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Fundamental studies in selective wet etching and corrosion processes for high-performance semiconductor devices.

机译：高性能半导体器件的选择性湿法蚀刻和腐蚀工艺的基础研究。

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As multistep, multilayer processing in semiconductor industry becomes more complex, the role of cleaning solutions and etching chemistries are becoming important in enhancing yield and in reducing defects. This thesis demonstrates successful formulations that exhibit copper and tungsten compatibility, and are capable of Inter Layer Dielectric (ILD) cleaning and selective Ti etching.;The corrosion behavior of electrochemically deposited copper thin films in deareated and non-dearated cleaning solution containing hydrofluoric acid (HF) has been investigated. Potentiodynamic polarization experiments were carried out to determine active, active-passive, passive, and transpassive regions. Corrosion rates were calculated from tafel slopes. ICP-MS and potentiodynamic methods yielded comparable Cu dissolution rates. Interestingly, the presence of hydrogen peroxide in the cleaning solution led to more than an order of magnitude suppression of copper dissolution rate. We ascribe this phenomenon to the formation of interfacial CuO which dissolves at slower rate in dilute HF. A kinetic scheme involving cathodic reduction of oxygen and anodic oxidation of Cu0 and Cu+1 is proposed. It was determined that the reaction order kinetics is first order with respect to both HF and oxygen concentrations.;The learnings from copper corrosion studies were leveraged to develop a wet etch/clean formulation for selective titanium etching. The introduction of titanium hard-mask (HM) for dual damascene patterning of copper interconnects created a unique application in selective wet etch chemistry. A formulation that addresses the selectivity requirements was not available and was developed during the course of this dissertation. This chemical formulation selectively strips Ti HM film and removes post plasma etch polymer/residue while suppressing the etch rate of tungsten, copper, silicon oxide, silicon carbide, silicon nitride, and carbon doped silicon oxide. Ti etching selectivity exceeding three orders of magnitude was realized. Surprisingly, it exploits the use of HF, a chemical well known for its SiO2 etching ability, along with a silicon precursor to protect SiO2. The ability to selectively etch the Ti HM without impacting key transistor/interconnect components has enabled advanced process technology nodes of today and beyond. This environmentally friendly formulation is now employed in production of advanced high-performance microprocessors and produced in a 3000 gallon reactor.
机译：随着半导体工业中多层处理的逐步发展，清洁溶液和蚀刻化学的作用在提高产量和减少缺陷方面变得越来越重要。本文证明了成功的配方具有铜和钨的相容性，并且能够进行层间介电（ILD）清洗和选择性Ti蚀刻。;电化学沉积的铜薄膜在含有氢氟酸的脱气和非脱脂清洁溶液中的腐蚀行为（ HF）已被调查。进行了电位动力极化实验，以确定主动，主动-被动，被动和跨被动区域。腐蚀速率是从杂物斜率计算得出的。 ICP-MS和电位动力学方法得出的铜溶解速率相当。有趣的是，清洁溶液中过氧化氢的存在导致铜溶解速率的抑制超过一个数量级。我们将此现象归因于界面CuO的形成，该界面以较慢的速度在稀HF中溶解。提出了一种动力学方案，包括氧的阴极还原以及Cu0和Cu + 1的阳极氧化。已确定，相对于HF和氧气浓度，反应阶次动力学是一阶。；利用铜腐蚀研究的经验，开发了用于选择性钛腐蚀的湿法腐蚀/清洁配方。用于铜互连的双镶嵌图案的钛硬掩模（HM）的引入在选择性湿法蚀刻化学中产生了独特的应用。解决选择性要求的配方尚不可用，并且是在本论文过程中开发的。该化学配方选择性地剥离Ti HM膜并去除等离子体蚀刻后的聚合物/残留物，同时抑制了钨，铜，氧化硅，碳化硅，氮化硅和碳掺杂的氧化硅的蚀刻速率。实现了超过三个数量级的Ti蚀刻选择性。出人意料的是，它利用了HF（一种以SiO2刻蚀能力而闻名的化学药品）以及保护SiO2的硅前体的使用。在不影响关键晶体管/互连组件的情况下选择性蚀刻Ti HM的能力使当今及以后的先进工艺技术节点成为可能。现在，这种环保配方已用于生产高级高性能微处理器，并在3000加仑反应堆中生产。

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  • 作者

    Mistkawi, Nabil George.;

  • 作者单位

    Portland State University.;

  • 授予单位 Portland State University.;
  • 学科 Chemistry Physical.;Engineering Electronics and Electrical.;Engineering Chemical.
  • 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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