EFFECTS OF NONIONIC SURFACTANTS ON PERFORMANCE OF COPPER CHEMICAL MECHANICAL POLISHING

During copper chemical mechanical polishing (Cu-CMP), the physical properties of slurry, such as the dispersion and suspension stability of abrasives, the interaction between particles and the polished surface, and the rheological characteristics, greatly affect the planarization efficiency. In this study, several nonionic surfactants were added to change the aforementioned physical characteristics of slurry and Cu-CMP performance. Their effects were investigated. The experimental results showed that Al₂O₃ slurry with 300 ppm Triton DF-16 could enhance the wettability of the Cu surface and stabilize the dispersion of abrasives in the slurry. Therefore, the passivation reaction on the Cu surface during CMP would occur uniformly, and the removal of particles during post cleaning could be improved. Cu CMP using the slurry with an adequate amount of nonionic surfactants, Triton DF-16, is proposed to reduce the surface roughness, enhancing the planarity.     

碱性阻挡层抛光液中ULK介质抛光性能的研究

研究了化学机械抛光(CMP)过程中抛光液的Si02磨料质量分数和表面活性剂对多孔SiOCH薄膜(ULK介质)介电常数(k)及抛光速率的影响.所用抛光液(pH = 10)主要由0％-4％(质量分数,下同)SiC2、0.075％H202、1％邻苯二甲酸氢钾和不同质量浓度的表面活性剂组成,其中表面活性剂为非离子表面活性剂脂肪...     

Chemical-mechanical polishing of low dielectric constant poly(silsesquioxane): HSQ

In this study, the chemical-mechanical polishing (CMP) characteristics of the low dielectric constant poly(silsesquioxane) (HSQ) were investigated. CMP behavior was studied using different kinds of slurries, additives, and pads. The slurriesused included SiO₂ based slurry (SS-25), ZrO₂ based slurry (A-1), and Al₂O₃ based slurry (WA400). The additives used to change the surface interaction behavior were Triton X-100 and HNO₃. The role of the polishing pad was investigated by a hard pad (IC 1400) and a soft pad (Politex). The experimental results suggested that the hardness of the abrasives and pads and the electrostatic interaction between the abrasive and polymer surface were responsible for the polishing results.     

表面活性剂水溶液池热核沸腾传热的试验研究

对表面活性剂SDS、CTAB、Triton X-114和Triton X-100水溶液物性及其池核沸腾传热进行了试验,重点探讨了表面活性剂分子结构参数和溶液物性对沸腾传热的影响。结果表明：表面活性剂溶液沸腾传热效果、表面活性剂相对分子质量对表面活性剂溶液沸腾传热的影响规律都与表面活性剂的电离特性密切相关,离子型表面活性剂SDS与CTAB溶液的沸腾传热系数比值与相对分子质量的比值成－0.22的指数关系,而非离子表面活性剂Triton X-114和Triton X-100溶液不存在指数关系。动态表面张力和热流密度相等时,SDS和CTAB溶液沸腾传热特性差异主要受相对分子质量和平衡接触角的影响,而Triton X-100和Triton X-114溶液则受质量分数、EO基团数、浊点和动力黏度的综合作用。     

A flexible nanobrush pad for the chemical mechanical planarization of Cu/ultra-low-к materials

A new idea of polishing pad called flexible nanobrush pad (FNP) has been proposed for the low down pressure chemical mechanical planarization (CMP) process of Cu/ultra-low-к materials. The FNP was designed with a surface layer of flexible brush-like nanofibers which can ‘actively’ carry nanoscale abrasives in slurry independent of the down pressure. Better planarization performances including high material removal rate, good planarization, good polishing uniformity, and low defectivity are expected in the CMP process under the low down pressure with such kind of pad. The FNP can be made by template-assisted replication or template-based synthesis methods, which will be driven by the development of the preparation technologies for ordered nanostructure arrays. The present work would potentially provide a new solution for the Cu/ultra-low-к CMP process.     

Surface planarization of zirconia ceramic achieved by polyacrylamide grafted nanodiamond composite abrasives through chemical mechanical polishing

Zirconia ceramics are the promising materials for cell phone backplanes in the 5G era, and smoother surfaces and higher removal efficiency are sought after for their precision machining. Although nanodiamond abrasives have high polishing rates, it is easy to bring mechanical scratches and pits on the ceramic surface because of their high hardness, resulting in degradation of the surface quality of the finished workpiece. Therefore, polyacrylamide grafted nanodiamond particles were prepared by solution polymerization method for polishing ceramic wafers. As confirmed by Fourier transform infrared spectroscopy (FTIR), the polyacrylamide has been grafted on the nanodiamond surface. According to the scanning electron microscopy (SEM) and particle size distribution, the composite abrasives have better dispersion than pure nanodiamond abrasives. The results of chemical mechanical polishing (CMP) experiments showed that the composite abrasives could reduce the average surface roughness (Sa, arithmetic mean height) of zirconia ceramic from 28.31 nm to 2.68 nm (scanning area is 500 μm × 500 μm), and the polishing rate remained high compared to pure nanodiamond abrasives, showing superior CMP performance. X-ray photoelectron spectroscopy (XPS) demonstrated that solid-phase chemical reactions occurred during the polishing process to form ZrSiO₄. Meanwhile, contact-wear model combined with contact angle testing indicates that the introduction of polyacrylamide increases the contact area of the nanodiamond on the zirconia wafer surface, thereby significantly enhanced the mechanical effect.     

Trp89 in the lid ofHumicola lanuginosa lipase is important for efficient hydrolysis of tributyrin

To determine whether Trp89 located in the lid of the lipase (EC 3.1.1.3) fromHumicola lanuginosa is important for the catalytic property of the enzyme, site-directed mutagenesis at Trp89 was carried out. The kinetic properties of wild type and mutated enzymes were studied with tributyrin as substrate. Lipase variants in which Trp89 was changed to Phe, Leu, Gly or Glu all showed less than 14% of the activity compared to that of the wild type lipase. The Trp89Glu mutant was the least active with only 1% of the activity seen with the wild type enzyme. All Trp mutants had the same binding affinity to the tributyrin substrate interface as did the wild type enzyme. Wild type lipase showed saturation kinetics against tributyrin when activities were measured with mixed emulsions containing different proportions of tributyrin and the nonionic alkyl polyoxyethylene ether surfactant, Triton DF-16. Wild type enzyme showed a V_max=6000±300 mmol·min⁻¹·g⁻¹ and an apparent K_m=16±2% (vol/vol) for tributyrin in Triton DF-16, while the mutants did not show saturation kinetics in an identical assay. The apparent K_m for tributyrin in Triton DF-16 was increased as the result of replacing Trp89 with other residues (Phe, Leu, Gly or Glu). The activities of all mutants were more sensitive to the presence of Triton DF-16 in the tributyrin substrate than was wild type lipase. The activity of the Trp89Glu mutant was decreased to 50% in the presence of 2 vol% Triton DF-16 compared to the activity seen with pure tributyrin as substrate. Wild type lipase and all mutants except Trp89Glu had the same affinity for the substrate interface formed by 15.6 vol% tributyrin in Triton DF-16. The Trp89Glu mutant showed a lower affinity than all the other lipase variants for the interface of 15.6 vol% tributyrin in Triton DF-16. The study showed that Trp89 located in the lid ofH. lanuginosa lipase is important for the efficient hydrolysis of tributyrin and that this residue plays a role in the catalytic steps after adsorption of the lipase to the substrate interface.     

Nano-scale surface of ZrO2 ceramics achieved efficiently by peanut-shaped and heart-shaped SiO2 abrasives through chemical mechanical polishing

Zirconia ceramics are regarded as the best development target for 5G mobile phone rear covers. However, it is necessary and urgent to improve the surface quality and processing efficiency of zirconia ceramics. Non-spherical silica abrasives were prepared by the KH550 induction method and were used in chemical mechanical polishing (CMP) of zirconia ceramics for the first time. While achieving low surface roughness of 1.9 nm, it has an efficient polishing rate of 0.31 μm/h which is superior to conventional abrasives. Silica particles are peanut-shaped and heart-shaped in the scanning electron microscopy image, and its distinctive morphology provides the possibility of its excellent polishing performance. X-ray photoelectron spectroscopy analysis shows that during the CMP process, silica abrasives and zirconia ceramic undergo a solid phase chemical reaction to form ZrSiO₄. At the same time, the contact wear model established in combination with the coefficient of friction indicates that the two-dimensional surface contact mode of non-spherical silica abrasives on the surface of zirconia ceramics greatly improves its mechanical effect.     

Effect of surfactant on structure and performance of catalysts for DME synthesis in slurry bed

The Cu-Zn-Al slurry catalysts prepared via modified sol-emulsion-gel method by adding different water-soluble surfactants were studied for CO hydrogenation to produce dimethyl ether (DME) in slurry bed reactor. The results indicated that the catalyst adding Tween80 or PEG600 had higher activity than the catalyst with the PVP additive. All the catalysts had good stability. X-ray diffraction (XRD) results showed that Cu and Cu₂O existed in the pre-reduced Cu-Zn-Al catalysts, while ZnO did not appear. Nitrogen adsorption studies showed that the catalyst prepared with the additives of PEG600 or Tween80 was mesoporous structure with higher specific surface area compared with the one prepared with the additive of PVP. X-ray photoelectron spectroscopy (XPS) results indicated that the Cu/Zn ratio on the surface of all catalysts increased after subject to reduction and reaction. The morphology and size of the catalyst particles could be adjusted by adding water-soluble surfactants.     

7003铝合金CMP后表面SiO2纳米颗粒清洗研究

通过在弱酸环境的水溶液条件下加入非离子表面活性剂辛基苯基聚氧乙烯醚,缓蚀剂焦磷酸二氢二钠和苯并三氮唑(BTA),并结合超声波的湿化学清洗方法,对化学机械抛光(CMP)后的7003铝合金表面的清洗进行了研究.利用扫描电子显微镜(SEM)和原子力显微镜(AFM)对清洗前后铝合金表面形貌进行对比分析.研究结果表明,辛基苯基聚氧乙烯醚能够保持颗粒和表面之间处于容易清洗的物理吸附状态,结合超声波协同作用可以对铝合金表面残留的SiO2颗粒进行有效的清洗.在一定范围内随着活性剂质量分数的递增,表面清洗效果逐渐改善,当质量分数为2%时,表面残留的SiO2颗粒基本被清洗干净,得到最优表面且未发生腐蚀现象.清洗后表面形成活性剂保护层,防止了颗粒的再次吸附.     

颜料酞菁绿表面处理与易分散性

以酞菁绿膏状物为原料,用不同类型的表面活性剂对其实施表面处理,研究了表面活性剂种类及添加量对酞菁绿分散性的影响。结果表明,添加某些非离子表面活性剂及两种不同类型物质组成的复配添加剂,可明显提高酞菁绿的分散性和分散稳定性。添加量为颜料量的５％～７％（质量分数）。     

非离子表面活性剂作用下分散染料对棉沾色机理研究

通过研究非离子表面活性剂结构和浓度对C.I.分散红60增溶量、分散体系的高温稳定性、C.I.分散红60的上染率以及染浴中染料残留量的影响,探讨了在非离子表面活性剂作用下C.I.分散红60对棉沾色的机理。结果表明:非离子表面活性剂用量较低(0.5 g/L左右)时,分散体系有较好的高温稳定性,此时非离子表面活性剂对分散染料的增溶量为影响沾色的主要因素,分散染料的增溶有利于减少其对棉的沾色;随着非离子表面活性剂用量的增加(≥1 g/L),染料的上染百分率和分散体系的高温稳定性降低,分散染料对棉的沾色加重,沾色等级降低到2级。     

Development of Short-Range Repulsive Potentials by Short-Chain Surfactants in Aqueous Slurries

The effect of both cationic ( n -trimethylammonium bromide, C _n TAB) and zwitterionic (phosphocholine, C _n C _n PC) surfactants on the properties of aqueous slurries of Si₃N₄ was studied. These surfactants were expected to adsorb to the surface of Si₃N₄ particles to produce short-range repulsive interparticle potentials that might be useful for the colloidal processing of advanced ceramic powders. Electrophoretic, adsorption, and viscosity measurements showed that longer-chain-length surfactants (C _n TAB, n ≥ 12, and C _n C _n PC, n ≥ 9) strongly adsorb. Surfactants with shorter chain lengths were highly soluble and did not adsorb. Although the C _n TAB, n ≥ 12, surfactants produced very weak particle networks with a low viscosity, the packing density during consolidation was very low, and the bodies were brittle (cracked before plastic deformation). The less-soluble, longer-chained C _n C _n PC, n ≥ 9, surfactants did produce high particle-packing densities but also produced brittle bodies. In all cases, it appeared that the surfactants could be pushed away from the surface during particle packing.     

Effect of fine solid particles on absorption rate of gaseous CO

The influence of the properties of solid particles in slurry on the absorption of CO₂ in the slurry was investigated in a stirred thermostatic reactor. The absorption experiments were carried out in three different slurries consisting of water, cyclohexane and soybean oil, respectively, and three kinds of solid particles (active carbon, active alumina and silica gel) were incorporated into each of the above mentioned slurries separately. The experimental results show that the active carbon particles could enhance the absorption rate of gaseous CO₂ in the aqueous slurry, while in the cyclohexane slurry, active carbon particles indicated no the absorption enhancement effect. However, it was observed that the active alumina and silica gel particles could enhance the absorption rate of CO₂ in the cyclohexane slurry. These phenomena indicate that the solid particles, which could enhance the gaseous CO₂ absorption rate, should possess two properties simultaneously, i.e. they rejected the solvent and had higher adsorption capacity for the solute. The experimental results also show that, as for those solid particles which could enhance the gas absorption rate, the enhancement increased quickly with the increase of solid concentration in slurry at first, and then reached a constant value gradually. It was also found that the enhancement factor was related to the coverage fraction of solid particles on the gas-liquid interface, and due to the reduction of surface fraction with increasing stirred speed, the enhancement factor decreased.     

Aqueous Surfactant Two‐Phase Systems for the Continuous Countercurrent Cloud Point Extraction

Aqueous nonionic surfactant solutions split into two phases if the temperature is increased beyond a certain temperature, the so‐called cloud point temperature. Presently many different types of nonionic surfactants are produced commercially, out of these numerous have been considered as potential solvent for the cloud point extraction. In this work the crucial thermophysical properties of nonionic surfactants are investigated to determine the potential of surfactant systems for extraction processes. Phase equilibria of the binary system Triton X‐114/water and the ternary system Triton X‐114/water/phenol were measured. Based on these data the cloud point extraction was implemented in a continuous stirred extraction column. It was found, that increasing temperature within the column reduces the loss of surfactant and leads to an increasing enrichment factor. This work demonstrates that surfactant/water systems represent a suitable alternative to conventional solvents and can effectively be processed in continuous extraction columns.     

Effect of mixed-shaped silica sol abrasives on surface roughness and material removal rate of zirconia ceramic cover

Zirconia ceramic, as mobile phone body-materials, will become increasingly important with the coming of 5G communication technology. Surface quality and material removal rate of zirconia ceramic cover are vital factors to determine its wide application. Therefore, mixed-shaped silica sol abrasives were prepared by ion connecting-inducting method and applied to achieve a good surface quality and a high material removal rate on zirconia ceramic cover by using chemical mechanical polishing (CMP). Mixed-shaped silica sol abrasives contained spherical and beaded shapes were measured by scanning electron microscopy (SEM). Si–O–Al bonds were formed in the mixed-shaped silica sol abrasives and were proved by X-ray photoelectron spectroscopy (XPS). Results of CMP tests showed that zirconia ceramic cover obtained a low surface roughness of 1.824 nm and an efficient material removal rate of 0.33 μm/h. Compared with traditional spherical silica sol abrasives, the polishing rate of mixed-shaped silica sol abrasives increased by 242%. Additionally, solid-phase chemical reactions happened to formed ZrSiO₄, ZrAl₂Si₂O₉ in the CMP process. Moreover, friction coefficient was tested and polishing mechanism had been explored by a contact-friction model in this work.     

集成电路铜互连钌阻挡层异质材料去除选择性的研究

针对集成电路铜互连钌阻挡层异质材料(包括Cu、Ru、TEOS)在化学机械抛光(CMP)中选择性差的问题,在SiO2 H2O2体系抛光液中研究了(NH4)2SO4和2,2′{[(甲基1H苯并三唑1基)甲基]亚氨基}双乙醇(TT)对Cu、Ru、TEOS去除速率的影响,并使用钌阻挡层图形片对抛光液的平坦化性能进行验证。结果表明,(NH4)2SO4的添加可以提高Cu、Ru和TEOS的去除速率,进一步加入TT后,Cu的去除速率减小,Ru和TEOS的去除速率基本不变。采用由5%(质量分数,下同)SiO2、0.15%H2O2、40 mmol/L(NH4)2SO4和1 g/L TT组成的抛光液对钌阻挡层图形片化学机械抛光30 s后,碟形坑和蚀坑的深度得到了有效降低。     

纳米ATO水性分散液的制备及其分散稳定性研究

采用球磨法制备了3种纳米锑掺杂二氧化锡(简称ATO)水性分散液,包括未加分散剂,以非离子型高分子分散剂改性和以阴离子分散剂与非离子高分子分散剂复合改性3种情况,并通过Zeta电位仪、激光粒度仪、透射电镜、静止沉降实验等测试方法对纳米ATO水性分散液的稳定性进行了表征.结果发现,ATO纳米颗粒通过分散剂复合改性后,其水性分散液的稳定性最佳,当阴离子分散剂与非离子高分子分散剂的质量比为1∶2,复合分散剂用量为ATO粉体质量的6%时,所得ATO水性分散液的稳定性最好.     

On the measurement of critical micelle concentrations of pure and technical-grade nonionic surfactants

The critical micelle concentrations (CMC) of nine commercial nonionic surfactants (Tween 20, 22, 40, 60, and 80; Triton X-100; Brij 35, 58, and 78) and two pure nonionics [C₁₂(EO)₅ and C₁₂(EO)₈] were determined by surface tension and dye micellization methods. Commercially available nonionic surfactants (technical grade) usually contain impurities and have a broad molecular weight distribution owing to the degree of ethoxylation. It was shown that the surface tension method (Wilhelmy plate) is very sensitive to the presence of impurities. Much lower CMC values were obtained with the surface tension method than with the dye micellization method (up to 6.5 times for Tween 22). In the presence of highly surfaceactive impurities, the air/liquid interface is already saturated at concentrations well below the true CMC, leading to a wrong interpretation of the break in the curve of surface tension (γ) vs. concentration of nonionic surfactant (log C). The actual onset of micellization happens at higher concentrations, as measured by the dye micellization method. Furthermore, it was shown that when a commercial surfactant sample (Tween 20) is subjected to foam fractionation, thereby removing species with higher surface activity, the sample yields almost the same CMC values as measured by surface tension and dye micellization methods. It was found that for monodisperse pure nonionic surfactants, both CMC determination methods yield the same results. Therefore, this study indicates that precaution should be taken when determining the CMC of commercial nonionic surfactants by the surface tension method, as it indicates the surface concentration of all surface-active species at the surface only, whereas the dye method indicates the presence of micelles in the bulk solution.     

表面活性剂及其在分散体系中的应用

本文就悬浮体、乳状液、多乳状液,微乳状液,囊泡等典型固／液、液／液分散体和软固体的制备的原理、体系的物理化学稳定性能以及表面活性剂在这些分散体系中的作用综述性介绍。