CN1193128A - 化学增强的光刻胶 - Google Patents

化学增强的光刻胶 Download PDF

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CN1193128A
CN1193128A CN98100895A CN98100895A CN1193128A CN 1193128 A CN1193128 A CN 1193128A CN 98100895 A CN98100895 A CN 98100895A CN 98100895 A CN98100895 A CN 98100895A CN 1193128 A CN1193128 A CN 1193128A
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井谷俊郎
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Abstract

通过解决由光吸收引起的圆锥状光刻胶图形的问题,提供具有良好分辨率、聚焦和尺寸精度的化学增强的光刻胶,并同时产生高的热稳定性和对干法刻蚀的足够的抗蚀性,将具有芳环的树脂加入到含有一种脂环丙烯酸聚合物和一种光酸发生剂的化学增强的光刻胶中。该具有芳环的树脂最好为多羟苯乙烯聚合物、酚醛清漆聚合物或t－BOC保护的多羟苯乙烯聚合物。这些聚合物最佳的加入量为1至10重量份比100重量份的基质聚合物。

Description

化学增强的光刻胶
本发明涉及化学增强的光刻胶，它包括一种脂环丙烯酸(alicyclicacrylic polymer)聚合物和一种光酸发生剂(photoacid generator)，并加入一种芳环树脂。它可被用作正胶，例如应用于图形生成，其中这种正胶形成于半导体基片上，经一块掩模或一块原版受到ArF激光器发射光的曝光，经过PEB(曝光后烘烤)处理，并用显影剂显影。
在常规的光刻技术中，主要使用溶解性被抑制的正胶；其中使用了酚醛清漆聚合物作为基质聚合物，  加入萘醌二叠氮基(naphthoquinonediazido)作为对g-谱线(436nm)或i-谱线(365nm)曝光的感光剂。但随着半导体集成电路精细刻蚀的发展，需要使用远紫外线例如248nm或193nm的激光的光刻方法。对于受激发射的激光，上述常规的光刻胶并不适用，这是由于需与其过分增强的光灵敏度一起获得良好的光刻胶图形，它的光吸收太强了。因而，人们提出了使用酸催化剂感光的化学增强的光刻胶，该酸催化剂得自光酸发生剂(下文称作PAG)，并开始扩展成短波长光刻或电子束刻蚀所需高灵敏度的光刻胶。
但是，应用于波长为193nm的ArF激光曝光的光刻方法中光刻胶就存在严重的光吸收问题，因而光刻胶材料中各组分的使用受到了严格的根制。对于用于ArF激光的化学增强的光刻胶来说，已提出了两组分的由不存在光吸收的问题的脂环丙烯酸聚合物和一种PAG组成的正胶(例如，请参阅Nakano等，“positive Chemically Amplified Resistfor ArF Excimer Laser Lithography Composed of a Novel TransparentPhotoacid Generator and an Alicyclic Terpolymer”，Proceedingsof the Society of Photo-optical Instrumentation Engineers，Vol.2438，pp.433-444)。但是，这种两组分正胶并不实用，因为它有低的热稳定性，并且对于在一层基底膜上对一光刻胶的显影图形进行干法刻蚀的抗蚀性很差。
至于具有提高的热稳定性和对干法刻蚀抗蚀性的光刻胶材料，在临时公开号No.323610/’93的日本专利申请中提出了由一种酚醛聚合物和一种PAG组成并包括一种交取剂的化学增强的光刻胶。但是，用这种对ArF激光具有强的光吸收的光刻胶材料无法得到矩形截面的光刻胶图形，在图2中示意绘示出晶片201上显影的光刻胶图形202变成圆锥形。这种圆锥形光刻胶图形对于精细图形形成来说尤其是致命的，它降低了分辨率、聚焦和尺寸的精度。
因而，本发明的主要目的是提供一种化学增强的光刻胶，它在分辨率、聚焦和尺寸精度方面有良好的性能，解决了起因于光吸收的圆锥状的光刻胶图形问题，并同时具有高的热稳定性和对干法刻蚀的足够的抗蚀性，从而解决了现有技术中的上述问题。
为达到这一目的，在含有一种脂环丙烯酸聚合物和一种光酸发生剂的本发明的化学增强的光刻胶中加入具有一种芳香环的树脂。
通过向常规的由一种不存在对ArF激光有光吸收问题的脂环丙烯酸聚合物和一种PAG组成的两组分化学增强的光刻胶中加入具有提高热稳定性和对干法刻蚀的抗蚀性的芳香环树脂，得到了一种最适用于ArF激光光刻方法的光刻胶材料，它圆满地保持住了上述特性。位于芳香环中的碳原子和双键具有提高热稳定性和干法刻蚀中光刻胶膜的耐蚀的作用。
本发明的上述及其它的目的、特征和优点从以下说明、所附权利要求以及附图中将会显然可见。其中：
图1表示用本发明一个实施例的第一例化学增强光刻胶得到的正胶图形的横切面；和
图2表示用常规的化学增强的光刻胶在晶片201上产生的圆锥状的光刻胶图形202的横切面。
在本发明的优选实施例描述如下。
在本发明的化学增强的光刻胶中，一种脂环丙烯酸聚合物被用作基质聚合物。
对于该脂环丙烯酸聚合物来说，用作化学增强的光刻胶基质聚合物的常规树脂，例如具有各种极性基团的脂环甲基丙烯酸酯聚合物或脂环丙烯酸酯聚合物可根据目的使用。一个具体的例子是聚(TCDA-THMPA-MAA：三环(5.2.1.0.2，6)癸烷基丙烯酸酯-co-四氢吡喃基甲基丙烯酸酯-co-甲基丙烯酸)，描述于Nakano等人的上述文章。
对于需要加入到本发明化学增强的光刻胶中的PAG来说，可以使用常规的PAG，使如翁盐，或二磺酰重氮基甲烷PAG，使用的种类和量可根据目的来确定。通常的情况是1至10重量份的PAG加入到100重量份的基质聚合物中。
本发明的化学增强的光刻胶的特征在于其中加入了具有芳环的树脂。
对于该具有芳环的树脂来说，其种类和用量没有限制，只要芳环中的碳原子和双键能够起到改善稳定性和光刻胶膜对干法刻蚀的抗蚀的作用。优选的平均分子量为8000至30000，该平均分子量是用GPC(气体渗透色谱)法测量的苯乙烯转换表示的。
最佳的具有芳环的树脂是有下式(1)的多羟苯乙烯聚合物：
其它优选的具有芳环的树脂有具有下式(2)的酚醛清漆聚合物，或具有一种微碱溶性保护基团的多羟苯乙烯聚合物，如下式(3)所示的t-BOC(叔丁氧羰基)保护的多羟苯乙烯聚合物。
Figure A9810089500061
这些具有芳环的聚合物的加入量最好为1至10重量份比100重量份的基质聚合物，即脂环丙烯酸聚合物。
这里应强调的是，这些聚合物具有互不相同的碱溶解性，对光刻胶的分辨率和截面图形产生不同的影响。因而，对于需要加入的树脂来说，按照基质聚合物的组成最好选用适当的种类、分子量比率、混合比率和保护系数。也就是说，通过适当地选择这些因素，可进一步改善热稳定性和对干法刻蚀的抗蚀性并保持适当的溶解对比度，这对光刻胶的分辨率来说最为重要。
而且，具有芳环的树脂在193nm波长的ArF激光处具有强的光吸引。因而，通过选择需加入树脂的适当种类、分子量比率或量，它也可起到染料的作用。为达到本发明的目的，光刻胶膜在193nm的透光性最好被制作成40至70％/μm，最佳为50％/μm。这样，可以得到有效阻止反射的光吸收，抑制从基底散射的反射光所引起的光刻胶图形变形，从而抑制分辨率降低。
再者，在本发明的化学增强的光刻胶中可任选地加入交联剂或其它添加剂。
下文描述本实施例的一些示例和实验结果。
作为本实施例的第一示例，制备了用于ArF激光的液态化学增强的光刻胶，其中含有100重量份的平均分子量为20000的聚(TCDA-THPMA-MAA)作为基质聚合物，5重量份的鎓盐作为PAG，2重量份的平均分子量为12000的多羟苯乙烯作为具有芳环的树脂，和80重量份的PGMEA(聚丙烯二醇单甲基乙醚乙酸脂)作为溶剂。
将该化学增强的光刻胶液体涂敷在硅晶片上，其厚度为0.5μm，用经一掩模聚焦的193nm的ArF激光曝光，进行100°的PEB处理90秒钟，并用碱性显影剂显影，从而得到0.18μm标准的正胶图形。
图1表示用按照本实施例第一示例的化学增强的光刻胶得到的正胶图形的横切面，其中，在晶片101上得到了矩形的光刻胶图形102，它有很好的分辨率和尺寸精度。
然后将这种正胶图形，用CL2HBr气体，在100mm乇(Torr)的气压中以120w进行干法刻蚀120秒钟，得到了很好的干蚀效果，没有光刻胶膜受损或是光刻胶图形变形。与下述的比较示例相比，在热稳定性和对干法刻蚀的抗蚀性方面得到约10％的改善。
作为一项比较示例，制备了具有与本实施例第一示例相同组成的化学增强的光刻胶液体，不同的是没有加入多羟苯乙烯聚合物。将以同样方式得到的光刻胶图形进行干法刻蚀，其中观察到了光刻胶膜的受损和光刻胶图形的变形。
在第二示例中，仅将第一示例中的具有芳环的树脂用1重量份的20000分子量的多羟苯乙苯烯替换，以与第一示例相同的方式获得了同样好的效果。
如上文所述，用本发明的加入了具有芳环的树脂的化学增强的光刻胶，在ArF光刻方法中抑制了干法刻蚀中的光刻胶膜受损并能改善热稳定性。因而抑制了曝光后烘焙或干法刻蚀中光刻胶图形的变形，获得了高的分辨率。而且，具有芳环的树脂具有染料的作用。
因而，根据本发明光刻方法的分辨率，聚焦和尺寸精确度可以得到改善，还能得到精细集成的器件图形。也就是说，本发明的化学增强光刻胶对形成超精细的图形非常有效，并对光刻胶的高性能或精细分辨率作出了一定的贡献。

Claims (4)

1、含有一种脂环丙烯酸聚合物和一种光酸发生剂的化学增强的光刻胶，其特征在于，在它当中加入了具有芳环的树脂。
2、按照权利要求1所述的化学增强的光刻胶，其特征在于，所说的具有芳环的树脂为酚醛清漆聚合物和多羟苯乙烯聚合物中的至少一种。
3、按照权利要求1所述的化学增强的光刻胶，其特征在于，所说的具有芳环的树脂为一种具有一种微碱溶性保护基团的多羟苯乙烯聚合物。
4、按照权利要求1所述的化学增强的光刻胶，其特征在于，将1至10重量份的具有芳环的树脂加入到100重量份的脂环丙烯酸聚合物中。
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