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Fundamental studies on the removal of copper in hydroxylamine based chemistries of interest to copper chemical-mechanical planarization

机译：在对铜化学机械平面化感兴趣的基于羟胺的化学物质中去除铜的基础研究

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摘要

The advancement of IC technology has led to an increasing demand for faster and cheaper microelectronic devices. One of the key processing steps in fabricating ultra-large scale integration devices is copper chemical-mechanical planarization (CMP). Traditional copper CMP slurries use hydrogen peroxide as an oxidant. A novel copper CMP slurry based on hydroxylamine chemistry is being considered as an alternative to hydrogen peroxide based slurries. The main goal of the research reported in this dissertation is to understand the removal of copper in hydroxylamine based chemistries. Copper removal experiments were performed on a regular CMP tool and a specially designed electrochemical abrasion cell (EC-AC). The effects of applied pressure and abrasion speed were investigated on both tools. The electrochemistry of copper in hydroxylamine based chemistry was investigated using electrochemical techniques on the EC-AC tool. The techniques include electrochemical polarization and voltammetry. The effects of solution pH and hydroxylamine concentration on the polarization of copper were systematically investigated. The fate of hydroxylamine and other nitrogen-based species were studied using capillary electrophoresis chromatography. The removal rates of copper obtained from a regular CMP tool were twice as much as the rates obtained from the EC-AC tool. However, the removal rates from both tools showed the same trend with respect to pH. Interestingly, a maximum peak in copper removal rates occurs at a pH value of 6, and a significant decrease in rates occur at pH values deviating from 6. The copper removal results obtained from the EC-AC tool with and without abrasion showed that the high removal rate at pH 6 is largely due to chemical attack. The reactions involved in the oxidation of copper are dependent on the decomposition and complexation behaviors of hydroxylamine. Electrochemical analysis showed the removal of copper may be dependent on the reduction of nitric oxide (NO) to hyponitrous specie (H₂N₂O₂). Capillary electrophoresis chromatography analyses showed the consumption of hydroxylamine and species generated from the autooxidation/reduction of hydroxylamine. In slightly alkaline pH conditions, the removal of copper was predominantly due to mechanical abrasion of the surface oxide. This was supported by the potential-pH diagrams and the analysis of applied pressure and relative velocity. At pH values ranging from 3 to 5, the removal of copper was due to oxidation of Cu to Cu²⁺.
机译：IC技术的进步导致对更快，更便宜的微电子设备的需求不断增长。制造超大规模集成器件的关键工艺步骤之一是铜化学机械平面化（CMP）。传统的铜CMP浆料使用过氧化氢作为氧化剂。一种基于羟胺化学的新型铜CMP浆料被认为是基于过氧化氢的浆料的替代品。本论文报道的研究的主要目的是了解羟胺基化学物质中铜的去除。在常规的CMP工具和专门设计的电化学磨损池（EC-AC）上进行了除铜实验。在两种工具上研究了施加压力和磨损速度的影响。使用EC-AC工具上的电化学技术研究了铜在羟胺基化学中的电化学。该技术包括电化学极化和伏安法。系统研究了溶液的pH值和羟胺浓度对铜极化的影响。使用毛细管电泳色谱法研究了羟胺和其他氮基物种的命运。从常规CMP工具获得的铜去除率是从EC-AC工具获得的铜去除率的两倍。但是，从两种工具的去除率方面显示出相同的pH趋势。有趣的是，铜去除率的最大峰值出现在pH值为6的情况下，而pH值偏离6时出现了明显的下降趋势。从EC-AC工具获得的铜去除率在有磨损和无磨损的情况下显示出pH为6时的去除率很大程度上是由于化学侵蚀。铜氧化所涉及的反应取决于羟胺的分解和络合行为。电化学分析表明，铜的去除可能取决于一氧化氮（NO）还原为次硝酸（H 2 N 2 O 2）。毛细管电泳色谱分析显示羟胺的消耗和羟胺的自氧化/还原产生的物质。在弱碱性pH条件下，铜的去除主要是由于表面氧化物的机械磨损。电位-pH图以及所施加压力和相对速度的分析对此提供了支持。在pH值为3-5的情况下，铜的去除是由于Cu氧化成Cu 2+所致。

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    Huang Wayne Hai-Wei;

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  • 年度 2003
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