WO2014071689A1

WO2014071689A1 - Cleaning solution for removing photoresist residue

Info

Publication number: WO2014071689A1
Application number: PCT/CN2013/001336
Authority: WO
Inventors: 刘兵; 彭洪修; 孙广胜; 颜金荔; 徐海玉
Original assignee: Anji Microelectronics Shanghai Co Ltd
Current assignee: Anji Microelectronics Shanghai Co Ltd
Priority date: 2012-11-12
Filing date: 2013-11-05
Publication date: 2014-05-15
Anticipated expiration: 2015-05-12
Also published as: TW201418913A; CN103809393A

Abstract

A cleaning solution for removing photoresist residues, containing alcohol amine, organic solvent, gallic acid and ester thereof, and 3-amino-1, 2, 4- triazole. The cleaning solution for removing photoresist residues contains no water, hydroxylamine or fluoride, and basically causes no corrosion to substrate materials such as the metals aluminum, silver, copper, titanium and tungsten as well as nonmetals silicon dioxide, gallium nitride and the like, while removing photoresist residues from a wafer, thus having a good application prospect in the field of semiconductor and LED wafer cleaning.

Description

一种去除光阻残留物的清洗液技术领域 Cleaning liquid for removing photoresist residues

本发明涉及一种清洗液，更具体地说，涉及一种去除光阻残留物的清洗液。背景技术 The present invention relates to a cleaning solution, and more particularly to a cleaning solution for removing photoresist residues. Background technique

在通常的 LED和半导体制造工艺中，通过在一些材料的表面上形成光刻胶的掩膜，曝光后进行图形转移，在得到需要的图形之后，进行下一道工序之前，需要剥去残留的光刻胶。在这个过程中要求完全除去不需要的光刻胶，同时不能腐蚀任何基材。 In the usual LED and semiconductor manufacturing processes, by forming a mask of photoresist on the surface of some materials, pattern transfer after exposure, after obtaining the desired pattern, it is necessary to remove residual light before proceeding to the next process. Engraved. In this process it is required to completely remove the unwanted photoresist while not corroding any substrate.

目前，光刻胶清洗液主要由极性有机溶剂、强碱和 /或水等组成，通过将半导体晶片浸入清洗液中或者利用清洗液冲洗半导体晶片，去除半导体晶片上的光刻胶。其中一类是含有水的光刻胶清洗液，其含水量一般大于 5%; 如 JP1998239865公开了一种含水体系的清洗液，其组成是四甲基氢氧化铵 At present, the photoresist cleaning liquid is mainly composed of a polar organic solvent, a strong alkali, and/or water, and the photoresist on the semiconductor wafer is removed by immersing the semiconductor wafer in the cleaning liquid or rinsing the semiconductor wafer with the cleaning liquid. One type is a photoresist cleaning solution containing water, which generally has a water content of more than 5%; and JP 1998239865 discloses an aqueous cleaning solution having a composition of tetramethylammonium hydroxide.

(TMAH) 、二甲基亚砜（DMSO) 、 1,3， -二甲基 -2-咪唑烷酮（DMI) 和水。将晶片浸入该清洗液中，于 50~100°C下除去金属和电介质基材上的 20 以上的光刻胶；其对半导体晶片基材的腐蚀略高，且不能完全去除半导体晶片上的光刻胶，清洗能力不足；又例如 US5529887公开了由氢氧化钾(TMAH), dimethyl sulfoxide (DMSO), 1,3,-dimethyl-2-imidazolidinone (DMI) and water. Immersing the wafer into the cleaning solution to remove more than 20 photoresists on the metal and dielectric substrate at 50-100 ° C; the etching of the semiconductor wafer substrate is slightly higher, and the light on the semiconductor wafer cannot be completely removed. Gluing, insufficient cleaning ability; for example, US Pat. No. 5,529,887 discloses potassium hydroxide

(KOH)、垸基二醇单垸基醚、水溶性氟化物和水等组成碱性清洗液，将晶片浸入该清洗液中，在 40~90°C下除去金属和电介质基材上的光刻胶。其对半导体晶片基材的腐蚀较高。在这类清洗液中由于含有游离的强碱性基团一 OH，而且存在水，故其对金属基材往往会造成一定的腐蚀。而另一类是基本上不含有水的光刻胶清洗液，其含水量一般小于 5%，甚至基本上不含有水。如 US5480585公开了一种含非水体系的清洗液，其组成是乙醇胺、环丁砜或二甲亚砜和邻苯二酚，能在 40~120°C下除去金属和电介质基材上的光刻胶，对金属基本无腐蚀。又例如 US2005119142公开了一种含有烷氧基的聚合物、二丙二醇垸基醚、 N-甲基吡咯烷酮和甲基异丁基酮的非水性清洗液。该清洗液可以同时适用于正性光刻胶和负性光刻胶的清洗。非水性光刻胶清洗液由于不含有水，其对金属基材基本无腐蚀；但该类清洗液在操作体系中混有少量的水的时候，其金属的腐蚀速率会显著上升，从而导致金属基材的腐蚀。故存在操作窗口较小的问题。 An alkaline cleaning solution consisting of (KOH), mercapto diol monodecyl ether, water-soluble fluoride and water, immersing the wafer in the cleaning solution, and removing light on the metal and dielectric substrate at 40-90 ° C Engraved. It has a high corrosion to the semiconductor wafer substrate. In such a cleaning liquid, since it contains a free strong basic group, OH, and water is present, it tends to cause some corrosion to the metal substrate. The other type is a photoresist cleaning solution that is substantially free of water, typically having a water content of less than 5%, or even substantially no water. For example, US Pat. No. 5,480,585 discloses a cleaning solution containing a non-aqueous system consisting of ethanolamine, sulfolane or dimethyl sulfoxide and catechol, capable of removing metal and dielectric substrates at 40 to 120 ° C. Photoresist, which is essentially non-corrosive to metals. Further, for example, US2005119142 discloses a non-aqueous cleaning solution comprising an alkoxy group-containing polymer, dipropylene glycol decyl ether, N-methylpyrrolidone and methyl isobutyl ketone. The cleaning solution can be applied to both positive photoresist and negative photoresist cleaning. The non-aqueous photoresist cleaning solution has no corrosion to the metal substrate because it does not contain water; however, when the cleaning liquid is mixed with a small amount of water in the operating system, the corrosion rate of the metal is significantly increased, thereby causing the metal. Corrosion of the substrate. Therefore, there is a problem that the operation window is small.

由此可见，寻找更为有效抑制金属腐蚀抑制方法和较大操作窗口的光刻胶清洗液该类光刻胶清洗液努力改进的优先方向。发明内容 It can be seen that the photoresist cleaning solution which is more effective in suppressing the metal corrosion suppression method and the larger operation window is sought to improve the priority direction of the photoresist cleaning liquid. Summary of the invention

本发明所要解决的技术问题是提供一种用于去除光阻残留物的清洗液及其组成。该清洗液在去除晶圆上的光阻残留物同时，对于基材如金属铝、银、铜、钛、钨和非金属二氧化硅、氮化镓等基本无腐蚀，同时对 LED制成中 Pad的清洗效果更好，在半导体及 LED晶片清洗等领域具有良好的应用前景。 The technical problem to be solved by the present invention is to provide a cleaning liquid for removing photoresist residue and its composition. The cleaning solution removes the photoresist residues on the wafer while substantially non-corrosive to substrates such as aluminum, silver, copper, titanium, tungsten and non-metal silicon dioxide, gallium nitride, etc. Pad has a better cleaning effect and has a good application prospect in the fields of semiconductor and LED wafer cleaning.

为了解决上述技术问题，本发明提供了一种新型清洗液，其含有醇胺，有机溶剂，没食子酸及其酯以及 3-氨基 -1，2,4-三氮唑。 In order to solve the above technical problems, the present invention provides a novel cleaning liquid comprising an alcohol amine, an organic solvent, gallic acid and its ester, and 3-amino-1,2,4-triazole.

其中，醇胺的含量为 5-50wt% (质量百分比)，优选为 10-45 wt %。其中，有机溶剂的含量为 40-90wt%，优选为 50-85 wt % Among them, the content of the alkanolamine is 5 to 50% by weight (% by mass), preferably 10 to 45% by weight. Wherein, the content of the organic solvent is 40-90% by weight, preferably 50-85% by weight.

其中，没食子酸及其酯的含量为 0.05~5 wt %，优选为 0.1-3 wt % 其中， 3-氨基 -1,2,4-三氮唑的含量为 0.01-5 wt %, 优选为 0.05-3 wt % 上述含量均为质量百分比含量；且本发明所公开的去除光阻残留物的清洗液中，优选的，可不含有水、羟胺和 /或氟化物。 Wherein, the content of gallic acid and its ester is 0.05 to 5 wt%, preferably 0.1 to 3 wt%, wherein the content of 3-amino-1,2,4-triazole is 0.01-5 wt%, preferably 0.05 -3 wt % The above contents are all by mass percentage; and in the cleaning liquid for removing photoresist residues disclosed in the present invention, preferably, water, hydroxylamine and/or fluoride may not be contained.

本发明中，醇胺较佳的为单乙醇胺、 N-甲基乙醇胺、二乙醇胺、三乙醇胺、异丙醇胺、乙基二乙醇胺、 N， N-二乙基乙醇胺、 N-(2-氨基乙基)乙醇胺和二甘醇胺。优选单乙醇胺、二甘醇胺及其混合物。本发明中，有机溶剂较佳的为亚砜、砜、咪唑垸酮、吡咯垸酮、咪唑啉酮、酰胺和醇醚中的一种或多种；亚砜较佳的为二甲基亚砜和甲乙基亚砜中的一种或多种；砜较佳的为甲基砜、环丁砜中的一种或多种；咪唑烷酮较佳的为 2-咪唑烷酮和 1，3-二甲基 -2-咪唑垸酮中的一种或多种；吡咯垸酮较佳的为 N-甲基吡咯烷酮、 N-环己基吡咯烷酮和 N-羟乙基吡咯垸酮中的一种或多种；咪唑啉酮较佳的为 1,3-二甲基 -2-咪唑啉酮酰胺较佳的为二甲基甲酰胺和二甲基乙酰胺中的一种或多种；醇醚较佳的为乙二醇烷基醚、丙二醇烧基醚中的一种或多种。乙二醇垸基醚较佳的为乙二醇单乙醚、二乙二醇单甲醚和二乙二醇单丁醚中的一种或多种；丙二醇垸基醚较佳的为丙二醇单甲醚、丙二醇单丁醚和二丙二醇单甲醚中的一种或多种。 In the present invention, the alcoholamine is preferably monoethanolamine, N-methylethanolamine, diethanolamine, triethanolamine, isopropanolamine, ethyldiethanolamine, N,N-diethylethanolamine, N-(2-amino group Ethyl)ethanolamine and diglycolamine. Preference is given to monoethanolamine, diglycolamine and mixtures thereof. In the present invention, the organic solvent is preferably one or more of sulfoxide, sulfone, imidazolium, pyrrolidone, imidazolidinone, amide and alcohol ether; the sulfoxide is preferably dimethyl sulfoxide. And one or more of methyl ethyl sulfoxide; the sulfone is preferably one or more of methyl sulfone and sulfolane; the imidazolidinone is preferably 2-imidazolidinone and 1,3-dimethyl One or more of the group 2-imidazolium; the pyrrolidone is preferably one or more of N-methylpyrrolidone, N-cyclohexylpyrrolidone and N-hydroxyethylpyrrolidone; The imidazolinone is preferably 1,3-dimethyl-2-imidazolidinone amide, preferably one or more of dimethylformamide and dimethylacetamide; the alcohol ether is preferably One or more of ethylene glycol alkyl ether and propylene glycol alkyl ether. The ethylene glycol decyl ether is preferably one or more of ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monobutyl ether; the propylene glycol decyl ether is preferably propylene glycol monomethyl One or more of ether, propylene glycol monobutyl ether and dipropylene glycol monomethyl ether.

本发明中，没食子酸及其酯较佳的为没食子酸、没食子酸甲酯、没食子酸乙酯、没食子酸丁酯、没食子酸辛酯、没食子酸月桂酯、 1-没食子酸甘油酯中的一种或多种。 In the present invention, gallic acid and its ester are preferably one of gallic acid, methyl gallate, ethyl gallate, butyl gallate, octyl gallate, lauryl gallate, 1-gallate glyceride. Or a variety.

本发明中的清洗液，可以在 50°C至 90°C下清洗晶圆上的光阻残留物。具体方法如下：将含有光阻残留物的晶圆浸入本发明中的清洗液中，在 50 °C至 90°C下浸泡 10-30min后，取出漂洗后用高纯氮气吹干。 In the cleaning liquid of the present invention, the photoresist residue on the wafer can be cleaned at 50 ° C to 90 ° C. The specific method is as follows: The wafer containing the photoresist residue is immersed in the cleaning liquid of the present invention, and after immersing at 50 ° C to 90 ° C for 10-30 min, it is taken out and rinsed, and then dried by high-purity nitrogen gas.

本发明的积极进步效果在于： The positive effects of the present invention are:

1 ) 本发明的清洗液该在去除晶圆上的光阻残留物同时，对于基材如金属铝、银、铜、钛、钨和非金属二氧化硅、氮化镓等基本无腐蚀； 1) The cleaning solution of the present invention removes photoresist residue on the wafer while substantially no corrosion to substrates such as metal aluminum, silver, copper, titanium, tungsten and non-metal silicon dioxide, gallium nitride, and the like;

2)对 LED制成中金属垫 Pad的清洗效果更好。本发明所用试剂及原料均市售可得。本发明的清洗液由上述成分简单均匀混合即可制得。具体实施方式 2) The cleaning effect of the metal pad in the LED is better. The reagents and materials used in the present invention are commercially available. The cleaning liquid of the present invention can be obtained by simply and uniformly mixing the above components. detailed description

下面通过具体实施例进一步阐述本发明的优点，但本发明的保护范围不仅仅局限于下述实施例。 The advantages of the present invention are further illustrated by the following specific examples, but the scope of the present invention is not limited to the following embodiments.

按照表 1 和表 2中各实施例以及对比实施例的成分及其比例配制抛光合均匀。表 1本发明实施例 1-2的配方 Polishing according to the ingredients of each of the examples in Tables 1 and 2 and the comparative examples Evenly. Table 1 Formulations of Examples 1-2 of the present invention

3-氨基醇胺有机溶剂没食子酸及其酯实施 -1,2,4-二氮例唑的含量，名称含量，％名称含量，％名称含量，％ 3-Amino Alcoholamine Organic Solvent Gallic acid and its ester Implementation -1,2,4-Dinitrogen Example Content of oxazole, Name Content, % Name Content, % Name Content, %

% 乙二醇单 % ethylene glycol single

1 单乙醇胺 5 90 没食子酸 3 2 1 monoethanolamine 5 90 gallic acid 3 2

乙醚 Ether

N-甲基乙二乙二醇没食子酸 N-methylethylene glycol, gallic acid

2 50 40 5 5 2 50 40 5 5

醇胺单甲醚甲酯 Alcohol amine monomethyl ether methyl ester

没食子酸 Gallic acid

3 二乙醇胺 50 甲基砜 45 2 3 3 Diethanolamine 50 Methyl sulfone 45 2 3

乙酯 Ethyl ester

没食子酸 Gallic acid

4 三乙醇胺 44.94 环丁砜 55 0.05 0.01 4 triethanolamine 44.94 sulfolane 55 0.05 0.01

丁酯 Butyl ester

2-咪唑烷没食子酸 2-imidazolidine gallic acid

5 异丙醇胺 47.95 50 2 0.05 5 isopropanolamine 47.95 50 2 0.05

酮辛酯 Ketone octyl ester

1,3-二甲 1,3-dimethyl

乙基二乙没食子酸 Ethyldiethylgallate

6 35.9 基 -2-咪 60 4 0.1 6 35.9 base -2- microphone 60 4 0.1

醇胺月桂酯 Alcohol amine lauryl ester

唑烷酮 Oxazolidinone

N, N-二 N, N-two

丙二醇单 1-没食子 Propylene glycol mono-1-negative

7 乙基乙醇 34.4 65 0.1 0.5 7 ethyl alcohol 34.4 65 0.1 0.5

甲醚酸甘油酯 Methyl ether glyceride

胺 Amine

N-(2-氨 N-(2-ammonia

丙二醇单 Propylene glycol

8 28.5 70 没食子酸 0.5 1 8 28.5 70 gallic acid 0.5 1

丁醚 Dibutyl ether

乙醇胺 Ethanolamine

N-羟乙基没食子酸 N-hydroxyethyl gallic acid

9 二甘醇胺 23.7 75 1 0.3 9 diethylene glycolamine 23.7 75 1 0.3

吡咯烷酮甲酯 Pyrrolidone methyl ester

U-二甲 U-dimethyl

没食子酸 Gallic acid

10 单乙醇胺 19 基 -2-咪 80 0.3 0.7 10 monoethanolamine 19 base -2-mi 80 0.3 0.7

乙酯 Ethyl ester

唑啉酮 Oxazolinone

二甲基甲没食子酸 Dimethylmethyl gallic acid

11 单乙醇胺 13 85 0.7 1.3 11 monoethanolamine 13 85 0.7 1.3

酰胺丁酯 Amide butyl ester

二甲基乙没食子酸 Dimethylethyl gallic acid

12 单乙醇胺 10 88 1.8 0.2 12 monoethanolamine 10 88 1.8 0.2

酰胺辛酯 Amide octyl ester

二甲基亚 Dimethyl

13 单乙醇胺 15 84.5 没食子酸 0.3 0.2 13 monoethanolamine 15 84.5 gallic acid 0.3 0.2

砜 Sulfone

甲乙基亚 1- Methyl ethyl 1-

14 没食子 14 食子

二甘醇胺 45 54 0.5 0.5 Diethylene glycolamine 45 54 0.5 0.5

砜酸甘油酯 Sulfonamide

二乙二醇 Diethylene glycol

15 二甘醇胺 40 58 没食子酸 1 1 15 diethylene glycolamine 40 58 gallic acid 1 1

单丁醸 Single Ding

N-甲基吡没食子酸 N-methylpyrrolidonic acid

16 二甘醇胺 30 67 1.5 1.5 16 Diethylene glycolamine 30 67 1.5 1.5

咯垸酮甲酯 Acetyl ketone

N-环己基 N-cyclohexyl

17 没食子酸 17 gallic acid

二甘醇胺 25 74.8 0.1 0.1 Diethylene glycolamine 25 74.8 0.1 0.1

吡咯烷爾乙酯 Pyrrolidine ethyl ester

18 二丙二醇没食子酸 18 dipropylene glycol gallic acid

单乙醇胺 20 79 0.8 0.2 Monoethanolamine 20 79 0.8 0.2

单甲醚月桂酯 Monomethyl ether lauryl ester

19 单乙醇胺 10 二甲基亚 59.1 没食子酸 0.5 0.4 二甘醇胺 30 砜月桂酯 19 monoethanolamine 10 dimethyl sub 59.1 gallic acid 0.5 0.4 Diethylene glycolamine 30 sulfone lauryl ester

单乙醇胺 20 N-甲基吡没食子酸 Monoethanolamine 20 N-methylpyrugallic acid

20 54.2 0.5 0.3 20 54.2 0.5 0.3

二甘醇胺 25 咯垸酮甲酯 Diethylene glycolamine 25 ketone ketone methyl ester

表 2本发明对比例 1-3的配方 Table 2 Formulation of Comparative Example 1-3 of the present invention

效果实施例 1

Effect Example 1

为了进一步考察该类清洗液的清洗情况，本发明采用了如下技术手段：即将含有光阻残留物的 LED金属垫 (Pad) 晶圆分别浸入清洗液中，在 50°C 至 90°C下利用恒温振荡器以约 60转 /分的振动频率振荡 10~30分钟，然后经漂洗后用高纯氮气吹干。光阻残留物的清洗效果和清洗液对晶片的腐蚀情况如表 3所示。 In order to further investigate the cleaning of the cleaning liquid, the present invention adopts the following technical means: immersing the LED metal pad (Pad) wafer containing the photoresist residue in the cleaning liquid, and using it at 50 ° C to 90 ° C The constant temperature oscillator was shaken at a vibration frequency of about 60 rpm for 10 to 30 minutes, and then rinsed and then dried with high purity nitrogen gas. The cleaning effect of the photoresist residue and the corrosion of the cleaning solution on the wafer are shown in Table 3.

表 3部分实施例和对比例 1-3的晶圆清 ¾fe1t况 Table 3 Part of the examples and comparative examples 1-3 wafer clearing

LED金属实施清洗温度清洗时间基材腐蚀情况 LED metal implementation cleaning temperature cleaning time substrate corrosion

垫晶圆清例 Pad wafer clearing

CC) (min) 金属铝氮化镓洗结果 CC) (min) Metal Aluminum Gallium Nitride Wash Results

2 50 15 ◎ ◎ ◎ 2 50 15 ◎ ◎ ◎

4 90 10 ◎ ◎ 4 90 10 ◎ ◎

6 85 25 ◎ ◎ ◎ 6 85 25 ◎ ◎ ◎

7 80 15 ◎ ◎ ◎ 7 80 15 ◎ ◎ ◎

10 55 30 ◎ ◎ ◎ 10 55 30 ◎ ◎ ◎

12 65 30 ◎ ◎ ◎ 12 65 30 ◎ ◎ ◎

13 85 30 ◎ ◎ ◎ 对比例 1 85 30 O ◎ 〇对比例 2 85 30 o ◎ ◎ 对比例 3 85 30 o ◎ ◎ 15 70 25 ◎ ◎ ◎ 13 85 30 ◎ ◎ ◎ Comparative Example 1 85 30 O ◎ 〇 Comparative Example 2 85 30 o ◎ ◎ Comparative Example 3 85 30 o ◎ ◎ 15 70 25 ◎ ◎ ◎

18 80 20 ◎ ◎ ◎ 18 80 20 ◎ ◎ ◎

19 80 25 ◎ ◎ ◎ 19 80 25 ◎ ◎ ◎

从表 3可以看出，本发明的清洗液对含有光阻残留物 LED金属垫 (Pad) 晶圆具有良好的清洗效果，使用温度范围广。从对比例 1与实施例 13可以看出，在其他组分一样且操作条件相同的条件下，不加入没食子酸及其酯， LED金属垫的清洗有残留同时金属铝稍有腐蚀；从对比例 2与实施例 13可以看出，在其他组分一样且操作条件相同的条件下，不加入 3-氨基 -1,2,4- 三氮唑， LED金属垫的清洗虽然干净但金属铝稍有腐蚀，说明在该体系中没食子酸及其酯和 3-氨基 -1,2,4-三氮唑对金属铝的腐蚀抑制存在协同效应。从对比例 3与实施例 13可以看出，在其他组分一样且操作条件相同的条件下，用 5-氨基 -1，2，4-三氮唑代替 3-氨基 -1，2，4-三氮唑未见有同样的协同效应。

As can be seen from Table 3, the cleaning liquid of the present invention has a good cleaning effect on a photoresist metal pad (Pad) wafer containing a photoresist residue, and has a wide temperature range. It can be seen from Comparative Example 1 and Example 13 that, under the conditions of the same other components and the same operating conditions, no gallic acid and its ester are added, the cleaning of the LED metal pad remains and the metal aluminum is slightly corroded; 2 and Example 13 can be seen, under the same conditions of other components and the same operating conditions, without adding 3-amino-1,2,4-triazole, the cleaning of the LED metal pad is clean but the metal aluminum is slightly Corrosion indicates that there is a synergistic effect on the corrosion inhibition of metal aluminum by gallic acid and its esters and 3-amino-1,2,4-triazole in this system. It can be seen from Comparative Example 3 and Example 13 that 5-amino-1,2,4-triazole was used instead of 3-amino-1,2,4- under the same conditions of other components and the same operating conditions. Triazole did not show the same synergistic effect.

效果实施例 2 Effect Example 2

为了进一步考察该类清洗液对金属的腐蚀抑制的情况，本发明采用了如下技术手段：即将没有图案的各种金属晶圆（铝、银、铜、钛、钨）分别浸入清洗液中，在 85°C下利用恒温振荡器以约 60转 /分的振动频率振荡 60分钟，然后经漂洗后用高纯氮气吹干。用四点探针仪测试其浸泡前后电阻变化，并计算出其腐蚀速率，同时目检其表面金属光泽有无变化。其结果见表 4。表 4部分实施例 85 的下金属腐蚀速率， A/min In order to further investigate the corrosion inhibition of the metal by the cleaning liquid, the present invention adopts the following technical means: immersing various metal wafers (aluminum, silver, copper, titanium, tungsten) without a pattern into the cleaning liquid, respectively, The mixture was shaken at 85 ° C for 60 minutes at a vibration frequency of about 60 rpm using a constant temperature oscillator, and then rinsed and then dried with high purity nitrogen gas. The resistance change before and after immersion was tested by a four-point probe instrument, and the corrosion rate was calculated, and the surface metallic luster was visually inspected for change. The results are shown in Table 4. Table 4 Partial Example 85 Corrosion rate of the lower metal, A/min

从表 4中可以看出本发明的清洗液，其金属腐蚀速率较小，金属表观的金属光泽在清洗前后保持良好。 It can be seen from Table 4 that the cleaning liquid of the present invention has a small metal corrosion rate, and the apparent metallic luster of the metal remains good before and after washing.

综上，本发明的积极进步效果在于： In summary, the positive progress of the present invention is:

1 ) 本发明的清洗液该在去除晶圆上的光阻残留物同时，对于基材如金属铝、银、铜、钕、钨和非金属二氧化硅、氮化镓等基本无腐蚀； 1) The cleaning solution of the present invention removes photoresist residues on the wafer while substantially non-corrosive to substrates such as metal aluminum, silver, copper, tantalum, tungsten and non-metal silicon dioxide, gallium nitride, and the like;

2) 对 LED制成中 Pad的清洗效果更好。 2) It is better to clean the pad in the LED.

应当理解的是，本发明所述 wt%均指的是质量百分含量。 It should be understood that the wt% of the present invention refers to the mass percentage.

以上对本发明的具体实施例进行了详细描述，但其只是作为范例，本发明并不限制于以上描述的具体实施例。对于本领域技术人员而言，任何对本发明进行的等同修改和替代也都在本发明的范畴之中。因此，在不脱离本发明的精神和范围下所作的均等变换和修改，都应涵盖在本发明的范围内。 The specific embodiments of the present invention have been described in detail above, but by way of example only, the invention is not limited to the specific embodiments described above. Any equivalent modifications and substitutions of the present invention are also within the scope of the invention. Accordingly, equivalent changes and modifications may be made without departing from the spirit and scope of the invention.

Claims

Claims: A cleaning solution for removing a photoresist residue, characterized in that the cleaning liquid comprises an alcohol amine, an organic solvent, gallic acid and an ester thereof, and 3-amino-1,2,4-triazole.

The cleaning solution according to claim 1, wherein the content of the alcoholamine is 5 to 50% by weight _o

The cleaning solution according to claim 2, wherein the content of the alcoholamine is 10-45% by weight.

The cleaning liquid according to claim 1, wherein the organic solvent is contained in an amount of from 40 to 90% by weight.

A cleaning solution according to claim 4, wherein the content of said organic solvent is 50-85wt% _o

The cleaning solution according to claim 1, wherein the gallic acid and the ester thereof are contained in an amount of from 0.05 to 5 % by weight.

The cleaning solution according to claim 6, wherein the gallic acid and the ester thereof are contained in an amount of from 0.1 to 3% by weight.

The cleaning solution according to claim 1, wherein the 3-amino-1,2,4-triazole is contained in an amount of from 0.01 to 5% by weight.

The cleaning solution according to claim 8, wherein the 3-amino-1,2,4-triazole is contained in an amount of from 0.05 to 3 wt%.

The cleaning solution according to claim 1, wherein the alcohol amine is selected from the group consisting of monoethanolamine, N-methylethanolamine, diethanolamine, triethanolamine, isopropanolamine, ethyldiethanolamine, N, One or more of N-diethylethanolamine, N-(2-aminoethyl)ethanolamine, and diglycolamine.

The cleaning solution according to claim 10, wherein the alcohol amine is selected from the group consisting of ethanol Amines, diglycolamines, and mixtures thereof.

The cleaning solution according to claim 1, wherein the organic solvent is one or more selected from the group consisting of sulfoxide, sulfone, imidazolium, pyrrolidone, imidazolidinone, amide and alcohol ether. 3. The cleaning solution according to claim 12, wherein the sulfoxide is selected from one or more of dimethyl sulfoxide and methyl sulfoxide; and the sulfone is selected from the group consisting of methyl sulfone. One or more of sulfolane; the imidazolidinone is one or more selected from the group consisting of 2-imidazolidinone and 1,3-dimethyl-2-imidazolium; The ketone is selected from one or more of N-methylpyrrolidone, N-cyclohexylpyrrolidone and N-hydroxyethylpyrrolidone; the imidazolidinone is selected from the group consisting of 1,3-dimethyl-2-imidazole a ketone; the amide is one or more selected from the group consisting of dimethylformamide and dimethylacetamide; and the alcohol ether is selected from the group consisting of ethylene glycol alkyl ether and propylene glycol alkyl ether. Or a variety.

The cleaning solution according to claim 13, wherein the ethylene glycol decyl ether is one of ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monobutyl ether or A plurality of; the propylene glycol decyl ether is one or more of propylene glycol monomethyl ether, propylene glycol monobutyl ether and dipropylene glycol monomethyl ether.

The cleaning solution according to claim 1, wherein the gallic acid and ester thereof are selected from the group consisting of gallic acid, methyl gallate, ethyl gallate, butyl gallate, octyl gallate, gallic acid. One or more of lauryl ester and 1-gallate glyceride.

The cleaning solution according to claim 1, wherein the cleaning liquid does not contain water,