适于ULSI的一种新的铜的CMP抛光液

采用纳米级二氧化硅代替国际上惯用的三氧化二铝作磨料,解决了抛光液的悬浮问题,得到了很好的抛光表面.采用无金属离子的有机碱作络合剂及pH调制剂,使用了无金属离子的氧化剂解决了铜离子沾污问题和制约硅溶胶作磨料的凝胶问题.从而得到一种适用于甚大规模集成电路(ULSI)制备中铜互连线技术的化学机械抛光(CMP)的新型抛光液.     

pH值对低磨料碱性铜抛光液稳定性的影响

稳定性是衡量化学机械抛光(CMP)中抛光液性能的一个重要指标,低磨料和低pH值是抛光液发展的方向.研究了不同pH值对低磨料碱性铜抛光液稳定性的影响.选取了磨料质量分数为1％的抛光液,加入磷酸调节pH值,得到pH值分别为7.3,8.11,9.21,10.02和11.04抛光液,测量比较了各组抛光液随存放时间的变化其pH值、磨料粒径、Zeta电位和铜去除速率的变化.结果表明,低磨料碱性铜抛光液的pH值随时间的延长而降低,磨料粒径也随存放时间的延长而变大,抛光液的Zeta电位的绝对值随pH值的降低而降低,铜的去除速率随抛光液的存放时间的增加而降低,当pH值为9.21～10.02时,抛光液存放时间超过48 h.     

无氧化剂条件下铜钴CMP去除速率的控制北大核心

利用不含氧化剂的碱性抛光液对铜和钴进行化学机械抛光,深入分析了抛光液组分包括硅溶胶磨料、FA/O螯合剂以及非离子表面活性剂对两种金属去除速率的影响规律及作用机理。实验结果表明,铜和钴的去除速率随着磨料质量分数的增加而升高,并且在磨料质量分数低于5%时钴的去除速率为20~30 nm/min,而铜的去除速率几乎为零;加入FA/O螯合剂可增强其与金属离子的络合,从而加快铜和钴的去除速率;非离子表面活性剂可以有效降低铜和钴的表面粗糙度。在抛光液各组分的协同作用下,可以达到两种材料的低表面粗糙度和高去除速率选择性。     

ULSI铜多层布线中钽阻挡层CMP抛光液的研究与优化

以高浓度纳米SiO2水溶胶为磨料,H2O2为氧化剂的碱性抛光液,研究了适用于终抛铜/钽的CMP抛光液.通过调节pH值,降低抛光液的氧化,增强有机碱的作用,来降低铜的去除速率并提高钽的去除速率,得到了很好的铜/钽抛光选择性.     

ULSI铜多层布线中钽阻挡层CMP抛光液的研究与优化

以高浓度纳米SiO2水溶胶为磨料,H2O2为氧化剂的碱性抛光液,研究了适用于终抛铜/钽的CMP抛光液.通过调节pH值,降低抛光液的氧化,增强有机碱的作用,来降低铜的去除速率并提高钽的去除速率,得到了很好的铜/钽抛光选择性.     

用于铜的化学机械抛光液的研究

文中介绍了一种以碱性抛光液对铜进行全局平面化的方法 ,讨论了以 Si O2 水溶胶为磨料的抛光液在Cu-CMP过程中的化学 (络合 )作用及反应机理 ,并给出了抛光液的配比及上机实验结果。结果表明 :该抛光液用于对带有阻挡层和介质层的铜抛光 ,达到了对铜层的高去除速率和高选择比 ,取得了较好的全局平面化效果     

不同磨料质量分数对化学机械平坦化的影响

采用自主研发的碱性铜抛光液,在E460E机台上研究了不同磨料质量分数对铜和钽抛光速率与膜厚一致性的影响;分析了磨料质量分数为2%,2.8%和3.6%时,膜厚一致性对平坦化的影响。抛光结果显示:当磨料质量分数高于2.8%时,抛光液开始对钽进行有效的抛光;随着磨料浓度的增加,抛光液的膜厚一致性提高趋于平缓。磨料质量分数为2.8%和3.6%时,抛光后膜厚一致性变好,碟形坑满足工业生产要求;磨料质量分数为2%时,抛光后膜厚一致性比抛光前恶化,碟形坑相对较大。由此可见,当磨料质量分数为2.8%时,抛光液能有效去除残余铜,并且抛光后膜厚一致性好,有利于实现平坦化,尤其是对提高成品率和优品率有重要的作用。     

优化CMP碱性铜抛光液配比的新方法

采用响应曲面法(RSM)和人工神经网络(ANN)分别对化学机械抛光(CMP)碱性铜抛光液的主要成分(SiO2磨料、FA/O型螯合剂、H2O2氧化剂)进行优化研究.采用RSM优化,当抛光液中磨料、氧化剂和FA/O型螯合剂的体积分数分别为10.57％,1.52％和2.196％时,Cu的抛光速率的预测值和实测值分别为924.29和908.96 nm/min;采用ANN结合人工蜂群算法(ABC)优化,当抛光液中磨料、氧化剂和FA/O型螯合剂的体积分数分别为11.58％,1.467％和2.313％时,Cu的抛光速率的预测值和实测值分别为947.58和943.67 nm/min,其拟合度为99.36％,高于RSM的94.63％,且均方根误差较低为0.199 3.结果表明,在抛光液配比优化方面,RSM和ANN都是可行的,但后者比前者具有更好的拟合度和预测准确度,为更加高效科学地优化抛光液配比提供了一种新的思路和方法.     

磨料粒径对多层Cu布线CMP的影响北大核心

阐述了碱性抛光液中磨料的质量传递作用对多层Cu布线化学机械抛光(CMP)过程中抛光速率和抛光后晶圆表面状态的影响,通过对比不同磨料粒径抛光液在3英寸(1英寸=2.54 cm)铜晶圆上的抛光实验结果,分析了不同磨料粒径抛光液的抛光速率以及抛光后晶圆的表面状态,选择了一种粒径为100 nm、质量分数为3%的磨料,粗抛(P1)的抛光速率达到650 nm/min,抛光后晶圆表面粗糙度由10.5 nm降至2.5 nm,大大提高了抛光后晶圆的表面状态以及平坦化效果,可对多层Cu布线CMP过程中磨料的选择提供一定的参考。     

Cu CMP抛光液对速率的影响分析及优化

在超大规模集成电路多层Cu布线CMP工艺中,抛光液是决定抛光速率、抛光表面状态和平坦化能力的重要因素。采用Plackett-Burman(PB)筛选实验对抛光液成分(磨料、氧化剂、活性剂、螯合剂)进行显著性因素分析,得出磨料、FA/O螯合剂Ⅱ型和氧化剂为显著性因素,并采用响应曲面法对其进行优化并建立了模型,最终得到以去除速率为评价条件的综合最优抛光液配比,为Cu抛光液配比优化及对CMP的进一步发展提供了新的思路与途径。     

ULSI铜互连线CMP抛光液的研制

介绍了一种碱性抛光液,选用有机碱做介质,SiO2水溶胶做磨料,依据强络合的反应机理,克服了SiO2水溶胶做磨料对铜去除速率低及在溶液中凝胶的难点.实验结果表明:该抛光液适用于Cu化学机械抛光过程第一阶段的抛光,并达到了高抛光速率及铜/钽/介质层间的高选择性的效果.     

基于化学机械动力学的碱性铜抛光液平坦化机理研究

The planarization mechanism of alkaline copper slurry is studied in the chemical mechanical polishing (CMP) process from the perspective of chemical mechanical kinetics.Different from the international dominant acidic copper slurry,the copper slurry used in this research adopted the way of alkaline technology based on complexation. According to the passivation property of copper in alkaline conditions,the protection of copper film at the concave position on a copper pattern wafer surface can be achieved without the corrosion inhibitors such as benzotriazole(BTA),by which the problems caused by BTA can be avoided.Through the experiments and theories research,the chemical mechanical kinetics theory of copper removal in alkaline CMP conditions was proposed. Based on the chemical mechanical kinetics theory,the planarization mechanism of alkaline copper slurry was established. In alkaline CMP conditions,the complexation reaction between chelating agent and copper ions needs to break through the reaction barrier.The kinetic energy at the concave position should be lower than the complexation reaction barrier,which is the key to achieve planarization.     

Surface-enhanced fluorescence from copper nanoparticles on silicon nanowires

A method to enhance surface plasmon coupled fluorescence from copper nanoparticles on silicon nanowires is presented. Owing to resonant plasmons oscillation on the surface of Cu/Si nanostructure, the fluorescence peaks of several lanthanide ions (praseodymium ions, Pr3+,neodymium ions Nd3+, holmium ions Ho3+, and erbium ions Er3+) were markedly enhanced with the enhancement of maximal 2 orders of magnitude, which was larger than that caused by unsupported Cu nanoparticles. These results might be explained by the local field overlap originated from the closed and fixed copper nanoparticles on silicon nanowires.     

半导体硅上激光诱导选择性化学镀铜

利用YAG脉冲激光在n型硅基底上制备出了铜化学镀薄层,由激光剥离形成的微型图元通过化学镀铜工艺在硅基底上形成铜的微型结构。在化学镀工艺过程中为了使得化学镀铜沉积能够连续进行,要对基底表面先进行活化。实验表明,预处理及其后的清洗工艺对选择性镀膜质量影响很大;采用丙酮或硝酸水清洗,有助于获得清晰的微型图元结构。     

Cu􀀁CMP 中磨料粒子的机械作用实验分析

本文介绍的Cu-CMP实验中的磨料粒子是纳米硅溶胶（SiO2,20－30nm）。为得到高质量、高平整度的铜表面，采用SiO2溶胶抛光液对铜进行抛光实验，在给定的条件下，得到了磨料粒子的浓度与抛光速率间的机械作用曲线。实验结果表明：当SiO2溶胶浓度增大时，机械作用增强，抛光速率随之增加。当SiO2溶胶浓度控制在一定范围，使抛光表面在低表面张力下进行抛光时，抛光后的液体呈蓝色，抛光后的铜表面光亮无划伤，此时铜表面实现了高速率及高平整度的最佳效果。     

Treatment of Copper from Cu CMP Waste Streams Using Polyethyleneimine

Commercially available Cu CMP waste treatment processes involve: 1) pretreatment chemistry using oxidizers to break down complexed copper resulting in precipitation of copper in the form of copper hydroxide; 2) microfiltration of both slurry particles and copper hydroxide; and 3) ion exchange to remove ${rm Cu}^{2+}$ ions. Ion exchange resins used to remove ${rm Cu}^{2+}$ ions are limited to only removing cations and also have a low efficiency in binding ${rm Cu}^{2+}$ ions. The treatment strategy to be evaluated here only requires using two processes to remove the copper from Cu CMP waste—filtration to remove the particles followed by chelation. This paper focuses on the chelation step. The chelator of interest is polyethyleneimine (PEI) bound to agarose beads. PEI removes both ${rm Cu}^{2+}$ ions and Cu-complexes. The particles from slurry in the actual Cu CMP waste were removed by filtration before the experiment. The results show that PEI has a higher binding capacity for ${rm Cu}^{2+}$ ions than ion exchange resins. Its performance and reproducibility did not change after multiple regenerations. Furthermore, PEI has the ability to bind Cu-complexes through electrostatic attraction. Although the bonds aren't strong, the result is more overall copper removal from the waste stream. The copper component of the Cu CMP waste was concentrated 12 fold using this system.      

Dependency of dishing on polish time and slurry chemistry in Cu CMP

In this paper the influences of slurry chemistry and thickness of the copper layer on dishing will be discussed. The dishing is studied for different patterns and variable polishing times. We found that the concentration of the oxidiser and the thickness of copper layer have a strong impact on dishing. The larger Cu features develop dishing at a higher rate than smaller structures during overpolishing. The experimental results lead to the following hypothesis for the Cu removal and surface passivation. The oxidizer (H₂O₂) reacts with Cu in an acidic slurry (pH 4) and Cu²⁺ ions are formed. The anions of the carboxylic acid react with Cu²⁺ ions and form an insoluble salt (R(COO)₂Cu) which passivates the surface. This passivation layer is removed in protruding areas by mechanical abrasion. Once removed from the surface, the ‘metallic soap’ particles are swept away by the turbulent motion in the slurry.     

ULSI制备中多层布线导体铜的抛光液与抛光技术的研究

提出了在碱性浆料中ULSI多层布线导体铜化学机械抛光的模型,对铜CMP所需达到的平面化、选择性、抛光速率控制、浆料的稳定及洁净度、抛光液成分的优化选择进行了实验研究。     

ULSI制备中多层布线导体铜的抛光液与抛光技术的研究

提出了在碱性浆料中 UL SI多层布线导体铜化学机械抛光的模型 ,对铜 CMP所需达到的平面化、选择性、抛光速率控制、浆料的稳定及洁净度、抛光液成分的优化选择进行了实验研究。     

The Effect of Ionic Contaminants on Silicon Transistor Stability

The development of the beam-lead sealed-junction (BLSJ) technology (beam-lead contact metals-silicon nitride passivation) included many experiments to study the effects of various ionic contaminants on silicon transistor stability. Stress aging was performed on standard n-p-n silicon transistors (aluminum contacts and silicon dioxide protection) under various conditions of temperature, bias, contamination, and ambient. These experiments showed the following results. 1) Alkali ions and copper in a reducing ambient are detrimental to the devices. 2) A hydrogen ambient accelerates the effect of alkali ions on the transistor degradation. 3) The degradation is approximately a linear function of the reverse bias and the contamination level from 4 to 400 ? of sodium chloride. 4) Anions have only a secondary effect on the migration of alkali ions in the oxide. The BLSJ technology was developed to protect unencapsulated silicon devices from the degradation seen on standard transistors during the preceding experiments. Results have shown that the median time to failure of sodium-contaminated BLSJ transistors aged in air at 300°C is higher than that for standard silicon transistors aged under identical conditions.