纹扩展阻力计算公式, 构建了BNNT对Si₃N₄陶瓷裂纹屏蔽区的裂纹扩展阻力的数学模型。用该模型的计算结果与Si₃N₄陶瓷的裂纹扩展阻力进行了对比。结果表明: BNNT/Si₃N₄复合材料的弯曲强度和断裂韧性明显高于Si₃N₄陶瓷, 说明BNNT对Si₃N₄陶瓷的裂纹扩展有阻力作用, 摩擦拔出是Si₃N₄陶瓷抗裂纹扩展能力提高的主要原因; BNNT对Si₃N₄陶瓷有明显的升值阻力曲线行为。通过有限元模拟裂纹尖端应力分布, 发现BNNT使Si₃N₄陶瓷裂纹尖端的最大应力转移到纳米管上, 而且BNNT降低了Si₃N₄陶瓷裂纹尖端的应力, 对Si₃N₄陶瓷尖端的裂纹有屏蔽作用, 从而提高了Si₃N₄陶瓷的裂纹扩展阻力。     

添加BaTiO3的热压烧结Si3N4陶瓷的力学和介电性能

本研究以Al₂O₃和Nd₂O₃为烧结助剂, 采用热压烧结法制备Si₃N₄陶瓷, 系统研究了添加BaTiO₃对Si₃N₄陶瓷力学和介电性能的影响。研究结果表明, 随着BaTiO₃含量的增加, 相对密度、抗弯强度和维氏硬度都随之降低, 而断裂韧性有所升高; 即使添加5wt%~20wt%的BaTiO₃, Si₃N₄陶瓷的抗弯强度依然可以保持在600 MPa以上。Si₃N₄陶瓷的介电常数可以提高到9.26~11.50, 而介电损耗保持在10^-3量级。在Si₃N₄陶瓷中未检测到BaTiO₃结晶相, 可以认为Si₃N₄陶瓷介电常数的提高主要来源于烧结过程中形成的TiN。这些结果有助于拓展Si₃N₄陶瓷的应用领域。     

1450℃反应烧结Fe3Si-Si3N4复合耐火材料的相组成

以Si粉和Fe₃Si-Si₃N₄为原料,在高纯N₂气氛下制备Si₃N₄/Fe₃Si-Si₃N₄复合材料。氮化烧成后Si₃N₄结合Fe₃Si-Si₃N₄复合耐火材料试样中物相为Si₃N₄、Fe₂Si、FeSi和Si₂N₂O。其中Si₂N₂O含量约6%,且在试样中心和外部分布不均匀。Fe₃Si-Si₃N₄原料是Fe₃Si和Si₃N₄两相共存材料,热力学评估和材料的微观结构分析表明,Fe₃Si和部分Si粉形成新的低熔点硅铁合金,使靠近试样表面部位的部分开口气孔被液态硅铁合金所堵塞或填充,试样中心部位的微量氧不能迁移至外部,N₂中微量氧将Fe₃Si-Si₃N₄原料中Si₃N₄氧化,形成Si₂N₂O包裹,导致试样中心Si₂N₂O含量比边缘部位高。Si₂N₂O的形成使体系氧分压降至Si₃N₄稳定存在的氧分压时,Si粉直接氮化形成柱状Si₃N₄,而非纤维状Si₃N₄,同时在1 450℃氮化烧成条件下,Fe的存在促进了α-Si₃N₄向β-Si₃N₄的转变。     

颗粒级配对Si_(3)N_(4)w/Si_(3)N_(4)复合材料弯曲强度与介电性能的影响EI北大核心CSCD

为了获得一种弯曲和介电性能良好的氮化物陶瓷材料,本工作首先以氮化硅晶须(Si_(3)N_(4w))为原料,采用喷雾造粒工艺制备3种具有不同粒径分布的Si_(3)N_(4w)球形颗粒粉体,研究雾化盘转速对Si_(3)N_(4w)球形颗粒粉体粒径分布的影响。然后以喷雾造粒得到的Si_(3)N_(4w)球形颗粒为原料,采用干压法制备3种颗粒级配的Si_(3)N_(4w)预制体,研究颗粒级配Si_(3)N_(4w)预制体的孔径分布。采用化学气相渗透(CVI)和先驱体浸渍裂解(PIP)工艺在3种颗粒级配的Si_(3)N_(4w)预制体中进一步制备Si_(3)N_(4)基体,研究Si_(3)N_(4w)/Si_(3)N_(4)复合材料制备过程中的物相和微结构演变以及颗粒级配对Si_(3)N_(4w)/Si_(3)N_(4)复合材料的微结构、密度、弯曲强度和介电性能的影响。结果表明:3种颗粒级配的Si_(3)N_(4w)预制体均具有二级孔隙特征,其中小孔孔径均约为0.7μm,大孔孔径分别为45.2,30.1μm和21.3μm。在制备的3种颗粒级配的Si_(3)N_(4w)/Si_(3)N_(4)复合材料中,S13样品的颗粒级配效果最好,复合材料的弯曲强度达到81.59 MPa。此外,该样品的介电常数和介电损耗分别为5.08和0.018。良好的弯曲强度和介电性能表明制备的Si_(3)N_(4w)/Si_(3)N_(4)复合材料有望应用于导弹天线罩领域。     

Atomic layer deposition of tungsten using sequential surface chemistry with a sacrificial stripping reaction

Tungsten (W) films were grown with atomic layer control using a novel sequence of self-limiting surface reactions. The tungsten film growth was achieved by dividing the binary reaction WF₆+Si₂H₆→W+2SiHF₃+2H₂ into two separate half-reactions. Alternating exposures to WF₆ and Si₂H₆ in an ABAB… sequence produced tungsten deposition at temperatures between 425 and 600 K. The Si₂H₆ reactant served only a sacrificial role to strip fluorine from tungsten without incorporating into the film. FTIR spectroscopic investigations demonstrated that the WF₆ and Si₂H₆ half-reactions were complete and self-limiting at T>400 K. In situ spectroscopic ellipsometry measurements determined a tungsten growth rate of 2.5 Å/AB cycle with WF₆ and Si₂H₆ reactant exposures sufficient for complete half-reactions. The surface topography of the deposited tungsten films was flat indicating smooth film growth. The tungsten films were either amorphous or composed of very small crystalline grains and contained no measurable silicon or fluorine. These results represent the first demonstration of atomic layer deposition of smooth single-element metal films using sequential surface chemistry.     

浆料固相含量对数字光处理成形Si3N4陶瓷性能的影响

随着科技的不断发展, Si₃N₄陶瓷在航空、机械、生物医疗等高新领域发挥着越来越重要的作用。本工作采用包覆助烧剂Al₂O₃-Y₂O₃后的Si₃N₄粉体为原材料, 利用数字光处理(Digital light processing, DLP)技术成功制备出Si₃N₄陶瓷, 并系统研究了浆料固相含量对Si₃N₄陶瓷浆料、DLP成形Si₃N₄陶瓷素坯和陶瓷性能的影响。研究表明, 浆料固相含量低于40.0% (体积分数)时, 浆料在30 s^-1剪切速率下的粘度均小于2 Pa·s, 可用于DLP成形。在这种情况下, 浆料的单层固化深度随浆料固相含量的增加而减小。随着浆料固相含量的增大, DLP成形Si₃N₄陶瓷的相对密度和抗弯强度先升高后降低。固相含量为37.5% (体积分数)的样品获得最大的相对密度和抗弯强度, 分别为89.8%和162.5 MPa, 较固相含量为32.5% (体积分数)的样品分别提升了10%和16%。本研究通过对陶瓷浆料性能的优化, 提升了DLP成形Si₃N₄陶瓷的性能, 为Si₃N₄等非氧化物陶瓷光固化成形奠定了实验基础。     

自蔓延高温合成氮化硅多孔陶瓷的研究进展

多孔氮化硅陶瓷兼具有高气孔率和陶瓷的优异性能, 在吸声减震、过滤等领域具有非常广泛的应用。然而, 目前常规的制备方法如气压/常压烧结、反应烧结-重烧结以及碳热还原烧结存在烧结时间长、能耗高、设备要求高等不足, 导致多孔Si₃N₄陶瓷的制备成本居高不下。因此, 探索新的快速、低成本的制备方法具有重要意义。近年来, 采用自蔓延高温合成法直接制备多孔氮化硅陶瓷展现出巨大潜力, 其可以利用Si粉氮化的剧烈放热同时完成多孔氮化硅陶瓷的烧结。本文综述了自蔓延反应的引发以及所制备多孔氮化硅陶瓷的微观形貌、力学性能和可靠性。通过组分设计和工艺优化, 可以制备得到氮化完全、晶粒发育良好、力学性能与可靠性优异的多孔氮化硅陶瓷。此外还综述了自蔓延合成多孔Si₃N₄陶瓷晶界相性质与高温力学性能之间的关系, 最后展望了自蔓延高温合成多孔Si₃N₄陶瓷的发展方向。     

原位引入BN-SiC燃烧合成Si3N4-BN-SiC复合材料

Si₃N₄-BN-SiC复合材料以其良好的力学性能和抗氧化性能而具有良好的工程应用前景。本研究以Si、Si₃N₄稀释剂、B₄C和Y₂O₃为原料, 采用燃烧合成法成功制备了Si₃N₄-BN-SiC复合材料。通过Si、B₄C和N₂气之间的反应, 在Si₃N₄陶瓷中原位引入BN和SiC, 制备的Si₃N₄-BN-SiC复合材料由长棒状的β-Si₃N₄和空心球形复合材料组成。实验研究了空心球微结构的形成机理, 结果表明, 生成的SiC、BN颗粒及玻璃相覆盖在原料颗粒上, 当原料颗粒反应完全时, 形成空心球形微结构。并进一步研究了B₄C含量对Si₃N₄-BN-SiC复合材料力学性能的影响。原位引入SiC和BN在一定程度上可以提高复合材料的力学性能。当B₄C添加量为质量分数0~20%时, 获得了抗弯强度为28~144 MPa、断裂韧性为0.6~2.3 MPa·m ^1/2, 杨氏模量为17.4~54.5 GPa, 孔隙率为37.7%~51.8%的Si₃N₄-BN-SiC复合材料。     

Si_3N_4原位增强Cu基复合材料的制备

采用感应炉熔炼及水雾化工艺制得了Cu-Si合金粉末,经N2、H2混合气体选择氮化和真空放电等离子烧结(SPS)成型,制备得到了Si3N4原位增强Cu基复合材料(Si3N4/Cu),利用萃取法研究了选择性氮化产物及其晶体结构。结果表明:复合粉末中N含量随氮化温度的升高和氮化时间的延长而增大。在1 000℃下氮化,持续时间大于60h时,粉末中的N含量明显提高;Cu的衍射峰出现整体向大角度方向的明显偏移,同时晶格常数变小,表明Si从Cu基体中脱溶,与N反应生成Si3N4;Si3N4/Cu复合材料的增强体以β-Si3N4为主;随着氮化温度的升高和氮化时间的延长,Si3N4/Cu复合材料的电导率和硬度逐步提高。     

CHEMICAL VAPOR DEPOSITION OF TITANIUM CARBIDE ON AISI M2 TOOL STEELS AND Si3N4-TiC CERAMIC COMPOSITE

TiC deposition experiments were performed on high speed steel and on Si₃N₄-TiC composite ceramic cutting tools through chemical vapor deposition (CVD) using gaseous mixture of TiCl₄, CH₄, and H₂. The effects of the deposition temperature and the composition of reactant gases on deposition rate, structure and microhardness of the TiC film were investigated. Experimental apparatus and deposition procedures are also presented. Deposition at 1323K with (CH₄/TiCl₄) ratio of 1.2 gives the optimum mechanical properties of the film for AISI M2 steel substrate while Si₃ N₄-TiC composite shows its maximum strength at 1373K and 1.3(CH₄/TiCl₄).     

Dielectric reference coatings for the evaluation of thin film characterization techniques

Thin film technology has an increasing demand for industrial reliable characterization techniques. A precise absolute determination of layer thickness, interface width and the quantification of depth profiles in dependence on resolution limits of the measurement are required. Certified reference materials, certified reference coatings (CRCs) and non-destructive evaluation techniques can meet these requirements. Dielectric reference coatings (SiO₂, Si₃N₄) were used for metallographic preparation (e.g. bevelled cross-sections), optical characterization techniques (e.g. spectroscopic ellipsometry (SE)), and films of SiO₂, Si₃N₄ and Al₂O₃ were applied to reference measurements in depth profiling of layer stacks (e.g. radio frequency glow discharge optical emission spectroscopy). Thickness and refractive index of these dielectric single-and multilayer coatings on different substrate materials are accurately determined in advance by means of SE. These values are subsequently used for precise angle determination of bevelled cross-sections, for reference and re-calibration purposes in thin film characterization (system reproducibility) and in surface analysis (determination of sputter and erosion rates, depth profiles). Examples are discussed for different applications and the calculated data are compared with experimental results. It is shown that reproducible commercial coatings are also of importance for use as CRCs.     

Effect of seed particles content on texture formation of Si_3N_4 ceramics by gel-casting in a strong magnetic field

In this paper,the textured Si_3N_4 ceramics were prepared by adding seed particles during gel-casting in the magnetic field of 6 T,followed by pressureless sintering.The effect of pH on the stability and dispersibility of Si_3N_4 slurry and the effect of seed particles content on texture formation of Si_3N_4 ceramics were both studied.Those results showed that the slurry with good stability and dispersibility was obtained when pH was about 11.6.The a or b-axis of Si_3N_4particles or crystals was aligned parallel to the direction of the magnetic field in the magnetic field of 6 T.The degree of texture of Si_3N_4 ceramics further increased during sintering.With the increasing of additional β-Si_3N_4 particles in the magnetic field of 6 T,the degree of texture increased from0.19 without seed particles to 0.76 with 9%(mass fraction)seed particles.The increase of seed particles content promoted the texture formation of Si_3N_4 ceramics.     

基于TiC_(0.5)N_(0.5)/Si_3N_4复相陶瓷基体的PVD及CVD涂层刀具性能

首先,以15vol%或25vol%的TiC0.5N0.5粉体为导电第二相,利用热压烧结法制备了TiC0.5N0.5/Si3N4复相陶瓷;然后,分别通过物理气相沉积(PVD)和化学气相沉积(CVD)技术在TiC0.5N0.5/Si3N4陶瓷刀具表面沉积了CrAlN和TiN/Al2O3/TiN涂层;最后,通过对TiC0.5N0.5/Si3N4刀具进行连续切削灰铸铁实验,研究了TiC0.5N0.5含量和涂层类型对刀具磨损特征的影响,并探讨了刀具的磨损机制。结果表明:TiC0.5N0.5含量的增加有利于提高TiC0.5N0.5/Si3N4复相陶瓷刀具基体的硬度和电导率,但对耐磨性和切削寿命的影响较小;采用PVD技术沉积CrAlN涂层时,随着TiC0.5N0.5含量的增加,涂层的厚度、结合强度和硬度都得到提高,涂层刀具的磨损性能显著提高,切削寿命也明显延长;而采用CVD技术沉积TiN/Al2O3/TiN涂层时,TiC0.5N0.5含量的变化对涂层的厚度、结合强度和硬度基本没有影响,TiN/Al2O3/TiN涂层刀具整体切削性能变化不大。CrAlN涂层和TiN/Al2O3/TiN涂层都可明显改善TiC0.5N0.5/Si3N4复相陶瓷刀具的耐磨性和切削寿命;相对于TiN/Al2O3/TiN涂层,CrAlN涂层具有更高的涂层硬度和粘着强度,但TiN/Al2O3/TiN涂层具有较大的涂层厚度,TiN/Al2O3/TiN涂层刀具表现出更加优异的耐磨性和切削寿命。TiC0.5N0.5/Si3N4复相陶瓷刀具的磨损机制以机械摩擦导致的磨粒磨损为主,伴随有少量的粘结磨损。     

稀土氧化物对常压烧结氮化硅陶瓷性能的影响

高导热氮化硅陶瓷是大功率电力电子器件散热的关键候选材料。研究采用稀土氧化物(Re₂O₃)和氧化钛(TiO₂)烧结助剂体系, 通过低温常压烧结方法来制备氮化硅陶瓷, 以有效降低成本, 满足实际应用的需求。系统研究了烧结助剂种类及含量对Si₃N₄陶瓷的致密化行为、热导率、显微结构以及力学性能的影响。研究发现随着稀土离子半径的增大, 材料的致密度和热导率均呈现下降趋势, 添加Sm₂O₃后样品最高密度仅为3.14 g/cm³。但是当Sm₂O₃-TiO₂烧结助剂含量为8wt%时, 样品断裂韧性可达5.76 MPa•m^1/2。当添加Lu₂O₃且烧结助剂含量为12wt%时, 材料的密度可达3.28 g/cm³, 但是大量存在的第二相导致热导率仅为42.3 W/(m∙K)。研究发现该材料具有良好的断裂韧性。经1600℃退火8 h后, Er₂O₃-TiO₂烧结助剂样品的热导率达到51.8 W/(m∙K), 基本满足一些功率电路基板材料的实际应用需求。     

Improved sinterability of SiC(w)/Si3N4 composites by whisker-oriented alignment

Effects of whisker-oriented alignment on sintering behavior of SiC(w)/Si₃N₄ composites were investigated by sintering curves of SiC(w)/Si₃N₄ compacts with different whisker alignment (random and unidirectionally oriented). It was found that whisker-oriented alignment led to considerable anisotropy of linear shrinkage and sintering rate of SiC(w)/Si₃N₄ compacts during sintering. Whisker-oriented alignment could improve the sinterability of the SiC(w)/Si₃N₄ composites and consequently improve the maximum fraction of whisker addition and reduce the content of sintering additives without obviously lowering the density, which are more beneficial to exert the best reinforcing effects of whiskers and mechanical properties of SiC(w)/Si₃N₄ composites at elevated temperature.     

Machining of Hypereutectic Al-Si Alloy with CVD Diamond Coated Si4N4. Inserts

Due to its excellent mechanical properties, diamond can be used for many applications in mechanical engineering. With the help of the Chemical Vapor Deposition (CVD) method it is possible to deposit polycrystalline diamond films on different substrate materials of nearly any shape and surface. So diamond cutting tools with complex geometry are now possible. In this investigation diamond coatings deposited by microwave plasma CVD (MW-PACVD) on Si₃N₄ inserts were used for turning experiments. By means of changes in the CH₄/H₂ gas ratio two different types of film morphology were generated, one rather highly faceted and the other one fine-grained ballas-type surface microstructure. The cutting performance of the CVD diamond coated triangular silicon nitride inserts was analyzed for continuous dry turning of the hypereutectic AISi 17Cu4Mg alloy with different cutting speeds. During the experiments no wear of the diamond films could be detected; nevertheless, the adhesion to the Si₃N₄ substrate has still to be improved. The results of the cutting tests gave valuable information for favorable geometry and clamping devices of cutting tools coated with CVD diamond and for suitable machining parameters.     

Cost effective combustion synthesis of silicon nitride

The feasibility of mechanical activation (MA)-assisted combustion synthesis (CS) of Si₃N₄ was demonstrated by using Si/NH₄Cl as reactants under a nitrogen pressure of 2 MPa. MA treatment significantly enhances the reactivity of Si powders, which effectively promotes the nitridation of silicon. The NH₄Cl had the same effect as Si₃N₄ diluent in preventing extensive melting of Si within the combustion wave zone. Full nitridation of Si was achieved at diluent levels as low as 5 wt%. Si₃N₄ powders with -phase contents of up to 90.6 wt% were obtained. The temperature gradient induced by heat release through radiation was responsible for discrepancies in the phase composition and morphologies of the as-synthesized product at different locations.