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.     

铜互连制程中酸碱性抛光液的平坦化效果评估

We observed and analyzed the acid and HEBUT alkaline of Cu chemical mechanical polishing(CMP)slurry to evaluate their effects. Material analysis has shown that the planarity surfaces and the removal rate of alkaline slurry are better than the acid slurry during metal CMP processes. The global surface roughness and the small-scale surface roughness by 1010 m2 of copper film polished by the SVTC slurry are 1.127 nm and2.49 nm. However, it is found that the surface roughnesses of copper films polished by the HEBUT slurry are 0.728 nm and 0.215 nm. All other things being equal, the remaining step heights of copper films polished by the SVTC slurry and HEBUT slurry are respectively 150 nm and 50 nm. At the end of the polishing process, the dishing heights of the HEBUT slurry and the SVTC slurry are approximately both 30 nm, the erosion heights of the HEBUT slurry and the SVTC slurry are approximately both 20 nm. The surface states of the copper film after CMP are tested,and the AFM results of two samples are obviously seen. The surface polished by SVTC slurry shows many spikes.This indicates that the HEBUT alkaline slurry is promising for inter-level dielectric(ILD) applications in ultra large-scale integrated circuits(ULSI) technology.     

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.     

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.     

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.     

低PH值螯合剂在TSV抛光液中的应用

硅通孔技术(Through Silicon Via,TSV)是一种新兴的技术,与传统的封装技术相比,硅通孔技术实现了芯片的微型化,并且使摩尔定律得以进一步扩展。化学机械抛光(CMP)是TSV技术中的关键步骤之一,低压低磨料低PH值是CMP抛光液的主要发展趋势。本文研究了含有FA / O II型螯合剂的抛光液和含有FA / O IV型螯合剂的抛光液在CMP过程中的影响。本实验中使用的抛光液都是碱性抛光液,并且不含任何抑制剂。对比实验结果我们可以知道不论是在铜膜的去除速率还是抛光后铜膜表面的粗糙度,低PH值的FA / O IV型螯合剂都明显优于FA / O II类螯合剂。     

碱性阻挡层CMP后铜布线粗糙度的影响机理分析

The surface roughness seriously affects the performance of devices after barrier CMP. Due to the high surface roughness of copper line, the local resistance of a device will be high when working, then the copper line will overheat prompting the generation of electro-migration and the circuit will lose efficacy. Reducing the surface roughness of the copper line in barrier CMP is still an important research topic. The main factors influencing the surface roughness of copper line in alkaline barrier slurry are analyzed in the paper. Aimed at influencing the law on the surface roughness of copper line, using a new type of alkaline barrier slurry with a different p H of the chelating agent and changing the content of non-ionic surfactant, we then analyze the influencing law both on the surface roughness of copper line, and the influence mechanism. The experimental results show that with a chelating agent with a low p H value in the barrier slurry, the surface roughness of the copper line is 1.03 nm and it is the lowest in all of the barrier slurries, and with the increase of non-ionic surfactant concentration, the surface roughness of copper line is reduced to 0.43 nm, meeting the demand of further development of integrated circuits.     

CMP碱性抛光液中的各组成成分对抛光速率影响程度的量化研究

本文结合神经网络和人工蜂群算法提出了CMP铜抛光速率预测模型,根据该模型,采用敏感性分析方法定量研究了碱性铜抛光液中的各成分（螯合剂、氧化剂、磨料和活性剂）及其交互作用对抛光速率的影响。结果表明：螯合剂、氧化剂、磨料和活性剂对抛光速率的相对影响系数分别为0.78、0.53、0.29、0.19;当抛光液中螯合剂和氧化剂含量的比例在2-7之间时,其交互作用对速率的影响最大,其敏感性系数在5-9之间;当磨料和氧化剂含量的比例>=5时,其交互作用对速率的影响比较大,其敏感性系数在2.5-6之间;活性剂和氧化剂的交互作用对抛光速率的影响不大,其敏感性系数小于3。因此,通过对神经网络和人工蜂群算法的改进,提出的CMP铜抛光速率预测模型可量化分析铜CMP抛光液的性能。     

光学石英基片CMP表面粗糙度的研究

In order to achieve a high-quality quartz glass substrate and to improve the performance of Ti O2 antireflection coating,chemical mechanical polishing(CMP) method was used.During CMP process,some process parameters including pressure,polishing head speed,platen speed,slurry flow rate,polishing time,and slurry temperature were optimized to obtain lower quartz surface roughness.According to the experiment results,when pressure was 0.75 psi,polishing head speed was 65 rpm,platen speed was 60 rpm,slurry flow rate 150 m L/min,slurry temperature 20°C,and polishing time was 60 s,the material removal rate(MRR) was 56.8 nm/min and the surface roughness(Ra) was 1.93 °(the scanned area was 1010 m2/.These results were suitable for the industrial production requirements.     

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.     

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.     

Cu CMP工艺中新型低pH碱性抛光液稳定性的研究

Abstract： The stability of a novel low-pH alkaline slurry （marked as slurry A, pH = 8.5） for copper chemical mechanical planarization was investigated in this paper. First of all, the stability mechanism of the alkaline slurry was studied. Then many parameters have been tested for researching the stability of the slurry through comparing with a traditional alkaline slurry （marked as slurry B, pH = 9.5）, such as the pH value, particle size and zeta potential. Apart from this, the stability of the copper removal rate, dishing, erosion and surface roughness were also studied. All the results show that the stability of the novel low-pH alkaline slurry is better than the traditional alkaline slurry. The working-life of the novel low-pH alkaline slurry reaches 48 h.     

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.     

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。     

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.