TW201829763A - 洗淨液以及洗淨基板之方法 - Google Patents
洗淨液以及洗淨基板之方法 Download PDFInfo
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- TW201829763A TW201829763A TW106137695A TW106137695A TW201829763A TW 201829763 A TW201829763 A TW 201829763A TW 106137695 A TW106137695 A TW 106137695A TW 106137695 A TW106137695 A TW 106137695A TW 201829763 A TW201829763 A TW 201829763A
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- cleaning solution
- formula
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- cleaning
- mass
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- 238000004140 cleaning Methods 0.000 title claims abstract description 89
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 26
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
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- 239000007788 liquid Substances 0.000 claims description 14
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 abstract description 24
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- GDHRQDYGUDOEIZ-UHFFFAOYSA-N n,n,2-trimethylpropan-1-amine Chemical compound CC(C)CN(C)C GDHRQDYGUDOEIZ-UHFFFAOYSA-N 0.000 description 1
- DNJDQMRARVPSHZ-UHFFFAOYSA-N n,n,n',n'-tetrabutylethane-1,2-diamine Chemical compound CCCCN(CCCC)CCN(CCCC)CCCC DNJDQMRARVPSHZ-UHFFFAOYSA-N 0.000 description 1
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- NCIVMPNELJTZFT-UHFFFAOYSA-N n,n-diethyl-2-hydroxy-2-methylpropanamide Chemical compound CCN(CC)C(=O)C(C)(C)O NCIVMPNELJTZFT-UHFFFAOYSA-N 0.000 description 1
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- QJZXMQBYTOWWFO-UHFFFAOYSA-N n-ethyl-2-hydroxy-n,2-dimethylpropanamide Chemical compound CCN(C)C(=O)C(C)(C)O QJZXMQBYTOWWFO-UHFFFAOYSA-N 0.000 description 1
- RUFMRRIYNIOMBR-UHFFFAOYSA-N n-ethyl-n-[(4-methylbenzotriazol-1-yl)methyl]ethanamine Chemical compound C1=CC=C2N(CN(CC)CC)N=NC2=C1C RUFMRRIYNIOMBR-UHFFFAOYSA-N 0.000 description 1
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 1
- RCALDWJXTVCBAZ-UHFFFAOYSA-N oct-1-enylbenzene Chemical group CCCCCCC=CC1=CC=CC=C1 RCALDWJXTVCBAZ-UHFFFAOYSA-N 0.000 description 1
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- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- CYFIHPJVHCCGTF-UHFFFAOYSA-N prop-2-enyl 2-hydroxypropanoate Chemical compound CC(O)C(=O)OCC=C CYFIHPJVHCCGTF-UHFFFAOYSA-N 0.000 description 1
- ZQMAPKVSTSACQB-UHFFFAOYSA-N prop-2-enyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCC=C ZQMAPKVSTSACQB-UHFFFAOYSA-N 0.000 description 1
- HAFZJTKIBGEQKT-UHFFFAOYSA-N prop-2-enyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC=C HAFZJTKIBGEQKT-UHFFFAOYSA-N 0.000 description 1
- HPCIWDZYMSZAEZ-UHFFFAOYSA-N prop-2-enyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC=C HPCIWDZYMSZAEZ-UHFFFAOYSA-N 0.000 description 1
- QLGGKSSLRJWNNV-UHFFFAOYSA-N propoxymethanamine Chemical compound CCCOCN QLGGKSSLRJWNNV-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- QVOFCQBZXGLNAA-UHFFFAOYSA-M tributyl(methyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(CCCC)CCCC QVOFCQBZXGLNAA-UHFFFAOYSA-M 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- ZASZWSTYEJKHIN-UHFFFAOYSA-N tripropylazanium;hydroxide Chemical compound [OH-].CCC[NH+](CCC)CCC ZASZWSTYEJKHIN-UHFFFAOYSA-N 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 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
- C11D7/08—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in 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
- 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
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
-
- 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
- C11D7/3281—Heterocyclic 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
- C11D7/50—Solvents
-
- 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
-
- 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
-
- 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
-
- 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
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloyl morpholine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F126/10—N-Vinyl-pyrrolidone
-
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Abstract
本發明之課題係提供去除光阻圖型之殘渣物,或蝕刻殘渣物等所使用之洗淨液中,相對於氮化矽具有優良防蝕性之洗淨液,及使用其洗淨基板之方法。 解決方法為,含有氫氟酸(A)及溶劑(S)之洗淨液中,添加作為防蝕劑(B)用之含有來自具有羧酸醯胺鍵(-CO-N<)與不飽和雙鍵之特定結構的化合物之單位的聚合物。作為防蝕劑(B)用之聚合物較佳為聚乙烯吡咯烷酮。
Description
[0001] 本發明係有關洗淨液,及使用其洗淨基板之方法。
[0002] 製造IC、LSI等之半導體元件及液晶面板等之顯示元件時,首先係於矽晶圓、玻璃等之基板上形成蒸鍍CVD之金屬膜或SiO2
膜等之絕緣膜。其次於金屬膜或絕緣膜上形成光阻圖型或金屬硬遮罩。再以該光阻圖型或硬遮罩作為遮罩乾蝕處理基板,形成微細電路。其次進行研磨加工,再使用洗淨液洗淨去除光阻圖型之殘渣物及硬遮罩之殘渣物。 [0003] 一般寄望洗淨去除光阻圖型之殘渣物及硬遮罩之殘渣物所使用之洗淨液,除了可有效洗淨去除該等殘渣物,相對於金屬也具有優良防蝕性。有關該類洗淨液曾提案,使用氫氟酸及作為其逆胺(counter amine)用之氨的化合物(參考專利文獻1~3),及使用氫氟酸及作為其逆胺用之1,8-二氮雜二環[5.4.0]十一烯-7的化合物(參考專利文獻4)等。 先前技術文獻 專利文獻 [0004] [專利文獻1] 特開2001-83713號公報 [專利文獻2] 特開平9-197681號公報 [專利文獻3] 特開2000-47401號公報 [專利文獻4] 特開2000-181083號公報
發明所欲解決之課題 [0005] 半導體元件等之製造過程中進行化學式研磨(CMP)時,為了保護不接受研磨之材料係設置抑制層。抑制層之材質係廣泛使用硬質材料之氮化矽。 因此使用專利文獻1~4所記載之洗淨液的洗淨對象之基板表面多半為,含有由氮化矽所形成之表面。 [0006] 但專利文獻1~4所記載之含有氫氟酸之洗淨液易腐蝕氮化矽。氮化矽被腐蝕後,進行CMP時會研磨本來不接受研磨之材料。 [0007] 有鑑於上述課題,本發明之目的為,提供去除光阻圖型之殘渣物或蝕刻殘渣物等所使用之洗淨液中,相對於氮化矽具有優良防蝕性之洗淨液,及使用其洗淨基板之方法。 解決課題之方法 [0008] 本發明者們發現,藉由含有氫氟酸(A)及溶劑(S)之洗淨液中,添加含有來自具有羧酸醯胺鍵(-CO-N<)與不飽和雙鍵之特定結構的化合物之單位的聚合物,可解決上述課題,而完成本發明。更具體為,本發明係提供下述之物。 [0009] 本發明之第一態樣為一種洗淨液,其為含有氫氟酸(A)、防蝕劑(B)與溶劑(S), 防蝕劑為含有含下述式(b1)或式(b2):(式(b1)中,Rb1
及Rb2
為各自獨立之氫原子,或碳原子數1以上6以下之烴基,Rb1
與Rb2
可相互鍵結形成環; 式(b2)中,Rb3
為氫原子或甲基,Rb4
及Rb5
為各自獨立之氫原子,或可被1以上之羥基取代的碳原子數1以上6以下之烴基,Rb4
與Rb5
可相互鍵結形成環) 所表示之一種以上的單位之聚合物。 [0010] 本發明之第二態樣為使用第一態樣之該洗淨液洗淨基板之方法。 發明之效果 [0011] 藉由本發明可提供去除光阻圖型之殘渣物或蝕刻殘渣物等所使用之洗淨液中,相對於氮化矽具有優良防蝕性之洗淨液,及使用其洗淨基板之方法。 實施發明之形態 [0012] <<洗淨液>> 洗淨液為,含有氫氟酸(A)、防蝕劑(B)與溶劑(S)。 洗淨液為含有作為防蝕劑(B)用,含有下述式(b1)或式(b2):(式(b1)中,Rb1
及Rb2
為各自獨立之氫原子,或碳原子數1以上6以下之烴基,Rb1
及Rb2
可相互鍵結形成環; 式(b2)中,Rb3
為氫原子或甲基,Rb4
及Rb5
為各自獨立之氫原子,或可被1以上之羥基取代的碳原子數1以上6以下之烴基,Rb4
與Rb5
可相互鍵結形成環) 所表示之一種以上之單位的聚合物。 洗淨液因含有上述聚合物,故相對於氮化矽備有優良防蝕性。 下面將詳細說明洗淨液所含有之必須或任意成分。 [0013] <氫氟酸(A)> 洗淨液為,必須含有氫氟酸。 氫氟酸之含量較佳為,洗淨液中之0.001質量%以上0.5質量%以下,更佳為0.08質量%以上0.32質量%以下。氫氟酸之含量為該類範圍內時,可更有效得到光阻圖型之殘渣物或蝕刻殘渣物之洗淨去除性,與相對於氮化矽之防蝕性的平衡性。 [0014] <防蝕劑(B)> 洗淨液為,必須含有作為防蝕劑(B)用,含有下述式(b1)或式(b2):(式(b1)中,Rb1
及Rb2
為各自獨立之氫原子,或碳原子數1以上6以下之烴基,Rb1
及Rb2
可相互鍵結形成環; 式(b2)中,Rb3
為氫原子或甲基,Rb4
及Rb5
為各自獨立之氫原子,或可被1以上之羥基取代的碳原子數1以上6以下之烴基,Rb4
與Rb5
可相互鍵結形成環) 所表示之一種以上之單位的聚合物。洗淨液可藉由含有防蝕劑(B),而顯著提高洗淨液相對於氮化矽之防蝕性。 [0015] 上述含有式(b1)所表示之單位及/或式(b2)所表示之單位的聚合物之質量平均分子量為,可得所希望之防蝕效果下無特別限定。 上述聚合物之質量平均分子量較佳為1000以上2000000以下,又以5000以上500000以下為佳,更佳為10000以上300000以下,又以40000以上200000以下更佳,特佳為80000以上1800000以下,最佳為100000以上160000以下。 又,聚合物之質量平均分子量超過2000000時,雖可調製洗淨液,但將聚合物溶解於後述溶劑(S)時需長時間或加熱。 使用該類具有上述範圍內之質量平均分子量的聚合物時,易使防蝕劑(B)之聚合物均勻溶解於洗淨液,且相對於氮化矽易得到所希望之防蝕效果。 [0016] 含有式(b1)所表示之單位及/或式(b2)所表示之單位的聚合物可為,僅由式(b1)所表示之單位及/或式(b2)所表示之單位所形成的聚合物,或含有式(b1)所表示之單位及式(b2)所表示之單位以外其他單位的共聚合物。 [0017] 上述聚合物為含有式(b1)所表示之單位及式(b2)所表示之單位以外之其他單位時,賦予該其他單位之單體化合物如,不飽和羧酸、(甲基)丙烯酸烷基酯、(甲基)丙烯酸羥基烷基酯、具有醚鍵之(甲基)丙烯酸酯、上述其他之(甲基)丙烯酸酯、烯丙基化合物、乙烯基醚類、乙烯基酯類、苯乙烯類、二羧酸二酯類、共軛二烯烴、含有腈基之聚合性化合物及含有氯之聚合性化合物。 聚合物中該其他單位之含量較佳為30質量%以下,又以20質量%以下為佳,更佳為10質量%以下。 聚合物最佳為,僅由式(b1)所表示之單位及/或式(b2)所表示之單位所形成。 [0018] 不飽和羧酸如,(甲基)丙烯酸、巴豆酸等之單羧酸;馬來酸、富馬酸、檸康酸、中康酸、衣康酸等。 [0019] (甲基)丙烯酸烷基酯如,甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、n-丙基(甲基)丙烯酸酯、n-丁基(甲基)丙烯酸酯、戊基(甲基)丙烯酸酯、tert-辛基(甲基)丙烯酸酯等之直鏈狀或支鏈狀烷基(甲基)丙烯酸酯。 [0020] (甲基)丙烯酸羥基烷基酯如,2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、2-二甲基羥基丙基(甲基)丙烯酸酯、三羥甲基丙烷單(甲基)丙烯酸酯等。 [0021] 具有醚鍵之(甲基)丙烯酸酯如,2-甲氧基乙基(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、3-甲氧基丁基(甲基)丙烯酸酯、乙基卡必醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯、四氫糠基(甲基)丙烯酸酯,較佳為2-甲氧基乙基(甲基)丙烯酸酯及甲氧基三乙二醇(甲基)丙烯酸酯。 [0022] 上述其他之(甲基)丙烯酸酯如,氯乙基(甲基)丙烯酸酯、苄基(甲基)丙烯酸酯、苯基(甲基)丙烯酸酯。 [0023] 烯丙基化合物如,乙酸烯丙酯、己酸烯丙酯、辛酸烯丙酯、月桂酸烯丙酯、棕櫚酸烯丙酯、硬脂酸烯丙酯、苯甲酸烯丙酯、乙醯乙酸烯丙酯、乳酸烯丙酯等之烯丙基酯類;烯丙氧基乙醇等。 [0024] 乙烯基醚類如,己基乙烯醚、辛基乙烯醚、癸基乙烯醚、乙基己基乙烯醚、甲氧基乙基乙烯醚、乙氧基乙基乙烯醚、氯乙基乙烯醚、1-甲基-2,2-二甲基丙基乙烯醚、2-乙基丁基乙烯醚、羥基乙基乙烯醚、二乙二醇乙烯醚、二甲基胺基乙基乙烯醚、二乙基胺基乙基乙烯醚、丁基胺基乙基乙烯醚、苄基乙烯醚、四氫糠基乙烯醚等之烷基乙烯醚;乙烯基苯基醚、乙烯基甲苯基醚、乙烯基氯苯基醚、乙烯基-2,4-二氯苯基醚、乙烯基萘基醚、乙烯基蒽基醚等之乙烯基芳基醚等。 [0025] 乙烯基酯類如,乙烯基乙酸酯、乙烯基丁酸酯、乙烯基異丁酸酯、乙烯基三甲基乙酸酯、乙烯基二乙基乙酸酯、乙烯基戊酸酯、乙烯基己酸酯、乙烯基氯乙酸酯、乙烯基二氯乙酸酯、乙烯基甲氧基乙酸酯、乙烯基丁氧基乙酸酯、乙烯基苯基乙酸酯、乙烯基乙醯乙酸酯、乙烯基乳酸酯、乙烯基-β-苯基丁酸酯、苯甲酸乙烯酯、水楊酸乙烯酯、氯苯甲酸乙烯酯、四氯苯甲酸乙烯酯、萘甲酸乙烯酯等。 [0026] 苯乙烯類如,苯乙烯;甲基苯乙烯;二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、二乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、己基苯乙烯、環己基苯乙烯、癸基苯乙烯、苄基苯乙烯、氯甲基苯乙烯、三氟甲基苯乙烯、乙氧基甲基苯乙烯、乙醯氧基苯乙烯等之烷基苯乙烯;甲氧基苯、4-甲氧基-3-甲基苯乙烯、二甲氧基苯乙烯等之烷氧基苯乙烯;氯苯乙烯、二氯苯乙烯、三氯苯乙烯、四氯苯乙烯、五氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘苯乙烯、氟苯乙烯、三氟苯乙烯、2-溴-4-三氟甲基苯乙烯、4-氟-3-三氟甲基苯乙烯等之鹵苯乙烯等。 [0027] 二羧酸二酯類如,馬來酸二乙酯、富馬酸二丁酯。 [0028] 共軛二烯烴如,丁二烯、異戊二烯。 [0029] 含有腈基之聚合性化合物如,(甲基)丙烯腈。 [0030] 含有氯之聚合性化合物如,氯乙烯、偏氯乙烯。 [0031] 下面將說明式(b1)所表示之單位,與式(b2)所表示之單位。 [0032] 下述式(b1):式中,Rb1
及Rb2
為各自獨立之氫原子,或碳原子數1以上6以下之烴基,Rb1
與Rb2
可相互鍵結形成環。 [0033] Rb1
及Rb2
中碳原子數1以上6以下之烴基可為由1個以上6個以下之碳原子與氫原子所構成之基,無特別限定。 [0034] Rb1
及Rb2
之各定義中,碳原子數1以上6以下之烴基可為脂肪族烴基、脂環式烴基及芳香族烴基中任一種,且可具有不飽和鍵。烴基之結構可為直鏈狀、支鏈狀、環狀及該等結構之組合中任一種。 [0035] Rb1
及Rb2
中碳原子數1以上6以下之烴基較佳如,烷基、鏈烯基、環烷基、環鏈烯基及芳基等。 [0036] Rb1
及/或Rb2
為烷基或鏈烯基等,該烷基或鏈烯基係碳原子數1以上6以下時可為直鏈狀或支鏈狀。 烷基之具體例較佳如,甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、n-戊基、異戊基、tert-戊基、及n-己基等。鏈烯基之具體例較佳如,乙烯基、烯丙基、3-丁烯基、2-丁烯基、1-丁烯基、4-戊烯基、5-己烯基等。 [0037] Rb1
及/或Rb2
為環烷基時具體例較佳如,環丁基、環戊基,及環己基等。 Rb1
及/或Rb2
為碳環鏈烯基時具體例較佳如,對應環烷基所列舉之較佳例示的基之環鏈烯基。 [0038] Rb1
及/或Rb2
為芳基時較佳如,苯基。 [0039] Rb1
與Rb2
可相互鍵結所形成之環結構如,吡咯烷酮環結構、哌啶酮環結構、吖庚環結構等。 [0040] 式(b1)所表示之單位的具體例如下述單位。[0041][0042] 下述式(b2):式中,Rb3
為氫原子或甲基,Rb4
及Rb5
為各自獨立之氫原子,或碳原子數1以上6以下之烴基,Rb4
與Rb5
可相互鍵結形成環。 [0043] Rb4
及Rb5
為不具有取代基的碳原子數1以上6以下之烴基時,該無取代的碳原子數1以上6以下之烴基與Rb1
及Rb2
中碳原子數1以上6以下之烴基相同。 Rb4
及Rb5
為被1以上之羥基取代的碳原子數1以上6以下之烴基時,羥基之取代數較佳為1。 被羥基取代的碳原子數1以上6以下之烴基較佳如,羥甲基、2-羥基乙基、3-羥基丙基、4-羥基丁基、5-羥基戊基、6-羥基己基、4-羥基環戊基、4-羥基苯基、3-羥基苯基,及2-羥基苯基。該等之中較佳如羥甲基、2-羥基乙基、3-羥基乙基,更佳為2-羥基乙基。 Rb4
與Rb5
可相互鍵結所形成之環結構如,吡咯烷環結構、哌啶環結構,及六伸甲基亞胺環結構。 [0044] 式(b2)所表示之單位如下述單位。 [0045][0046][0047] 就相對於氮化矽易得特別優良之防蝕效果的洗淨液,賦予式(b1)所示單位之化合物更佳為,下述式(b1-1)所表示之單位。 又以式(b1-1):(式(b1-1)中,p為1以上10以下之整數) 所表示之單位的聚合物為佳。 [0048] 式(b1-1)中,p為1以上10以下之整數,較佳為1以上8以下之整數,更佳為1以上5以下之整數,特佳為1以上3以下之整數,最佳為1。 [0049] 上述式(b1-1)所表示之單位於p為1時係含有吡咯烷酮環,p為2時係含有哌啶酮環,p為3時係含有吖庚環。 [0050] p為1時,賦予式(b1-1)所表示之單位的化合物為N-乙烯基-2-吡咯烷酮。p為2時,賦予式(b1-1)所表示之單位的化合物為N-乙烯基-2-哌啶酮。p為3時,賦予式(b1-1)所表示之單位的化合物為N-乙烯基-2-吖庚。 [0051] 與含有上述式(b1)所表示之單位的聚合物相同,含有式(b1-1)所表示之單位的聚合物可為,式(b1-1)所表示之單位均聚物,或含有式(b1-1)所表示之單位與式(b1-1)所表示之單位以外的其他單位之共聚物。較佳為僅由式(b1-1)所表示之單位所形成的聚合物,更佳為僅由式(b1-1)所表示且p為1之單位所形成的聚合物,即聚乙烯基吡咯烷酮。 [0052] 上述所說明之防蝕劑(B)於洗淨液中的使用量無特別限定。洗淨液中防蝕劑(B)之含量較佳為0.01質量%以上10質量%以下,更佳為0.03質量%以上5質量%以下,特佳為0.05質量%以上1質量%以下。 使用含量為該範圍內之防蝕劑(B)時,易得兼具相對於各種殘渣物之優良洗淨效果,與相對於氮化矽之優良防蝕效果的洗淨液。 [0053] <溶劑(S)> 洗淨液需含有溶劑(S)。典型之溶劑(S)主要係由水所形成之溶劑,但可為僅由水所形成之溶劑,或水與水溶性有機溶劑之混合溶劑,或僅由水溶性有機溶劑所形成之溶劑。 水之含量較佳為洗淨液中之1.0質量%以上99.9質量%以下。溶劑(S)以水為主體時更佳為洗淨液中水之含量為80質量%以上99.9質量%以下,特佳為90質量%以上99.9質量%以下,又以95質量%以上99.9質量%以下為佳,最佳為98質量%以上99.9質量%以下。溶劑(S)含有水與水溶性有機溶劑時,洗淨液中水之含量例如可為15質量%以上40質量%以下。 又,溶劑(S)為水與水溶性有機溶劑之混合溶劑時,洗淨液中之水溶性有機溶劑含量較佳為1.0質量%以上90質量%以下,更佳為10質量%以上80質量%以下,特佳為20質量%以上50質量%以下。 [0054] 洗淨液可含有之水溶性有機溶劑如,二甲基亞碸等之亞碸類;二甲基碸、二乙基碸、雙(2-羥基乙基)碸、四伸甲基碸等之碸類;N,N-二甲基甲醯胺、N-甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基乙醯胺、N,N-二乙基乙醯胺等之醯胺類;N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-丙基-2-吡咯烷酮、N-羥基甲基-2-吡咯烷酮、N-羥基乙基-2-吡咯烷酮等之內醯胺類;1,3-二甲基-2-咪唑啉酮、1,3-二乙基-2-咪唑啉酮、1,3-二異丙基-2-咪唑啉酮等之咪唑啉酮類;γ-丁內酯、δ-戊內酯等之內酯類;乙二醇、丙二醇、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚等之多價醇類及其衍生物等。 [0055] 又,下述式(s-1)所表示之N,N-二烷基脂肪酸醯胺也適用為水溶性有機溶劑。洗淨液含有式(s-1)所表示之N,N-二烷基脂肪酸醯胺時,易得持續使用也不易改變蝕刻速度之洗淨液。 [0056](一般式(s-1)中,R1s
表示異丙基,或1-羥基-1-甲基乙基,R2s
及R3s
表示各自獨立之碳原子數1以上4以下之烷基)。 [0057] R2s
及R3s
為各自獨立之碳原子數1以上4以下之烷基。該烷基可為直鏈狀或支鏈狀。碳原子數1以上4以下之烷基具體例如,甲基、乙基、n-丙基、異丙基、n-丁基、sec-丁基、異丁基,及tert-丁基。該等之烷基中較佳為甲基及乙基。 [0058] 式(s-1)所表示之N,N-二烷基脂肪酸醯胺之具體例如,N,N-二甲基異丁基醯胺、N-乙基,N-甲基異丁基醯胺、N,N-二乙基異丁基醯胺、2-羥基-N,N,2-三甲基丙烷醯胺、N-乙基-2-羥基-N,2-二甲基丙烷醯胺,及N,N-二乙基-2-羥基-2-甲基丙烷醯胺等。該等之中較佳為N,N-二甲基異丁基醯胺、N-乙基,N-甲基異丁基醯胺、2-羥基-N,N,2-三甲基丙烷醯胺,及N-乙基-2-羥基-N,2-二甲基丙烷醯胺,特佳為N,N-二甲基異丁基醯胺,及2-羥基-N,N,2-三甲基丙烷醯胺。 洗淨液中水溶性有機溶劑可含有二種以上之N,N-二烷基脂肪酸醯胺組合物。 [0059] 又,下述式(s-2)所表示之3-烷氧基-3-甲基-1-丁醇也適用為水溶性有機溶劑。3-烷氧基-3-甲基-1-丁醇具有特別優良殘渣去除性能。(式中,R4s
表示碳原子數1以上5以下之烷基)。 [0060] 式(s-2)中,R4s
所表示之碳原子數1以上5以下之烷基如,甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、t-丁基、n-戊基等。其中就溶解力之觀點較佳為碳原子數1以上3以下之烷基,更佳為甲基或乙基,特佳為甲基。 式(s-2)所表示之3-烷氧基-3-甲基-1-丁醇,特佳為3-甲氧基-3-甲基-1-丁醇(MMB)。 [0061] <鹼性化合物(C)> 洗淨液可含有前述防蝕劑(B)以外之鹼性化合物(C)。 鹼性化合物(C)之種類無特別限定,可由先前洗淨光阻等之殘渣物所使用的洗淨液中,所添加之無機或有機鹼性化合物中適當選擇。 鹼性化合物(C)較佳為含氮鹼性化合物。 [0062] 洗淨液可含有之無機鹼性化合物的具體例如,氨、羥基胺、肼、氫氧化鉀、氫氧化鈉等之鹼金屬氫氧化物、碳酸鉀、碳酸鈉等之鹼金屬碳酸鹽、碳酸氫鉀、碳酸氫鈉等之鹼金屬碳酸氫鹽等。 [0063] 洗淨液可含有之有機鹼性化合物的具體例如,四甲基銨氫氧化物、四乙基銨氫氧化物、四丙基銨氫氧化物、四丁基銨氫氧化物、甲基三丙基銨氫氧化物、甲基三丁基銨氫氧化物、膽鹼等之四級銨氫氧化物;六甲基二矽氮烷、六乙基二矽氮烷等之矽氮烷化合物;三甲基矽烷基二甲基胺、三甲基矽烷基二乙基胺等之胺基矽烷化合物;二乙基羥基胺等之羥基胺化合物。 又,下述有機胺類也適用為鹼性化合物(C)。有機胺類之具體例如,甲氧基甲基胺、甲氧基乙基胺、甲氧基丙基胺、甲氧基丁基胺、乙氧基甲基胺、乙氧基乙基胺、乙氧基丙基胺、乙氧基丁基胺、丙氧基甲基胺、丙氧基乙基胺、丙氧基丙基胺、丙氧基丁基胺、丁氧基甲基胺、丁氧基乙基胺、丁氧基丙基胺、丁氧基丁基胺、甲基胺、乙基胺、丙基胺、丁基胺、N,N-二甲基胺、N,N-二乙基胺、N,N-二丙基胺、N,N-二丁基胺、三甲基胺、三乙基胺、三丙基胺、三丁基胺、二甲基胺基丙基胺、2-乙基己基胺、四氫糠基胺、四甲基伸乙基二胺、四乙基伸乙基二胺、四丙基伸乙基二胺,及四丁基伸乙基二胺、甲基胺基丁基胺、乙基胺基丁基胺、丙基胺基丁基胺、丁基胺基丁基胺、吡啶、吡咯、哌嗪、吡咯烷、哌啶、皮考啉、嗎啉、甲基嗎啉、二氮雜二環辛烷、二氮雜二環壬烷,及二氮雜二環十一烯等。 [0064] 又,下述式(c-1)所表示之化合物也適用為鹼性化合物(C)。(式(c-1)中,R1c
至R5c
表示各自獨立之氫原子,或可具有羥基、羧基、胺基或膦酸基的碳原子數1以上6以下之烷基,R1c
至R5c
中至少一個為氫原子。R1c
至R4c
中任一個可與R5c
相互鍵結形成環結構。Y1c
及Y2c
表示各自獨立之碳原子數1以上3以下之伸烷基,n表示0以上5以下之整數。n為2以上時,複數R5c
相互間及複數Y1c
相互間可相同或相異,R5c
相互間可鍵結形成環結構。 [0065] R1c
至R5c
可使用的碳原子數1以上6以下之烷基可為直鏈狀或支鏈狀中任一種,較佳為直鏈狀,具體例如,甲基、乙基、n-丙基、n-丁基、n-戊基、n-己基等。該等之中最佳為乙基。 該烷基可具有羥基、羧基、胺基或膦酸基。該具體例如,2-羥基乙基、2-羧基乙基、2-胺基乙基、2-膦酸乙基等。 [0066] R1c
至R4c
中任一個與R5c
可相互鍵結形成之環結構,或R5c
相互間可相互鍵結形成之環結構如,哌嗪環等。 [0067] Y1c
及Y2c
可使用的碳原子數1以上3以下之伸烷基可為直鏈狀或支鏈狀中任一種,較佳為直鏈狀。具體例如,伸甲基、伸乙基、伸丙基等。該等之中最佳為伸乙基。 [0068] n表示0以上5以下之整數,更佳為0以上2以下之整數。 [0069] 上述式(c-1)所表示之鹼性化合物的具體例如,伸乙基二胺、N-(2-胺基乙基)-1,2-乙烷二胺(=二伸乙基三胺)、N,N’-雙(2-胺基乙基)-1,2-乙烷二胺(=三伸乙基四胺)、三(2-胺基乙基)胺、N,N’-雙(2-胺基乙基)哌嗪、N-[(2-胺基乙基)-2-胺基乙基]哌嗪、N-(2-胺基乙基)-N’-{2-[(2-胺基乙基)胺基]乙基}-1,2-乙烷二胺(=四伸乙基五胺)、4-(2-胺基乙基)-N-(2-胺基乙基)-N’-{2-[(2-胺基乙基)胺基]乙基}-1,2-乙烷二胺、1-(2-胺基乙基)-4-{[(2-胺基乙基)胺基]乙基}哌嗪、1-{2-[[2-[(2-胺基乙基)胺基]乙基]胺基]乙基}哌嗪、1-哌嗪乙烷胺、2-[(2-胺基乙基)胺基]乙醇等。 [0070] 上述式(c-1)所表示之鹼性化合物中較佳為,下述一般式(c-2)所表示之鹼性化合物。 [0071](式(c-2)中,Y1c
、Y2c
及n與式(c-1)同義)。 [0072] 式(c-2)所表示之鹼性化合物的具體例如,伸乙基二胺、N-(2-胺基乙基)-1,2-乙烷二胺(=伸乙基三胺)、N,N’-雙(2-胺基乙基)-1,2-乙烷二胺(=三伸乙基四胺)、四伸乙基五胺、五伸乙基六胺、二伸甲基三胺、三伸甲基四胺等。 [0073] 該等之中特佳為N-(2-胺基乙基)-1,2-乙烷二胺(=二伸乙基三胺)、N,N’-雙(2-胺基乙基)-1,2-乙烷二胺(=三伸乙基四胺)。 [0074] 上述所說明之鹼性化合物(C)可單獨使用,或二種以上組合使用。 [0075] 鹼性化合物(C)之含量可因應氫氟酸之含量而適當調整,但洗淨液中較佳為0.01質量%以上2.00質量%以下,更佳為0.01質量%以上1.24質量%以下。易更有效率取得相對於各種殘渣物之洗淨去除性,與相對於氮化矽之防蝕性的平衡性。 [0076] 添加或未添加鹼性化合物(C)之狀態下洗淨液的pH,就洗淨性能與相對於氮化矽之防蝕效果具有優良平衡性之觀點,較佳為2以上7以下,特佳為2以上6以下。 又,洗淨液之pH為25℃下測定之值。 [0077] <其他成分> 洗淨液除了上述防蝕劑(B)以外,可含有先前洗淨液所添加之防蝕劑。 該防蝕劑無特別限定,可使用先前已知之防蝕劑,較佳為苯并三唑系化合物或含有巰基之化合物。 [0078] 上述苯并三唑系化合物如下述式(d-1)所表示之化合物。 [0079][0080] 上述式(d-1)中,R1d
、R2d
表示各自獨立之氫原子、可具有取代基的碳原子數1以上10以下之烴基、羧基、胺基、羥基、氰基、甲醯基、磺醯烷基,或磺基,Q表示氫原子、羥基、可具有取代基的碳原子數1以上14以下之烴基(但該烴基可被醯胺鍵或酯鍵中斷),或下述一般式(d-2)所表示之基。 [0081][0082] 上述式(d-2)中,R3d
表示碳原子數1以上6以下之伸烷基,R4d
及R5d
表示各自獨立之氫原子、羥基,或碳數1以上6以下之羥基烷基或烷氧基烷基。 [0083] 又,上述式(d-1)中,R1d
、R2d
、Q之各定義中的烴基可為芳香族烴基及脂肪族烴基中任一種,可具有不飽和鍵,可為直鏈狀、支鏈狀或環狀中任一種。芳香族烴基如苯基、p-甲苯基等。直鏈狀之脂肪族烴基如,甲基、n-丙基、乙烯基等。支鏈狀之脂肪族烴基如,異丁基、tert-丁基等。環狀之脂肪族烴基如,環戊基、環己基等。具有取代基之烴基如,羥基烷基、烷氧基烷基等。 [0084] 又,上述式(d-1)中,Q較佳為上述式(d-2)所表示之基。特佳為選擇上述式(d-2)所表示之基中,R4d
及R5d
為各自獨立之碳原子數1以上6以下之羥基烷基或烷氧基烷基的基。 [0085] 又以所選擇之Q可使上述式(d-1)所表示之化合物具有水溶性為佳。具體上較佳為氫原子、碳原子數1以上3以下之烷基(即甲基、乙基、丙基、異丙基)、碳原子數1以上3以下之羥基烷基、羥基等。 [0086] 苯并三唑系化合物具體如,苯并三唑、5,6-二甲基苯并三唑、1-羥基苯并三唑、1-甲基苯并三唑、1-胺基苯并三唑、1-苯基苯并三唑、1-羥基甲基苯并三唑、1-苯并三唑羧酸甲酯、5-苯并三唑羧酸、1-甲氧基-苯并三唑、1-(2,2-二羥基乙基)-苯并三唑、1-(2,3-二羥基丙基)苯并三唑;BASF公司販售之「IRGAMET」系列的2,2’-{[(4-甲基-1H-苯并三唑-1-基)甲基]亞胺基}雙乙醇、2,2’-{[(5-甲基-1H-苯并三唑-1-基)甲基]亞胺基}雙乙醇、2,2’-{[(4-甲基-1H-苯并三唑-1-基)甲基]亞胺基}雙乙烷、2,2’-{[(4-甲基-1H-苯并三唑-1-基)甲基]亞胺基}雙丙烷等。 該等之中較佳為1-(2,3-二羥基丙基)-苯并三唑、2,2’-{[(4-甲基-1H-苯并三唑-1-基)甲基]亞胺基}雙乙醇、2,2’-{[(5-甲基-1H-苯并三唑-1-基)甲基]亞胺基}雙乙醇等。 該等之苯并三唑化合物可單獨使用,或二種以上組合使用。 [0087] 上述含有巰基之化合物較佳為,鍵結於巰基之碳原子的α位、β位中至少一方具有羥基及/或羧基之化合物。該類化合物具體如,1-硫甘油、3-(2-胺基苯基硫基)-2-羥基丙基硫醇、3-(2-羥基乙基硫基)-2-羥基丙基硫醇、2-巰基丙酸、3-巰基丙酸等。該等之中特佳為使用1-硫甘油。 該等含有巰基之化合物可單獨使用,或二種以上組合使用。 [0088] 含有防蝕劑時,其含量於洗淨液中較佳為0.1質量%以上10質量%以下,更佳為0.5質量%以上5質量%以下。 [0089] 又,本發明之洗淨液亦可另含有表面活性劑。 該表面活性劑無特別限定,可使用先前已知之表面活性劑,但較佳為炔醇系表面活性劑。 [0090] 含有表面活性劑時,其含量於洗淨液中較佳為0.01質量%以上5質量%以下,更佳為0.05質量%以上2質量%以下。 [0091] 洗淨液藉由必須含有上述(A)成分、(B)成分及(S)成分,而適合洗淨光阻圖型之殘渣物或蝕刻殘渣物,且相對於氮化矽具有優良防蝕性。 因此上述所說明之洗淨液適用於洗淨基板之表面的至少部分係由氮化矽所形成時的基板。 上述所說明之洗淨液特別適用為,使用含有由氮化矽所形成之層,例如抑制層的基板進行化學式研磨(CMP)時所使用之洗淨液。 [0092] 洗淨方法無特別限定,例如浸漬法、噴霧法等,可分批式或單片式(Single Wafer Type)進行處理。洗淨去除時間無特別限定,一般分批處理時約為10分鐘以上30分鐘以下,單片處理時約為0.5分鐘以上3分鐘以下。本發明之洗淨液較佳為使用單片處理。洗淨液之溫度無特別限定,一般為25℃以上70℃以下之程度。 使用洗淨液洗淨後,可實施使用純水或低級醇等之漂洗處理及乾燥處理。
實施例 [0093] 下面將舉本發明之實施例更詳細說明本發明,但本發明非限定於下述實施例。 [0094] [實施例1~6及比較例1~7] (調製洗淨液) 均勻混合氫氟酸0.1質量%、表1所記載之種類的防蝕劑0.1質量%與殘分之水,調製實施例1~6及比較例2~7之洗淨液。 比較例1之洗淨液除了未使用防蝕劑外,其他同實施例調製洗淨液。 各實施例及比較例之洗淨液於25℃下測定之pH值如表1所示。 [0095] 各實施例及比較例中,防蝕劑係使用下述B1~ B12。 B1:聚乙烯基吡咯烷酮(質量平均分子量9,000) B2:聚乙烯基吡咯烷酮(質量平均分子量40,000) B3:聚乙烯基吡咯烷酮(質量平均分子量45,000) B4:聚乙烯基吡咯烷酮(質量平均分子量80,000) B5:聚乙烯基吡咯烷酮(質量平均分子量140,000) B6:聚乙烯基吡咯烷酮(質量平均分子量1,200,000) B7:N-乙烯基吡咯烷酮 B8:吡唑 B9:吡咯 B10:咪唑 B11:1,2,4-三唑 B12:5-胺基四唑 [0096] (評估氮化矽防蝕性) 使用備有作為最外層之厚100nm氮化矽層的基板評估防蝕性。將基板浸漬於50℃下之各實施例及比較例之洗淨液中30分鐘。浸漬後以水漂洗基板表面,再藉由吹氮使基板乾燥。 以橢圓計測定乾燥後基板之氮化矽層的膜厚(Å),再測定浸漬後氮化矽層之膜厚(Å)。 由浸漬前後之氮化矽層的膜厚變化,求取氮化矽層之膜減少量。 膜減少量(Å/30分鐘)之測定結果如表1所示。 [0097][0098] 藉由實施例及比較例得知,相對於使用含有作為防蝕劑之聚乙烯基吡咯烷酮的實施例之洗淨液時,可明顯抑制氮化矽膜減少,使用含有聚乙烯基吡咯烷酮以外之含氮雜環化合物,或不含防蝕劑的比較例之洗淨液時,會明顯減少氮化矽膜。 [0099] 即,由實施例與比較例之比較得知,聚乙烯基吡咯烷酮可減少腐蝕氮化矽。 [0100] [實施例7] 混合氫氟酸0.1質量%、防蝕劑之聚(N-(2-羥基乙基)丙烯醯胺)0.5質量%與殘分之水,得實施例7之洗淨液。 使用實施例7之洗淨液評估氮化矽防蝕性,結果氮化矽膜減少量為,不含防蝕劑之比較例1的洗淨液之膜減少量的50%以下。 [0101] [實施例8] 混合氫氟酸0.1質量%、防蝕劑之聚(N,N-二甲基丙烯醯胺)0.5質量%與殘分之水,得實施例8之洗淨液。 使用實施例8之洗淨液評估氮化矽防蝕性,結果氮化矽之膜減少量為,不含防蝕劑之比較例1的洗淨液之膜減少量的50%以下。
Claims (9)
- 一種洗淨液,其為含有氫氟酸(A)、防蝕劑(B)與溶劑(S), 前述防蝕劑為含有,含有下述式(b1)或式(b2):(式(b1)中,Rb1 及Rb2 為各自獨立之氫原子,或碳原子數1以上6以下之烴基,Rb1 與Rb2 可相互鍵結形成環; 式(b2)中,Rb3 為氫原子或甲基,Rb4 及Rb5 為各自獨立之氫原子,或可被1以上之羥基取代的碳原子數1以上6以下之烴基,Rb4 與Rb5 可相互鍵結形成環) 所表示之一種以上之單位的聚合物。
- 如請求項1之洗淨液,其中前述式(b1)所表示之單位為,下述式(b1-1):(式(b1-1)中,p為1以上10以下之整數) 所表示之單位。
- 如請求項2之洗淨液,其中p為1。
- 如請求項1或2之洗淨液,其中前述聚合物為聚乙烯基吡咯烷酮。
- 如請求項1或2之洗淨液,其中前述聚合物之質量平均分子量為1000以上2000000以下。
- 如請求項1或2之洗淨液,其中前述溶劑(S)為含有水。
- 如請求項1或2之洗淨液,其係使用於洗淨含有由氮化矽所形成之層的基板。
- 一種方法,其為使用如請求項1~7中任一項之洗淨液洗淨基板。
- 如請求項8之方法,其中前述基板含有由氮化矽所形成之層。
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