KR20120029808A - A detergent composition for a substrate of flat panel display device and cleaning method using the same - Google Patents
A detergent composition for a substrate of flat panel display device and cleaning method using the same Download PDFInfo
- Publication number
- KR20120029808A KR20120029808A KR1020100091870A KR20100091870A KR20120029808A KR 20120029808 A KR20120029808 A KR 20120029808A KR 1020100091870 A KR1020100091870 A KR 1020100091870A KR 20100091870 A KR20100091870 A KR 20100091870A KR 20120029808 A KR20120029808 A KR 20120029808A
- Authority
- KR
- South Korea
- Prior art keywords
- flat panel
- panel display
- cleaning composition
- cleaning
- ether
- Prior art date
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- 238000004140 cleaning Methods 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000000758 substrate Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims description 15
- 239000003599 detergent Substances 0.000 title description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 13
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 11
- -1 alkyl glycosides Chemical class 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 8
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical group COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 3
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- 239000000811 xylitol Substances 0.000 claims description 3
- 235000010447 xylitol Nutrition 0.000 claims description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 3
- 229960002675 xylitol Drugs 0.000 claims description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 claims description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KAZBKCHUSA-N D-altritol Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KAZBKCHUSA-N 0.000 claims description 2
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 239000004386 Erythritol Substances 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 2
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 2
- 235000019414 erythritol Nutrition 0.000 claims description 2
- 229940009714 erythritol Drugs 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 235000010356 sorbitol Nutrition 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical compound OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 0.000 claims 1
- 239000008367 deionised water Substances 0.000 abstract description 4
- 229930182470 glycoside Natural products 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 3
- 239000011146 organic particle Substances 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000356 contaminant Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 239000011521 glass Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 7
- 239000000809 air pollutant Substances 0.000 description 6
- 231100001243 air pollutant Toxicity 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- CWMNZUQURAVJQX-UHFFFAOYSA-N COC(COCCO)C.C(COCCO)O Chemical compound COC(COCCO)C.C(COCCO)O CWMNZUQURAVJQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UNXHWFMMPAWVPI-QWWZWVQMSA-N D-threitol Chemical compound OC[C@@H](O)[C@H](O)CO UNXHWFMMPAWVPI-QWWZWVQMSA-N 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
-
- 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
-
- 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
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
Description
본 발명은 평판 디스플레이 기판용 세정제 조성물 및 이를 이용한 세정방법에 관한 것이다. The present invention relates to a cleaning composition for a flat panel display substrate and a cleaning method using the same.
일반적으로, 평판 디스프레이(flat panel display device; FPD)는, 반도체 디바이스와 같이, 성막, 노광, 에칭 등의 공정을 거쳐 제품이 제조된다. 하지만, 이러한 제조공정에 의해서, 기판 표면에 각종의 유기물이나 무기물 등의 크기가 1㎛ 이하인 매우 작은 파티클(Particle)로 인해, 부착 오염이 발생한다. 이러한 파티클을 부착한 채로, 다음의 공정 처리를 실시했을 경우, 막의 핀홀이나 피트, 배선의 단선이나 브릿지(Bridge)가 발생하여, 제품의 제조 수율이 저하된다.In general, flat panel display devices (FPDs), like semiconductor devices, are manufactured through processes such as film formation, exposure, and etching. However, by such a manufacturing process, adhesion contamination occurs due to very small particles having various organic and inorganic substances having a size of 1 μm or less on the substrate surface. When the following process is performed with these particles attached, pinholes, pits, disconnection or bridges of the wires are generated, and the yield of the product is reduced.
이러한 문제를 극복하기 위한 세정제에 대하여 공지되어 있다. 예를 들어, 대한민국 등록특허 제10-0305314 호에는 금속이온이 없는 알칼리성 수용액과 2 내지 10의 -OH기 그룹을 포함하는 폴리하이드록실 화합물로 구성된 마이크로일렉트로닉스 웨이퍼물질 표면 세척방법에 대하여 기재되어 있으나, 이는 기판 표면을 친수성으로 개질시키는 효과를 달성하기 어려우며 오일과 같은 유기오염물의 제거력도 떨어지는 문제점이 남아있다.Known cleaners for overcoming these problems are known. For example, Korean Patent No. 10-0305314 discloses a method of cleaning a surface of a microelectronic wafer material composed of an alkali aqueous solution free of metal ions and a polyhydroxyl compound containing 2 to 10 -OH groups. This is difficult to achieve the effect of modifying the surface of the substrate to hydrophilic, and the problem remains that the removal power of organic contaminants such as oil is also poor.
대한민국 등록특허 제 10-0730521호에는 글리콜에테르, 수용성유기용제 및 암모늄화합물을 포함하는 세정액을 제안하였다. 이와 같은 조성은 포토레지스트 박리공정에는 효과가 있을 수 있으나 기판표면을 친수성으로 개질시키지 못하며 다량의 유기용제가 잔류되어 표면 접촉각을 증가시킨다.Korean Patent No. 10-0730521 proposes a cleaning solution containing a glycol ether, a water-soluble organic solvent, and an ammonium compound. Such a composition may be effective in the photoresist stripping process, but does not modify the surface of the substrate to be hydrophilic and a large amount of organic solvent remains to increase the surface contact angle.
또한, 대한민국 등록특허 제 10-05522845 호에는 아민 및 플루오르화염으로부터 선택한 적어도 1종의 용해제와 폴리비닐피롤리돈과 같은 알킬글리코사이드를 포함하는 세정액을 제안하였으나 플루오르화염이 첨가되었을 경우 실리콘 기반의 유리기판이나 실리콘질화막을 부식시키며 구리와 같은 금속에도 부식이 발생하는 문제점을 갖고 있다.In addition, Korean Patent No. 10-05522845 proposed a cleaning solution containing at least one solubilizer selected from amines and fluoride salts and alkylglycosides such as polyvinylpyrrolidone, but silicone-based glass when fluoride salts were added Corrosion of the substrate or silicon nitride film and corrosion of metal such as copper has a problem.
따라서, 본 발명의 목적은 기판 상에 존재하는 오염물질을 제거함으로써, 세정효과 및 생산성을 증대시킬 수 있는 평판 디스플레이 기판용 세정제 조성물 및 이를 이용한 세정방법을 제공하는 것이다. Accordingly, an object of the present invention is to provide a cleaning composition for a flat panel display substrate and a cleaning method using the same, by removing contaminants present on the substrate, thereby increasing the cleaning effect and productivity.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 알킬글리코사이드;In order to achieve the above object, the present invention is an alkyl glycoside represented by the formula (1);
하기 화학식 2로 표시되는 글리콜에테르계 유기용매;A glycol ether organic solvent represented by Formula 2;
다가알코올;Polyhydric alcohol;
제4급 암모늄수산화물; 및Quaternary ammonium hydroxides; And
물을 포함하는 평판 디스플레이 기판용 세정제 조성물을 제공한다.It provides a cleaning composition for a flat panel display substrate containing water.
<화학식 1><Formula 1>
상기 화학식 1에서,In Chemical Formula 1,
R1은 수소 또는 탄소수 1 내지 3의 직쇄 또는 분지쇄 알킬이고, R 1 is hydrogen or straight or branched chain alkyl of 1 to 3 carbon atoms,
R2는 탄소수 1 내지 4의 직쇄 또는 분지쇄 알킬이다.R 2 is straight or branched chain alkyl of 1 to 4 carbon atoms.
<화학식 2><Formula 2>
상기 화학식 2에서,In Chemical Formula 2,
R1은 메틸기 또는 에틸기이며, R 1 is a methyl group or an ethyl group,
R2는 수소 또는 히드록시에틸기이며,R 2 is hydrogen or a hydroxyethyl group,
n은 2 내지 3의 정수이며, n is an integer of 2 to 3,
x는 1 내지 3의 정수이다.x is an integer of 1-3.
또한, 본 발명은 상기 평판 디스플레이 기판의 세정제 조성물을 이용한 평판 디스플레이 기판의 세정 방법을 제공한다.Moreover, this invention provides the cleaning method of a flat panel display substrate using the cleaning composition of the said flat panel display substrate.
본 발명의 평판 디스플레이 기판용 세정제 조성물은 기판 표면을 친수성으로 만들어 코팅성을 향상시킴으로써, 평판 디스플레이 기판의 유리 및 절연막과 구리 및 구리합금을 포함하는 금속막 표면에 대한 유기물 오염물 및 파티클 제거능력이 우수하고, 다량의 탈이온수를 포함하여 취급이 용이하며 환경적으로 유리한 효과를 가진다.The cleaning composition for a flat panel display substrate of the present invention makes the surface of the substrate hydrophilic and improves coating properties, thereby excellent in removing organic contaminants and particles on the glass and insulating film of the flat panel display substrate and the metal film surface including copper and copper alloy. And, including a large amount of deionized water is easy to handle and has an environmentally beneficial effect.
도 1은 각각의 실시예 10 및 비교예 3의 세정제 조성물을 이용하여 지문오염물 제거력을 평가한 실험 결과이다.
도 2는 각각의 실시예 4 및 비교예 4의 세정제 조성물을 이용하여 유성펜자국 제거력을 평가한 실험 결과이다1 is an experimental result of evaluating fingerprint dirt removal power using the cleaning composition of each of Example 10 and Comparative Example 3.
2 is an experimental result of evaluating the oil-based pen marks removal force using the cleaning composition of each of Example 4 and Comparative Example 4.
이하, 본 발명에 대해 상세히 설명한다. Hereinafter, the present invention will be described in detail.
본 발명은 알킬글리코사이드, 글리콜에테르계 유기용매, 다가알코올, 제4급 암모늄수산화물 및 물을 포함하는 평판 디스플레이 기판용 세정제 조성물에 관한 것으로, 보다 구체적으로는 조성물 총중량에 대하여 알킬글리코사이드 0.0001 내지 5 중량%, 글리콜에테르계 유기용매 0.05 내지 40 중량%, 다가알코올 0.01 내지 5 중량%, 제4급 암모늄수산화물 0.05 내지 5중량% 및 잔량의 물을 포함하는 것이 바람직하다.
The present invention relates to a cleaning composition for a flat panel display substrate comprising an alkylglycoside, a glycol ether organic solvent, a polyhydric alcohol, a quaternary ammonium hydroxide, and water, and more specifically, an alkylglycoside 0.0001 to 5 based on the total weight of the composition. It is preferable to include the weight%, the glycol ether organic solvent 0.05 to 40% by weight, the polyhydric alcohol 0.01 to 5% by weight, the quaternary ammonium hydroxide 0.05 to 5% by weight and the balance of water.
본 발명의 평판 디스플레이 기판용 세정제 조성물에 포함되는 알킬글리코사이드는 하기 화학식 1에 표시되는 것이 바람직하다.It is preferable that the alkylglycoside contained in the cleaning composition for flat panel display substrates of this invention is represented by following General formula (1).
상기 화학식 1에서,In Chemical Formula 1,
R1은 수소 또는 탄소수 1 내지 3의 직쇄 또는 분지쇄 알킬이고, R 1 is hydrogen or straight or branched chain alkyl of 1 to 3 carbon atoms,
R2는 탄소수 1 내지 4의 직쇄 또는 분지쇄 알킬이다.R 2 is straight or branched chain alkyl of 1 to 4 carbon atoms.
이때, R2의 탄소수가 4를 초과하게 되면 게면활성제 특성을 가지게 되어 세정 작업 시 거품이 과도하게 발생하며, 생분해성이 떨어져 폐수처리 효율이 떨어질 수 있다.At this time, if the carbon number of R 2 exceeds 4 will have a surfactant properties, the foam excessively generated during the cleaning operation, the biodegradability is lowered may reduce the wastewater treatment efficiency.
상기 화학식 1로 표시되는 알킬글리코사이드는 메틸글리코사이드, 에틸글리코사이드, 프로필글리코사이드 및 부틸글리코사이드에서 선택된 1종 또는 2종이상의 혼합물일 수 있으나, 이에 한정되는 것은 아니다.The alkyl glycoside represented by Formula 1 may be one or a mixture of two or more selected from methylglycoside, ethylglycoside, propylglycoside and butylglycoside, but is not limited thereto.
본 발명에서의 상기 알킬글리코사이드는 물에 대한 용해도가 좋으며, 구리, 구리합금 금속막, 몰리브덴, 몰리브덴합금 금속막과 같은 금속 표면의 부식을 억제하며, 소수성 표면을 친수성 표면으로 개질시킴으로 유기오염물, 파티클의 제거에 용이하다.The alkylglycoside in the present invention has good solubility in water, inhibits corrosion of metal surfaces such as copper, copper alloy metal film, molybdenum, molybdenum alloy metal film, and modifies the hydrophobic surface with a hydrophilic surface, resulting in organic contaminants, Easy to remove particles
상기 화학식 1로 표시되는 알킬글리코사이드의 함량은 세정제 조성물 총중량에 대하여 0.0001 내지 5 중량%을 포함되는 것이 바람직하며, 보다 바람직하게는 0.001 내지 2 중량%를 포함할 수 있다. 상기 함량이 0.0001 중량% 미만이면 기판 표면에 금속표면의 부식을 억제하는 성질이 현저히 감소하는 문제점이 있다. 상기 함량이 5 중량%를 초과하면, 표면에 흡착력이 강하여 기판 표면에 세정제가 잔류함으로써, 린스공정에서 알킬글리코사이드가 기판에 잔류하게 되고, 세정제의 점도 상승으로 인한 거품 발생 정도가 심해져서 공정상 작업성이 저하되는 문제가 있다.
The content of the alkylglycoside represented by Chemical Formula 1 may include 0.0001 to 5% by weight, and more preferably 0.001 to 2% by weight, based on the total weight of the detergent composition. If the content is less than 0.0001% by weight, there is a problem that the property of inhibiting corrosion of the metal surface on the substrate surface is significantly reduced. When the content exceeds 5% by weight, the adsorption force is strong on the surface and the cleaning agent remains on the surface of the substrate, so that alkylglycoside remains on the substrate in the rinsing process, and the degree of foaming due to the increase in viscosity of the cleaning agent becomes severe. There is a problem that workability is degraded.
본 발명에 포함되는 상기 글리콜에테르계 유기용매는 하기 화학식 2로 표시되는 것이 바람직하다.The glycol ether organic solvent included in the present invention is preferably represented by the following formula (2).
상기 화학식 2에서,In Chemical Formula 2,
R1은 메틸기 또는 에틸기이며, R1 is a methyl group or an ethyl group,
R2는 수소 또는 히드록시에틸기이며, R2 is hydrogen or hydroxyethyl group,
n은 2 내지 3의 정수이며, n is an integer of 2 to 3,
x는 1 내지 3의 정수이다.
x is an integer of 1-3.
이때, 상기 글리콜에테르계 유기용매는 기판 표면의 습윤성을 증가시켜 기판 표면의 오일성분과 같은 유기오염물질의 제거능력, 즉 세정력을 향상시킨다. 또한, 상기 글리콜에테르계 유기용매는 본 발명의 세정제 조성물의 물에 대한 용해력 및 린스력을 향상시킬 수 있으며, 구체적인 예로는 에틸렌글리콜모노메틸에테르(Ethylene Glycol Monomethyl Ether; MG), 디에틸렌글리콜모노메틸에테르(Diethylene Glycol Monomethyl Ether; MDG), 디에틸렌글리콜모노에틸에테르(Diethylene Glycol Monoethyl Ether; EDG, carbitol), 에틸렌글리콜모노에틸에테르(Ethylene Glycol Monoethyl Ether; EG), 트리에틸렌글리콜모노에틸에테르(Triethylene Glycol Monoethyl Ether; ETG), 트리에틸렌글리콜모노메틸에테르(Triethylene Glycol Monomethyl Ether; MTG), 디프로필렌글리콜 모노메틸에테르(Dipropylene Glycol Monomethyl Ether; MFDG), 프로필렌글리콜 모노메틸에테르(Propylene Glycol Monomethyl Ether; MFG) 로 이루어진 군으로부터 선택되는 1종 또는 2종이상의 혼합물일 수 있으나, 이에 한정하는 것은 아니다.At this time, the glycol ether-based organic solvent increases the wettability of the surface of the substrate to improve the ability to remove organic contaminants such as oil components on the surface of the substrate, that is, cleaning ability. In addition, the glycol ether-based organic solvent may improve the dissolving and rinsing power of the cleaning composition of the present invention, specific examples include ethylene glycol monomethyl ether (MG), diethylene glycol monomethyl Diethylene Glycol Monomethyl Ether (MDG), Diethylene Glycol Monoethyl Ether (EDG, carbitol), Ethylene Glycol Monoethyl Ether (EG), Triethylene Glycol Monoethyl Ether (Triethylene Glycol) Monoethyl Ether (ETG), Triethylene Glycol Monomethyl Ether (MTG), Dipropylene Glycol Monomethyl Ether (MFDG), Propylene Glycol Monomethyl Ether (MFG) It may be one or a mixture of two or more selected from the group consisting of, but is not limited thereto. is.
상기 글리콜에테르계 유기용매의 함량은 조성물 총중량에 대하여 0.05 내지 40 중량%을 포함하는 것이 바람직하며, 더욱 바람직하게는 0.5 내지 20 중량% 이다. 상기 글리콜에테르계 유기용매의 함량이 조성물 총중량에 대하여 0.05 중량% 미만이면 글리콜에테르의 추가에 기인한 세정제 조성물의 유기오염물에 대한 용해력을 증가시킬 수 없고, 40 중량%를 초과하면 기판 표면의 습윤성 부여가 부족하며, 비경제적이다.
The content of the glycol ether-based organic solvent is preferably included 0.05 to 40% by weight, more preferably 0.5 to 20% by weight relative to the total weight of the composition. If the content of the glycol ether-based organic solvent is less than 0.05% by weight relative to the total weight of the composition, it is not possible to increase the dissolving power of the cleaning composition due to the addition of the glycol ether to the organic contaminants, if the content exceeds 40% by weight gives the wettability of the substrate surface Is scarce and uneconomical.
본 발명의 세정제 조성물에 있어서, 기판 표면의 습윤성을 증가시켜 오일성분을 제거능력을 향상시키고, 조성물의 물에 대한 용해력 및 린스력을 향상시킬 목적으로 다가알코올을 포함할 수 있다. In the cleaning composition of the present invention, it may include a polyhydric alcohol for the purpose of increasing the wettability of the surface of the substrate to improve the ability to remove oil components, and to improve the solubility and rinsing power of the composition in water.
상기 다가알코올은 에틸렌글리콜, 프로필렌글리콜, 1,3-프로판디올, 1,2-부탄디올, 1,3-부탄디올, 2,3-부탄디올, 1,4-부탄디올, 2-메틸-1,3-프로판디올, 글리세롤, 헥사글리세롤, 트리메틸올에탄, 트리메틸올프로판, 펜타에리스리톨(pentaerythritol), 크실리톨(자일리톨), 만니톨(mannitol), 솔비톨(sorbitol), 에리스리톨(erythritol), 아도니톨(anonitol), 트레이톨(threitol), 아라비톨(arabitol) 및 탈리톨(talitol)로 이루어진 군에서 선택된 1종 또는 2종 이상의 혼합물인 것이 바람직하나, 이에 한정되는 것은 아니다.The polyhydric alcohol is ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propane Diol, glycerol, hexaglycerol, trimethylolethane, trimethylolpropane, pentaerythritol, xylitol (xylitol), mannitol, sorbitol, erythritol, adonitol, It is preferably one or a mixture of two or more selected from the group consisting of threitol, arabitol, and talitol, but is not limited thereto.
조성물 총 중량에 대하여, 상기 다가알코올은 0.01 내지 5 중량%로 포함되는 것이 바람직하고, 0.1 내지 3 중량%로 포함되는 것이 보다 바람직하다. 상기 다가알코올이 0.01 중량% 미만으로 포함되면 유리기판 표면에 대한 습윤성 부여가 부족하고, 5 중량%를 초과하면 비경제적이다.
With respect to the total weight of the composition, the polyhydric alcohol is preferably included in 0.01 to 5% by weight, more preferably contained in 0.1 to 3% by weight. If the polyhydric alcohol is contained in less than 0.01% by weight lacking the wettability on the surface of the glass substrate, when the content exceeds 5% by weight is uneconomical.
상기 제4급 암모늄수산화물은 일반식 [N-(R)4]+?OH- (R은 탄소수 1 내지 3의 알킬기)로 표시될 수 있으며, 이는 고알칼리성을 가짐으로써 고분자의 유기오염물이나 오일성 유기화합물의 저분자량화와 박리성을 높이고 세정성능을 부여할 수 있다. 상기 제4급 암모늄수산화물의 구체적인 예로는 수산화테트라메틸암모늄, 수산화테트라에틸암모늄, 수산화테트라프로필암모늄 및 수산화테트라부틸암모늄으로 이루어진 군으로부터 선택된 1종 또는 2종 이상의 혼합물인 것이 바람직하나, 이에 한정하는 것은 아니다.The quaternary ammonium hydroxide of the general formula [N- (R) 4] + OH -? May be represented by (R is an alkyl group having 1-3 carbon atoms), which has a high alkalinity as organic impurities in the organic polymer or oily The molecular weight and peelability of the compound can be enhanced and the cleaning performance can be imparted. Specific examples of the quaternary ammonium hydroxide are one or a mixture of two or more selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide, but is not limited thereto. no.
상기 제4급 암모늄수산화물은 조성물 총중량에 대하여 0.05 내지 5 중량%로 포함되는 것이 바람직하다. 상기 제4급 암모늄수산화물이 0.05 중량% 미만으로 포함될 경우에는 기판 위에 부착된 파티클이나 유기오염물 제거가 용이하지 않으며, 5 중량%를 초과하는 경우에는 세정효과가 더 이상 증가되지 않으며, 세정제의 가격이 상승하여 경제적이지 못하고, 환경적인 문제를 유발할 수 있다.
The quaternary ammonium hydroxide is preferably contained in 0.05 to 5% by weight based on the total weight of the composition. When the quaternary ammonium hydroxide is included in less than 0.05% by weight, it is not easy to remove particles or organic contaminants attached to the substrate, and when the content exceeds 5% by weight, the cleaning effect is no longer increased, and the price of the cleaner is It can rise, not economically, and cause environmental problems.
또한, 본 발명의 평판 디스플레이 기판용 세정제 조성물에 포함되는 물은 특별히 한정되는 것은 아니나, 반도체 공정용의 물로서, 바람직하게는 비정항값이 18Ω/㎝ 이상인 탈이온수를 사용할 수 있다. 상기 물의 함량은 총중량이 100중량% 되도록 잔량 포함되는 것으로, 다른 구성성분의 함량에 따라 조정될 수 있다. In addition, although the water contained in the cleaning composition for flat panel display substrates of this invention is not specifically limited, As water for semiconductor processes, Deionized water of preferably 18 kV / cm or more of non-limiting value can be used. The water content is to be included in the remaining amount so that the total weight is 100% by weight, it can be adjusted according to the content of the other components.
본 발명의 평판 디스플레이 기판용 세정제 조성물은 pH 12 이상인 것이 바람직하다.It is preferable that the cleaning composition for flat panel display substrates of this invention is pH12 or more.
본 발명의 평판 디스플레이 기판용 세정제 조성물은 전술한 성분 이외에 통상의 첨가제를 더 포함할 수 있으며, 상기 첨가제로는 금속 이온 봉쇄제 및 pH 조절제 등을 들 수 있다.
The cleaning composition for a flat panel display substrate of the present invention may further include a conventional additive in addition to the above components, and the additive may include a metal ion blocking agent, a pH adjusting agent and the like.
본 발명의 평판 디스플레이 기판용 세정제 조성물은 평판표시장치의 유리기판의 표면에 대한 유기물 오염물 및 파티클 제거력이 우수하다. 본 발명의 세정제 조성물은 린스 후 잔류물이 없고 다량의 탈이온수를 포함하므로 취급이 용이하고 환경적으로 유리하다.
The cleaning composition for a flat panel display substrate of the present invention is excellent in removing organic contaminants and particles on the surface of the glass substrate of the flat panel display device. The detergent composition of the present invention is easy to handle and environmentally advantageous because it contains no residue after rinsing and contains a large amount of deionized water.
또한, 본 발명의 평판 디스플레이 기판용 세정제 조성물을 이용한 평판 디스플레이 기판의 세정 방법을 제공한다.
The present invention also provides a method for cleaning a flat panel display substrate using the cleaning composition for a flat panel display substrate of the present invention.
이하에서, 실시예, 비교예 및 시험예를 통하여 본 발명을 더욱 상세하게 설명한다. 그러나, 본 발명의 범위가 하기 실시예, 비교예 및 시험예에 의하여 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Test Examples. However, the scope of the present invention is not limited by the following examples, comparative examples and test examples.
실시예 1 내지 실시예 10 및 비교예 1 내지 비교예 5: 세정제 조성물의 제조Examples 1 to 10 and Comparative Examples 1 to 5 Preparation of Cleaning Composition
교반기가 설치되어 있는 혼합조에 하기 표 1에 기재된 성분들을 표 1에 기재된 조성비에 따라 혼합하고, 상온에서 1시간 동안 500rpm의 속도로 교반하여 세정제 조성물을 제조하였다.
In the mixing tank equipped with a stirrer, the components shown in Table 1 were mixed according to the composition ratios shown in Table 1, and stirred at a speed of 500 rpm for 1 hour at room temperature to prepare a cleaning composition.
1) 메틸글리코사이드1) methylglycoside
2) 에틸글리코사이드2) ethylglycoside
3) 부틸글리코사이드3) Butyl Glycoside
4) 카테콜4) Catechol
a) 1,4-부탄디올 a) 1,4-butanediol
b) 글리세롤b) glycerol
c) 헥사글리세롤c) hexaglycerol
TMAH : 수산화테트라에틸암모늄(Tetramethylammoniumhydroxide)TMAH: Tetramethylammoniumhydroxide
TEAH : 수산화테트라에틸암모늄(Tetraethylammoniumhydroxide)TEAH: Tetraethylammoniumhydroxide
EG : 에틸렌글리콜모노에틸에테르 EG: ethylene glycol monoethyl ether
MG : 에틸렌글리콜모노메틸에테르 MG: Ethylene Glycol Monomethyl Ether
EDG : 디에틸렌글리콜모노에틸에테르EDG: diethylene glycol monoethyl ether
MDG : 디에틸렌글리콜모노메틸에테르MDG: Diethylene Glycol Monomethyl Ether
MTG : 트리에틸렌글리콜모노메틸에테르
MTG: Triethylene Glycol Monomethyl Ether
실험예Experimental Example : 파티클세정력 및 유기오염물 세정력 평가 : Evaluation of particle cleaning power and organic pollutant cleaning power
본 발명에 따른 세정제 조성물의 파티클 세정력 및 유기오염물 세정력을 평가하기 위하여, 하기와 같은 실험을 수행하였다.In order to evaluate particle cleaning power and organic pollutant cleaning power of the cleaning composition according to the present invention, the following experiment was performed.
1) 대기 중 오염물 제거력 평가1) Air Pollutant Removal
상기 실시예 1 내지 10 및 비교예 1 내지 4의 세정제 조성물 100㎖를 각각 용량 250㎖의 비이커에 넣었다. 오염물의 제거력 평가를 위해 2cm x 6cm 크기로 형성된 유리기판(제조사:SEMES)과 몰리브덴(Mo)기판과 구리(Copper)기판을 대기 중에 3일간 방치시켜 오염시켰다. 상기 오염된 기판을 스프레이식 유리기판 세정장치를 이용하여 1분 동안 상온에서 실시예 1 내지 10 및 비교예 1 내지 4의 세정제로 세정하였다. 세정 후 초순수에 30초 세척한 후 질소로 건조하였다. 오염물의 제거 정도는 접촉각 측정장치(모델명: DSA100, 제조사 : KRUSS)를 이용하여 세정전과 세정후의 접촉각 감소량으로 평가하였고, 그 결과를 표2로 나타내었다.
100 ml of the cleaning composition of Examples 1 to 10 and Comparative Examples 1 to 4 were placed in a beaker with a volume of 250 ml, respectively. In order to evaluate the removal power of the contaminants, glass substrates (manufactured by SEMES), molybdenum (Mo), and copper (Copper) substrates having a size of 2 cm x 6 cm were left for 3 days in the air for contamination. The contaminated substrate was cleaned with the cleaning agents of Examples 1 to 10 and Comparative Examples 1 to 4 at room temperature for 1 minute using a spray glass substrate cleaning apparatus. After washing for 30 seconds in ultrapure water and dried with nitrogen. The degree of removal of contaminants was evaluated by the contact angle reduction before and after cleaning using a contact angle measuring device (model name: DSA100, manufacturer: KRUSS), and the results are shown in Table 2.
2) 지문오염물 제거력 평가2) Fingerprint Contaminant Removal
지문오염물의 제거력 평가를 위해 2cm x 6cm 크기로 형성된 유리기판 위에 사람의 지문 자국으로 오염시키고, 오염된 기판을 스프레이식 유리 기판 세정장치를 이용하여 1분 동안 상온에서 실시예 1 내지 10 및 비교예 1 내지 4의 세정제로 세정하였다. 세정 후 초순수에 30초 세척한 후 질소로 건조하였다. In order to evaluate the removal power of fingerprint contaminants, the fingerprint substrate was contaminated with human fingerprints on a glass substrate formed of 2 cm x 6 cm, and the contaminated substrate was sprayed with a glass substrate cleaning device for 1 minute at room temperature in Examples 1 to 10 and Comparative Examples. It was washed with 1 to 4 cleaners. After washing for 30 seconds in ultrapure water and dried with nitrogen.
이때 유기오염물의 제거 유무는 제거가 되었을 때 ○, 제거가 되지 않았을 때 x로 표시하였으며, 그 결과를 표 2 및 도 1에 나타내었다.
At this time, the presence or absence of the organic contaminants were removed when the ○, when not removed was represented by x, the results are shown in Table 2 and FIG.
(몰리브덴기판)Air pollutants
Molybdenum Substrate
(구리기판)Air pollutants
Copper Board
< 유리기판의 대기 중 오염물 제거력 평가> <Evaluation of Removal of Air Pollutants from Glass Substrate>
◎: 우수(30°이상감소), ○: 양호(20~30°감소) (Double-circle): Excellent (decrease more than 30 degrees), (circle): Good (20-30 degrees decrease)
△: 미흡 (5~20°감소), X: 불량(5°미만감소)(Triangle | delta): Inadequate (5-20 degrees decrease), X: Bad (less than 5 degrees decrease)
< 몰리브덴막 및 구리막의 대기 중 오염물 제거력 평가><Evaluation of Moisture Removal Efficiency of Molybdenum Film and Copper Film>
◎: 우수(15°이상감소), ○: 양호(10~15°감소)(Double-circle): Excellent (decrease more than 15 degrees), (circle): Good (10-15 degrees decrease)
△: 미흡 (0~10°감소), X: 불량(0°미만감소)
(Triangle | delta): Inadequate (0-10 degrees reduced), X: Bad (less than 0 degrees)
표 2의 결과로부터 알 수 있는 바와 같이 실시예 1 내지 10의 경우에는 대기중오염물 및 지문오염의 제거능력이 있음을 보였다. 반면 알킬글리코사이드, 글리콜에테르계 유기용매, 다가알코올 또는 제4급 암모늄수산화물이 하나이상 첨가되지 않거나 바람직한 범위를 초과 또는 미만으로 포함하는 경우의 비교예 1 내지 4의 세정제 조성물은 오염물 제거력이 감소함을 알 수 있다. As can be seen from the results of Table 2, Examples 1 to 10 showed that the air pollutants and fingerprint contamination can be removed. On the other hand, when the alkylglycoside, glycol ether-based organic solvent, polyhydric alcohol or quaternary ammonium hydroxide are not added or contain more than or less than the preferred range, the cleaning composition of Comparative Examples 1 to 4 has a reduced pollutant removal ability. It can be seen.
또한, 도 1을 참조하면, 실시예 10의 세정제 조성물를 이용한 것이 비교예 3의 세정제 조성물을 이용한 것보다 효과적으로 오염물이 제거되었음을 알 수 있다.
In addition, referring to Figure 1, it can be seen that the use of the cleaning composition of Example 10 is more effective in removing contaminants than using the cleaning composition of Comparative Example 3.
3) 유성펜자국 제거력 평가3) Evaluation of oil pen removal ability
유기오염물의 제거력 평가를 위해 2cm x 6cm 크기로 형성된 유리기판 위에 유성사인펜으로 오염시키고, 오염된 기판을 스프레이식 기판 세정장치를 이용하여 1분 동안 상온에서 상기의 세정제 중 실시예 2 내지 4와 비교예 4로 세정하였다. 세정 후 초순수에 30초 세척한 후 질소로 건조하였다. In order to evaluate the removal power of organic contaminants, the oil-based pen was contaminated on a glass substrate formed to a size of 2 cm x 6 cm, and the contaminated substrate was compared with Examples 2 to 4 in the above-described cleaning agents at room temperature for 1 minute using a spray type substrate cleaning device. It washed with Example 4. After washing for 30 seconds in ultrapure water and dried with nitrogen.
유성사인펜의 제거 유무는 제거가 되었을 때 ○, 제거가 되지 않았을 때 x로 표시하였다. 그 결과를 표 3에 기재하였다. 또한, 실시예 4 및 비교예 4의 세정액 조성물에 의한 유성펜자국의 제거력 결과를 도 2에 나타내었다.
The presence or absence of the oily pen is indicated by ○ when removed and x when not removed. The results are shown in Table 3. In addition, the removal force of the oily pen marks by the cleaning liquid compositions of Example 4 and Comparative Example 4 is shown in FIG.
4) 파티클 제거력 평가4) Particle Removal
상기 실시예 2 내지 4 및 비교예 4의 세정제 조성물을 사용하여 유기 파티클 솔루션으로 오염시킨 유리기판에 대한 세정을 실시하였다. 즉, 유리기판을 평균 입자 크기가 0.8㎛인 유기 파티클 솔루션으로 오염시키고 1분간 3000rpm으로 스핀(spin) 드라이한 후 스프레이식 유리 기판 세정장치를 이용하여 2분동안 40℃에서 각각의 세정제로 세정하였다. 세정 후 초순수에 30초 세척한 후 질소로 건조하였다. 세정 전후의 파티클 수는 표면입자측정기(Topcon WM-1500)로 0.3㎛ 이상의 파티클 수를 측정하였고, 그 결과를 표 3에 나타내었다.
The cleaning substrates were contaminated with the organic particle solution using the cleaning composition of Examples 2 to 4 and Comparative Example 4. That is, the glass substrate was contaminated with an organic particle solution having an average particle size of 0.8 μm, spin dried at 3000 rpm for 1 minute, and then washed with each detergent at 40 ° C. for 2 minutes using a spray-type glass substrate cleaner. . After washing for 30 seconds in ultrapure water and dried with nitrogen. The number of particles before and after cleaning was measured by a particle size measuring instrument (Topcon WM-1500) of 0.3 ㎛ or more, the results are shown in Table 3.
상기 표 3 및 도 2의 결과로부터, 실시예 2 내지 4의 세정제 조성물을 이용하면 유성펜 자국 제거능력 및 파티클 제거능력이 우수한 것을 알 수 있었다. 반면에 알킬글리코사이드 대신 폴리하이드록시벤젠 구조의 카테콜이 첨가된 비교예 4의 세정제 조성물은 세정력이 감소하였다.
From the results of Table 3 and FIG. 2, it was found that the use of the cleaning composition of Examples 2 to 4 was excellent in the oil pen removal ability and particle removal ability. On the contrary, the cleaning composition of Comparative Example 4, in which catechol of polyhydroxybenzene structure was added instead of alkylglycoside, was reduced.
Claims (8)
하기 화학식 2로 표시되는 글리콜에테르계 유기용매;
다가알코올;
제4급 암모늄수산화물; 및
물을 포함하는 것을 특징으로 하는 평판 디스플레이 기판용 세정제 조성물:
<화학식 1>
상기 화학식 1에서,
R1은 수소 또는 탄소수 1 내지 3의 직쇄 또는 분지쇄 알킬이고,
R2는 탄소수 1 내지 4의 직쇄 또는 분지쇄 알킬이다.
<화학식 2>
상기 화학식 2에서,
R1은 메틸기 또는 에틸기이며,
R2는 수소 또는 히드록시에틸기이며,
n은 2 내지 3의 정수이며,
x는 1 내지 3의 정수이다.Alkylglycosides represented by Formula 1 below;
A glycol ether organic solvent represented by Formula 2;
Polyhydric alcohol;
Quaternary ammonium hydroxides; And
A cleaning composition for flat panel display substrates comprising water:
<Formula 1>
In Chemical Formula 1,
R 1 is hydrogen or straight or branched chain alkyl of 1 to 3 carbon atoms,
R 2 is straight or branched chain alkyl of 1 to 4 carbon atoms.
<Formula 2>
In Chemical Formula 2,
R 1 is a methyl group or an ethyl group,
R 2 is hydrogen or a hydroxyethyl group,
n is an integer of 2 to 3,
x is an integer of 1-3.
알킬글리코사이드 0.0001 내지 5 중량%;
글리콜에테르계 유기용매 0.05 내지 40 중량%;
다가알코올 0.01 내지 5 중량%;
제4급 암모늄수산화물 0.05 내지 5 중량%; 및
잔량의 물을 포함하는 것을 특징으로 하는, 평판 디스플레이 기판용 세정제 조성물.The method according to claim 1, wherein the total weight of the composition
0.0001 to 5 weight percent alkylglycoside;
0.05 to 40% by weight of a glycol ether organic solvent;
0.01 to 5 wt% polyhydric alcohol;
0.05 to 5% by weight of quaternary ammonium hydroxide; And
The residual amount of water is contained, The cleaning composition for flat panel display substrates characterized by the above-mentioned.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140113116A (en) * | 2013-03-15 | 2014-09-24 | 동우 화인켐 주식회사 | Composition for cleaning flat panel display and cleaning method using the same |
| KR20150069868A (en) * | 2013-12-16 | 2015-06-24 | 삼성전자주식회사 | Organic material-cleaning composition and method of forming a semiconductor device using the composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6887846B2 (en) * | 2017-03-28 | 2021-06-16 | 株式会社東京精密 | Grinding device |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140113116A (en) * | 2013-03-15 | 2014-09-24 | 동우 화인켐 주식회사 | Composition for cleaning flat panel display and cleaning method using the same |
| KR20150069868A (en) * | 2013-12-16 | 2015-06-24 | 삼성전자주식회사 | Organic material-cleaning composition and method of forming a semiconductor device using the composition |
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