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Kinetic Modeling of Halogen-Based Plasma Etching of Complex Oxide Films and its Application to Predictive Feature Profile Simulation.

机译：复杂氧化物薄膜的基于卤素的等离子体刻蚀动力学模型及其在预测特征轮廓模拟中的应用。

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摘要

In this work, a comprehensive framework for predicting etching behavior is developed using the test case of hafnium lanthanate (HfxLa yOz) in Cl2/BCl3 chemistry, starting from detailed thermodynamic analysis in the form of volatility diagrams. Through these calculations, it was predicted that at typical plasma reactor operating pressures, the reactions of molecular Cl2 and Cl radicals with La2O3 and HfO2 could generate sufficiently high partial pressures of OxCly for measurable material removal to occur.;The etch rate of Hf0.25La0.12O0.63 as a function of ion energy was characterized in situ using a quartz crystal microbalance. The etch rate data was found to exhibit a dual ion energy dependence with a maximum etch rate of ∼27 Å/min at E ion = 175 eV. The overall etch rate was found to be approximately half that of a pure HfO2 film etched at the same conditions, due to the formation of non-volatile LaClx compounds.;QMS measurements of HfLaO in Cl2 chemistry showed LaOCl and LaCl as the primary La-containing etch products. XPS analysis of pure La 2O3 films provided further evidence of this hypothesis, showing significant Cl retention (∼10%) compared to HfLaO and also revealing the presence of Cl-O-La bonding. A kinetics-based bulk scale (TML) model was fit to the aforementioned experimental data and good agreement was shown between the TML model's simulated results and etch rate data. An additional degree of validation was provided through a comparison of the model's predicted composition of the surface mixing layer and the XPS-measured film compositions after plasma exposure.;The final validation of this approach was to assess the fitted kinetic parameters for complex oxide etching in Cl-based chemistry (such as reaction rate coefficients, threshold energies and sticking probabilities) at feature scale levels. The results from the TML model were coupled to a Monte Carlo based feature profile simulator and used to predict the variation of the etched feature profiles of Hf0.25La0.12O0.63 films for varying aspect ratios (1.5, 3 and 6) and ion energies (75, 100 and 175 eV). In order to compare to experimental results, features of varying aspect ratio were achieved using an e-beam tool to pattern a ZEP520A photoresist mask on HfLaO followed by etching in Cl2 . Good agreement was achieved with the etched profile at 100 eV and AR = 5. As a test of the model's ability to handle variations in gas chemistry with a material system besides that of high-k dielectrics, this methodology was also applied to the shallow trench isolation process (Si etching in Cl22/O2 chemistry). The model showed good fitting of the major process parameters (etch rate, etch product ratios and surface composition) and showed an ability to predict the profile variation with 0, 2, 6 and 8% oxygen addition to a pure Cl 2 plasma for the etching of Si.
机译：在这项工作中，从挥发度图形式的详细热力学分析开始，使用在Cl2 / BCl3化学中的镧ha（HfxLa yOz）测试用例，开发了一个用于预测蚀刻行为的综合框架。通过这些计算，可以预测在典型的等离子反应器工作压力下，分子Cl2和Cl自由基与La2O3和HfO2的反应会产生足够高的OxCly分压，从而发生可测量的材料去除; Hf0.25La0的蚀刻速率使用石英晶体微量天平原位表征了0.1200.63作为离子能量的函数。发现在E ion = 175 eV时，蚀刻速率数据显示出双离子能量依赖性，最大蚀刻速率约为〜27Å/ min。由于形成了非挥发性LaClx化合物，发现总蚀刻速率约为在相同条件下蚀刻的纯HfO2膜的一半。; Cl2化学性质中HfLaO的QMS测量表明，LaOCl和LaCl是主要的La-包含蚀刻产品。对纯La 2O3薄膜的XPS分析提供了这一假设的进一步证据，与HfLaO相比，Cl保留显着（约10％），并且还揭示了Cl-O-La键的存在。基于动力学的体积尺度（TML）模型适合上述实验数据，并且在TML模型的模拟结果和蚀刻速率数据之间显示出良好的一致性。通过比较等离子暴露后模型的表面混合层的预测组成与XPS测量的膜组成之间的比较，进一步验证了该方法的有效性；该方法的最终验证是评估复杂氧化物蚀刻过程中拟合的动力学参数。基于Cl的化学（例如反应速率系数，阈值能量和粘着概率）处于特征尺度水平。 TML模型的结果耦合到基于Monte Carlo的特征轮廓模拟器，并用于预测Hf0.25La0.12O0.63膜的蚀刻特征轮廓随纵横比（1.5、3和6）和离子能量的变化。 （75、100和175 eV）。为了与实验结果进行比较，使用电子束工具在HfLaO上对ZEP520A光致抗蚀剂掩模进行构图，然后在Cl2中进行蚀刻，从而实现了不同纵横比的特征。在100 eV且AR = 5的情况下，刻蚀轮廓达到了良好的一致性。作为测试该模型处理除高k电介质之外的材料系统中气体化学变化的能力的一种方法，该方法还适用于浅沟槽隔离工艺（在Cl22 / O2化学中进行Si蚀刻）。该模型显示出对主要工艺参数（蚀刻速率，蚀刻产物比率和表面组成）的良好拟合，并显示了预测在纯Cl 2等离子体中添加0、2、6和8％氧气时的轮廓变化的能力。的

著录项

  • 作者

    Marchack, Nathan Philip.;

  • 作者单位

    University of California, Los Angeles.;

  • 授予单位 University of California, Los Angeles.;
  • 学科 Engineering Chemical.
  • 学位 Ph.D.
  • 年度 2012
  • 页码 327 p.
  • 总页数 327
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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