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     

铜CMP碱性抛光液中氧化剂的电化学行为研究

化学机械抛光(CMP)工艺是IC工艺中大马士革工序的关键步骤。抛光液的电化学行为研究对抛光质量的控制具有重要意义。采用电化学测试手段,研究碱性抛光液中氧化剂(H₂O₂)对铜表面钝化膜的成膜影响,分析H₂O₂对抛光速率、表面粗糙度的影响机理。通过实验确定,在0.5% SiO₂磨料和3% 表面活性剂的碱性抛光液中,添加0.5%的H₂O₂和3%的FA/OⅡ型螯合剂可获得大于800 nm/min的高抛光速率和表面粗糙度为22.2 nm的较佳平坦效果。     

抛光液中缓蚀剂对铜硅片的影响

以硝酸铁为氧化剂选用不同缓蚀剂对铜化学机械抛光用抛光液的缓蚀效果进行了研究.通过测试不同缓蚀剂作用下铜的电化学极化曲线,来获得的腐蚀电流值和计算不同缓蚀剂的缓蚀效率.采用表面粗糙度为1.42nm的铜硅片进行静腐蚀和抛光实验,利用ZYGO粗糙度仪测试了硅片表面的粗糙度变化,并采用原子力显微镜分析腐蚀表面形貌.研究结果表明,在以硝酸铁为氧化剂的酸性环境中,苯丙氮三唑(BTA)作为铜抛光液的缓蚀剂具有良好的缓蚀效果.根据电化学参数计算出1.5wt%硝酸铁溶液中添加0.1wt%BTA的缓蚀率达99.1%;无论在静腐蚀还是在抛光过程中,在抛光液中添加BTA均可避免硅片严重腐蚀,使表面光滑.     

ULSI铜布线阻挡层Ta CMP及抛光液的研究

ULSI多层铜互连线中,由于Cu与Ta的硬度不同带来抛光速率的差异,使得在CMP过程中各种缺陷如碟形坑缺陷、磨蚀缺陷极易发生。研究分析了H2O2、有机碱对Cu和Ta抛光速率的影响,并进行了不同抛光液配比的试验。实验证明,在温度为30℃、压力0.08 MPa,转速60 r/min、抛光液流量为160 mL/min、抛光液成份为V(H2O2)∶V(有机碱)∶V(活性剂)∶V(螯合剂)=5∶15∶15∶25时,抛光速率一致性较好,能够有效降低碟形坑的出现几率;Cu、Ta的抛光速率均为500 nm/min左右,实现了CMP的全局平坦化。     

新型碱性抛光液对300mm TaN镀膜片CMP效果评估

TaN由于其良好的性能广泛用于布线铜与介质之间的阻挡层和黏附层.在对直径为300 mm的TaN镀膜片进行化学机械抛光(CMP)后,对比并分析了两种碱性抛光液对TaN去除速率、片内非均匀性、去除速率选择性和表面粗糙度的影响.结果表明,经过自主研发且不合氧化剂的碱性阻挡层抛光液抛光后,TaN的去除速率为40.1 nm/min,片内非均匀性为3.04％,介质、TaN与Cu的去除速率之比为1.69∶1.26∶1,中心、中间以及边缘的表面粗糙度分别为0.371,0.358和0.366 nm.与商用抛光液抛光结果相比,虽然采用自主研发的抛光液抛光的去除速率低,但片内非均匀性以及选择性均满足商用要求,且抛光后TaN表面粗糙度小,易清洗,无颗粒沾污.综合实验结果表明,自主研发的高性能碱性抛光液对TaN镀膜片具有良好的抛光效果,适合工业生产.     

基于新型抛光液研究工艺参数对片内非均匀性的影响

基于正交实验研究了抛光压力、相对转速、抛光液体积流量和表面活性剂体积分数四个因素对抛光速率一致性的影响,采用方差分析确定各因素对抛光速率一致性的显著影响.研究结果表明:各因素对抛光速率一致性均有显著的影响.通过单因素实验研究了各因素对铜抛光速率一致性的影响规律,并阐述了相关的影响机制.实验结果表明:抛光压力和活性剂体积...     

抛光液中各组分对Co CMP性能的影响

钴(Co)的化学机械抛光(CMP)要求有较高的去除速率(大于100 nm/min)和洁净平整的表面。采用新型弱碱性抛光液,研究不同成分(如过氧化氢(H₂O₂)、1,2,4-三氮唑(TAZ)、异辛醇聚氧乙烯醚(JFCE))对Co CMP性能的影响。结果表明,抛光液中H₂O₂体积分数为0.4%、pH值为8、甘氨酸(GLY)浓度为0.266 mol/L时,Co的去除速率最大,为763.53 nm/min。为了缓解Co表面的化学腐蚀,加入0.022 mol/L的TAZ作为抑制剂和体积分数为1.3%的JFCE作为表面活性剂后,Co的去除速率得到有效抑制,为489.74 nm/min。对抛光前后的Co表面进行原子力显微镜(AFM)测试,结果表明,Co表面湿润性增加,表面粗糙度明显下降。研究结果对Co布线的工业应用具有一定的指导意义。     

碱性抛光液中H_2O_2对铜布线CMP的影响

化学机械平坦化(CMP)过程中,抛光液的化学作用对平坦化效果起着不可替代的作用。介绍了碱性抛光液中氧化剂(H2O2)对铜布线CMP的作用:H2O2对铜的强氧化性可以将铜氧化为离子状态,然后在螯合剂的螯合作用下快速去除铜膜;H2O2对铜的钝化作用可以保护凹处铜膜不被快速去除,从而有效降低高低差。此外,还研究了碱性抛光液中不同H2O2浓度对铜的静态腐蚀速率、动态去除速率及铜布线平坦化结果的影响。研究表明:抛光液对铜的静态腐蚀速率随H2O2浓度的增大逐渐降低然后趋于饱和;铜的动态去除速率随H2O2浓度的增大而逐渐降低;抛光液的平坦化能力随H2O2浓度的增大逐渐增强再趋于稳定。     

碱性抛光液对铜与钽CMP选择比的影响

在ULSI多层铜布线中,由于钽与铜在物理及化学性质上的差别导致这两者的CMP去除速率不同,从而在抛光结束后出现蝶形坑等缺陷,影响器件性能。通过实验分析碱性抛光液中磨料、螯合剂、氧化剂、pH值、活性剂对铜与钽CMP选择比的影响。根据铜与钽的CMP去除机理,从实验结果分析出对铜、钽去除速率影响较为明显的成分,调节这些成分得到特定配比的抛光液,分别实现了铜与钽的去除速率相等、铜的去除速率大于钽、铜的去除速率小于钽。使用上述铜去除速率小于钽的抛光液对12英寸(1英寸=2.54 cm)图形片进行抛光,通过原子力显微镜观察,证明了这种抛光液能有效地修复多层布线CMP中的蝶形坑等缺陷。     

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.     

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.     

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.     

碱性铜粗抛液中氧化剂对化学机械平坦化的影响

针对不合腐蚀抑制剂苯并三氮唑(BTA)的碱性铜粗抛液,通过对3英寸(1英寸=2.54 cm)铜片上的动态抛光速率和静态腐蚀速率的研究来模拟评估氧化剂对晶圆表面平坦化的影响.在12英寸铜镀膜片和TM1图形片上分别研究氧化剂体积分数对表面平坦化的影响.实验结果表明:动态抛光速率和静态腐蚀速率均随着氧化剂体积分数的增加先逐渐增大,达到最大值,然后下降,趋于平缓.片内非均匀性和剩余高低差均随H2O2体积分数的增加,先呈下降趋势,后缓慢上升.当氧化剂体积分数为3％时,动态去除速率(vRR)为398.988 nm/min,静态腐蚀速率vER为6.834 nm/min,vRR/vER比值最大,片内非均匀性最小为3.82％,台阶高低差最小为104.6 nm/min,此时晶圆片有较好的平坦化效果.     

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。     

在铜CMP过程中降低抛光压力与磨料的机械作用

Chemical mechanical planarization(CMP) is a critical process in deep sub-micron integrated circuit manufacturing. This study aims to improve the planarization capability of slurry, while minimizing the mechanical action of the pressure and silica abrasive. Through conducting a series of single-factor experiments, the appropriate pressure and the optimum abrasive concentration for the alkaline slurry were confirmed. However, the reduced mechanical action may bring about a decline of the polishing rate, and further resulting in the decrease of throughput.Therefore, we take an approach to compensating for the loss of mechanical action by optimizing the composition of the slurry to enhance the chemical action in the CMP process. So 0.5 wt% abrasive concentration of alkaline slurry for copper polishing was developed, it can achieve planarization efficiently and obtain a wafer surface with no corrosion defect at a reduced pressure of 1.0 psi. The results presented here will contribute to the development of a “softer gentler polishing” technique in the future.     

A new weakly alkaline slurry for copper planarization at a reduced down pressure

This study reports a new weakly alkaline slurry for copper chemical mechanical planarization （CMP）, it can achieve a high planarization efficiency at a reduced down pressure of 1.0 psi. The slurry is studied through the polish rate, planarization, copper surface roughness and stability. The copper polishing experiment result shows that the polish rate can reach 10032 A/rain. From the multi-layers copper CMP test, a good result is obtained, that is a big step height （10870 A） that can be eliminated in just 35 s, and the copper root mean square surface roughness （sq） is very low （〈 1 rim）. Apart from this, compared with the alkaline slurry researched before, it has a good progress on stability of copper polishing rate, stable for 12 h at least. All the results presented here are relevant for further developments in the area of copper CMP.     

碱性铜精抛液中表面活性剂ADS对平坦化效果的影响

研究了阴离子表面活性剂十二烷基硫酸铵(ADS)在弱碱性铜抛光液中对晶圆平坦化效果的影响.对不同质量分数的阴离子表面活性剂ADS下的抛光液表面张力、铜去除速率、抛光后铜膜的碟形坑高度、晶圆片内非均匀性和表面粗糙度进行了测试.实验结果表明,当阴离子表面活性剂ADS的质量分数为0.2％时,抛光液的表面张力降低,铜的去除速率为202.5 nm·min-1,去除速率片内非均匀性减小到4.15％,抛光后铜膜的碟形坑高度从132 nm降低到68.9 nm,表面粗糙度减小到1.06 nm.与未添加表面活性剂相比,晶圆表面的平坦化效果得到改善.     

低磨料浓度的碱性铜抛光液平坦化性能的研究

A novel alkaline copper slurry that possesses a relatively high planarization performance is investigated under a low abrasive concentration.Based on the action mechanism of CMP,the feasibility of using one type of slurry in copper bulk elimination process and residual copper elimination process,with different process parameters,was analyzed.In addition,we investigated the regular change of abrasive concentration effect on copper and tantalum removal rate and within wafer non-uniformity(WIWNU) in CMP process.When the abrasive concentration is 3 wt%,in bulk elimination process,the copper removal rate achieves 6125 °/min,while WIWNU is 3.5%,simultaneously.In residual copper elimination process,the copper removal rate is approximately 2700°/min,while WIWNU is 2.8%.Nevertheless,the tantalum removal rate is 0 °/min,which indicates that barrier layer isn’t eliminated in residual copper elimination process.The planarization experimental results show that an excellent planarization performance is obtained with a relatively high copper removal rate in bulk elimination process.Meanwhile,after residual copper elimination process,the dishing value increased inconspicuously,in a controllable range,and the wafer surface roughness is only 0.326 nm(sq < 1 nm) after polishing.By comparison,the planarization performance and surface quality of alkaline slurry show almost no major differences with two kinds of commercial acid slurries after polishing.All experimental results are conducive to research and improvement of alkaline slurry in the future.     

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.     

新型碱性抛光液各组分对铜化学机械平坦化性能的影响

随着集成电路特征尺寸的减小、晶圆尺寸的增大以及布线层的逐渐增多,加工晶圆过程中实现较高的材料去除速率、较小的片内非一致性(WIWNU)及较小的表面粗糙度已经成为铜化学机械抛光工艺的几大难点.采用正交实验法选取5组抛光液进行Cu CMP实验,系统研究了含有双氧水、脂肪醇聚氧乙烯醚(AEO)、FA/O Ⅰ型螯合剂与苯骈三氮唑(BTA)的碱性抛光液化学组分对铜去除速率、WIWNU的影响,并对铜CMP的各种变化规律做出机理分析.结果表明:采用pH值约为8.6,体积分数为3％的H202,质量分数为0.08％的非离子表面活性剂AEO与体积分数为1.5％的螯合剂的碱性抛光液,在12英寸(1英寸=2.54 cm)铜镀膜片抛光后有助于去除速率达到629.1 nm/min,片内非一致性达到4.7％,粗糙度达到1.88 nm.