TW200304585A - Thinner composition for removing photosensitive resin - Google Patents
Thinner composition for removing photosensitive resin Download PDFInfo
- Publication number
- TW200304585A TW200304585A TW092107202A TW92107202A TW200304585A TW 200304585 A TW200304585 A TW 200304585A TW 092107202 A TW092107202 A TW 092107202A TW 92107202 A TW92107202 A TW 92107202A TW 200304585 A TW200304585 A TW 200304585A
- Authority
- TW
- Taiwan
- Prior art keywords
- propylene glycol
- weight
- ether acetate
- diluent composition
- substrate
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 239000011347 resin Substances 0.000 title claims abstract description 29
- 229920005989 resin Polymers 0.000 title claims abstract description 29
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 44
- -1 polyethylene Polymers 0.000 claims abstract description 15
- 239000004065 semiconductor Substances 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000004698 Polyethylene Substances 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 9
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 229920000573 polyethylene Polymers 0.000 claims abstract description 9
- 150000001346 alkyl aryl ethers Chemical class 0.000 claims abstract description 8
- 239000003085 diluting agent Substances 0.000 claims description 57
- 239000000126 substance Substances 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 8
- 150000003997 cyclic ketones Chemical class 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 3
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 claims description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 claims description 2
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 claims description 2
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 claims 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 30
- 229960004063 propylene glycol Drugs 0.000 abstract 1
- 235000013772 propylene glycol Nutrition 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 53
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 8
- 229940116333 ethyl lactate Drugs 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 238000001259 photo etching Methods 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- HKLAIJDFTUAIKX-UHFFFAOYSA-N C(C)(=O)OC(COC1=CC=CC=2C3=CC=CC=C3CC12)C Chemical compound C(C)(=O)OC(COC1=CC=CC=2C3=CC=CC=C3CC12)C HKLAIJDFTUAIKX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000700159 Rattus Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WDFZWSZNOFELJY-OLQVQODUSA-N (1R,6S)-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound C1=CC=C[C@H]2O[C@H]21 WDFZWSZNOFELJY-OLQVQODUSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- 206010000234 Abortion spontaneous Diseases 0.000 description 1
- YZXOZEBOZMDHKX-UHFFFAOYSA-N C(C)(=O)OCCOC1=CC=CC=2C3=CC=CC=C3CC12 Chemical compound C(C)(=O)OCCOC1=CC=CC=2C3=CC=CC=C3CC12 YZXOZEBOZMDHKX-UHFFFAOYSA-N 0.000 description 1
- GUULDSPVKPKYMQ-UHFFFAOYSA-N C(CCCCC(C)C)C=1C(=C(C=CC1)O)CC1=CC=CC=C1 Chemical compound C(CCCCC(C)C)C=1C(=C(C=CC1)O)CC1=CC=CC=C1 GUULDSPVKPKYMQ-UHFFFAOYSA-N 0.000 description 1
- 101100310948 Caenorhabditis elegans srd-1 gene Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000283073 Equus caballus Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical class CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000009429 distress Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- 208000015994 miscarriage Diseases 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000005404 monopole Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- LIXVMPBOGDCSRM-UHFFFAOYSA-N nonylbenzene Chemical compound CCCCCCCCCC1=CC=CC=C1 LIXVMPBOGDCSRM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 208000000995 spontaneous abortion Diseases 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D9/00—Chemical paint or ink removers
- C09D9/005—Chemical paint or ink removers containing organic 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
- 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
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions 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
- C11D3/43—Solvents
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
-
- 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
-
- 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
-
- C11D2111/22—
Abstract
Description
200304585 炊、發明說明 【發明所屬之技術領域】 本發明係關於一種可於半導體裝置製造過程中用來去 除光敏樹脂的稀釋劑組合物。詳言之，本發明係關於一種 於光蝕刻製程中用來去除仍殘留在基材邊緣及背面之光敏 樹脂的稀釋劑組合物。 【先前技術】 光蝕刻製程是一種在基材上覆鍍一層光敏薄膜、於基 材上晝出設計圖案並蝕刻該圖案用以製造半導體裝置及液 晶顯示裝置以建構一電路的製程。 此光蝕刻製程包括下列步驟： a) 一覆鍍步驟，其係可在基材上覆鍍一層均勻 的光敏樹脂組合物； b) 一軟烘烤步驟，其係可將揮發性溶劑自該覆 鍍之光敏樹脂薄膜上揮發，藉以使該覆鍍之 光敏樹脂薄膜黏附在基材表面； c) 一曝光步驟，其係以諸如紫外光之類的光源 將基材曝光，並將光罩圖案轉移至基材上藉 以於光罩上重複畫出一電路圖案； d) 一顯影步驟，藉以選擇性去除因曝光後以顯 影溶液顯影所致之具不同物理性質（如，溶解 度）的部分； e) 一硬烘烤步驟，其係可使基材上剩餘之光敏 4 200304585 f) g) 藉此 體積體電 在電路圖 上的顆粒 問題，因 在光 並旋轉該 佈，並藉 光敏樹脂 形成一光 材轉移過 或是在曝 這些 的製造效 射喷嘴， 除這些不 稀釋 來決定。 可以多快 樹脂薄膜可牢牢地黏附在基材表面； 一蝕刻步驟，其係可依據圖案來蝕刻基材； 及 一剝除步驟，藉以去除基材上殘存之不需要 的光敏樹脂薄膜。 光蝕刻製程可於基材上形成許多用以建構一半導 路之微電路。在此製程中，很重要的一點是不要 的小間隙中併入任何外來物質顆粒。殘存在基材 可能會在後續的蝕刻或離子植入製程中導致許多 而降低整體製程產率。 餘刻製程中，提供一光敏樹脂組合物於基材上， 基材，藉離心力使該光敏樹脂組合物被均勻地塗 以形成一球形的光敏物質。在此旋塗過程中，該 組合物係藉由離心力被驅向基材邊緣及背面，並 敏物質之球形小顆粒。這些球形顆粒可能會在基 程中剝落，導致製程設備中出現此小顆粒物質； 光過程中造成光線無法聚焦。 不欲求的光敏物質會污染設備並降低半導體裝置 能。因此，可藉由一安裝於基材邊緣及背面的注 注入一包含有機溶劑組成之稀釋劑組合物，來移 欲求的光敏物質。 劑組合物的效率係由其溶解速率、揮發性等因素 一稀釋劑組合物的溶解速率係指該稀釋劑組合物 、多有效地溶解一光敏樹脂的能力，且這點是非 200304585 常重要的。至於沖洗基材邊緣這件事，只有在溶解速率係 恰當的情況下，方有可能對基材進行溫和的表面處理。如 果溶解速率過高，可能會導致光敏薄膜層受到攻擊。但如 果溶解速率太低，則可能導致光敏薄膜層溶解不完全，造 成殘存的光敏薄層懸浮於基材上。以目前高集成及高密度 半導體積體電路基材放大的趨勢來看，以旋塗機進行沖洗 之製程，勢必需要降低旋轉速率。在低速清洗製程中，如 果溶解速率不足以配合注射速率，稀釋劑溶液可能會被撞 掉’因此將會需要用到大量的稀釋劑溶液。因此，在低速 凊洗製程中’需要一具有較傳統高速清洗製程更強之溶解 速率的稀釋劑組合物。 此稀釋劑組合物需能輕易地揮發，且在去除了光敏樹 脂膜後不應仍然殘留在基材表面。如果稀釋劑組合物的揮 發性太低致使稀釋劑仍殘留在基材表面，其將成為下一製 程步驟（特別是蝕刻步驟）的污染源，並因而降低半導體裝 置的品質。相反的，如果稀釋劑組合物的揮發性太高，基 材上所塗佈光敏樹脂層的厚度變化可能很大，揮發的稀釋 劑可能會污染工作環境《此將成為導致諸如殘存的光敏薄 層懸浮於基材上或光敏薄膜層受到攻擊的主要原因，進而 造成半導體裝置品質下降。 習知的稀釋劑組合物如下示。 曰本專利公告號Sho 63-69563揭示了 一種可去除不 欲求光敏薄層的方法，其係藉由讓稀釋劑接觸一基材之_ 邊緣的上部、一邊緣部及一邊緣的背部來達成。此專利使 6 200304585200304585 Cooking and invention description [Technical field to which the invention belongs] The present invention relates to a diluent composition that can be used to remove photosensitive resin in the manufacturing process of semiconductor devices. Specifically, the present invention relates to a diluent composition for removing a photosensitive resin remaining on the edge and back of a substrate in a photolithography process. [Prior technology] A photo-etching process is a process in which a photosensitive film is plated on a substrate, a design pattern is formed on the substrate, and the pattern is etched to manufacture a semiconductor device and a liquid crystal display device to construct a circuit. This photoetching process includes the following steps: a) a plating step, which can be plated with a uniform photosensitive resin composition on the substrate; b) a soft baking step, which can remove volatile solvents from the coating The plated photosensitive resin film is volatilized so that the plated photosensitive resin film adheres to the surface of the substrate; c) an exposure step, which exposes the substrate with a light source such as ultraviolet light, and transfers the mask pattern To the substrate to repeatedly draw a circuit pattern on the photomask; d) a developing step to selectively remove parts with different physical properties (such as solubility) caused by developing with a developing solution after exposure; e) A hard bake step, which can make the remaining light on the substrate 4 200304585 f) g) the problem of particle size on the circuit diagram due to the volume of electricity, because the cloth is rotated by light, and a light material is formed by the photosensitive resin Transfer or expose these manufacturing nozzles, except that these are not diluted to determine. How fast the resin film can be firmly adhered to the surface of the substrate; an etching step which can etch the substrate according to a pattern; and a stripping step to remove the unwanted photosensitive resin film remaining on the substrate. The photo-etching process can form a number of microcircuits on the substrate to build half the path. In this process, it is important that any foreign material particles are not incorporated into the small gaps. Residual substrates can cause many in subsequent etching or ion implantation processes and reduce overall process yield. In the remaining process, a photosensitive resin composition is provided on a substrate, and the substrate is uniformly coated by centrifugal force to form a spherical photosensitive substance. In this spin coating process, the composition is driven to the edges and back of the substrate by centrifugal force, and small spherical particles of sensitive material. These spherical particles may peel off during the process, causing this small particle to appear in the process equipment; the light cannot be focused during the light process. Unwanted photosensitive materials can contaminate equipment and reduce semiconductor device performance. Therefore, a desired photosensitive material can be transferred by injecting a diluent composition containing an organic solvent by injection molding mounted on the edge and back of the substrate. The efficiency of a diluent composition is determined by its dissolution rate, volatility, and other factors. The dissolution rate of a diluent composition refers to the ability of the diluent composition to effectively dissolve a photosensitive resin, and this is often important. As for rinsing the edges of the substrate, it is only possible to apply mild surface treatment to the substrate if the dissolution rate is appropriate. If the dissolution rate is too high, the photosensitive film layer may be attacked. However, if the dissolution rate is too low, it may result in incomplete dissolution of the photosensitive thin film layer, resulting in the remaining photosensitive thin layer being suspended on the substrate. Judging from the current trend of enlargement of high-integration and high-density semiconductor integrated circuit substrates, the process of rinsing with a spin coater is bound to reduce the rotation rate. In the low-speed cleaning process, if the dissolution rate is not sufficient to match the injection rate, the diluent solution may be knocked out 'and therefore a large amount of diluent solution will be required. Therefore, in the low-speed decanting process, a diluent composition is required which has a stronger dissolution rate than the conventional high-speed washing process. The diluent composition needs to be easily volatile and should not remain on the surface of the substrate after the photosensitive resin film is removed. If the volatility of the diluent composition is too low so that the diluent remains on the surface of the substrate, it will become a source of contamination in the next process step (especially the etching step) and thus degrade the quality of the semiconductor device. On the contrary, if the volatility of the diluent composition is too high, the thickness of the photosensitive resin layer applied on the substrate may vary greatly, and the volatile diluent may contaminate the working environment. The main reason for being suspended on the substrate or being attacked by the photosensitive thin film layer is to reduce the quality of the semiconductor device. The conventional diluent composition is shown below. Japanese Patent Publication No. Sho 63-69563 discloses a method for removing an undesired photosensitive thin layer by contacting a thinner with an upper part of an edge of an substrate, an edge part, and a back of the edge. This patent makes 6 200304585
用諸如溶纖劑（cello solve)、2-乙氧乙基醋酸酯、聚乙二醇 醚、及丙二醇醚醋酸酯之類的醚類或醚之醋酸酯；諸如丙 ’、甲乙酮、甲異丁酮及環己酮之類的酮類；或諸如乳酸 甲醋、乳酸乙酯、乙酸甲酯、乙酸乙酯及乙酸丁酯之類的 醋類作為稀釋劑。且曰本專利公告號Hei-4-49938揭示以 丙二醇單曱基醚醋酸酯（PGMEA)作為稀釋劑。且，且日本 專利公告號Hei-4-42523揭示使用丙酸烷基烷氧酯作為稀 釋劑的方法。 這些習知的稀釋劑大半都使用一種單一溶劑，例如乙 二醇單曱基醚醋酸酯（EGMEA)、丙二醇單曱基醚醋酸酯 (PGMEA)及乳酸乙酯（el)。這些稀釋劑溶劑具有如下之缺 點。 亦即’雖然乙一醇卓曱基醋酸醋具有極優異的溶解 速率’但其極易揮發並易著火，且會誘發低白血球症及流 產且’乳酸乙酯黏度極高且溶解速率低，因此單獨使用 時無法提供一充分的清洗效果。且諸如丙_及曱乙酮之類 的溶劑因燃點低，係屬危險物品。Use of ethers such as cello solve, 2-ethoxyethyl acetate, polyethylene glycol ether, and propylene glycol ether acetate or ether acetate; such as propyl ', methyl ethyl ketone, methyl isobutyl Ketones such as ketones and cyclohexanone; or vinegars such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, and butyl acetate as diluents. Furthermore, Japanese Patent Publication No. Hei-4-49938 discloses that propylene glycol monofluorenyl ether acetate (PGMEA) is used as a diluent. And, Japanese Patent Publication No. Hei-4-42523 discloses a method using an alkyl alkoxy propionate as a diluent. Most of these conventional diluents use a single solvent, such as ethylene glycol monofluorenyl ether acetate (EGMEA), propylene glycol monofluorenyl ether acetate (PGMEA), and ethyl lactate (el). These diluent solvents have the following disadvantages. That is, 'Although Glycol Acetyl Acetate has a very good dissolution rate', it is very volatile and easily catches fire, and it can induce hypoleukemia and miscarriage. Does not provide a sufficient cleaning effect during use. And solvents such as propane and acetophenone are dangerous goods because of their low flash point.
為了解決上述問題，展開了一連串結合前技單一溶劑 之研發工作。日本專利公告號Hei-4-1307i5据-、， A J 询不以一種 包含丙嗣酸烷基酯及曱乙酮之混合溶劑作 P馬稀釋劑的方 法。日本專利公告號Hei-7-1465 62揭示一插山^ 裡由丙二醇烷 暴峻、乙酸丁酯及乳酸乙酯所組成之混合物 稀釋劑組合物，或是一種由乙酸丁醋、乳酸己輯及：成的 烧基崎醋酸酯所組成之混合物所製作而成一醇 π稀釋劑組合 7 200304585 物。日本專利公告號 Hei-7-1 6 000 8揭示一種由丙二醇烷 基醚丙酸酯及甲乙酮所組成之混合物所製作而成的稀釋劑 組合物，或是一種由丙二醇烷基醚丙酸酯及乙酸丁酯所組 成之混合物所製作而成的稀釋劑組合物。美國專利 49 8 3 490使用一種包含乳酸乙酯及甲乙酮之混合物作為一 種稀釋劑組合物。In order to solve the above problems, a series of research and development work combining a single solvent with the previous technology has been launched. According to Japanese Patent Publication No. Hei-4-1307i5, A, J, A, B, and A, have not been proposed to use a mixed solvent containing an alkyl propionate and ethyl ethyl ketone as a diluent for P equine. Japanese Patent Publication No. Hei-7-1465 62 discloses a diluent composition consisting of propylene glycol, butyl acetate and ethyl lactate, or a mixture of butyl acetate, lactic acid and : A mixture of yakizaki acetate made of monool π diluent combination 7 200304585. Japanese Patent Publication No. Hei-7-1 6 000 8 discloses a diluent composition made of a mixture of propylene glycol alkyl ether propionate and methyl ethyl ketone, or a propylene glycol alkyl ether propionate and A diluent composition made from a mixture of butyl acetate. U.S. Patent No. 49 8 3 490 uses a mixture containing ethyl lactate and methyl ethyl ketone as a diluent composition.
但是，將這些溶劑混合物用於半導體裝置及液晶顯示 裝置亦有一些限制。舉例來說，包含丙酮酸烷基酯及曱乙 酮的溶劑混合物並無法將1，2-二疊氮蕃骶（其係為光敏樹 脂薄層的主要成分）完全溶解。當以一揮發性相當高的溶 劑混合物（如，丙二醇烷基醚丙酸酯及乙酸丁酯）進行清洗 時，將造成光敏薄膜厚度將有明顯變化。當使用一揮發性 低的溶劑混合物（如，乳酸乙酯及甲乙酮）進行清洗時，基 材邊緣的清洗力降會下降。特別是，諸如丙酮酸甲酯及丙 酮酸乙酯乃是習知之於長期使用後會侵蝕連接於一旋塗機 之廢液桶金屬部分的溶劑。However, there are some limitations to using these solvent mixtures in semiconductor devices and liquid crystal display devices. For example, a solvent mixture containing alkyl pyruvate and acetophenone does not completely dissolve 1,2-diazide carbamidine, which is the main component of a thin layer of photosensitive resin. When cleaning with a relatively volatile solvent mixture (such as propylene glycol alkyl ether propionate and butyl acetate), the thickness of the photosensitive film will change significantly. When cleaning with a less volatile solvent mixture (such as ethyl lactate and methyl ethyl ketone), the cleaning power of the edge of the substrate decreases. In particular, solvents such as methyl pyruvate and ethyl propionate are solvents which are known to erode the metal part of a waste tank connected to a spin coater after long-term use.
雖然已知相較於習知的乙二醇單甲醚來說，丙二醇單 曱醚可增加感光樹脂的感光速率（換言之，其可將光活化 的物質溶解的非常好），但其卻會發出不愉快的氣味並造 成生物上的困擾。為解決這個問題，曾有人試圖將其與丙 二醇單曱醚醋酸酯混合後來使用（美國專利第4,983,490 號）。但是，仍然無法完全消除該不愉快的氣味。 【内容】 8 200304585 本發明目的之一是要提供一用來均勻地去除半導體積 體電路裝置及液晶顯示裝置之基材邊緣及背面之光敏溶液 的稀釋劑組合物。 本發明的另一目的是提供一種可去除光敏樹脂的稀釋 劑組合物’其係可防止未移除的光敏樹脂因溶解力不足而 於晶圓末端凝集。 本發明的另一目的是提供一可去除光敏樹脂之稀釋劑 組合物’其係可完全去除去基材表面上的殘餘物質。 本發明的另一目的是提供一可去除光敏樹脂之稀釋劑 組合物’其係對光敏樹脂具有優異的溶解能力及優異的揮 發性。 本發明之再一目的係提供一可去除光敏樹脂之稀釋劑 組合物’其係對色素光敏樹脂具有良好的溶解力。 本發明的再一目的是提供一可去除光敏樹脂之稀釋劑 組合物’其係在與光敏溶液接觸時具有優異的可散佈性， 藉由注入該稀釋劑組合物可有效地去除一晶圓上的光敏樹 脂組合物並獲得一柔軟表面。 本發明之再一目的係提供一可去除光敏樹脂之稀釋劑 組合物’其係不對人體有毒害，不會散發出不愉快的氣味 且不會腐姓金屬，故可安全地使用。 為達到上述這些目的，本發明提供一種於半導體裝置 及液晶顯不裝置製造過程中用來清洗的稀釋劑組合物，其 至少包含： a)丙二醇單烷基醚醋酸酯； 9 200304585 b) 環酮； c) 聚乙烯為底之縮聚物；及 d) 氟化之丙烯酸共聚物。 較佳是，該稀釋劑組合物至少包含： a) 1至80份重量之丙二醇單烷基醚醋酸酯； b) 1至99份重量之環酮； c) 0.001至1份重量之聚乙烯為底之縮聚物；及Although it is known that propylene glycol monomethyl ether can increase the speed of photosensitive resin (in other words, it can dissolve light-activated substances very well) compared to the conventional ethylene glycol monomethyl ether, it will emit Unpleasant smell and cause biological distress. To solve this problem, there have been attempts to mix it with propylene glycol monomethyl ether acetate and use it later (U.S. Patent No. 4,983,490). However, the unpleasant odor cannot be completely eliminated. [Content] 8 200304585 One object of the present invention is to provide a diluent composition for uniformly removing a photosensitive solution on the edges and back of a substrate of a semiconductor integrated circuit device and a liquid crystal display device. Another object of the present invention is to provide a thinner composition for removing photosensitive resin, which can prevent the unremoved photosensitive resin from aggregating at the wafer end due to insufficient solvent power. Another object of the present invention is to provide a diluent composition ' for removing photosensitive resin, which is capable of completely removing residual substances on the surface of a substrate. Another object of the present invention is to provide a diluent composition 'capable of removing the photosensitive resin, which has excellent solubility and excellent volatility for the photosensitive resin. Still another object of the present invention is to provide a diluent composition 'capable of removing a photosensitive resin, which has a good dissolving power for a pigment photosensitive resin. Another object of the present invention is to provide a thinner composition capable of removing photosensitive resin, which has excellent dispersibility when in contact with a photosensitive solution, and can be effectively removed from a wafer by injecting the thinner composition The photosensitive resin composition and obtain a soft surface. Still another object of the present invention is to provide a thinner composition for removing photosensitive resin, which is not harmful to human body, does not emit unpleasant odor, and does not rot metal, so it can be used safely. In order to achieve the above objects, the present invention provides a diluent composition for cleaning in the manufacturing process of semiconductor devices and liquid crystal display devices, which at least comprises: a) propylene glycol monoalkyl ether acetate; 9 200304585 b) cyclic ketone C) a polyethylene-based polycondensate; and d) a fluorinated acrylic copolymer. Preferably, the diluent composition comprises at least: a) 1 to 80 parts by weight of propylene glycol monoalkyl ether acetate; b) 1 to 99 parts by weight of cyclic ketone; c) 0.001 to 1 part by weight of polyethylene is Polycondensate on the bottom; and
d) 0.001至1份重量之氟化之丙烯酸共聚物。 【實施方式】 本發明詳細說明如下： 本發明係基於當上述四種組成的比例恰當時，所提申 之一種可去除光敏溶液之稀釋劑組合物。 在本發明一組合物中，所使用之丙二醇單烷基醚醋酸 酯、環丙酮及烷基側酸酯均需具有半導體級之純度。或是， 亦可使用再經0.1微米過濾之VLSI級溶液。d) 0.001 to 1 part by weight of a fluorinated acrylic copolymer. [Embodiment] The present invention is described in detail as follows: The present invention is based on a thinner composition capable of removing a photosensitive solution when the ratio of the above four compositions is appropriate. In a composition of the present invention, the propylene glycol monoalkyl ether acetate, cycloacetone, and alkyl pendant esters all need to have semiconductor-grade purity. Alternatively, a VLSI-grade solution filtered through 0.1 micron can also be used.
在丙二醇單燒基鍵g皆酸酯中，該烧基可以具1至5個 碳原子。舉例來說，可使用丙二醇單甲基醚醋酸酯、丙二 醇單乙基醚醋酸酯、丙二醇單丙基醚醋酸酯、丙二醇單丁 基醚醋酸酯等。 對環酮而言，可使用環戊酮、環己酮、環庚酮等。 該聚乙烯為底之縮聚物的功能是作為一種非離子性的 表面活性劑。舉例來說，可用烷基苯酚之聚乙烯縮聚物。 詳言之，係藉由將1莫耳烷基苯酚（其係具有直鏈或支鏈之 10 200304585In the propylene glycol monoalkyl group g all esters, the alkyl group may have 1 to 5 carbon atoms. For example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, and the like can be used. For cyclic ketones, cyclopentanone, cyclohexanone, cycloheptanone, and the like can be used. The polyethylene-based polycondensate functions as a nonionic surfactant. For example, polyethylene polycondensates of alkylphenols can be used. In detail, by using 1 mol alkylphenol (which has a linear or branched chain 10 200304585
CerC〗2烷基團）與5至25莫耳的環氧乙烷縮 物。該烷基苯酚可衍生自聚丙烯、聚二異， 聚壬嫦。這類化合物的例子包括由1莫耳苯 氣乙统縮聚而成之壬基苯紛；由1莫耳苯齡 乙烷縮聚而成之十二烷基苯酚；由丨莫耳笨 氧乙烷縮聚而成之二異辛基笨酚。 這些化合物極易溶於水及其他溶劑中 接觸到光敏樹脂時降低溶解度差異。對已 說，有東南化學產業非離子性單普系列表 這類表面活性劑的含量低於〇 · 〇〇 i份重量， 的揮發性及清洗能力將顯箸下降。此外，如 份重量時’將會產生過量的泡沫。 該氟化之丙烯酸共聚物在水及其他溶 解度。商業產品有大日本公司及化學物所4 R-08。較佳是，其係以〇·001至1份重量混 物含量低於〇·〇οι份重量，溶解光敏溶液 降《如果其用量超過1份重量時，雖然介 張力下降導致去除能力獲得改善，但是會產 致使流動感應器將無法正常運作。 已知空氣中的丙二醇單曱醚醋酸酯對 此外，以代謝觀點來看亦很安全，因其於 解成丙二醇及醇類。對老鼠而言，致死之€ 鼠）為每公斤8.5克’且其會被迅速水解。其 沸點=146°C ;燃點=42°C (以密閉法測定） 聚而成之一縮聚 T烯、聚辛烯或 盼與9 · 5莫耳環 與12莫耳環氧 紛與15莫耳環 ’並可於稀釋劑 有的商業產品來 面活性劑。如果 基材末端稀釋劑 果其用量超過1 劑中有極高的溶 L 產之 Megapace 合。如果此共聚 的能力將顯著下 面處因動態介面 生過量的泡沫， 人類並無危害。 人體内可迅速分 1服劑量LD5。（老 .物理性質如下： ;黏度（25°C下） 200304585 - 1.17cps;表面張力=每平方公分26達因。 己酮為一種可溶解數種樹脂之環酮。詳言之，其可溶 解極難溶的色素光敏樹脂。 乙酸丁酯為一種具有極低表面張力、揮發性極高的乙 酸烧基酯，並且只要添加少量即可展現出優異的介面性質。 對氟化之丙烯酸共聚物而言，較佳是使用具下列物理 特性之共聚物：重量平均分子量介於3〇〇〇至1〇〇〇〇間；燃 點200 c (以開放式法測定）；比重為每毫升1 10克（25。〇）； 黏度為2100 cst ( 20 ec )且在乳酸乙酯中之表面張力為 24.0mN/m。一般來說，其係先以乳酸乙酯稀釋後才使用。 本發明組合上述四種組成並以光敏溶液旋塗機覆鍍一 層光敏樹脂。之後，藉由浸泡或喷灑稀釋劑組合物來移除 基材邊緣及側面的光敏物質球形顆粒。可視光敏樹脂的種 類、膜層厚度等因素來控制稀釋劑用量在介於5至iOO毫 升/分鐘間。注入稀釋劑後，可以光蝕刻製程來形成一微電 路。 以下’本發明將藉由實施例及比較實施例作詳細說明。 但是’下列實施例僅係為了闡述本發明之用，本發明範疇 並不僅限於此。 實施例 用於實施例中的基材樣品係以下列方式製備。 於兩種包含過氧化氫及硫酸之溶液令沖洗一 8英吋之 氧化梦基材’分別浸泡5分鐘，接續以超純水沖洗❶此過 12 200304585 程係於特別設計的潔淨設備上進行。之後，於旋乾機 (VERTEQ ;型號SRD 1 800-6)中將基材乾燥。之後，以一旋 塗機（韓國半導體科技；型號EBr TRACK)於基材上鍍上一 層光敏層。 對旋塗製程而言，在基材中心滴入1〇毫升的光敏薄層 組合物。之後，以旋塗機於500 rpm速度旋塗3秒將該光敏 薄層組合物散佈開來。之後，以2〇〇〇至4〇〇〇 rpm的速度旋 轉以控制薄層的厚度。旋轉約20至30秒。CerC 2 alkyl group) and 5 to 25 moles of ethylene oxide condensate. The alkylphenol can be derived from polypropylene, polydiiso, and polynonane. Examples of such compounds include nonylbenzene which is formed by polycondensation of 1 mole of benzene gas; dodecylphenol formed by condensation of 1 mole of benzene age ethane; polycondensation of mole benzene oxide Is the second isooctyl benzyl phenol. These compounds are very soluble in water and other solvents, reducing solubility differences when exposed to photosensitive resins. It has been said that there is a non-ionic single-supply series in the Southeast Chemical Industry. The content of such surfactants is less than 0.001 parts by weight, and the volatility and cleaning ability will be significantly reduced. In addition, 'parts by weight' will cause excessive foaming. The fluorinated acrylic copolymer is soluble in water and other solvents. Commercial products include Dainippon Corporation and Chemical Institute 4 R-08. Preferably, it is from 0.001 to 1 part by weight and the content of the mixed solution is lower than 0.000 parts by weight, and the photosensitive solution is dissolved. However, it will cause the flow sensor to malfunction. Propylene glycol monomethyl ether acetate in the air is also known to be safe from a metabolic point of view because it is decomposed into propylene glycol and alcohols. For rats, the lethal rat) is 8.5 grams per kilogram 'and it is rapidly hydrolyzed. Its boiling point = 146 ° C; ignition point = 42 ° C (measured by closed method), one of polycondensation Tene, polyoctene or Pan and 9 · 5 Mo earrings and 12 Mole epoxy and 15 Mo earrings' Surfactants can be used in commercial products of diluents. If the substrate end diluent is used in an amount exceeding 1 part, there is a very high solubility of Megapace. If this ability to copolymerize would be significant below, there would be too much foam due to the dynamic interface, and there would be no harm to humans. The human body can be divided into 1 dose of LD5 quickly. (Old. The physical properties are as follows:; viscosity (at 25 ° C) 200304585-1.17cps; surface tension = 26 dyne per square centimeter. Hexanone is a cyclic ketone that can dissolve several resins. In particular, it can dissolve Extremely poorly soluble pigment photosensitive resin. Butyl acetate is a kind of ethyl acetate with extremely low surface tension and high volatility, and exhibits excellent interface properties with a small amount of addition. For fluorinated acrylic copolymers, In other words, it is preferable to use a copolymer having the following physical characteristics: a weight average molecular weight between 3,000 and 10,000; a flash point of 200 c (determined by an open method); and a specific gravity of 110 g per milliliter ( 25.0); The viscosity is 2100 cst (20 ec) and the surface tension in ethyl lactate is 24.0 mN / m. Generally speaking, it is used after diluted with ethyl lactate. The present invention combines the above four types Make up and coat a layer of photosensitive resin with a photosensitive solution spin coater. After that, remove the spherical particles of photosensitive material at the edges and sides of the substrate by dipping or spraying the diluent composition. The type of photosensitive resin, film thickness, etc Factors to control The amount of release agent is between 5 and 100 ml / min. After injecting the diluent, a photo-etching process can be used to form a microcircuit. The following 'The present invention will be described in detail through examples and comparative examples. But' the following implementation The examples are only for the purpose of illustrating the present invention, and the scope of the present invention is not limited to these. Examples The substrate samples used in the examples were prepared in the following manner. Rinse 8 with two solutions containing hydrogen peroxide and sulfuric acid. The inches of oxidized dream substrates were soaked for 5 minutes, followed by rinsing with ultrapure water. This process was performed on a specially designed clean equipment after 12 200304585. After that, it was processed in a spin dryer (VERTEQ; model SRD 1 800-6). ), The substrate is dried. Then, a spin coater (Korea Semiconductor Technology; model EBr TRACK) is used to plate a photosensitive layer on the substrate. For the spin coating process, 10 ml of Photosensitive thin-layer composition. Then, spin-coat the spin-coater at 500 rpm for 3 seconds to spread the photosensitive thin-layer composition. After that, spin at a speed of 2,000 to 4,000 rpm to control the thickness. The thickness of the layer. About 20 to 30 seconds.
實施例I-4及比鲂實施例U 表1 ·_^釋劑組合物 ( 類別 :重量份數） 實施例1 實施例2 實施例3 比較實施 例1 比較實施 例2 PGMEA 40 40 40 100 30 環戊酮 - 60 - - - 組风 環己酮 60 - 60 - 50 NP-1019 0.01 - - - OIM015 - 0.01 0.01 - 0.01 R-08 0.01 0.01 0.01 0.01 - 在表1中： PGMEA代表丙二醇單甲基醚醋酸酯； NP-109是購自東南化學產業，型號M〇nop〇i N〇_ 1019’其係藉由在^莫耳的壬基苯酚中縮聚9莫耳環氧乙 烷所製備而成。 13 200304585 OP-1015是購自東南化學產業’型號Monopol NO-1015，其係藉由在1莫耳的壬基苯盼中縮聚5莫耳環氧乙 烷所製備而成。 R-08是購自大日本公司及化學物’型號R-08，其係 為一種氟化的丙烯酸共聚物。Example I-4 and Comparative Example U Table 1 __release agent composition (type: parts by weight) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 PGMEA 40 40 40 100 30 Cyclopentanone-60---group wind cyclohexanone 60-60-50 NP-1019 0.01---OIM015-0.01 0.01-0.01 R-08 0.01 0.01 0.01 0.01-In Table 1: PGMEA stands for propylene glycol monomethyl Ethyl acetate; NP-109 was purchased from Southeast Chemical Industry, model No. Monopoi No. 1019 ', which was prepared by polycondensing 9 moles of ethylene oxide in non-molecular phenol. 13 200304585 OP-1015 was purchased from Southeast Chemical Industry's model Monopol NO-1015, which was prepared by polycondensing 5 moles of ethylene oxide in 1 mole of nonylbenzyl. R-08 was purchased from Dainippon Corporation and Chemicals' model R-08, which is a fluorinated acrylic copolymer.
這些稀釋劑組合物也可用來去除黏附於不合格基材上 的光敏層，這些不合格基材係在光蝕刻製程中隨機挑選出 來進行測試之後發現不合格而淘汰下來的基材《依據本發 明製備而成的稀釋劑組合物具有優良的溶解速率，因此可 簡化回收製程。 老陰不歌求先倣層之 光敏層組合物係塗覆於8英吋的氧化矽晶圓上。之後， 以本發明稀釋劑組合物及習知的稀釋劑組合物分別來測試 ^去除基材邊緣上不欲求光敏層的效果，所進行的測試稱 「去除邊緣顆粒測試（Edge Bead Removing Test)」，以下簡 稱「EBR測試」。以用來塗覆光敏層於基材上之相 機來進行EBR測試。 、These diluent compositions can also be used to remove the photosensitive layer adhered to unqualified substrates. These unqualified substrates are randomly selected in the photoetching process and tested after being rejected and rejected. The prepared diluent composition has an excellent dissolution rate, thereby simplifying the recycling process. Lao Yin does not urge the first layer of the photosensitive layer composition is coated on an 8-inch silicon oxide wafer. Afterwards, the effect of removing the photosensitivity layer on the edge of the substrate without removing the photosensitive layer is tested with the diluent composition of the present invention and the conventional diluent composition. The test performed is called "Edge Bead Removing Test" , Hereinafter referred to as "EBR Test". The EBR test was performed using a camera for coating a photosensitive layer on a substrate. ,
將如表1所示之稀釋劑組合物經由EBR s 了备主。 貝策/主入於塗 復^古表2所示之光敏樹脂組合物的基材上，並以 1示的條件進行㈣來去除基材邊緣部分之純 形顆粒。將稀釋劑組合物自-配備了壓力表的壓力… 入。壓力ΑίΛ 壓力閥中餵 力4 10 Kgf，來自EBR噴嘴之 介於每分鐘10-20毫升間。 物的流速 14 200304585 每一光敏樹脂組合物之EBR測試的結果示於表4。 表2 類別 組合物形式 組合物品名 層厚度 (μιη) 光敏樹脂組合物 供I-譜線式之正型 DPR-600D 2.36 液晶顯示裝置 表3 EBR測試條件 類別 旋轉速率（rpm) 時間（秒） 分配條件 500 3 旋塗 視光敏層厚 1而進行調整 EBR條件1 2000 7 EBR條件2 2000 9 EBR條件3 2500 5 表4 EBR測試結果 類別 實施例1 實施例2 實施例3 比較實施 比較實施 例1 例2 EBR測試1 ◎ ◎ ◎ X Δ EBR測試2 ◎ ◎ ◎ X 〇 邊緣部分有EBR殘留 無 無 無 無 有看到 物The diluent composition shown in Table 1 was prepared via EBR s. Betzer / mainly applied to the substrate coated with the photosensitive resin composition shown in Table 2 and subjected to the conditions shown in 1 to remove the pure particles at the edge of the substrate. The diluent composition is pressured-in with a pressure gauge. Pressure ΑίΛ The pressure in the pressure valve is 4 10 Kgf, from the EBR nozzle between 10-20 ml per minute. The flow rate of the material 14 200304585 The results of the EBR test of each photosensitive resin composition are shown in Table 4. Table 2 Category composition form Combination item name Layer thickness (μιη) Photosensitive resin composition for I-line type positive DPR-600D 2.36 LCD display device Table 3 EBR test conditions Category rotation rate (rpm) Time (seconds) Distribution Condition 500 3 Spin coating to adjust the thickness of the photosensitive layer 1 and adjust EBR conditions 1 2000 7 EBR conditions 2 2000 9 EBR conditions 3 2500 5 Table 4 EBR test result categories Example 1 Example 2 Example 3 Comparative implementation Comparative example 1 Example 2 EBR test 1 ◎ ◎ ◎ X Δ EBR test 2 ◎ ◎ ◎ X 〇 EBR residue on the edge part No No No No Nothing
在表4中，◎代表在EBR測試後基材邊緣變得非常乾 淨；〇代表在EBR測試後基材具有不錯的線形邊緣（80%以 15 200304585 上）；△代表在EBR測試後基材邊緣部分出現扭曲變形；且 X代表在EBR測試後基材邊緣仍有光敏層覆蓋之殘留物。In Table 4, ◎ indicates that the substrate edge becomes very clean after the EBR test; ○ indicates that the substrate has a good linear edge after the EBR test (80% to 15 200304585); △ indicates that the substrate edge after the EBR test Partial distortion occurred; and X represents the residue of the photosensitive layer covering the edge of the substrate after the EBR test.
如表4所示，本發明稀釋劑組合物對所有光敏層均表 現出優良的EBR結果（乾淨的基材邊緣），至於習知的稀釋 劑組合物則視所適用光敏層的不同而有明顯不同的效果， 同時其基材邊緣表現也較差。特別是，習知的稀釋劑組合 物無法防止具較厚光敏塗層的基材邊緣不致出現仍有殘留 物覆蓋的情況。此變成導致半導體裝置及液晶顯示裝置產 律下降及設備污染的主要原，因。 本發明稀釋劑組合物對不同的EBR轉速條件均提供優 異截面結果。這點對許多測試條件都適用，並非只是針對 某一特別條件所會有的結果❶因此，本發明稀釋劑組合物 較習知的稀釋劑組合物更能適用於不同的製程條件。As shown in Table 4, the diluent composition of the present invention shows excellent EBR results (clean substrate edges) for all photosensitive layers. As for the conventional diluent composition, it is obvious depending on the applicable photosensitive layer. Different effects, while its substrate edge performance is also poor. In particular, conventional diluent compositions cannot prevent the edges of substrates with thicker photosensitive coatings from remaining covered by residues. This has become a major cause of semiconductor device and liquid crystal display device production decline and equipment pollution. The diluent composition of the present invention provides excellent cross-section results for different EBR speed conditions. This is applicable to many test conditions, not just the results obtained for a particular condition. Therefore, the diluent composition of the present invention is more applicable to different process conditions than the conventional diluent composition.
本發明稀釋劑組合物可經濟、迅速地於EBR製程中去 除大型基材末端或背面上許多不同類型的光敏層，因此可 簡化半導體裝置及液晶顯示裝置的製程操作，並改善其品 質。特別是，本發明稀釋劑組合物在去除液晶顯示裝置製 作過程中基材邊緣的殘餘物上效果非常好。此外，本發明 稀釋劑組合物也可用來去除黏附於不合格基材上的光敏 層，這些不合格基材係在光姓刻製程中隨機挑選出來進行 測試之後發現不合格而淘汰下來的基材，因此可使這些基 材被回收且以具經濟效益的方式再次被使用。 16The diluent composition of the present invention can economically and quickly remove many different types of photosensitive layers on the end or back of a large substrate in an EBR process, so that it can simplify the manufacturing operations of semiconductor devices and liquid crystal display devices and improve their quality. In particular, the diluent composition of the present invention is very effective in removing residues on the edge of a substrate during the manufacturing process of a liquid crystal display device. In addition, the diluent composition of the present invention can also be used to remove the photosensitive layer adhered to unqualified substrates. These unqualified substrates are randomly selected during the Guangming engraving process and tested after being found to be unqualified and eliminated. , So that these substrates can be recycled and reused in an economical way. 16
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| KR100718639B1 (en) * | 2004-10-27 | 2007-05-16 | 주식회사 이엔에프테크놀로지 | Thinner composition for removing pigment dispersed photoresist |
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| JP2007163983A (en) * | 2005-12-15 | 2007-06-28 | Tokyo Ohka Kogyo Co Ltd | Detergent |
| CN1987663B (en) * | 2005-12-23 | 2010-12-01 | 新应材股份有限公司 | Light resistance washing agent |
| KR100812085B1 (en) | 2006-12-22 | 2008-03-07 | 동부일렉트로닉스 주식회사 | Method for singulating a semiconductor device |
| US20120108067A1 (en) * | 2010-10-29 | 2012-05-03 | Neisser Mark O | Edge Bead Remover For Coatings |
| KR102347910B1 (en) | 2016-11-07 | 2022-01-06 | 동우 화인켐 주식회사 | Thinner composition for improving applying performance a photosensitive resin and anti-reflective coating, and removing the photosensitive resin and anti-reflective coating |
| KR102652985B1 (en) | 2016-11-07 | 2024-03-29 | 동우 화인켐 주식회사 | Thinner composition for improving applying performance a photosensitive resin and anti-reflective coating, and removing the photosensitive resin and anti-reflective coating |
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| JPS58105182A (en) * | 1981-12-18 | 1983-06-22 | Olympus Optical Co Ltd | Reproducing method of photoreceptor |
| US4948697A (en) * | 1985-10-28 | 1990-08-14 | Hoechst Celanese Corporation | Positive photoresist with a solvent mixture of propylene glycol alkyl ether and propylene glycol alkyl ether acetate |
| US4983490A (en) * | 1985-10-28 | 1991-01-08 | Hoechst Celanese Corporation | Photoresist treating composition consisting of a mixture of propylene glycol alkyl ether and propylene glycol alkyl ether acetate |
| KR100594815B1 (en) * | 1999-12-24 | 2006-07-03 | 삼성전자주식회사 | thinner for rinsing photoresist and method of treating photoresist layer |
-
2002
- 2002-03-29 KR KR10-2002-0017385A patent/KR100503967B1/en active IP Right Grant
-
2003
- 2003-03-28 AU AU2003214682A patent/AU2003214682A1/en not_active Abandoned
- 2003-03-28 TW TW092107202A patent/TWI226978B/en not_active IP Right Cessation
- 2003-03-28 WO PCT/KR2003/000632 patent/WO2003083032A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| KR100503967B1 (en) | 2005-07-26 |
| KR20030078374A (en) | 2003-10-08 |
| WO2003083032A1 (en) | 2003-10-09 |
| TWI226978B (en) | 2005-01-21 |
| AU2003214682A1 (en) | 2003-10-13 |
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| Date | Code | Title | Description |
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| MM4A | Annulment or lapse of patent due to non-payment of fees |