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首页> 外文学位 >Electrochemical studies of Copper, Tantalum and Tantalum Nitride surfaces in aqueous solutions for applications in chemical-mechanical and electrochemical-mechanical planarization.
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Electrochemical studies of Copper, Tantalum and Tantalum Nitride surfaces in aqueous solutions for applications in chemical-mechanical and electrochemical-mechanical planarization.

机译：用于化学机械和电化学机械平面化的水溶液中铜，钽和氮化钽表面的电化学研究。

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摘要

This report will investigate fundamental properties of materials involved in integrated circuit (IC) manufacturing. Individual materials (one at a time) are studied in different electrochemical environmental solutions to better understand the kinetics associated with the polishing process. Each system tries to simulate a real CMP environment in order to compare our findings with what is currently used in industry. To accomplish this, a variety of techniques are used.;The voltage pulse modulation technique is useful for electrochemical processing of metal and alloy surfaces by utilizing faradaic reactions like electrodeposition and electrodissolution. A theoretical framework is presented in chapter 4 to facilitate quantitative analysis of experimental data (current transients) obtained in this approach. A typical application of this analysis is demonstrated for an experimental system involving electrochemical removal of copper surface layers, a relatively new process for abrasive-free electrochemical mechanical planarization of copper lines used in the fabrication of integrated circuits. Voltage pulse modulated electrodissolution of Cu in the absence of mechanical polishing is activated in an acidic solution of oxalic acid and hydrogen peroxide. The current generated by each applied voltage step shows a sharp spike, followed by a double-exponential decay, and eventually attains the rectangular shape of the potential pulses.;For the second system in chapter 5, open-circuit potential measurements, cyclic voltammetry and Fourier transform impedance spectroscopy have been used to study pH dependent surface reactions of Cu and Ta rotating disc electrodes (RDEs) in aqueous solutions of succinic acid (SA, a complexing agent), hydrogen peroxide (an oxidizer), and ammonium dodecyl sulfate (ADS, a corrosion inhibitor for Cu). The surface chemistries of these systems are relevant for the development of a single-slurry approach to chemical mechanical planarization (CMP) of Cu lines and Ta barriers in the fabrication of semiconductor devices. It is shown that in non-alkaline solutions of H2O2, the SA-promoted surface complexes of Cu and Ta can potentially support chemically enhanced material removal in low-pressure CMP of surface topographies overlying fragile low-k dielectrics. ADS can suppress Cu dissolution without significantly affecting the surface chemistry of Ta.;Chapter 6 discusses anodic corrosion of Ta, which is examined as a possible route to voltage induced removal of Ta for potential applications in electrochemical mechanical planarization (ECMP) of diffusion barriers. This strategy involves electro-oxidation of Ta in the presence of NO3- anions to form mechanically weak surface oxide films, followed by removal of the oxide layers by moderate mechanical abrasion. This NO3 - system is compared with a reference solution of Br -. In both electrolytes, the voltammetric currents of anodic oxidation exhibit oscillatory behaviors in the initial cycles of slow (5 mV s-1) voltage scans. The frequencies of these current oscillations are show signature attributes of localized pitting or general surface corrosion caused by Br- or NO3 -, respectively. Scanning electron microscopy, cyclic voltammetry, polarization resistance measurements, and time resolved Fourier transform impedance spectroscopy provide additional details about these corrosion mechanism. Apart from their relevance in the context of ECMP, the results also address certain fundamental aspects of pitting and general corrosions. The general protocols necessary to combine and analyze the results of D.C. and A.C. electrochemical measurements involving such valve metal corrosion systems are discussed in detail.;In chapter 7 potassium salts of certain oxyanions (nitrate, sulfate and phosphate in particular) are shown to serve as effective surface-modifying agents in chemically enhanced, low-pressure chemical mechanical planarization (CMP) of Ta and TaN barrier layers for interconnect structures. The surface reactions that form the basis of this CMP strategy are investigated here in detail using the electrochemical techniques of cyclic voltammetry, open circuit potential analysis, polarization resistance measurements, and Fourier transform impedance spectroscopy. The results suggest that forming structurally weak oxide layers on the CMP samples is a key to achieving the goal of chemically controlled CMP of Ta/TaN at low down-pressures. (Abstract shortened by UMI.)
机译：该报告将调查集成电路（IC）制造中涉及的材料的基本特性。在不同的电化学环境溶液中研究一种材料（一次一次），以更好地了解与抛光过程相关的动力学。每个系统都试图模拟一个实际的CMP环境，以便将我们的发现与当前行业中使用的结果进行比较。为此，使用了多种技术。电压脉冲调制技术通过利用诸如电沉积和电溶解的法拉第反应可用于金属和合金表面的电化学处理。第4章介绍了一个理论框架，以促进对通过这种方法获得的实验数据（电流瞬变）进行定量分析。对于涉及电化学去除铜表面层的实验系统证明了该分析的典型应用，这是一种用于集成电路制造的铜线无磨擦电化学机械平面化的相对较新的方法。在草酸和过氧化氢的酸性溶液中，可以在不进行机械抛光的情况下激活铜的电压脉冲调制电溶解。每个施加的电压阶跃产生的电流会显示一个尖峰，随后是双指数衰减，最终变为电势脉冲的矩形。;对于第5章中的第二个系统，开路电势测量，循环伏安法和傅里叶变换阻抗光谱已用于研究在琥珀酸（SA，络合剂），过氧化氢（氧化剂）和十二烷基硫酸铵（ADS）的水溶液中Cu和Ta旋转圆盘电极（RDE）的pH依赖表面反应。 ，铜的腐蚀抑制剂）。这些系统的表面化学性质与开发半导体设备制造中铜线和Ta势垒的化学机械平面化（CMP）的单浆方法有关。结果表明，在H2O2的非碱性溶液中，SA促进的Cu和Ta的表面络合物可以潜在地支持覆盖易碎的低k电介质的表面形貌的低压CMP中化学增强的材料去除。 ADS可以抑制Cu的溶解，而不会显着影响Ta的表面化学。第六章讨论了Ta的阳极腐蚀，这被认为是电压诱导去除Ta的一种可能途径，可用于扩散阻挡层的电化学机械平面化（ECMP）。该策略涉及在NO3-阴离子的存在下Ta的电氧化，以形成机械强度较弱的表面氧化膜，然后通过适度的机械磨损去除氧化层。将此NO3-系统与Br-的参考溶液进行了比较。在两种电解质中，阳极氧化的伏安电流在缓慢（5 mV s-1）电压扫描的初始循环中均表现出振荡行为。这些电流振荡的频率分别显示了由Br-或NO3-引起的局部点蚀或一般表面腐蚀的特征属性。扫描电子显微镜，循环伏安法，极化电阻测量和时间分辨傅里叶变换阻抗光谱学提供了有关这些腐蚀机理的更多详细信息。除了在ECMP中的相关性外，结果还涉及点蚀和一般腐蚀的某些基本方面。详细讨论了组合和分析涉及此类阀门金属腐蚀系统的DC和AC电化学测量结果所必需的一般协议。;在第7章中，某些氧阴离子（尤其是硝酸根，硫酸根和磷酸根）的钾盐被用作Ta和TaN阻挡层的化学增强低压化学机械平坦化（CMP）中的有效表面改性剂，用于互连结构。本文使用循环伏安法，开路电势分析，极化电阻测量和傅里叶变换阻抗光谱学等电化学技术，详细研究了构成该CMP策略基础的表面反应。结果表明，在CMP样品上形成结构较弱的氧化物层是实现Ta / TaN在低压下进行化学控制CMP的目标的关键。 （摘要由UMI缩短。）

著录项

  • 作者

    Sulyma, Christopher Michael.;

  • 作者单位

    Clarkson University.;

  • 授予单位 Clarkson University.;
  • 学科 Chemistry Inorganic.;Engineering Chemical.;Physics General.;Engineering Materials Science.
  • 学位 Ph.D.
  • 年度 2010
  • 页码 224 p.
  • 总页数 224
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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