CN114942569A - 感光性高分子及包含它的抗蚀剂组合物 - Google Patents

感光性高分子及包含它的抗蚀剂组合物 Download PDF

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CN114942569A
CN114942569A CN202210138721.3A CN202210138721A CN114942569A CN 114942569 A CN114942569 A CN 114942569A CN 202210138721 A CN202210138721 A CN 202210138721A CN 114942569 A CN114942569 A CN 114942569A
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chemical formula
group
photosensitive polymer
hydrogen
resist composition
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崔相俊
金永善
吴载范
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Camiper Co Ltd
Olas Ltd
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Olas Ltd
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Abstract

本发明公开了一种包含衍生自化学式1或化学式2的乙烯基杂芳族化合物的重复单元的感光性高分子和包含该感光性高分子的抗蚀剂组合物。[化学式1]
Figure DDA0003505292060000011
[化学式2]
Figure DDA0003505292060000012
在所述化学式1或2中,R1、R2是氢或甲基,X是碳、硫或氮原子,n表示1或2。

Description

感光性高分子及包含它的抗蚀剂组合物
技术领域
本公开涉及一种感光性高分子及包含它的抗蚀剂组合物,该感光性高分子包含衍生自乙烯基杂芳族化合物的重复单元。
背景技术
随着半导体制造工艺变得复杂以及半导体元件的集成度增加,需要形成微细的图案。就抗蚀剂材料而言,相较于现有的利用KrF准分子激光(248nm)的抗蚀剂材料,更使用利用ArF准分子激光(193nm)的抗蚀剂材料,而ArF准分子激光采用短波长。
然而,在容量为16吉比特(Gigabit)以上的半导体元件中,由于设计规则要求图案尺寸为70nm以下,抗蚀剂膜的厚度逐渐变小,随着在蚀刻下膜层的工艺中工艺裕度减小,利用ArF准分子激光的抗蚀剂材料的使用也越来越受到限制。
与现有的抗蚀剂材料相比,这种利用ArF准分子激光的光刻中使用的抗蚀剂材料在商业化方面存在诸多问题。最典型的问题可以列举抗蚀剂对干式蚀刻的抗性。
作为迄今为止已知的现有ArF抗蚀剂,主要使用了丙烯酸或甲基丙烯酸高分子,其中最普遍使用的是聚(甲基丙烯酸酯)类高分子材料。这些高分子的严重问题是对干式蚀刻的抗性非常差。也就是说,由于这些材料在半导体元件制造工艺的使用等离子气体的干式蚀刻工艺中选择比太低,难以进行蚀刻工艺。
因此,为了增加对干式蚀刻的抗性,已经采用了引入对干式蚀刻具有较强抗性的物质脂环族化合物(alicyclic compound)的方法,例如将异冰片基(isobornyl group)、金刚烷基(adamantyl group)、三环癸基(tricyclodecanyl group)等作为高分子的取代基。然而,为了满足对显影液的溶解度以及对下膜层的粘合特性,它们的高分子形式主要具有三元共聚物(terpolymer)以上的结构,其中脂环基所占部分很小,因此对干式蚀刻的抗性仍然较差。此外,由于脂环族化合物是疏水性(hydrophobic),当如上所述的三元共聚物结构中包含很多脂环族化合物时,抗蚀剂膜对下膜层的粘合特性会变差。
作为根据另一现有技术的聚合物提出了COMA(cycloolefin-maleic anhydride)交替聚合物。在COMA形式共聚物的制备中,原料(raw material)成本低廉,但制备聚合物时合成收率和分辨率方面仍然存在问题。
另外,合成为上述结构的聚合物作为骨架具有疏水性很强的脂环基,因此对膜层粘合特性差。此外,不管怎样,对于所述COMA形式的感光性树脂,在抗蚀剂组合物的保存稳定性方面存在缺点。
发明内容
技术问题
本公开旨在提供一种感光性高分子,其包含衍生自乙烯基杂芳族化合物的重复单元,对干式蚀刻的抗性优异。
本公开旨在提供一种抗蚀剂组合物,其与KrF和ArF用抗蚀剂材料相比,干式蚀刻特性非常优异,适合于制造未来下一代半导体。
技术方案
根据实施例的感光性高分子包含衍生自化学式1或化学式2的乙烯基杂芳族化合物的重复单元。
[化学式1]
Figure BDA0003505292050000021
[化学式2]
Figure BDA0003505292050000022
在所述化学式1或2中,R1、R2是氢或甲基,X是碳、硫或氮原子,n表示1或2。
根据实施例的抗蚀剂组合物,其包含所述包含衍生自化学式1或化学式2的乙烯基杂芳族化合物的重复单元的感光性高分子、光酸产生剂和有机溶剂。
所述感光性高分子还包含衍生自选自由下述化学式3、化学式4和化学式5所组成的群组中的化合物的一个以上重复单元。
[化学式3]
Figure BDA0003505292050000031
[化学式4]
Figure BDA0003505292050000032
[化学式5]
Figure BDA0003505292050000033
在所述化学式3、化学式4和化学式5中,
R3和R5各自独立地为氢或甲基,
R4是在酸催化剂存在下分解的C4至C20的酸敏基团(acid-labile group)或内酯(lactone)衍生物,
R6是包含选自由氢、羟基、羧基和它们的组合所组成的群组中的极性基团(polargroup)的烷基或环烷基,
R7是包含选自由氢、羟基、羧基、磺酰基和它们的组合所组成的群组中的极性基团(polar group)的烷基或环烷基。
有益效果
根据实施例的感光性高分子,其包含衍生自乙烯基杂芳族化合物的重复单元,因此制造成本低廉,而且对干式蚀刻的蚀刻抗性以及对下膜层的粘合特性优异,在由金属材料构成的膜层中显示出防腐功能。
根据实施例的抗蚀剂组合物,其与现有的KrF和ArF用抗蚀剂材料相比,干式蚀刻特性非常优异,并且对下膜层的粘合特性优异,因此非常适合用于制造未来下一代半导体元件。
具体实施方式
在下文中,将详细描述实施例,以使本技术领域的普通技术人员容易实施。实施例能够以各种不同方式实施,不限于本文所描述的具体实施例。
除非本公开中使用的一些术语在下文中另有定义,否则本申请中使用的所有技术和科学术语具有与本发明所属技术领域的技术人员通常理解的相同含义。
除非另有说明,否则“烷基”是指C1至C20的烷基,更优选是指C1至C12的烷基,“低级烷基”是指C1至C4的烷基,“烷氧基”是指C1至C20的烷氧基,更优选是指C1至C12的烷氧基,“亚烷基”是指C1至C20的亚烷基,更优选是指C1至C12的亚烷基,“芳基”是指C6至C20的芳基,更优选是指C6至C12的芳基,“环烷基”是指C3至C14的环烷基。
根据本发明的一个实施方案的感光性高分子,其包含衍生自下述化学式1或化学式2的乙烯基杂芳族化合物的重复单元。
[化学式1]
Figure BDA0003505292050000041
[化学式2]
Figure BDA0003505292050000042
在所述化学式中,R1、R2是氢或甲基,X是碳、硫或氮原子,并且n表示1或2。
所述乙烯基杂芳族化合物优选可为选自由如下化合物所组成的群组中的任何一种。
Figure BDA0003505292050000051
所述乙烯基杂芳族化合物通过与具有各种功能性取代基的(甲基)丙烯酸类单体或苯乙烯类单体的自由基聚合容易合成感光性高分子(共聚物)。
通过如上所述的方法来制备的感光性高分子具有对干式蚀刻的蚀刻抗性,同时对下膜层的粘合特性优异,在由金属材料构成的膜层中具有防腐功能,从而非常有利于形成抗蚀剂图案。因此,克服了现有的KrF或ArF抗蚀剂材料所具有的对干式蚀刻的抗性以及对下膜层的粘合特性的缺点,在需要更高分辨率的半导体器件中也能充分发挥蚀刻掩模的作用。
所述感光性高分子包含所述衍生自乙烯基杂芳族化合物的重复单元和衍生自选自由下述化学式3、化学式4和化学式5所组成的群组中的化合物的一个以上重复单元。
[化学式3]
Figure BDA0003505292050000052
[化学式4]
Figure BDA0003505292050000061
[化学式5]
Figure BDA0003505292050000062
在所述化学式3、化学式4和化学式5中,R3和R5各自独立地为氢或甲基,R4是在酸催化剂存在下分解的C4至C20的酸敏基团(acid-labile group)或内酯(lactone)衍生物。
作为所述酸敏基团,优选选自由降冰片基、异冰片基、环癸基、金刚烷基、被低级烷基取代的降冰片基、被低级烷基取代的异冰片基、被低级烷基取代的环癸基、被低级烷基取代的金刚烷基、烷氧基羰基、烷氧基羰基烷基、戊氧基羰基、戊氧基羰基烷基、2-四氢吡喃氧基羰基烷基、2-四氢呋喃氧基羰基烷基、叔烷基和缩醛基所组成的群组中,更优选可选自由2-甲基-2-降冰片基、2-乙基-2-降冰片基、2-甲基-2-异冰片基、2-乙基-2-异冰片基、8-甲基-8-三环癸基、8-乙基-8-三环癸基、2-甲基-2-金刚烷基、2-乙基-2-金刚烷基、2-丙基-2-金刚烷基、叔丁氧基羰基、叔丁氧基羰基甲基、t-戊氧基羰基、t-戊氧基羰基甲基、1-乙氧基乙氧羰基甲基、2-四氢吡喃氧基羰基烷基、2-四氢呋喃氧基羰基烷基、叔丁基、三乙基二价碳基(triethylcarbyl)、1-甲基环己基、1-乙基环戊基、叔戊基和缩醛基所组成的群组中。
另外,对于所述内酯(lactone)衍生物,作为内酯(lactone)衍生物基团,优选可以列举具有下述化学式6和化学式7的结构的取代基。
[化学式6]
Figure BDA0003505292050000071
X1至X4中的两个各自独立地为C=O和O,除了C=O和O之外,其余为CR8,R8为氢、烷基或与五元环形成稠环的亚烷基。
[化学式7]
Figure BDA0003505292050000072
X5至X9中的两个各自独立地为C=O和O,除了C=O和O之外,其余为CR9,R9为氢、烷基或与六元环形成稠环的亚烷基,或者,
X5至X9均为CR9,R9为氢、烷基或与六元环形成稠环的含酯基的亚烷基,
至少两个R9相互连接而形成内酯环。
更优选地,R4选自由丁内酯基、戊内酯基、1,3-环己烷碳内酯基(1,3-cyclohexanecarbolactonyl)、2,6-降冰片烷碳内酯-5-基(2,6-norbonanecarbolacton-5-yl)和7-氧杂-2,6-降冰片烷碳内酯-5-基(7-oxa-2,6-norbornanecarbolacton-5-yl)所组成的群组中。
R6是包含选自由氢、羟基、羧基和它们的组合所组成的群组中的极性基团(polargroup)的烷基或环烷基。烷基是C2至C14的烷基,环烷基是C3至C14的环烷基。优选地,可以是2-羟基乙基、3-羟基-1-金刚烷基等。
R7是包含选自由氢、羟基、羧基、磺酰基和它们的组合所组成的群组中的极性基团(polar group)的烷基或环烷基。所述烷基是C2至C14的烷基,环烷基是C3至C14的环烷基。优选地,可以是氢、羟基、氟、甲基、甲氧基等。
也就是说,所述感光性高分子会具有所述化学式1或化学式2的乙烯基杂芳族化合物和所述化学式3至5的化合物的无规共聚物形式。优选地,所述感光性高分子具有3000至30000的重均分子量(Mw)。更优选地,具有5000至20000的重均分子量(Mw)。
另外,所述感光性高分子优选具有1.5至2.5的分散度(Mw/Mn)。在所述范围内,可以显示出优异的蚀刻抗性和分辨率。
根据本发明的实施方案的感光性高分子是包含衍生自具有新功能的乙烯基杂芳族化合物的重复单元的高分子(共聚物)形式,与现有的抗蚀剂材料相比,其优点是可获得对干式蚀刻和金属腐蚀的抗性非常优异的抗蚀剂组合物。
将如此获得的抗蚀剂组合物适用于光刻工艺时,可获得非常优异的光刻性能。
根据本发明的又一个实施方案,提供一种包含所述感光性高分子的抗蚀剂组合物。
具体地,所述抗蚀剂组合物包含所述(a)感光性高分子、(b)光酸产生剂(PAG:photoacid generator)和(c)溶剂。
在下文中,将详细描述根据本发明的一个实施方案的抗蚀剂组合物中包含的各成分。
(a)感光性高分子
感光性高分子如前所述。相对于抗蚀剂组合物100重量份,所述感光性高分子优选包含5至50重量份。当抗蚀剂组合物中包含的所述感光性高分子含量在如上所述的范围内时,可获得优异的蚀刻抗性和粘合特性。
(b)光酸产生剂(PAG)
所述光酸产生剂可选自由无机鎓盐(inorganic onium salts)、有机磺酸盐(organic sulfonates)及其混合物所组成的群组中。具体地,可以使用选自三芳基锍盐(triarylsulfonium salts)、二芳基碘鎓盐(diaryliodonium salts)、磺酸盐(sulfonates)或其混合物的锍盐或碘鎓盐。更优选地,选自由三芳基锍三氟甲磺酸盐、二芳基碘鎓三氟甲磺酸盐、三芳基锍全氟丁基磺酸盐、二芳基碘鎓全氟丁基磺酸盐、琥珀酰亚胺三氟甲磺酸盐、2,6-二硝基苄基磺酸盐及其混合物所组成的群组中。
相对于感光性高分子100重量份,所述光酸产生剂优选包含1至10重量份。如果所述光酸产生剂的含量小于1重量份,则对抗蚀剂组合物的曝光量可能会过度增加,而如果所述光酸产生剂的含量大于10重量份,则可能会存在对抗蚀剂组合物的穿透率不足的问题。
(c)有机溶剂(solvent)
作为有机溶剂,可以使用选自由丙二醇甲醚醋酸酯(PGMEA)、丙二醇甲醚(PGME)、乳酸乙酯(EL)、环己酮(cyclohexanone)、2-庚酮(2-heptanone)、γ-丁内酯(GBL)等所组成的群组中的一种以上。
有机溶剂作为剩余成分包含在抗蚀剂组合物中,其含量不受特别限制,但是相对于抗蚀剂组合物100重量份,优选包含50重量份至95重量份。
(d)酸抑制剂(acid quencher)
除了所述(a)至(c)的组分之外,所述抗蚀剂组合物还可包含有机碱(base),以控制曝光量以及形成抗蚀剂轮廓。
所述有机碱主要为三价胺(amine)形式,例如可以使用选自三乙胺、三异丁胺、三辛胺、三异癸胺、三乙醇胺或其混合物的胺类化合物。
相对于感光性高分子100重量份,所述有机碱的含量优选为0.01至1重量份。如果有机碱的含量小于0.01重量份,则无法期待所需的效果,而如果有机碱的含量大于1重量份,则曝光量会过度增加,甚至可能无法形成图案。
采用如下工艺,以利用具有上述组分的抗蚀剂组合物形成所需的图案。
准备裸硅晶片(bare silicon wafer)或上表面形成有氧化硅层、氮化硅层、氧氮化硅层或含金属的下膜层的硅晶片,对所述硅晶片进行HMDS处理或有机抗反射层处理。然后,在所述硅晶片上以约100至500nm的厚度涂布所述抗蚀剂组合物,以形成抗蚀剂膜。
对形成有所述抗蚀剂膜的所述硅晶片在约90至150℃的温度下进行预烘烤(SB)约60至120秒以去除溶剂,并利用各种曝光光源如KrF、ArF或EUV(极紫外)、电子束等进行曝光,然后在约90至120℃的温度下实施曝光后烘烤(PEB)约60至120秒,以在所述抗蚀剂膜的曝光区域引起化学反应。
然后,用2.38wt%四甲基氢氧化铵(TMAH)溶液对所述抗蚀剂膜进行显影,此时在曝光部分对碱性水溶液显影液显示出非常大的溶解度,因此在显影时容易溶解被去除。当所使用的曝光光源为ArF准分子激光时,可以在约5至30mJ/cm2的剂量(dose)下形成80至100nm的线与间隙图案(line and space pattern)。
将经由如上所述的过程而得到的抗蚀剂图案用作掩模,并使用特定的蚀刻气体如卤素气体或CxFy气体等等离子体,对下膜层进行蚀刻。接着,用剥离器(stripper)去除残留在晶片上的抗蚀剂图案,从而可以形成所需的图案。
在下文中,将列举实施例进一步详细描述本发明,但下述实施例是本发明的优选实施例而已,本发明不限于下述实施例。
实施例-1)感光性高分子的合成
Figure BDA0003505292050000101
将1-乙烯基咪唑(20mmol)、甲基丙烯酸叔丁酯(40mmol)、γ-丁内酯甲基丙烯酸酯(GBLMA)(20mmol)和3-羟基-1-金刚烷基甲基丙烯酸酯(HAMA)(20mmol)放入圆底烧瓶中使其溶解于二恶烷溶剂(单体总重量的3倍)后,其中作为聚合引发剂加入BPO(单体浓度的2%),并用氮气吹扫约20分钟,然后在80℃的温度下聚合约20小时。
聚合完成后,使反应物在过量的甲醇/水共溶剂中缓慢沉淀,对所生成的沉淀物进行过滤后,再将沉淀物溶解于适量的THF中,使其在甲醇/水共溶剂中重新沉淀。然后,将所得沉淀物在80℃的真空烘箱中干燥约24小时,从而合成出高分子(收率:80%)。
所合成的聚合物的重均分子量(Mw)为14900,分散度(Mw/Mn)为1.7。
实施例-2)感光性高分子的合成
Figure BDA0003505292050000102
通过与实施例-1)相同的方法将1-乙烯基-1,2,4-三唑(20mmol)、甲基丙烯酸叔丁酯(40mmol)、γ-丁内酯甲基丙烯酸酯(GBLMA)(20mmol)和3-羟基-1-金刚烷基甲基丙烯酸酯(HAMA)(20mmol)进行聚合,从而合成出高分子(收率:75%)。
此时,所得聚合物的重均分子量(Mw)为14600,分散度(Mw/Mn)为1.7。
实施例-3)感光性高分子的合成
Figure BDA0003505292050000111
通过与实施例-1)相同的方法将4-乙烯基吡啶(20mmol)、甲基丙烯酸叔丁酯(40mmol)、γ-丁内酯甲基丙烯酸酯(GBLMA)(20mmol)和3-羟基-1-金刚烷基甲基丙烯酸酯(HAMA)(20mmol)进行聚合,从而合成出高分子(收率:75%)。
此时,所得聚合物的重均分子量(Mw)为15500,分散度(Mw/Mn)为1.7。
实施例-4)感光性高分子的合成
Figure BDA0003505292050000112
通过与实施例-1)相同的方法将2-乙烯基吡嗪(20mmol)、甲基丙烯酸叔丁酯(40mmol)、γ-丁内酯甲基丙烯酸酯(GBLMA)(20mmol)和3-羟基-1-金刚烷基甲基丙烯酸酯(HAMA)(20mmol)进行聚合,从而合成出高分子(收率:75%)。
此时,所得聚合物的重均分子量(Mw)为14500,分散度(Mw/Mn)为1.8。
实施例-5)感光性高分子的合成
Figure BDA0003505292050000121
通过与实施例-1)相同的方法将1-乙烯基咪唑(20mmol)、甲基丙烯酸叔丁酯(40mmol)、苯乙烯(20mmol)和3-羟基-1-金刚烷基甲基丙烯酸酯(HAMA)(20mmol)进行聚合,从而合成出高分子(收率:75%)。
此时,所得聚合物的重均分子量(Mw)为14800,分散度(Mw/Mn)为1.7。
实施例-6)感光性高分子的合成
Figure BDA0003505292050000122
通过与实施例-1)相同的方法将1-乙烯基-1,2,4-三唑(20mmol)、甲基丙烯酸叔丁酯(40mmol)、苯乙烯(20mmol)和3-羟基-1-金刚烷基甲基丙烯酸酯(HAMA)(20mmol)进行聚合,从而合成出高分子(收率:70%)。
此时,所得聚合物的重均分子量(Mw)为14600,分散度(Mw/Mn)为1.7。
实施例-7)感光性高分子的合成
Figure BDA0003505292050000123
通过与实施例-1)相同的方法将4-乙烯基吡啶(20mmol)、甲基丙烯酸叔丁酯(40mmol)、苯乙烯(20mmol)和3-羟基-1-金刚烷基甲基丙烯酸酯(HAMA)(20mmol)进行聚合,从而合成出高分子(收率:75%)。
此时,所得聚合物的重均分子量(Mw)为14800,分散度(Mw/Mn)为1.7。
实施例-8)感光性高分子的合成
Figure BDA0003505292050000131
通过与实施例-1)相同的方法将1-乙烯基咪唑(20mmol)、甲基丙烯酸叔丁酯(40mmol)、苯乙烯(20mmol)和4-羟基苯乙烯(20mmol)进行聚合,从而合成出高分子(收率:70%)。
此时,所得聚合物的重均分子量(Mw)为16100,分散度(Mw/Mn)为1.7。
实施例-9)感光性高分子的合成
Figure BDA0003505292050000132
通过与实施例-1)相同的方法将1-乙烯基咪唑(20mmol)、甲基丙烯酸叔丁酯(40mmol)、苯乙烯(20mmol)和γ-丁内酯甲基丙烯酸酯(GBLMA)(20mmol)进行聚合,从而合成出高分子(收率:75%)。
此时,所得聚合物的重均分子量(Mw)为15100,分散度(Mw/Mn)为1.7。
实施例-10)感光性高分子的合成
Figure BDA0003505292050000133
通过与实施例-1)相同的方法将1-乙烯基咪唑(20mmol)、甲基丙烯酸叔丁酯(40mmol)、4-羟基苯乙烯(20mmol)和γ-丁内酯甲基丙烯酸酯(GBLMA)(20mmol)进行聚合,从而合成出高分子(收率:75%)。
此时,所得聚合物的重均分子量(Mw)为16200,分散度(Mw/Mn)为1.7。
实施例-11)感光性高分子的合成
Figure BDA0003505292050000141
通过与实施例-1)相同的方法将1-乙烯基咪唑(20mmol)、甲基丙烯酸叔丁酯(40mmol)、4-羟基苯乙烯(20mmol)和1-金刚烷基丙烯酸酯(20mmol)进行聚合,从而合成出高分子(收率:75%)。
此时,所得聚合物的重均分子量(Mw)为15500,分散度(Mw/Mn)为1.7。
实施例-12)感光性高分子的合成
Figure BDA0003505292050000142
通过与实施例-1)相同的方法将1-乙烯基咪唑(20mmol)、γ-丁内酯甲基丙烯酸酯(20mmol)、苯乙烯(20mmol)和2-甲基-2-金刚烷基甲基丙烯酸酯(40mmol)进行聚合,从而合成出高分子(收率:75%)。
此时,所得聚合物的重均分子量(Mw)为15300,分散度(Mw/Mn)为1.7。
对比实施例)感光性高分子的合成
Figure BDA0003505292050000143
通过与实施例-1)相同的方法将甲基丙烯酸叔丁酯(40mmol)、γ-丁内酯甲基丙烯酸酯(GBLMA)(40mmol)和3-羟基-1-金刚烷基甲基丙烯酸酯(HAMA)(20mmol)进行聚合,从而合成出高分子(收率:80%).
此时,所得聚合物的重均分子量(Mw)为15900,分散度(Mw/Mn)为1.7。
实施例-13)抗蚀剂组合物的制备和光刻性能
将所述实施例-1~12和对比实施例中合成的各感光性高分子(1g)与三苯基锍全氟丁基磺酸盐(0.02g)一起溶解于PGMEA/EL(6/4)(17g)中,然后加入有机碱三乙醇胺(1mg)使其完全溶解,以制备各抗蚀剂组合物。
实施例-14)评价抗蚀剂分辨率
利用0.1μm膜过滤器对所述实施例-13)中制备的各抗蚀剂溶液进行过滤。将过滤后的抗蚀剂溶液以140nm的厚度涂布在经过厚度为
Figure BDA0003505292050000152
的有机BARC(AR46,Rhom&HassCompany)处理的硅晶片上,然后在130度的温度下预烘烤(soft baking:SB)60秒。
使用ArF扫描仪(0.78NA,dipole)以20~50mj/cm2进行曝光后,在110度的温度下实施PEB(post-exposure bake)60秒,然后在2.38重量%的TMAH溶液中显影60秒。其结果,获得了如下表1所示的干净的90~100nm的L/S图案,分辨率优于对比实施例的高分子。
【表1】
Figure BDA0003505292050000151
Figure BDA0003505292050000161
实施例-15)评价蚀刻抗性
为了评价所述实施例-13)中制备的各抗蚀剂组合物的蚀刻特性,按照RIE(反应离子蚀刻)方式在CF4气体(组分;功率100W,压力5Pa,流速30ml/min)条件下进行整体蚀刻(bulk etch)评价。此时,对于所采用的参考值(reference),以KrF用抗蚀剂聚羟基苯乙烯(PHS)高分子(KrF用高分子)的蚀刻速度(etching rate)为准进行标准化(normalized),以作为评价的参考值。测量结果示于表2中,在本发明的高分子的情况下,相对于KrF用高分子,分别显示出约1.1倍(normalized)的蚀刻速度,在对比实施例的高分子的情况下,显示出1.5倍左右的蚀刻速度,可以确认本发明的高分子具有很强的蚀刻抗性。
【表2】
高分子种类 PHS(normalized) 蚀刻速度(%)
实施例1 100% 110
实施例2 100% 110
实施例3 100% 110
实施例4 100% 110
实施例5 100% 108
实施例6 100% 108
实施例7 100% 108
实施例8 100% 103
实施例9 100% 105
实施例10 100% 105
实施例11 100% 103
实施例12 100% 102
对比实施例 100% 150
在上文中,已经描述了各种实施例,但是权利范围不限于上述实施例。所实施的方式可在说明书和附图范围内以各种方式变形实施,这些自然也落入权利范围内。

Claims (12)

1.一种感光性高分子,其包含衍生自下述化学式1或化学式2的乙烯基杂芳族化合物的重复单元,
[化学式1]
Figure FDA0003505292040000011
[化学式2]
Figure FDA0003505292040000012
在所述化学式1或2中,
R1、R2是氢或甲基,
X是碳、硫或氮原子,
n表示1或2。
2.根据权利要求1所述的感光性高分子,其中,
所述乙烯基杂芳族化合物是选自由具有下述结构的化合物所组成的群组中的任何一种,
Figure FDA0003505292040000013
3.一种感光性高分子,其包含衍生自下述化学式1或化学式2的乙烯基杂芳族化合物的重复单元;以及
[化学式1]
Figure FDA0003505292040000021
[化学式2]
Figure FDA0003505292040000022
在所述化学式1或2中,
R1、R2是氢或甲基,
X是碳、硫或氮原子,
n表示1或2,
衍生自选自由下述化学式3、化学式4和化学式5所组成的群组中的化合物的一个以上重复单元,
[化学式3]
Figure FDA0003505292040000023
[化学式4]
Figure FDA0003505292040000024
[化学式5]
Figure FDA0003505292040000031
在所述化学式3、化学式4或化学式5中,
R3和R5各自独立地为氢或甲基,
R4是在酸催化剂存在下分解的C4至C20的酸敏基团或内酯衍生物基团,
R6是包含选自由氢、羟基、羧基和它们的组合所组成的群组中的极性基团的烷基或环烷基,
R7是包含选自由氢、羟基、羧基、磺酰基和它们的组合所组成的群组中的极性基团的烷基或环烷基。
4.根据权利要求3所述的感光性高分子,其中,
所述酸敏基团是选自由降冰片基、异冰片基、环癸基、金刚烷基、被低级烷基取代的降冰片基、被低级烷基取代的异冰片基、被低级烷基取代的环癸基、被低级烷基取代的金刚烷基、烷氧基羰基、烷氧基羰基烷基、戊氧基羰基、戊氧基羰基烷基、2-四氢吡喃氧基羰基烷基、2-四氢呋喃氧基羰基烷基、叔烷基和缩醛基所组成的群组中的任何一个。
5.根据权利要求3所述的感光性高分子,其中,
所述内酯衍生物基团是具有下述化学式6或7的结构的取代基,
[化学式6]
Figure FDA0003505292040000032
在所述化学式6中,X1至X4中的两个各自独立地为C=O和O,除了C=O和O之外,其余为CR8,R8为氢、烷基或与五元环形成稠环的亚烷基,
[化学式7]
Figure FDA0003505292040000041
在所述化学式7中,X5至X9中的两个各自独立地为C=O和O,除了C=O和O之外,其余为CR9,R9为氢、烷基或与六元环形成稠环的亚烷基,
X5至X9均为CR9,R9为氢、烷基或与六元环形成稠环的含酯基的亚烷基,
至少两个R9相互连接而形成内酯环。
6.根据权利要求5所述的感光性高分子,其中,
所述内酯衍生物基团为丁内酯基、戊内酯基、1,3-环己烷碳内酯基、2,6-降冰片烷碳内酯-5-基或7-氧杂-2,6-降冰片烷碳内酯-5-基。
7.根据权利要求3所述的感光性高分子,其中,
所述乙烯基杂芳族化合物是选自由具有下述结构的化合物所组成的群组中的任何一种,
Figure FDA0003505292040000042
8.根据权利要求3所述的感光性高分子,其中,
所述感光性高分子的分子量是重均分子量(Mw)为3000至30000。
9.一种抗蚀剂组合物,其包含:
(a)根据权利要求1至8中任何一项所述的感光性高分子;
(b)光酸产生剂(PAG);以及
(c)有机溶剂。
10.根据权利要求9所述的抗蚀剂组合物,其中,
相对于所述抗蚀剂组合物100重量份,所述感光性高分子包含5至50重量份。
11.根据权利要求9所述的抗蚀剂组合物,其中,
相对于所述感光性高分子100重量份,所述光酸产生剂包含1至10重量份。
12.根据权利要求9所述的抗蚀剂组合物,其中,
相对于所述感光性高分子100重量份,所述抗蚀剂组合物包含有机碱0.01至1重量份。
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