内核尺寸对核/壳结构PS/SiO_2复合磨料抛光特性的影响

核/壳结构有机/无机复合微球作为一种新型抛光介质,在实现高效无损伤抛光方面具有重要的应用价值。以无皂乳液聚合法制备的聚苯乙烯(PS)为内核,通过溶胶-凝胶法合成了一系列具有不同内核尺寸的PS/SiO2复合微球。利用FT-IR、FESEM和TEM等手段对样品进行表征,并借助AFM考察了复合磨料内核尺寸对SiO2介质层抛光质量的影响规律。结果表明,所制备单分散PS微球尺寸在200~600 nm,复合微球的壳层由SiO2纳米颗粒(5~10nm)所组成,壳厚在10~15 nm。材料去除率(MRR)随复合磨料内核尺寸的减小而降低,而抛光后晶片表面粗糙度(RMS)的变化则不明显。当复合磨料内核尺寸为210 nm时,抛光后RMS和MRR分别为0.217 nm和126.2 nm/min。提出将核壳结构有机/无机复合磨料理解成一种表面布满无机纳米颗粒的微型"抛光垫",尝试用有效磨料数量以及壳层中单个SiO2颗粒的压入深度对CMP实验结果进行解释,并进一步讨论了有机内核在抛光过程中的作用。     

Silica particles settling characteristics and removal performances of oxide chemical mechanical polishing wastewater treated by electrocoagulation technology

The purpose of this study was to explore the feasibility of removing silica particles and reducing turbidity from oxide chemical mechanical polishing (oxide-CMP) wastewater. Based on the dynamic characteristics of batch electrocoagulation, three operating stages (lag, reactive, and stabilizing) are proposed to identify the relationships among the zeta potential of the silica particles, solution turbidity, and the corresponding mean particle size of the silica. Experimental results show that the silica particles were destabilized and settled at the critical mean particle size, which was estimated to be above 520 nm after 10 min, and the corresponding turbidity removal mostly occurred during the reactive stage. Furthermore, the corresponding mean particle size varied from 520 to 1900 nm as the treatment time progressed from 10 to 20 min, which also occurred during the reactive stage. Several parameters, including different electrode pairs, electrolyte concentration, applied voltage, and the optimum condition of power input were investigated. Experimental results indicate that a Fe/Al electrode pair is the most efficient choice of the four electrode pair combinations in terms of energy consumption. The optimum electrolyte concentration and applied voltage were found to be 200 ppm NaCl and 30 V, respectively.     

Effect of slurry composition on the chemical mechanical polishing of thin diamond films

Nanocrystalline diamond (NCD) thin films grown by chemical vapour deposition have an intrinsic surface roughness, which hinders the development and performance of the films’ various applications. Traditional methods of diamond polishing are not effective on NCD thin films. Films either shatter due to the combination of wafer bow and high mechanical pressures or produce uneven surfaces, which has led to the adaptation of the chemical mechanical polishing (CMP) technique for NCD films. This process is poorly understood and in need of optimisation. To compare the effect of slurry composition and pH upon polishing rates, a series of NCD thin films have been polished for three hours using a Logitech Ltd. Tribo CMP System in conjunction with a polyester/polyurethane polishing cloth and six different slurries. The reduction in surface roughness was measured hourly using an atomic force microscope. The final surface chemistry was examined using X-ray photoelectron spectroscopy and a scanning electron microscope. It was found that of all the various properties of the slurries, including pH and composition, the particle size was the determining factor for the polishing rate. The smaller particles polishing at a greater rate than the larger ones.     

Sm掺杂核-壳结构介孔SiO2@CeO2复合颗粒的制备和抛光性能

在低模量介孔SiO2(Mesoporous silica, mSiO2)微球表面负载Sm掺杂CeO2纳米粒子,制备了具有均匀完整核-壳结构的非刚性mSiO2@Ce1-xSmxO2(x=0, 0.23)复合颗粒。借助XRD、 SEM、 HRTEM、 STEM-EDX Mapping、 Raman光谱和N2吸-脱附等技术对产物进行结构表征,利用AFM和三维光学轮廓仪评价Sm元素掺杂处理对mSiO2@Ce1-xSmxO2(x=0, 0.23)复合颗粒抛光效果的影响。讨论了Sm掺杂复合磨粒的高效无损超精密抛光机制。结果表明:掺杂处理可使mSiO2@Ce1-xSmxO2(x=0, 0.23)复合颗粒的抛光效率提高近36%,达到84 nm/min,同时获得具有原子量级精度的加工表面,抛光后SiO2薄膜的粗糙度平均值和均方根分别为0.14和0.17 nm。     

Structural regulation and polishing performance of dendritic mesoporous silica (D-mSiO2) supported with samarium-doped cerium oxide composites

Ceria (CeO₂) particles are prevalent polishing abrasive materials. Trivalent lanthanide ions are the popular category of dopants for enriched surface defects and thus improved physicochemical properties, since they are highly compatible with CeO₂ lattices. Herein, a series of dendritic-like mesoporous silica (D-mSiO₂)-supported samarium (Sm)-doped CeO₂ nanocrystals were synthesized via a facile chemical precipitation method. The relation of the structural characteristics and chemical mechanical polishing (CMP) performances were investigated to explore the effect of Sm-doping amounts on the D-mSiO₂/Sm_xCe_1?xO_2?δ (x = 0–1) composite abrasives. The involved low-modulus D-mSiO₂ cores aimed to eliminate surface scratch and damage, resulting from the optimized contact behavior between abrasives and surfaces. The trivalent cerium (Ce³⁺) and oxygen vacancy (V_O) at CeO₂ surfaces were expected to be reactive sites for the material removal process over SiO₂ films. The optimal oxide-CMP performances in terms of removal efficiency and surface quality were achieved by the 40% Sm-doped composite abrasives. It might be attributed to the high Ce³⁺ and V_O concentrations and the enhancement of tribochemical reactivity between CeO₂SiO₂ interfaces. Furthermore, the relationship between the surface chemistry, polishing performance as well as the actual role in oxide-CMP of the D-mSiO₂/Sm_xCe_1?xO_2?δ abrasives were also discussed.     

大面积金刚石自支撑膜机械抛光的优化工艺研究

研究了一种用于抛光等离子体溅射CVD法制备的金刚石自支撑膜的高效安全的抛光工艺.试验探索了转盘转速、金刚石粉颗粒尺寸、磨盘表面形状对金刚石自支撑膜磨抛速率的影响.研究表明:带槽盘对金刚石自支撑膜的粗研磨效果明显,速率较高,平面盘对提高金刚石自支撑膜的表面粗糙度有利;不同颗粒的金刚石粉对应着各自合适的能充分利用其磨削能力的转速,在这个转速下,金刚石自支撑膜的磨抛速率在12μm/h左右.本文通过对新的工艺参数的探索,为金刚石自支撑膜后续加工提供有力的技术支持.     

Preparation of porous Fe2O3/SiO2 nanocomposite abrasives and their chemical mechanical polishing behaviors on hard disk substrates

Abrasives play an important role in chemical mechanical polishing (CMP) processes. Compact solid silica particles, which have been widely used as abrasive in CMP slurries, may cause surface defects because of their high hardness. Porous silica abrasive exhibits better surface planarization and fewer scratches than traditional solid silica abrasive during the polishing of hard disk substrates. However, the improvement in material removal rate (MRR) was not significant. Therefore, porous Fe₂O₃/SiO₂ nanocomposite abrasives were prepared and their CMP performances on hard disk substrates were investigated. Experiment results indicate that the MRR of slurry containing porous Fe₂O₃/SiO₂ nanocomposite abrasives is obviously higher than that of slurry containing pure porous silica abrasive under the same testing conditions. MRR increases with the increase of the molar content of iron in porous Fe₂O₃/SiO₂ nanocomposite abrasives. Moreover, surfaces polished by slurries containing the porous Fe₂O₃/SiO₂ nanocomposite abrasives exhibit lower surface roughness, fewer scratches as well as lower topographical variations than that by pure porous silica abrasive.     

增强颗粒含量和尺寸对SiCp/Fe复合材料性能的影响

利用电流直加热动态热压烧结工艺,分别制备了增强颗粒体积含量从5%到15%,尺寸从3 μm到45 μm的SiCp/Fe复合材料,研究了粒子含量与尺寸对复合材料硬度、强度、延伸率和耐磨性能的影响.研究表明:增强颗粒的体积含量从5%提高到10%,可以明显提高材料的性能;随着增强颗粒含量进一步提高,颗粒团聚将导致材料性能降低;...     

还原温度与SiO2壳层对Co/SiO2复合颗粒尺寸和相结构的影响

利用非均相沉淀-H2还原方法制得了平均粒径为20～30nm的Co/SiO2纳米复合颗粒.探讨了非均相沉淀-H2还原法的还原温度和SiO2壳层对Co/SiO2纳米复合颗粒尺寸和组织的影响.实验结果表明,在复合颗粒中,非晶SiO2壳层对纳米Co颗粒成功地进行了包覆.纳米尺度的fcc结构芯核Co可以在室温存在,但颗粒尺寸大于某一临界尺寸时,芯核Co将由fcc向hcp相转变.通过试验得出芯核Co由fcc向hcp相转变的临界尺寸,该试验结果和理论数据相吻合.并证明,还原过程中fcc结构Co的出现对应于一个临界温度,当还原温度低于该临界温度时,不能得到fcc结构的Co.     

Al particles size effect on the microstructure of the co-deposited Ni-Al composite coatings

Micrometer and nanometer Al particles were codeposited with nickel by electrodeposition from a nickel sulfate bath containng a similar content of Al particles. The effect of Al particles size on the microstructure of the electrodeposited Ni-Al composite coatings was analyzed. The results indicated that at a given Al particles content the incorporation of Al nanoparticles instead of the microscale countparts significantly increased the particle number per unit volume in the composite, led to a more homogeneous distribution of particles, and finer Ni grains due to nucleation of smaller Ni grains on the surface of Al nanoparticles, which changed the direction of the local Ni growth and caused the formation of a fine equiaxed grain structure.     

Studying the effect of temperature on the copper oxidation process using hydrogen peroxide for use in multi-step chemical mechanical planarization models

Given that the mechanism responsible for removal during copper chemical mechanical planarization (CMP) is generally accepted to be based on the cyclic oxidation of copper and the subsequent removal of copper oxide, this study characterizes the copper oxide growth process as a function of temperature in aqueous hydrogen peroxide solutions. A copper oxidation model was proposed based on cation migration to adequately represent measured copper oxide growth profiles as a function of temperature. The two parameters extracted to fit the oxidation profiles, W and V, in the proposed model are related to activation energy of cation migration and the potential developed across the oxide film, respectively. The potential was found to be 0.95 V and did not vary with temperature. The activation energy was found to be 0.84 ± 0.01 eV and increased slightly with temperature. This slight increase, on the order of 2 to 3 kcal, has been previously reported and attributed to an increase in activation energy of cation solution in the oxide. The oxidized copper formation rates calculated suggest that the typical oxide thicknesses involved during the cyclic oxide growth and removal mechanism in copper CMP are between 7 and 12 Å. Though the oxidation model parameters are extracted from copper oxidation experiments on the minute time scale, there are a number of experimental, physical, and theoretical arguments that suggest the model represents the actual physical system and is applicable to the sub-second timescales involved during the oxidation processes in copper CMP.     

轻质高导电镀银复合粒子的制备研究

采用分散聚合工艺,以聚乙烯吡咯烷酮为分散剂,偶氟二异丁腈为引发剂,无水乙醇为分散介质,制备出粒径2.0μm、表面光滑、分散均匀的聚苯乙烯微球.将其进行表面磺化处理后运用化学镀工艺制备出了具有轻质高导电特性的聚苯乙烯/银复合粒子.对所制备的复合粒子进行了扫描电镜、红外光谱以及体积电阻率的测试.结果表明:所制备的复合粒子包覆均匀、导电性能良好;表面修饰提高了PS微球表面的电负性和亲水性并引入了磺酸基团,对PS微球表面镀银起到了重要作用;另外,随着PdCl2浓度和AgNO3/PS质量比的增加,复合粒子包覆完整性和导电性能都随之增加,最佳体积电阻率为1.61×10 -4Ω·cm.     

Effect of core–shell composite particles on the sintering behavior and properties of nano-Al2O3/polystyrene composite prepared by SLS

Nano-Al₂O₃ particles coated with polystyrene (PS) by emulsion polymerization were used as fillers to reinforce PS based composites prepared by selective laser sintering (SLS). The influences of the treated and untreated nanoparticles on the sintering behavior and mechanical properties of the laser sintered specimens were investigated. It was found that there were many uneven holes in the untreated composites. However, for the treated composites, due to the nanoparticle surfaces treated by emulsion polymerization, the absorbance of laser was improved and the nanoparticles dispersed well in the polymer matrix; a full dense structure was obtained and the properties were enhanced, such as the notched impact strength increased 50%, the maximum value was 12.1 kJ/m²; the tensile strength increased up to 300%, the maximum value was 31.2 MPa, comparing to the unfilled PS. FE-SEM studied the tensile fractured surfaces of the sintered specimens. It was noted that the fractured surfaces of composites with treated nanoparticles were rougher than those of unfilled PS and those of the untreated composite. Drawing from the results, it can be confirmed that a full dense structure can be obtained and the polystyrene matrix was strengthened and toughened when the nanoparticles were coated with PS by emulsion polymerization. This work forms a theoretical and technique basis for the production of selective laser sintered nano-Al₂O₃/PS functional products.     

Influence of particle size of the dispersoid on compressibility and sinterability of TiO2 dispersed Al 7075 alloy composites prepared by mechanical milling

Particulate TiO₂ (with varying particle size produced by mechanical milling) dispersed AA7075 composites are synthesised by short duration milling (10 min) followed by room temperature unidirectional compaction (with varying pressure) and sintering. Apparent and relative density of the alloy powder and composites are measured. The effect of reinforcement particle size on the compressibility behaviour of the composites is demonstrated. Mechanically milled (for 25 h) alloy powder shows lower relative density than coarse alloy powder. In addition, compressibility of the alloy composites decreases with decreasing particle size of the reinforcement. In contrast, the sinterability of the composites increases with decreasing dispersoid’s size due to easy filling up of finer pores and particle induced precipitation.     

喷丸处理对TiB_2/Al复合材料表面基体力学性能的影响

通过X射线衍射线形分析表征了喷丸表面的组织结构,利用原位拉伸X射线衍射应力分析研究了TiB2/6351Al复合材料喷丸表面基体的力学行为.结果表明,喷丸后复合材料表面基体的屈服强度提高了26%,整体强度提高约28%,显微硬度提高50%以上.喷丸前、后复合材料基体承载系数分别为81%和83%,喷丸后的基体承载系数略有提高.喷丸表面基体的晶块尺寸及位错密度分别约51 nm和3.05×1014 m-2,晶块细化及位错密度增高是导致表面基体力学性能提高的主要原因.