WO2008071077A1 - Composé nettoyant pour éliminer un photorésist - Google Patents
Composé nettoyant pour éliminer un photorésist Download PDFInfo
- Publication number
- WO2008071077A1 WO2008071077A1 PCT/CN2007/003518 CN2007003518W WO2008071077A1 WO 2008071077 A1 WO2008071077 A1 WO 2008071077A1 CN 2007003518 W CN2007003518 W CN 2007003518W WO 2008071077 A1 WO2008071077 A1 WO 2008071077A1
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- WO
- WIPO (PCT)
- Prior art keywords
- cleaning agent
- agent according
- mass
- monophenyl ether
- cleaning
- Prior art date
Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 35
- 238000004140 cleaning Methods 0.000 title claims abstract description 22
- 150000001875 compounds Chemical class 0.000 title 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 alkyl glycol mono phenyl ether Chemical compound 0.000 claims abstract description 8
- 239000012459 cleaning agent Substances 0.000 claims description 51
- 238000005260 corrosion Methods 0.000 claims description 16
- 230000007797 corrosion Effects 0.000 claims description 16
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical group OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 claims description 4
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 229960005323 phenoxyethanol Drugs 0.000 claims description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 3
- UEGKGPFVYRPVCC-UHFFFAOYSA-N 2,5-dimethylhexane-3,4-diol Chemical compound CC(C)C(O)C(O)C(C)C UEGKGPFVYRPVCC-UHFFFAOYSA-N 0.000 claims description 3
- ZUAURMBNZUCEAF-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethanol Chemical compound OCCOCCOC1=CC=CC=C1 ZUAURMBNZUCEAF-UHFFFAOYSA-N 0.000 claims description 3
- LCVQGUBLIVKPAI-UHFFFAOYSA-N 2-(2-phenoxypropoxy)propan-1-ol Chemical compound OCC(C)OCC(C)OC1=CC=CC=C1 LCVQGUBLIVKPAI-UHFFFAOYSA-N 0.000 claims description 3
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 claims description 3
- 229940102253 isopropanolamine Drugs 0.000 claims description 3
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims 2
- 125000003396 thiol group Chemical class [H]S* 0.000 claims 2
- 239000002184 metal Substances 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 4
- 229910001092 metal group alloy Inorganic materials 0.000 abstract description 2
- 235000012431 wafers Nutrition 0.000 description 21
- 239000004065 semiconductor Substances 0.000 description 12
- 239000010949 copper Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- RBRMRNWFSHTPPN-UHFFFAOYSA-N 2-phenoxypropan-2-ol Chemical compound CC(C)(O)OC1=CC=CC=C1 RBRMRNWFSHTPPN-UHFFFAOYSA-N 0.000 description 1
- 241000272517 Anseriformes Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- OZELNHNUXJENDW-UHFFFAOYSA-M hydrazine;tetramethylazanium;hydroxide Chemical compound [OH-].NN.C[N+](C)(C)C OZELNHNUXJENDW-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- QMYDVDBERNLWKB-UHFFFAOYSA-N propane-1,2-diol;hydrate Chemical compound O.CC(O)CO QMYDVDBERNLWKB-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- 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
- C11D7/06—Hydroxides
-
- 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
- C11D7/263—Ethers
-
- 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
- C11D7/34—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
- C23G5/02854—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons characterised by the stabilising or corrosion inhibiting additives
- C23G5/02893—Sulfur-containing compounds
-
- 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
-
- 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
Definitions
- the present invention relates to a cleaning agent for cleaning thick film photoresists.
- a pattern of photoresist is formed on a surface of a metal such as silicon dioxide, Cu (copper) or the like and a low-k material, and the pattern is transferred by wet or dry etching after exposure.
- a metal such as silicon dioxide, Cu (copper) or the like and a low-k material
- Thick film photoresists above ⁇ are increasingly used in semiconductor wafer fabrication processes, and cleaning agents for cleaning thick film photoresists are increasingly becoming an important research direction for semiconductor wafer fabrication processes.
- cleaning agents often cause corrosion of the wafer substrate during the chemical cleaning of the photoresist by the semiconductor wafer.
- metal corrosion is a relatively common and very serious problem, often resulting in a significant reduction in wafer yield.
- the photoresist cleaning agent is mainly composed of a polar organic solvent, a strong alkali, and/or water, and the photoresist on the semiconductor wafer is removed by immersing the semiconductor wafer in a cleaning agent or rinsing the semiconductor wafer with a cleaning agent.
- a cleaning agent or rinsing the semiconductor wafer with a cleaning agent.
- JP1998239865 discloses an alkaline cleaning agent consisting of tetramethylammonium hydroxide hydrazine, dimethyl sulfoxide (DMSO), 1,3,-dimethyl-2-imidazolium (DMI) and water And so on.
- the wafer was immersed in the cleaning agent to remove a thick film photoresist of 20 ⁇ m or more on the metal and dielectric substrate at 50 to 100 °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 US Pat. No. 5,529,887 discloses an alkaline cleaning agent consisting of potassium hydroxide, alkyl glycol monodecyl ether, water soluble fluoride, water and the like. Immerse the wafer in the cleaning agent at 40 ⁇ 90 °C Thick film photoresist on metal and dielectric substrates is removed. The cleaning agent has a high corrosion to the semiconductor wafer substrate.
- Patent document US 5,962,197 discloses an alkaline cleaning agent consisting of potassium hydroxide, N-methylpyrrolidone, propylene glycol ether, water, and a surfactant.
- the wafer was immersed in the cleaning agent and immersed at 105 ° C for 40 minutes to remove thick film photoresist on metal and dielectric substrates.
- the cleaning agent needs to be used at 105 ° C, and the cleaning temperature is high, which causes corrosion of the semiconductor wafer substrate.
- the photoresist of a thickness of ⁇ or more can be cleaned at 50 to 70 °C.
- the photoresist wafer containing the photoresist is immersed in the photoresist cleaning agent of the present invention, and slowly shaken at 50 to 70 ° C for 30 to 120 minutes with a constant temperature oscillator, followed by washing with deionized water, followed by high purity nitrogen gas. Blow dry.
- the cleaning agent of the present invention contains: dimethyl sulfoxide (DMSO), potassium hydroxide, alkyl alcohol amine, and alkyl glycol monophenyl ether.
- the content of the dimethyl sulfoxide is preferably 35 to 95% by mass, more preferably 60 to 95% by mass ; and the content of the potassium hydroxide is preferably a mass percentage. 0.1-5%, more preferably 0.5 to 3% by mass; the content of the alkyl alcohol amine is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass;
- the content of the mercaptodiol monophenyl ether is preferably from 1 to 40% by mass, more preferably from 5 to 25% by mass.
- the mercapto alcohol amine is preferably monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA) or isopropanolamine. Among them, monoethanolamine is preferred.
- the alkyl glycol monophenyl ether is preferably ethylene glycol monophenyl ether.
- EMMPE ethylene glycol monophenyl ether
- PGMPE propylene glycol monophenyl ether
- isopropyl glycol monophenyl ether diethylene glycol monophenyl ether, dipropylene glycol monophenyl ether or diisopropyl glycol monophenyl ether.
- ethylene glycol monophenyl ether, propylene glycol monophenyl ether or isopropyl glycol monophenyl ether is preferred.
- the cleaning agent may further contain a corrosion inhibitor.
- the corrosion inhibitor is preferably benzotriazole (BTA), 2-mercaptobenzoxazole (MBO) or 2-mercaptobenzothiazole (MBT). Among them, 2-mercaptobenzothiazole is preferred.
- the content of the corrosion inhibitor is preferably less than or equal to 5% by mass, more preferably 0.05 to 2% by mass.
- the cleaning agent of the present invention can be obtained by uniformly mixing the above components.
- the positive progress of the present invention is that the cleaning agent of the present invention can remove a thick film photoresist (photoresist) having a thickness of ⁇ or more on a metal, a metal alloy or a dielectric substrate, and has good properties in the field of microelectronics such as semiconductor wafer cleaning. Application prospects.
- Table 1 shows the formulations of the cleaning agents of Examples 1 to 6 for cleaning thick film photoresists.
- the components listed in Table 1 and their contents were simply mixed uniformly, and the cleaning agents of the respective examples were prepared.
- Triethanolamine 10 Isopropanediol monophenyl ether 1 1 4 60 3 10 isopropanolamine 25 diethylene glycol monophenyl ether 2 2-mercaptobenzoxazole
- Table 2 shows the formulations of cleaning agents 1 to 6, according to the components listed in Table 2 and their contents, simply mixed evenly, that is, each cleaning agent is prepared.
- the cleaning agents 1 to 6 were used to clean blank Cu wafers and wafers containing photoresists having a thickness of ⁇ or more, and tested for corrosion resistance to metallic Cu and cleaning ability to thick film photoresists. The results are shown in Table 3. .
- the cleaning method is: immersing a blank Cu wafer and a wafer containing a photoresist having a thickness of ⁇ or more into a photoresist cleaning agent, slowly shaking with a constant temperature oscillator at 50 to 70 ° C for 30 to 120 minutes, and then washing with deionized water. It is then dried by high purity nitrogen.
- the reagents used in the present invention are all commercially available.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Metallurgy (AREA)
- Emergency Medicine (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Description
清洗厚膜光刻胶的清洗剂 技术领域
本发明涉及一种清洗厚膜光刻胶的清洗剂。 技术背景
在通常的半导体制造工艺中， 通过在二氧化硅、 Cu (铜）等金属以及低 k材料等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。 ΙΟΟμιη以上的厚膜光刻胶越来越多地应用于半导体晶片制造工艺中， 因 而用于清洗厚膜光刻胶的清洗剂日益成为半导体晶片制造工艺的重要研究 方向。 另外， 在半导体晶片进行光刻胶的化学清洗过程中， 清洗剂常会造成 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。
目前， 光刻胶清洗剂主要由极性有机溶剂、强碱和 /或水等组成， 通过将 半导体晶片浸入清洗剂中或者利用清洗剂冲洗半导体晶片， 去除半导体晶片 上的光刻胶。 - 专利文献 JP1998239865 公开了一种碱性清洗剂， 由四甲基氢氧化铵 ΤΜΑΗ、 二甲基亚砜 （DMSO)、 1，3，-二甲基 -2-咪唑垸酮 （DMI ) 和水等组 成。将晶片浸入该清洗剂中，于 50〜100°C下除去金属和电介质基材上的 20μηι 以上的厚膜光刻胶。 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 US5529887公开了一种碱性清洗剂， 由氢氧化钾、烷基二醇单 垸基醚、 水溶性氟化物和水等组成。 将晶片浸入该清洗剂中， 在 40〜90°C下
除去金属和电介质基材上的厚膜光刻胶。该清洗剂对半导体晶片基材的腐蚀 较高。
专利文献 US5962197 公开了一种碱性清洗剂， 由氢氧化钾、 N-甲基吡 咯垸酮、丙二醇醚、水和表面活性剂等组成。将晶片浸入该清洗剂中，于 105°C 下浸没 40min， 可除去金属和电介质基材上的厚膜光刻胶。 该清洗剂需要在 105°C下使用， 其清洗温度较高， 会造成半导体晶片基材的腐蚀。
本发明中的光刻胶清洗剂，可以在 50~70°C下清洗 ΙΟΟμιη以上厚度的光 刻胶。 将含有光刻胶的半导体晶片浸入本发明中的光刻胶清洗剂， 在 50~70 °C下， 用恒温振荡器缓慢振荡 30〜120分钟， 再用去离子水洗涤， 之后用高 纯氮气吹干。
发明概要 本发明的目的是公开一种清洗厚膜光刻胶的清洗剂。
本发明的清洗剂含有： 二甲基亚砜 （DMSO)、 氢氧化钾、 烷基醇胺和 烷基二醇单苯基醚。 本发明中， 所述的二甲基亚砜的含量较佳的为质量百分比 35~95%， 更 佳的为质量百分比 60〜95%; 所述的氢氧化钾的含量较佳的为质量百分比 0.1-5%, 更佳的为质量百分比 0.5~3%； 所述的烷基醇胺的含量较佳的为质 量百分比 0.1〜20%， 更佳的为质量百分比 0.5〜10%； 所述的垸基二醇单苯基 醚的含量较佳的为质量百分比 1〜40%， 更佳的为质量百分比 5〜25%。 本发明中，所述的垸基醇胺较佳的为单乙醇胺 (MEA)、二乙醇胺 (DEA)、 三乙醇胺 （TEA) 或异丙醇胺。 其中， 优选单乙醇胺。
本发明中， 所述的烷基二醇单苯基醚较佳的为乙二醇单苯基醚
(EGMPE)、 丙二醇单苯基醚 （PGMPE)、 异丙二醇单苯基醚、 二乙二醇单 苯基醚、 二丙二醇单苯基醚或二异丙二醇单苯基醚。 其中， 优选乙二醇单苯 基醚、 丙二醇单苯基醚或异丙二醇单苯基醚。
本发明中， 所述的清洗剂还可含有缓蚀剂。 所述的缓蚀剂较佳的为苯并 三氮唑（BTA)、 2-巯基苯并噁唑（MBO)或 2-巯基苯并噻唑（MBT)。其中， 优选 2-巯基苯并噻唑。所述的缓蚀剂的含量较佳的为小于或等于质量百分比 5%, 更佳的为质量百分比 0.05~2%。
本发明的清洗剂由上述组分混合均匀， 即可制得。
本发明的积极进步效果在于： 本发明的清洗剂可以除去金属、 金属合金 或电介质基材上的 ΙΟΟμιη以上厚度的厚膜光刻胶 （光阻）， 在半导体晶片清 洗等微电子领域具有良好的应用前景。
发明内容
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在 所述的实施例范围之中。
实施例 1~6 清洗厚膜光刻胶的清洗剂
表 1给出了清洗厚膜光刻胶的清洗剂实施例 1~6的配方，按表 1中所列 组分及其含量， 简单混合均匀， 即制得各实施例的清洗剂。 清洗厚膜光刻胶的清洗剂实施例 1~6
实 二鸭 氢氧化 烷基醇胺 垸基二醇单苯基醚 缓蚀剂 施 亚砜含 钾含量 含量 含量 含量
具体物质 具体物质 具体物质 例 量 wt% wt% wt% wt% wt%
1 70 0.1 20 单乙醇胺 9.9 乙二醇单苯基醚 1 1
2 35 5 15 二乙醇胺 40 丙二醇单苯基醚 5 苯并三氮唑
3 88.9 1 0.1 三乙醇胺 10 异丙二醇单苯基醚 1 1
4 60 3 10 异丙醇胺 25 二乙二醇单苯基醚 2 2-巯基苯并噁唑
5 95 0.5 3.45 单乙醇胺 1 二丙二醇单苯基醚 0.05 2-巯基苯并噻唑
6 93.5 1 0.5 单乙醇胺 5 二异丙二醇单苯基醚 1 1 效果实施例
表 2给出了清洗剂 1〜6的配方， 按表 2中所列组分及其含量， 简单混合 均匀， 即制得各清洗剂。
表 2 清洗厚膜光刻胶的清洗剂 1
将清洗剂 1〜6用于清洗空白 Cu晶片和含有 ΙΟΟμπ 以上厚度的光刻胶的 晶片， 测试其对金属 Cu的腐蚀性及其对厚膜光刻胶的清洗能力， 结果如表 3所示。
清洗方法为： 将空白 Cu晶片和含有 ΙΟΟμπι以上厚度的光刻胶的晶片浸 入光刻胶清洗剂， 50~70°C下用恒温振荡器缓慢振荡 30〜120分钟， 再用去离 子水洗涤， 之后用高纯氮气吹干。
表 3 清洗剂 1~6对金属 Cu的腐蚀性及其对厚膜光刻胶的清洗能力 厚膜光刻胶清洗
清洗剂 金属 Cu的腐蚀情况
清洗时间 /min 清洗温度 /°c 清洗效果
1 良好 90 65 完全
2 良好 90 65 完全
3 良好 30 70 基本完全
4 良好 120 50 完全
5 良好 90 60 完全
6 良好 90 65 完全 从表 3可以看出， 清洗剂 1~6表现出对金属 Cu的低腐蚀性以及对厚膜 光刻胶良好的清洗能力。
本发明所用试剂均市售可得。
Claims
1. 一种清洗厚膜光刻胶的清洗剂， 其特征在于含有： 二甲基亚砜、 氢氧化 钾、 烷基醇胺和垸基二醇单苯基醚。
2. 如权利要求 1 所述的清洗剂， 其特征在于： 所述的二甲基亚砜的含量为 质量百分比 35~95%。
3. 如权利要求 2 所述的清洗剂， 其特征在于： 所述的含量为质量百分比 60〜95%。
4. 如权利要求 1 所述的清洗剂， 其特征在于： 所述的氢氧化钾的含量为质 量百分比 0.1~5%。
5. 如权利要求 4 所述的清洗剂， 其特征在于： 所述的含量为质量百分比 0.5〜3%。
6. 如权利要求 1 所述的清洗剂， 其特征在于： 所述的烷基醇胺的含量为质 量百分比 0.1~20%。
7. 如权利要求 6 所述的清洗剂， 其特征在于： 所述的含量为质量百分比 0.5~10%。
8. 如权利要求 1所述的清洗剂， 其特征在于： 所述的垸基二醇单苯基醚的 含量为质量百分比 1~40%。
9. 如权利要求 8 所述的清洗剂， 其特征在于： 所述的含量为质量百分比 5〜25%。
10.如权利要求 1所述的清洗剂， 其特征在于： 所述的烷基醇胺为单乙醇胺、 二乙醇胺、 三乙醇胺或异丙醇胺。
1 1.如权利要求 1 所述的清洗剂， 其特征在于： 所述的垸基二醇单苯基醚为 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、 二丙二醇单苯基醚或二异丙二醇单苯基醚。
12.如权利要求 1所述的清洗剂， 其特征在于： 所述的清洗剂还含有缓蚀剂。
13.如权利要求 12所述的清洗剂， 其特征在于： 所述的缓蚀剂的含量为小于 或等于质量百分比 5%。
14.如权利要求 13 所述的清洗剂， 其特征在于： 所述的含量为质量百分比 0.05~2%。
15.如权利要求 12所述的清洗剂，其特征在于：所述的缓蚀剂为苯并三氮唑、 2-巯基苯并噁唑或 2-巯基苯并噻唑。
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| CN101738880A (zh) * | 2008-11-10 | 2010-06-16 | 安集微电子（上海）有限公司 | 一种厚膜光刻胶清洗剂 |
| CN102051283B (zh) * | 2009-10-30 | 2014-11-05 | 安集微电子（上海）有限公司 | 一种含羟胺的清洗液及其应用 |
| CN102096345A (zh) * | 2009-12-11 | 2011-06-15 | 安集微电子（上海）有限公司 | 一种厚膜光刻胶清洗液及其清洗方法 |
| CN103436898B (zh) * | 2013-07-22 | 2016-04-06 | 武汉亿强科技开发有限公司 | 一种酸洗缓蚀抑雾剂及其制备方法 |
| CN103789780B (zh) * | 2014-02-26 | 2016-06-08 | 苏州禾川化学技术服务有限公司 | 一种ic元件用碱性通用型去毛刺液 |
| JP6226144B2 (ja) * | 2014-02-27 | 2017-11-08 | 荒川化学工業株式会社 | 洗浄剤組成物原液、洗浄剤組成物および洗浄方法 |
| CN104531397A (zh) * | 2014-11-18 | 2015-04-22 | 惠晶显示科技（苏州）有限公司 | 一种平板玻璃基板减薄预清洗用清洗液及其应用 |
| CN105467783A (zh) * | 2016-01-04 | 2016-04-06 | 仲恺农业工程学院 | 一种碱性感光聚合显影分泌物清洗剂及其制备方法 |
| CN105676600A (zh) * | 2016-04-06 | 2016-06-15 | 东莞市广华化工有限公司 | 防腐蚀碱性显影液 |
| CN105676599A (zh) * | 2016-04-06 | 2016-06-15 | 东莞市广华化工有限公司 | 基于新聚合物及应用于图像显影技术的显影液 |
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| US20030181344A1 (en) * | 2002-03-12 | 2003-09-25 | Kazuto Ikemoto | Photoresist stripping composition and cleaning composition |
| US20050119143A1 (en) * | 1999-01-27 | 2005-06-02 | Egbe Matthew I. | Compositions for the removal of organic and inorganic residues |
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| US20050119143A1 (en) * | 1999-01-27 | 2005-06-02 | Egbe Matthew I. | Compositions for the removal of organic and inorganic residues |
| US6599370B2 (en) * | 2000-10-16 | 2003-07-29 | Mallinckrodt Inc. | Stabilized alkaline compositions for cleaning microelectronic substrates |
| US20030181344A1 (en) * | 2002-03-12 | 2003-09-25 | Kazuto Ikemoto | Photoresist stripping composition and cleaning composition |
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