CN113544248B - 半导体晶片清洗液组合物及利用其的清洗方法 - Google Patents
半导体晶片清洗液组合物及利用其的清洗方法 Download PDFInfo
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- CN113544248B CN113544248B CN202080019528.7A CN202080019528A CN113544248B CN 113544248 B CN113544248 B CN 113544248B CN 202080019528 A CN202080019528 A CN 202080019528A CN 113544248 B CN113544248 B CN 113544248B
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- 125000006353 oxyethylene group Chemical group 0.000 claims 4
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 3
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- 239000012535 impurity Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
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- 238000011109 contamination Methods 0.000 description 2
- -1 etc. Chemical compound 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
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- 235000011090 malic acid Nutrition 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- 235000006408 oxalic acid Nutrition 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 2
- 229940005605 valeric acid Drugs 0.000 description 2
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 235000019253 formic acid Nutrition 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
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- 238000005389 semiconductor device fabrication Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
- B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
- C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3409—Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
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- C11D2111/22—
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2079—Monocarboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
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Abstract
本发明涉及在半导体器件制造中使用的半导体晶片清洗用组合物及利用其的半导体晶片清洗方法,本发明的半导体晶片清洗用组合物由以化学式1及化学式2形成的表面活性剂、无机酸或有机酸、余量的水组成,本发明的半导体晶片清洗方法是使半导体晶片浸渍于清洗用组合物100至500秒的方法。根据本发明的清洗用组合物及清洗方法在半导体器件制造用晶片表面的研磨工艺中,提供针对污染物质,特别是,对有机蜡显著增大的去除效率及有效的清洗力,从而使晶片表面高度清洁,表现出能够制造高可靠度的半导体元件的效果。
Description
技术领域
本发明涉及在半导体晶片的清洗步骤中适用的清洗液组合物及利用其的半导体晶片的清洗方法。
背景技术
随着半导体器件的进步及发展,越来越重视消除作为器件最基础的晶片的缺陷和诸如有机物及金属的污染源。
以多晶硅为原材料而制造的晶片(wafer)广泛用作半导体器件制造材料,一般经过被称为锭的单晶生长、切割、包装(wrapping)、蚀刻、研磨以及清洗工艺等而制造。
在研磨晶片一面的研磨工艺中,利用化学机械式研磨装置的研磨方法大致利用作为粘合剂之一的有机蜡(脂溶性蜡、水溶性蜡)在载体附着晶片后,以既定压力对研磨垫上部加压而贴紧。在此状态下,载体和旋转台以各自的驱动轴为中心彼此旋转。附着于载体的晶片的研磨面与研磨垫摩擦而被研磨成镜面。
在经过这种研磨工艺的晶片表面,大量附着有用作粘合剂的蜡及工艺中发生的污染物质,因而需通过清洗工艺应被完全去除,在未完全去除的情况下,在半导体器件制造时,成为收率低下的原因。
(专利文献1)大韩民国注册专利公报第10-0725891号
(专利文献2)大韩民国注册专利公报第10-1799282号
(专利文献3)大韩民国公开专利公报第10-2017-0095537号
(专利文献4)大韩民国公开专利公报第10-2017-0105549号
发明内容
技术问题
本发明旨在解决如上所述问题,本发明要解决的技术课题目的在于提供一种能够有效去除有机物特别是在研磨工艺中使用的有机蜡的半导体晶片清洗用组合物。
解决问题的方案
为了达到所述目的,本发明提供一种半导体晶片清洗用组合物,包括由下述化学式1及化学式2形成的非离子性表面活性剂、无机酸或有机酸及去离子水。
[化学式1]
R1-(AO)n-R2
(在所述式中,R1及R2分别独立地为氢原子(-H)、羟基(-OH)、碳数为1至20的直链或支链烷基,或者碳数为1至20的直链或支链烯基,A为碳原子数为2至4的亚烷基,n为1至20范围的整数。)
[化学式2]
R3-(AO)m-R4
(在所述式中,R3及R4分别独立地为氢原子(-H)、羟基(-OH)、碳数为1至20的直链或支链烷基,或者碳数为1至20的直链或支链烯基,A为碳原子数为2至4的亚烷基,m为5至25范围的整数。)
在本发明的一个优选体现例中,半导体晶片清洗用组合物的所述非离子性表面活性剂在清洗用组合物总重量中包含0.1至40重量%,非离子性表面活性剂化学式1与化学式2的重量比为3:1至1:3的范围内。
在本发明的一个优选体现例中,所述有机酸可以例如磺酸、羧酸等,磺酸可以例如甲磺酸和对甲苯磺酸,羧酸可以为选自由戊酸、乙醇酸、戊二酸、酪酸、马来酸、丙二酸、苹果酸、苯甲酸、水杨酸、琥珀酸、柠檬酸、茴香酸、乙酸、草酸、乳酸、甲酸、富马酸、丙酸、苯二甲酸组成的组的至少一种。
在本发明的一个优选体现例中,所述无机酸可以为选自由盐酸、磷酸、硝酸和硫酸组成的组的至少一种。
在本发明的一个优选体现例中,所述有机酸及无机酸可以在清洗用组合物总重量中包含0.01至5重量%。
在本发明的一个优选体现例中,使用所述晶片清洗用组合物的半导体晶片清洗方法可以是使半导体晶片浸渍于清洗用组合物100至500秒的半导体晶片清洗方法。
在本发明的一个优选体现例中,使用所述晶片清洗用组合物的半导体晶片清洗方法可以是在使半导体晶片浸渍于清洗用组合物的工艺中,在适用超声波的情形下使晶片浸渍于清洗用溶液的半导体晶片清洗方法。
在本发明的一个优选体现例中,使用所述晶片清洗用组合物的半导体晶片清洗方法可以是在使半导体晶片浸渍于清洗用组合物进行清洗后用去离子水洗涤1至5次的半导体晶片清洗方法。
在本发明的一个优选体现例中,使用所述晶片清洗用组合物的半导体晶片清洗方法可以是使半导体晶片浸渍于清洗用组合物进行清洗的工艺的清洗温度为40℃至80℃的半导体晶片清洗方法。
发明的效果
根据本发明的清洗用组合物提供针对半导体器件制作用晶片表面的污染物质,特别是,有机蜡显著增大的去除效率及有效的清洗力。因而使晶片表面高度清洁,表现出能够制造高可靠度的半导体元件的效果。
最佳实施方式
只要未以其他方式定义,本说明书中使用的所有技术性及科学性术语具有与本发明所属技术领域的熟练专家通常所理解的内容相同的意义。一般而言,本说明书中使用的命名法是本技术领域熟知和通常使用的。
在本申请通篇说明书中,当提到某部分“包括”某种构成要素时,只要没有特别相反的记载,则意味着不排除其他构成要素,可以还包括其他构成要素。
根据本发明的清洗液组合物作为用于清洗半导体晶片的溶液,其特征在于,包括由以下述化学式1及化学式2表示的非离子性表面活性剂、有机酸或无机酸和去离子水。
当在用于去除晶片表面的污染物质特别是有机蜡的清洗工艺中利用这种清洗液组合物时,借助于以下述化学式1及化学式2表示的非离子性表面活性剂,晶片表面的表面弹力下降而润湿性提高,容易去除有机蜡,并防止去除的蜡颗粒再附着于晶片表面,因而清洗效果显著增大,由此可以制造高可靠度的半导体元件。
本发明的半导体晶片清洗用组合物包括由以下述化学式1及化学式2表示的非离子性表面活性剂。
[化学式1]
R1-(AO)n-R2
在所述式中,R1及R2分别独立地为氢原子(-H)、羟基(-OH)、碳数为1至20的直链或支链烷基,或者碳数为1至20的直链或支链烯基,A为碳原子数为2至4的亚烷基,n为1至25范围的整数。
[化学式2]
R3-(AO)m-R4
(在所述式中,R3及R4分别独立地为氢原子(-H)、羟基(-OH)、碳数为1至20的直链或支链烷基,或者碳数为1至20的直链或支链烯基,A为碳原子数为2至4的亚烷基,m为5至25范围的整数。)
根据本发明的表面活性剂是为了改善作为去除对象的蜡的溶解度而添加,可以根据作为去除对象的蜡而选择适宜的表面活性剂,例如,非离子性表面活性剂可以单独或混合2种以上使用。
根据本发明的非离子性表面活性剂对含量不特别限定,例如,可以在清洗用组合物总重量中包含0.01至40重量%。
在非离子性表面活性剂的含量不足0.01重量%的情况下,污染物质去除效果会小,在超过40重量%的情况下,由于不溶解于水,污染物质去除效果会小。
从这种层面,优选可以包含0.1重量%至40重量%。
本发明的半导体晶片清洗用组合物包含酸性化合物。
酸性化合物分解及溶解在作为清洗对象的晶片表面残留的杂质,引起清洗液中溶解的蜡颗粒间的电排斥力而提高分散性,从而具有清洗力改善效果。
酸性化合物只要是酸性,则不特别限定,例如,可以包括无机酸、有机酸或它们的混合物。另外,也可以用作保持适宜pH的pH调节剂。
作为无机酸的更具体示例,可以为选自由磷酸、硝酸及硫酸组成的组的单独或2种以上的混合物。
作为有机酸的更具体示例,可以例如羧酸、磺酸,羧酸可以例如甲酸、乙酸、丙酸、酪酸、戊酸、苯醋酸、茴香酸、草酸、丙二酸、琥珀酸、戊二酸、马来酸、富马酸、苯二甲酸、水杨酸、乙醇酸、乳酸、苹果酸、柠檬酸等,磺酸可以例如甲磺酸和对甲苯磺酸等。他们分别可以为单独或2种以上的混合物。
无机酸、有机酸的含量不被特别限定,例如,优选地,相对于清洗用组合物总重量,包含0.01至5重量%。在所述范围中,清洗力可以表现最优异。
在无机酸或有机酸的含量不足0.01重量%的情况下,清洗效果会微弱。另外,在超过5重量%的情况下,由于超过适度pH范围,因而清洗效果会微弱。
根据本发明的水溶解各成分并调节全体组成,全体组合物的余量被水占据。优选地,以所述成分具有前述含量范围的方式进行调节。
水并不被特别限定,但作为半导体工艺用水,优选使用比电阻值为18MΩ㎝以上的去离子水。
本发明的半导体晶片清洗用组合物可以利用其本身,另外,也可以利用去离子水将本发明的清洗用组合物稀释10倍至100倍而利用。
使用本发明的半导体晶片清洗用组合物的半导体晶片清洗方法可以是使半导体晶片浸渍于清洗用组合物100至500秒的。
使用本发明的半导体晶片清洗用组合物的半导体晶片清洗方法,在清洗时适用超声波,从而可以表现出优异的清洗效果。
使用本发明的半导体晶片清洗用组合物的半导体晶片清洗方法,不仅在常温下使用本发明的半导体晶片清洗用组合物时,而且在加热以使清洗用组合物的温度达到40℃至80℃的情况下使用时,可以表现出优异的清洗效果。
使用本发明的半导体晶片清洗用组合物的半导体晶片清洗方法,在用本发明的半导体晶片清洗用组合物进行清洗后,以去离子水洗涤1至5次,从而可以表现出优异的清洗效果。
下面通过实施例及比较例,更详细地说明本发明的半导体晶片清洗液组合物。但是,这些实施例只用于示例本发明,不得解释为本发明的范围由这些实施例限定,这是本行业的普通技术人员不言而喻的。
具体实施方式
【实施例及比较例】
根据下表1记载的组成成分及组成比率,制备了实施例1至15及比较例1至7的半导体晶片清洗用组合物。
【表1】
[实验例1]蜡去除力评价
准备4英寸P型硅晶片并进行初始重量测量后,在旋涂机(制造商:TEL,型号名称:Mark-VZ)中使硅晶片镜面朝上,注入3cc蜡(制造商:日华精工公司(Nikka SeikoCo.Ltd.),型号名称:Skyliquid)后,以2,500rpm涂覆30秒,在100℃下加热60秒后,在23℃下冷却30秒后,测量晶片重量。
然后,制备在表1记载的实施例及比较例的清洗用组合物药液,用65℃加温后浸渍所述晶片300秒后,取出晶片,在装有去离子水的清洗槽中洗涤3次,每次10秒,利用高纯度氮气干燥晶片表面。
测量干燥的晶片重量后,根据下述计算式求出清洗用组合物的蜡去除率(清洗力)。
蜡去除率(%)=100×[(涂蜡后晶片重量-清洗后晶片重量)/(涂蜡后晶片重量-涂蜡前晶片重量)]
结果显示于下表2中。
【表2】
No. | 蜡去除率(%) | No. | 蜡去除率(%) |
实施例1 | 94.5 | 实施例12 | 97.5 |
实施例2 | 95.0 | 实施例13 | 98.0 |
实施例3 | 95.0 | 实施例14 | 97.0 |
实施例4 | 95.5 | 实施例15 | 98.5 |
实施例5 | 95.5 | 比较例1 | 89.5 |
实施例6 | 95.5 | 比较例2 | 87.5 |
实施例7 | 96.0 | 比较例3 | 86.5 |
实施例8 | 96.0 | 比较例4 | 87.5 |
实施例9 | 96.5 | 比较例5 | 89.0 |
实施例10 | 99.4 | 比较例6 | 86.9 |
实施例11 | 97.0 | 比较例7 | 88.0 |
如果参考上表2,可以确认实施例1至15的清洗液组合物表现出94.5%至99.4%的优异清洗力。
与此相比,可以确认比较例1至7的清洗用组合物表现出86.5%至89.5%的清洗力,清洗力大幅下降,蜡成分大量残留。
[实验例2]污染源再附着性评价
准备4英寸P型硅晶片,在旋涂机(制造商:TEL,型号名称:Mark-VZ)中使硅晶片镜面朝上,注入3cc蜡(制造商:日华精工公司(Nikka Seiko Co.Ltd.),型号名称:Skyliquid),以2,500rpm涂覆30秒时间,在100℃下加热60秒后,在常温下放置30秒。
然后,制备在表1记载的实施例及比较例的清洗用组合物药液,将涂布有蜡的4英寸晶片,在装有清洗用组合物的清洗槽中,以65℃各自维持300秒的情形下,浸渍大量的晶片而使大量的蜡成分溶解于清洗用组合物药液后,取出晶片,在装有去离子水的清洗槽中洗涤3次,每次10秒,用高纯度氮气干燥晶片表面。
通过光学光学显微镜观察经干燥的晶片的表面。
结果显示于下表3中。
【表3】
如果参考所述表3,可以确认实施例1至15的清洗液组合物在清洗后晶片表面完全没有或没有污染物的再附着,大部分表现出非常良好或良好的结果。
与此相比,可以确认比较例1至7的清洗用组合物,在清洗后晶片表面有或有大量污染物的再附着,大部分表现出差或非常差的结果。
[实验例3]金属杂质去除力评价
将硅晶片按横向×纵向准备成30㎜×30㎜大小后,用包含氨水-过氧化氢混合溶液和1%氢氟酸的溶液清洗硅晶片,利用旋涂机,使铁、铜、镍、铝及铅污染达到1.0×1013原子/cm2的表面浓度。
然后,制备表1记载的实施例及比较例的清洗用组合物药液,将经污染处理的晶片向各清洗液在60℃无搅拌浸渍300秒后,取出晶片,在装有去离子水的清洗槽中洗涤3次,每次10秒,用高纯度氮气干燥晶片表面。
针对干燥的晶片,利用二次离子质量分析装置(Secondary Ion MassSpectrometry:SIMS),测量晶片表面的金属浓度,评价金属杂质去除能力。
将结果显示于表4中。
【表4】
根据所述表4,可以确认实施例1至15的清洗液组合物在清洗后晶片表面的金属离子残留1.0×1010原子/cm2以下,表现出优异结果。
与此相比,可以确认比较例1至7的清洗用组合物在清洗后晶片表面的金属离子残留超过1.0×1010原子/cm2水平,表现出不良结果。
如上所述,本发明以限定的实施例进行了说明,但本发明并非限定于上述实施例,只要是本发明所属技术领域的普通技术人员,便可以从这种记载进行多样修改及变形。
因此,本发明的范围不局限于说明的实施例进行确定,应根据后述权利要求书以及与该权利要求书均等的内容确定。
Claims (5)
1.一种半导体晶片清洗用组合物,由下述成分组成:
a)由下述化学式1及化学式2形成的3至50重量%的非离子性表面活性剂;
b)0.1至1重量%的无机酸;及
c)余量的水,
[化学式1]
为下述化学式a1或a2,
a1 CnH2n+1-O-(EO)x-H,n=2, x=12,EO=氧乙烯基,
a2 CnH2n+1-O-(EO)x-H,n=16,x =12,EO=氧乙烯基;
[化学式2]
为下述化学式b1或b2,
b1 CnH2n+1-(EO)x-H,n=10, x=8,EO=氧乙烯基,
b2 CnH2n+1-(EO)x-H,n=13, x=8,EO=氧乙烯基;
作为所述非离子性表面活性剂的化学式1与化学式2的重量比为3 : 1至1 : 3。
2.根据权利要求1所述的半导体晶片清洗用组合物,其特征在于,
所述无机酸为选自由磷酸、硫酸或其2种混合物。
3. 一种半导体晶片清洗方法,包括:
a)使半导体晶片浸渍于根据权利要求1或2所述的半导体晶片清洗用组合物100秒至500秒而进行清洗的步骤;及
b)用去离子水洗涤1至5次的步骤。
4.根据权利要求3所述的半导体晶片清洗方法,其特征在于,
在所述a)步骤中,在使半导体晶片浸渍于清洗用组合物进行清洗的情形下适用超声波。
5.根据权利要求3所述的半导体晶片清洗方法,其特征在于,
在a)步骤中,使半导体晶片浸渍于清洗用组合物进行清洗的温度为40℃至80℃。
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US20220135903A1 (en) | 2022-05-05 |
CN113544248A (zh) | 2021-10-22 |
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