CN102047184B - 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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- CN102047184B CN102047184B CN200980121263.5A CN200980121263A CN102047184B CN 102047184 B CN102047184 B CN 102047184B CN 200980121263 A CN200980121263 A CN 200980121263A CN 102047184 B CN102047184 B CN 102047184B
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- plasma etching
- washing liquid
- residual washing
- ether
- etching residual
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- 238000004140 cleaning Methods 0.000 title claims abstract description 50
- 238000001020 plasma etching Methods 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- -1 hydroxyl tertiary amine Chemical class 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 25
- 239000012530 fluid Substances 0.000 claims description 20
- 239000003352 sequestering agent Substances 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 7
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- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical compound O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 claims description 4
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- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 4
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- 235000013772 propylene glycol Nutrition 0.000 claims description 4
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- RDTCWQXQLWFJGY-UHFFFAOYSA-N 1-(methylamino)butan-2-ol Chemical compound CCC(O)CNC RDTCWQXQLWFJGY-UHFFFAOYSA-N 0.000 claims description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
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- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- RLNZSUSARYWGKS-UHFFFAOYSA-N 2,2,2-trihydroxyethylazanium fluoride Chemical compound [F-].OC(C[NH3+])(O)O RLNZSUSARYWGKS-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
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 claims description 2
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- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical group COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
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- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 claims description 2
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 2
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- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 claims description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 2
- 229960002449 glycine Drugs 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 2
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 claims description 2
- 230000003628 erosive effect Effects 0.000 claims 1
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine group Chemical group NO AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 abstract description 3
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- 238000012360 testing method Methods 0.000 description 7
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- 150000002500 ions Chemical class 0.000 description 3
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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
- G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
-
- 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
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
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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
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3218—Alkanolamines or alkanolimines
-
- 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
- C11D7/3245—Aminoacids
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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
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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
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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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- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
一种用于除去等离子蚀刻残留物的清洗液,其含有溶剂、水、氟化物、螯合剂、羟基叔胺和羟基伯胺。该清洗液具有较强的清洗能力,能够有效清除金属和半导体上的等离子蚀刻残留物。该清洗液适用于较宽的温度范围,并具有较大的操作窗口。该清洗液保持较低的金属铝和非金属TEOS腐蚀速率,并有效地降低了铜的腐蚀。
Description
技术领域
本发明涉及一种半导体制造工艺中的清洗液,具体涉及一种等离子刻蚀残留物清洗液。
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。
现有技术中典型的清洗液有以下几种:胺类清洗液,半水性胺基(非羟胺类)清洗液以及氟类清洗液。其中前两类清洗液需要在高温下清洗,一般在60℃到80℃之间,存在对金属的腐蚀速率较大的问题;而现存的氟类清洗液虽然能在较低的温度(室温到50℃)下进行清洗,但仍然存在着各种各样的缺点,例如不能同时控制金属和非金属基材的腐蚀,清洗后容易造成通道特征尺寸的改变,从而改变半导体结构;另一方面由于其较大蚀刻速率,清洗操作窗口比较小等。专利US 6,828,289公开的清洗液组合物包括:酸性缓冲液、有机极性溶剂、氟化物和水,且PH值在3~7之间,其中的酸性缓冲液由有机羧酸或多元酸与所对应的铵盐组成,组成比例为10∶1至1∶10之间。如专利US 5,698,503公开了含氟清洗液,但大量使用乙二醇,其清洗液的粘度与表面张力都很大,从而影响清洗效果。如专利US 5,972,862公开了含氟物质的清洗组合物,其包括含氟物质、无机或有机酸、季铵盐和有机极性溶剂,PH为7~11,由于其清洗效果不是很稳定,存在多样的问题。
因此尽管已经揭示了一些清洗液组合物,但还是需要而且近来更加需要制备一类更合适的清洗组合物或体系,适应新的清洗要求,比如环境更为友善、低缺陷水平、低刻蚀率以及较大操作窗口。
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中的清洗过程中,传统的胺类清洗液和半水性胺基清洗液需要在高温下清洗而对金属的腐蚀率较大,现存的含氟类清洗液清洗后又容易造成通道特征尺寸的改变并且清洗操作窗口比较小,而提供了一种安全、健康和有效的等离子刻蚀残留物清洗液。
本发明公开了一种等离子刻蚀残留物清洗液,其含有溶剂、水、氟化物和螯合剂,其还含有羟基叔胺和羟基伯胺。
其中,所述的羟基叔胺的重量百分比较佳的为0.1%~20%;所述的羟基伯胺的重量百分比较佳的为0.01%~5%,更佳的为0.1%~1%;所述的溶剂的重量百分比较佳的为30%~75%;所述的水的重量百分比较佳的为15%~65%;所述的氟化物的重量百分比较佳的为0.1%~20%;所述的螯合剂的重量百分比较佳的为0.1%~20%,更佳的为1%~10%。
本发明中,所述的羟基叔胺较佳的为N,N-二甲基乙醇胺、N,N-甲基乙基乙醇胺、N-甲基二乙醇胺和三乙醇胺中的一种或多种,优选三乙醇胺;所述的羟基伯胺较佳的为单乙醇胺、丙醇胺、丁醇胺和二甘醇胺中的一种或多种,优选单乙醇胺。
本发明中,所述的溶剂可为本领域等离子刻蚀残留物清洗液中常用溶剂,较佳的为亚砜、砜、咪唑烷酮、吡咯烷酮、咪唑啉酮、酰胺和醚中的一种或多种。
其中,所述的亚砜优选为二甲基亚砜、二乙基亚砜和甲乙基亚砜中的一种或多种;所述的砜优选为甲基砜、乙基砜和环丁砜中的一种或多种;所述的咪唑烷酮优选为2-咪唑烷酮、1,3-二甲基-2-咪唑烷酮和1,3-二乙基-2-咪唑烷酮中的一种或多种;所述的吡咯烷酮优选为N-甲基吡咯烷酮、N-乙基吡咯烷酮、N-环己基吡咯烷酮和N-羟乙基吡咯烷酮中的一种或多种;所述的咪唑啉酮优选为1,3-二甲基-2-咪唑啉酮;所述的酰胺优选为二甲基甲酰胺和/或二甲基乙酰胺;所述的醚优选为乙二醇单烷基醚、二乙二醇单烷基醚、丙二醇单烷基醚、二丙二醇单烷基醚和三丙二醇单烷基醚中的一种或多种。
其中,所述的乙二醇单烷基醚优选为乙二醇单甲醚、乙二醇单乙醚和乙二醇单丁醚中的一种或多种;所述的二乙二醇单烷基醚优选为二乙二醇单甲醚、二乙二醇单乙醚和二乙二醇单丁醚中的一种多种;所述的丙二醇单烷基醚优选为丙二醇单甲醚、丙二醇单乙醚和丙二醇单丁醚中的一种或多种;所述的二丙二醇单烷基醚优选为二丙二醇单甲醚、二丙二醇单乙醚和二丙二醇单丁醚中的一种或多种;所述的三丙二醇单烷基醚优选为三丙二醇单甲醚。
本发明中,所述的氟化物可为本领域含氟类清洗液中常用氟化物,较佳地为氟化氢(HF)、氟化氢铵(NH4HF2)、氟化氢与碱形成的盐。其中,所述的碱较佳的为氨水、季胺氢氧化物和醇胺中的一种或多种;所述的氟化氢与碱形成的盐优选氟化铵(NH4F)、四甲基氟化铵(N(CH3)4F)和三羟乙基氟化铵(N(CH2OH)3HF)中的一种或多种。
本发明中,所述的螯合剂为本领域等离子刻蚀残留物清洗液中常用螯合剂,通常指具有螯合金属离子功能的化合物,如草酸和柠檬酸等。较佳的,本发明的螯合剂选择含有氮原子的多官能团的有机物,如多氨基有机胺和/或氨基酸。
其中,所述的多氨基有机胺优选为二乙烯三胺、五甲基二乙烯三胺和多乙烯多胺中的一种或多种,更优选五甲基二乙烯三胺;所述的氨基酸优选为2-氨基乙酸、2-氨基苯甲酸、亚氨基二乙酸、氨三乙酸和乙二胺四乙酸中的一种或多种,更优选亚氨基二乙酸。所述的螯合剂最优选多氨基有机胺和氨基酸的复配螯合剂,如亚氨基二乙酸和五甲基二乙烯三胺的复配螯合剂,氨三乙酸和五甲基二乙烯三胺的复配螯合剂,或亚氨基二乙酸和二乙烯三胺的复配螯合剂。
本发明的清洗液还可含有其他本领域的常规添加剂,如金属铝铜的腐蚀抑制剂(如苯并三氮唑)。
本发明所用的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。
本发明的等离子刻蚀残留物清洗液适用较大范围的使用温度,一般在室温到55℃范围内,且适用于多种清洗方式,如批量浸泡式(wet Batch)、批量旋转喷雾式(Batch-spray)和单片旋转式清洗。
本发明的积极进步效果在于:
(1)本发明的清洗液可以有效地清洗金属和半导体制造过程中产生的等离子刻蚀残留物,而且不会侵蚀SiO2、离子增强四乙氧基硅烷二氧化硅(PETEOS)、硅,低介质材料和一些金属物质(如Ti,Al,Cu),可以使金属晶圆(Metal wafer)在清洗时,金属细线比较光滑。
(2)本发明的清洗液能在一个温度比较大的范围内发挥作用,一般在室温到55℃范围内,同时,本发明的清洗液还保持较小的金属和电介物质刻蚀率。
(3)本发明的清洗液在保持了较低的金属铝和非金属TEOS腐蚀速率的基础上,有效地降低了铜的腐蚀。
(4)本发明的清洗液清洗能力强,能同时对金属线(Metal)/通道(Via)/金属垫(Pad)晶圆清洗。
(5)本发明的清洗液具有较大的操作窗口,能适用于批量浸泡式(wetBatch)/批量旋转喷雾式(Batch-spray)/单片旋转式(single wafer tool)处理器中。
附图说明
图1为未清洗金属晶圆清洗的SEM图片。
图2为对比实施例进行金属晶圆清洗后的SEM图片。
图3为实施例33对金属晶圆清洗的SEM图片。
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。
实施例1~29
表1为实施例1~29,将每一实施例中的各组分简单混匀即可得等离子刻蚀残留物清洗液。
表1等离子刻蚀残留物清洗液实施例1~29
实施例30
N-甲基吡咯烷酮60wt%;去离子水28wt%;氟化铵1.5wt%;苯并三氮唑(BTA)0.3wt%;亚氨基二乙酸1wt%;二乙烯三胺3wt%;三乙醇胺5.2wt%;单乙醇胺1wt%。
实施例31
N-甲基吡咯烷酮60wt%;去离子水28wt%;氟化铵1.5wt%;柠檬酸0.3wt%;亚氨基二乙酸3wt%;二乙烯三胺3wt%;三乙醇胺3.2wt%;单乙醇胺1wt%。
实施例32
N-甲基吡咯烷酮60wt%;去离子水28wt%;氟化铵1.5wt%;草酸0.05wt%;亚氨基二乙酸3wt%;二乙烯三胺3wt%;三乙醇胺3.2wt%;单乙醇胺1.25wt%。
效果实施例
为了进一步体现本发明的效果,选用了实施例33~35和对比实施例进行了金属铝、铜和非金属TEOS的腐蚀速率测试,实施例33和对比实施例配方的金属晶圆清洗效果见图2和图3。
溶液的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35℃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合适的程序可计算出其腐蚀速率。
溶液的非金属腐蚀速率测试方法:
1)利用Nanospec6100测厚仪测试4*4cm PETEOS硅片的厚度(T1);
2)将该4*4cmPETEOS硅片浸泡在预先已经恒温到35℃的溶液中30分钟;
3)取出该4*4cmPETEOS硅片,用去离子水清洗,高纯氮气吹干,再利用Nanospec6100测厚仪测试4*4cmPETEOS硅片的厚度(T2);
4)重复第二和第三步再测试一次厚度记为T3;
5)把上述厚度值和浸泡时间输入到合适的程序可计算出其腐蚀速率。
表2实施例33-35和对比实施例配方对比
结论:
从表2中可以看出,采用醇伯胺和醇叔胺复配的方式,在保持了较低的金属铝和非金属TEOS腐蚀速率的基础上,有效地降低了铜的腐蚀。对比实施例和实施例33其金属晶圆清洗的结果见图2和图3。
从图1中可以看出未清洗金属晶圆金属线上有较多的光阻残留物。图2表明:虽然对比实施例也能清洗金属晶圆上的光阻残留物,但金属细线表面比较粗,有一些凹坑。图3表明本发明的清洗液不仅能清洗金属晶圆上的光阻残留物,同时金属细线表面比较光滑。从而有利于提高半导体器件的性能。
综上,本发明的清洗液在保持了较低的金属铝和非金属TEOS腐蚀速率的基础上,有效地降低了铜的腐蚀;且其不仅能清洗金属晶圆上的光阻残留物,同时金属细线表面比较光滑,有利于提高半导体器件的性能。
Claims (15)
1.一种等离子刻蚀残留物清洗液,其含有溶剂、水、氟化物和螯合剂,其特征在于:其还含有羟基叔胺和羟基伯胺,其中所述的羟基叔胺的重量百分比为0.1%~20%,所述的羟基伯胺的重量百分比为0.01%~5%,所述的羟基叔胺为N,N-二甲基乙醇胺、N,N-甲基乙基乙醇胺、N-甲基二乙醇胺和三乙醇胺中的一种或多种,所述的羟基伯胺为单乙醇胺、丙醇胺、丁醇胺和二甘醇胺中的一种或多种。
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:所述的清洗液由下述成分组成:溶剂、水、氟化物、螯合剂、羟基叔胺和羟基伯胺。
3.如权利要求1或2所述的等离子刻蚀残留物清洗液,其特征在于:所述的溶剂的重量百分比为30%~75%。
4.如权利要求1或2所述的等离子刻蚀残留物清洗液,其特征在于:所述的水的重量百分比为15%~65%。
5.如权利要求1或2所述的等离子刻蚀残留物清洗液,其特征在于:所述的氟化物的重量百分比为0.1%~20%。
6.如权利要求1或2所述的等离子刻蚀残留物清洗液,其特征在于:所述的螯合剂的重量百分比为0.1%~20%。
7.如权利要求1或2所述的等离子刻蚀残留物清洗液,其特征在于:所述的溶剂为亚砜、砜、咪唑烷酮、吡咯烷酮、咪唑啉酮、酰胺和醚中的一种或多种。
8.如权利要求7所述的等离子刻蚀残留物清洗液,其特征在于:所述的亚砜为二甲基亚砜、二乙基亚砜和甲乙基亚砜中的一种或多种;所述的砜为甲基砜、乙基砜和环丁砜中的一种或多种;所述的咪唑烷酮为2-咪唑烷酮、1,3-二甲基-2-咪唑烷酮和1,3-二乙基-2-咪唑烷酮中的一种或多种;所述的吡咯烷酮为N-甲基吡咯烷酮、N-乙基吡咯烷酮、N-环己基吡咯烷酮和N-羟乙基吡咯烷酮中的一种或多种;所述的咪唑啉酮为1,3-二甲基-2-咪唑啉酮;所述的酰胺为二甲基甲酰胺和/或二甲基乙酰胺;所述的醚为乙二醇单烷基醚、二乙二醇单烷基醚、丙二醇单烷基醚、二丙二醇单烷基醚和三丙二醇单烷基醚中的一种或多种。
9.如权利要求8所述的等离子刻蚀残留物清洗液,其特征在于:所述的乙二醇单烷基醚为乙二醇单甲醚、乙二醇单乙醚和乙二醇单丁醚中的一种或多种;所述的二乙二醇单烷基醚为二乙二醇单甲醚、二乙二醇单乙醚和二乙二醇单丁醚中的一种多种;所述的丙二醇单烷基醚为丙二醇单甲醚、丙二醇单乙醚和丙二醇单丁醚中的一种或多种;所述的二丙二醇单烷基醚为二丙二醇单甲醚、二丙二醇单乙醚和二丙二醇单丁醚中的一种或多种;所述的三丙二醇单烷基醚为三丙二醇单甲醚。
10.如权利要求1或2所述的等离子刻蚀残留物清洗液,其特征在于:所述的氟化物为氟化氢、氟化氢铵和氟化氢与碱形成的盐中的一种或多种。
11.如权利要求10所述的等离子刻蚀残留物清洗液,其特征在于:所述的碱为氨水、季胺氢氧化物和醇胺中的一种或多种。
12.如权利要求10所述的等离子蚀残留物清洗液,其特征在于:所述的氟化氢与碱形成的盐为氟化铵、四甲基氟化铵和三羟乙基氟化铵中的一种或多种。
13.如权利要求1或2所述的等离子刻蚀残留物清洗液,其特征在于:所述的螯合剂为多氨基有机胺和/或氨基酸。
14.如权利要求13所述的等离子刻蚀残留物清洗液,其特征在于:所述的多氨基有机胺为二乙烯三胺、五甲基二乙烯三胺和多乙烯多胺中的一种或多种;所述的氨基酸为2-氨基乙酸、2-氨基苯甲酸、亚氨基二乙酸、氨三乙酸和乙二胺四乙酸中的一种或多种。
15.如权利要求13所述的等离子刻蚀残留物清洗液,其特征在于:所述的螯合剂为亚氨基二乙酸和五甲基二乙烯三胺的复配螯合剂,氨三乙酸和五甲基二乙烯三胺的复配螯合剂,或亚氨基二乙酸和二乙烯三胺的复配螯合剂。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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CN200980121263.5A CN102047184B (zh) | 2008-06-06 | 2009-06-03 | 一种等离子刻蚀残留物清洗液 |
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KR101114502B1 (ko) * | 2010-06-28 | 2012-02-24 | 램테크놀러지 주식회사 | 세정용 조성물 및 이를 이용한 반도체 패턴의 형성방법 |
JP2013533631A (ja) * | 2010-07-16 | 2013-08-22 | アドバンスド テクノロジー マテリアルズ,インコーポレイテッド | エッチング後残渣を除去するための水性洗浄剤 |
CN102827707A (zh) * | 2011-06-16 | 2012-12-19 | 安集微电子科技(上海)有限公司 | 一种等离子刻蚀残留物清洗液 |
CN102827708A (zh) * | 2011-06-16 | 2012-12-19 | 安集微电子(上海)有限公司 | 一种等离子刻蚀残留物清洗液 |
CN103809394B (zh) * | 2012-11-12 | 2019-12-31 | 安集微电子科技(上海)股份有限公司 | 一种去除光阻蚀刻残留物的清洗液 |
EP3104398B1 (en) * | 2013-12-06 | 2020-03-11 | Fujifilm Electronic Materials USA, Inc. | Cleaning formulation and method for removing residues on surfaces |
CN104946429A (zh) * | 2014-03-26 | 2015-09-30 | 安集微电子科技(上海)有限公司 | 一种低蚀刻的去除光阻蚀刻残留物的清洗液 |
JP6231423B2 (ja) * | 2014-04-09 | 2017-11-15 | 東京応化工業株式会社 | フォトリソグラフィ用剥離液及びパターン形成方法 |
CN108121175B (zh) * | 2016-11-29 | 2021-02-02 | 安集微电子科技(上海)股份有限公司 | 一种含氟清洗液 |
CN106637270A (zh) * | 2016-12-27 | 2017-05-10 | 昆山欣谷微电子材料有限公司 | 干蚀刻清洗剥离防护液 |
CN109976108A (zh) * | 2017-12-27 | 2019-07-05 | 安集微电子(上海)有限公司 | 一种用于半导体的清洗液 |
EP3774680A4 (en) | 2018-03-28 | 2021-05-19 | FUJIFILM Electronic Materials U.S.A, Inc. | CLEANING COMPOSITIONS |
CN112863999B (zh) * | 2019-11-26 | 2023-10-27 | 中芯国际集成电路制造(上海)有限公司 | 刻蚀方法 |
CN113430069A (zh) * | 2020-03-23 | 2021-09-24 | 上海新阳半导体材料股份有限公司 | 一种低羟胺水基清洗液、其制备方法及应用 |
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CN116218610B (zh) * | 2021-12-06 | 2024-07-09 | 上海新阳半导体材料股份有限公司 | 一种聚酰亚胺清洗液的制备方法 |
CN116218612B (zh) * | 2021-12-06 | 2024-07-09 | 上海新阳半导体材料股份有限公司 | 一种聚酰亚胺清洗液在清洗半导体器件中的应用 |
CN116218611B (zh) * | 2021-12-06 | 2024-06-21 | 上海新阳半导体材料股份有限公司 | 一种聚酰亚胺清洗液 |
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