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首页> 外文会议>Conference on advances in resist materials and processing technology XXVI; 20090223-25; San Jose, CA(US) >Quantitative measurement of resist outgassing during exposure
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Quantitative measurement of resist outgassing during exposure

机译：曝光过程中抗蚀剂脱气的定量测量

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Determination of both the identity and quantity of species desorbing from photoresists during exposure at any wavelength - 248nm, 193nm and EUV - has proved to be very challenging, adding considerable uncertainty to the evaluation of risks posed by specific photoresists to exposure tool optics. Measurements using a variety of techniques for gas detection and solid film analysis have been reported but analytical results have not in general been easy to compare or even in apparent agreement, in part due to difficulties in establishing absolute calibrations. In this work we describe two measurement methods that can be used for any exposure wavelength, and show that they provide self-consistent quantitative outgassing data for 2 all-organic and 2 Si-containing 193 nm resists. The first method, based upon gas collection, uses two primary chromatographic techniques. Organic products containing C, S and Si are determined by collection of vapors emitted during exposure in a cold trap and analysis by Gas Chromatography-Flame Ionization Detector-Pulsed Flame Photometric Detector-Mass Spectrometry (GC-FID-PFPD-MS). Inorganic products such as SO_2 are identified by adsorbent bed with analysis by Gas Particle-Ion Chromatography (GP-IC). The calibration procedure used provides reasonable accuracy without exhaustive effort. The second method analyzes the elemental concentrations in resist films before and after exposure by secondary ion mass spectrometry technique (SIMS), which requires only knowledge of the resist compositions to be quantitative. The extent of outgassing of C and S determined by the two methods is in good agreement for all 4 resists, especially when taking their fundamentally different characters into account. Overall, the gas collection techniques yielded systematically lower outgassing numbers than did SIMS, and the origins of the spread in values, which likely bracket the true values, as well as detection limits will be discussed. The data for Si were found to differ significantly, however, and we show that the discrepancy is due to photo-induced reactions at the polymer surface with the gas atmosphere present above the resist during exposure. For example, photolytic oxidation of the C-Si bonds in air causes volatile Si-containing products to be formed from an otherwise stable polymer, showing it is important to take the gas environment during exposure into account when designing resist polymers for low Si outgassing.
机译：事实证明，在任何波长（248nm，193nm和EUV）下曝光期间，从光致抗蚀剂中脱附的物质的种类和数量都非常困难，这给特定光致抗蚀剂对曝光工具光学器件带来的风险评估带来了极大的不确定性。已经报道了使用多种技术进行气体检测和固体膜分析的测量结果，但是分析结果通常不易于比较甚至没有明显的一致性，部分原因是难以建立绝对校准。在这项工作中，我们描述了两种可用于任何曝光波长的测量方法，并表明它们为2种全有机和2种含Si的193 nm抗蚀剂提供了自洽的定量脱气数据。基于气体收集的第一种方法使用两种主要的色谱技术。含有C，S和Si的有机产物是通过收集在冷阱中暴露期间散发的蒸气并通过气相色谱-火焰电离检测器-脉冲火焰光度检测器-质谱法（GC-FID-PFPD-MS）进行分析而确定的。诸如SO_2之类的无机产品通过吸附床进行鉴定，并通过气相颗粒离子色谱法（GP-IC）进行分析。所使用的校准程序可提供合理的准确性，而无需花费大量精力。第二种方法是通过二次离子质谱技术（SIMS）分析曝光前后抗蚀剂膜中的元素浓度，该技术仅需要知道抗蚀剂成分是定量的即可。通过这两种方法确定的C和S脱气程度对于所有4种抗蚀剂都非常吻合，尤其是考虑到其根本不同的特性时。总体而言，与SIMS相比，气体收集技术产生的排气量系统地降低了，并且将讨论值分布的起源（可能在真实值之内以及检测极限）。然而，发现Si的数据存在显着差异，并且我们发现差异是由于在曝光期间聚合物表面与抗蚀剂上方存在的气体气氛引起的光诱导反应。例如，空气中C-Si键的光解氧化导致由稳定的聚合物形成挥发性的含Si产物，这表明在设计用于低Si脱气的抗蚀剂聚合物时，考虑到曝光期间的气体环境非常重要。

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