CN1577112B - 去除tft-lcd制造工艺中彩色抗蚀剂的剥离组合物 - Google Patents
去除tft-lcd制造工艺中彩色抗蚀剂的剥离组合物 Download PDFInfo
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- CN1577112B CN1577112B CN2004100624001A CN200410062400A CN1577112B CN 1577112 B CN1577112 B CN 1577112B CN 2004100624001 A CN2004100624001 A CN 2004100624001A CN 200410062400 A CN200410062400 A CN 200410062400A CN 1577112 B CN1577112 B CN 1577112B
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- 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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- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G02F1/1333—Constructional arrangements; Manufacturing methods
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133707—Structures for producing distorted electric fields, e.g. bumps, protrusions, recesses, slits in pixel electrodes
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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
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- G—PHYSICS
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Abstract
本发明涉及一种去除TFT-LCD制造工艺中彩色抗蚀剂的剥离组合物,更特别地涉及一种剥离组合物,该剥离组合物在滤色器工艺期间选择性除去质量差的衬底的彩色抗蚀剂,因此能够重复使用衬底。本发明的剥离组合物具有经济的优点,由于它能够实现滤色器衬底的循环使用,而先前该衬底由于彩色抗蚀剂图案难以脱除而被浪费。
Description
技术领域
本发明涉及一种去除TFT-LCD制造工艺中彩色抗蚀剂的剥离组合物,更特别地涉及一种剥离组合物,该剥离组合物在滤色器工艺期间选择性的除去质量差的衬底的彩色抗蚀剂,因此能够重复使用衬底。
背景技术
滤色器衬底包括:红色、绿色和蓝色滤色器图案;一个黑色基质,它阻断在每个象素之间的光泄漏和增强对比度;和一个通常的电极,它施加电压到液晶池。根据如下方法制造滤色器。
将Cr/CrOx或无机材料作为黑色基质涂敷在玻璃衬底上并形成图案。在形成黑色掩模图案之后,由光刻工艺形成彩色抗蚀剂图案。将彩色抗蚀剂涂敷在玻璃衬底上并曝光,以通过光聚合固化彩色抗蚀剂。然后,除去没有曝光的彩色抗蚀剂部分,并焙烘衬底。
由颜料分散、染色或电泳沉积制备彩色抗蚀剂。其中,颜料分散是最典型的方法。一般情况下,在彩色抗蚀剂中分散一种有机颜料,该有机颜料向光敏引发剂、单体或粘结剂提供颜色,它是如光刻胶的感光组合物。光敏引发剂是当曝露于光时产生自由基的高度敏感性化合物。如果由自由基引发聚合,单体转变成聚合物,则该聚合物不溶于显影溶剂。粘结剂在室温下保护液体单体免受显影溶液的影响和控制颜料分散稳定性和红色、绿色和蓝色图案的耐热性、耐光性和耐化学品性。
目前,几乎不可能从滤色器工艺期间产生的质量差的滤色器衬底上除去一次固化的彩色抗蚀剂而再使用该衬底。同样,由于几乎没有可除去彩色抗蚀剂的溶剂,大多数质量差的滤色器在没有进一步的加工下被浪费。
彩色抗蚀剂具有负性特性。一般情况下,负性类型抗蚀剂与正性类型相比更难以剥离。因此,负性类型抗蚀剂要求强效的剥离特性。为此原因,采用RIE(反应性离子蚀刻),它使用无机剥离溶液或等离子体。无机剥离溶液的使用对人体是有害,并可引起着火,这是由于硫酸、硝酸、发烟硫酸或硝酸和过氧化氢的混合物溶液必须加热到120℃或更高。因此,需要极其注意。无机剥离溶液的具体例子有:烷基苯磺酸和沸点为150℃或更高的无卤素芳族烃(halogen-free aromatic hydrocarbon)溶剂的混合物溶液(公开于日本专利公开No.昭51-72503),烷基芳基磺酸、氢化质子的(hydroprotic)芳族磺酸和无卤素芳族烃溶剂的混合物溶液(公开于U.S.专利No.4,165,294);和剥离剂,其中将极性和非极性有机溶剂加入到有机磺酸和1,2-二羟基苯中(公开于欧洲专利公开No.0119337)。
使用等离子体的RIE方法的例子对固化的彩色抗蚀剂进行蚀刻,该抗蚀剂采用通常的湿法蚀刻不能被去除,而需连续使用O2-RIE和SF6-RIE(公开于U.S.专利No.5,756,239)并蚀刻包括聚酯、聚酰胺或线性酚醛清漆树脂的吸收剂层和聚硅烷、聚硅氧烷、有机硅化合物、二氧化硅或氮化硅的屏蔽层的固化的彩色抗蚀剂,其中吸收剂层由O2-RIE蚀刻,屏蔽层由SF6-RIE或NF3-RIE蚀刻(公开于U.S.专利No.5,059,500)。然而,使用等离子体对滤色器蚀刻要求高真空和高能量,并且加工条件复杂。同样,方法对于大尺寸滤色器是不适合的,并且需要昂贵的设备。
因此,采用蚀刻彩色抗蚀剂的常规技术,难以稳定地蚀刻大量彩色抗蚀剂。并且,安全性、生产率和产量均受到限制。
发明内容
本发明的目的是提供剥离组合物,该剥离组合物可以在TFT-LCD滤色器制造工艺期间选择性除去彩色抗蚀剂图案,使得原本大多被浪费的质量差的滤色器衬底,可以被再使用。
附图说明
图1显示在60℃下实施例5和对比例1的彩色抗蚀剂剥离组合物对彩色抗蚀剂脱除能力的对比的扫描电子显微照片(采用日立的S-4100拍摄)。
具体实施方式
为达到目的,本发明提供一种剥离组合物,该剥离组合物包括:
(a)1~10wt%无机碱金属氢氧化物或氢氧化烷基铵;
(b)40~95wt%二甲亚砜;和
(c)4~50wt%水。
优选,本发明的组合物可进一步包括(d)每100wt%剥离组合物中含0.05~111wt%一种或多种选自如下的化合物:水溶性胺、N-烷基-2-吡咯烷酮、亚烷基二醇醚、无机碱金属乙酸盐和链烷醇胺。
以下,更详细描述本发明。
本发明涉及在TFT-LCD滤色器制造工艺期间除去质量差的衬底的彩色抗蚀剂图案以重复使用的剥离组合物。
本发明的剥离组合物包括a)无机碱金属氢氧化物或氢氧化烷基铵。由于滤色器工艺不受剩余的金属影响,所有可以使用无机碱金属氢氧化物。由于氢氧化烷基铵不稳定,优选,将它溶于水中。
每100wt%组合物中包括1~10wt%的无机碱金属氢氧化物或氢氧化烷基铵。由于不能充分渗透到组成彩色抗蚀剂的聚合物中,所以如果无机碱金属氢氧化物或氢氧化烷基铵的含量小于1wt%,则难以完全除去彩色抗蚀剂。另外,如果含量超过10wt%,溶胀变得强烈,对组成彩色抗蚀剂的聚合物的溶解度降低。
优选,无机碱金属氢氧化物是一种或多种选自氢氧化钠和氢氧化钾的化合物。和优选,氢氧化烷基铵是一种或多种选自如下的化合物:氢氧化四乙基铵、氢氧化四甲基铵、氢氧化四丁基铵、氢氧化三甲基苄基铵和氢氧化铵。
本发明的剥离组合物也包括b)二甲亚砜。二甲亚砜渗透到组成彩色抗蚀剂的聚合物中,并将彩色抗蚀剂从玻璃衬底上分离。优选,每100wt%的组合物中含有40~95wt%的二甲亚砜。如果二甲亚砜的含量小于40wt%,向彩色抗蚀剂中的渗透不充分,使得彩色抗蚀剂不能完全除去。另外,如果含量超过95wt%,彩色抗蚀剂剥离组合物的粘度和凝固点上升,使它变得难以处理。
在本发明的剥离组合物中,c)水是一个基本的组分。优选使用通过离子交换树脂过滤的纯水,和更优选使用电阻系数为18MΩ或更大的超纯水。
优选,每100wt%的组合物中包括4~50wt%的水。如果水的含量小于4wt%,就不能完全活化氢氧化烷基铵,使得对彩色抗蚀剂的渗透不充分。另外,如果含量超过50wt%,由于在加工温度下水的蒸发使组合物产生较大变化,因此降低使用期限。
本发明的剥离组合物可进一步包括d)每100wt%的剥离组合物中含有0.05~111wt%的一种或多种选自如下的化合物:水溶性胺、N-烷基-2-吡咯烷酮、亚烷基二醇醚、无机碱金属乙酸盐和链烷醇胺。
水溶性胺用于改进剥离组合物的性能。优选,羟基胺用作水溶性胺。羟基胺协助从水和质子色料(proton color)的反应产生的氢氧离子有效渗透到抗蚀剂和衬底间的界面上,溶解聚合物并溶解聚合物和颜料的配合物。优选,使用50%羟基胺水溶液。优选,每100wt%的剥离组合物中包括2~20wt%的水溶性胺。如果水溶性胺的含量小于2wt%,难以完全除去彩色抗蚀剂。另外,如果含量超过20wt%,底层变得易于腐蚀。
一种N-烷基-2-吡咯烷酮可用于本发明的彩色抗蚀剂剥离组合物以改进它的性能。N-烷基-2-吡咯烷酮溶解聚合物并诱导溶胀。优选,每100wt%的剥离组合物中包括2~20wt%的N-烷基-2-吡咯烷酮。如果N-烷基-2-吡咯烷酮的含量小于2wt%,对聚合物的溶解力降低,而该聚合物是彩色抗蚀剂的主要组分。另外,如果含量超过20wt%,对彩色抗蚀剂的渗透变得不充分。
优选,N-烷基-2-吡咯烷酮是一种或多种选自N-乙基-2-吡咯烷酮和N-甲基-2-吡咯烷酮的化合物。
本发明的彩色抗蚀剂剥离组合物可包括亚烷基二醇醚以改进它的性能。亚烷基二醇醚将彩色抗蚀剂从玻璃衬底上剥离,渗透到聚合物中并溶解聚合物和颜料粒子的配合物。优选,每100wt%的剥离组合物中包括2~50wt%的亚烷基二醇醚。如果亚烷基二醇醚的含量小于2wt%,对彩色抗蚀剂的溶解力降低。另外,如果含量超过50wt%,由于使二甲亚砜含量减少而降低了渗透力。
优选,亚烷基二醇醚是一种或多种选自如下的化合物:二甘醇乙基醚、二甘醇二甲基醚、二甘醇单甲基醚、二甘醇单丁基醚、二甘醇二乙酸酯、二甘醇单丁基醚乙酸酯、二甘醇单乙基醚、二丙二醇单丙基醚、二丙二醇单丁基醚、二丙二醇单甲基醚和二丙二醇单乙基醚。
本发明的彩色抗蚀剂剥离组合物可包括一种无机碱金属乙酸盐以改进它的性能。无机碱金属乙酸盐渗透到聚合物或颜料中以改进氢氧化烷基铵和氢氧化烷芳基铵的性能。优选,每100wt%的剥离组合物中包括0.05~1wt%的无机碱金属乙酸盐。如果无机碱金属乙酸盐的含量小于0.05wt%,则不能改进对聚合物的渗透力,而该聚合物是彩色抗蚀剂的主要组分。另外,如果含量超过1wt%,无机碱金属乙酸盐的溶解力将降低,则可能发生沉淀。
优选,无机碱金属乙酸盐是一种或多种选自乙酸钾和乙酸钠的化合物。
本发明的彩色抗蚀剂剥离组合物可包括一种链烷醇胺以改进它的性能。链烷醇胺由于对感光化合物的优异溶解力以及溶解聚合物和颜料的配合物的能力,而促进氢氧化烷基铵向聚合物中渗透。优选,每100wt%的剥离组合物中包括2~20wt%链烷醇胺。如果链烷醇胺的含量小于2wt%,由于对感光化合物和配合物的溶解力差而达不到预期的性能的改进。另外,如果含量超过20wt%,则除去彩色抗蚀剂的性能变差。
优选链烷醇胺是一种或多种选自如下的化合物:单乙醇胺、二乙醇胺、 三乙醇胺、甲基乙醇胺、乙基乙醇胺、二甲基乙醇胺、二乙基乙醇胺和氨基乙氧基乙醇。
以下,通过实施例更详细描述本发明。然而,以下实施例仅用于对本发明的理解而不限制本发明的范围。除非另外说明,百分比和混合比均基于重量。
实施例
使用由A公司生产的滤色器衬底,评价实施例和对比例彩色抗蚀剂剥离组合物的彩色抗蚀剂去除性能。
(1)彩色抗蚀剂脱除测试
测试样品的制备:
在一个沉积Cr/CrOx的LCD角化玻璃上形成滤色器图案。根据光刻工艺以红色、绿色和蓝色的顺序涂敷彩色抗蚀剂。将通常使用的彩色抗蚀剂组合物(由Dongjin Semichem生产的DCR-725S)旋涂使最终厚度为1.7μm。将抗蚀剂膜在热板上90℃下预焙烘120秒。曝光之后,使用2.38%氢氧化四甲基铵(TMAH)显影溶液在21℃下进行显影60秒。将形成图案的样品在烘箱中220℃下硬焙烘20分钟。
彩色抗蚀剂脱除测试:
将每个测试样品分别在60℃下浸入彩色抗蚀剂剥离组合物中5分钟、10分钟和15分钟。将测试样品从彩色抗蚀剂剥离组合物中取出,采用超纯水洗涤并用氮气干燥。用扫描电子显微镜观察图案中剩余的彩色抗蚀剂。采用以下标准评价彩色抗蚀剂脱除性能。结果见下表2。
◎:完全除去所有的红色、绿色和蓝色图案。
○:仅除去绿色和蓝色图案。
△:仅除去蓝色图案。
×:没能除去红色、绿色和蓝色图案中的任何一个。
(2)金属膜腐蚀测试
金属膜腐蚀测试:
将每个测试样品分别在60℃下浸入彩色抗蚀剂剥离组合物中30分钟。将测试样品从彩色抗蚀剂剥离组合物中取出,采用超纯水洗涤并用氮气干燥。采用扫描电子显微镜观察图案金属部分的底切(undercut)。由如下标准评价腐蚀程度。结果见下表3。
○:底部金属膜中没有底切。
△:底部金属膜中有轻微底切。
×:底部金属膜中有强烈底切。
实施例1~7和对比例1~2
根据下表1中给出的组成制备实施例1~7和对比例1~2的彩色抗蚀剂剥离组合物。对于每个获得的彩色抗蚀剂剥离组合物,进行(1)彩色抗蚀剂脱除测试和(2)金属膜腐蚀测试。结果见表2和表3。
表1
备注:
TMAH:氢氧化四甲基铵
HDA:羟基胺
NM:N-甲基-2-吡咯烷酮
PGME:1-甲氧基-2-丙醇
卡必醇:二甘醇单乙基醚
彩色抗蚀剂剥离组合物的彩色抗蚀剂脱除性能:
表2
金属布线腐蚀测试:
表3
如在表2和表3中看到的那样,与对比例1~2相比,本发明的剥离组合物(实施例1~7)显示可比的或更好的金属布线腐蚀性和非常优异的彩色抗蚀剂脱除性能。
图1显示比较在60℃下实施例5和对比例1的彩色抗蚀剂剥离组合物 的彩色抗蚀剂脱除能力的扫描电子显微照片(采用日立的S-4100拍摄)。
如图中看到的那样,当使用本发明的剥离组合物(实施例5)时,彩色抗蚀剂被干净地除去。
如上所述,本发明的彩色抗蚀剂剥离组合物可容易地在短时间内除去彩色抗蚀剂。同样,它可以最小化彩色抗蚀剂脱除工艺期间对金属布线的腐蚀。此外,可以采用水进行清洗而不必使用有机溶剂,如异丙醇和二甲亚砜。
尽管参考优选的实施方案详细描述了本发明,本领域技术人员应理解,可以对其进行各种改进和替换而不背离在所附权利要求中说明的本发明的精神和范围。
Claims (3)
1.一种用于除去彩色抗蚀剂的剥离组合物,包括:
(a)1~10wt%无机碱金属氢氧化物或氢氧化烷基铵;
(b)40~95wt%二甲亚砜;和
(c)4~50wt%水,
基于组分(a)、(b)和(c)的重量百分比之和100wt%,
其中,所述组合物进一步包括(d)1wt%的水溶性羟基胺、2wt%的N-甲基-2-吡咯烷酮和3wt%的1-甲氧基-2-丙醇的混合物;
2wt%的水溶性羟基胺、2wt%的N-甲基-2-吡咯烷酮、0.1wt%的乙酸钾和10wt%的N-甲基乙基胺的混合物;
2wt%的水溶性羟基胺、2wt%的N-甲基-2-吡咯烷酮、0.3wt%的乙酸钾和10wt%的N-甲基乙基胺的混合物;或者
1wt%的水溶性羟基胺、3wt%的1-甲氧基-2-丙醇和0.3wt%的乙酸钾的混合物;并且
其中所述组合物用于在滤色器工艺期间选择性除去质量差的衬底的彩色抗蚀剂,因而使玻璃衬底能被再使用。
2.权利要求1的剥离组合物,其中该无机碱金属氢氧化物是选自氢氧化钠和氢氧化钾的一种或多种化合物。
3.权利要求1的剥离组合物,其中该氢氧化烷基铵是一种或多种选自如下的化合物:氢氧化四乙基铵、氢氧化四甲基铵、氢氧化四丁基铵、氢氧化三甲基苄基铵和氢氧化铵。
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- 2004-07-09 CN CN2004100624001A patent/CN1577112B/zh not_active Expired - Lifetime
- 2004-07-09 JP JP2004203078A patent/JP4395020B2/ja not_active Expired - Lifetime
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CN1501179A (zh) * | 2002-10-10 | 2004-06-02 | ͬ�Ϳ�ҵ��ʽ���� | 光刻法用洗涤液和基板的处理方法 |
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CN1577112A (zh) | 2005-02-09 |
TW200506552A (en) | 2005-02-16 |
JP4395020B2 (ja) | 2010-01-06 |
KR20050006980A (ko) | 2005-01-17 |
KR101043397B1 (ko) | 2011-06-22 |
JP2005031682A (ja) | 2005-02-03 |
TWI350949B (en) | 2011-10-21 |
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