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.     

新型GLSI弱碱性铜抛光液稳定性研究

随着极大规模集成电路(GLSI)技术节点逐渐降低至28 nm,多层铜布线化学机械抛光过程中弱碱性抛光液的稳定性成为人们研究的热点.以四乙基氢氧化铵作为pH调节剂,配制不同pH值的新型弱碱性抛光液,研究各组抛光液的pH值、粒径、Zeta电位以及铜去除速率、表面粗糙度和去除速率一致性随存放时间(0,12,24,36和48 h)的变化,并与KOH作为pH调节剂的抛光液进行了对比.结果表明,pH值、粒径、Zeta电位在存放时间内基本不变.pH值大于10时平坦化效果较差,pH值为9.0时,平坦化效果较好,0和48 h铜去除速率为530 nm/min和493.1 nm/min,抛光后铜表面粗糙度为0.718和0.855 nm,铜去除速率一致性为4.31％和4.54％,该抛光液加入双氧水后可以稳定存放48 h以上,可满足工业生产的要求.     

Effect of 1,2,4-triazole on galvanic corrosion between cobalt and copper in CMP based alkaline slurry

Cobalt has become a new type of barrier material with its unique advantages since the copper-interconnects in the great-large scale integrated circuits (GLSI) into 10 nm and below technical nodes,but cobalt and copper have severe galvanic corrosion during chemical-mechanical flattening.The effect of 1,2,4-triazole on Co/Cu galvanic corrosion in alkaline slurry and the control of rate selectivity of copper and cobalt were investigated in this work.The results of electrochemical experiments and polishing experiments had indicated that a certain concentration of 1,2,4-triazole could form a layer of insoluble and dense passive film on the surface of cobalt and copper,which reduced the corrosion potential difference between cobalt and copper.Meantime,the removal rate of cobalt and copper could be effectively controlled according to demand during the CMP process.When the study optimized slurry was composed of 0.5 wt％ colloidal silica,0.1％vol.hydrogen peroxide,0.05 wt％ FA/O,345 ppm 1,2,4-triazole,cobalt had higher corrosion potential than copper and the galvanic corrosion could be reduced effectively when the corrosion potential difference between them decreased to 1 mV and the galvanic corrosion current density reached 0.02 nA/cm2.Meanwhile,the removal rate of Co was 62.396 nrn/min,the removal rate of Cu was 47.328 nm/min,so that the removal rate ratio of cobalt and copper was 1.32:1,which was a good amendment to the dishing pits.The contact potential corrosion of Co/Cu was very weak,which could be better for meeting the requirements of the barrier CMP.     

配置一种不加BTA和氧化剂的弱碱性阻挡层抛光液的机理分析

在阻挡层化学机械抛光中,实现可控的铜,钽,介质去除速率选择比是一项挑战。双氧水作为氧化剂加上BTA作为抑制剂的作用被认为是一种有效的方法。但是,由于双氧水易于分解使得含有双氧水的抛光液使用寿命短。另外,BTA对抛光后清洗带来挑战：在片子表面残留有毒的有机物和颗粒。最近,我们一直致力于研究一种不加氧化剂和BTA的阻挡层抛光液。在这些工作的基础上,本文的目的是通过实验研究抛光液中不同的组分（包括硅溶胶,FA/O螯合剂,溶液PH,硝酸）胍）对铜,钽,介质去除速率的影响来讨论配置这种新型的不加BTA和氧化剂的阻挡层抛光液的机理。相关可能的抛光机也会在本论文中提出。     

ULSI中多层Cu布线CMP表面粗糙度的分析和研究

分析介绍了Cu层表面粗糙度对器件性能的影响以及超大规模集成电路中多层Cu布线CMP的作用机理,研究分析了碱性抛光液对Cu的表面粗糙度的影响因素,如磨料、氧化剂、pH值、表面活性剂等对表面粗糙度的影响。实验证明,在一定的抛光条件下,选用SiO2为磨料、双氧水为氧化剂的碱性抛光液可以有效降低Cu层的表面粗糙度,使之达到纳米级,得到良好的抛光效果,从而解决了超大规模集成电路多层Cu布线化学机械抛光中比较重要的技术问题。     

碱性多羟多胺螯合剂对Cu CMP后BTA去除作用及机理

苯并三唑(BTA)在微电子领域常被用于铜抛光液中的抗蚀剂,抛光后的BTA残留需要通过化学机械抛光(CMP)后清洗工序从晶圆表面去除,否则会影响器件的性能.通过实验研究了碱性多羟多胺类螯合剂对抛光后晶圆表面残留BTA的去除效果及机理.首先通过傅里叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)研究了BTA在铜表面的吸附状态,发现铜表面的氧化程度会影响BTA在晶圆表面的吸附状态;然后采用体积分数为0.02％、pH值为10.3的碱性多羟多胺螯合剂去除铜表面BTA薄膜.FTIR和XPS测试结果显示,碱性多羟多胺螯合剂可以有效去除铜表面BTA薄膜;最后,通过实验数据研究了碱性多羟多胺螯合剂去除BTA的机理.     

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.     

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.     

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。     

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.     

新型碱性阻挡层抛光液对铜布线化学机械平坦化的评估研究

化学机械平坦化(CMP)是铜互连制备过程中唯一的全局平坦化技术。但是由于互连线铜与扩散阻挡层物理及化学性质上的差异,在阻挡层的化学机械平坦化过程中将加剧导致碟形坑的产生。目前,国际上抛光液以酸性为主,但是其存在固有的问题,如酸性气体挥发,腐蚀严重等。本论文研发出一种新型碱性阻挡层抛光液,与商用的阻挡层抛光液做对比,评估了其抛光性能。实验结果表明,新型碱性阻挡层抛光液抛光后表面状态好,粗糙度较低。另外,碟形坑及电阻测试结果表明,新型碱性阻挡层抛光后铜布线的表面形貌好,碟形坑小,能够应用于铜布线阻挡层的CMP中。     

用于硬盘NiP基片CMP的一种碱性SiO_2抛光液

在NiP基片的化学机械抛光中,针对现有酸性抛光液存在的易腐蚀、易污染和以Al2O3为磨料造成易划伤表面的质量问题,尝试使用SiO2水溶胶作为抛光磨料,通过加入非离子表面活性剂和螯合剂等,配制成一种碱性环境下的硬盘基片抛光液。通过化学机械抛光试验,发现这种碱性SiO2抛光液在硬盘NiP基片抛光中具有250nm/min的抛光速率,抛光后的表面粗糙度为0.8nm,表面光滑,几乎观察不到划痕及其他微观缺陷。     

GLSI多层铜布线CMP后BTA去除研究

本文通过静态腐蚀速率的方法分析确立了碱性清洗剂中FA/OⅡ型螯合剂和FA/OⅠ型表面活性剂对BTA的去除规律。通过单因素实验和复合清洗剂的实验优化,确定了去除BTA的清洗剂配方,并通过接触角实验进一步证实实验结果的有效性。最后,将优化后的清洗剂配方在实际生产线上做试验,结果表明能有效去除BTA、CuO晶粒及磨料SiO2,且基本无界面腐蚀。解决了一直难以解决的多层铜布线CMP后有效去除BTA的难题,且该清洗剂成分简单,成本低而且环保。     

非离子型活性剂在ULSI碱性Cu抛光液中的性能

使用四种非离子表面活性剂分别添加到以SiO2水溶胶为磨料、H2O2为氧化剂的碱性Cu抛光液中进行抛光实验.结果表明,所选用的非离子型表面活性剂对材料去除率的影响不大,当烷基酚聚氧乙烯醚在质量分数为0.25%时,抛光表面质量提高,表面粗糙度(Ra)由1.354 nm下降到了0.897 6 nm,同时有效地减轻了Cu抛光表面的划痕和腐蚀,其原因是聚氧乙烯链可以通过醚键与水分子形成氢键,在聚氧乙烯周围形成一层溶剂化的水膜保护了被吸附表面.     

GLSI钨插塞CMP碱性抛光液组分优化的研究

钨插塞化学机械平坦化(CMP)是极大规模集成电路(GLSI)铜互连多层布线的关键工艺之一。首先研究了钨在碱性条件下化学机械抛光机理;接着采用单因素实验方法分析了抛光液组分中纳米SiO2水溶胶磨料、氧化剂、有机碱(pH调节剂)和表面活性剂对W-CMP速率的影响。最后通过正交优化实验,确定抛光液最优配比为V(纳米SiO2水溶胶)∶V(去离子水)=1∶1,氧化剂体积分数为20 mL/L,pH调节剂体积分数为4 mL/L,表面活性剂体积分数为20 mL/L时,此时抛光液的pH值为10.36,获得的去除速率为85 nm/min,表面粗糙度为0.20 nm。     

Influence of slurry components on uniformity in copper chemical mechanical planarization

Many researchers studying copper chemical mechanical planarization (CMP) have been focused on mechanisms of copper removal using various chemicals. On the basis of these previous works, we studied the effect of slurry components on uniformity. Chemical mechanical planarization of copper 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. As citric acid was added to copper CMP slurry (pH 4) containing 3 vol% hydrogen peroxide and 3 wt% colloidal silica, the material removal (MRR) at the wafer center was higher than its edge. Hydrogen peroxide could not induce a remarkable change in the profile of MRR. Colloidal silica, used as an abrasive in copper CMP slurry containing 0.01 M of citric acid and 3 vol% of hydrogen peroxide, controlled the profile of MRR by abrading the wafer edge. BTA as a corrosion inhibitor decreased the MRR and seems to control the material removal around the wafer center. All the results of in this study showed that the MRR profile of copper CMP could be controlled by the contents of slurry components.     

不同压力下螯合剂浓度在碱性Cu CMP中的影响

We propose the action mechanism of Cu chemical mechanical planarization(CMP) in an alkaline solution.Meanwhile,the effect of abrasive mass fraction on the copper removal rate and within wafer non-uniformity(WIWNU) have been researched.In addition,we have also investigated the synergistic effect between the applied pressure and the FA/O chelating agent on the copper removal rate and WIWNU in the CMP process.Based on the experimental results,we chose several concentrations of the FA/O chelating agent,which added in the slurry can obtain a relatively high removal rate and a low WIWNU after polishing,to investigate the planarization performance of the copper slurry under different applied pressure conditions.The results demonstrate that the copper removal rate can reach 6125 °/min when the abrasive concentration is 3 wt.%.From the planarization experimental results,we can see that the residual step height is 562 ° after excessive copper of the wafer surface is eliminated.It denotes that a good polishing result is acquired when the FA/O chelating agent concentration and applied pressure are fixed at 3 vol% and 1 psi,respectively.All the results set forth here are very valuable for the research and development of alkaline slurry.     

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。     

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.     

Acid colloidal silica slurry for Cu CMP

Semi-abrasive free slurry for copper chemical mechanical planarisation (CMP) with below 0.5% acid colloidal silica provides good hydrogen peroxide stability, excellent colloidal silica dispersion ability and easiness of post-CMP cleaning. This approach may be useful for the application of singleand first-step copper CMP slurry with one package system.