籽晶添加对氮化硅陶瓷显微结构与力学性能的影响

以不同配比的Y₂O₃-Al₂O₃为烧结助剂, 通过添加3wt%的单分散β-Si₃N₄籽晶, 采用气压烧结制备了氮化硅陶瓷, 并对所得材料的相组成、密度、室温和高温力学性能及显微结构进行了研究. 结果表明: 不同烧结助剂配比的α-Si₃N₄粉体在1800℃保温2 h即全部转化为β-Si₃N₄, 且各烧结体的相对密度都达到了97%以上. 在6wt%Y₂O₃和4.5wt%Al₂O₃为烧结助剂时, 添加3wt%籽晶的样品其室温强度和1200℃高温强度分别提高了20%和16%, 断裂韧性提高了8%.     

β-Si3N4单晶体的制备

在自增韧Si3N4陶瓷的烧结过程中,添加作为晶种的长柱状β-Si3N4单晶体对于改善陶瓷的强度和韧性是非常有效的。本研究旨在制备出长柱状β-Si3N4单晶体,并对其尺寸和形貌进行有效的控制。通过对87.3wt/α-SiN4 8.3wt/Y2O3 4.4wt/SiO2体系进行气压烧结,经去除掉玻璃相等漂洗工艺后,制得β-Si3N4单晶体,其直径为1－2μm、长度为4－6μm。同时对不同烧结工艺下制得的β-Si3N4单晶体的尺寸和工艺参数的关系进行了研究。     

Effects of Phase Composition on Microstructure and Mechanical Properties of Lu_2O_3-doped Porous Silicon Nitride Ceramics

Porous silicon nitride ceramics(Si3N4) were fabricated by pressureless sintering using different particle size of silicon nitride powder.Lu2O3 was used as sintering additive.According to phase relationships in the ternary system Si3N4-SiO2-Lu2O3,porous Si3N4 ceramics with different phase composition were designed through the change of the content of SiO2 which was formed by the oxidation at 800℃ in air.Porous Si3N4 with different phase compositions was obtained after sintering at 1800℃ in N2atmosphere.A small content of SiO2 favored the formation of secondary phase Lu4Si2O7N2,while large content of SiO2 favored the formation of secondary phase Lu2Si2O7 and Si2N2O.Porous Si3N4 ceramics with secondary phase Lu4Si2O7N2 had a flexural strength of 207 MPa,while that with secondary phase Si2N2O and Lu2Si2O7 had lower flexural strength.     

In situ Auger electron spectroscopy investigation of the chemical bonding of ion-beam-deposited silicon nitride

The necessity of knowing the atomic ratio of nitrogen to silicon and the contamination of silicon nitride to obtain layers with reproducible physical, chemical and electrical properties is reviewed. Ion-beam-sputtered thin films of various nitrogen-to-silicon ratios with an oxygen content of less than 1% are analysed by in situ Auger electron spectroscopy. By deliberately allowing a pure silicon-rich nitride layer to become oxidized, the different signals contributing to the line shape of the derivative Si LVV peak are unambiguously identified. Assuming the peak-to-background ratio to be an intrinsic measurement, we propose a method to evaluate the composition of non-stoichiometric silicon nitride layers from the study of the Si LVV peak recorded in the EN(E) mode. This peak is reconstituted by using a linear combination of experimental Si LVV peaks from pure silicon and completely nitrided silicon. A realistic background is deduced from a step-by-step deposition of Si₃N₄ onto carbon. The results are compared with Rutherford backscattering spectrometry measurements and discussed.     

Effect of high-energy electron-beam irradiation on the optical properties of ion-beam-sputtered silicon oxynitride thin films

Silicon oxynitride thin films are prepared by ion-beam sputtering, and the optical properties and surface chemical composition are studied by spectrophotometric and x-ray photoelectron spectroscopy, respectively. It is seen that the films sputtered by use of nitrogen alone as the sputtering species from a silicon nitride target are completely transparent (k < 0.005) and have a refractive-index dispersion from 1.85 to 1.71 over the visible and near-infrared spectral regions, and the films show distinct spectral lines that are due to silicon, Si(2s), nitrogen, N(1s), and oxygen, O(1s). Sputter deposition of argon and of argon and nitrogen produces silicon-rich silicon oxynitride films that are absorbent and have high refractive indices. These films have a direct electronic transition, with a threshold energy of 1.75 eV. Electron irradiation transforms optically transparent silicon oxynitride films into silicon-rich silicon oxynitride films that have higher refractive indices and are optically absorbing owing to the presence of nonsaturated silicon in the irradiated films. The degradation in current responsivity of silicon photodetectors, under electron irradiation, is within 3% over the wavelength region from 450 to 750 nm, which is entirely due to the degradation of optical properties of silicon oxynitride antireflection coatings.     

气体流量比对反应溅射Si3N4薄膜的影响

利用射频磁控反应溅射法，以高纯Si为靶材，高纯N2气为反应气体，在Si衬底上制备出了Si3N4薄膜，研究了气体流量比对薄膜质量的影响。结果表明，薄膜的沉积速率主要与气体的流量比有关，随着气体流量比的增加，沉积速率下降，靶面的溅射由金属模式过渡到氮化物模式；薄膜中N／Si的原子比增加；红外吸收谱的Si—N键的振动峰向标准峰逼近。     

Effects of bombardment on optical properties during the deposition of silicon nitride by reactive ion-beam sputtering

Thin silicon nitride (Si(1_x)N(x)) films were synthesized without substrate heating by means of reactive argon-ion sputtering of either silicon or a silicon nitride target in the 1000-1500-eV energy range at a nitrogen partial pressure of 1.3 × 10(-2) Pa and with simultaneous nitrogen ion-assisted bombardment in the 300-500-eV low energy range. The extinction coefficient and refractive index of the films were directly dependent on the N(+) ion-to-atom arrival ratio, assisted ion energy, film growth rate, and indicated a correlation with film stoichiometry and disorder. Si(3)N(4) films were obtained for N(+) ion/Si atom arrival ratios from 0.6 to 1.7 and for different Si:N atom arrival rates and had a refractive index as high as 2.04 (633 nm) and a low hydrogen content as indicated by IR spectra.     

无压烧结制备氧氮化硅陶瓷

以β－Si3N4和ＳiO2粉末为原料,以ＭgAl2O4为烧结添加剂,通过无压烧结制备出致密的Ｓi2N2O陶瓷材料,所得材料由柱状Ｓi2N2O颗粒和少量β－Si3N4颗粒复合组成,研究了烧结温度对材料显微结构的影响,发现材料的断裂大部分是穿晶断裂。     

Preparation and Properties of Macroporous Silicon Nitride Ceramics by Gelcasting and Carbonthermal Reaction

1. IntroductionIn recent years, porous Si3N4 ceramics have re-ceived increasing attention for their extensive applicationin many high-tech areas such as bio ceramics[1], cata-lyst supports[2], hot gases filter[3], liquid purification[4],sensors[5], and membrane reactors[6]. Their appeal ismainly because of their unique and inherent proper-ties. Si3N4 ceramics are materials with excellent me-chanical properties, good corrosion resistance and oxida-tion resistance[7]. Since better performance …     

Surface Modification of Ceramic Materials Using Excimer Laser

1' IatroductionThe surface modification of materials by lasertreatment is an attractive technology, which has beenavailable to materials scientists and engineers forabout 30 years. For example, excimer lasers can provide a rapid and efficient means for surface modification of ceramic materials. After excimer laser, irradiation, surface morphology and structure were modified,and surface properties, such as electric conductivity,catalytic activity and bending strength of ceramics,. Iwere improve…     

Interaction of TEMAHf precursor with OH-terminated Si (001) surface: a first principles study

We performed a first principles study to investigate the interaction of tetrakis-ethylmethylaminohafnium (4[(C2H5)(CH3)N]Hf, TEMAHf) precursors with an OH-terminated Si (001) surface that is the initial stage of atomic layer deposition (ALD). When TEMAHf reacted on the OH-terminated Si surface, there were two reaction mechanisms. One was the reaction with one -OH, and the other was the reaction with two -OH's. When TEMAHf reacted with an -OH on the Si (001) surface, an ethylmethylamine ((C2H5)(CH3)NH, EMA) was produced as a by-product and the trikis-ethylmethylaminohafnium group (3[(C2H5)(CH3)N]Hf) was attached to the O atom of the -OH. There were five reaction sites for TEMAHf to react with two -OH's to form the dikis-ethylmethylaminohafnium group (2[(C2H5)(CH3)N]Hf): Inter-dimer, intra-dimer, inter-row, cross-dimer, and cross-row. The reaction with two -OH's on the inter-dimer, intra-dimer, and inter-row sites were more favorable than the reaction with one -OH. Since the inter-dimer reaction was the most favorable, the energy barrier on the inter-dimer site for the reaction of the trikis-ethylmethylaminohafnium group with -OH to form the dikis-ethylmethylaminohafnium group was calculated, and the result was 0.19 eV. An extra energy of 0.25 eV was needed to remove EMA from the surface. Four TEMAHf's reacted with the surface and these reactions were exothermic by -7.77 eV, and the calculated Hf coverage of the first-half ALD cycle was 1.67 x 10(14)/cm2.     

Optical and structural features of silicon-rich hydrogenated amorphous silicon nitride thin films

A systematic study of fabrication and effect of post-deposition processing on the optical and structural features of silicon-rich hydrogenated amorphous silicon nitride thin films deposited by Hg-sensitized Photo-Chemical Vapour Deposition technique is presented. Both deposition parameters and post-deposition thermal treatment resulted into substantial change in the refractive index associated with the densification of the film. Our studies reveal that the presence of hydrogen and its out-diffusion upon thermal treatment play a crucial role in the overall structural evolution, specially the stabilization of individual phases such as Si and Si3N4. We further report the room-temperature photoluminescence from as-deposited films, which is due to formation of silicon nanostructures in crystalline and amorphous forms. These studies are of great interest from the prospective of commercially viable Si-based technology.     

晶须增强氮化硅陶瓷自生复合材料

本文提出了两种制备氮化硅陶瓷自生复合材料的方法:以氟化钙为添加剂,对硅坯体直接进行氮化;经预氮化后的反应烧结氮化硅多孔体,在含酚醛树脂和硅酸乙酯的无水乙醇溶液中浸渍处理后,再经过高温热处理,分别可得到以β-Si₃N₄和β-SiC晶须增强的氮化硅陶瓷复合材料。同时,还对生长条件对晶须的形态,以及自生晶须对氮化硅陶瓷力学性能的影响进行了探讨。     

以AC发泡剂为添加剂燃烧合成α-Si3N4粉体

以硅粉和Si3N4粉体为反应剂,偶氮二甲酰胺(AC发泡剂)为添加剂,利用燃烧合成技术在较低氮气压力下制备了高α相含量的Si3N4粉体.采用X射线衍射和扫描电镜分别对产物的物相组成及显微结构进行了表征,研究了AC发泡剂对α相Si3N4粉体的形成和产物颗粒形貌的影响.结果表明,AC发泡剂能促进硅粉快速氮化,产物中α-Si3N4的含量随着AC发泡剂添加量的增加而增加.当AC发泡剂的添加量为24wt%时,产物中α-Si3N4的含量高达85.2wt%.对AC发泡剂作用下的燃烧合成Si3N4的反应机理做了初步探讨,研究表明:AC发泡剂的分解产物N2、CO、NH3不仅增加了坯体的透气性,而且改变了燃烧反应的传热和传质路线,从而促进了硅粉快速氮化和α-Si3N4粉体的生成.     

溶胶-凝胶法制备纳米Si_3N_4(Y_2O_3)粉末的研究

本文以硅溶胶、尿素和炭黑为原料，采用溶胶-凝胶碳热氮化法在1500℃、2h条件下制得粒径为50～80nm的Si3N4纳米粉末．比较了由硅溶胶与尿素经氨解合成的前驱体和硅溶胶二种不同起始物料的反应活性，研究了氮化条件对合成反应的影响．结果表明：氨解前驱体使硅溶胶中的结构水排除，有助于加快反应速率，提高产物氮含量．本文同时以Y（NO3）3为添加剂，在溶液状态与硅源混合，合成了Si3N4－Y2O3纳米复合粉末.     

LPCVD氮化硅薄膜的化学组成

分别采用X光电子能谱(XPS)、俄歇电子能谱(AES)、傅立叶红外光谱(FTIR)以及弹性反冲探测(ERD)等方法,分析了三氯硅烷-氨气-氮气体系低压化学气相沉积(LPCVD)氮化硅(SiNx)薄膜的化学组成,并利用原子力显微镜(AFM)观察了SiNx薄膜的表面形貌.XPS分析结果表明,当原料气中氨气与三氯硅烷的流量之比小于3时获得富Si的SiNx薄膜,当流量之比大于4时获得近化学计量的SiNx薄膜(x=1.33).AES深度分析与XPS分析结果很好地吻合,在835cm-1产生的强红外吸收峰表明Si-N键的形成,ERD分析表明所制备SiNx薄膜中的氢含量很低(1.2at.%).AFM分析结果表明,所沉积的SiNx薄膜均匀、平整,薄膜的均方根粗糙度RMS仅为0.47nm.     

Evolution of silicon nanoclusters and hydrogen in SiNx:H films: Influence of high hydrostatic pressure under annealing

Hydrogenated silicon-rich nitride (SRN) films of various stoichiometry (SiN_x:H, 0.7 < x ≤ 1.3) were deposited on single-crystalline Si substrates with the use of plasma enhanced chemical vapor deposition at a temperature of 100 °С. Furnace annealing for 5 h in ambient Ar at 1130 °С under atmospheric and enhanced hydrostatic pressure (HP — 11 kbar, 1.1 GPa) was applied to modify the structure of the films. The properties of as-deposited and annealed films were studied using ellipsometry, Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, photoluminescence (PL), as well as high-resolution transmittance electron microscopy (HRTEM). According to the Raman data, the as-deposited film, in which the stoichiometry parameter x is below 1.0, contains amorphous silicon nanoclusters. Furnace annealing leads to crystallization of the nanoclusters. From the HRTEM and Raman data, the average size of the Si nanocrystals in the annealed films was 6-7 nm. No silicon nanoclusters were observed in the as-deposited films with relatively low concentration of excessive silicon atoms (the case of SiN_x:H, x > 1); furnace annealing leads to segregation of the Si and Si₃N₄ phases, so, the amorphous Si clusters were observed in annealed films according to Raman data. Surprisingly, after annealing with such high thermal budget, according to the FTIR data, the SRN film with parameter x close to that of the stoichiometric silicon nitride contains hydrogen in the form of SiH bonds. From analysis of the FTIR data of the SiN bond vibrations one can conclude that silicon nitride is partly crystallized in the films with x > 1 after annealing for 5 h. No influence of HP on the structure of Si nanoclusters was observed in the case of SRN films with x ≤ 1.1. Dramatic changes in the PL spectra of the SRN films with the x parameter close to that of the stoichiometric silicon nitride (x ≈ 1.3), annealed under atmospheric pressure and HP, were observed. HP stimulates the formation of very small hydrogenated amorphous nanoclusters. The size of amorphous Si nanoclusters determined from the quantum size effect model describing the PL spectra, should be 2-4 nm in this case.     

自增韧热压氮化硅陶瓷的研究

本文对自增韧热压Si₃N₄陶瓷材料进行了研究,着重研究了材料的自增韧机理,Y₂O₃与La₂O₃之间的配比和(Y₂O₃+La₂O₃)的重量含量对自增韧热压氮化硅陶瓷结构及性能的影响。对最优助剂含量和配比的热压氮化硅试样进行了氧化行为和抗热震性的研究。研究发现热压氮化硅陶瓷材料的自增韧机理为β-Si₃N₄柱状晶使裂纹发生桥接和偏转。当Y₂O₃La₂O₃=11且(Y₂O₃+La₂O₃)为20wt%时,1350℃时的抗弯强度达最大值(σf1350℃为715MPa),且(Y₂O₃+La₂O₃)为16wt%时,室温的断裂韧性达最大值(K_ICRT为7.8MPa·m1/2).1150℃热压氮化硅材料经200小时氧化处理,内部析出针状晶体。经1100℃→100℃多次热循环后,强度下降的主要原因是裂纹的产生和扩展。     

Influence of silicon dioxide-silicon interface trap charges on the performance of monolithic metal-zinc oxide-silicon nitride-silicon dioxide-silicon convolver

An enhancement in the convolution efficiency is obtained by annihilating the SiO/sub 2/-Si interface trap charges in the metal-ZnO-Si/sub 3/N/sub 4/-SiO/sub 2/-Si convolver structure. The annealing process uses a source of hydrogen created underneath the SiO/sub 2/-Si interface by implanting H/sub 3//sup +/ ion followed by rapid thermal anneal of 5s at 900/spl deg/C. The silicon nitride layer is inducted to protect ZnO films from hydrogen influx during low temperature oxygen anneal.     

Photocatalytic decomposition of acephate in irradiated TiO2 suspensions

In the present study, the photocatalytic degradation of acephate (O,S-dimethyl acetyl phosphoramidothioate ((CH(3)O)(CH(3)S)P(O)NHCOCH(3))) in aqueous TiO2 suspensions is extensively investigated, pertaining to the concentration of photocatalyst and substrate on degradation rate of acephate. It is found that the acephate can be degradated and mineralized. The high-degradation rate is obtained with 4 g/L concentration of TiO2. Moreover, Langmuir-Hinshelowood rate expression is employed for the degradation of acephate with adsorption constant and rate constant, i.e., 2.0 L/mmol and 0.6 mmol/(min L), respectively. The main target is to identify the products by a number of analytical techniques, such as HPLC, IC, ESR and GC-MS. Under acidic condition, the primary products are phosphorothioic acid, O,O',S-trimethyl ester (CH(3)O(CH(3)S)P(O)OCH(3)) and phosphoramidothioic acid, O,S-dimethyl ester (CH(3)O(CH(3)S)P(O)NH(2)), etc. It indicates that the decomposition of acephate begin from the destruction of C-N and P-N bonds. Subsequently, the P-S, P-O, P-C bonds may be oxidized gradually or simultaneously, and the final products such as CO(2), H(3)PO(4), were formed. About 100% sulfur atoms are transformed into SO(4)(2-) in 180 min, however; only 3% nitrogen atoms and 2% phosphorus atoms were transformed into NO(3)(-) and PO(4)(3-).