CN101981510B - 一种等离子刻蚀残留物清洗液 - Google Patents
一种等离子刻蚀残留物清洗液 Download PDFInfo
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- CN101981510B CN101981510B CN200980111450.5A CN200980111450A CN101981510B CN 101981510 B CN101981510 B CN 101981510B CN 200980111450 A CN200980111450 A CN 200980111450A CN 101981510 B CN101981510 B CN 101981510B
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- carboxylic
- azanol
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- 238000001020 plasma etching Methods 0.000 title claims abstract description 30
- 239000003599 detergent Substances 0.000 title abstract 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000049 pigment Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
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- 239000000126 substance Substances 0.000 claims description 25
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
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- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 claims description 5
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 4
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- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical group Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 4
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- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 4
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000003457 sulfones Chemical class 0.000 claims description 4
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
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- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical group CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229940074391 gallic acid Drugs 0.000 claims description 2
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- 229960004194 lidocaine Drugs 0.000 claims description 2
- CPQCSJYYDADLCZ-UHFFFAOYSA-N n-methylhydroxylamine Chemical compound CNO CPQCSJYYDADLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 7
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- 230000003628 erosive effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/34—Organic compounds containing sulfur
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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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5009—Organic solvents containing phosphorus, sulfur or silicon, e.g. dimethylsulfoxide
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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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5013—Organic solvents containing nitrogen
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- 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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- 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
- H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
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- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
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- C11D2111/14—Hard surfaces
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- 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
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- Manufacturing & Machinery (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
一种等离子刻蚀残留物清洗液含有羟胺和/或其衍生物、溶剂、水、螯合剂、含羧基的聚合物与含颜料亲和基团的聚合物。
Description
技术领域
本发明涉及一种半导体制造工艺中的一种清洗液,具体涉及一种等离子刻蚀残留物的清洗液。
技术背景
在半导体元器件制造过程中,光阻层的涂敷、曝光和成像对元器件的图案制造来说是必要的工艺步骤。在图案化的最后(即在光阻层的涂敷、成像、离子植入和蚀刻之后)进行下一工艺步骤之前,光阻层材料的残留物需彻底除去。在掺杂步骤中离子轰击会硬化光阻层聚合物,因此使得光阻层变得不易溶解从而更难于除去。至今在半导体制造工业中一般使用两步法(干法灰化和湿蚀刻)除去这层光阻层膜。第一步利用干法灰化除去光阻层(PR)的大部分;第二步利用缓蚀剂组合物湿蚀刻/清洗工艺除去且清洗掉剩余的光阻层,其步骤一般为清洗液清洗/漂洗/去离子水漂洗。在这个过程中要求只能除去残留的聚合物光阻层和无机物,而不能攻击损害金属层如铝层。
在目前的湿法清洗工艺中,用得最多的清洗液是含有羟胺类的清洗液,这类清洗液目前主要是有EKC和ACT两家公司开发,并占有80%左右的市场。其典型的专利有US6319885、US5672577、US6030932、US6825156和US5419779等。经过不断改进,其溶液本身对金属铝的腐蚀速率已经大幅降低,但该类清洗液由于其在水中漂洗时金属铝的腐蚀速率较大,在清洗完等离子刻蚀物后,常采用溶剂漂洗。所用的溶剂主要有异丙醇和N-甲基吡咯烷酮。前者由于闪点比较低、易挥发,在一些半导体制造公司已经逐步被淘汰;而后者虽然闪点比较高、不易挥发在好多半导体制造公司一直使用;但是随着环保意识增强和成本压力加大,越来越多的公司希望能用去离子水直接漂洗,而不造成金属的腐蚀。
发明概要
本发明所要解决的技术问题是为了克服在半导体制造工艺的湿法清洗步骤中,采用传统羟胺类清洗液之后直接用水漂洗会导致金属(尤其是铝)腐蚀,需采用溶剂漂洗步骤而造成的成本较高,污染较大的缺陷,而提供一种可以直接用水漂洗,但不会造成金属腐蚀,且能保证较好的清洗效果的等离子刻蚀残留物清洗液。
本发明的等离子刻蚀残留物清洗液含有羟胺和/或其衍生物、溶剂、水、螯合剂,其还含有含羧基的聚合物与含颜料亲和基团的聚合物。
本发明中,所述的含羧基聚合物的含量较佳的为质量百分比0.001~3%。
本发明中,所述的含羧基的聚合物选自含羧基的均聚物、含羧基的共聚物、含羧基的均聚物盐和含羧基的共聚物盐中的一种或多种。其中,所述的含羧基的均聚物较佳的为聚马来酸酐(HPMA)、聚丙烯酸(PAA)、聚甲基丙烯酸中的一种或多种,更佳的为聚马来酸酐和/或聚丙烯酸;所述的含羧基的共聚物较佳的为含羧基的单体之间的共聚物(如:丙烯酸与马来酸共聚物,甲基丙烯酸与马来酸共聚物),或含乙烯基单体与含羧基的单体之间的共聚物(如:苯乙烯与丙烯酸共聚物、苯乙烯与马来酸共聚物、丙烯腈与马来酸共聚物、乙烯与丙烯酸共聚物、丙烯腈与丙烯酸共聚物、苯乙烯与甲基丙烯酸共聚物、乙烯与甲基丙烯酸共聚物和丙烯腈与甲基丙烯酸共聚物等等中的一种或多种),更佳的为丙烯酸与马来酸共聚物;所述的盐较佳的是铵盐、钾盐和/或钠盐中的一种或多种,更佳的为铵盐,如聚丙烯酸铵。
本发明中,只要是现有技术中已有的含羧基的聚合物均可用于本发明的等离子刻蚀残留物清洗液中,含羧基的聚合物分子量大小并不影响实现本发明的目的。若本发明的等离子刻蚀残留物清洗液中具有一定质量浓度的聚合物,该等离子刻蚀残留物清洗液中也相应地具有一定浓度的羧基。这是因为对于一定质量浓度的聚合物而言,若聚合物的分子量大,等离子刻蚀残留物清洗液中聚合物的摩尔数就相应地少;若聚合物的分子量小,等离子刻蚀残留物清洗液中聚合物的摩尔数也就相应地多,也就是说,组成一定的聚合物,其一定质量浓度的聚合物上也就相应地含有一定浓度的羧基。不管该聚合物的分子量大小,只要该聚合物上的羧基在等离子刻蚀残留物清洗液中达到一定的浓度即可。
本发明中,所述的含颜料亲和基团的聚合物的含量较佳的为质量百分比0.001~3%。
本发明中,所述的颜料亲和基团较佳的为羟基或氨基。众所周知,羧基也是一种颜料亲和基团,但在本发明中所谓含颜料亲和基团聚合物中可以含有羧基,也可以不含有羧基。本发明中,对含颜料亲和基团的聚合物的分子量无特别要求。
本发明中,所述的含颜料亲和基团的聚合物较佳的为含颜料亲和基团的丙烯酸酯类聚合物,更佳的为含羟基和/或氨基的丙烯酸酯类聚合物,优选丙烯酸羟乙酯类单体与除其外的其他丙烯酸酯类单体的共聚物,丙烯酸酯类单体与丙烯酰胺类单体的共聚物,丙烯酸羟乙酯类单体与除其外的其他丙烯酸酯类单体和含乙烯基单体的三元共聚物,以及丙烯酸酯类单体、丙烯酰胺类单体和含乙烯基单体的三元共聚物中的一种或多种。
其中,所述的丙烯酸羟乙酯类单体与除其外的其他丙烯酸酯类单体和含乙烯基单体的三元共聚物较佳的为丙烯酸羟乙酯、丙烯酸甲酯和苯乙烯的三元共聚物;所述的丙烯酸酯类单体、丙烯酰胺类单体和含乙烯基单体的三元共聚物较佳的为丙烯酸丁酯、丙烯酰胺和丙烯酸的三元共聚物。
其中,所述的丙烯酸酯类单体较佳的为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、甲基丙烯酸羟乙酯或丙烯酸羟乙酯;所述的丙烯酸羟乙酯类单体较佳的为甲基丙烯酸羟乙酯或丙烯酸羟乙酯。
本发明中,所述的羟胺及其衍生物的含量较佳的为质量百分比1~30%。
本发明中,所述的羟胺和/或其衍生物较佳的选自羟胺、羟胺与无机酸形成的盐类(如:羟胺盐酸盐)、羟胺上胺基和/或羟基上氢原子被C1~C2的取代基取代的衍生物中的一种或多种(如N-甲基羟胺、N,N-二甲基羟胺、乙酰基羟胺,1-甲氧基胺中的一种或多种)。其结构式如下:
其中:R1,R2和R3各自独立的为一般少于3个碳原子的取代基,如甲基、乙基、甲氧基、乙氧基和乙酰基等。
本发明中,所述的溶剂含量较佳的为质量百分比20~70%。
本发明中,所述的溶剂可为本领域常用溶剂,较佳的选自亚砜、砜、咪唑烷酮、吡咯烷酮、咪唑啉酮、醚、酰胺和醇胺中的一种或多种,优选醇胺。所述的亚砜较佳的为二甲基亚砜;所述的砜较佳的为环丁砜;所述的咪唑烷酮较佳的为1,3-二甲基-2-咪唑烷酮;所述的吡咯烷酮较佳的为N-甲基吡咯烷酮;所述的咪唑啉酮较佳的为1,3-二甲基-2-咪唑啉酮;所述的醚较佳的为丙二醇单甲醚和/或二丙二醇单甲醚;所述的酰胺较佳的为二甲基甲酰胺;所述的醇胺较佳的为单乙醇胺、二乙醇胺、三乙醇胺、异丙醇胺、2-(二乙氨基)乙醇、乙基二乙醇胺和二甘醇胺中的一种或多种。
本发明中,所述的螯合剂的含量较佳的为质量百分比0.1~20%。
本发明中,所述的螯合剂可为本领域常用螯合剂,一般为含有多个官能团的芳基化合物,优选邻苯二酚、邻巯基苯酚、邻羟基苯甲酸、连苯三酚和没食子酸中的一种或多种。
本发明中,所述的水含量较佳的为质量百分比10~45%。
本发明所用试剂及原料均市售可得。
本发明的等离子刻蚀残留物清洗液可以由上述成分简单均匀混合即可制得。
本发明还涉及本发明的等离子刻蚀残留物清洗液的使用方法:在用等离子刻蚀残留物清洗液去除晶圆上等离子刻蚀残留物以后,直接用去离子水漂洗之后干燥即可。
本发明的积极进步效果在于:本发明的等离子刻蚀残留物清洗液保持了传统羟胺类半导体晶圆清洗液的清洗能力,而且在清洗之后的漂洗过程中可以直接用水漂洗而不会产生金属(尤其是铝)的腐蚀问题,省去了传统羟胺类清洗液在清洗后为避免金属腐蚀而需要溶剂漂洗的步骤,有利于减少污染、降低成本。
附图说明
图1为未经清洗的金属铝铜结构的晶圆(Metal wafer)扫描电镜图。
图2为经实施例16配方配制的清洗液清洗后,接着去离子水漂洗后金属铝铜结构的晶圆(Metal wafer)扫描电镜图。
图3为经传统羟胺类清洗液清洗后,去离子水漂洗后金属铝铜结构的晶圆(Metal wafer)扫描电镜图。
发明内容
下面用实施例来进一步说明本发明,但本发明并不受其限制。下述实施例中,百分比均为质量百分比。
实施例1~24
表1给出了本发明的等离子刻蚀残留物清洗液实施例1~24的配方,按表1中所列组分及其含量,简单混合均匀,即制得等离子刻蚀残留物清洗液。
表1本发明的等离子刻蚀残留物清洗液实施例1~24
效果实施例1
70℃下,测实施例16的清洗液对金属铝的腐蚀速率。
金属腐蚀速率测试方法:
1)利用Napson四点探针仪测试4*4cm铝空白硅片的电阻初值(Rs1);
2)将该4*4cm铝空白硅片浸泡在预先已经恒温到70℃的溶液中30分钟;
3)取出该4*4cm铝空白硅片,用去离子水清洗,高纯氮气吹干,再利用Napson四点探针仪测试4*4cm铝空白硅片的电阻值(Rs2);
4)重复第二和第三步再测试一次,电阻值记为Rs3;
5)把上述电阻值和浸泡时间输入到计算程序中计算出其腐蚀速率。
测试结果为:1.93A/min(第一个三十分钟)和1.81A/min(第二个三十分钟)。以上数据小于业界公认的要小于2A/min的要求。
效果实施例2
用实施例16的清洗剂和作为对比的传统羟胺类清洗剂(参考专利文献US5672577配制,羟胺:20%;去离子水:22%;乙醇胺,48;邻苯二酚:10)对金属铝铜结构的晶圆(Metal wafer)进行清洗,之后用水漂洗,然后经SEM拍照表征结果,分别如图2和3所示。图1为晶圆清洗前的SEM照片。
从图1可以看出,未清洗金属铝铜结构的晶圆(Metal wafer)上有很多等离子刻蚀残留物需要去除。图2表明实施例16能够有效地去除金属铝铜结构的晶圆(Metal wafer)上的等离子刻蚀残留物,直接用水漂洗,并没有产生金属线的腐蚀问题。而图3中传统羟胺类清洗液清洗后,经水漂洗,虽然也能够有效地去除光阻残留物,但金属线产生了腐蚀。
综上,本发明的清洗剂保持了传统羟胺类半导体晶圆清洗液的清洗能力,而且在清洗之后的漂洗过程中可以直接用水漂洗而不会产生金属(尤其是铝)的腐蚀问题,解决了传统羟胺类清洗液在清洗后为避免金属腐蚀而需要溶剂漂洗的问题,有利于减少污染、降低成本。
Claims (7)
1.一种等离子刻蚀残留物清洗液,其含有羟胺和/或其衍生物、溶剂、水、螯合剂,其特征在于:其还含有含羧基的聚合物与含颜料亲和基团的聚合物,
其中,所述的含羧基的聚合物选自含羧基的均聚物、含羧基的共聚物、含羧基的均聚物盐和含羧基的共聚物盐中的一种或多种,所述的含羧基的均聚物是聚马来酸酐、聚丙烯酸和聚甲基丙烯酸中的一种或多种;所述的含羧基的共聚物是含羧基的单体之间的共聚物,和/或含乙烯基单体与含羧基的单体之间的共聚物;所述的盐是铵盐、钾盐和钠盐中的一种或多种,所述的含羧基的单体之间的共聚物选自丙烯酸与马来酸共聚物,和/或甲基丙烯酸与马来酸共聚物;所述的含乙烯基单体与含羧基的单体之间的共聚物选自苯乙烯与丙烯酸共聚物、苯乙烯与马来酸共聚物、丙烯腈与马来酸共聚物、乙烯与丙烯酸共聚物、丙烯腈与丙烯酸共聚物、苯乙烯与甲基丙烯酸共聚物、乙烯与甲基丙烯酸共聚物和丙烯腈与甲基丙烯酸共聚物中的一种或多种;所述的铵盐为聚丙烯酸铵,其中,所述的含颜料亲和基团的聚合物为含颜料亲和基团的丙烯酸酯类聚合物,所述的颜料亲和基团为羟基或氨基,所述的含颜料亲和基团的丙烯酸酯类聚合物选自丙烯酸羟乙酯类单体与除其外的其他丙烯酸酯类单体的共聚物,丙烯酸酯类单体与丙烯酰胺类单体的共聚物,丙烯酸羟乙酯类单体、除其外的其他丙烯酸酯类单体和含乙烯基单体的三元共聚物,以及丙烯酸酯类单体、丙烯酰胺类单体和含乙烯基单体的三元共聚物中的一种或多种,所述的丙烯酸羟乙酯类单体、除其外的其他丙烯酸酯类单体和含乙烯基单体的三元共聚物为丙烯酸羟乙酯、丙烯酸甲酯和苯乙烯的三元共聚物;所述的丙烯酸酯类单体、丙烯酰胺类单体和含乙烯 基单体的三元共聚物为丙烯酸丁酯、丙烯酰胺和丙烯酸的三元共聚物。
2.如权利要求1所述的等离子刻蚀残留物清洗液,其特征在于:所述的含羧基聚合物的含量为质量百分比0.001~3%。
3.如权利要求1所述的等离子刻蚀残留物清洗液,其特征在于:所述的含颜料亲和基团的聚合物的含量为质量百分比0.001~3%。
4.如权利要求1所述的等离子刻蚀残留物清洗液,其特征在于:所述的丙烯酸酯类单体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、甲基丙烯酸羟乙酯或丙烯酸羟乙酯;所述的丙烯酸羟乙酯类单体为甲基丙烯酸羟乙酯或丙烯酸羟乙酯。
5.如权利要求1所述的等离子刻蚀残留物清洗液,其特征在于:所述的羟胺及其衍生物的含量为质量百分比1~30%;所述的溶剂含量为质量百分比20~70%;所述的水含量为质量百分比10~45%;所述的螯合剂的含量为质量百分比0.1~20%。
6.如权利要求1所述的等离子刻蚀残留物清洗液,其特征在于:所述的羟胺和/或其衍生物选自羟胺,羟胺与无机酸形成的盐类,以及羟胺上胺基和/或羟基上氢原子被C1~C2的取代基取代的衍生物中的一种或多种;所述的溶剂选自亚砜、砜、咪唑烷酮、吡咯烷酮、咪唑啉酮、醚、酰胺和醇胺中的一种或多种;所述的螯合剂是含有多个官能团的芳基化合物。
7.如权利要求6所述的等离子刻蚀残留物清洗液,其特征在于:所述的羟胺与无机酸形成的盐类为羟胺盐酸盐;所述的羟胺上胺基和/或羟基上氢原子被C1~C2的取代基取代的衍生物为N-甲基羟胺、N,N-二甲基羟胺、乙酰基羟胺和1-甲氧基胺中的一种或多种;所述的亚砜为二甲基亚砜;所述的砜为环丁砜;所述的咪唑 烷酮为1,3-二甲基-2-咪唑烷酮;所述的吡咯烷酮为N-甲基吡咯烷酮;所述的咪唑啉酮为1,3-二甲基-2-咪唑啉酮;所述的醚为丙二醇单甲醚和/或二丙二醇单甲醚;所述的酰胺为二甲基甲酰胺;所述的醇胺为单乙醇胺、二乙醇胺、三乙醇胺、异丙醇胺、2-(二乙氨基)乙醇、乙基二乙醇胺和二甘醇胺中的一种或多种;所述的螯合剂为邻苯二酚、邻巯基苯酚、邻羟基苯甲酸、连苯三酚和没食子酸中的一种或多种。
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