Corrosion electrochemical mechanism ofchemical mechanical polishing of copper in K3Fe（CN）6 solution

1　ＩＮＴＲＯＤＵＣＴＩＯＮＣｈｅｍｉｃａｌ ｍｅｃｈａｎｉｃａｌ ｐｏｌｉｓｈｉｎｇ (ＣＭＰ )ｉｓｔｈｅｍｏｓｔｉｍｐｏｒｔａｎｔｇｌｏｂａｌｐｌａｎａｒｉｚａｔｉｏｎｔｅｃｈｎｏｌｏｇｙａｔｐｒｅ ｓｅｎｔ.Ｓｐｅｃｉａｌｌｙｔｏｐｏｌｉｓｈｉｎｇｏｆｍｅ     

基于光助芬顿反应的碳化硅化学机械抛光工艺优化

目的 高效快速获得紫外光辅助作用下碳化硅(SiC)化学机械抛光(Chemical mechanical polishing, CMP)的最佳加工参数。方法 根据化学作用与机械作用相平衡时达到最佳抛光条件的理论,通过电化学测试的方法探究抛光液pH值、过氧化氢(Hydrogen peroxide, H2O2)浓度、Fe²⁺浓度、紫外光功率等对基体表面氧化膜形成速率(化学作用)的影响;在最大氧化膜形成速率条件下,以材料去除率(Material removal rate, MRR)和表面粗糙度(Average roughness, Ra)为指标,通过调节抛光压力、抛光盘转速、抛光液流量等工艺参数,探究工艺参数对碳化硅加工过程中氧化膜去除速率(机械作用)的作用规律,寻求机械作用与化学作用的平衡点,获取紫外光辅助作用下SiC CMP的最佳工艺参数。结果 在pH值为3、H2O2的质量分数为4%、Fe²⁺浓度为0.4 mmol/L、紫外光功率为32 W时,化学作用达到最大值。在最大化学作用条件下,抛光压力、抛光盘转速、抛光液流量分别为38.68 kPa、120 r/min、90 mL/min时,化学作用与机械作用最接近于平衡点,此时材料去除率为92 nm/h,表面粗糙度的最低值为0.158 nm。结论 根据研究结果,电化学测试可以作为探究晶片表面氧化速率较高时所需加工参数的有效手段,进一步调节工艺参数,使化学作用速率与机械去除速率相匹配,高效地获得了材料去除率和表面质量较高的晶片。     

Mechanical effect of process condition and abrasive concentration on material removal rate profile in copper chemical mechanical planarization

Recently, many researchers have studied the material removal mechanism of copper chemical mechanical planarization (CMP). On the basis of their previous works, we studied the mechanical effect of copper (Cu) CMP on the material removal rate profile. Copper CMP was performed using citric acid (C₆H₈O₇), hydrogen peroxide (H₂O₂), colloidal silica, and benzotriazole (BTA, C₆H₄N₃H) as a complexing agent, an oxidizer, an abrasive, and a corrosion inhibitor, respectively. In this paper, the abrasives and process condition are main mechanical factors of CMP. The colloidal silica, used as an abrasive in copper CMP slurry containing 0.01 M citric acid and 3 vol% hydrogen peroxide, controlled the wafer edge profile by abrading the wafer edge. The polishing pressure did not contribute to the material removal rate (MRR) profile, but did to the MRR. As the rotational velocity of the polishing head and table increased, the deviation of MRR profile became smaller. The results of this paper showed that the abrasive concentration was the key factor which controlled the wafer edge profile, and also the rotational velocity was the key factor which controlled wafer center profile of MRR.     

Combined ultrasonic vibration and chemical mechanical polishing of copper substrates

This paper introduces an ultrasonic, vibration-assisted, chemical mechanical polishing (UV-CMP) method and an ultrasonic, vibration-assisted, traditional diamond disk (UV-TDD) dressing method. A copper substrate is polished by traditional CMP and UV-CMP. UV-CMP combines the functions of traditional CMP and ultrasonic machining (USM) with small-amplitude, high-frequency tool vibration to improve the fabrication process and machining efficiency. The removal rate of the copper substrate, torque force, and polished surface morphology of CMP and UV-CMP are compared. The polishing pad is also dressed by traditional diamond disk (TDD) and UV-TDD. The pad cut rate, torque force, and pad surface profiles of TDD and UV-TDD are also investigated in experiments. Experimental results reveal that UV-TDD can produce twice the pad cut rate and reduce torque force compared to TDD. Consequently, a dressing time reduction by half is expected, and hence, the diamond life is extended. It is found that the removal rate of the copper substrate polished by UV-CMP is increased by approximately 50-90% relative to that of traditional CMP because in UV-CMP, a passive layer on the copper surface, formed by the chemical action of the slurry, will be removed not only by the mechanical action of CMP but also by ultrasonic action. In addition, the surface roughness improves and the torque force reduces dramatically. This result suggests that the combination processes of CMP/USM and TDD/USM are feasible methods for improving polishing and dressing efficiency.     

Mechanical effect of colloidal silica in copper chemical mechanical planarization

The mechanical effect of colloidal silica concentration in copper chemical mechanical planarization (CMP) is considered in this paper by using friction force monitoring system. The copper peak was detected in the result of the energy-dispersive X-ray (EDX) spectra of the polishing residues. The addition of colloidal silica into copper CMP slurry increased both the material removal rate and the friction force. During CMP, as the concentration of the colloidal silica was increased, the temperature generated by the friction force also increased. To understand effect of abrasive concentration on the material removal and friction force, we considered the material removal and the friction energy for a single abrasive. The surface of the polished copper film was measured by X-ray photoelectron spectroscopy (XPS). All the material removal rates as a function of friction energy after polishing with various concentrations of colloidal silica had a non-linear characteristic.     

基于响应面法的单晶硅CMP抛光工艺参数优化

为提高单晶硅化学机械抛光(chemical mechanical polishing,CMP)的表面质量和抛光速度,通过响应面法优化CMP抛光压力、抛光盘转速和抛光液流量3个工艺参数,结果表明抛光压力、抛光盘转速、抛光液流量对材料去除率和抛光后表面粗糙度的影响依次减小。通过数学模型和试验验证获得最优的工艺参数为:抛光压力,48.3 kPa;抛光盘转速,70 r/min;抛光液流量,65 mL/min。在此工艺下,单晶硅CMP的材料去除率为1 058.2 nm/min,表面粗糙度为0.771 nm,其抛光速度和表面质量得到显著提高。      

304不锈钢绿色化学机械抛光

目的 采用对环境友好的抛光工艺来改善304不锈钢表面抛光质量。方法 基于化学机械抛光（CMP）工艺,采用主要成分为氧化铝（Al₂O₃）磨料、L-苹果酸、过氧化氢（H₂O₂）、乳化剂OP-10、甘氨酸的绿色环保抛光液,设计并试验了pH值,H₂O₂、乳化剂OP-10、甘氨酸质量分数的4因素4水平CMP正交试验。采用极差法分析了4个因素对表面粗糙度和材料去除率的影响。采用电化学工作站,通过动电位极化曲线法,分析304不锈钢在不同抛光液环境下的静态腐蚀特性。通过X射线光电子能谱（XPS）,分析304不锈钢在不同抛光液环境下的表面元素和化学组分变化。结果 开发了一种不含任何强酸、强碱等危化物品的新型环保化学机械抛光液。通过绿色CMP加工,在70μm×50μm范围内将304不锈钢平均表面粗糙度从CMP前的7.972 nm降至0.543 nm。与之前报道的304不锈钢抛光相比,绿色CMP抛光后的表面粗糙度最低。通过正交试验,得到了绿色CMP加工的最优抛光液参数：pH=3...     

抛光垫特性对硬质合金刀片CMP加工效果的影响

目的研究不同种类的抛光垫对硬质合金刀片表面化学机械抛光(Chemical Mechanical Polishing/Planarization,CMP)加工过程的影响,为实现硬质合金刀片高效精密CMP加工提供有效参考。方法利用Nanopoli-100智能抛光机,通过自制的Al2O3抛光液,分别采用9种不同种类的抛光垫对牌号为YG8的硬质合金刀片进行CMP实验,将0~40、40~80、80~120 min三个加工阶段获得的材料去除率和表面粗糙度进行对比,同时观察最佳的表面形貌,分析抛光垫特性对CMP加工效果的影响。结果在抛光转速60 r/min,抛光压力177.8 k Pa的实验条件下,9种不同类型的抛光垫中仅有5种适合用于YG8硬质合金CMP加工。而且抛光垫的表面粗糙度在YG8刀片CMP加工过程中的影响最为显著,抛光垫表面粗糙度越高,CMP加工的材料去除率越高。此外,抛光垫的使用时间对CMP过程也有影响,抛光垫使用时间越长,CMP的材料去除率越小。结论 YG8硬质合金刀片经5种不同类型抛光垫CMP加工后,其表面的烧伤、裂纹等缺陷均得到了极大改善。当使用细帆布加工40 min时,材料去除率最高,为47.105 nm/min;当使用细帆布加工80min时,表面粗糙度最低,为0.039μm。     

Electrochemical Performance of Passive Film Formed on Ti-Al-Nb-Zr Alloy in Simulated Deep Sea Environments

Titanium alloy Ti-Al-Nb-Zr has high specific strength and becomes a promising structural material used in the deep sea.The excellent corrosion resistance of the alloy is derived from the protective passive film formed on its surface.By now,full agreement on interpretation of the anti-corrosion performance of the film in marine environment,especially in the deep sea,has not been reached.In this work,the electrochemical performance of two-surface-state Ti-Al-Nb-Zr alloys which are treated by mechanical polishing and anodizing pre-passivation in the simulated shallow sea,1000 m and 3000 m deep sea environments,is investigated.By interpreting the electrochemical kinetic parameters,it is found that the dominant cathodic process becomes hydrogen evolution in simulated deep sea environments,but the reduction rate is restrained by high hydrostatic pressure,which arrests the passivation of the alloy.Assisted by X-ray photoelectron spectroscopy analysis,it is found that the passive film mainly consists of titanium oxides.There are intermediate oxides with non-stoichiometric ratio involved in the film formation due to the low dissolved oxygen concentration and low temperature.The results of Mott-Schottky and electrochemical impedance show that the film has n-type semiconducting property with oxygen vacancies as the main point defects.The anti-corrosion performance in simulated deep sea environments is one order of magnitude lower than that in the simulated shallow sea environment.However,from 1000 to 3000 m,the corrosion resistance is reduced very slightly.In the inner layers of the passive film and the passive film formed in simulated deep sea environments,the proportion of lowvalence titanium oxides is relatively high.The doping of low-valence titanium(Ti(Ⅱ) or Ti(Ⅲ)) results in a porous structure and ion permeability of the passive film,as well as relatively low corro sion resistance.     

乙醇对低磨料CMP过程中铜膜凹凸处去除速率选择性的影响

根据相似相容原理,在低磨料浓度CMP过程中,利用乙醇对多羟多胺螯合剂的降黏特性来提高铜膜表面凹凸处抛光速率的选择性。根据抛光液中各组分浓度对动态和静态条件下铜膜去除速率的影响获得乙醇加入量的最大值;通过螯合剂、氧化剂与乙醇对动静态条件下铜膜去除速率的相互作用关系来确定各组分的最佳浓度。最终得出当各组的体积分数为:磨料0.5%,螯合剂10%,H2O20.5%,乙醇1%时,铜膜表面拥有最大的凸处和凹处速率比。在MIT 854铜布线片上进行平坦化试验,结果表明:该抛光液能够很大程度的减小布线表面的高低差,拥有较强的平坦化能力。红外光谱检测结果表明:在CMP过程中,铜膜表面不会生成副产物乙酸乙酯。上述结果进一步证实了该抛光液的实用性。     

A wafer-scale material removal rate profile model for copper chemical mechanical planarization

Chemical mechanical polishing (CMP) models based on the Preston equation, which states that the material removal rate (MRR) is proportional to the product of the pressure and relative velocity, have focused on representing the average MRR as a function of the pressure and relative velocity. In this study, we tried to establish a semi-empirical CMP model, which can provide the MRR profile. The model is based on a modified form of the Preston equation and involves the use of a spatial parameter (Ω). The relative velocity distribution, normal contact stress distribution, and chemical reaction rate distribution are considered for obtaining the MRR profile in the copper CMP process. The results of the modeling and experimental analysis performed in this study facilitate process optimization and provide information that can contribute to the development of a wafer-scale CMP simulator.     

深海环境对纯镍腐蚀行为的影响Ⅲ-静水压力对纯镍点蚀机制的影响

利用光学显微镜、扫描电子显微镜和电化学测量方法研究纯镍在3.5%NaCl溶液中,静水压力为常压和8 MPa条件下的腐蚀行为.结果表明,在常压和静水压力为8 MPa条件下,纯镍钝化膜均为二维形核;8 MPa的静水压力对纯镍的腐蚀行为有三方面的影响:(1)降低纯镍的钝化膜形成速度;(2)抑制点蚀形成的B1过程,促进A3过程...     

Investigation on the Electrochemical-Mechanical Polishing of NiP Substrate of Hard Disk

利用自制的抛光液和改造的抛光机对NiP基板进行电化学机械抛光,研究了抛光电压、抛光台转速、抛光压力和抛光液流速对材料去除速率的影响,对电化学机械抛光的机理做了初步的分析。研究结果表明, NiP基板可以用低压力 (3.5 kPa)抛光, 材料的去除速率可以通过调整抛光电压, 抛光台转速和抛光液流速进行控制     

铜化学机械抛光的弱缓蚀剂研究

利用电化学、接触角、化学机械抛光等试验研究一种新型环保的铜缓蚀剂聚乙烯吡咯烷酮(polyvinyl pyrrolidone,PVP)的效果。结果表明:PVP在铜化学机械抛光中具有一剂多用的效果,将其与另一种环保弱缓蚀剂1, 2, 4-三氮唑(1, 2, 4-triazole,TAZ)混合使用,既能保证平坦化效果,又能实现工业生产所需的低压高去除率抛光,在粗糙度为2.28 nm时, 去除率达到1 291 nm/min。      

双层Mo薄膜的制备工艺与性能

(锇有可能作为大规模集成电路铜互连扩散阻挡层新材料.)利用自制的抛光液对金属锇片进行抛光,研究在双氧水-磷酸体系抛光液中H2O2浓度和抛光液pH值对抛光速率的影响.结果表明,当抛光液中主要成分仅为氧化剂H2O2时,并不能在金属锇表面达到好的腐蚀效果.在磷酸体系抛光液中,H2O2能够通过促进阴极反应的进行从而增强抛光液对金属锇的化学作用;低浓度H2O2通过增强抛光液对金属锇的化学腐蚀能力,从而增加了抛光速率值:较高浓度H2O2的加入对抛光速率值影响较小.H3PO4能够在抛光液中起到抑制剂、pH调节剂和络合剂的作用.当抛光液pH值为4.0时,金属锇表面生成的钝化膜最致密.当pH值为4.0或5.0时,金属锇表面生成的钝化膜OCP值大于金属锇的OCP值,且此条件下的抛光速率值较高.     

硬质合金刀具材料化学机械抛光机理研究

目的研究硬质合金刀具材料化学机械抛光(CMP)机理,为改善硬质合金刀具表面质量提供理论支持。方法分析硬质合金刀具材料在酸性抛光液中的化学反应,研究硬质合金刀具材料CMP的化学反应机理。基于接触力学理论计算抛光垫与工件的实际接触面积和单个磨粒的实际切削面积,在运动学分析的基础上,建立硬质合金刀具材料CMP的材料去除率模型,通过实验验证材料去除率模型的有效性。结果在酸性抛光液中,硬质合金被氧化成Co_3O_4。当工件、抛光垫、磨粒类型、工件安装位置确定时,材料去除率与抛光载荷、磨粒浓度和抛光盘转速有关。常用硬质合金抛光条件下,抛光YG8刀具的修正系数Kcm为8.53,抛光后刀具的最低表面粗糙度能达到48nm,材料去除率为62.381nm/min,材料去除率的理论值和实验值的最大相对误差为13.25%,消除了表面缺陷,获得了较好的镜面效果。结论建立的材料去除率模型具有一定的有效性,对硬质合金刀具材料进行化学机械抛光能消除刀具的表面缺陷,改善表面质量。     

Effect of passive film on the galvanic corrosion of titanium alloy Ti60 coupled to copper alloy H62

Ti alloys exhibit high potential because of the compact passive film. However, the effect of passive film on galvanic corrosion is not clear. On the one hand, the great potential difference can accelerate the galvanic corrosion of other metals with low potential. On the other hand, the passive film can hinder the electrochemical reactions, inhibiting the galvanic corrosion. To clarify this question, the galvanic corrosion of titanium alloy Ti60 coupled to copper alloy H62 was studied using zero‐resistance ammeter, scanning vibrating electrode technique, scanning electron microscopy, and potentiodynamic polarization measurements. The chemical composition and electrical properties of the passive film on Ti60 were detected using X‐ray photoelectron spectroscopy and Mott‐Schottky plots. The results indicate the galvanic corrosion of Ti60‐H62 coupling is ignorable in spite of the great galvanic potential difference between them. It can be attributed to the low electron donor density of passive film, which inhibits the electron charge transfer process at the film/solution interface, causing the slow cathodic reaction rate on Ti60.     

蓝宝石衬底CMP中氧化硅磨粒粒度分布对抛光液体系性能影响研究

目的 化学机械抛光(CMP)包含化学腐蚀和机械磨削两方面,抛光液pH、磨粒粒径和浓度等因素均会不同程度地影响其化学腐蚀和机械磨削能力,从而影响抛光效果。方法 采用30~150 nm连续粒径磨粒抛光液、120 nm均一粒径磨粒抛光液、50 nm和120 nm配制而成的混合粒径磨粒抛光液,分别对蓝宝石衬底晶圆进行循环CMP实验,研究CMP过程中抛光液体系的变化。结果 连续粒径磨粒抛光液中磨粒大规模团聚,满足高材料去除率的抛光时间仅有4 h,抛光后的晶圆表面粗糙度为0.665 nm;均一粒径磨粒抛光液中磨粒稳定,无团聚现象,抛光9 h内材料去除率较连续粒径磨粒抛光液高94.7%,能至少维持高材料去除率18 h,抛光后的晶圆表面粗糙度为0.204 nm;混合粒径磨粒抛光液初始状态下磨粒稳定性较高,抛光9 h内材料去除率较连续粒径磨粒抛光液高114.8%,之后磨粒出现小规模团聚现象,后9 h材料去除率仅为均一粒径磨粒抛光液的59.6%,18 h内材料去除率仅为均一粒径磨粒抛光液的87.7%,但抛光后的晶圆表面粗糙度为0.151 nm。结论 一定时间内追求较高的材料去除率和较好的晶圆表面粗糙度选用混合粒径磨粒抛光液,但需要长时间CMP使用均一粒径磨粒抛光液更适合,因此,在工业生产中需要根据生产要求配合使用混合粒径磨粒抛光液和均一粒径磨粒抛光液。     

The passivation behaviour of copper-containing high-performance ferritic stainless steels in the cathode environment of polymer electrolyte membrane fuel cells

The passivation behaviour of copper-containing high-performance ferritic stainless steels in the cathode environment of polymer electrolyte membrane fuel cells was investigated using electrochemical tests and XPS surface analyses. The addition of copper to the alloy deteriorated the corrosion resistance at a passive region of 0.6 V_SCE. With an increase of the copper content, the passivity of the alloy degraded due to an increase of the formation of Cr-containing inclusions, and a decrease of the Cr oxide and hydroxide in the passive film.     

Electrochemical behavior and polishing properties of silicon wafer in alkaline slurry with abrasive CeO2

The electrochemical behavior of silicon wafer in alkaline slurry with nano-sized CeO2 abrasive was investigated. The variations of corrosion potential （φcorr） and corrosion current density （Jcorr） of the P-type （100） silicon wafer with the slurry pH value and the concentration of abrasive CeO2 were studied by polarization curve technologies. The dependence of the polishing rate on the pH and the concentration of CeO2 in slurries during chemical mechanical polishing（CMP） were also studied. It is discovered that there is a large change of φcorr and Jcorr when slurry pH is altered and the Jcorr reaches the maximum （1.306 μA/cm^2） at pH 10.5 when the material removal rate（MRR） comes to the fastest value. The Jcorr increases gradually from 0.994 μA/cm^2 with 1% CeO2 to 1.304 μA/cm^2 with 3% CeO2 and reaches a plateau with the further increase of CeO2 concentration. There is a considerable MRR in the slurry with 3% CeO/at pH 10.5. The coherence between Jcorr and MRR elucidates that the research on the electrochemical behavior of silicon wafers in the alkaline slurry could offer theoretic guidance on silicon polishing rate and ensure to adjust optimal components of slurry.