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.     

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。     

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.     

铜化学机械抛光材料去除机理研究

本文根据铜CMP过程中表面材料的磨损行为,建立了铜CMP时的材料去除率构成成分模型,并通过材料去除率实验,得出了各机械、化学及其交互作用所引起的材料去除率及其作用率:当np=nw=200r/min时,有最佳材料去除率,此时单纯的机械作用率为9.2%;单纯的化学作用率为仅为2.1%,抛光垫的机械与化学交互作用率为5.08%;磨粒的机械与化学交互作用率为83.6%。通过对实验结果进行分析,可得如下结论:硅片化学机械抛光中,一定的参数下有一个最优的抛光速度;在最优的速度下,机械与化学之间交互作用达到平衡,这时可获得最高的材料去除率;硅片化学机械抛光过程是一个多变的动态过程,仅仅通过增加机械作用或化学作用不能获得理想的材料去除效果。本文的研究结果可为进一步研究硅片CMP时的材料去除机理提供理论参考依据。     

基于叶序仿生抛光垫的化学机械抛光的运动分析

为了改善化学机械抛光的接触状态和被加工工件的表面形态,基于生物学的叶序理论设计了仿生结构的抛光垫。从单颗磨粒切削理论出发,建立了抛光运动方程和材料去除率分布模型。利用所建立的运动方程和材料去除率分布模型进行了晶片表面材料去除率分布的计算分析,得到抛光机的运动参数及抛光垫的叶序参数对材料去除率的影响规律。结果表明:当抛光盘的转速较大、工件转速适中、摆臂摆动频率较小、摆臂中心角较小及叶序参数取值较小时可以获得更好的材料去除分布。     

硒化锌晶体精细雾化抛光液及去除机理研究

目的配制适合硒化锌雾化施液化学机械抛光的最优抛光液。方法选取氧化铝磨粒、pH调节剂四甲基氢氧化铵、氧化剂过氧化氢、表面活性剂聚乙烯吡咯烷酮为主要活性成分,以材料去除速率和表面粗糙度为评价指标,通过正交试验对硒化锌晶体进行精细雾化抛光,分析材料去除机理,并与传统抛光对比。结果氧化铝质量分数为9%、pH值为11、过氧化氢含量为3.5%、聚乙烯吡咯烷酮含量为0.75%时,材料去除率较高,为923.67 nm/min,同时表面粗糙度较小,为2.13 nm。在相同工况条件下,传统抛光材料的去除率和表面粗糙度分别为965.53 nm/min和2.27 nm。结论抛光液各组分对试验结果影响最大的为氧化铝磨粒,然后依次为氧化剂、pH值、表面活性剂。精细雾化抛光效果与传统抛光相近,但抛光液用量仅为后者的1/8。     

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.     

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。     

用碱性抛光液化学机械抛光304不锈钢片研究

为提高化学机械抛光的加工效果,我们研究了pH值、氧化剂种类和氧化剂含量对材料去除率和表面粗糙度的影响。结果表明:不同氧化剂的抛光液在各自的最佳pH值时达到最大的材料去除率,分别为181 nm/min（H₂O₂抛光液,pH=9）,177 nm/min（Cr₂O₃抛光液,pH=11）,172 nm/min（Na₂Cr₂O₇抛光液,pH=11）和147 nm/min（NaClO抛光液,pH=13）;抛光液中氧化剂含量、pH值对抛光后不锈钢的表面粗糙度影响较小。其中,材料去除率较高的H₂O₂和Cr₂O₃可作为304不锈钢化学机械抛光碱性抛光液的氧化剂。      

Process state estimation in chemical mechanical polishing (CMP) by inverse analysis of in-process data

This study proposed a new technique for model-based estimation of the dynamic process state in chemical mechanical polishing (CMP). There is an uneven distribution of material removal efficiency the wafer surface, which further changes with processing time. Considering Preston's law, the linear relationship between the polishing force and material removal rate was modeled. Inverse analysis was conducted to identify motor torques of the CMP machine, material removal rate profile, and model parameters to estimate the dynamic process state in CMP. Moreover, the uneven distribution of the material removal efficiency and its dynamic variation were experimentally verified.     

精细雾化Cu-CMP抛光液抛光效果的试验研究

以磨料白炭黑、氧化剂H2O2、有机碱三乙醇胺、分散剂聚乙二醇为原料,通过正交设计的方法配制一系列抛光液,通过四甲基氢氧化铵调节抛光液的pH值为12,然后在研磨抛光机上对铜片进行超声波精细雾化化学机械抛光（CMP）。对抛光盘转速与材料去除率的关系进行了研究,并对传统抛光和雾化抛光效果进行了对比。试验结果表明,分散剂、白炭黑、有机碱、氧化剂对抛光去除率的影响依次减弱。随着抛光盘转速的增加,雾化抛光的去除率经历了先缓慢增加、再急剧增加、后缓慢增加的变化过程。在同等的试验条件下,传统抛光的去除率为223 nm/min,铜片表面粗糙度为7.93 nm,雾化抛光去除率和铜片表面粗糙度分别为125 nm/min和3.81 nm;虽然去除率略有不及前者,但抛光液用量仅为前者的十几分之一。     

抛光液pH值、温度和浓度对蓝宝石抛光效率的影响

目的研究抛光液pH值、温度和浓度对化学机械抛光蓝宝石去除率的影响,以提高抛光效率。方法采用CP4单面抛光试验机对直径为50.8 mm C向蓝宝石晶元进行化学机械抛光,通过电子分析天平对蓝宝石抛光过程中的材料去除率进行了分析,采用原子力显微镜(AFM)对蓝宝石晶元抛光前后的表面形貌和粗糙度(Ra)进行了评价。结果蓝宝石在化学机械抛光过程中的材料去除率均随抛光液pH值和温度的升高呈先增大后减小趋势。当抛光原液与去离子水按1:1的体积比混合配制抛光液,KOH调节pH值为12.2,水浴加热抛光液35℃时,蓝宝石抛光的材料去除率(MRR)达到1.119μm/h,Ra为0.101 nm。结论随着pH的增大,化学作用逐渐增强,而机械作用逐渐减弱,在pH为12.2的时候能达到平衡点,此时的MRR最佳;随着温度的升高,化学作用逐渐增强,而机械作用保持不变,抛光液温度为35~40℃时,化学作用与机械作用达到平衡,MRR最佳,当温度高于40℃后,抛光液浓度明显增大,而过高的浓度会导致MRR的减小。抛光液的相关性能优化后,化学机械抛光蓝宝石的MRR较优化前提高了71.4%。     

紫外光催化辅助SiC抛光过程中化学反应速率的影响

目的为了探究紫外光催化辅助抛光过程中,化学反应速率对SiC化学机械抛光的影响规律。方法通过无光照、光照抛光盘和光照抛光液3种光照方式,研究紫外光催化辅助作用对单晶SiC抛光过程中材料去除率的影响。测量不同条件下光催化反应过程中的氧化还原电位(ORP)值,来表征光催化反应速率,并进行了单晶SiC的紫外光催化辅助抛光实验,考察光催化反应速率对抛光效果的影响规律。结果实验表明,引入紫外光催化辅助作用后,材料去除率提高14%～20%,随着材料去除率的增加,光催化辅助作用对材料去除率的影响程度变小。光照射抛光液方式的材料去除率明显高于光照射抛光盘。不同条件下的抛光结果显示,化学反应速率越快,溶液的ORP值越高,材料去除率越大,表面粗糙度越低。在光照抛光液、H_2O_2体积分数4.5%、TiO_2质量浓度4 g/L、光照强度1500 mW/cm~2、pH=11的条件下,用W0.2的金刚石磨料对SiC抛光120 min后,能够获得表面粗糙度Ra=0.269 nm的光滑表面。结论在单晶SiC的紫外光催化辅助抛光过程中,光催化反应速率越快,溶液ORP值越高,抛光效率越高,表面质量越好。在H_2O_2浓度、TiO_2浓度、光照强度、pH等4个因素中,对抛光效果影响最大的是H_2O_2浓度,光照强度主要影响光催化反应达到稳定的时间。     

紫外光催化辅助Ga面GaN化学机械抛光试验研究

目的 探究在紫外光催化辅助抛光过程中,相关因素对氮化镓晶片Ga面去除率(MRR)及表面粗糙度(Ra)的影响规律,提高单晶氮化镓高效率低损伤的超光滑表面质量。方法 通过结合紫外光与化学机械进行抛光,采用单因素试验方案,对GaN晶片的Ga面进行紫外光催化辅助化学机械抛光试验,比较在无光照、光照抛光盘、光照抛光液3种抛光方式和不同TiO₂浓度、pH值、H₂O₂含量、抛光压力、抛光盘转速和抛光液流条件下的抛光效果。最后通过正交试验进行抛光工艺参数优化,通过测量不同条件下紫外光催化辅助化学机械抛光过程中的MRR值和Ra值,探究GaN晶片Ga面抛光效果。结果在紫外光催化辅助抛光条件下,通过对单因素试验和正交试验的抛光参数进行分析和优化,GaN晶片材料去除率可以达到698.864nm/h,通过白光干涉仪观测可以获得表面粗糙度Ra值为0.430nm的亚纳米级超光滑GaN晶体表面。结论 基于紫外光催化辅助GaN晶片Ga面化学机械抛光试验,紫外光辅助化学机械的复合抛光方式能够促进GaN表面生成物Ga₂O₃     

络合剂对316L不锈钢化学机械抛光效果的影响

为提高316L不锈钢化学机械抛光（chemical-mechanical polishing,CMP）效率,针对络合剂类型对316L不锈钢加工效果的影响及影响机制进行研究。以材料去除率（material removal rate,MRR）和表面粗糙度（R_a）为指标,探究络合剂类型（甘氨酸、草酸和柠檬酸）及浓度对抛光效果的影响。利用电化学工作站、接触角测量仪和X射线光电子能谱仪（XPS）分析络合剂对316L不锈钢CMP加工影响机制。结果表明:当甘氨酸质量分数为0.2%时,能够同时获得较高的材料去除率和较低的R_a,分别为210 nm/min和1.613 nm。高浓度的络合剂对316L不锈钢材料去除率的抑制作用来源于络合剂增强了316L不锈钢表面耐蚀性,降低了表面氧化速度。XPS分析表明部分甘氨酸络合物会吸附于316L不锈钢表面产生缓蚀作用。      

Tribological approaches to material removal rate during chemical mechanical polishing

In this study, the effect of the friction and wear of a polishing pad on the material removal rate of a silicon oxide wafer was investigated during chemical mechanical polishing (CMP) with ceria slurry. Further, the effect of surface properties of the polishing pad, such as surface roughness and hardness, on the variation in the material removal rate was examined. From a tribological viewpoint, the in-situ friction force was monitored during the CMP process, and wear of the polishing pad was controlled by different types of conditioners. After CMP, the pad surface roughness was measured by optical profiling and scanning electron microscopy. Experimental results showed that the material removal rate was almost linearly proportional to the friction force between the pad and the wafer surface, irrespective of the properties of the pad. Experiments on the dependency of the pad wear rate on the material removal rate showed that the material removal rate increased with a decrease in the pad wear rate. Experiments and pad characterization confirmed that such a correlation was attributed to the pad surface roughness and the friction force.     

6H-SiC单晶紫外光催化抛光中光照方式和磨料的影响

研究紫外光辅助催化抛光6H-SiC单晶。用分光光度法定性检测不同光催化反应时间下甲基橙颜色变化和羟基自由基(·OH)浓度,研究无光照、光照抛光盘、光照抛光液3种光照方式及金刚石、碳化硅、二氧化硅、二氧化钛、硅溶胶5种磨料对6H-SiC单晶抛光的影响。结果表明:随着光照时间增加,·OH浓度增加;在3种光照方式下,不同磨料的材料去除率(MRR)均呈现光照抛光液>光照抛光盘>无光照的规律,且光照抛光液时的MRR比无光照时的MRR提升了18%～58%。随磨料硬度降低,光催化辅助作用对MRR的提高幅度升高,即紫外光催化辅助作用越明显;金刚石、碳化硅、二氧化硅、硅溶胶4种磨料抛光后的表面粗糙度都随MRR的增大而减小,但二氧化钛磨料的则相反,原因是二氧化钛磨料同时兼作光催化剂,增强了SiC表面的化学反应速率,使其化学反应速率大于机械去除速率。      

基于多源数据融合的半导体晶片CMP抛光材料去除率预测

目的 对半导体晶片抛光过程中的工艺参数、耗材使用量、抛光垫状态参数等多源数据预处理后进行数据融合,建立材料去除率(MRR)预测模型,为实现半导体晶片抛光加工工艺的决策和处理奠定基础。方法 研究晶片抛光加工中的数据特点及数据融合需求,提取数据集中每个晶片加工过程中的统计特征并生成新数据集,同时引入邻域特征以应对晶片加工过程中动态因素对材料去除率的影响。提出基于深度自动编码器的多源数据融合及材料去除率预测方法。设计深度自动编码器参数,优化深度自动编码器的损失函数从而增强深度自动编码器对强相关性特征变量的重建。基于深度自动编码器进行多源传感器信号融合,降低数据维度。使用超参数搜索算法优化BP神经网络超参数,利用BP神经网络方法将融合后的数据进行半导体晶片抛光过程中的材料去除率预测。结果 采用PHM2016数据集对模型进行验证,均方误差MSE达到7.862,相关性R²达到91.2%。结论 基于多源数据的融合模型能有效预测MRR,可以对半导体晶片CMP工艺过程的智能决策与控制起到良好的辅助作用。     

Shear-thickening polishing method

A shear-thickening polishing (STP) method utilizing the shear thickening mechanism of non-Newtonian power-law fluid based slurry is proposed for curved surface polishing. The STP principle and micro-material removal action are analyzed. The high-performance STP slurry with the shear-thickening rheological behaviors has been prepared. To achieve the material removal mechanism of STP process, based on the Preston formula, fluid dynamics and shear thickening mechanism, the material removal rate (MRR) model is established and the difference of MRR between theoretical and experimental results is 6.12%. The experimental and theoretical tests of STP process are conducted to investigate the influences of polishing velocity, abrasive concentration and grain size on MRR and surface roughness. Compared with Newtonian fluid slurry, STP slurry can achieve much higher MRR and better surface quality due to shear-thickening effect. MRR of Cr12Mo1V1 (die steel) is up to 13.69 μm/h, and surface roughness is reduced from R_a 105.95 nm to R_a 5.1 nm within 0.5 h of processing. This indicates that STP is a promising processing method for precision finishing or polishing.     

固结磨料抛光垫的凸起图案对其加工性能的影响

抛光垫是化学机械抛光中的重要组成部分,其磨损均匀性能是影响加工后工件平面度的重要因素。本文比较了具有优化凸起图案的固结磨料抛光垫、凸起均布的固结磨料抛光垫和聚氨酯抛光垫的研磨抛光性能,结果表明:利用优化凸起图案的固结磨料抛光垫加工,可以得到更加优异且稳定的表面质量,材料去除效率远高于聚氨脂抛光垫游离磨料的加工方式。