CN1288902A - 用于抗反射涂层的有机聚合物和其制备方法 - Google Patents

用于抗反射涂层的有机聚合物和其制备方法 Download PDF

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CN1288902A
CN1288902A CN00131746A CN00131746A CN1288902A CN 1288902 A CN1288902 A CN 1288902A CN 00131746 A CN00131746 A CN 00131746A CN 00131746 A CN00131746 A CN 00131746A CN 1288902 A CN1288902 A CN 1288902A
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郑载昌
孔根圭
郑旼镐
洪圣恩
李根守
白基镐
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SK Hynix Inc
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Abstract

公开了一种适合用于超微平版印刷的抗反射薄膜组合物,包括一种含如下化学通式11的化合物作为交联剂和生色团及如下化学通式12的化合物。本发明的有机抗反射薄膜有效吸收通过涂于抗反射薄膜上的光刻胶薄膜渗透的光,由此大大降低驻波影响。因此,本发明的有机抗反射薄膜可形成清晰的超细轮廓的图形,大大有助于半导体元件的高集成。其中:a,b和c为摩尔数,其满足条件:比例a∶b为0.1—1.0∶0.1—1.0和c为1:R′和R″独立地为氢或甲基;R1、R2和R4为相同或不同的,各自表示含1—5个碳原子的取代或末取代的线性或支化烷基;和R3为氢或含1—5个碳原子的取代或未取代的线性或支化烷基。

Description

用于抗反射涂层的有机聚合物和其制备方法
本发明涉及适合用于超微平版印刷的抗反射薄膜组合物。更具体地，本发明涉及含有在适用于超微平版印刷的波长下具有高吸收的生色团，由此使得稳定形成适用于高集成半导体元件的超细图形的有机抗反射薄膜组合物。本发明还涉及用该有机抗反射薄膜组合物形成超细图形的方法。
在超微平版印刷方法中，由于涂于硅片上的底层的光学性能，和涂于其上的光刻胶膜的厚度变化和因来自低层的衍射和反射光造成的CD(临界尺寸)变化，因此不可避免地出现驻波和光波的反射刻痕。为解决这些问题，人们已提出将抗反射层加入光刻胶薄膜的底层部分，所述抗反射层由对适用于超微平版印刷的波长的光吸收性高的材料制成。
在不存在该反射层的情况下，当来自紫外线光源的光照射到光刻胶薄膜上时，该光渗入光刻胶薄膜中，并反射回来，或从其底层或半导体硅片的底层散射。因此加入抗反射层防止直接影响光刻胶的超微平版印刷的反射或光散射。
根据使用的材料属于无机物还是有机物，在机理上通常将抗反射薄膜分为吸收抗反射薄膜和干扰抗反射薄膜。
对于使用I-线(365nm)作为光源的超微平版印刷，通常使用无机抗反射薄膜。其中，吸收的抗反射层主要由TiN或无定形碳制成，而干扰抗反射层主要基于SiON。这些基于SiON的抗反射薄膜也用于形成超细图形，其中使用KrF(248nm)作为光源。
对于波长比上述两种光源短的ArF，还未针对超微平版印刷开发一种利用短波长光的优点的抗反射薄膜。未提出控制ArF波长(即193nm)处的干扰的无机抗反射薄膜。最近，已进行了广泛深入研究，并相继开发出有机抗反射薄膜，该薄膜适用于采用ArF光的超微平版印刷。
下面是对有机抗反射层的基本要求：
首先，当进行平版印刷时，应不发生因溶于有机抗反射层的溶剂中造成的光刻胶层剥离。为此，设计有机抗反射材料，以使其固化薄膜具有不生成副产品的交联结构。
其次，应没有化学物质迁移，如酸或胺渗入或渗出反射层。若酸从反射层迁移入正性光刻胶的未曝光区域，则感光图形显影不足，同时碱如胺流出，造成镶边现象。
再其次，与在上层感光薄膜中相比，在抗反射层中应实现更快的刻蚀速度，使刻蚀过程平稳进行，其中感光薄膜起到掩蔽的作用。
最后，有机抗反射层应尽可能薄，同时具有优异的防止光反射的性能。
本发明人经广泛深入地研究，开发出一种抗反射树脂，该树脂满足上述要求并适用于通过采用ArF光形成超细图形，从而得到本发明。
因此，本发明目的在于克服现有技术中遇到的上述问题，并提供一种新的有机化合物，该化合物可用作使用ArF激光器(193nm)的超微平版印刷的抗反射材料。
本发明另一目的是提供一种制备有机化合物的方法，该有机化合物可在超微平版印刷中防止因曝光造成的散射和反射。
本发明另一目的是提供一种含该有机防散射/反射化合物的抗反射组合物，和制备该组合物的方法。
本发明再一目的是提供一种在半导体元件上形成图形的方法，当使用ArF激光器进行超微平版印刷时，该图形大大降低了驻波的影响。
本发明又一目的是提供一种半导体元件，在该元件上通过超微平版印刷由所述抗反射组合物形成图形。
附图1是一张本发明的照片，该照片表示由有机抗反射薄膜组合物形成的清晰的正交图形。
根据本发明实施方案，提供一种含如下化学通式11的化合物作为交联剂和如下化学通式12的化合物以及热酸生成剂和有机溶剂的有机抗反射组合物。
式11
Figure 0013174600101
其中：
a，b和c为摩尔数，其满足条件：比例a∶b为0.1-1.0∶0.1-1.0和c为1；
R′和R″独立地为氢或甲基；
R1、R2和R4为相同或不同的，各自表示含1-5个碳原子的取代或未取代的线性或支化烷基；和
R3为氢或含1-5个碳原子的取代或未取代的线性或支化烷基。
适用于本发明的抗反射薄膜组合物的溶剂选自3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、丙二醇甲基醚乙酸酯、2-庚酮、四氢呋喃和其混合物。基于化学通式11或12的化合物重量，有机溶剂的用量优选为2，000至4，000wt％。
在一个实施方案中，基于化学通式11和12的化合物的总重量，适用于抗反射薄膜组合物的热酸生成剂的用量优选为0.1-10wt％，该热酸生成剂为选自如下化学通式7至10的化合物：
式7
Figure 0013174600111
Figure 0013174600112
化学通式11的化合物的分子量优选为4，000至12，000。
根据本发明的另一实施方案，提供一种制备化学通式11的化合物的方法：即将构成化学通式11的化合物的单体溶于有机溶剂中，并使所得溶液在聚合引发剂存在下在氮气或氩气气氛中反应。在一个优选的实施方案中，这些单体为下面化学通式1表示的化合物和化学通式2表示的化合物：
式1
Figure 0013174600121
在本发明的另一实施方案中，该溶剂选自四氢呋喃、甲苯、苯、甲基乙基酮、二噁烷和其混合物。在另一变化形式中，聚合引发剂选自2，2-偶氮二异丁腈(AIBN)、过氧化苯甲酰、过氧化乙酰、过氧化月桂酰、叔丁基氧化物和其混合物。
根据本发明又一实施方案，提供一种用有机抗反射薄膜组合物形成有机反射薄膜图形的方法，该方法包括如下步骤：将有机抗反射薄膜组合物涂于要进行刻蚀的层上；烘烤所涂敷的有机抗反射薄膜组合物的层；通过将光刻胶膜涂于有机抗反射薄膜上，将该光刻胶薄膜暴露于光源下并使曝光的光刻胶薄膜显影，产生光刻胶图形；将有机抗反射薄膜和要刻蚀的层顺序刻蚀，其中光刻胶图形起到刻蚀掩蔽的作用。
在该实施方案的一个变化形式中，烘烤步骤优选在100-250℃下进行1-5分钟。在另一变化形式中，形成抗反射薄膜图形的方法还包括在曝光步骤之前和/或之后的烘烤步骤。在此情况下，烘烤步骤优选在70-200℃下进行。
按照另一变化，光源选自包括ArF、KrF和EUV的远紫外光束，电子束、X-射线、离子束和其组合。曝光步骤优选在具有能量0.1-20mJ/cm2的光源下进行。
根据本发明的另一实施方案，提供一种借助上面制备的抗反射薄膜图形制备的半导体元件。
借助用于详细说明而非限制本发明的实施例更好地了解本发明。实施例1合成化学通式3的化合物
式3
在250ml圆底烧瓶中，将0.2mol(11.2g)化学通式1的单体和0.2mol(20.8g)化学通式2的单体溶于66g四氢呋喃中，然后将所得溶液在65℃在0.64g 2，2-偶氮二异丁腈(AIBN)聚合引发剂存在下在惰性气氛如氮气或氩气中反应6小时。反应完成后，将产品在乙醚中沉淀并干燥，得到所需化合物(12.8g：收率40％)。在500ml圆底烧瓶中随产品一起放入300g甲醇，并加入0.08ml三氟甲磺酸，接着在85℃下回流10小时。完成回流后，用氢氧化四甲基铵将溶液控制在pH7。然后，将未反应的甲醇在真空蒸发器中蒸发，并将残余物在水中沉淀，得到化学通式3的化合物(10.24g；收率80％)。实施例2合成化学通式4的化合物
式4
在250ml圆底烧瓶中，将0.2mol(11.2g)化学通式1的单体和0.2mol(20.8g)化学通式2的单体溶于66g四氢呋喃中，然后将所得溶液在65℃在0.64g 2，2-偶氮二异丁腈(AIBN)聚合引发剂存在下在惰性气氛如氮气或氩气中反应6小时。反应完成后，将产品在乙醚中沉淀并干燥，得到所需化合物(12.8g：收率40％)。在500ml圆底烧瓶中随产品一起放入300g乙醇，并加入0.08ml三氟甲磺酸，接着在85℃下回流10小时。完成回流后，用氢氧化四甲基铵将溶液控制在pH7。然后，将未反应的乙醇在真空蒸发器中蒸发，并将残余物在水中沉淀，得到化学通式4的化合物。实施例3 用化学通式3的化合物制备抗反射薄膜组合物和由其形成图形。
在1000g丙二醇甲基醚乙酸酯中，溶解20.0g化学通式3的化合物和13.3g如下化学通式5的化合物。与0.33g化学通式7的热酸生成剂混合后，将该溶液通过0.2μm细过滤器过滤，得到有机抗反射薄膜组合物。将该溶液喷涂于硅片上，然后在205℃下烘烤固化90秒。在该固化的抗反射薄膜上，涂布光敏剂DHA 1001接着在110℃下烘烤90秒。然后将该多涂层硅片借助ArF微步器(如由ISI制造的)曝光，接着在110℃下烘烤90秒。用2.38wt％氢氧化甲基铵水溶液将该硅片显影，观察到清晰的正交图形。实施例4 用化学通式3的化合物制备抗反射薄膜组合物和由其形成图形。
在1000g丙二醇甲基醚乙酸酯中，溶解20.0g化学通式3的化合物和13.3g如下化学通式6的化合物。与0.33g化学通式7的热酸生成剂混合后，将该溶液通过0.2μm细过滤器过滤，得到有机抗反射薄膜组合物。将该溶液喷涂于硅片上，然后在205℃下烘烤固化90秒。在该固化的抗反射薄膜上，涂布光敏剂DHA 1001接着在110℃下烘烤90秒。然后将该多涂层硅片借助ArF微步器(如由ISI制造的)曝光，接着在110℃下烘烤90秒。用2.38wt％氢氧化甲基铵水溶液将该硅片显影，观察到清晰的正交图形。
式6实施例5：用化学通式4的化合物制备抗反射薄膜组合物和由其形成图形
在1000g丙二醇甲基醚乙酸酯中，溶解20.0g化学通式4的化合物和13.3g如下化学通式5的化合物。与0.33g化学通式7的热酸生成剂混合后，将该溶液通过0.2μm细过滤器过滤，得到有机抗反射薄膜组合物。将该溶液喷涂于硅片上，然后在205℃下烘烤固化90秒。在该固化的抗反射薄膜上，涂布光敏剂DHA 1001接着在110℃下烘烤90秒。然后将该多涂层硅片借助ArF微步器(如由ISI制造的)曝光，接着在110℃下烘烤90秒。用2.38wt％氢氧化甲基铵水溶液将该硅片显影，观察到清晰的正交图形。实施例6：用化学通式4的化合物制备抗反射薄膜组合物和由其形成图形
在1000g丙二醇甲基醚乙酸酯中，溶解20.0g化学通式4的化合物和13.3g如下化学通式6的化合物。与0.33g化学通式7的热酸生成剂混合后，将该溶液通过0.2μm细过滤器过滤，得到有机抗反射薄膜组合物。将该溶液喷涂于硅片上，然后在205℃下烘烤固化90秒。在该固化的抗反射薄膜上，涂布光敏剂DHA 1001接着在110℃下烘烤90秒。然后将该多涂层硅片借助ArF微步器(如由ISI制造的)曝光，接着在110℃下烘烤90秒。用2.38wt％氢氧化甲基铵水溶液将该硅片显影，观察到清晰的正交图形。
由上述化学通式11表示的交联剂和化学通式12表示的含醇基团的有机抗反射基体所形成的本发明的抗反射薄膜，不受覆盖该抗反射薄膜的光刻胶溶液影响，即它不被光刻胶溶液溶解，但充分吸收通过光刻胶薄膜渗透的光，由此大大降低了驻波的影响。因此，本发明的有机抗反射薄膜可形成清晰的超细构型的图形，大大有助于半导体元件的高集成。
本发明已按示例性的方式进行了详细描述，但所用的术语是用于描述的而不限定本发明。根据上面的教导可以对本发明进行很多改进和变化。因此，应理解，在后面定义的权利要求范围内，本发明可按不同于上面描述的方式进行实施。

Claims (21)

1．一种如下化学通式11的表示的化合物：式11
Figure 0013174600021
其中：
a和b分别为摩尔数，其满足条件：比例a∶b为0.1-1.0∶0.1-1.0；
R′为氢或甲基；
R1和R2为相同或不同的，各自表示含1-5个碳原子的取代或未取代的线性或支化烷基；和
R3为氢或含1-5个碳原子的取代或未取代的线性或支化烷基。
2．如权利要求1所述的化合物，其中R′和R3分别为氢原子，R1和R2为相同或不同的，各自表示甲基或乙基，得到下面化学通式2或3：
式2
Figure 0013174600022
式3
Figure 0013174600031
3．如权利要求1的化合物，其中化合物具有分子量4，000-12，000。
4．一种制备通式11的化合物的方法，包括如下步骤：
将构成化学通式11的化合物的单体溶于有机溶剂中；和
使所得溶液在聚合引发剂存在下在氮气或氩气气氛中反应。
5．如权利要求4所述的方法，其中单体分别为下面化学通式1表示的化合物和化学通式2表示的化合物：
式1
Figure 0013174600032
式2
Figure 0013174600033
6．如权利要求4的方法，其中溶剂选自四氢呋喃、甲苯、苯、甲基乙基酮、二噁烷和其混合物。
7．如权利要求4的方法，其中聚合引发剂选自2，2-偶氮二异丁腈(AIBN)、过氧化苯甲酰、过氧化乙酰、过氧化月桂酰、叔丁基过氧化物和其混合物。
8．一种有机抗反射薄膜组合物，包括一种含化学通式11的化合物和如下化学通式12的化合物：
式12
Figure 0013174600041
其中：c为1；
R″为氢或甲基；
R1为含1-5个碳原子的取代或未取代的线性或支化烷基。
9．如权利要求8的方法，其中R4为乙基或丙基，得到如下化学通式5或6：式5
Figure 0013174600042
式6
Figure 0013174600043
10．一种有机抗反射薄膜组合物，包括化学通式11的一种化合物、通式12的一种化合物、一种有机溶剂和一种热酸生成剂。
11．如权利要求10的有机抗反射薄膜组合物，其中有机溶剂选自3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、丙二醇甲基醚乙酸酯、2-庚酮、四氢呋喃和其混合物。
12．如权利要求10或11的有机抗反射薄膜组合物，其中，基于化学通式11或12的化合物重量，有机溶剂的用量优选为2，000至4，000wt％。
13．如权利要求10的有机抗反射薄膜组合物，其中热酸生成剂为选自如下化学通式7至10的化合物和其混合物：
式7
式8
Figure 0013174600061
14．如权利要求10或13的有机抗反射组合物，其中，基于通式11和12的化合物的总量，热酸生成剂的用量为0.1-10wt％。
15．一种用有机抗反射薄膜组合物形成有机反射薄膜图形的方法，该方法包括如下步骤：
将有机抗反射薄膜组合物涂于要进行刻蚀的层上；
烘烤该有机抗反射薄膜组合物涂布的层；
通过将光刻胶膜涂于有机抗反射薄膜上，将该光刻胶薄膜暴露于光源下并使曝光的光刻胶薄膜显影；
将有机抗反射薄膜和要刻蚀的层顺序刻蚀，其中光刻胶图形起到刻蚀掩蔽的作用。
16．如权利要求15的方法，其中烘烤步骤在100-250℃下进行1-5分钟。
17．如权利要求15的方法，其中还包括在曝光步骤之前和/或之后的烘烤步骤。
18．如权利要求16的方法，其中烘烤步骤在70-200℃下进行。
19．如权利要求15或17的方法，其中曝光步骤在选自包括ArF、KrF和ELV的远紫外光束，电子束、X-射线、离子束和其组合的光源下进行。
20．如权利要求13或15的方法，其中曝光在具有能量0.1-20mJ/cm2的光源下进行。
21．一种借助如权利要求16形成的抗反射薄膜图形制各的半导体元件。
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