CN1702560A - 感光性树脂去除用的稀释剂组合物 - Google Patents
感光性树脂去除用的稀释剂组合物 Download PDFInfo
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Classifications
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Abstract
提供感光性树脂去除用稀释剂组合物,用于液晶显示设备中使用的玻璃基板及半导体制造时所用的晶片的周边和背面部分,短时间内可高效去除附着的没用的感光性树脂。本发明提供感光性树脂去除用稀释剂组合物,其包含a)烷基酰胺;和b)乙酸烷基酯。上述稀释剂组合物优选含有a)烷基酰胺1~99重量份;b)乙酸烷基酯1~80重量份。此外,本发明提供使用上述稀释剂组合物的半导体元件及液晶显示装置的制造方法。
Description
技术领域
本发明涉及感光性树脂去除用稀释剂组合物,具体来说,所述组合物用于液晶显示设备中所使用的玻璃基板及制造半导体时所用的晶片的周边及背面部分,能够在短时间内高效去除所附着的没用的感光性树脂,而且可应用于多种工艺,尤其是非旋转(spin-less)PR(感光性树脂)工艺,并可简化制造工艺,在经济效益上提高生产率。
背景技术
在半导体制造工艺中的光平版印刷术(photo lithography)工艺是首先将感光性树脂涂在晶片上,然后转印预先设计成的图案,沿着转印得到的图案进行适当的切削,通过这样的蚀刻工序制成电路,该工艺是非常重要的作业之一。
此平版印刷术工艺可大致分为:
1)在晶片表面均一涂布感光性树脂的步骤;
2)将涂布的感光性树脂中的溶剂蒸发,使感光性树脂粘附于晶片表面的轻度烘干步骤;
3)用紫外线等光源将掩模上的电路图案反复依次地在减少投影的同时使晶片曝光,将掩模上的图案复写到晶片上的曝光步骤;
4)使用显影液选择性地去除通过曝露于光源的感光而形成的诸如溶解度不同等物理性质各异的部分,进行显影步骤;
5)显影作业后为了加强晶片上残留的感光性树脂与基板的紧密附着,进行强烘干步骤;
6)沿着显影后的晶片的图案对规定部位进行蚀刻的蚀刻步骤;以及
7)在上述步骤之后,将无用的感光性树脂去除的剥离步骤等。
此平版印刷工艺中,在上述(2)轻烘干工艺之后,必须去除误涂于晶片边缘(edge)部分及背面的感光性树脂,因为如果在晶片边缘(edge)部分及背面存在感光性树脂的情况下进行蚀刻,这些感光性树脂的存在会给导入离子等后续步骤带来不良影响,也会带来导致整个半导体设备的收率降低的问题。
以前为了去除晶片边缘(edge)及背面存在的感光性树脂,主要采用在晶片边缘部分的上下安置喷射用喷嘴,并从所述喷嘴中向边缘及背面喷射由有机溶剂组成的稀释剂的方法。
作为以前用于去除感光性树脂的稀释剂组合物,下述专利文献1公开的方法是使用溶纤剂、乙酸溶纤剂、丙二醇醚、丙二醇醚醋酸酯等醚及醚醋酸酯类;丙酮、甲基乙基酮、甲基异丁基酮、环已酮等酮类;乳酸甲酯、乳酸乙酯、醋酸甲酯、醋酸乙酯、醋酸丁酯等酯类作为稀释剂组合物,将所述稀释剂与附着于基板的主道部、连道部、背部的无用的感光性树脂接触,从而将其去除。此外,下述专利文献2提出使用丙二醇甲基醚醋酸酯作为稀释剂组合物的方法,专利文献3中提出使用烷氧基丙酸烷基酯作为稀释剂组合物的方法。
在上述乙二醇单乙基醚醋酸酯的情况下,溶解速度很快,但易挥发并易燃,尤其还存在诱发白血球减少病、胎儿流产等生殖毒性的问题。另外,乳酸乙酯粘度高、溶解速度低,所以存在单独使用时无法充分洗净的问题。
因此,实情决定必须研发出一种用于液晶显示设备中所使用的玻璃基板及半导体制造用晶片的周边和背部,能在短时间内高效去除所附着的无用感光性树脂的稀释剂组合物。
[专利文献1]特开昭63-69563号
[专利文献2]特开平4-49938号
[专利文献3]特开平4-42523号
发明内容
为解决以往技术的问题,本发明的目的是提供感光性树脂去除用的稀释剂组合物,其用于液晶显示设备中所使用的玻璃基板及半导体制造时所用的晶片的周边和背面部分,可短时间内将所附着的没用的感光性树脂高效去除。
本发明的另一目的是提供感光性树脂去除用的稀释剂组合物,其对人体安全性高、对于作业人员更加安全,能适用于多种工艺,尤其能适用于非旋转(Spin-less)PR工艺,且可提高液晶显示设备及半导体制造工艺的生产率。
为了达成上述目的,本发明提供含有a)烷基酰胺;及b)乙酸烷基酯的用于去除感光性树脂的稀释剂组合物。
优选上述稀释剂组合物含有a)烷基酰胺1~99重量份;和b)乙酸烷基酯1~80重量份。
另外,本发明提供使用上述稀释剂组合物的半导体元件及液晶显示设备的制造方法。
本发明提供含有a)亚烷基二醇单烷基醚醋酸酯;b)烷基酰胺;及c)乙酸烷基酯的感光性树脂去除用稀释剂组合物。
优选上述稀释剂组合物含有a)亚烷基二醇单烷基醚醋酸酯1~80重量份;b)烷基酰胺1~98重量份;及c)乙酸烷基酯1~80重量份。
另外,本发明提供使用上述稀释剂组合物的半导体元件及液晶显示设备的制造方法。
本发明提供的感光性树脂去除用稀释剂组合物用于液晶显示设备中所使用的基板及半导体制造时所用的晶片时,不但短时间内可将所附着的没用的感光性树脂高效去除,而且对人体安全性高、对于作业人员更加安全,能适用于多种工艺,尤其能适用于非旋转(Spin-less)PR工艺,可简化液晶显示设备及半导体制造工艺,经济效益上提高生产收率。此外,本发明的感光性树脂去除用稀释剂组合物在去除残留于PR喷射头,即PR喷射用狭缝式喷嘴(slit nozzle)上无用的PR时有卓越的效果。
具体实施方式
以下对本发明进行详细说明。
本发明的感光性树脂去除用稀释剂组合物的特征为,含有a)烷基酰胺及b)乙酸烷基酯。
本发明中使用的烷基酰胺、乙酸烷基酯及亚烷基二醇单烷基醚醋酸酯在稀释剂组合物中用作溶剂,可使用各种半导体等级的极纯物质,并且可以使用过滤达到VLSI等级中0.1μm水准的物质。
本发明中使用的上述a)烷基酰胺可提高初期溶解速度,解决了液晶显示设备中所使用的玻璃基板及半导体制造工艺中发生的问题。
上述烷基酰胺可以使用N-甲基乙酰胺、二甲基甲酰胺或二甲基乙酰胺等,尤其优选二甲基乙酰胺。
上述烷基酰胺的含量优选占稀释剂组合物的1重量份~99重量份,其含量在此范围内时有利于提高挥发度及溶解力。
本发明中使用的上述b)乙酸烷基酯优选烷基的碳原子数为1~4的乙酸烷基酯,具体来说有乙酸甲酯、乙酸乙酯、乙酸异丙酯、乙酸正丙酯及乙酸丁酯等。
更优选的是上述乙酸烷基酯中粘性比较低、挥发度适中的乙酸异丙酯、乙酸正丙酯及乙酸丁酯。最优选乙酸丁酯,乙酸丁酯对于各种树脂的溶解性能良好,不仅仅表面张力低,而且即使向稀释剂组合物中只添加指定量的乙酸丁酯也能发挥其出色的界面特性。上述乙酸丁酯的毒性实验结果是小鼠的口服50%致死量LD50(mouse)为7.0g/kg,物理性质中沸点为126.1℃、燃点(闭杯式方法测定)为23℃、粘度(25℃)为0.74cps、表面张力为25dyne/cm2。
上述乙酸烷基酯的含量优选占稀释剂组合物的1重量份~80重量份,其含量在此范围内时有着合适的挥发度及溶解力,具有能够有效去除感光性树脂的优点。
本发明提供含a)亚烷基二醇单烷基醚醋酸酯、b)烷基酰胺及c)乙酸烷基酯的感光性树脂去除用稀释剂组合物,所述稀释剂组合物含a)亚烷基二醇单烷基醚醋酸酯1重量份~80重量份;b)烷基酰胺1重量份~98重量份;及c)乙酸烷基酯1重量份~80重量份。
本发明中使用的上述a)亚烷基二醇单烷基醚醋酸酯优选使用烷基的碳原子数为1~5个的亚烷基二醇单烷基醚醋酸酯,具体来说丙二醇单甲基醚醋酸酯、丙二醇单乙基醚醋酸酯、丙二醇单丙基醚醋酸酯、丙二醇单丁基醚醋酸酯等更好,尤其优选使用对高分子拥有卓越溶解力的丙二醇单甲基醚醋酸酯。
上述丙二醇单甲基醚醋酸酯暴露在空气中对人体的安全性高,从物质代谢方面来说,可以在人体中迅速分解成丙二醇和乙醇所以也很安全。毒性实验中,小鼠的口服50%致死量LD50(mouse)为8.5g/kg,并且因水解而迅速被分解。
上述亚烷基二醇单烷基醚醋酸酯优选占稀释剂组合物的1重量份~80重量份,其含量在此范围内时有着合适的挥发度及溶解力,能够更有效去除感光性树脂。
本发明中使用的b)烷基酰胺及c)乙酸烷基酯毋庸置疑可使用与上述相同的物质。
本发明提供使用上述稀释剂组合物的半导体元件及液晶显示装置的制造方法。
将含有上述成分的本发明的感光性树脂去除用稀释剂组合物通过滴加或喷嘴喷射的方式喷出,去除基板边缘及背面部分的无用感光性树脂。
上述感光性树脂去除用稀释剂组合物的滴加量或喷射量可根据感光性树脂的种类、膜的厚度进行调节,特别优选在5毫升/分钟~100毫升/分钟的范围内选择使用。此外,本发明在如上所述喷射稀释剂组合物后,经过后续的平版印刷工艺可形成微细电路的图案。
上述本发明的感光性树脂去除用稀释剂组合物和用其制造的半导体元件或液晶显示设备的方法,不仅能够短时间内将附着于液晶显示设备中所使用的玻璃基板或半导体制造中所使用的晶片的周边及背面部分的无用感光性树脂高效去除,而且对人体安全性高、对于作业人员更加安全,能适用于多种工艺,尤其能适用于非旋转(Spin-less)PR工艺,可简化液晶显示设备及半导体制造工艺,在经济上提高生产产率。此外,本发明的感光性树脂去除用稀释剂组合物在去除残留于PR喷射头,即PR喷射用狭缝喷嘴(slit nozzle)上无用的PR时有卓越的效果。
以下,举出优选的实施例以更好的理解本发明,但下文中的实施例只是例子而已,并不意味着本发明的范围只限于下述实施例。
实施例
实施例1
将70重量份醋酸正丁酯(n-buthyl acetate、nBA)及30重量份二甲基乙酰胺(dimethyl acetamide、DMAc)均匀混合,制成稀释剂组合物。
实施例2~7、及比较例1~5
上述实施例1中除了应用下表1所示的成分与组成比之外,采用与上述实施例1相同的方法制造稀释剂组合物。表1的单位为重量份。
[表1]
分类 | 实施例 | 比较例 | ||||||||||
1 | 2 | 3 | 4 | 5 | 6 | 7 | 1 | 2 | 3 | 4 | 5 | |
nBA | 70 | 60 | 40 | 30 | 20 | 30 | 45 | - | 50 | 30 | 60 | 80 |
nPAc | - | - | - | - | - | - | - | - | 50 | - | - | - |
DMAc | 30 | 40 | 10 | 10 | 10 | 20 | 10 | - | - | - | - | - |
PGMEA | - | - | 50 | 60 | 70 | 50 | 45 | 50 | - | 10 | - | 10 |
PGME | - | - | - | - | - | - | - | 50 | - | 60 | 40 | 10 |
[注]nBA:醋酸正丁酯(n-buthyl acetate)nPAc:醋酸正丙酯(n-propyl acetate)DMAc:二甲基乙酰胺(dimethyl acetamide)PGMEA:丙二醇单甲基醚醋酸酯(propyleneglycol monomethyl ether acetate)PGME:丙二醇单甲基醚(propyleneglycol monomethyl ether) |
为了测定上述实施例1~7及比较例1~5中所制稀释剂组合物对无用的感光性树脂的去除(Edge Bead Removing、EBR)程度,进行以下的EBR实验,其结果如下表4所示。
首先,在各含有过氧化氢/硫酸混合物的2个浴槽(bath)中将直径为8英寸的氧化硅基板洗净(每个浴槽中浸泡5分钟)后,用超纯水涮洗。此过程在定制的清洗设备中进行。然后,将这些基板在旋转干燥机(SRD 1800-6、VERTEQ社)中进行旋转干燥。之后,使用旋转被覆器(EBRTRACK、コリヨ半导体社)将下表2中所示的各种感光性树脂被覆在基板的上部表面形成一定厚度。上述旋转被覆操作中将10毫升感光性树脂滴在停止的基板中央。然后用旋转被覆器以500rpm的速度3秒钟将感光性树脂分布于基板后,使基板以约500rpm~1000rpm的旋转速度加速将各感光性树脂调整至规定的厚度。此时,旋转时间约为20秒~30秒。
分别向如上述那样准备的已被覆感光性树脂的基板上喷射上述实施例1~7及比较例1~5所制的稀释剂组合物,在下表3的条件去除感光性树脂。此时,各稀释剂组合物由配有压力计的加压筒(pressurizingvessel)供给,此时的加压压力为1.0kgf,EBR喷嘴中喷出的稀释剂组合物的流量为10毫升/分钟~20毫升/分钟。
[表2]
分类 | 组合物种类 | 组合物产品名 | 膜的厚度(μm) |
感光性树脂 | 正型 | DTFR-2000 | 1.5 |
g-line型正型 | DNR-H100PL | 4 | |
有机EL用PI | DL-1003 | 1.5 | |
ArF用 | DHA-TG2 | 2 |
[表3]
分类 | 旋转速度(rpm) | 时间(秒) |
分配(dispense)条件 | 300 | 3 |
旋涂 | 根据感光性树脂的厚度进行调节 | |
EBR条件 | 400 | 7 |
500 | 7 | |
500 | 10 |
[表4]
分类 | EBR条件 | 实施例 | 比较例 | ||||||||||
1 | 2 | 3 | 4 | 5 | 6 | 7 | 1 | 2 | 3 | 4 | 5 | ||
正型 | 400rpm7秒 | ○ | ◎ | ○ | ○ | ○ | ○ | ◎ | △ | × | × | △ | × |
500rpm7秒 | ◎ | ◎ | ○ | ○ | ○ | ○ | ◎ | △ | × | △ | △ | △ | |
500rpm10秒 | ◎ | ◎ | ○ | ○ | ○ | ○ | ◎ | △ | × | △ | △ | △ | |
g-line型负型 | 400rpm7秒 | ○ | ◎ | ○ | ○ | ○ | ○ | ◎ | △ | × | × | △ | × |
500rpm7秒 | ◎ | ◎ | ○ | ○ | ○ | ○ | ◎ | △ | × | × | △ | △ | |
500rpm10秒 | ◎ | ◎ | ○ | ○ | ○ | ○ | ◎ | △ | × | △ | △ | △ | |
有机EL型PI | 400rpm7秒 | ○ | ◎ | ○ | ○ | ○ | ○ | ◎ | △ | × | × | △ | × |
500rpm7秒 | ◎ | ◎ | ○ | ○ | ○ | ○ | ◎ | △ | × | × | △ | × | |
500rpm10秒 | ◎ | ◎ | ○ | ○ | ○ | ○ | ◎ | △ | × | △ | △ | △ | |
ArF用 | 400rpm7秒 | ○ | ◎ | ○ | ○ | ○ | ○ | ◎ | △ | × | × | △ | × |
500rpm7秒 | ◎ | ◎ | ○ | ○ | ○ | ○ | ◎ | △ | × | × | △ | × | |
500rpm10秒 | ◎ | ◎ | ○ | ○ | ○ | ○ | ◎ | △ | × | △ | △ | △ | |
[注]◎:EBR后,对于感光性树脂的EBR线均匀性保持一定○:EBR后,对于感光性树脂的EBR线均匀性大于等于80%,良好的直线状态△:EBR后,对于感光性树脂的EBR线均匀性大于等于50%,良好的直线状态×:EBR后,对于感光性树脂的EBR线均匀性不足50%,边缘部位的感光性树脂有拖尾现象发生 |
从上表4中可知,对于所有的感光性树脂本发明的实施例1~7的组合物具有出色的ERB性能(ERB线均匀性优良与否),相反也得知,对于感光性树脂的渗透抑制性能,与实施例相比,比较例1~5的性能明显降低。
Claims (9)
1.感光性树脂去除用稀释剂组合物,其含有a)烷基酰胺;及b)乙酸烷基酯。
2.如权利要求1所述的感光性树脂去除用稀释剂组合物,其含有1重量份~99重量份a)烷基酰胺;及1重量份~80重量份b)乙酸烷基酯。
3.如权利要求1所述的感光性树脂去除用稀释剂组合物,其特征在于,所述a)烷基酰胺是选自由N-甲基乙酰胺、二甲基甲酰胺及二甲基乙酰胺组成的组中的一种或一种以上。
4.如权利要求1所述的感光性树脂去除用稀释剂组合物,其特征在于,所述b)乙酸烷基酯是选自由烷基的碳原子数为1~4的乙酸甲酯、乙酸乙酯、乙酸异丙酯、乙酸正丙酯及乙酸丁酯组成的组中的一种或一种以上。
5.半导体元件或液晶显示设备的制造方法,其特征在于,使用权利要求1~4任意一项所述的感光性树脂去除用稀释剂组合物。
6.感光性树脂去除用稀释剂组合物,其含有a)亚烷基二醇单烷基醚醋酸酯;b)烷基酰胺;及c)乙酸烷基酯。
7.如权利要求6所述的感光性树脂去除用稀释剂组合物,其含有1重量份~80重量份a)亚烷基二醇单烷基醚醋酸酯;1重量份~98重量份b)烷基酰胺;及1重量份~80重量份c)乙酸烷基酯。
8.如权利要求6所述的感光性树脂去除用稀释剂组合物,其特征在于,所述a)的亚烷基二醇单烷基醚醋酸酯是选自由丙二醇单甲基醚醋酸酯、丙二醇单乙基醚醋酸酯、丙二醇单丙基醚醋酸酯及丙二醇单丁基醚醋酸酯组成的组中的一种或一种以上。
9.半导体元件或液晶显示设备的制造方法,其特征为,使用权利要求6~8中的任意一项所述的感光性树脂去除用稀释剂组合物。
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KR100843984B1 (ko) * | 2002-02-22 | 2008-07-07 | 주식회사 동진쎄미켐 | 감광성 수지 조성물을 제거하기 위한 씬너 조성물 |
-
2004
- 2004-05-25 KR KR1020040037385A patent/KR101142868B1/ko active IP Right Grant
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2005
- 2005-05-19 TW TW094116294A patent/TWI405051B/zh not_active IP Right Cessation
- 2005-05-19 JP JP2005146572A patent/JP4669737B2/ja not_active Expired - Fee Related
- 2005-05-25 CN CN2005100740420A patent/CN1702560B/zh not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106773562A (zh) * | 2016-12-23 | 2017-05-31 | 昆山艾森半导体材料有限公司 | 一种去除az光刻胶的去胶液 |
Also Published As
Publication number | Publication date |
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JP4669737B2 (ja) | 2011-04-13 |
KR101142868B1 (ko) | 2012-05-10 |
TW200604760A (en) | 2006-02-01 |
KR20050112333A (ko) | 2005-11-30 |
CN1702560B (zh) | 2011-08-03 |
TWI405051B (zh) | 2013-08-11 |
JP2005338825A (ja) | 2005-12-08 |
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