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.     

不含抑制剂的碱性抛光液对铜布线平坦化的研究

本文提出一种碱性铜布线抛光液,其不含通用的腐蚀抑制剂,并对其化学机械抛光和平坦化 (CMP)性能进行了研究。首先研究了此抛光液对铜的静态腐蚀速率和抛光速率,并与含抑制 剂的铜抛光液做了对比实验。在静态条件下,此不含抑制剂的碱性铜抛光液对铜基本无腐蚀速率,而在动态抛光过程中对铜有较高的速率。而含抑制剂的抛光液对静态腐蚀速率略有降低,但是却大幅度降低了铜的去除速率。另外,对铜布线的化学机械平坦化研究表明,此不含抑制剂的碱性铜抛光液能够有效的去除铜布线表面的高低差,有较高的平坦化能力。此抛光液能够应用于铜CMP的第一步抛光,能够去除大量多余铜时初步实现平坦化。     

The stability of a novel weakly alkaline slurry of copper interconnection CMP for GLSI

Chemical mechanical polishing (CMP) is one of the important machining procedures of multilayered copper interconnection for GLSI,meanwhile polishing slurry is a critical factor for realizing the high polishing performance such as high planarization efficiency,low surface roughness.The effect of slurry components such as abrasive (colloidal silica),complexing agent (glycine),inhibitor (BTA) and oxidizing agent (H2O2) on the stability of the novel weakly alkaline slurry of copper interconnection CMP for GLSI was investigated in this paper.First,the synergistic and competitive relationship of them in a peroxide-based weakly alkaline slurry during the copper CMP process was studied and the stability mechanism was put forward.Then 1 wt％ colloidal silica,2.5 wt％ glycine,200 ppm BTA,20 mL/L H2O2 had been selected as the appropriate concentration to prepare copper slurry,and using such slurry the copper blanket wafer was polished.From the variations of copper removal rate,root-mean square roughness (Sq) value with the setting time,it indicates that the working-life of the novel weakly alkaline slurry can reach more than 7 days,which satisfies the requirement of microelectronics further development.     

ULSl制备中Cu布线的CMP技术及抛光液的研究

对ULSI制备中铜布线技术作了系统的介绍,对CMP相关技术抛光机理、浆料的种类及成分均作了整体的分析和论述,并对目前存在问题及解决的方法和发展方向进行了分析讨论。此外,还对新研制的一种新型、高效、无污染的浆料进行介绍了。     

新型碱性精抛液对300mm铜膜全局平坦化的影响

The copper removal rate and uniformity of two types copper slurries were investigated, which was performed on the 300 mm chemical mechanical planarization （CMP） platform. The experiment results illustrate that the removal rate of the two slurries is nearly the same. Slurry A is mainly composed ofa FA/OI1 type chelating agent and the uniformity reaches to 88.32%. While the uniformity of slurry B is 96.68%, which is mainly composed of a FA/OV type chelating agent. This phenomenon demonstrates that under the same process conditions, the uniformity of different slurries is vastly different. The CMP performance was evaluated in terms of the dishing and erosion values. In this paper, the relationship between the uniformity and the planarization was deeply analyzed, which is mainly based on the endpoint detection mechanism. The experiment results reveal that the slurry with good uniformity has low dishing and erosion. The slurry with bad uniformity, by contract, increases Cu dishing significantly and causes copper loss in the recessed region. Therefore, the following conclusions are drawn： slurry B can improve the wafer leveling efficiently and minimize the resistance and current density along the line, which is helpful to improve the device yield and product reliability. This investigation provides a guide to improve the uniformity and achieve the global and local planarization. It is very significant to meet the requirements for 22 nm technology nodes and control the dishing and erosion efficiently.     

碱性铜抛光液在300mm平坦化系统中CMP工艺优化的研究

CMP process optimization for bulk copper removal based on alkaline copper slurry was performed on a 300 mm Applied Materials Reflexion LK system. Under the DOE condition, we conclude that as the pressure increases, the removal rate increases and non-uniformity is improved. As the slurry flow rate increases, there is no significant improvement in the material removal rate, but it does slightly reduce the WIWNU and thus improve uniformity. The optimal variables are obtained at a reduced pressure of 1.5 psi and a slurry flow rate of 300 ml/min. Platen/carrier rotary speed is set at a constant value of 97/103 rpm. We obtain optimized CMP characteristics including a removal rate over 6452 A/min and non-uniformity below 4% on blanket wafer and the step height is reduced by nearly 8000 A/min in the center of the wafer on eight layers of copper patterned wafer, the surface roughness is reduced to 0.225 nm.     

化学机械抛光制程中铜抛光液平坦化能力的评估

The evaluation methods of planarization capability of copper slurry are investigated.Planarization capability and material removal rate are the most essential properties of slurry.The goal of chemical mechanical polishing(CMP) is to achieve a flat and smooth surface.Planarization capability is the elimination capability of the step height on the copper pattern wafer surface,and reflects the passivation capability of the slurry to a certain extent.Through analyzing the planarization mechanism of the CMP process and experimental results,the planarization capability of the slurry can be evaluated by the following five aspects:pressure sensitivity,temperature sensitivity,static etch rate,planarization efficiency and saturation properties.     

ULSI多层铜布线钽阻挡层及其CMP抛光液的优化

分析了铜多层布线中阻挡层的选取问题,根据铜钽在氧化剂存在的情况下,抛光速率对pH值的不同变化趋势,提出优化碱性抛光液配比进而改变pH值,以达到铜钽抛光一致性的方法,并进行了相应的实验研究.     

三种胍盐对低磨料浓度碱性阻挡层抛光液性能的影响

The influence of three kinds of guanidinium salt on the removal rate selectivity of different materials was studied during the barrier chemical mechanical polishing(CMP) process at first.The three kinds of guanidine saltguanidine hydrochloride,guanidine nitrate and guanidine carbonate.Then we compared the effect of the three kinds of guanidine salt on the dishing,erosion and surface roughness value.In the end,the reaction mechanism was studied through electrochemical analysis.All the results indicate that there is a better performance of the slurry with guanidine hydrochloride than the slurries with the other two kinds of guanidine salt.It effectively improved the removal rate selectivity and the surface roughness under the premise of low abrasive concentration and low polishing pressure,which is good for the optimization of the alkaline slurry for the barrier CMP process.     

铜抛光液对片内非均匀性影响的研究

对于低介电常数材料和铜互连结构在低压化学机械抛光中,研发新的抛光液和调整工艺参数是非常必要的。抛光液的研发是减少抛光表面划伤和解决磨料剩余的关键。抛光液组成由片内非均匀性和铜抛光去除速率特性来优化。氧化剂浓度1Vol%;磨料浓度0.8Vol%;螯合剂浓度2Vol%。工作压力1kPa。抛光后表面缺陷减小并且表面干净无污染。去除速率289nm/min,片内非均匀性0.065。化学机械抛光后用原子力测量粗糙度为0.22 nm。     

Effect of copper slurry on polishing characteristics

The composition of the polishing solution is optimized by investigating the impact of the WIWNU (the so-called within-wafer-non-uniformity WIWNU) and the removal rate(RR) on the polishing characteristics of copper.The oxidizer concentration is 1 Vol%;the abrasive concentration is 0.8 Vol%;the chelating agent of the solution is 2 Vol%.The working pressure is 1 kPa.The defect on the surface is degraded and the surface is clean after polishing.The removal rate is 289 nm/min and the WIWNU is 0.065.The surface roughness measured by AFM after CMP(chemical mechanical planarization) is 0.22 nm.     

碱性Cu抛光液中非离子表面活性剂和氧化剂作用的研究

化学机械抛光是集成电路制造工艺中十分精密的技术。在本文中,为了改善抛光效果,分表讨论了非离子表面活性剂和氧化剂在CMP过程中作用。我们主要分析了非离子表面活性剂对片内非均匀性和表面粗糙度的影响。同时,我们从静态腐蚀速率、电化学曲线和剩余高低差的角度,讨论了在不加BTA条件下,不同氧化剂浓度的抛光液的钝化特性。实验结果明显地表明：加入了非离子表面活性剂的抛光液,更有利于改善抛光后的片内非均匀性和表面粗糙度,并确定2vol%体积分数是比较合适的浓度。当抛光液中氧化剂浓度超过3vol%,抛光液拥有较好的钝化能力,能够有效减小高低差,并有助于获得平整和光滑的表面。根据这些实验结果,非离子表面活性剂和氧化剂的作用进一步被了解,将有助于抛光液性能的改善。     

氮化钛阻挡层化学机械抛光液的研究

为了解决Cu互连线污染和形成高阻铜硅化物以及Cu与SiO2粘附性差等问题,提出增加扩散阻挡层的解决方案。主要关于氮化钛阻挡层化学机械抛光的研究。分析了氮化钛的抛光机理,研究了氧化剂浓度及抛光液的pH对抛光速率的影响,最后配制了适合氮化钛阻挡层的碱性抛光液。     

Electrochemical investigation of copper chemical mechanical planarization in alkaline slurry without an inhibitor

This work investigates the static corrosion and removal rates of copper as functions of H202 and FA/OIIconcentration, and uses DC electrochemical measurements such as open circuit potential （OCP）, Tafel ana- lysis, as well as cyclic voltammetry （CV） to study HaOa and FA/OIIdependent surface reactions of Cu coupon electrode in alkaline slurry without an inhibitor. An atomic force microscopy （AFM） technique is also used to measure the surface roughness and surface morphology of copper in static corrosion and polishing conditions. It is shown that 0.5 vol.% H202 should be the primary choice to achieve high material removal rate. The electro- chemical results reveal that the addition of FA/O II can dissolve partial oxide film to accelerate the electrochemical anodic reactions and make the oxide layer porous, so that the structurally weak oxide film can be easily removed by mechanical abrasion. The variation of surface roughness and morphology of copper under static conditions is consistent with and provides further support for the reaction mechanisms proposed in the context of DC electro- chemical measurements. In addition, in the presence of H202, 3 vol.% FA/O II may be significantly effective from a surface roughness perspective to obtain a relatively flat copper surface in chemical mechanical planarization （CMP） process.     

CMP中铜的碟形缺陷的研究

具体分析了铜的碟形缺陷并非由于抛光垫的弯曲造成,但是与抛光垫的表面形态有关,在此基础上,分析了铜CMP的作用机制,初步定性指出造成铜的碟形缺陷的原因,并对缺陷进行建模。比较了铜的碟形缺陷的电阻实际测量值和理论计算值,发现带碟形缺陷的电阻均大于理论值,并且随着铜的线宽增大,碟形缺陷也呈增大趋势。详细比较了选择性抛光液和非选择性抛光液对碟形缺陷的作用,从理论和测绘图形上证明选择性抛光液是造成碟形缺陷重要因素之一。采用了综合的工艺实验,最后得出抛光垫的种类及选择性抛光液在过抛光的情况下,是造成铜碟形缺陷的主要因素。     

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.     

Effects of pattern characteristics on copper CMP

Copper chemical mechanical polishing(CMP)is influenced by geometric characteristics such as line width and pattern density,as well as by the more obvious parameters such as slurry chemistry,pad type,polishing pressure and rotational speed.Variadons in the copper thickness across each die and across the wafer Can impact the circuit performance and reduce the yield.In this paper,we propose a modeling method to simulate the polishing behavior as a function of layout pattern factors.Under the same process conditions,the pattern density,the line width and the line spacing have a strong influence on copper dishing,dielectric erosion and topography.The test results showed:the wider the copper line or the spacing,the higher the copper dishing;the higher the density,the higher the dielectric erosion;the dishing and erosion increase slowly as a function of increasing density and go into saturation when the density is more than 0.7.     

版图图形特征对铜化学研磨的影响

Copper chemical mechanical polishing （CMP） is influenced by geometric characteristics such as line width and pattern density, as well as by the more obvious parameters such as slurry chemistry, pad type, polishing pressure and rotational speed. Variations in the copper thickness across each die and across the wafer can impact the circuit performance and reduce the yield. In this paper, we propose a modeling method to simulate the polishing behavior as a function of layout pattern factors. Under the same process conditions, the pattern density, the line width and the line spacing have a strong influence on copper dishing, dielectric erosion and topography. The test results showed： the wider the copper line or the spacing, the higher the copper dishing; the higher the density, the higher the dielectric erosion; the dishing and erosion increase slowly as a function of increasing density and go into saturation when the density is more than 0.7.     

铜布线化学机械抛光的失效研究

分析了铜电连接在今后晶片制造中的主导作用,阐述了铜布线的结构,即在由钽作为阻挡层及采用电镀铜形成的电连接的情况下,抛光规律符合经典普莱斯顿方程;在粗抛磨料采用氧化铝,精抛配比采用武亚红提出的方案情况下,采用旋转式低速较大下压力情况下抛光,整个晶片依然存在较大的不均匀性。分析100μm线宽的碟形缺陷会逐渐减小但最后会有少许增大。整个晶片的侵蚀会和其图案密度成正比,但在同种分布情况下,精抛时间越长,则侵蚀缺陷越大。最后指出了今后发展的高速底压力会显著解决当前不均匀性问题,但失效机制分析意义依然很重大。     

铜CMP中SiO2抛光液的凝胶及其消除实验

SiO2在不同的pH值抛光液中容易产生凝胶现象而使抛光液失效。通过控制实验时抛光液的pH值及加入适量的添加剂而使SiO2抛光液的凝胶问题得到解决。结果表明,当SiO2抛光液pH≤8时,产生凝胶;当SiO2抛光液pH≥9时,在抛光液中加入适量的活性剂和螯合剂,消除了SiO2凝胶现象,得到较好的抛光结果。