WO2008046305A1 - A low etched photoresist cleaning agent and cleaning method of using same - Google Patents

A low etched photoresist cleaning agent and cleaning method of using same Download PDF

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Publication number
WO2008046305A1
WO2008046305A1 PCT/CN2007/002935 CN2007002935W WO2008046305A1 WO 2008046305 A1 WO2008046305 A1 WO 2008046305A1 CN 2007002935 W CN2007002935 W CN 2007002935W WO 2008046305 A1 WO2008046305 A1 WO 2008046305A1
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Prior art keywords
cleaning agent
ether
agent according
low
resist cleaning
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PCT/CN2007/002935
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French (fr)
Chinese (zh)
Inventor
Libbert Hongxiu Peng
Robert Yongtao Shi
Bing Liu
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Anji, Microelectronics (Shanghai) Co., Ltd.
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Priority to CNA2007800375301A priority Critical patent/CN101523300A/en
Publication of WO2008046305A1 publication Critical patent/WO2008046305A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides

Definitions

  • the present invention relates to the field of cleaning processes in semiconductor manufacturing, and in particular to a low etch photoresist cleaning agent and a cleaning method therefor.
  • a photoresist mask is formed on the surface of a metal such as silicon dioxide, copper or the like, or a low-k material, and the pattern is transferred by wet or dry etching after exposure.
  • the higher pH cleaning agent can cause corrosion of the wafer substrate.
  • metal corrosion is a relatively common and very serious problem, often resulting in a significant reduction in wafer yield.
  • achieving a low temperature and rapid cleaning process is an important direction in the development of the field.
  • Patent document WO03104901 immersing a wafer into the cleaning agent by using an alkaline cleaning agent consisting of tetramethylammonium hydroxide (TMAH), sulfolane (SFL), trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA), and water.
  • TMAH tetramethylammonium hydroxide
  • SFL sulfolane
  • CyDTA trans-1,2-cyclohexanediaminetetraacetic acid
  • water water.
  • the photoresist on the metal and dielectric substrates is removed by immersing at 20 to 30 ⁇ at 50 to 70 °C.
  • the cleaning agent has a slightly high corrosion to the semiconductor wafer substrate, and the photoresist of the semiconductor wafer cannot be completely removed, and the cleaning ability is insufficient.
  • Patent document WO04059700 immersing a wafer with an alkaline cleaning agent using tetramethylammonium hydroxide ( ⁇ ), ⁇ -methylmorpholine- ⁇ -oxide ( ⁇ ), 2-mercaptobenzimidazole ( ⁇ ) and water
  • the cleaning agent was immersed at 7 CTC for 15 to 60 minutes to remove the photoresist on the metal and dielectric substrates.
  • the cleaning temperature is relatively high, and the cleaning speed is relatively slow, which is not conducive to improving the cleaning efficiency of the semiconductor wafer.
  • Confirmation JP1998239865 uses an alkaline cleaning agent consisting of TMAH, dimethyl sulfoxide (DMSO), 1,3,-dimethyl-2-imidazolidinone (DMI) and water to immerse the wafer in the cleaning agent at 50 ⁇ 10 (rC removes 20 ⁇ m or more of thick film photoresist on metal and dielectric substrates.
  • TMAH dimethyl sulfoxide
  • DMI 1,3,-dimethyl-2-imidazolidinone
  • JP2001215736 utilizes tetramethylammonium hydroxide ( ⁇ ), two An alkaline cleaning agent is composed of methyl sulfoxide (DMSO), ethylene glycol (EG), and water, and the wafer is immersed in the cleaning agent to remove the photoresist on the metal and dielectric substrate at 50 to 70 °C. Similarly, the higher cleaning temperature causes corrosion of the semiconductor wafer substrate. JP200493678 uses an alkaline cleaning agent such as TMAH, N-methylpyrrolidone (NMP), water or methanol to immerse the wafer in the cleaning agent. The photoresist on the metal and dielectric substrates is removed at 25 to 85 ° C. However, the increase in the cleaning temperature causes a significant increase in the corrosion of the semiconductor wafer substrate.
  • TMAH methyl sulfoxide
  • EG ethylene glycol
  • water water
  • the object of the present invention is to reduce metal corrosion during cleaning in a semiconductor manufacturing process while also ensuring a low temperature of the cleaning process, providing a low etch photoresist cleaning agent.
  • the above object of the present invention is achieved by the following technical solutions:
  • the low etching photoresist cleaning agent of the present invention comprises dimethyl sulfoxide and quaternary ammonium hydroxide, and is characterized in that it further comprises the formula (1)
  • R 2 is H or an aryl group
  • m 2 to 6
  • n 1 to 6.
  • the alkyl glycol aryl ether or a derivative thereof is ethylene glycol monophenyl ether, propylene glycol monophenyl ether, isopropyl glycol monophenyl ether, diethylene glycol monophenyl ether, two Propylene glycol monophenyl ether, diisopropyl glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol monobenzyl ether, isopropyl glycol monobenzyl ether, hexanediol mononaphthyl ether or hexaethylene glycol diphenyl Ether.
  • ethylene glycol monophenyl is preferred.
  • the content thereof is preferably from 0.01 to 9 S.99 wt%, more preferably from 5.0 to 40.0 wt%.
  • the content of the dimethyl sulfoxide is preferably from 1 to 99.98% by weight, more preferably from 60 to 95% by weight.
  • the quaternary ammonium hydroxide is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or benzyltrimethylammonium hydroxide.
  • tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrabutylammonium hydroxide, more preferably tetramethylammonium hydroxide 9 is preferably 0.01 to 15% by weight, more preferably It is 0.5 to 10.0% by weight.
  • the low etch resist cleaning agent may further comprise a polar organic cosolvent, a corrosion inhibitor, a surfactant, and/or water.
  • the content of the polar organic co-solvent is preferably from 0 to 98.98 wt%, more preferably from 10 to 50 wt%;
  • the corrosion inhibitor content is preferably from 0 to 15 wt%, more preferably 0.05.
  • the surfactant content is preferably 0 ⁇ 15wt%, more preferably 0.05 ⁇ 5.0wt%;
  • the water content is preferably 0 ⁇ 95wt%, more preferably 0.5 ⁇ 25wt%.
  • the polar organic co-solvent is sulfoxide, sulfone, imidazolium and/or mercaptodiol monodecyl ether.
  • the sulfoxide is diethyl sulfoxide or methyl ethyl sulfoxide;
  • the sulfone is methyl sulfone, ethyl sulfone or sulfolane, preferably sulfolane;
  • the imidazolidinone is 2-imidazole An alkyl ketone, 1,3-dimethyl-2-imidazolium or 1,3-diethyl-2-imidazolium, preferably 1,3-dimethyl-2-imidazolium;
  • the mercapto diol monoalkyl ether is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobuty
  • the corrosion inhibitor is a phenolic, carboxylic acid (ester), acid anhydride or phosphonic acid (ester) corrosion inhibitor.
  • the phenol is 1,2-dihydroxyphenol, p-hydroxyphenol or pyrogallol, preferably pyrogallol;
  • the carboxylic acid is benzoic acid, p-aminobenzene Formic acid, phthalic acid, gallic acid or propyl gallate, preferably p-aminobenzoic acid, phthalic acid or gallic acid;
  • the acid anhydride is acetic anhydride, propionic anhydride, hexanoic anhydride or (poly) Maleic anhydride, preferably polymaleic acid;
  • the phosphonic acid type is 1,3-(hydroxyethyl)-2,4,6-triphosphonic acid, aminotrimethylenephosphonic acid Or 2-phosphonium butyrate-1,2,4-tricarboxylic acid, preferably 1,3-(hydroxyethyl)-2,4,6-triphosphonic acid.
  • the low etch resist cleaning agent can be obtained by simply mixing the components described above.
  • Another object of the present invention is to provide a cleaning method using the above-described low etching photoresist cleaning agent, the specific steps of which: immersing a semiconductor wafer containing a photoresist in the low etching property of the present invention at room temperature to 85 ° C The photoresist cleaner is cleaned and then blown dry.
  • the wafer is washed with a cleaning agent, and then the wafer is washed with isopropyl alcohol.
  • the cleaning method can be carried out by slow shaking, and the time is preferably 10 to 30 minutes.
  • the blow drying step is preferably carried out under high purity nitrogen.
  • the positive progress of the present invention is that the low etch resist cleaning agent is packaged therein.
  • the alkyl diol aryl ether or its derivative can form a protective film on the surface of the wafer substrate to prevent attack of the substrate by a halogen atom, a hydroxide ion or the like, thereby reducing corrosion of the substrate.
  • the cleaning agent can be used to remove photoresist (photoresist) and other residues of 30 ⁇ m or more on a metal, metal alloy or dielectric substrate, and has properties for metals such as silicon dioxide, Cu (copper), and low-k materials.
  • the low etching rate has a good application prospect in the field of microelectronics such as semiconductor wafer cleaning. The effect will be further illustrated by comparative experiments in the examples. Summary of the invention
  • the cleaning agents of Examples 27 to 34 in Table 1 and the cleaning agent of Comparative Example 1 were used to clean blank Cu wafers, and the etching rate of the metal Cu was measured. The results are shown in Table 2. Test Methods and Conditions - Dip the blank Cu wafer into the cleaning agent, shake it slowly for 30 minutes at a specific temperature listed in Table 2, then wash it with deionized water and then dry it with high purity nitrogen. Needle test The etch rate of the above-mentioned cleaning agent to the metal Cu was calculated by changing the surface resistance of the blank Cu wafer before and after etching.
  • Low etch photoresist cleaning agent 84.35wt% dimethyl sulfoxide, 2.50wt% tetramethylammonium hydroxide, 8.00 wt% ethylene glycol monophenyl ether, 0.15 wt% polyoxyethylene ether and 5.00 wt% water.
  • the photoresist-containing semiconductor wafer was immersed in a low-etching photoresist cleaning agent at room temperature for a period of 30 minutes, washed with deionized water, and then dried under high-purity nitrogen.
  • Low etch resist cleaning agent 84.35 wt % dimethyl sulfoxide, 2.50 wt % tetramethylammonium hydroxide, 8.00 wt % ethylene glycol monophenyl ether, 0.15 wt % polyoxyethylene ether and 5.00 wt % water.
  • the semiconductor wafer containing the photoresist is immersed in a low-etching photoresist cleaning agent at 45 ° C.
  • the mixture was washed for 20 min, washed with isopropyl alcohol, washed with deionized water, and then dried under high purity nitrogen.
  • Low etch photoresist cleaning agent 84.35 wt % dimethyl sulfoxide, 2.50 wt % tetramethylammonium hydroxide, 8.00 wt % ethylene glycol monophenyl ether, 0.15 wt % polyoxyethylene ether and 5.00 % water .
  • the semiconductor wafer containing the photoresist was immersed in a low-etching photoresist cleaning agent and slowly oscillated for 10 minutes, washed with isopropyl alcohol, washed with deionized water, and then dried under high-purity nitrogen.
  • the raw materials and reagents used in the present invention are all commercially available products.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Detergent Compositions (AREA)

Abstract

A low etched photoresist cleaning agent and cleaning method of using same are provided. The low etched photoresist cleaning agent comprises dimethyl sulphoxide, quaternary ammonium hydroxide, alkyldiol aryl ether which has general formula of R1O-[-(-CHmH2m-)-O-]n-R2 or its derivate, wherein R1 is aryl, R2 is H or aryl, m=2-6, n=1-6. The cleaning agent can be used for removing photoresist and other residue on the metal, metal alloy or dielectric substrate. At the same time, the cleaning agent has lower etched rate for the silicon dioxide, metal such as copper and low κ material and the like.

Description

一种低蚀刻性光刻胶清洗剂及其清洗方法 技术领域  Low etching photoresist cleaning agent and cleaning method thereof
本发明涉及半导体制造中清洗工艺领域，具体涉及一种低蚀刻性的光刻 胶清洗剂及其清洗方法。  The present invention relates to the field of cleaning processes in semiconductor manufacturing, and in particular to a low etch photoresist cleaning agent and a cleaning method therefor.
在通常的半导体制造工艺中， 先在二氧化硅、铜等金属或低 k材料等的 表面上形成光刻胶的掩模， 曝光后利用湿法或干法刻蚀进行图形转移。在半 导体晶片进行光刻胶的化学清洗过程中， 较高 pH的清洗剂会造成晶片基材 的腐蚀。特别是在利用化学清洗剂除去金属刻蚀残余物的过程中， 金属腐蚀 是较为普遍而且非常严重的问题，往往导致晶片良率的显著降低。 此外， 使 清洗工艺实现低温快速是本领域发展的重要方向。 In a typical semiconductor manufacturing process, a photoresist mask is formed on the surface of a metal such as silicon dioxide, copper or the like, or a low-k material, and the pattern is transferred by wet or dry etching after exposure. During the chemical cleaning of the photoresist on the semiconductor wafer, the higher pH cleaning agent can cause corrosion of the wafer substrate. In particular, in the process of removing metal etching residues by chemical cleaning agents, metal corrosion is a relatively common and very serious problem, often resulting in a significant reduction in wafer yield. In addition, achieving a low temperature and rapid cleaning process is an important direction in the development of the field.
因此，减少清洗过程中的金属腐蚀，同时还要保证清洗工艺的低温快速， 是本领域亟待解决的问题。 专利文献 WO03104901 利用四甲基氢氧化铵 (TMAH)、 环丁砜（SFL)、 反 -1,2-环己垸二胺四乙酸 （CyDTA)和水等组 成碱性清洗剂， 将晶片浸入该清洗剂中， 于 50〜70°C下浸没 20〜30πώι， 除去 金属和电介质基材上的光刻胶。 但该清洗剂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的光刻胶，清洗能力不足。专利文献 WO04059700 利用四甲基氢氧化铵 （ΤΜΑΗ)、 Ν-甲基吗啡啉 -Ν-氧化物 （ΜΟ)、 2-巯基苯 并咪唑（ΜΒΙ)和水等组成碱性清洗剂， 将晶片浸入该清洗剂中， 于 7CTC下 浸没 15〜60min， 除去金属和电介质基材上的光刻胶。 但其清洗温度较高， 且清洗速度相对较慢， 不利于提高半导体晶片的清洗效率。 专利文献  Therefore, it is an urgent problem to be solved in the art to reduce the corrosion of the metal during the cleaning process and to ensure the low temperature of the cleaning process. Patent document WO03104901 immersing a wafer into the cleaning agent by using an alkaline cleaning agent consisting of tetramethylammonium hydroxide (TMAH), sulfolane (SFL), trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA), and water. The photoresist on the metal and dielectric substrates is removed by immersing at 20 to 30 πι at 50 to 70 °C. However, the cleaning agent has a slightly high corrosion to the semiconductor wafer substrate, and the photoresist of the semiconductor wafer cannot be completely removed, and the cleaning ability is insufficient. Patent document WO04059700 immersing a wafer with an alkaline cleaning agent using tetramethylammonium hydroxide (ΤΜΑΗ), Ν-methylmorpholine-Ν-oxide (ΜΟ), 2-mercaptobenzimidazole (ΜΒΙ) and water The cleaning agent was immersed at 7 CTC for 15 to 60 minutes to remove the photoresist on the metal and dielectric substrates. However, the cleaning temperature is relatively high, and the cleaning speed is relatively slow, which is not conducive to improving the cleaning efficiency of the semiconductor wafer. Patent literature
1  1
确认本 JP1998239865利用 TMAH、 二甲基亚砜（DMSO)、 1，3，-二甲基 -2-咪唑烷酮 (DMI)和水等组成碱性清洗剂，将晶片浸入该清洗剂中， 于 50~10(rC下除 去金属和电介质基材上的 20μιη以上的厚膜光刻胶。 但其较高的清洗温度会 造成半导体晶片基材的腐蚀。 JP2001215736利用四甲基氢氧化铵（ΤΜΑΗ)、 二甲基亚砜（DMSO)、 乙二醇 （EG) 和水等组成碱性清洗剂， 将晶片浸入 该清洗剂中， 于 50~70°C下除去金属和电介质基材上的光刻胶。 同样， 其较 高的清洗温度会造成半导体晶片基材的腐蚀。 JP200493678利用 TMAH、 N- 甲基吡咯垸酮 （NMP)、 水或甲醇等组成碱性清洗剂， 将晶片浸入该清洗剂 中， 于 25〜85°C下除去金属和电介质基材上的光刻胶。 但其清洗温度的升高 使得半导体晶片基材的腐蚀明显增强。 Confirmation JP1998239865 uses an alkaline cleaning agent consisting of TMAH, dimethyl sulfoxide (DMSO), 1,3,-dimethyl-2-imidazolidinone (DMI) and water to immerse the wafer in the cleaning agent at 50~ 10 (rC removes 20 μm or more of thick film photoresist on metal and dielectric substrates. However, its higher cleaning temperature causes corrosion of the semiconductor wafer substrate. JP2001215736 utilizes tetramethylammonium hydroxide (ΤΜΑΗ), two An alkaline cleaning agent is composed of methyl sulfoxide (DMSO), ethylene glycol (EG), and water, and the wafer is immersed in the cleaning agent to remove the photoresist on the metal and dielectric substrate at 50 to 70 °C. Similarly, the higher cleaning temperature causes corrosion of the semiconductor wafer substrate. JP200493678 uses an alkaline cleaning agent such as TMAH, N-methylpyrrolidone (NMP), water or methanol to immerse the wafer in the cleaning agent. The photoresist on the metal and dielectric substrates is removed at 25 to 85 ° C. However, the increase in the cleaning temperature causes a significant increase in the corrosion of the semiconductor wafer substrate.
发明概要 Summary of invention
本发明的目的是减少半导体制造工艺中清洗过程中的金属腐蚀， 同时还 要保证清洗工艺的低温快速， 提供一种低蚀刻性光刻胶清洗剂。  SUMMARY OF THE INVENTION The object of the present invention is to reduce metal corrosion during cleaning in a semiconductor manufacturing process while also ensuring a low temperature of the cleaning process, providing a low etch photoresist cleaning agent.
本发明的上述目的是通过下列技术方案来实现的：本发明的低蚀刻性光 刻胶清洗剂包含二甲基亚砜、季铵氢氧化物， 其特征在于还包含通式为 （1 )
Figure imgf000003_0001
The above object of the present invention is achieved by the following technical solutions: The low etching photoresist cleaning agent of the present invention comprises dimethyl sulfoxide and quaternary ammonium hydroxide, and is characterized in that it further comprises the formula (1)
Figure imgf000003_0001
其中， 为芳基， R2为 H或芳基， m=2~6, n=l〜6。 Wherein, it is an aryl group, R 2 is H or an aryl group, m = 2 to 6, and n = 1 to 6.
本发明中， 所述的烷基二醇芳基醚或其衍生物为乙二醇单苯基醚、丙二 醇单苯基醚、 异丙二醇单苯基醚、 二乙二醇单苯基醚、 二丙二醇单苯基醚、 二异丙二醇单苯基醚、 乙二醇单苄基醚、 丙二醇单苄基醚、 异丙二醇单苄基 醚、 己二醇单萘基醚或六缩乙二醇二苯基醚。 其中， 较佳的为乙二醇单苯基 醚、丙二醇单苯基醚、异丙二醇单苯基醚。其含量较佳的为 0.01〜9S.99wt%， 更佳的为 5.0〜40.0wt%。 In the present invention, the alkyl glycol aryl ether or a derivative thereof is ethylene glycol monophenyl ether, propylene glycol monophenyl ether, isopropyl glycol monophenyl ether, diethylene glycol monophenyl ether, two Propylene glycol monophenyl ether, diisopropyl glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol monobenzyl ether, isopropyl glycol monobenzyl ether, hexanediol mononaphthyl ether or hexaethylene glycol diphenyl Ether. Among them, ethylene glycol monophenyl is preferred. Ether, propylene glycol monophenyl ether, isopropyl glycol monophenyl ether. The content thereof is preferably from 0.01 to 9 S.99 wt%, more preferably from 5.0 to 40.0 wt%.
本发明中， 所述的二甲基亚砜的含量较佳的为 l~99.98wt%， 更佳的为 60〜95wt%。  In the present invention, the content of the dimethyl sulfoxide is preferably from 1 to 99.98% by weight, more preferably from 60 to 95% by weight.
本发明中， 所述的季铵氢氧化物为四甲基氢氧化铵、 四乙基氢氧化铵、 四丙基氢氧化铵、 四丁基氢氧化铵或苄基三甲基氢氧化铵。其中， 较佳的为 四甲基氢氧化铵、 四乙基氢氧化铵或四丁基氢氧化铵， 更较佳的为四甲基氢 氧化铵 9 其含量较佳的为 0.01~15wt%， 更佳的为 0.5〜10.0wt%。 In the present invention, the quaternary ammonium hydroxide is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or benzyltrimethylammonium hydroxide. Preferably, tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrabutylammonium hydroxide, more preferably tetramethylammonium hydroxide 9 is preferably 0.01 to 15% by weight, more preferably It is 0.5 to 10.0% by weight.
本发明中， 所述的低蚀刻性光刻胶清洗剂还可包含极性有机共溶剂、缓 蚀剂、 表面活性剂及 /或水。 所述的极性有机共溶剂含量较佳的为 0〜98.98wt%， 更佳的为 10~50wt%; 所述的缓蚀剂含量较佳的为 0~15wt%， 更佳的为 0.05~5.0wt%; 所述的表面活性剂含量较佳的为 0~15wt%， 更佳的 为 0.05~5.0wt%; 所述的水含量较佳的为 0~95wt%， 更佳的为 0.5~25wt%。  In the present invention, the low etch resist cleaning agent may further comprise a polar organic cosolvent, a corrosion inhibitor, a surfactant, and/or water. The content of the polar organic co-solvent is preferably from 0 to 98.98 wt%, more preferably from 10 to 50 wt%; the corrosion inhibitor content is preferably from 0 to 15 wt%, more preferably 0.05. 5.0wt%; the surfactant content is preferably 0~15wt%, more preferably 0.05~5.0wt%; the water content is preferably 0~95wt%, more preferably 0.5~ 25wt%.
本发明中，所述的极性有机共溶剂为亚砜、砜、咪唑垸酮和 /或垸基二醇 单垸基醚。  In the present invention, the polar organic co-solvent is sulfoxide, sulfone, imidazolium and/or mercaptodiol monodecyl ether.
其中， 所述的亚砜为二乙基亚砜或甲乙基亚砜； 所述的砜为甲基砜、 乙 基砜或环丁砜， 较佳的为环丁砜； 所述的咪唑烷酮为 2-咪唑烷酮、 1,3-二甲 基 -2-咪唑垸酮或 1,3-二乙基 -2-咪唑垸酮， 较佳的为 1,3-二甲基 -2-咪唑垸酮； 所述的垸基二醇单烷基醚为乙二醇单甲醚、 乙二醇单乙醚、 乙二醇单丁醚、 二乙二醇单甲醚、 二乙二醇单乙醚、 二乙二醇单丁醚、 丙二醇单甲醚、 丙二 醇单乙醚、 丙二醇单丁醚、 二丙二醇单甲醚、 二丙二醇单乙醚或二丙二醇单 丁醚， 较佳的为乙二醇单甲醚、 二乙二醇单甲醚、 丙二醇单甲醚或二丙二醇 单甲醚。 ' 本发明中， 所述的表面活性剂为聚乙烯醇、 聚乙烯吡咯垸酮、 聚氧乙烯 醚或聚硅氧烷。 Wherein, the sulfoxide is diethyl sulfoxide or methyl ethyl sulfoxide; the sulfone is methyl sulfone, ethyl sulfone or sulfolane, preferably sulfolane; the imidazolidinone is 2-imidazole An alkyl ketone, 1,3-dimethyl-2-imidazolium or 1,3-diethyl-2-imidazolium, preferably 1,3-dimethyl-2-imidazolium; The mercapto diol monoalkyl ether is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether or dipropylene glycol monobutyl ether, preferably ethylene glycol monomethyl ether, diethylene glycol Monomethyl ether, propylene glycol monomethyl ether or dipropylene glycol monomethyl ether. ' In the present invention, the surfactant is polyvinyl alcohol, polyvinylpyrrolidone, polyoxyethylene ether or polysiloxane.
本发明中， 所述的缓蚀剂为酚类、 羧酸（酯）类、 酸酐类或膦酸 （酯） 类缓蚀剂。  In the present invention, the corrosion inhibitor is a phenolic, carboxylic acid (ester), acid anhydride or phosphonic acid (ester) corrosion inhibitor.
其中， 所述的酚类为 1,2-二羟基苯酚、 对羟基苯酚或连苯三酚， 较佳的 为连苯三酚； 所述的羧酸（酯）类为苯甲酸、 对氨基苯甲酸、 邻苯二甲酸、 没食子酸或没食子酸丙酯，较佳的为对氨基苯甲酸、邻苯二甲酸或没食子酸； 所述的酸酐类为乙酸酐、 丙酸酐、 己酸酐或（聚）马来酸酐， 较佳的为聚马 来酸軒； 所述的膦酸 （酯）类为 1,3- (羟乙基） -2,4,6-三膦酸、 氨基三亚甲 基膦酸或 2-膦酸丁垸 -1,2,4-三羧酸， 较佳的为 1,3- (羟乙基） -2,4,6-三膦酸。  Wherein, the phenol is 1,2-dihydroxyphenol, p-hydroxyphenol or pyrogallol, preferably pyrogallol; the carboxylic acid is benzoic acid, p-aminobenzene Formic acid, phthalic acid, gallic acid or propyl gallate, preferably p-aminobenzoic acid, phthalic acid or gallic acid; the acid anhydride is acetic anhydride, propionic anhydride, hexanoic anhydride or (poly) Maleic anhydride, preferably polymaleic acid; the phosphonic acid type is 1,3-(hydroxyethyl)-2,4,6-triphosphonic acid, aminotrimethylenephosphonic acid Or 2-phosphonium butyrate-1,2,4-tricarboxylic acid, preferably 1,3-(hydroxyethyl)-2,4,6-triphosphonic acid.
本发明中，所述的低蚀刻性光刻胶清洗剂由上面所述组分简单混合即可 制得。  In the present invention, the low etch resist cleaning agent can be obtained by simply mixing the components described above.
本发明的另一目的是提供使用上述低蚀刻性光刻胶清洗剂的清洗方法， 具体步骤为：室温至 85°C下，将含有光刻胶的半导体晶片浸入本发明所述的 低蚀刻性光刻胶清洗剂进行清洗， 然后吹干即可。  Another object of the present invention is to provide a cleaning method using the above-described low etching photoresist cleaning agent, the specific steps of which: immersing a semiconductor wafer containing a photoresist in the low etching property of the present invention at room temperature to 85 ° C The photoresist cleaner is cleaned and then blown dry.
本发明实例中， 若清洗温度高于 45°C， 晶片用清洗剂清洗后， 再用异 丙醇洗涤晶片。  In the example of the present invention, if the cleaning temperature is higher than 45 ° C, the wafer is washed with a cleaning agent, and then the wafer is washed with isopropyl alcohol.
在本发明实例中， 清洗方式可采用缓慢振荡清洗， 时间较佳的为 10〜30 分钟。  In the example of the present invention, the cleaning method can be carried out by slow shaking, and the time is preferably 10 to 30 minutes.
本发明实例中， 低蚀刻性光刻胶清洗剂清洗后， 可再用去离子水清洗。 在本发明实例中， 吹干步骤较佳的在高纯氮气下进行。  In the example of the present invention, after the low etch photoresist cleaning agent is cleaned, it can be washed again with deionized water. In the present invention, the blow drying step is preferably carried out under high purity nitrogen.
本发明的积极进步效果在于：所述的低蚀刻性光刻胶清洗剂由于其中包 含的烷基二醇芳基醚或其衍生物能够在晶片基材表面形成一层保护膜， 阻止 卤素原子、 氢氧根离子等对基材的攻击， 从而降低基材的腐蚀。 该清洗剂可 用于除去金属、 金属合金或电介质基材上 30μιη以上厚度的光刻胶 （光阻） 和其它残留物， 同时对于二氧化硅、 Cu (铜）等金属以及低 k材料等具有较 低的蚀刻速率， 在半导体晶片清洗等微电子领域具有良好的应用前景。其效 果将通过实施例中的对比实验进一步说明。 发明内容 The positive progress of the present invention is that the low etch resist cleaning agent is packaged therein. The alkyl diol aryl ether or its derivative can form a protective film on the surface of the wafer substrate to prevent attack of the substrate by a halogen atom, a hydroxide ion or the like, thereby reducing corrosion of the substrate. The cleaning agent can be used to remove photoresist (photoresist) and other residues of 30 μm or more on a metal, metal alloy or dielectric substrate, and has properties for metals such as silicon dioxide, Cu (copper), and low-k materials. The low etching rate has a good application prospect in the field of microelectronics such as semiconductor wafer cleaning. The effect will be further illustrated by comparative experiments in the examples. Summary of the invention
下面通过实施例的方式进一步说明本发明，并不因此将本发明限制在所 述的实施例范围之中。  The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
实施例 1~34及对比实施例 1  Examples 1 to 34 and Comparative Example 1
低蚀刻性光刻胶清洗剂实施例 1~34及对比实施例 1  Low Etching Photoresist Cleaning Agent Examples 1 to 34 and Comparative Example 1
烷基二醇芳基醚及其衍  Alkyl glycol aryl ether and its derivative
季铵氢氧化物 其它 亚砜 生物  Quaternary ammonium hydroxide other sulfoxide
施 Shi
含量 含量  Content
例 含量 Example
具体物质 具体物质 具体物质 wt% wt% wt% wt%  Specific substance specific substance specific substance wt% wt% wt% wt%
1 10 四甲基氢氧化铵 89 乙二醇单苯基醚 \ \ 1 10 tetramethylammonium hydroxide 89 ethylene glycol monophenyl ether
2 四乙基氢氧化 2 tetraethyl hydroxide
99.98 0.01 0.01 丙二醇单苯基醚 \ \ 铵  99.98 0.01 0.01 Propylene glycol monophenyl ether \ \ Ammonium
3 1 0.01 四丙基氢氧化铵 98.99 异丙二醇单苯基醚 \ \ 3 1 0.01 tetrapropylammonium hydroxide 98.99 isopropyl glycol monophenyl ether
4 5 15 四甲基氢氧化铵 65 二乙二醇单苯基醚 15 苯甲酸4 5 15 tetramethylammonium hydroxide 65 diethylene glycol monophenyl ether 15 benzoic acid
5 60 5 苯基醚 5 60 5 phenyl ether
四丁基氢氧化铵 20 二丙二醇单 15 聚 烯吡咯烷酮 Tetrabutylammonium hydroxide 20 dipropylene glycol mono 15 polypyrrolidone
6 1 2 苄基三甲基氢氧化铵 2 二异丙二醇单苯基醚 95 水6 1 2 benzyltrimethylammonium hydroxide 2 diisopropyl glycol monophenyl ether 95 water
7 10 2 四甲基氢氧化铵 80 丙二醇单苄基醚 8 二乙基亚砜 7 10 2 tetramethylammonium hydroxide 80 propylene glycol monobenzyl ether 8 diethyl sulfoxide
4.5 甲乙基亚砜 4.5 methyl ethyl sulfoxide
0.25 1,2-二羟基苯酚0.25 1,2-dihydroxyphenol
8 60 2 单 基醚 8 60 2 monoether ether
四甲基氢氧化铰 8 乙二醇  Tetramethyl hydroxide hinge 8 ethylene glycol
0.25 聚乙烯醇 7.5 甲基砜 0.25 polyvinyl alcohol 7.5 Methyl sulfone
1 对羟基苯酚 1 p-hydroxyphenol
5 3 四甲基氢氧化铵 82 异丙一醇单苄基醚 5 3 tetramethylammonium hydroxide 82 isopropanol monobenzyl ether
1 聚氧乙烯醚 1 polyoxyethylene ether
0.5 水 0.5 water
4 乙基砜  4 ethyl sulfone
25 3 四甲基氢氧化铵 62 乙二醇单苯基醚 1 连苯三酚  25 3 tetramethylammonium hydroxide 62 ethylene glycol monophenyl ether 1 pyrogallol
5 聚硅氧垸 5 polysiloxane
9 环丁砜 9 sulfolane
35 3 四甲基氢氧化铵 52 乙一醇单苯基醚  35 3 tetramethylammonium hydroxide 52 ethyl alcohol monophenyl ether
1 对氨基苯甲酸 1 p-aminobenzoic acid
9 2-咪唑烷酮9 2-imidazolidinone
45 5 四甲基氢氧化铵 40 乙二醇单苯基醚 45 5 tetramethylammonium hydroxide 40 ethylene glycol monophenyl ether
1 邻苯二甲酸 1 phthalic acid
9 1,3-二甲基 -2-咪唑垸酮9 1,3-dimethyl-2-imidazolium
55 3 四甲基氢氧化钹 32 乙一醇单苯基醚 55 3 tetramethylphosphonium hydroxide 32 ethyl alcohol monophenyl ether
1 没食子酸 1 gallic acid
9 1 ,3-二乙基 -2-咪唑烷酮9 1 ,3-diethyl-2-imidazolidinone
65 3 四甲基氢氧化铵 22 乙二醇单苯基醚 65 3 tetramethylammonium hydroxide 22 ethylene glycol monophenyl ether
1 没食子酸丙酯 1 propyl gallate
9 乙二醇单甲醚9 ethylene glycol monomethyl ether
75 3 四甲基氢氧化铵 12 己二醇单萘基醚 75 3 tetramethylammonium hydroxide 12 hexanediol mononaphthyl ether
1 - 乙酸酐 1 - acetic anhydride
1 乙二醇单乙醚1 ethylene glycol monoethyl ether
95 0.5 四甲基氢氧化铵 2.5 六缩乙二醇二苯基醚 95 0.5 tetramethylammonium hydroxide 2.5 hexaethylene glycol diphenyl ether
1 丙酸酐  1 propionic anhydride
6 乙二醇单丁醚 6 ethylene glycol monobutyl ether
70 3 四甲基氢氧化铵 20 乙二醇单苯基醚 70 3 tetramethylammonium hydroxide 20 ethylene glycol monophenyl ether
1 己酸酐  1 hexanoic anhydride
4  4
15 3 四甲基氢氧化铵 77 乙二醇单笨基醚 二乙二醇单甲醚  15 3 tetramethylammonium hydroxide 77 ethylene glycol mono-phenyl ether diethylene glycol monomethyl ether
1 马来酸西干 1 maleic acid
4 二乙二醇单乙醚4 diethylene glycol monoethyl ether
20 3 四乙基氢 ft化铵 72 乙二醇单苯基醚 20 3 tetraethyl hydrogen ft ammonium bromide 72 ethylene glycol monophenyl ether
1 聚马来酸酐 1 polymaleic anhydride
4 4
10 5 四乙基氢氧化铵 80 乙二醇单苯基醚 二乙二醇单丁醚  10 5 tetraethylammonium hydroxide 80 ethylene glycol monophenyl ether diethylene glycol monobutyl ether
1 1，3- (羟乙基） -2,4,6-三膦酸 1 1,3-(hydroxyethyl)-2,4,6-triphosphonic acid
1 0.01 四乙基氢氧化铵 0.01 乙二醇单苯基醚 98.98 丙二醇单甲醚 1 0.01 Tetraethylammonium hydroxide 0.01 Ethylene glycol monophenyl ether 98.98 Propylene glycol monomethyl ether
10 丙二醇单乙醚 10 propylene glycol monoethyl ether
79.95 2 四乙基氢氧化铵 8 乙二醇单苯基醚 79.95 2 Tetraethylammonium hydroxide 8 Ethylene glycol monophenyl ether
0.05 氨基三亚甲基膦酸 0.05 aminotrimethylenephosphonic acid
5 丙二醇单丁醚5 propylene glycol monobutyl ether
80 2 四乙基氢氧化铵 8 乙二醇单苯基醚 80 2 tetraethylammonium hydroxide 8 ethylene glycol monophenyl ether
5 2-膦酸丁烷 -1 ,2,4-三羧酸 5 2-phosphonic acid butane -1 , 2,4-tricarboxylic acid
40 2 四乙基氢氧化铵 8 乙二醇单苯基醚 50 二丙二醇单甲醚40 2 tetraethylammonium hydroxide 8 ethylene glycol monophenyl ether 50 dipropylene glycol monomethyl ether
80 2 四丙基氢氧化铵 8 乙二醇单苯基醚 10 二丙二醇单乙醚 5 二丙二醇单丁醚80 2 tetrapropylammonium hydroxide 8 ethylene glycol monophenyl ether 10 dipropylene glycol monoethyl ether 5 dipropylene glycol monobutyl ether
26 80 2 四丁基氢氧化铵 8 乙二醇单苯基醚 2 2-咪唑烷酮 26 80 2 tetrabutylammonium hydroxide 8 ethylene glycol monophenyl ether 2 2-imidazolidinone
3 .甲基砜  3. Methyl sulfone
27 87 1 四甲基氢氧化铵 5 乙二醇单苯基醚 7 水  27 87 1 tetramethylammonium hydroxide 5 ethylene glycol monophenyl ether 7 water
28 82 1 四甲基氢氧化铰 10 乙二醇单苯基醚 7 水  28 82 1 tetramethyl hydroxide hinge 10 ethylene glycol monophenyl ether 7 water
0.15 聚氧乙烯醚 0.15 polyoxyethylene ether
29 81.35 1.25 四甲基氢氧化铵 10 乙二醇单苯基醚 29 81.35 1.25 Tetramethylammonium hydroxide 10 Ethylene glycol monophenyl ether
7.25 水  7.25 water
0.15 聚氧乙烯醚 0.15 polyoxyethylene ether
30 87.35 1.75 四甲基氢氧化铵 5 乙二醇单苯基醚 30 87.35 1.75 Tetramethylammonium hydroxide 5 Ethylene glycol monophenyl ether
5.75 水  5.75 water
0.15 聚氧乙烯醚 0.15 polyoxyethylene ether
31 84.35 2.5 四甲基氢氧化铰 8 乙二醇单苯基醚 31 84.35 2.5 Tetramethylhydroxide hinge 8 Ethylene glycol monophenyl ether
5 水  5 water
0.05 聚乙烯吡咯垸酮 0.05 polyvinylpyrrolidone
32 84.35 2.5 四甲基氧氧化铵 8 糊 0.1 - 邻苯二甲酸 32 84.35 2.5 tetramethyloxmonium oxide 8 paste 0.1 - phthalic acid
5 . 水  5. Water
0.15 没食子酸 0.15 gallic acid
33 84.35 2.5 四甲基氢氧化铵 8 乙一醇单苯基醚 33 84.35 2.5 Tetramethylammonium hydroxide 8 Ethyl alcohol monophenyl ether
5 水  5 water
0.15 聚氧乙烯醚 0.15 polyoxyethylene ether
34 83.05 2.75 四甲基氢氧化铰 8 乙二醇单苯基醚 0.15 1 ,3- (羟乙基） -2,4,6-三膦酸 34 83.05 2.75 Tetramethylhydroxide hinge 8 Ethylene glycol monophenyl ether 0.15 1 ,3- (Hydroxyethyl)-2,4,6-triphosphonic acid
5.9 水 对  5.9 Water Pair
比 Than
实 Real
92 1 四甲基氢氧化铵 \ \ 7 水 施  92 1 tetramethylammonium hydroxide \ \ 7 water
例 example
1  1
效果实施例 1-9 Effect Example 1-9
将表 1中实施例 27〜34的清洗剂和对比实施例 1的清洗剂用于清洗空白 Cu晶片， 测定其对金属 Cu的蚀刻速率， 结果列于表 2。 测试方法和条件- 将空白 Cu晶片浸入清洗剂， 在表 2所列的特定温度下， 用恒温振荡器缓慢 振荡 30分钟， 然后经去离子水洗涤后用高纯氮气吹干， 利用四极探针仪测 定空白 Cu晶片蚀刻前后表面电阻的变化计算得到上述清洗剂对金属 Cu的 蚀刻速率。 The cleaning agents of Examples 27 to 34 in Table 1 and the cleaning agent of Comparative Example 1 were used to clean blank Cu wafers, and the etching rate of the metal Cu was measured. The results are shown in Table 2. Test Methods and Conditions - Dip the blank Cu wafer into the cleaning agent, shake it slowly for 30 minutes at a specific temperature listed in Table 2, then wash it with deionized water and then dry it with high purity nitrogen. Needle test The etch rate of the above-mentioned cleaning agent to the metal Cu was calculated by changing the surface resistance of the blank Cu wafer before and after etching.
表 2实施例 27〜34及对比实施例 1的清洗剂 对空白 Cu晶片的蚀刻速率及其对光刻胶的清洗能力  Table 2 Examples 27 to 34 and Comparative Example 1 Cleaning Agent The etching rate of the blank Cu wafer and its cleaning ability to the photoresist
Figure imgf000009_0001
由表 2结果显示， 与对比实施例 1的清洗剂相比， 实施例 27〜34的清洗 剂对于金属 Cu表现出低蚀刻性及良好的光刻胶清洗能力。
Figure imgf000009_0001
From the results of Table 2, the cleaning agents of Examples 27 to 34 exhibited low etching property and good photoresist cleaning ability for metallic Cu as compared with the cleaning agent of Comparative Example 1.
方法实施例 1 Method embodiment 1
低蚀刻性光刻胶清洗剂： 84.35wt%二甲基亚砜， 2.50wt% 四甲基氢氧 化铵， 8.00 wt % 乙二醇单苯基醚， 0.15 wt %聚氧乙烯醚和 5.00 wt %水。  Low etch photoresist cleaning agent: 84.35wt% dimethyl sulfoxide, 2.50wt% tetramethylammonium hydroxide, 8.00 wt% ethylene glycol monophenyl ether, 0.15 wt% polyoxyethylene ether and 5.00 wt% water.
室温下，将含有光刻胶的半导体晶片浸入低蚀刻性光刻胶清洗剂缓慢振 荡清洗 30min， 用去离子水清洗， 之后高纯氮气下吹干。  The photoresist-containing semiconductor wafer was immersed in a low-etching photoresist cleaning agent at room temperature for a period of 30 minutes, washed with deionized water, and then dried under high-purity nitrogen.
方法实施例 2 Method embodiment 2
低蚀刻性光刻胶清洗剂： 84.35 wt %二甲基亚砜， 2.50 wt % 四甲基氢 氧化铵， 8.00 wt % 乙二醇单苯基醚， 0.15 wt %聚氧乙烯醚和 5.00 wt %水。  Low etch resist cleaning agent: 84.35 wt % dimethyl sulfoxide, 2.50 wt % tetramethylammonium hydroxide, 8.00 wt % ethylene glycol monophenyl ether, 0.15 wt % polyoxyethylene ether and 5.00 wt % water.
45°C下，将含有光刻胶的半导体晶片浸入低蚀刻性光刻胶清洗剂缓慢振 荡清洗 20min， 经异丙醇洗涤后用去离子水清洗， 之后高纯氮气下吹干。 方法实施例 3 The semiconductor wafer containing the photoresist is immersed in a low-etching photoresist cleaning agent at 45 ° C. The mixture was washed for 20 min, washed with isopropyl alcohol, washed with deionized water, and then dried under high purity nitrogen. Method embodiment 3
低蚀刻性光刻胶清洗剂： 84.35 wt %二甲基亚砜， 2.50 wt % 四甲基氢 氧化铵， 8.00 wt % 乙二醇单苯基醚， 0.15 wt %聚氧乙烯醚和 5.00 ％水。  Low etch photoresist cleaning agent: 84.35 wt % dimethyl sulfoxide, 2.50 wt % tetramethylammonium hydroxide, 8.00 wt % ethylene glycol monophenyl ether, 0.15 wt % polyoxyethylene ether and 5.00 % water .
85Ό下，将含有光刻胶的半导体晶片浸入低蚀刻性光刻胶清洗剂缓慢振 荡清洗 lOmin, 经异丙醇洗涤后用去离子水清洗， 之后高纯氮气下吹干。  At 85 Å, the semiconductor wafer containing the photoresist was immersed in a low-etching photoresist cleaning agent and slowly oscillated for 10 minutes, washed with isopropyl alcohol, washed with deionized water, and then dried under high-purity nitrogen.
本发明所使用的原料和试剂均为市售产品。  The raw materials and reagents used in the present invention are all commercially available products.

Claims

权利要求 Rights request
1. 一种低蚀刻性光刻胶清洗剂，包含二甲基亚砜、季铵氢氧化物，其特征在 于还包含通式为 （1 ) 的垸基二醇芳基醚或其衍生物： A low etch resist cleaning agent comprising dimethyl sulfoxide, quaternary ammonium hydroxide, characterized by further comprising a mercapto diol aryl ether of the formula (1) or a derivative thereof:
R,0-{irCmH2m^O- -R2 Q ) 其中， 为芳基， R2为 H或芳基， m=2~6， n=l〜6。 R,0-{irC m H 2m ^O- -R 2 Q ) wherein, is an aryl group, R 2 is H or an aryl group, m=2~6, n=l~6.
2. 根据权利要求 1所述的低蚀刻性光刻胶清洗剂，其特征在于：所述的垸基 二醇芳基醚或其衍生物为乙二醇单苯基醚、丙二醇单苯基醚、异丙二醇单 苯基醚、 二乙二醇单苯基醚、 二丙二醇单苯基醚、 二异丙二醇单苯基醚、 乙二醇单苄基醚、丙二醇单苄基醚、异丙二醇单苄基醚、 己二醇单萘基醚 或六缩乙二醇二苯基醚。  2. The low-etching photoresist cleaning agent according to claim 1, wherein the mercapto glycol aryl ether or a derivative thereof is ethylene glycol monophenyl ether or propylene glycol monophenyl ether. , isopropyl glycol monophenyl ether, diethylene glycol monophenyl ether, dipropylene glycol monophenyl ether, diisopropyl glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol monobenzyl ether, isopropyl glycol monobenzyl Ether ether, hexanediol mono-naphthyl ether or hexaethylene glycol diphenyl ether.
3. 根据权利要求 1所述的低蚀刻性光刻胶清洗剂，其特征在于：所述的垸基 二醇芳基醚或其衍生物的含量为 0.01〜98.99wt%。  The low etching resist cleaning agent according to claim 1, wherein the mercapto glycol aryl ether or a derivative thereof is contained in an amount of from 0.01 to 98.99% by weight.
4. 根据权利要求 3所述的低蚀刻性光刻胶清洗剂，其特征在于：所述的烷基 二醇芳基醚或其衍生物的含量为为 5.0~40.0wt%。  The low etching resist cleaning agent according to claim 3, wherein the alkyl glycol aryl ether or a derivative thereof is contained in an amount of from 5.0 to 40.0% by weight.
5. 根据权利要求 1所述的低蚀刻性光刻胶清洗剂，其特征在于：所述的二甲 基亚砜的含量为 1.0〜99.98wt%。 The low etching resist cleaning agent according to claim 1, wherein the dimethyl sulfoxide is contained in an amount of from 1.0 to 99.98% by weight.
6. 根据权利要求 5所述的低蚀刻性光刻胶清冼剂，其特征在于：所述的二甲 基亚砜的含量为 60〜95wt%。  The low-etching photoresist clearing agent according to claim 5, wherein the dimethyl sulfoxide is contained in an amount of 60 to 95% by weight.
7. 根据权利要求 1所述的低蚀刻性光刻胶清洗剂，其特征在于：所述的季铵 氢氧化物的含量为 0.01〜15wt%。 The low etching resist cleaning agent according to claim 1, wherein the quaternary ammonium hydroxide is contained in an amount of 0.01 to 15% by weight.
8. 根据权利要求 7所述的低蚀刻性光刻胶清洗剂，其特征在于：所述的季铵 氢氧化物的含量为 0.5〜10.0wt%。  The low etching resist cleaning agent according to claim 7, wherein the quaternary ammonium hydroxide is contained in an amount of from 0.5 to 10.0% by weight.
9. 根据权利要求 1所述的低蚀刻性光刻胶清洗剂，其特征在于：所述的季铵 氢氧化物为四甲基氢氧化铵、 四乙基氢氧化铵、 四丙基氢氧化铵、 四丁基 氢氧化铵或苄基三甲基氢氧化铵。 9. The low etch resist cleaning agent according to claim 1, wherein the quaternary ammonium hydroxide is tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrapropylammonium hydroxide. Ammonium, tetrabutyl Ammonium hydroxide or benzyltrimethylammonium hydroxide.
10.根据权利要求 1所述的低蚀刻性光刻胶清洗剂，其特征在于：所述的低蚀 刻性光刻胶清洗剂还包含极性有机共溶剂、缓蚀剂、表面活性剂及 /或水。 10. The low etch photoresist cleaning agent according to claim 1, wherein the low etch resist cleaning agent further comprises a polar organic cosolvent, a corrosion inhibitor, a surfactant, and/or Or water.
11.根据权利要求 10所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的极 性有机共溶剂含量为 0〜98.98wt%。 The low etching resist cleaning agent according to claim 10, wherein the polar organic co-solvent content is from 0 to 98.98% by weight.
12.根据权利要求 11所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的极 性有机共溶剂含量为 10~50wt%。  The low etching resist cleaning agent according to claim 11, wherein the polar organic co-solvent is 10 to 50% by weight.
13.根据权利要求 10所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的缓 蚀剂含量为 0~15wt%。  The low etching resist cleaning agent according to claim 10, wherein the corrosion inhibitor has a content of 0 to 15% by weight.
14.根据权利要求 13所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的缓 蚀剂含量为 0.05~5.0wt%。  The low etching resist cleaning agent according to claim 13, wherein the corrosion inhibitor is contained in an amount of from 0.05 to 5.0% by weight.
15.根据权利要求 10所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的表 面活性剂含量为 0〜15wt%。  The low-etching photoresist cleaning agent according to claim 10, wherein the surfactant is contained in an amount of from 0 to 15% by weight.
16.根据权利要求 15所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的表 面活性剂含量为 0.05〜5.0wt%。  The low etching resist cleaning agent according to claim 15, wherein the surfactant is contained in an amount of from 0.05 to 5.0% by weight.
17.根据权利要求 10所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的水 含量为 0〜95wt%。  The low etching resist cleaning agent according to claim 10, wherein the water content is 0 to 95% by weight.
18.根据权利要求 17所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的水 含量为 0.5〜25wt%。  The low etching resist cleaning agent according to claim 17, wherein the water content is 0.5 to 25 wt%.
19.根据权利要求 10所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的极 性有机共溶剂为亚砜、 砜、 咪唑烷酮和 /或垸基二醇单烷棊醚。  The low etching photoresist cleaning agent according to claim 10, wherein the polar organic co-solvent is sulfoxide, sulfone, imidazolidinone and/or mercaptodiol monoalkyl ether. .
20.根据权利要求 19所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的亚 砜为二乙基亚砜或甲乙基亚砜。 The low etching resist cleaning agent according to claim 19, wherein: said sub- The sulfone is diethyl sulfoxide or methyl ethyl sulfoxide.
21.根据权利要求 19所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的砜 为甲基砜、 乙基砜或环丁砜。  The low etching resist cleaning agent according to claim 19, wherein the sulfone is methyl sulfone, ethyl sulfone or sulfolane.
22.根据权利要求 19所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的咪 唑垸酮为 2-咪唑垸酮、 1,3-二甲基 -2-咪唑垸酮或 1 ,3-二乙基 -2-咪唑烷酮。 The low etching resist cleaning agent according to claim 19, wherein the imidazolium is 2-imidazolium, 1,3-dimethyl-2-imidazolium or 1 , 3-diethyl-2-imidazolidinone.
23.根据权利要求 19所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的烷 基二醇单烷基醚为乙二醇单甲醚、 乙二醇单乙醚、 乙二醇单丁醚、二乙二 醇单甲醚、二乙二醇单乙醚、二乙二醇单丁醚、丙二醇单甲醚、丙二醇单 乙醚、丙二醇单丁醚、二丙二醇单甲醚、二丙二醇单乙醚或二丙二醇单丁 醚。 The low etching resist cleaning agent according to claim 19, wherein the alkyl glycol monoalkyl ether is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or ethylene glycol. Monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol single Ether or dipropylene glycol monobutyl ether.
24.根据权利要求 10所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的表 ' 面活性剂为聚乙烯醇、 聚乙烯吡咯烷酮、 聚氧乙烯醚或聚硅氧烷。  The low etching resist cleaning agent according to claim 10, wherein the surfactant is polyvinyl alcohol, polyvinyl pyrrolidone, polyoxyethylene ether or polysiloxane.
25.根据权'利要求 10所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的缓 蚀剂为酚类、 羧酸 （酯）类、 酸酐类或膦酸 （酯）类缓蚀剂。  25. The low etch resist cleaning agent according to claim 10, wherein the corrosion inhibitor is a phenol, a carboxylic acid, an acid anhydride or a phosphonic acid ester. Corrosion inhibitor.
26.根据权利要求 25所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的酚 类为 1,2-二羟基苯酚、 对羟基苯酚或连苯三酚。  The low etching resist cleaning agent according to claim 25, wherein the phenol is 1,2-dihydroxyphenol, p-hydroxyphenol or pyrogallol.
27.根据权利要求 25所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的羧 酸（酯）类为苯甲酸、对氨基苯甲酸、邻苯二甲酸、没食子酸或没食子酸 丙酯。  The low etching resist cleaning agent according to claim 25, wherein the carboxylic acid is benzoic acid, p-aminobenzoic acid, phthalic acid, gallic acid or gallic acid. Propyl ester.
28.根据权利要求 25所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的酸 酐类为乙酸酐、 丙酸酐、 己酸酐或（聚） 马来酸酐。  The low etching resist cleaning agent according to claim 25, wherein the acid anhydride is acetic anhydride, propionic anhydride, hexanoic anhydride or (poly)maleic anhydride.
29.根据权利要求 25所述的低蚀刻性光刻胶清洗剂， 其特征在于： 所述的膦 酸（酯）类为 1,3- (羟乙基） -2，4,6-三膦酸、 氨基三亚甲基膦酸或 2-膦酸 丁垸 -1,2,4-三羧酸。 The low etching resist cleaning agent according to claim 25, wherein: the phosphine The acid (ester) is 1,3-(hydroxyethyl)-2,4,6-triphosphonic acid, aminotrimethylenephosphonic acid or 2-phosphonic acid butyl hydrazine-1,2,4-tricarboxylic acid.
30.—种用权利要求 1 所述的低蚀刻性光刻胶清洗剂清洗半导体晶片上光刻 胶的方法， 其特征在于： 室温至 85°C下， 将含有光刻胶的半导体晶片浸 入低蚀刻性光刻胶清洗剂清洗， 之后吹干。  30. A method of cleaning a photoresist on a semiconductor wafer using the low etch resist cleaning agent of claim 1, wherein: immersing the semiconductor wafer containing the photoresist at a low temperature from room temperature to 85 ° C The etch resist cleaning agent is cleaned and then blown dry.
31.根据权利要求 30所述的方法， 其特征在于： 当清洗温度高于 45°C时， 晶 片经清洗剂清洗后， 再用异丙醇洗搽晶片， 然后再用去离子水清洗。  The method according to claim 30, wherein when the cleaning temperature is higher than 45 ° C, the wafer is washed with a cleaning agent, and then the wafer is washed with isopropyl alcohol and then washed with deionized water.
32.根据权利要求 30所述的方法， 其特征在于： 所述的低蚀刻性光刻胶清洗 剂清洗步骤的方式为缓慢振荡。  32. The method of claim 30 wherein: said low etch resist cleaning step is in a slow oscillating manner.
33.根据权利要求 30所述的方法， 其特征在于： 所述的低蚀刻性光刻胶清洗 剂清洗步骤的时间为 10〜30分钟。  33. The method of claim 30, wherein: said low etch resist cleaning step is 10 to 30 minutes.
34.根据权利要求 30所述的方法， 其特征在于： 低蚀刻性光刻胶清洗剂清洗 后， 再用去离子水洗涤。  34. The method of claim 30 wherein: the low etch photoresist paste is cleaned and then rinsed with deionized water.
35.根据权利要求 30所述的方法，其特征在于：吹干步骤在高纯氮气下进行。  35. The method of claim 30 wherein the blowing step is performed under high purity nitrogen.
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