CN1251030C - 光致抗蚀剂显影剂组合物 - Google Patents
光致抗蚀剂显影剂组合物 Download PDFInfo
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G—PHYSICS
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- Spectroscopy & Molecular Physics (AREA)
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Abstract
本发明公开一种在薄膜晶体管型液晶显示装置(TFT-LCD)或半导体制备中用于形成光致抗蚀剂图案的光致抗蚀剂显影剂组合物。该光致抗蚀剂显影剂组合物在总显影剂组合物中包括按重量计为1.0~10.0%的无机碱性化合物、按重量计为0.1~3.0%的有机溶剂、按重量计为1.0~20.0%的表面活性剂、按重量计为67~97.9%的水。优选的表面活性剂是阴离子表面活性剂和非离子表面活性剂的混合物,并且阴离子表面活性剂和非离子表面活性剂的比例按重量计为1∶10~1∶100。该显影剂组合物可用水稀释使得在最终显影剂组合物中该显影剂组合物按重量计为0.5~5.0%。该光致抗蚀剂显影剂组合物可防止曝光抗蚀剂区表面的侵蚀,并对非曝光抗蚀剂区具有较好的显影能力,及可最小化显影步骤后残渣的出现。
Description
技术领域
本发明涉及一种光致抗蚀剂显影剂组合物,特别涉及一种在薄膜晶体管型液晶显示装置(TFT-LCD)或半导体制备中用于形成光致抗蚀剂图案的光致抗蚀剂显影剂组合物。
背景技术
诸如TFT-LCD电路、半导体集成电路等微电路图案通常由以下步骤形成。首先,通过将包括粘合剂、光致聚合单体、引发剂、有机溶剂等的抗蚀剂组合物涂布于形成在基底上的绝缘层或导电金属层上,并烘焙经涂布的抗蚀剂组合物,从而形成抗蚀剂层。然后,将带有预定电路图案的掩膜置于该抗蚀剂层上,并用UV线、E-电子束或诸如X-射线的电子束照射该抗蚀剂层。曝光区和非曝光区在显影剂组合物中有不同的溶解性。因此,通过使用显影剂组合物显影曝光区或非曝光区可形成所需要的抗蚀剂图案。最后,将经显影的抗蚀剂图案曝光的绝缘层或导电金属层蚀刻以形成目标电路图案。
抗蚀剂显影步骤对于形成所需要的精细和精确抗蚀剂图案是非常重要的步骤。抗蚀剂图案的形状和线宽及抗蚀剂的溶解性取决于显影剂组合物的种类和pH及显影剂组合物中表面活性剂的种类和数量。通过将非离子或离子型表面活性剂和有机或无机碱性水溶液混合可制得常规显影剂组合物。有机显影剂组合物包括有机碱性化合物,如四甲基氢氧化铵、胆碱等。然而,有机显影剂组合物对于抗蚀剂具有较低的渗透性和较低的溶解性,从而增加显影抗蚀剂所需要的时间,并破坏抗蚀剂分布的形状和抗蚀剂图案的尺寸精度。因此,工业上更广泛使用的是无机显影剂组合物,其可通过混合非离子或离子型表面活性剂和无机碱性水溶液制得,无机碱性水溶液包括氢氧化钾、氢氧化钠、磷酸钠、硅酸钠、碳酸钠、碳酸氢钠水溶液等。由于无机显影剂组合物对水有较高的溶解性并具有较高的碱度,其对于抗蚀剂层具有更令人满意的渗透性。从而在显影抗蚀剂图案中无机显影剂组合物比有机显影剂组合物更有效。然而由于其组分的原因,无机显影剂组合物的渗透性不总是令人满意的,并且在显影步骤后可能留有残渣。由此,为了制备所需要的没有或带有少量残渣的精确抗蚀剂图案,工业上需要开发对抗蚀剂层有足够的渗透性并具有更佳显影性质的显影剂组合物。
发明内容
因此,本发明的目的是提供一种对光致抗蚀剂层具有足够的渗透性和溶解性的光致抗蚀剂显影剂组合物,其可形成所需要的精确光致抗蚀剂图案。本发明的另一个目的是提供一种光致抗蚀剂显影剂组合物,其组分彼此间具有更佳的相容性并且可最小化显影步骤后残渣的出现。本发明的另一个目的是提供一种光致抗蚀剂显影剂组合物,其可根据显影步骤的条件在用水稀释后使用。
为实现这些和其它的目的,本发明提供的光致抗蚀剂显影剂组合物在总显影剂组合物中包括按重量计为1.0~10.0%的无机碱性化合物、按重量计为0.1~3.0%的有机溶剂、按重量计为1.0~20.0%的表面活性剂及按重量计为67~97.9%的水。优选的表面活性剂是阴离子表面活性剂和非离子表面活性剂的混合物,并且阴离子表面活性剂和非离子表面活性剂的比例按重量计为1∶10~1∶100。
具体实施方式
结合下面的详细说明可更充分地理解本发明更全面的价值及其许多附随的优点。
本发明的光致抗蚀剂显影剂组合物包括无机碱性化合物、有机溶剂、表面活性剂和水。该无机碱性化合物可选自氢氧化钾、氢氧化钠、磷酸钠、硅酸钠、碳酸钠、碳酸氢钠及其混合物。在总显影剂组合物中无机碱性化合物的量优选按重量计为1.0~10.0%,更优选按重量计为1.0~5.0%。当无机碱性化合物的量按重量计小于1.0%时,光致抗蚀剂显影剂组合物进入抗蚀剂层的聚合物组分中的渗透性不足,欲显影的抗蚀剂区不能充分地溶解在光致抗蚀剂显影剂组合物中。当无机碱性化合物的量按重量计大于10.0%时,光致抗蚀剂显影剂组合物的渗透性过度增加,显影步骤后欲保留的抗蚀剂区会部分地被显影或侵蚀,从而破坏显影的抗蚀剂分布的形状。
在本发明的光致抗蚀剂显影剂组合物中,有机溶剂优选包括和水有充分混合性并能够溶解抗蚀剂层的有机化合物。示例性的有机溶剂包括甲醇、乙醇、1-丙醇、2-丙醇、丁醇、双丙酮醇、乙二醇单甲基醚、乙二醇单乙基醚、乙二醇单丁基醚、二乙二醇单甲基醚、二乙二醇单乙基醚、二丙二醇单甲基醚、二丙二醇单乙基醚及其混合物。在总显影剂组合物中有机溶剂的量优选按重量计为0.1~3.0%,更优选按重量计为0.5~2.0%。当有机溶剂的量按重量计小于0.1%时,抗蚀剂层中低分子量树脂的溶解性下降。当有机溶剂的量按重量计大于3.0%时,碱性化合物的电离度不合需要地下降。
在本发明的光致抗蚀剂显影剂组合物中,优选的表面活性剂包括阴离子表面活性剂和非离子表面活性剂。示例性的非离子表面活性剂包括聚氧化烷基醚(polyoxyalkylether),如聚氧化乙基醚、聚氧化丙基醚、聚氧化乙基辛基苯基醚、聚氧化丙基辛基苯基醚、聚氧化乙基丙基醚、聚氧化乙基丙基辛基苯基醚及其混合物,示例性的阴离子表面活性剂包括烷基硫酸钠,如月桂基醚硫酸钠等。优选的表面活性剂是可和水及有机溶剂混合的,并可溶解在水及有机溶剂中。阴离子表面活性剂可提高水及有机溶剂的溶解性。在总显影剂组合物中有机溶剂的量优选按重量计为1.0~20.0%,阴离子表面活性剂和非离子表面活性剂的比例优选按重量计为1∶10~1∶100。当表面活性剂的量按重量计小于1.0%时,显影剂组合物对抗蚀剂层的润湿性下降,并且对抗蚀剂层的显影能力也下降。当表面活性剂的量按重量计大于20.0%时,显影剂组合物的润湿性过度增加,显影步骤后欲保留的抗蚀剂区会部分地被显影或侵蚀,甚至在洗涤经显影的抗蚀剂图案后,多余的残渣也可能留在抗蚀剂图案上。当阴离子表面活性剂和非离子表面活性剂的比例小于1∶10时,对抗蚀剂层的显影能力不合需要地下降。当此比例大于1∶100时,显影剂组合物组分间的可混合性被破坏。
本发明的光致抗蚀剂显影剂组合物含有水,优选用离子交换树脂过滤的纯化水(去离子水)。更优选的水是具有大于18兆欧(MΩ)比电阻的纯化水。在总显影剂组合物中水的量优选按重量计为67~97.9%。当水的量按重量计小于67%时,难于处理显影抗蚀剂图案后产生的显影剂废物。当水的量按重量计大于97.9%时,显影剂的运输和储存成本不合需要地增加。
本发明的光致抗蚀剂显影剂组合物可用水稀释,以适合于显影步骤的条件,如抗蚀剂层的类型及制造TFT-LCD或半导体的其它步骤条件。当显影剂组合物被稀释时,优选稀释的本发明光致抗蚀剂显影剂组合物在最终显影剂组合物中按重量计为0.5~5.0%。当在最终显影剂组合物中本发明的显影剂组合物的量按重量计小于0.5%时,最终显影剂组合物的显影能力不充分。当在最终显影剂组合物中本发明的显影剂组合物的量按重量计大于5.0%时,难于处理显影抗蚀剂图案后产生的显影剂废物。
下文中为更好地理解本发明提供了本发明的优选实施例。然而下面的实施例是这了阐明本发明,但是本发明不限于这些实施例。在下面的实施例中如果没有特别指出百分比和比例分别是指重量百分比和重量比例。
实施例
试样的制备:将常规彩色抗蚀剂组合物(制造商:Fuji Film Arch Co.,Ltd.,商品名:CR-8131L、CR-8130L、CB-8140L、CR-8100L、CB-8100L)旋转涂布于沉积在LCD玻璃上的铬黑矩阵上,以制得厚度为1.5μm的抗蚀剂层。使用电烤盘在90℃下预烘焙该抗蚀剂层90秒,并将掩膜置于该抗蚀剂层上。用电子束曝光(200mJ/cm2)该抗蚀剂层以制得试样。
显影剂组合物的制备:如表1所示通过调节无机碱性化合物、有机溶剂、表面活性剂、水的量和种类制备实施例1~8和对比实施例1~4中的显影剂组合物。
表1
(a)无机碱性化合物 | (b)有机溶剂 | (c)表面活性剂 | (d)水 | ||||||||
实施例 | KOH | NaOH | Na2CO3 | MeOH | EtOH | EGEE | DPGME | POEO | ES | 水 | |
1 | 1.0 | 1.0 | 10.0 | 0.8 | 87.2 | ||||||
2 | 3.0 | 1.0 | 10.0 | 0.5 | 85.5 | ||||||
3 | 5.0 | 1.0 | 5.0 | 0.3 | 88.7 | ||||||
4 | 8.0 | 1.0 | 5.0 | 0.1 | 85.9 |
5 | 3.0 | 1.0 | 10.0 | 0.8 | 85.2 | ||||||
6 | 8.0 | 1.0 | 5.0 | 0.3 | 85.7 | ||||||
7 | 2.0 | 1.0 | 10.0 | 0.8 | 86.2 | ||||||
8 | 5.0 | 1.0 | 5.0 | 0.3 | 88.7 | ||||||
(a)无机碱性化合物 | (b)有机溶剂 | (c)表面活性剂 | (d)水 | ||||||||
对比实施例 | KOH | TMAH | MeOH | EtOH | EGEE | DPGME | POEO | ES | 水 | ||
1 | 0.5 | 2.0 | 5.0 | 0.1 | 92.4 | ||||||
2 | 5.0 | 5.0 | 0.5 | 89.5 | |||||||
3 | 3.0 | 3.0 | 10.0 | 0.5 | 83.5 | ||||||
4 | 8.0 | 1.0 | 5.0 | 0.3 | 83.7 |
在表1中,KOH是氢氧化钾,NaOH是氢氧化钠,Na2CO3是碳酸钠,MeOH代表甲醇,EtOH代表乙醇,EGEE代表乙二醇单乙基醚,DPGME代表二丙二醇单甲基醚,POEO代表聚氧化乙基辛基苯基醚,ES代表月桂基醚硫酸钠,TMAH代表四甲基氢氧化铵。
将表1所示的实施例和对比实施例中的显影剂组合物在100秒内喷射在曝光的抗蚀剂层上,并用去离水(D.I.水)洗涤该抗蚀剂层,再干燥。用裸眼和电子显微镜(制造商:LEICA Co.,Ltd.,型号:FTM-200)观察经显影的抗蚀剂层,根据显影区和非显影区形成的抗蚀剂图案的形状和表面状况测定经显影的抗蚀剂层是“好”或“差”。结果如表2所示。
表2
观察方法 | 裸眼观察 | 电子显微镜观察 |
实施例1 | 好 | 好 |
实施例2 | 好 | 好 |
实施例3 | 好 | 好 |
实施例4 | 好 | 好 |
实施例5 | 好 | 好 |
实施例6 | 好 | 好 |
实施例7 | 好 | 好 |
实施例8 | 好 | 好 |
对比实施例1 | 好 | 差 |
对比实施例2 | 好 | 差 |
对比实施例3 | 差 | 差 |
对比实施例4 | 差 | 差 |
如表2所示,当用本发明实施例的光致抗蚀剂显影剂组合物进行显影步骤时,曝光的残留图案区和未曝光的显影区形成所需要的形状分布。然而,当用对比实施例的光致抗蚀剂显影剂组合物进行显影步骤时,残留图案的形状被破坏并且是不合需要的。即本发明的光致抗蚀剂显影剂组合物在曝光的抗蚀剂区表面未引起侵蚀,并且对非曝光区具有较好的显影性质而没有留下残渣。
如前所述,本发明的光致抗蚀剂显影剂组合物克服了常规显影剂组合物的缺点,如难于洗涤、难于侵蚀曝光区表面等。此外,本发明的光致抗蚀剂显影剂组合物对抗蚀剂层具有较好的渗透性、具有较好的显影和溶解能力及对抗蚀剂层具有较好的润湿性。因此本发明的组合物可以形成所需要的高精确抗蚀剂图案,并且可最小化显影步骤后残渣的出现。
Claims (5)
1.一种光致抗蚀剂显影剂组合物,在总显影剂组合物中包括:
按重量计为1.0~10.0%的无机碱性化合物;
按重量计为0.1~3.0%的有机溶剂;
按重量计为1.0~20.0%的表面活性剂;及
按重量计为67~97.9%的水,其中
所述的无机碱性化合物选自氢氧化钾、氢氧化钠、磷酸钠、硅酸钠、碳酸钠、碳酸氢钠及其混合物;
所述的有机溶剂选自甲醇、乙醇、1-丙醇、2-丙醇、丁醇、双丙酮醇、乙二醇单甲基醚、乙二醇单乙基醚、乙二醇单丁基醚、二乙二醇单甲基醚、二乙二醇单乙基醚、二丙二醇单甲基醚、二丙二醇单乙基醚及其混合物;
所述的表面活性剂是阴离子表面活性剂和非离子表面活性剂的混合物;
所述的非离子表面活性剂选自聚氧化乙基醚、聚氧化丙基醚、聚氧化乙基辛基苯基醚、聚氧化丙基辛基苯基醚、聚氧化乙基丙基醚、聚氧化乙基丙基辛基苯基醚及其混合物,所述的阴离子表面活性剂是烷基硫酸钠。
2.如权利要求1所述的光致抗蚀剂显影剂组合物,其中所述的无机碱性化合物在总显影剂组合物中按重量计为1.0~5.0%。
3.如权利要求1所述的光致抗蚀剂显影剂组合物,其中所述的有机溶剂在总显影剂组合物中按重量计为0.5~2.0%。
4.如权利要求1-3任一权利要求所述的光致抗蚀剂显影剂组合物,其中所述的阴离子表面活性剂和所述的非离子表面活性剂的比例按重量计为1∶10~1∶100。
5.如权利要求1所述的光致抗蚀剂显影剂组合物,其中所述的显影剂组合物可用水稀释使得在最终显影剂组合物中所述的显影剂组合物的量按重量计为0.5~5.0%。
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