WO2010119753A1 - Composition décapante de photorésine et procédé de décapage d'une photorésine - Google Patents
Composition décapante de photorésine et procédé de décapage d'une photorésine Download PDFInfo
- Publication number
- WO2010119753A1 WO2010119753A1 PCT/JP2010/055034 JP2010055034W WO2010119753A1 WO 2010119753 A1 WO2010119753 A1 WO 2010119753A1 JP 2010055034 W JP2010055034 W JP 2010055034W WO 2010119753 A1 WO2010119753 A1 WO 2010119753A1
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- WO
- WIPO (PCT)
- Prior art keywords
- copper
- photoresist
- water
- weight
- copper alloy
- Prior art date
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 81
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052802 copper Inorganic materials 0.000 claims abstract description 72
- 239000010949 copper Substances 0.000 claims abstract description 72
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 52
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- OPTASPLRGRRNAP-UHFFFAOYSA-N cytosine Chemical compound NC=1C=CNC(=O)N=1 OPTASPLRGRRNAP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 229940109239 creatinine Drugs 0.000 claims abstract description 18
- 229940104302 cytosine Drugs 0.000 claims abstract description 18
- 238000005260 corrosion Methods 0.000 claims description 23
- 230000007797 corrosion Effects 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 7
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 7
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 6
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 229940102253 isopropanolamine Drugs 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 4
- 150000003462 sulfoxides Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 5
- 150000001412 amines Chemical class 0.000 abstract description 3
- 239000012964 benzotriazole Substances 0.000 abstract description 3
- -1 benzotriazole compound Chemical class 0.000 abstract description 3
- 239000003518 caustics Substances 0.000 abstract 1
- 230000003628 erosive effect Effects 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Images
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
- 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
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist 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
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
Definitions
- the present invention relates to a photoresist remover composition, and in particular, is preferably used for a flat panel display (hereinafter also referred to as FPD) substrate represented by a liquid crystal display or a copper or copper alloy wiring substrate of a semiconductor substrate.
- FPD flat panel display
- the present invention relates to a photoresist stripping composition excellent in corrosion resistance and stripping property, and a photoresist stripping method for a metal wiring board having a copper layer or a copper alloy layer using the composition.
- An FPD substrate or a semiconductor substrate has an electrode structure with fine wiring, and a photoresist is used in the manufacturing process.
- a photoresist is applied on a conductive metal layer such as aluminum, aluminum alloy, copper, or copper alloy formed on a substrate, or an insulating film such as SiO 2 film, and the resist is subjected to exposure and development. It is manufactured by forming a pattern, etching the conductive metal layer, insulating film, etc. using the patterned resist as a mask, forming fine wiring, and then removing the unnecessary photoresist layer with a release agent .
- a photoresist stripping composition a single solvent such as an organic alkali, an inorganic alkali, an organic acid, an inorganic acid, a polar solvent, or a mixed solution thereof has been used. It is also well known to use a mixed liquid of amine and water in order to improve photoresist peelability.
- the photoresist remover composition is required not to corrode fine wiring.
- aluminum has been widely used as a wiring material, and therefore various studies have been made on corrosion inhibition against aluminum.
- Patent Document 1 discloses a photoresist stripping composition mainly comprising an alkyl or alkanolamine, a polar organic solvent, water, and a heterocyclic hydroxyl group-containing compound in which the elements constituting the ring are nitrogen and carbon. Is disclosed.
- Patent Document 2 discloses an anticorrosive containing a heterocyclic compound having a 5- or 6-membered heterocyclic ring containing an atomic group of —C (OH) ⁇ N— or —CONH— and an alkanolamine as a semiconductor. In some cases, a metal layer such as copper formed on a wafer is prevented from being corroded.
- Patent Document 3 discloses a photoresist stripping composition containing a specific heterocyclic compound, a primary or secondary alkanolamine and a primary or secondary alkylamine, a polar organic solvent, a sugar alcohol, copper and a copper alloy.
- the photoresist can be peeled off without corroding.
- the conventional anticorrosive agent for copper or copper alloy has not always had sufficient anticorrosion properties.
- numerator are excellent in the anticorrosive property of copper or a copper alloy, when the board
- this deposit cannot be removed by ordinary washing, there is a problem that a separate deposit removal treatment is required.
- the present invention is excellent for copper or copper alloy wiring formed on a substrate without containing any of benzotriazoles and compounds having a thiol group in a copper or copper alloy wiring manufacturing process of a semiconductor substrate and an FPD substrate.
- An object of the present invention is to provide a photoresist stripping composition having anticorrosion properties and a photoresist stripping method using the composition.
- a photoresist remover composition containing cytosine and / or creatinine has excellent anticorrosive properties for copper or copper alloy wiring without inhibiting the photoresist peelability.
- the present invention has been completed.
- the present invention is a photoresist stripper composition containing cytosine and / or creatinine as a corrosion inhibitor for copper or a copper alloy together with a resist stripper.
- the present invention also includes (A) an alkanolamine, (B) a water-soluble organic solvent, and (C) water, and a photo containing cytosine and / or creatinine as an anticorrosive (D) for copper or a copper alloy. It is also a resist remover composition.
- the content of alkanolamine (A) is 1 to 50% by weight
- the content of water-soluble organic solvent (B) is 10 to 88.998% by weight.
- the water (C) content is 10 to 88.998% by weight, and the total content of the water-soluble organic solvent (B) and water (C) is 49.998 to 98.998.
- the content of the anticorrosive (D) is 0.002 to 1.0% by weight.
- the alkanolamine (A) is at least one selected from the group consisting of isopropanolamine, N-methylethanolamine, diethanolamine, N-methyldiethanolamine, and triethanolamine. You can.
- the water-soluble organic solvent (B) may be at least one selected from the group consisting of glycols, sulfoxides and amides.
- the present invention also provides a photoresist that is no longer necessary to prevent corrosion of the copper layer or the copper alloy layer when forming a metal wiring having a copper layer or a copper alloy layer on the substrate using the photoresist. It is also a photoresist stripping method for a metal wiring board having a copper layer or a copper alloy layer, in which stripping is removed using the photoresist stripping composition of the present invention.
- the present invention is not particularly distinguished.
- the present invention has the above configuration. (1) In the manufacturing process of copper or copper alloy wiring of a semiconductor substrate and an FPD substrate, it has excellent releasability from a photoresist. (2) Excellent corrosion resistance to copper or copper alloy wiring. (3) By using cytosine and / or creatinine, copper or a copper alloy that does not generate precipitates that are difficult to remove by ordinary cleaning as in the case of using a compound having a benzotriazole and a thiol group is used. An anticorrosive having excellent anticorrosive properties for wiring can be provided, and by providing a release agent using such an anticorrosive, excellent anticorrosion performance and resist stripping performance for copper or copper alloy wiring It is possible to provide a resist remover composition that exhibits both of the above.
- FIG. 1 The drawing substitute photograph which shows the remaining condition of the copper film of the board
- FIG. 1 The drawing substitute photograph which shows the remaining condition of the copper film of the board
- the photoresist remover composition of the present invention contains cytosine and / or creatinine as an anticorrosive agent for copper or a copper alloy together with the resist remover.
- the resist stripping agent is not particularly limited, and those using conventionally known stripping agent components can be applied.
- such a photoresist stripping composition contains (A) an alkanolamine, (B) a water-soluble organic solvent, and (C) water, and a copper or copper alloy corrosion inhibitor (D It is preferable to contain cytosine and / or creatinine as
- the alkanolamine (A) in the present invention may be only a primary alkanolamine, only a secondary alkanolamine, or only a tertiary alkanolamine, and any combination thereof, for example, a primary alkanolamine and a secondary alkanol.
- a combination with an amine a combination of a primary alkanolamine, a secondary alkanolamine and a tertiary alkanolamine, or the like may be used. Of these, only secondary alkanolamines, only tertiary alkanolamines, or combinations containing secondary alkanolamines and tertiary alkanolamines are preferred, and only tertiary alkanolamines are more preferred.
- alkanolamine (A) only 1 type may be used and 2 or more types may be used simultaneously.
- the primary alkanolamine (A) is not particularly limited, and examples thereof include monoethanolamine and isopropanolamine.
- Secondary alkanolamines are not particularly limited, and examples thereof include diethanolamine, N-methylethanolamine, N-ethylethanolamine and the like can be mentioned, and the tertiary alkanolamine is not particularly limited.
- Specific examples of preferred alkanolamines (A) in the present invention are isopropanolamine and N-methylethanolamine from the viewpoints of availability, releasability and anticorrosion against copper or copper alloys.
- Diethanolamine, N-methyldiethanolamine, triethanolamine, and any combination thereof are preferred. Furthermore, diethanolamine, N-methylethanolamine, N-methyldiethanolamine, triethanolamine, and any combination thereof are more preferable. N-methyldiethanolamine, triethanolamine, and combinations thereof are more preferred.
- the content of the alkanolamine (A) is preferably 1 to 50% by weight in the release agent composition. Within this range, the peelability is sufficiently good, and the viscosity is low and the handling is good. More preferably, it is 3 to 45% by weight.
- the water-soluble organic solvent (B) in the present invention is not particularly limited.
- acetone monoalcohols (for example, methanol, ethanol, etc.)
- glycols for example, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl) Ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol, propylene glycol methyl ether, dipropylene glycol, etc.
- pyrrolidones eg, N-methyl-2-pyrrolidone
- amides eg, N, N-dimethylacetamide, N , N-dimethylformamide
- nitriles eg, acetonitrile, etc.
- sulfoxides eg, dimethyl sulfoxide, etc.
- sulfo Emissions such, sulfolane
- glycols may be used alone or in combination of two or more.
- at least one selected from the group consisting of glycols, sulfoxides, and amides is preferable, and diethylene glycol monobutyl ether, propylene glycol, N, N-dimethylacetamide, diethylene glycol, and dimethyl sulfoxide are more preferable.
- the content of the water-soluble organic solvent (B) is preferably 10 to 88.998% by weight in the release agent composition. Within this range, the peelability of the photoresist and the corrosion resistance of copper or copper alloy are sufficiently satisfactorily exhibited. More preferably, it is 15 to 80% by weight.
- the release property of the photoresist is further improved, and even when the alkanolamine (A) and the water-soluble organic solvent (B) have a flash point, the release agent composition. It has the effect of eliminating the flash point as an object.
- water pure water used for semiconductor production is preferred.
- the content of water (C) in the present invention is preferably 10 to 88.998% by weight in the release agent composition.
- the content of water (C) is within the above range, the effect of improving the peelability of the photoresist is obtained, and the effect of eliminating the flash point is obtained.
- the concentration of other components may decrease, and the peelability of the photoresist may decrease. More preferably, it is 13 to 80% by weight, and further preferably 15 to 75% by weight.
- the total content of (B) and (C) is preferably 48.998 to 98.998% by weight, more preferably 54.998 to 94.998% by weight.
- Cytosine and / or creatinine is used as the anticorrosive agent (D) in the present invention.
- an anticorrosive agent (D) only cytosine may be sufficient, only creatinine may be sufficient, and the combination of cytosine and creatinine may be sufficient.
- cytosine and creatinine can also be used in the form of a salt (for example, hydrochloride, sulfate, sulfate hydrate, etc.).
- the content of the anticorrosive agent (D) is preferably 0.002 to 1.0% by weight in the release agent composition. When it is within this range, sufficient anticorrosion properties for copper or copper alloy can be obtained. When the content of the anticorrosive agent (D) is less than 0.002% by weight, the anticorrosive property for copper or copper alloy may not be sufficiently obtained. Although it is not necessarily inconvenient if the content of the anticorrosive agent (D) exceeds 1.0% by weight, it is uneconomical and may not be uniformly dissolved in the photoresist stripper composition. More preferably, it is 0.005 to 0.5% by weight.
- the total content of the alkanolamine (A), the water-soluble organic solvent (B), water (C) and the anticorrosive agent (D) can occupy 100% by weight in the composition.
- the photoresist stripper composition of the present invention has, in addition to the above components, a surfactant (for example, an alkylbenzene sulfonate, polyoxyethylene alkyl ether), an antifoaming agent (in the range not impairing the object of the present invention).
- a surfactant for example, an alkylbenzene sulfonate, polyoxyethylene alkyl ether
- an antifoaming agent in the range not impairing the object of the present invention.
- additives such as silicone oil
- the content of each additive depends on the type of the additive and is not generally determined.
- the content is preferably 0.001 to 5% by weight, more preferably 0.01 to 1% by weight.
- the photoresist remover composition of the present invention can be prepared by mixing the required amounts of the above components by a conventional method.
- the photoresist remover composition of the present invention can be used to remove a photoresist that is no longer necessary after an etching treatment of a metal wiring or the like in a manufacturing process of a semiconductor substrate or an FPD substrate.
- the photoresist remover composition of the present invention can be used by heating to room temperature, for example, 30 ° C. to 80 ° C.
- the time required for stripping depends on the degree of alteration of the photoresist, but is generally about 30 seconds to 10 minutes, for example. After the treatment, washing with water, air blow drying and the like can be performed as necessary.
- the method for removing a photoresist of a metal wiring board having a copper layer or a copper alloy layer using the photoresist remover composition of the present invention is a metal wiring having a copper layer or a copper alloy layer using a photoresist.
- the photoresist that is no longer needed is stripped and removed using the photoresist stripper composition of the present invention.
- the copper layer or the copper alloy layer is excessively corroded and the line width of the copper wiring or copper alloy wiring can be reduced, and the cross-sectional shape formed by etching is not impaired, and it is good.
- Metal wiring is formed.
- copper or copper alloy / two-layer wiring having a composition different from the upper layer, copper or copper alloy / molybten
- a cap metal such as titanium
- a cap metal / copper such as molybdenum or titanium / copper alloy / molybten
- a three-layer wiring of a cap metal such as titanium, or the like.
- a metal layer forming step including a step of forming a copper or copper alloy film on a substrate is performed, and then, after etching through a patterned photoresist, it becomes unnecessary.
- a multilayer metal wiring board having a copper layer or a copper alloy layer, in which the corrosion of the copper layer or the copper alloy layer is prevented, is produced by peeling and removing the photoresist using the photoresist remover composition of the present invention. be able to.
- Evaluation 1 Copper corrosion resistance A substrate on which a 50 nm thick copper film was formed on glass by sputtering was used as an evaluation object.
- the substrate was immersed in a photoresist remover composition adjusted to 50 ° C., and the treatment time was about 10 minutes or less, and the treatment was performed for 3 times that of 30 minutes. After the immersion treatment, the substrate was washed with water and air-dried. The remaining state of the copper film on the substrate was visually observed.
- This evaluation method can evaluate the result more directly than the method for obtaining the etching rate. As typical results, the results of Example 1 are shown in FIG. 1, the results of Comparative Example 11 are shown in FIG. 2, and the results of Comparative Example 19 are shown in FIG. FIG.
- FIG. 1 shows that the disappearance of the copper film was not observed.
- FIG. 2 shows the disappearance of the copper film in the lower left part of the substrate. In FIG. 3, the disappearance of the copper film is shown except for the upper left of the substrate.
- Judgment criteria Pass
- ⁇ The entire copper film remains (Failure)
- ⁇ It can be clearly seen that a part of the copper film has disappeared, but approximately 50% or more of the copper film remains.
- ⁇ Approximately 50% or more of the copper film has disappeared.
- Evaluation 2 Photoresist releasability A SiN film is formed on a glass substrate by CVD, a photoresist is formed, the photoresist is patterned by UV exposure and development, and then SiN is used with a fluorine-based gas.
- the substrate subjected to dry etching was evaluated. The substrate was immersed in a photoresist remover composition adjusted to 40 ° C. and treated for 30 seconds. After the immersion treatment, the substrate was washed with water and air-dried. The substrate was observed using an electron microscope to confirm the peeling of the photoresist. Judgment criteria (pass) ⁇ : No peeling residue (Failure) ⁇ : Peeling remaining
- evaluation 1 was performed, and evaluation 2 was performed for those having a determination of “ ⁇ ”.
- the photoresist stripper composition consisting only of BDG (Comparative Example 1) had a copper anticorrosion property of Evaluation 1 with a ⁇ evaluation, but a photoresist stripping property of Evaluation 2 with an x evaluation.
- Photoresist stripper composition (Comparative Examples 2 to 8) containing alkanolamine, water-soluble organic solvent and water but not containing cytosine or creatinine, alkanolamine, water-soluble organic solvent, water and A photoresist stripper composition containing no compound but containing cytosine or creatinine (Comparative Examples 9 to 11), an alkanolamine, a water-soluble organic solvent, water, and a compound described in Patent Document 2, The photoresist stripping compositions containing no cytosine or creatinine (Comparative Examples 12 to 16) had poor copper corrosion resistance as evaluated 1.
- a photoresist stripping composition (Comparative Examples 17 to 22) containing alkanolamine, a water-soluble organic solvent, water and a compound described in Patent Document 3 but containing neither cytosine nor creatinine was evaluated as described above. Copper corrosion resistance due to was bad.
- the photoresist stripping compositions of the present invention have very good copper anticorrosion properties in Evaluation 1, and the photoresist stripping properties in Evaluation 2 are the same in any composition. Also good results were obtained. From these results, it was found that the photoresist stripper containing cytosine or creatinine as a corrosion inhibitor significantly improved the corrosion resistance against copper and copper alloys as compared to the composition containing the conventional corrosion inhibitor. .
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- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
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KR1020117002294A KR101668126B1 (ko) | 2009-04-17 | 2010-03-24 | 포토레지스트 박리제 조성물 및 포토레지스트 박리 방법 |
JP2010550981A JP4725905B2 (ja) | 2009-04-17 | 2010-03-24 | フォトレジスト剥離剤組成物及びフォトレジスト剥離方法 |
CN201080002286.7A CN102124414B (zh) | 2009-04-17 | 2010-03-24 | 光致抗蚀剂剥离剂组合物以及光致抗蚀剂剥离方法 |
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Cited By (10)
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JP2012225959A (ja) * | 2011-04-15 | 2012-11-15 | Panasonic Corp | フォトレジスト用剥離液 |
WO2012160721A1 (fr) * | 2011-05-20 | 2012-11-29 | パナソニック株式会社 | Solution de décapage de résine photosensible, système de recyclage de solution de décapage et procédé de fonctionnement, et procédé pour recycler une solution de décapage |
JP2012242696A (ja) * | 2011-05-20 | 2012-12-10 | Panasonic Corp | フォトレジスト用剥離液 |
JP5575318B1 (ja) * | 2013-09-02 | 2014-08-20 | パナソニック株式会社 | レジスト剥離液 |
WO2014208088A1 (fr) * | 2013-06-27 | 2014-12-31 | パナソニックIpマネジメント株式会社 | Liquide décapant pour pellicules photorésistantes |
US20150007933A1 (en) * | 2013-06-21 | 2015-01-08 | Sanmina Corporation | Method of forming a laminate structure having a plated through-hole using a removable cover layer |
JP2015011356A (ja) * | 2014-07-18 | 2015-01-19 | パナソニックIpマネジメント株式会社 | フォトレジスト用剥離液 |
JP2015113379A (ja) * | 2013-12-10 | 2015-06-22 | 花王株式会社 | 半田フラックス残渣除去用洗浄剤組成物 |
WO2017065154A1 (fr) * | 2015-10-13 | 2017-04-20 | ナガセケムテックス株式会社 | Solution de retrait de photorésine |
JPWO2017208767A1 (ja) * | 2016-06-03 | 2019-03-28 | 富士フイルム株式会社 | 処理液、基板洗浄方法およびレジストの除去方法 |
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TWI518467B (zh) * | 2013-11-15 | 2016-01-21 | 達興材料股份有限公司 | 光阻脫除劑和電子元件及其製造方法 |
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JPWO2017208767A1 (ja) * | 2016-06-03 | 2019-03-28 | 富士フイルム株式会社 | 処理液、基板洗浄方法およびレジストの除去方法 |
JP2021052186A (ja) * | 2016-06-03 | 2021-04-01 | 富士フイルム株式会社 | 処理液、基板洗浄方法およびレジストの除去方法 |
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Also Published As
Publication number | Publication date |
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TW201042403A (en) | 2010-12-01 |
CN102124414A (zh) | 2011-07-13 |
JP4725905B2 (ja) | 2011-07-13 |
TWI617901B (zh) | 2018-03-11 |
KR20120000046A (ko) | 2012-01-03 |
JPWO2010119753A1 (ja) | 2012-10-22 |
KR101668126B1 (ko) | 2016-10-20 |
CN102124414B (zh) | 2014-04-02 |
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