Cation Effect on Copper Chemical Mechanical Polishing

We examine the effect of cations in solutions containing benzotriazole （BTA） and H202 on copper chemical mechanical polishing （CMP）. On the base of atomic force microscopy （AFM） and material removal rate （MRR） results, it is found that ammonia shows the highest MRR as well as good surface after CMP, while KOH demonstrates the worst performance. These results reveal a mechanism that small molecules with lone-pairs rather than molecules with steric effect and common inorganic cations are better for copper CMP process, which is indirectly confirmed by open circuit potential （OCP）.     

Effect of additives for higher removal rate in lithium niobate chemical mechanical planarization

High roughness and a greater number of defects were created by lithium niobate (LN; LiNbO₃) processes such as traditional grinding and mechanical polishing (MP), should be decreased for manufacturing LN device. Therefore, an alternative process for gaining defect-free and smooth surface is needed. Chemical mechanical planarization (CMP) is suitable method in the LN process because it uses a combination approach consisting of chemical and mechanical effects. First of all, we investigated the LN CMP process using commercial slurry by changing various process conditions such as down pressure and relative velocity. However, the LN CMP process time using commercial slurry was long to gain a smooth surface because of lower material removal rate (MRR). So, to improve the material removal rate (MRR), the effects of additives such as oxidizer (hydrogen peroxide; H₂O₂) and complexing agent (citric acid; C₆H₈O₇) in a potassium hydroxide (KOH) based slurry, were investigated. The manufactured slurry consisting of H₂O₂-citric acid in the KOH based slurry shows that the MRR of the H₂O₂ at 2 wt% and the citric acid at 0.06 M was higher than the MRR for other conditions.     

Ceria concentration effect on chemical mechanical polishing of optical glass

It was found material removal rate (MRR) sharply increased from 250 to 675 nm/min as the concentration decreased from 1 to 0.25 wt% in optical glass chemical mechanical polishing (CMP) using ceria slurries. Scanning electron microscopy was employed to characterize the ceria abrasive used in the slurry. Atomic force microscopy results showed good surface had been got after CMP. Schematic diagrams of the CMP process were shown. Furthermore, the absorption spectra indicated a sudden change from Ce⁴⁺ to Ce³⁺ of the ceria surface when the concentration decreased, which revealed a quantum origin of the phenomenon.     

Ultrasonic flexural vibration assisted chemical mechanical polishing for sapphire substrate

The sapphire substrates are polished by traditional chemical mechanical polishing (CMP) and ultrasonic flexural vibration (UFV) assisted CMP (UFV-CMP) respectively with different pressures. UFV-CMP combines the functions of traditional CMP and ultrasonic machining (USM) and has special characteristics, which is that ultrasonic vibrations of the rotating polishing head are in both horizontal and vertical directions. The material removal rates (MRRs) and the polished surface morphology of CMP and UFV-CMP are compared. The MRR of UFV-CMP is two times larger than that of traditional CMP. The surface roughness (root mean square, RMS) of the polished sapphire substrate of UFV-CMP is 0.83 Å measured by the atomic force microscopy (AFM), which is much better than 2.12 Å obtained using the traditional CMP. And the surface flatness of UFV-CMP is 0.12 μm, which is also better than 0.23 μm of the traditional CMP. The results show that UFV-CMP is able to improve the MRR and finished surface quality of the sapphire substrates greatly. The material removal and surface polishing mechanisms of sapphire in UFV-CMP are discussed too.     

Models of nanoparticles movement,collision, and friction in chemical mechanical polishing (CMP)

Nanoparticles have been widely used in polishing slurry such as chemical mechanical polishing (CMP) process. The movement of nanoparticles in polishing slurry and the interaction between nanoparticles and solid surface are very important to obtain an atomic smooth surface in CMP process. Polishing slurry contains abrasive nanoparticles (with the size range of about 10–100 nm) and chemical reagents. Abrasive nanoparticles and hydrodynamic pressure are considered to cause the polishing effect. Nanoparticles behavior in the slurry with power-law viscosity shows great effect on the wafer surface in polishing process. CMP is now a standard process of integrated circuit manufacturing at nanoscale. Various models can dynamically predict the evolution of surface topography for any time point during CMP. To research, using a combination of individual nanoscale friction measurements for CMP of SiO₂, in an analytical model, to sum these effects, and the results scale CMP experiments, can guide the research and validate the model. CMP endpoint measurements, such as those from motor current traces, enable verification of model predictions, relating to friction and wear in CMP and surface topography evolution for different types of CMP processes and patterned chips. In this article, we explore models of the microscopic frictional force based on the surface topography and present both experimental and theoretical studies on the movement of nanoparticles in polishing slurry and collision between nanoparticles, as well as between the particles and solid surfaces in time of process CMP. Experimental results have proved that the nanoparticle size and slurry properties have great effects on the polishing results. The effects of the nanoparticle size and the slurry film thickness are also discussed.     

Process characterization and statistical analysis of oxide CMP on a silicon wafer with sparse data

Continuous advancements in chemical mechanical planarization (CMP) process, such as new polishing pads, slurry materials, and abrasive particles necessitate optimization of the key process input parameters for maximum material removal rate (MRR) and/or minimum within wafer non-uniformity (WIWNU) using sparse experimental results. In this investigation a methodology is proposed for developing process models and optimization of input parameters (both main and interaction parameters) for maximum MRR and minimum WIWNU. This approach will be equally applicable for polishing other materials, such as copper, dielectrics and low-k materials. Complex relationships exist between several machine-specific and material-specific input parameters and the output performance variables, chiefly MRR and WIWNU. However, only a few of the input parameters are changed on a regular basis. Hence, only those subsets of relationships need to be considered for optimizing the CMP process. In this investigation, CMP process was characterized for polishing a thin layer of silicon dioxide on top of a silicon wafer. Statistical analysis of the experimental data was performed to obtain the order of significance of the input variables (machine and material parameters and their interactions). Both linear and logarithmic regression models were developed and used to determine optimum process conditions for maximizing MRR and minimizing WIWNU. While the main input parameters were responsible for maximum MRR, interaction parameters were found to be responsible for minimizing WIWNU. This may vary for different materials and polishing environments. PACS 81.00.00; 81.05.Gc; 81.65.Ps     

Effects of the ultrasonic flexural vibration on the interaction between the abrasive particles; pad and sapphire substrate during chemical mechanical polishing (CMP)

In this paper, the technique of ultrasonic flexural vibration assisted chemical mechanical polishing (UFV-CMP) was used for sapphire substrate CMP. The functions of the polishing pad, the silica abrasive particles, and the chemical additives of the slurry such as pH value regulator and dispersant during the sapphire's UFV-CMP were investigated. The results showed that the actions of the ultrasonic and silica abrasive particles were the main factors in the sapphire material removal rate (MMR) and the chemical additives were helpful to decrease the roughness of sapphire. Then the effects of the flexural vibration on the interaction between the silica abrasive particles, pad and sapphire substrate from the kinematics and dynamics were investigated to explain why the MRR of UFV-CMP was bigger than that of the traditional CMP. It indicated that such functions improved the sapphire's MRR: the increasing of the contact silica particles’ motion path lengths on the sapphire's surface, the enhancement of the contact force between the contact silica particles and the sapphire's surface, and the impaction of the suspending silica particles to the sapphire's surface.     

Localized corrosion effects and modifications of acidic and alkaline slurries on copper chemical mechanical polishing

This study demonstrates the CMP performance can be enhanced by modifying the corrosion effects of acidic and alkaline slurries on copper. A corrosion test-cell with a polishing platform is connected with the potentiostat to investigate the corrosion behaviors of copper CMP in various alumina slurries. Experiments show that the slurry needs to be maintained in acidic pH<4.56 or alkaline pH>9.05 surroundings and thus better dispersion of alumina particles and less residual contaminant on copper surface can be obtained. The surface defects after copper CMP using acidic and alkaline slurries are described by pitting corrosion mechanisms, and these mechanisms can be regarded as a basis to modify their corrosion effects. Experimental results indicate that it is necessary to modify the dissolution of HNO₃ and oxidization of NH₄OH for copper CMP slurries. Consequently, the slurries of 5 wt.% HNO₃ by adding 0.1 wt.% BTA or 5 wt.% KNO₃ by adding 1 wt.% NH₄OH achieve good CMP performance for copper with higher CMP efficiency factor (CMPEF), 1460 and 486, and lower surface roughness (R_q), 4.019 and 3.971 nm, respectively. It is found that AFM micrographs can support the effectiveness of corrosion modifications for copper CMP in various slurry chemistries.     

Ultra-smooth platinum surfaces for nanoscale devices fabricated using chemical mechanical polishing

A technique involving two steps of chemical mechanical polishing (CMP) has been developed to produce ultra-smooth metal surfaces with an RMS roughness better than 0.1 nm. A figure of merit termed degree of smoothness (DOS) is proposed for the purpose of quantifying the extent of smoothness of a polished metal surface. A post CMP metal slurry cleaning solution was used for cleaning Pt slurry for the first time and by applying special techniques, a very high quality clean surface was attained. Applications of the polished Pt electrodes in interfacing molecular switching devices with self-assembled monolayers of molecules have been found to dramatically improve the packing and orientation of the molecular monolayer with a huge improvement in the molecular electronics device yields. These smooth metal surfaces may open doors for new opportunities in future nanoscale devices. PACS 81.05.Bx; 81.16.Rf; 81.65.Ps     

基于模糊模型的CMP过程智能R2R预测控制方法

针对化学机械研磨(CMP)过程非线性、时变和产品质量不易在线测量的特性,提出了一种基于T-S模糊模型的CMP过程智能run-to-run(R2R)预测控制器FIPR2R;通过G-K聚类算法和最小二乘法对CMP过程的T-S模糊预测模型离线辨识,解决了复杂CMP过程难以建立精确数学模型的难题和提高了模型预测精度;通过双指数加权移动平均(dEWMA)中对过程扰动及漂移进行估计的方法实现反馈校正和基于克隆选择算法的滚动优化求取最优控制律,提高了控制精度;性能分析结果表明,FIPR2R控制器的控制性能优于dEWMA方法,有效抑制了过程扰动和漂移的影响。     

壳聚糖基聚合物碳点荧光材料合成及其自组装载药应用

荧光碳点具有化学稳定性好、毒性小、可表面功能化等优点,引起了人们极大的兴趣。近年来,由高分子多糖合成的聚合物碳点成为另一研究热点。本文通过水热法合成了一种壳聚糖基荧光聚合物碳点材料（P（CS-g-mPEG-CA）CDs）,并用于载药研究。基于壳聚糖和聚乙二醇既是碳点的碳源也是碳点的钝化试剂,本文选择壳聚糖接枝聚乙二醇单甲醚和柠檬酸衍生物作为聚合物碳点的碳源,以提高聚合碳点的量子产率。另外,聚合物碳点还可以保留聚乙二醇与壳聚糖分子结构,为其在载药方面的应用提供有利条件。采用红外光谱、紫外光谱、X射线衍射、光电子能谱、透射电子显微镜和光致发光光谱对P（CS-g-mPEG-CA）CDs进行了结构表征以及pH值稳定性的测试。结果表明,所合成的P（CS-g-mPEG-CA）CDs具有较高的荧光量子产率（66.81%）、较长的荧光寿命（15.247 ns）、良好的pH稳定性。以阿霉素为模型药物,利用该聚合物碳点进行了负载研究,结果表明,当聚乙二醇单甲醚取代度为11.9%时,聚合物碳点的载药量最高为51.3%,最大药物释放率为28.7%,此外,药物的装载和释放可以通过mPEG的接枝率进行控制。采用MTT法评价了聚合物的碳点对鼻咽癌细胞（CNE-2）的毒性作用。研究表明,空白聚合物碳点无明显细胞毒性,CNE-2细胞存活率随着载药胶束的增加而降低,说明载药胶束对CNE-2细胞有较强的抑制作用。可见该P（CS-g-mPEG-CA）CDs在荧光标记、药物递送、荧光示踪系统和控制释放方面,具有一定的应用前景。     

Effect of drying technique on the physicochemical properties of sodium silicate-based mesoporous precipitated silica

The conventional drying (oven drying) method used for the preparation of precipitated mesoporous silica with low surface area (>300 m²/g) and small pore volume is often associated with a high production cost and a time consuming process. Therefore, the main goal of this study was to develop a cost-effective and fast drying process for the production of precipitated mesoporous silica using inexpensive industrial grade sodium silicate and spray drying of the precipitated wet-gel silica slurry. The precipitated wet-gel silica slurry was prepared from an aqueous sodium silicate solution through the drop-wise addition of sulfuric acid. Mesoporous precipitated silica powder was prepared by drying the wet-gel slurry with different drying techniques. The effects of the oven drying (OD), microwave drying (MD), and spray drying (SD) techniques on the physical (oil, water absorption, and tapping density), and textural properties (specific BET surface area, pore volume, pore size, and % porosity) of the precipitated mesoporous silica powder were studied. The dried precipitated mesoporous silica powders were characterized with field-emission scanning electron microscopy; Brunauer, Emmett and Teller and BJH nitrogen gas adsorption/desorption methods; Fourier-transform infrared spectroscopy; thermogravimetric and differential analysis; N₂ physisorption isotherm; pore size distribution and particle size analysis. There was a significant effect of drying technique on the textural properties, such as specific surface area, pore size distribution and cumulative pore volume of the mesoporous silica powder. Additionally, the effect of the microwave-drying period on the physicochemical properties of the precipitated mesoporous silica powder was investigated and discussed.     

绿色环保化学机械抛光液的研究进展

原子级加工制造是实现半导体晶圆原子尺度超光滑表面的有效途径.作为大尺寸高精密功能材料的原子级表面制造的重要加工手段之一,化学机械抛光(chemical mechanical polishing,CMP)凭借化学腐蚀和机械磨削的耦合协同作用,成为实现先进材料或器件超光滑无损伤表面平坦化加工的关键技术,在航空、航天、微电子等众多领域得到了广泛应用.然而,为了实现原子层级超滑表面的制备,CMP工艺中常采用的化学腐蚀和机械磨削方法需要使用具有强烈腐蚀性和高毒性的危险化学品,对生态系统产生了不可逆转的危害.因此,本文以绿色环保高性能抛光液作为对象,对加工原子量级表面所采用的化学添加剂进行分类总结,详尽分析在CMP过程中化学添加剂对材料表面性质调制的作用机理,为在原子级尺度下改善表面性质提供可参考的依据.最后,提出了CMP抛光液在原子级加工研究中面临的挑战,并对未来抛光液发展方向作出了展望,这对原子尺度表面精度的进一步提升具有深远的现实意义.     

Surface modification of ceria nanoparticles and their chemical mechanical polishing behavior on glass substrate

To improve their chemical mechanical polishing (CMP) performance, ceria nanoparticles were surface modified with γ-aminopropyltriethoxysilane (APS) through silanization reaction with their surface hydroxyl group. The compositions, structures and dispersibility of the modified ceria particles were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), laser particle size analyzer, zeta potential measurement and stability test, respectively. The results indicated that APS had been successfully grafted onto the surface of ceria nanoparticles, which led to the modified ceria nanoparticles with better dispersibility and stability than unmodified ceria particles in aqueous fluids. Then, CMP performance of the modified ceria nanoparticles on glass substrate was investigated. Experimental results showed that the modified ceria particles exhibited lower material removal rate (MRR) but much better surface quality than unmodified ceria particles, which may be explained by the hardness reduction of ceria particles, the enhancement of lubrication of the particles and substrate surfaces, and the elimination of the agglomeration among the ceria particles.     

壳聚糖基聚合物点荧光材料的合成及其对纸张的抗紫外老化性能

以壳聚糖、柠檬酸、N-(2-羟乙基)乙二胺为原料,通过水热法合成了壳聚糖基聚合点(P(CS-g-CA)Ds)荧光材料,发现柠檬酸的接枝可明显提高壳聚糖聚合物点的量子产率。对P(CS-g-CA)Ds进行了红外光谱、紫外光谱、光电子能谱、透射电镜、热分解性能及光致发光光谱表征,测试了不同p H值下的荧光强度。结果表明,P(CS-g-CA)Ds在p H=4~12范围内有良好的稳定性。通过测试紫外老化前后宣纸的羰基指数和乙烯基指数研究了P(CS-g-CA)Ds在宣纸中的应用,结果表明其具有良好的抗紫外老化性能。     

Improving the hydrophilicity of poly(vinylidene fluoride) porous membranes by electron beam initiated surface grafting of AA/SSS binary monomers

Poly(vinylidene fluoride) (PVDF) membranes were pre-irradiated by electron beam in vacuum, and then the hydrophilic sulfonate groups were introduced by the single step grafting method with binary monomer solution of acrylic acid (AA) and sodium 4-styrenesulfonate (SSS). The effect of binary monomer ratio and pH of reaction solution on the degree of grafting was investigated. The surface chemical change was characterized by Fourier transform infrared attenuated total reflection spectroscopy (FT-IR-ATR) and X-ray photoelectron spectroscopy (XPS). Morphological changes on the membrane surface were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface hydrophilicity of the modified membrane was characterized through water contact angle measurement. It was found that the water contact angle of the membrane surface decreased significantly when compared with the original one, indicating the improvement of the surface hydrophilicity.     

Poly(acrylamide‐co‐acrylic acid)/Poly(vinyl pyrrolidone) Polymer Blends Prepared by Dispersion Polymerization

The structure and properties of a three‐component system, a poly(acrylamide‐co‐acrylic acid)/poly(vinyl pyrrolidone) [P(AM‐co‐AA)/PVP] polymer blend prepared by dispersion polymerization, were studied. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed that the resulting P(AM‐co‐AA) microspheres with diameters between 200–300 nm were well‐dispersed in the PVP matrix. Fourier transform infrared spectra (FTIR) showed that intermolecular hydrogen bonding interaction occurred between the dispersed phase and the continuous phase. The mechanical properties of P(AM‐co‐AA)/PVP polymer blends were also determined. With different mass ratios of acrylamide to acrylic acid, it was found that the blends had better mechanical properties with increased AA content.     

Preparation and Properties of Water-Soluble Sodium Polyacrylates

Butyl acrylate-acrylic acid copolymer and poly (butyl acrylate) were synthesized via suspension polymerization by using butyl acrylate as the main monomer and acrylic acid as a secondary monomer. Then these polymers were swollen in ethanol and hydrolyzed in an aqueous solution of sodium hydroxide. Finally, water-soluble sodium polyacrylates were obtained by washing and drying the hydrolyzed resultant. The influence of the mass fraction of acrylic acid in the monomer feed ratio, swelling time, and hydrolysis time on hydrophilicity, solubility, and absolute viscosity of the prepared sodium polyacrylates was researched. In addition, an Ubbelohde viscometer was used to determine the intrinsic viscosity of the aqueous solutions of the prepared sodium polyacrylates. The Mark–Houwink equation was applied to calculate their viscosity average molecular weight. Finally, their chemical structures and heat resistance properties were analyzed by using nuclear magnetic resonance spectroscopy and thermogravimetric analysis; additionally, the changes of the surface elements before and after hydrolysis were researched by using X-ray photoelectron spectroscopy.     

Static dissolution rate of tungsten film versus chemical adjustments of a reused slurry for chemical mechanical polishing

Tungsten is widely used as deposited layer for the multi-level interconnection structures of wafers. The chemical composition of abrasive slurry plays an important role in chemical mechanical polishing (CMP) process. Removal of tungsten is driven by complex oxidation mechanisms between slurry components. The slurry for tungsten CMP generally contains oxidizer, iron catalyst, complexing agents and stabilizers in a pH adjusted solution of abrasive particles. Interaction between iron complex and H₂O₂ in the slurry is the main factor governing the chemical mode of material removal, oxidation potencies and kinetics.In this study, we investigate the effects of chemical additives in silica (SiO₂)-based slurry on the removal rate of the tungsten film. Experiments were carried out in static batch as a preliminary study to understand and optimize chemical mechanisms in CMP-Tungsten process. Experiment designs were conducted to understand the influence of the chemical additives on the main performances of W-CMP. Used slurry, concentrated and retreated with chemical adjustments, is compared to the original slurry as a reference.