CN109844639B - 高耐蚀刻性旋涂式碳硬掩膜组合物以及利用该组合物的图案化方法 - Google Patents

高耐蚀刻性旋涂式碳硬掩膜组合物以及利用该组合物的图案化方法 Download PDF

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CN109844639B
CN109844639B CN201780063653.6A CN201780063653A CN109844639B CN 109844639 B CN109844639 B CN 109844639B CN 201780063653 A CN201780063653 A CN 201780063653A CN 109844639 B CN109844639 B CN 109844639B
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金起洪
李秀珍
李昇炫
李昇勋
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Abstract

本发明为了提供有用于半导体光刻工艺的具有高耐蚀刻性的硬掩膜组合物,提供包含二苯并咔唑(dibenzo carbazole)聚合物的旋涂式硬掩膜组合物以及通过旋涂将该组合物进行涂敷于被蚀刻层上部的工艺以及烘烤工艺形成硬掩膜层的图案化方法,本发明的硬掩膜具有能够承受多重蚀刻(mutil etch)过程的高耐蚀刻性、优秀的溶解度特性以及机械特性的效果。

Description

高耐蚀刻性旋涂式碳硬掩膜组合物以及利用该组合物的图案 化方法
技术领域
本发明涉及有用于半导体光刻工艺的具有高耐蚀刻性的硬掩膜组合物,更详细地说涉及具有能够承受多重蚀刻(mutil etch)过程的高耐蚀刻性的二苯并咔唑(dibenzocarbazole)聚合物的硬掩膜组合物与图案化方法。
背景技术
近来,随着半导体器件的小型化和集成化,正在要求精细的图案,作为形成这种精细图案的方法,通过曝光设备的开发或者通过附加工艺的导入的光致抗蚀剂图案精细化非常有效。
作为增加半导体装置的集成密度并且形成具有更加微小的纳米范围尺寸的结构的方法,正在开发具有高分辨率的光致抗蚀剂以及光刻工艺工具。
在制造半导体工艺中,过去使用波长为365nm的i线(i-line)光源在半导体基板上形成图案,但为了形成更加精细的图案需要具有更小波长带的光源。
实际上,从KrF(248nm)开始正在开发利用ArF(198nm)、EUV(extreme ultraviolet-极端紫外线,13.5nm)光源的光刻(lithography)技术,且目前已经商用化或者正在商用化,进而能够实现更加精细的波长。
随着图案尺寸变小,光致抗蚀剂的厚度逐渐变薄,以防止光致抗蚀剂图案的坍塌。使用变薄的光致抗蚀剂图案不能蚀刻被蚀刻层,因此在光致抗蚀剂层和蚀刻层之间导入具有优异的耐蚀刻性的膜,该膜被称为硬掩模。硬掩模工艺是指利用光致抗蚀剂图案蚀刻硬掩模进行图案化之后利用硬掩模的图案蚀刻被蚀刻层的工艺。所述硬掩膜由化学气相沉积(Chemical vapor deposition:CVD)方法或者旋涂(Spin On Coating)方法制造而成。
通过CVD方法制造的硬掩模膜具有由于使用蒸发器而出现的初始成本增加以及处理时间增加、颗粒问题等的缺点,因为这些缺点硬掩膜工艺正在利用可旋涂的材料而非沉积的材料,以持续努力缩短工艺时间。
旋涂法的硬掩膜工艺相比于CVD法具有初期投资成本低、涂敷均匀、容易控制涂敷厚度以及能够缩短工艺时间的优点。
另一方面,随着近年来半导体工艺变得更精细,线宽变得更窄,而高度保持不变或变得相对变高,使得图案的纵横比变高。随着硬掩模层的高度增加,在蚀刻工艺期间出现诸如弯曲(bowing)现象的问题,而且因为蚀刻的选择比不足而难以正常执行掩模功能。因此,正在要求改善蚀刻性的新的硬掩膜材料。
发明内容
(要解决的问题)
本发明涉及半导体制造工艺中的利用旋涂碳硬掩膜的高抗蚀性图案化方法以及组合物,目的在于提供蚀刻选择性高、对多次蚀刻具有足够的耐受性以及溶解性优秀的硬掩膜组合物以及利用该组合物的图案化方法.
(解决问题的手段)
根据本发明的一实施例,一种旋涂式硬掩膜组合物,具有由所述化学式1表示的二苯并咔唑(dibenzo carbazole)衍生物聚合物,并且重均分子量为3,000至8,000;
(化学式1)
Figure BDA0002027600080000031
在所述化学式中,l、m以及n的范围分别在1≤l≤20、1≤m≤20、1≤n≤20;
R1包含氢(H)、
Figure BDA0002027600080000032
中的任何一种;R2包含
Figure BDA0002027600080000033
Figure BDA0002027600080000034
中的任何一种;R3包含
Figure BDA0002027600080000035
Figure BDA0002027600080000036
Figure BDA0002027600080000041
中的任何一种。
根据本发明另一实施例,所述硬掩膜组合物包含:1重量%至50重量%的由所述化学式1表示的聚合物;50%至99重量%的有机溶剂;0至2重量%的表面活性剂。
根据本发明另一实施例,所述有机溶剂可从由丙二醇甲醚(PGME)、丙二醇甲醚醋酸酯(PGMEA)、环己酮、γ-丁内酯、乳酸乙酯(EL)、甲基乙基酮、n-乙酸正丁酯、N-甲基吡咯烷酮(NMP)、3-甲氧基丙酸甲酯(MMP)、3-乙氧基丙酸乙酯(EEP)、二甲基甲酰胺(DMF)中选择的一种或者两种以上的混合物组成的群组中选择。
根据本发明另一实施例,所述表面活性剂可从由聚氧乙烯烷基醚类、聚氧乙烯烷基苯基醚类、聚氧乙烯壬基苯醚类、聚氧乙烯辛基苯醚类、聚氧乙烯聚氧丙烯类、聚氧乙烯十二烷基醚类、聚氧乙烯山梨糖醇类中选择的一种或者两种以上的混合物组成的群组中选择。
根据本发明另一实施例,提供一种形成硬掩膜层的图案化方法,将所述组合物通过旋涂进行涂敷于被蚀刻层上部的工艺以及烘烤工艺。
根据本发明另一实施例,所述形成硬掩膜层的图案化方法是所述烘烤工艺在150℃至400℃的温度下进行1至5分钟。
(发明的效果)
本发明的高抗蚀性硬掩膜组合物可提供蚀刻选择性高、对多次蚀刻具有足够的耐受性以及溶解性优秀的效果。
附图说明
图1是由实施例2制造的聚合物的1H-NMR谱。
具体实施方式
以下,更加详细说明本发明。
本发明提供如下的旋涂式硬掩膜组合物:具有由以下化学式1表示的二苯并咔唑(dibenzo carbazole)衍生物聚合物或者包括该聚合物的结构,重均分子量在3,000至8,000,优选为3,500至7,000,更加优选为5,000至6,000;
(化学式1)
Figure BDA0002027600080000051
在所述化学式中,l、m以及n的范围分别在1≤l≤20、1≤m≤20、1≤n≤20;
R1包含氢(H)、
Figure BDA0002027600080000052
中的任何一种;R2包含
Figure BDA0002027600080000053
Figure BDA0002027600080000061
中的任何一种;R3包含
Figure BDA0002027600080000062
Figure BDA0002027600080000063
Figure BDA0002027600080000064
中的任何一种。
在所述化学式中,R2主要在酸(acid)催化剂条件下构成,具有提高所形成的高分子材料在有机溶剂中的溶解度的作用。
在所述化学式中,R3具有主要用于改善整个高分子结构的热固化反应性和蚀刻选择比的作用。
由所述化学式1表示的聚合物的特征在于,重均分子量为3,000至8,000,优选为3,500至7,000,更加优选为5,000至6,000。
在由所述化学式1表示的聚合物重均分子量未满3,500的情况下,不生成足够量的聚合物结构,因此降低耐蚀刻性;如果超过7,000的情况下,涂覆表面的物理性质可能不均匀。
所述硬掩膜组合物可包含:1重量%至50重量%的由所述化学式1表示的聚合物、50重量%至99重量%的有机溶剂、0至2重量%的表面活性剂。
所述聚合物成分未满1重量%或者超过50重量%的情况下,未满或者超过目标涂层厚度,因此难以正确调整涂层厚度;若超过涂层厚度,则涂敷性可变差。
所述有机溶剂可从由丙二醇甲醚(PGME)、丙二醇甲醚醋酸酯(PGME A)、环己酮、γ-丁内酯、乳酸乙酯(EL)、甲基乙基酮、n-乙酸正丁酯、N-甲基吡咯烷酮(NMP)、3-甲氧基丙酸甲酯(MMP)、3-乙氧基丙酸乙酯(EEP)、二甲基甲酰胺(DMF)中选择的一种或者一种以上的混合物构成的群组中选择。
所述表面活性剂是聚氧乙烯烷基醚类、聚氧乙烯烷基苯基醚类、聚氧乙烯壬基苯醚类、聚氧乙烯辛基苯醚类、聚氧乙烯聚氧丙烯类、聚氧乙烯十二烷基醚类、聚氧乙烯山梨糖醇类等非离子表面活性剂,可使用由这些表面活性剂单独或者混合物构成的群组中选择的。
所述表面活性剂可降低表面张力并增加铺展性和渗透性,进而可有助于可涂布性和间隙填充(Gapfill)性能。
根据本发明的另一实施例,提供一种图案化方法,通过旋涂将所述组合物进行涂敷于被蚀刻层上部以及烘烤工艺形成硬掩膜层。
对于所述组合物的涂敷厚度,不作特别限制,而是涂敷厚度可以是
Figure BDA0002027600080000071
Figure BDA0002027600080000072
Figure BDA0002027600080000073
所述烘烤工艺可在150℃至400℃的温度下进行1分钟至5分钟。在所述烘烤步骤中,所述组合物可引起自交联(self-crosslinking)反应。
(本发明的实施方式)
以下,说明本发明的优选实施例以及比较例。但是,以下的实施例不过是本发明的优选实施例,不得由以下的实施例限定本发明。
实施例1(合成二苯并咔唑系环聚合物)
Figure BDA0002027600080000081
加入20g的7-苯基二苯并[C,G]咔唑、9.7g的1,4-二甲氧基甲基苯、20.4g的9,9-双(4-羟基苯基)氟以及150g的丙二醇甲醚醋酸酯(PGMEA)之后制造氮环境。在此,加入0.16g的硫酸二乙酯将溶液加热至140℃并回流18小时。反应结束后,将所述溶液用己烷/甲醇/水(1:1:1)溶液提纯,并用甲醇/水(10:1)溶液再结晶,之后进行真空干燥,然后得到GPC测量结果,通过标准聚苯乙烯换算的重均分子量(Mw)为5,500的高分子化合物。
实施例2
Figure BDA0002027600080000082
除了添加26.2g的9,9-双(6-羟基-2-萘基)氟来代替9,9-双(4-羟基苯基)氟,以与实施例1相同的过程进行了合成。得到的高分子化合物的GPC测量结果,通过标准聚苯乙烯换算的重均分子量(Mw)为5,300。
实施例3
Figure BDA0002027600080000091
除了添加15.6g的3-羟基-二萘嵌苯来代替9,9-双(6-羟基-2-萘基)氟,以与实施例1相同的过程进行了合成。得到的高分子化合物的GPC测量结果,通过标准聚苯乙烯换算的重均分子量(Mw)为5,000。
实施例4
Figure BDA0002027600080000092
添加20g的7-(1-蒽基)二苯并[C,G]咔唑、7.5g的1,4-二甲氧基甲基苯、15.7g的9,9-双(4-羟基苯基)氟以及150g的丙二醇甲醚醋酸酯(PGMEA)。以与实施例1相同的方式合成之后得到的高分子化合物的GPC测量结果,通过标准聚苯乙烯换算的重均分子量(Mw)为5,400。
实施例5
Figure BDA0002027600080000101
除了添加20.2g的9,9-双(6-羟基-2-萘基)氟来代替9,9-双(4-羟基苯基)氟,以与实施例4相同的过程进行了合成。得到的高分子化合物的GPC测量结果,通过标准聚苯乙烯换算的重均分子量(Mw)为5,700。
实施例6
Figure BDA0002027600080000102
除了添加12g的3-羟基-二萘嵌苯来代替9,9-双(6-羟基-2-萘基)氟,以与实施例4相同的过程进行了合成。得到的高分子化合物的GPC测量结果,通过标准聚苯乙烯换算的重均分子量(Mw)为5,900。
实施例7
Figure BDA0002027600080000111
除了将反应时间改为10小时,以与实施例6相同的过程进行了合成。得到的高分子化合物的GPC测量结果,通过标准聚苯乙烯换算的重均分子量(Mw)为3,500。
实施例8
Figure BDA0002027600080000112
除了将反应时间改为27小时,以与实施例6相同的过程进行了合成。得到的高分子化合物的GPC测量结果,通过标准聚苯乙烯换算的重均分子量(Mw)为7,000。
比较例1
Figure BDA0002027600080000113
在20g的9,9-双(4-羟基苯基)氟与9.5g的1,4-二甲氧基甲基苯添加70g的PGEMA,之后添加0.16g的硫酸二乙酯。用与实施例1相同的方式合成之后得到的高分子化合物的GPC测量结果,通过标准聚苯乙烯换算的重均分子量(Mw)为5,600。
比较例2
除了将反应时间改为10小时,以与比较例1相同的过程进行了合成。得到的高分子化合物的GPC测量结果,通过标准聚苯乙烯换算的重均分子量(Mw)为3,300。
比较例3
除了将反应时间改为27小时,以与比较例1相同的过程进行了合成。得到的高分子化合物的GPC测量结果,通过标准聚苯乙烯换算的重均分子量(Mw)为7,200。
实验例1
加入2.5g的从实施例1中得到的高分子化合物、47.5g的丙二醇单甲醚乙酸酯,之后搅拌一天进行溶解。用0.2μm精细过滤器过滤该溶解液后制造了用于形成硬掩膜的组合物,并且利用旋涂机涂敷于硅晶片上。然后,在热板上以240℃加热一分钟以及连续以400℃加热一分钟形成了硬掩膜。
实验例2
除了使用2.5g的从实施例2得到的高分子化合物,以与实施例1相同的方法进行了实施。
实验例3
除了使用2.5g的从实施例3中得到的高分子化合物,以与实施例1相同的方法进行了实施。
实验例4
除了使用2.5g的从实施例4得到的高分子化合物,,以与实施例1相同的方法进行了实施。
实验例5
除了使用2.5g的从实施例5得到的高分子化合物,以与实施例1相同的方法进行了实施。
实验例6
除了使用2.5g的从实施例6得到的高分子化合物,以与实施例1相同的方法进行了实施。
实验例7
除了使用2.5g的从实施例7得到的高分子化合物,以与实施例1相同的方法进行了实施。
实验例8
除了使用2.5g的从实施例8得到的高分子化合物,以与实施例1相同的方法进行了实施。
比较实验例1
除了使用2.5g的从比较例1得到的高分子化合物,以与实施例1相同的方法进行了实施。
比较实验例2
除了使用2.5g的从比较例2得到的高分子化合物,以与实施例1相同的方法进行了实施。
比较实验例3
除了使用2.5g的从比较例3得到的高分子化合物,以与实施例1相同的方法进行了实施。
(测量重均分子量)
在所述实施例中得到的重均分子量是利用凝胶渗透色谱法(GPC)测量的。在测量中使用WATERS公司的GPC装置,且测量条件如下:
柱温度:40℃、流动相:四氢呋喃(THF)、流量:1mL/1min、GPC柱:使用STYRAGEL KF-801,802,803(WATERS公司,8X300mm)。
(光学性试验)
对从实验例1~实验例8以及比较实验例1~比较实验例3形成的硬掩膜分别测量了折射率(refractive index)n与消光系数(extinction cofficient)k,其结果显示于表1。使用设备利用了Ellipsometer(椭偏仪,Horiba)。
(表1)
样本 折射率(n@193nm) 消光系数(k@193nm)
实施例1 1.51 0.53
实施例2 1.52 0.53
实施例3 1.52 0.52
实施例4 1.53 0.52
实施例5 1.53 0.53
实施例6 1.54 0.53
实施例7 1.56 0.58
实施例8 1.57 0.59
比较例1 1.44 0.69
比较例2 1.44 0.70
比较例3 1.43 0.69
(评价干式蚀刻性)
对于实验例1~实验例8以及比较实验例1~比较实验例3形成的硬掩膜在干式蚀刻设备上使用CF4气体进行了10秒的干式蚀刻。干式蚀刻速度由【(干式蚀刻前的膜厚度-干式蚀刻后的膜厚度)/时间】定义。将ACL(amorphous carbon layer,非晶碳层)弄成100%的情况下,干式蚀刻特性显示硬掩膜的干式蚀刻速度,利用扫描电子显微镜(FE-SEM,Hitachi)确认横截面,并将测量结果显示于表2。
(表2)
Figure BDA0002027600080000151

Claims (14)

1.一种旋涂式硬掩膜组合物,其特征在于,
作为由以下化学式1表示的二苯并咔唑衍生物聚合物,包含重均分子量在3,000至8,000的聚合物;
化学式1
Figure FDA0003584812440000011
在所述化学式中,l、m以及n的范围分别在1≤l≤20、1≤m≤20、1≤n≤20;
R1为氢、
Figure FDA0003584812440000012
中的任何一种;R2为
Figure FDA0003584812440000013
R3为
Figure FDA0003584812440000014
Figure FDA0003584812440000015
中的任何一种。
2.根据权利要求1所述的旋涂式硬掩膜组合物,其特征在于,
聚合物的重均分子量在3,500至7,000。
3.根据权利要求2所述的旋涂式硬掩膜组合物,其特征在于,
聚合物的重均分子量在5,000至6,000。
4.根据权利要求1所述的旋涂式硬掩膜组合物,其特征在于,
所述硬掩膜组合物包含:二苯并咔唑衍生物聚合物、有机溶剂以及表面活性剂。
5.根据权利要求4所述的旋涂式硬掩膜组合物,其特征在于,
聚合物占据所述组合物总量的1至50重量%。
6.根据权利要求4所述的旋涂式硬掩膜组合物,其特征在于,
有机溶剂占据所述组合物总量的50至99重量%。
7.根据权利要求4所述的旋涂式硬掩膜组合物,其特征在于,
表面活性剂占据所述组合物总量的0至2重量%。
8.根据权利要求4所述的旋涂式硬掩膜组合物,其特征在于,
有机溶剂从由丙二醇甲醚、丙二醇甲醚醋酸酯、环己酮、γ-丁内酯、乳酸乙酯、甲基乙基酮、乙酸正丁酯、N-甲基吡咯烷酮、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、二甲基甲酰胺中选择的一种或者两种以上的混合物组成的群组中选择。
9.根据权利要求4所述的旋涂式硬掩膜组合物,其特征在于,
表面活性剂从由聚氧乙烯烷基醚类、聚氧乙烯烷基苯基醚类、聚氧乙烯聚氧丙烯类、聚氧乙烯山梨糖醇类中选择的一种或者两种以上的混合物组成的群组中选择。
10.根据权利要求4所述的旋涂式硬掩膜组合物,其特征在于,
聚合物占据所述组合物总量的1至50重量%;有机溶剂占据所述组合物总量的50至99重量%;表面活性剂占据所述组合物总量的0至2重量%。
11.根据权利要求10所述的旋涂式硬掩膜组合物,其特征在于,
有机溶剂从由丙二醇甲醚、丙二醇甲醚醋酸酯、环己酮、γ-丁内酯、乳酸乙酯、甲基乙基酮、乙酸正丁酯、N-甲基吡咯烷酮、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、二甲基甲酰胺中选择的一种或者两种以上的混合物组成的群组中选择。
12.根据权利要求10所述的旋涂式硬掩膜组合物,其特征在于,
表面活性剂从由聚氧乙烯烷基醚类、聚氧乙烯烷基苯基醚类、聚氧乙烯聚氧丙烯类、聚氧乙烯山梨糖醇类中选择的一种或者两种以上的混合物组成的群组中选择。
13.一种形成硬掩膜层的图案化方法,其特征在于,
将权利要求1至12中的任意一项的硬掩膜组合物通过旋涂进行涂敷于被蚀刻层上部的工艺以及烘烤工艺。
14.根据权利要求13所述的形成硬掩膜层的图案化方法,其特征在于,
所述烘烤工艺在150℃至400℃的温度下进行1至5分钟。
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WO2018070785A1 (ko) 2018-04-19
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