TWI397953B - 半導體元件或顯示元件用洗淨液及洗淨方法 - Google Patents
半導體元件或顯示元件用洗淨液及洗淨方法 Download PDFInfo
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- TWI397953B TWI397953B TW095144405A TW95144405A TWI397953B TW I397953 B TWI397953 B TW I397953B TW 095144405 A TW095144405 A TW 095144405A TW 95144405 A TW95144405 A TW 95144405A TW I397953 B TWI397953 B TW I397953B
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- Prior art keywords
- acid
- group
- cleaning
- semiconductor
- compound
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- 238000004140 cleaning Methods 0.000 title claims description 58
- 239000004065 semiconductor Substances 0.000 title claims description 38
- 238000000034 method Methods 0.000 title claims description 24
- 239000007788 liquid Substances 0.000 claims description 40
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 229920000768 polyamine Polymers 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 150000002222 fluorine compounds Chemical class 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 150000007514 bases Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 4
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005530 etching Methods 0.000 description 26
- 230000007797 corrosion Effects 0.000 description 18
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- 229920002120 photoresistant polymer Polymers 0.000 description 15
- 230000007613 environmental effect Effects 0.000 description 11
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- 238000001312 dry etching Methods 0.000 description 9
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- 239000002184 metal Substances 0.000 description 9
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- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
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- 229910019142 PO4 Inorganic materials 0.000 description 2
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- 239000007864 aqueous solution Substances 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
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- 238000000206 photolithography Methods 0.000 description 2
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- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229940114055 beta-resorcylic acid Drugs 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
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- GHWVXCQZPNWFRO-UHFFFAOYSA-N butane-2,3-diamine Chemical compound CC(N)C(C)N GHWVXCQZPNWFRO-UHFFFAOYSA-N 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 1
- 235000010350 erythorbic acid Nutrition 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
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- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- GGOZGYRTNQBSSA-UHFFFAOYSA-N pyridine-2,3-diol Chemical compound OC1=CC=CN=C1O GGOZGYRTNQBSSA-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 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 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- ASVMCHUOIVTKQQ-UHFFFAOYSA-M triethyl(methyl)azanium;fluoride Chemical compound [F-].CC[N+](C)(CC)CC ASVMCHUOIVTKQQ-UHFFFAOYSA-M 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
Classifications
-
- 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
-
- 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
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- 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
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- 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
-
- 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
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Description
本發明係關於一種在半導體元件或顯示元件之製造步驟中除去被處理物表面之附著物的洗淨液及洗淨方法,詳細地說,關於一種環境面之負荷小、在被處理物上之金屬配線和層間絕緣膜等之半導體基板並無造成損傷而除去被處理物表面之牢固之附著物的洗淨液及洗淨方法。
今日,作為高積體化之LSI等之半導體元件之製造方法一般係使用微影法。在藉由該微影法而製造半導體元件之狀態下,通常在矽晶圓等之基板上而將進行成為導電用配線材料之金屬膜等之導電薄膜或配線間之絕緣之目的之氧化矽膜等之層間絕緣膜予以形成之後,在其表面,均質地塗敷光阻劑而設置感光層,對其實施選擇性之曝光及顯影處理,形成要求之光阻圖案。接著,藉由以該光阻圖案作為遮罩,對下層部之薄膜實施選擇性之蝕刻處理,而在該薄膜形成要求之光阻圖案。接著,得到所謂完全地除去該光阻圖案之一連串之步驟。
在近年來,半導體元件係朝著高積體化前進,且形成0.18μm以下之圖案係為必要,隨著該加工尺寸之超微細化在前述之選擇性蝕刻處理中,乾式蝕刻法係為主流。乾式蝕刻處理中,已知會在形成之圖案周邊部,生成起因於乾式蝕刻氣體、光阻劑、被加工膜及乾式蝕刻裝置內之處理構件等之殘渣(以下,稱為蝕刻殘渣)。特別是蝕刻殘渣殘留於導通孔之內部及其周邊部時,會導致引起高電阻化或者是呈電氣地產生短路等之不理想之事態。
形成金屬配線之步驟中除去蝕刻殘渣之洗淨液係揭示有由烷醇胺和有機溶劑之混合系所構成之有機胺系剝離液(專利文獻1、2)。但是,這些洗淨液係在蝕刻殘渣及光阻劑等之除去後而進行水洗之狀態下,由於吸濕之水分解離胺而呈現鹼性,腐蝕金屬膜等,所以漂洗液中需要醇類等的有機溶劑,有安全面或環境面之負荷變大的問題點發生。
此外,作為蝕刻殘渣和光阻劑硬化層之除去能力更加高於有機胺系剝離液的洗淨劑,能使用由氟化合物、有機溶劑和防蝕劑等所構成之氟系洗淨液(專利文獻3、4)。但是,在近年來,由於半導體元件之製造步驟中乾式蝕刻之條件變得嚴苛,且光阻劑係進一步變質之故,因此前述之氟系水溶液係無法完全地除去。
包含多量之此等有機溶劑的有機胺系洗淨液或氟系洗淨液係在半導體之製造步驟中,安全對策或廢液處理等之經濟面、環境面之負荷大,需要過多之對策。因此,已揭示有機酸和還原劑之水溶液的酸系洗淨劑作為水溶性洗淨液(專利文獻5)。
但是,在該水溶性洗淨液,無法完全地除去牢固地變質之蝕刻殘渣。此外,還原劑係消耗於藥液成分或空氣中成分之還原,所以品質之保持期限變短,並且為了保持品質而需要特別之保管。此外,水溶性洗淨液係強酸,因此在廢棄上也需要特別之考量,不能說是充分地減低經濟面和環境面之負荷。
因此,強烈地要求:對於配線原料不造成損傷而能夠完全地除去蝕刻殘渣並且半導體製造步驟之安全及環境面之負荷小的洗淨液。
專利文獻1:日本特開昭62-49355號公報專利文獻2:日本特開昭64-42653號公報專利文獻3:日本特開平7-201794號公報專利文獻4:日本特開平11-67632號公報專利文獻5:日本特開2003-16730號公報
本發明之目的係提供一種能夠在短時間內,除去使用於半導體積體電路之半導體元件之配線步驟或顯示元件之配線步驟之乾式蝕刻後之殘留之蝕刻殘渣並且無氧化或腐蝕配線材料或者層間絕緣膜等而且環境面之負荷小的洗淨液以及使用該洗淨液的洗淨方法。
本發明人等係為了達成前述之目的,因此,全心地進行檢討,結果係發現:藉由使用將含有於碳鏈相鄰接之位置具有2個以上胺基之特定構造的聚胺類或其鹽之洗淨液、或者是更含有酸,性化合物或鹼性化合物之洗淨液、或者是更含有氟化合物之洗淨液可達成該目的,而完成本發明。
也就是說,本發明係提供以下之半導體元件或顯示元件用洗淨液及洗淨方法。
1.一種半導體元件或顯示元件用洗淨液,其特徵為:含有藉由下列之通式(1)或通式(2)所表示之聚胺類或其鹽。
(R1
~R4
係分別獨立地表示氫原子、烷基、芳烷基、烯基、芳基、羥烷基、胺烷基或烷氧烷基。其中,R1
和R4
為烷基之情形下,亦可互相結合而形成環。)
(R5
~R1 0
係分別獨立地表示氫原子、烷基、芳烷基、烯基、芳基、羥烷基、胺烷基或烷氧烷基;n係表示1至5之整數。)
2.如前述1之半導體元件或顯示元件用洗淨液,其係更含有酸性化合物及/或鹼性化合物。
3.無前述1或2之半導體元件或顯示元件用洗淨液,其係更含有氟化合物。
4.如前述3之半導體元件或顯示元件用洗淨液,其中氟化合物係為氟化氫酸、氟化銨或氟化四甲基銨。
5.一種半導體元件或顯示元件之洗淨方法,其特徵為:使用前述1~4中任一項之洗淨液。
本發明之半導體元件或顯示元件用洗淨液,其特徵為:不包含有害物質,並且於空氣中不變質,能夠以比較低之濃度來使用,因此安全性高且環境面之負荷變小。
藉由使用本發明之洗淨液,能夠在短時間內容易地除去半導體基板上之蝕刻殘渣,且此時能夠完全無腐蝕地微細加工配線材料,此外,並不需要使用例如醇之有機溶劑來作為漂洗液,可以僅利用水來進行漂洗。
首先,本發明之半導體元件或顯示元件用洗淨液(在以下、也僅稱為洗淨液),其特徵為:含有藉由下列之通式(1)或通式(2)所表示之聚胺類或其鹽。
通式(1)之R1
~R4
及通式(2)之R5
~R1 0
係分別獨立地表示氫原子、烷基、芳烷基、烯基、芳基、羥烷基、胺烷基或烷氧烷基。但是,通式(1)之R1
和R4
係可以在烷基之情形下,互相結合而形成環。此外,n係表示1至5之整數。
該通式(1)及通式(2)之烷基之碳數目係最好是1~5,芳烷基之碳數目係最好是7~11,烯基之碳數目係最好是2~6,芳基之碳數目係最好是6~10。
作為藉由化學式(1)所表示之聚胺類之具體例係列舉伸乙二胺、1,2-二胺基丙烷、2,3-二胺基丁烷、1,2-二胺基環己烷等。作為藉由化學式(2)所示聚胺類之具體例係列舉如二伸乙三胺、三伸乙四胺、四伸乙五胺、五伸乙六胺等。這些聚胺類係可以單獨使用,也可以組合2種以上而使用。
本發明之洗淨液之藉由通式(1)和通式(2)所表示之聚胺類之濃度,一般為0.005質量%以上、最好是0.01質量%以上。藉由0.005質量%以上,可有效地除去在乾式蝕刻後殘留之蝕刻殘渣等。由蝕刻殘渣除去性能之觀點來看的話,不需要設置上限,但是,必須考量經濟性或環境負荷、安全性而選擇適當之量。在考量環境面之負荷時,水的濃度係較佳為80質量%以上。
在本發明之洗淨液,除了前述之藉由通式(1)或通式(2)所表示之聚胺類以外,其目的係為了調整pH值的話,使用酸性化合物和鹼性化合物為佳。該酸性化合物和鹼性化合物係不包含金屬為佳。由於通式(1)或通式(2)所表示之聚胺類係在任意的pH值區域具有蝕刻殘渣除去性能,因此以防止配線金屬和層間絕緣膜之腐蝕性或金屬雜質之附著為目的時,能任意選擇洗淨液之pH值。
如果使用之酸性化合物和鹼性化合物係不在損害本發明目的之範圍內,則在種類或濃度並無特別地限制,可以使用無機酸、有機酸和鹼中之任一種。
作為無機酸之具體例係列舉硼酸、鹽酸、硝酸、亞硝酸、硫酸、亞硫酸、磷酸、亞磷酸、次亞磷酸等。
作為有機酸之具體例係列舉甲酸、乙酸、丙酸、丁酸、異丁酸、戊酸、庚烷酸、月桂酸、棕櫚酸、硬脂酸、丙烯酸、甲基丙烯酸、草酸、丙二酸、順丁烯二酸、丁二酸、己二酸、檸檬酸、抗壞血酸、異抗壞血酸、乙醛酸、安息香酸、甲苯酸、苯二甲酸、偏苯三酸、均苯四甲酸、苯磺酸、甲苯磺酸、水楊酸等。
作為鹼之具體例係列舉氨、氫氧化四甲基銨、氫氧化三甲基羥基乙基銨(胆碱)、乙醇胺、羥基胺等。
使用於本發明之酸性化合物及/或鹼性化合物係可以單獨使用,也可以適當地組合2種以上而使用。此外,酸性化合物及鹼性化合物之濃度係最好是由要求之pH值,來進行考量及決定。
本發明之洗淨液係即使是在不含氟化合物之情形下,也具有充分之蝕刻殘渣除去性能,但是,由於一起除去附著於層間絕緣膜之蝕刻殘渣和層間絕緣膜之表層之目的,添加氟化合物為佳。
作為使用之氟化合物係列舉氟化氫酸、氟化銨、酸性氟化銨以及藉由下列之通式(3)所表示之氟化季銨類。
在前述之通式中,R1 1
~R1 4
係分別獨立地表示氫原子、烷基、芳烷基、烯基、芳基、羥烷基、胺烷基或烷氧烷基。該通式(3)中,烷基之碳數目係1~5者為佳,芳烷基之碳數目係7~11者為佳,烯基之碳數目係2~6者為佳,芳基之碳數目係6~10者為佳。
作為藉由通式(3)所表示之氟化季銨類之具體例係列舉氟化四甲基銨、氟化四乙基銨、氟化三乙基甲基銨、氟化三甲基羥基乙基銨、氟化四乙醇銨、氟化甲基三乙醇銨等。其中,較佳係氟化氫酸、氟化銨及氟化四甲基銨。
在本發明之洗淨液,該氟化合物係可以單獨使用,也可以適當地組合2種以上而使用,此外,其濃度係最好是0.001~15質量%、更加理想是0.005~10質量%。
為了提高洗淨液之潤濕性,因此,可以添加界面活性劑,也可以使用陽離子性、陰離子性、非離子性及氟系界面活性劑之任何一種界面活性劑。界面活性劑係可以單獨使用,也可以適當地組合2種以上而使用。
為了更加地提高洗淨液之金屬配線腐蝕防止性,因此,可以添加腐蝕防止劑。作為腐蝕防止劑係並無特別限制,可以使用磷酸系螯合劑、羧酸系螯合劑、胺系螯合劑、肟系螯合劑、乙炔系螯合劑等之螯合化合物、芳香族羥基化合物、***或四唑化合物、糖醇及此等之鹽等。
作為螯合化合物之具體例係列舉1,2-丙烷二胺四亞甲基膦酸、羥基乙烷膦酸等之磷酸系螯合化合物;伸乙二胺四乙酸、二羥基乙甘氨酸、氰基三乙酸、草酸、檸檬酸、蘋果酸、酒石酸等之羧酸系螯合化合物;聯二吡啶、四苯基卜啉、菲繞啉、2,3-吡啶二元醇等之胺系螯合化合物;二甲基乙二肟、二苯基乙二肟等之肟系螯合化合物;苯基乙炔、2,5-二甲基-3-己炔-2,5-二元醇等之乙炔系螯合化合物等。
作為芳香族羥基化合物之具體例係列舉苯酚、甲酚、二甲苯酚、焦兒茶酚、t-丁基兒茶酚、間苯二酚、對苯二酚、焦棓酚、1,2,4-苯三元醇、水楊基醇、p-羥苄基醇、o-羥苄基醇、p-羥苯乙基醇、p-胺基苯酚、m-胺基苯酚、二胺基苯酚、胺基間苯二酚、p-羥基安息香酸、o-羥基安息香酸、2,4-二羥基安息香酸、2,5-二羥基安息香酸、3,4-二羥基安息香酸、3,5-二羥基安息香酸、沒食子酸等。
作為***或四唑化合物係列舉苯并***、胺基***、胺基四唑等。作為糖醇係列舉山梨糖醇、木糖醇、直輝中基性岩等為例。
這些腐蝕防止劑係可以單獨使用,或者是適當地組合2種以上而使用。
本發明之洗淨液之腐蝕防止劑之濃度係較佳為0.001~10質量%、更加理想是0.005~5質量%。
此外,可以在本發明之洗淨液,由於要求而在不損害本發明之目的之範圍,可配合以往使用於洗淨液之其他添加劑。
使用前述洗淨液之本發明之半導體元件或顯示元件之洗淨方法之洗淨溫度係通常是常溫~70℃,藉由蝕刻之條件或者是使用之半導體基體或配線金屬而適當地進行選擇。
使用於本發明之洗淨方法之半導體元件和顯示元件係包含:矽、非結晶質矽、多結晶矽、玻璃等之基板材料;氧化矽、氮化矽及此等之衍生物等之絕緣材料;鈦、氮化鈦、鉭、鉭化合物等之障蔽材料;銅、鎢、鈦-鎢、鋁、鋁合金、鉻、鉻合金等之配線材料;鎵-砷、鎵-磷、銦-磷等之化合物半導體;鉻氧化物等之氧化物半導體等,但是,藉由使用本發明之洗淨液,可對於此等原料不造成損傷來進行洗淨,完全地除去蝕刻殘渣等。
此外,本發明之洗淨方法係可以視其需要而併用超音波。
作為在藉由本發明之洗淨法而除去半導體基板上之蝕刻殘渣等之後的漂洗液,可不需要使用例如醇類之有機溶劑,僅藉由水而充分地進行漂洗。
接著,藉由實施例及比較例而更加具體地說明本發明。但是,本發明係並不因此些實施例而受到任何限制。
此外,在以下之實施例,在洗淨半導體元件後之評價基準係正如以下。
(1)蝕刻殘渣除去狀態A:完全除去。B:幾乎完全除去。C:部分殘留。D:大部分殘留。
(2)銅之腐蝕狀態A:完全沒看到腐蝕。B:幾乎看不到腐蝕。C:看到凹凸狀或孔洞狀之腐蝕。D:在銅層之整個面看到該腐蝕,並且看到銅層後移。
(3)層間絕緣膜之腐蝕狀態A:完全無看到腐蝕。B:幾乎無看到腐蝕。C:在導通孔之側壁,看到污點。D:導通孔之直徑變大。
在藉由CVD法而在銅配線體1之上呈依序地堆積氮化矽膜2和氧化矽膜3之後,塗敷光阻劑,使用通常之光微影技術,加工光阻劑,然後,使用乾式蝕刻技術,蝕刻加工前述之氧化矽膜而成為要求之圖案,將除去殘留之光阻劑之半導體元件之一部分之剖面,顯示在第1圖。在該銅電路元件,在導通孔之側壁,殘留蝕刻殘渣4。
在使用表1所示之洗淨液而以既定之條件來洗淨第1圖所示之銅電路元件之後,藉由超純水而進行漂洗,藉由氮流而進行乾燥。在常溫、1小時之後,藉由掃描型電子顯微鏡(SEM)而觀察表面狀態,就蝕刻殘渣之除去性及銅配線體之腐蝕而按照前述之判斷基準,來進行評價。將其結果,顯示在表1。
此外,在表1,界面活性劑之Phosphanol係東邦化學工業股份有限公司製之商品名稱。
由表1而明確地顯示:在適用本發明之洗淨液及洗淨法之實施例1~6,能夠完全無腐蝕銅而也完全無洗淨層間絕緣膜之腐蝕,具有良好之蝕刻殘渣之除去性。
本發明之半導體元件或顯示元件用洗淨液係安全性高,環境面之負荷變小,能夠在短時間內容易地除去半導體基板上之蝕刻殘渣,此時能夠完全無腐蝕地微細加工配線材料,此外,並不需要使用例如醇之有機溶劑來作為漂洗液,可以僅利用水來進行漂洗。
因此,如果藉由本發明之洗淨方法的話,則可以在半導體元件或顯示元件之製造,極為有利於工業地製造環境面之負荷小之高精度、高品質之電路配線。
1...下層銅配線體
2...氮化矽膜
3...氧化矽膜
4...蝕刻殘渣
第1圖係實施例中,在下層銅配線體上藉由CVD法而依序地堆積氮化矽膜和氧化矽膜之後,塗敷光阻劑,使用通常之光微影技術,加工光阻劑,然後使用乾式蝕刻技術,蝕刻、加工前述之氧化矽膜成為所期望之圖案,除去殘留之光阻劑的半導體元件之剖面圖。
Claims (5)
- 一種半導體元件或顯示元件用洗淨液,其係含有藉由下列之通式(1)或通式(2)所表示之聚胺類或其鹽、與水之半導體元件或顯示元件用洗淨液,其特徵在於聚胺類或其鹽的含量為0.01質量%以上,水的含量為80質量%以上,
- 如申請專利範圍第1項之半導體元件或顯示元件用洗淨液,其中更含有酸性化合物及/或鹼性化合物。
- 如申請專利範圍第1或2項之半導體元件或顯示元件用 洗淨液,其中更含有氟化合物。
- 如申請專利範圍第3項之半導體元件或顯示元件用洗淨液,其中氟化合物係氟化氫酸、氟化銨或氟化四甲基銨。
- 一種半導體元件或顯示元件之洗淨方法,其特徵為:使用如申請專利範圍第1至4項中任一項所記載之洗淨液。
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KR100795364B1 (ko) * | 2004-02-10 | 2008-01-17 | 삼성전자주식회사 | 반도체 기판용 세정액 조성물, 이를 이용한 세정 방법 및도전성 구조물의 제조 방법 |
JP4440689B2 (ja) | 2004-03-31 | 2010-03-24 | 東友ファインケム株式会社 | レジスト剥離剤組成物 |
EP1628336B1 (en) * | 2004-08-18 | 2012-01-04 | Mitsubishi Gas Chemical Company, Inc. | Cleaning liquid and cleaning method |
CN101755324B (zh) * | 2007-07-26 | 2011-10-12 | 三菱瓦斯化学株式会社 | 清洗和防腐用组合物及半导体元件或显示元件的制造方法 |
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2006
- 2006-11-24 EP EP06833212.1A patent/EP1959303B1/en active Active
- 2006-11-24 WO PCT/JP2006/323408 patent/WO2007063767A1/ja active Application Filing
- 2006-11-24 KR KR1020087012009A patent/KR101330509B1/ko active IP Right Grant
- 2006-11-24 JP JP2007547914A patent/JP5251128B2/ja active Active
- 2006-11-24 US US12/095,344 patent/US7998914B2/en active Active
- 2006-11-30 TW TW095144405A patent/TWI397953B/zh active
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EP1031884A2 (en) * | 1999-02-25 | 2000-08-30 | Mitsubishi Gas Chemical Company, Inc. | Resist stripping agent and process of producing semiconductor devices using the same |
TW557420B (en) * | 1999-09-28 | 2003-10-11 | Mitsubishi Gas Chemical Co | Resist stripping composition |
EP1400858A1 (en) * | 2001-06-29 | 2004-03-24 | Mitsubishi Gas Chemical Company, Inc. | Photoresist stripper composition |
Also Published As
Publication number | Publication date |
---|---|
JP5251128B2 (ja) | 2013-07-31 |
US20100152085A1 (en) | 2010-06-17 |
JPWO2007063767A1 (ja) | 2009-05-07 |
KR20080073299A (ko) | 2008-08-08 |
KR101330509B1 (ko) | 2013-11-15 |
EP1959303A4 (en) | 2010-01-27 |
TW200731371A (en) | 2007-08-16 |
EP1959303B1 (en) | 2017-08-23 |
WO2007063767A1 (ja) | 2007-06-07 |
EP1959303A1 (en) | 2008-08-20 |
US7998914B2 (en) | 2011-08-16 |
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