KR101700631B1 - Photoresist stripper - Google Patents
Photoresist stripper Download PDFInfo
- Publication number
- KR101700631B1 KR101700631B1 KR1020150098517A KR20150098517A KR101700631B1 KR 101700631 B1 KR101700631 B1 KR 101700631B1 KR 1020150098517 A KR1020150098517 A KR 1020150098517A KR 20150098517 A KR20150098517 A KR 20150098517A KR 101700631 B1 KR101700631 B1 KR 101700631B1
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- amine
- additive
- performance
- photoresist
- Prior art date
Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 239000000654 additive Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 26
- 150000001412 amines Chemical class 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000002798 polar solvent Substances 0.000 claims abstract description 21
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 65
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 42
- 230000000996 additive effect Effects 0.000 claims description 40
- 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 20
- 150000003335 secondary amines Chemical class 0.000 claims description 20
- 239000000908 ammonium hydroxide Substances 0.000 claims description 18
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 17
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 16
- 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 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000600 sorbitol Substances 0.000 claims description 13
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims description 12
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 12
- 150000003512 tertiary amines Chemical class 0.000 claims description 12
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 9
- 229950006191 gluconic acid Drugs 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012972 dimethylethanolamine Substances 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- 229960002887 deanol Drugs 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 48
- 230000007797 corrosion Effects 0.000 abstract description 47
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 46
- 239000005751 Copper oxide Substances 0.000 abstract description 45
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 45
- 239000010949 copper Substances 0.000 abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 37
- 229910052802 copper Inorganic materials 0.000 abstract description 37
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 16
- 230000002401 inhibitory effect Effects 0.000 abstract description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 230000005764 inhibitory process Effects 0.000 description 14
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 235000010356 sorbitol Nutrition 0.000 description 11
- 229960002920 sorbitol Drugs 0.000 description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 239000004471 Glycine Substances 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 239000000174 gluconic acid Substances 0.000 description 3
- 235000012208 gluconic acid Nutrition 0.000 description 3
- -1 glycol compound Chemical class 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 2
- 229960003681 gluconolactone Drugs 0.000 description 2
- 229960001031 glucose Drugs 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000003536 tetrazoles Chemical class 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- JPIGSMKDJQPHJC-UHFFFAOYSA-N 1-(2-aminoethoxy)ethanol Chemical compound CC(O)OCCN JPIGSMKDJQPHJC-UHFFFAOYSA-N 0.000 description 1
- IRTOOLQOINXNHY-UHFFFAOYSA-N 1-(2-aminoethylamino)ethanol Chemical compound CC(O)NCCN IRTOOLQOINXNHY-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- ZRUPXAZUXDFLTG-UHFFFAOYSA-N 1-aminopentan-2-ol Chemical compound CCCC(O)CN ZRUPXAZUXDFLTG-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- HEEACTTWORLLPM-UHFFFAOYSA-N 2-(1h-imidazol-5-yl)ethanol Chemical compound OCCC1=CNC=N1 HEEACTTWORLLPM-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- OZICRFXCUVKDRG-UHFFFAOYSA-N 2-[2-hydroxyethyl(propyl)amino]ethanol Chemical compound CCCN(CCO)CCO OZICRFXCUVKDRG-UHFFFAOYSA-N 0.000 description 1
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-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
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- LBOQZDCAYYCJBU-UHFFFAOYSA-N 4-methyl-2h-benzotriazole;5-methyl-2h-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21.CC1=CC=CC2=NNN=C12 LBOQZDCAYYCJBU-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- UCFCTSYWEPBANH-UHFFFAOYSA-N copper benzotriazol-1-ide Chemical class [Cu+2].C1=CC=C2[N-]N=NC2=C1.C1=CC=C2[N-]N=NC2=C1 UCFCTSYWEPBANH-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000012209 glucono delta-lactone Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229940021748 l- sorbitol Drugs 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000011342 resin composition Substances 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
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Abstract
The present invention relates to a photoresist stripper composition, and more particularly, to a photoresist stripper composition which has corrosion inhibiting ability against copper and which contains amines, ammonium hydroxides, polar solvents and additives to simultaneously remove copper oxide film and photoresist, A photoresist stripper solution composition is provided. Further, since removing the oxide film for increasing the wiring resistance does not require a separate copper oxide film removing step, the process efficiency can be improved and a photoresist stripping liquid composition more safe for human body can be provided.
Description
The present invention relates to a photoresist stripping liquid composition, and more particularly, to a photoresist stripping liquid composition which does not require a separate metal oxide film removing process by simultaneously removing a metal oxide film and a photoresist efficiently while suppressing metal corrosion.
An integrated circuit of a semiconductor device or a microcircuit manufacturing process of a flat panel display device includes a step of uniformly applying a photoresist on a conductive metal film or an insulating film formed on a substrate, selectively exposing the photoresist, The conductive metal film or the insulating film is etched using the patterned photoresist film as a mask to transfer the fine circuit pattern to the lower layer of the photoresist and the unnecessary photoresist layer is removed.
The conductive metal film is usually formed of aluminum or an aluminum alloy, copper or a copper alloy, and the insulating film is formed of a silicon oxide film, a silicon nitride film, or the like.
The photoresist pattern should have good adhesion to the underlying film, and be chemically stable to the etching solution, the plating solution, and the like.
On the other hand, in order to shorten the time of accurate patterning or plating in the etching process or the like, the mechanical strength of the photoresist pattern is getting stronger. After the etching process, the ion implantation process, and the plating process are performed using the photoresist pattern, A process of removing the pattern is required. In the process of removing the photoresist pattern, if the copper surface connected to the copper wiring layer is oxidized, there arises a problem causing resistance increase. Therefore, it is necessary to develop a technique for removing the copper oxide film, which is generated in the photoresist pattern removing capability and the photoresist pattern removing process, at the same time.
Korean Patent Laid-Open Publication No. 2001-0046940 (Stripping Composition) contains a secondary amine (aminoethylaminoethanol), a polar organic solvent (2-methyl-1,3-propanediol and dimethylsulfoxide), a corrosion inhibitor ). However, such a photoresist remover has a problem in that it can not sufficiently remove the copper oxide film.
Korean Patent Laid-Open Publication No. 2010-7009298 (compound for photoresist stripping) discloses a compound for photoresist stripping composed of a hydroxylamine, a quaternary ammonium compound, and a polar organic solvent, but the hydroxylamine is a copper metal There is a problem that the soft metal such as the above is easily corroded.
Korean Patent Laid-Open Publication No. 2003-0064547 discloses a process for producing a polyurethane resin composition comprising an amine (N-methylethanolamine), a glycol ether solvent (diethylene glycol ethyl ether or diethylene glycol butyl ether or triethylene glycol) ), A corrosion inhibitor (such as a tolyltriazole or a carboxybenzotriazole or a succinic acid), but a corrosion inhibitor such as a tolylithazole or a carboxybenzotriazole is used In the included composition, the residue is reabsorbed on the copper metal due to the hydrophobicity of the Cu-BTA (copper-benzotriazole derivative) layer, and the residue is confirmed on the surface, and the copper oxide film can not be sufficiently removed.
Korean Patent Application Publication No. 2006-0026758 (composition for removing bump forming photoresist) includes an alkanolamine (monoethanolamine), a glycol compound (methylethylene glycol), an organic hydroxide (TAMH), a polar solvent (dimethylacetamide; (DMAc), a corrosion inhibitor (pyrocatechol), and the like. However, since the corrosion inhibitor includes dimethylacetamide (DMAc) and pyrocatechol which are environmentally harmful substances There is a problem that it is difficult to actually apply under severe environmental regulations.
Korean Patent Application Publication No. 2012-0096430 (release film composition for a negative photoresist of a thick film) contains an amine (ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine), a polar solvent (DMSO or NMP or 2- Rawlidone or N-ethylpyrrolidone or DMAc or DMF), a negative photoresist peeling liquid composition of a hydroxide-based thick film has been disclosed, but corrosion control is not performed on the soft copper metal due to the absence of the corrosion inhibitor. Further, when the copper oxide film removing power is checked by the treatment time, it has a short life and is difficult to apply to the process.
Korean Patent Application Publication No. 2002-0087408 (a method for removing resist, etching residue and copper oxide from a substrate having copper and low-K dielectric materials) includes fluoride (NH4F / HF), water miscible organic (PGME) However, using fluoride alone can not sufficiently remove and dissolve the photoresist, and since fluoride is contained therein, it is difficult to apply to the process because of the presence of fluoride. It has disadvantages.
Korean Patent Application Publication No. 2013-0024603 (a stripper composition for removing photoresist and a method for peeling a photoresist using the same) includes amines (imidazolyl-4-ethanol, 2-aminoethoxy-1-ethanol and aminoethylethanolamine) (DMF), N, N-diethylcarboxamide (DCA), diethylene glycol monobutyl ether (BDG), diethylene glycol monomethyl ether (MDG) Discloses a stripper composition for removing photoresist composed of a water-soluble [(methyl-1H-benzotriazole) methyl] imino] bisethanol and water. (CuO), which is formed on the surface of the copper metal due to re-adsorption to the copper metal, is difficult to apply to the process due to insufficient removal of the copper oxide film formed under severe conditions.
SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a photoresist composition which selectively uses a secondary or tertiary amine, uses a specific additive and uses alkylammonium hydroxide, A photoresist stripper liquid composition containing the same.
It is another object of the present invention to provide a photoresist stripping liquid composition which can remove the metal oxide film which simultaneously increases the wiring resistance in the process of removing the photoresist, The purpose.
It is another object of the present invention to provide a photoresist stripper liquid composition containing a safer human additive instead of a harmful additive for photoresist stripping.
One embodiment of the present invention for solving the above problems provides a release liquid composition comprising at least one amine selected from a secondary amine and a tertiary amine, an alkyl ammonium hydroxide, a polar solvent, and an additive. Preferably, the additive is selected from the group consisting of fumaric acid, maleic acid, glycine, glycerin, glycolic acid, glyoxylic acid, D-glucose, D- gluconolactone, D- sorbitol, L- sorbitol, gluconic acid, Tetrazole, and tetrazole.
Preferably, the photoresist stripper composition of the present invention has a pH of 8 or more.
Preferably, the additive may be glycolic acid alone, glyconic acid alone, glycolic acid or sorbitol, or glycolic acid and 5-amine-1H-tetrazole.
The additive may be preferably 0.3 to 5.0% by weight based on the total composition. Preferably, when the glyoxylic acid is used alone as the additive, the release liquid composition may contain 0.1-5% by weight of glyoxylic acid and 89-91% by weight of a polar solvent with respect to the whole composition, and when the sorbitol is used alone, The alkylammonium is preferably used in an amount of 7% by weight or more based on the total composition based on 25% aqueous solution.
In addition, it is preferable that the amine is from 1 to 5% by weight and the alkyl ammonium hydroxide is from 7 to 10% by weight based on the total composition.
Also preferably, the alkylammonium hydroxide is tetramethylammonium hydroxide, tetraethylammonium hydroxide, or tetrabutylammonium hydroxide, and the alkylammonium hydroxide may be 7-10 wt%.
According to the present invention, by using a secondary or tertiary amine selectively and using specific additives and alkylammonium hydroxides or the like, it is possible to minimize the corrosion of wiring in a microcircuit manufacturing process of semiconductor, flat panel display, It is possible to provide a photoresist stripper liquid composition having excellent resist removal performance.
According to the present invention, since the metal oxide film for increasing the wiring resistance can be removed at the same time in the process of removing the photoresist, a separate metal oxide film removal process is not necessary, Can be provided.
Further, according to the present invention, it is possible to provide a photoresist stripper liquid composition containing a safer human additive instead of a harmful additive for photoresist stripping.
Hereinafter, the present invention will be described in detail.
The photoresist stripper liquid composition according to an embodiment of the present invention is a photoresist stripper liquid composition which removes at least one amine selected from secondary amines and tertiary amines, alkylammonium hydroxide, polar solvent, and metal oxide film, Additives.
The pH of the peeling solution composition of the present invention is preferably 8 or more. That is, the composition is preferably basic.
In the case of a photoresist stripping liquid composition having a low pH, it is difficult to remove the bulk photoresist (bulk PR), and the degree of corrosion of copper exposed to the stripping solution becomes worse.
Particularly, as the photoresist is removed, particles are present in the solution, and these particles are re-adsorbed on the copper surface. In the case of the peeling liquid having a high pH, the zeta potential (zeta potential ) Can prevent the particles from being re-adsorbed on the copper surface. The zeta potential has a "+" charge when the pH is low and a "-" charge when the pH is high. In the "-" charge state, lift-off polymer and repulsive forces (ie, van der waals force) are applied to the wafer "+" charge, preventing the particles from reattaching.
Therefore, it is preferable that the pH of the releasing solution composition of the present invention is 8 or more. This pH can be adjusted by selectively using secondary and tertiary amines, and by selecting specific amines, corrosion of metal wiring can be suppressed have.
Preferably, at least one of the secondary amines is selected from the group consisting of diethanolamine (DEA), monomethylethanolamine, 2-methylamine ethanol, propyl-monoethanolamine and butylethanolamine, The amines include at least one member selected from the group consisting of dimethylethanolamine, triethanolamine, monomethyl diethyanolamine, diethylethanolamine, ethyldiethanolamine, propyldiethanolamine and butyldiethanolamine. Is selected.
These secondary amines and tertiary amines have excellent photoresist peeling performance while minimizing copper or aluminum corrosion. In the case of the exfoliating liquid in which the primary amines are mixed, the lifetime is lowered, the polymer (particles) is not removed, and the metal wiring is severely corroded. However, when secondary amines or tertiary amines are used, The corrosion inhibiting performance against metal wiring is excellent.
The content of the secondary and tertiary amines may be 0.1-5.0 wt%, preferably 1-5 wt% of the total weight of the composition. If the content of amines is 0.1 wt% or less, the peeling performance and the removal performance of the copper oxide film of the modified photoresist deteriorate. If the content of the amines exceeds 5 wt%, the peeling performance and the removal performance of the copper oxide film are improved, but the corrosion resistance to the copper metal is increased.
The stripping solution composition according to an embodiment of the present invention may further include ammonium hydroxide, i.e., alkyl ammonium hydroxide. The alkylammonium hydroxide may be at least one selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH) and tetrabutylammonium hydroxide (TBAH).
The content of the alkyl ammonium hydroxide may be 1-10% by weight, preferably 7-10% by weight, based on the total weight of the composition, based on 25% aqueous solution. If the content of the alkyl ammonium hydroxide is less than 1% by weight, the peelability of the modified photoresist and the ability to remove the copper oxide film are deteriorated. If the content is more than 10% by weight, corrosiveness to copper metal increases.
The release liquid composition according to an embodiment of the present invention may include a protonic polar solvent and an aprotic polar solvent.
The aprotic polar solvent is selected from the group consisting of N-methyl-2-pyrrolidone, sulfolane, 1,2-dimethylimidazole, dimethylsulfoxide, 1,3- Dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, and NN-dimethylpropionamide, and the protonic polar solvent is at least one selected from the group consisting of diethylene glycol But are not limited to, monomethyl ether, diethyleneglycol monoethyl ether, diethyleneglycol monobutyl ether, ethylene glycol butyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol, diethyleneglycol, triethyleneglycol, tetraethylglycol, , Dipropylene glycol butyl ether, propylene glycol ethyl ether, propylene glycol methyl ether, monopropylene glycol, dipropylene glycol, tripropylene glycol, tetrabutyl glycol, polybutylene glycol It may be at least one selected from the group consisting of glycerin.
The content of the polar solvent is preferably 60-95 wt% of the total weight of the composition. When the content of the polar solvent is 60% by weight or less, the solubility in the photoresist is insufficient. When the content of the polar solvent exceeds 95% by weight, the photoresist peeling performance deteriorates.
The release liquid composition according to an embodiment of the present invention may include at least one additive that is effective in preventing corrosion and removing copper oxide. Such additives include fumaric acid, maleic acid, glycine, glycollic acid, glyoxylic acid, D-glucono-1,5- lactone, D-sorbitol, L-sorbitol, gluconic acid, and 5-Amine-1H-tetrazole And may include at least one selected species.
Additives such as D-sorbitol, L-sorbitol and 5-amine-1H-tetrazole are effective for metal corrosion, although the removal ability of copper oxide is somewhat deteriorated. Fumaric acid, maleic acid, glycine, glycolic acid, glyoxylic acid, D Additives such as glucose, D-gluconolactone, gluconic acid and the like have an excellent effect in preventing corrosion of metal wiring while simultaneously removing the copper oxide film.
These additives are used to improve the corrosion inhibiting performance and the copper oxide removal performance. The content of the additive is 0.01-5.0 wt%, preferably 1.0-5.0 wt%, more preferably 3-4 wt% . If the content of the additive is less than 0.01% by weight, the metal corrosion is intensified and the copper oxide film removal performance deteriorates. If the additive content exceeds 5% by weight, the metal corrosion inhibiting performance and the copper oxide film removal performance are improved but the photoresist peeling performance is deteriorated.
Preferably, the additive may be composed of glycolic acid alone, glyconic acid alone, glyoxal alone, sorbitol alone, a mixture comprising glycolic acid and sorbitol, or a mixture comprising glycolic acid and 5-amine-1H-tetrazole .
When glycolic acid (GA) alone, glyoxylic acid (GOA), or sorbitol (DS) is used alone as an additive, these additives are preferably used in an amount of 3% by weight of the stripping solution composition, and when using glyconic acid (GCA) %. When 5-amine-1H-tetrazole (5-ATZ) is used as an additive, it may be preferable to use 1 wt%. In the case of using glyoxylic acid alone, it is preferably 0.1 to 5% by weight, especially 3% by weight based on the total weight.
The glycolic acid (GA) may be used in combination with other additives, preferably with sorbitol or 5-amine-1H-tetrazole. At this time, it may be preferable that glycolic acid is 3% by weight based on the total composition and the remaining sorbitol or 5-amine-1H-tetrazole is 1% by weight based on the total composition.
Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
<Psalter Production>
Copper oxide specimens were prepared as follows to evaluate metal corrosion inhibiting ability and oxide removing ability. The following PR specimens were prepared to evaluate the peeling performance.
(1) Copper oxide specimen
The Cu wafer was baked at 160 캜 for 4 hours, and then the wafer was cut into a size of 2 cm x 2 cm to prepare an evaluation sample.
(2) PR specimen
After PR was applied on the Si wafer, the wafer was baked at 160 ° C for 4 hours, and the wafer was cut into a size of 2 cm × 2 cm to prepare an evaluation sample.
The meanings of the abbreviations used in the following table are referred to as the following compounds, and the release evaluation criteria and the corrosion evaluation standards are also indicated by the following standards.
<Meaning of Abbreviation>
MEA: monoethanolamine, DEA: diethanolamine, TEA: triethanolamine, MIPA: monoisopropanolamine
MMEA: 2-methylamine ethanol, DMEA: dimethylethanolamine, HAD: hydroxylamine
TMAH: Tetramethylammonium hydroxide (TMAH)
DMSO: dimethyl sulfoxide, NMP: N-methyl-2-pyrrolidone,
EG: ethylene glycol, BDG: diethylene glycol monobutyl ether,
GCA: Gluconic aicd, GA: Glycolic acid, GOA: Glyoxylic acid, CA1: Glycine, CA2: Citric acid, DS: Sorbitol (D -Sorbitol)
5-ATZ: 5-Amine-1H-tetrazole
<Peel Evaluation Standard>
⊚: Excellent peeling performance, ∘: Good peeling performance
△: poor peeling performance, Х: poor peeling performance
<Corrosion inhibiting performance evaluation standard>
◎: excellent corrosion inhibiting performance, ○: good corrosion inhibiting performance
△: No corrosion inhibition performance, Х: No corrosion inhibition performance
<Copper Oxide Removal Performance>
◎: Excellent removal performance, ○: Good removal performance
△: poor removal performance, Х: almost no removal performance
The weight percentages shown in Tables 1 to 3 are based on the total composition, and the 25% aqueous solution of TMAH is on a concentration basis.
< Comparative Example 1 > to < Comparative Example 8>
Table 1 below shows Comparative Examples 1 to 8 according to the composition and composition ratio of the release liquid composition. In the following table, the peeling performance is a PR specimen in the above specimen production, the copper corrosion inhibition performance and the copper oxide film removal performance are the same as those of the specimen The copper oxide specimens in the fabrication were measured.
[Table 1]
Referring to Table 1, it can be seen that peeling performance and copper corrosion inhibition performance are not good when only ammonium hydroxide and additives are used as in Comparative Example 1. In addition, as in Comparative Example 2, When using only aprotic polar solvent, the peeling performance and the copper oxide film removal performance are excellent. However, the use of these solvents results in deterioration of copper corrosion inhibition performance. In the case where mercapto benzimidazole is used as the primary amine and the additive as in Comparative Example 3 The copper oxide film removal performance is low and the copper corrosion inhibition performance is also poor.
In addition, when benzotriazole was used as the primary amine and ammonium hydroxide, the polar solvent and the additive as in Comparative Example 4, both the copper corrosion inhibiting performance and the copper oxide removing ability were not satisfactory. As in Comparative Example 5, the secondary amine and ammonium hydroxide , Polarized mercury and mercaptobenzimidazole were used as additives, the removal performance of copper oxide film was not good. In case of using pyrocatech as primary amine and ammonium hydroxide, polar solvent and additives as in Comparative Example 6, copper corrosion inhibition performance It is obvious that there is almost no removal capability of the copper oxide film.
Further, when 4-tert-butyl pyrocatechol or ascorbic acid was used as an additive without using alkylammonium hydroxide as in Comparative Examples 7 and 8, not only the copper corrosion inhibition performance was poor, but also the copper oxide removal power .
On the other hand, in Comparative Examples 3 and 5, although the additive was the same, the types of amines were different and the addition of the protonic solvent as the polar solvent and the composition ratio of the composition were different, so the re-corrosion inhibition performance and the ability to remove the copper oxide film were different .
Therefore, it is important to mix and use specific amines, ammonium hydroxides, polar solvents, and additives in appropriate quantities in order to have excellent or good peeling performance, copper corrosion inhibiting performance, and copper oxide removal performance required in the peeling solution .
Examples 1 to 15 in the following Table 2 show examples in which at least one of the peeling performance, the copper corrosion inhibiting performance, and the copper oxide film removing performance is excellent and the performance is little.
< Example 1 > to < Example 14>
The peeling performance in Examples 1 to 14 according to the composition and composition ratio of the peeling liquid composition is shown in Table 2 below. The peeling performance is a PR specimen in the above specimen production, the copper corrosion inhibition performance and the copper oxide film removal performance are the same as those of the specimen The copper oxide specimens in the fabrication were measured.
[Table 2]
In Examples 1 and 2 of Table 2, glycine (CA1) or citric acid (CA2) was used as the secondary amine and the additive, and it was found that the peeling performance was excellent but the copper corrosion inhibition performance was not good.
In addition, Example 3 using amine as secondary amine, glycolic acid (GA) as additive, Example 5, Example 8 using amine as tertiary, additive as glyoxylic acid (GOA) Amines and additives in the case of Examples 12 and 14 using glycolic acid (GA) and further sorbitol (DS) or 5-amine-1H-tetrazole (5-ATZ), peeling performance, copper corrosion- It can be seen that the oxide film removing performance is excellent.
Comparing Examples 3 and 4, it can be seen that although the same amount of glycolic acid (GA) was used as an additive, the amine used together was more excellent than the secondary amine of Example 4, which is the tertiary amine . Therefore, when glycolic acid (GA) is used as an additive, it is preferable to use a secondary amine as an amine.
Comparing Examples 5 to 7, it can be seen that the performance varies depending on the amount of glyoxylic acid used even when the same tertiary amine is used in the same amount and the same additive, glyoxylic acid (GOA) is used. Accordingly, when glyoxylic acid is used as an additive, it may be preferable to use 0.1-5.0 wt%. If the glyoxylic acid content is lower than 0.1 wt%, the copper corrosion inhibiting performance and the copper oxide film removal performance may be lowered. If the glyoxylic acid content is higher than 5.0 wt%, the peeling performance may be deteriorated. Comparing Examples 5 and 8, it can be seen that even if different kinds of tertiary amines are used, the overall performance is excellent when the weight of the glyoxylic acid as the additive is about 3.0 wt%.
Comparing Examples 10 and 11, it can be seen that the removal performance of the copper oxide film depends on the type of the secondary amine, the amount of the ammonium hydroxide, and the amount of the polar solvent even when the same additive is used in the same amount. It can be seen that Example 11 in which the weight of ammonium hydroxide is high is superior in the removal performance of copper oxide film as compared with Example 10.
Comparing Examples 12 and 14, it can be seen that, in the case of glycolic acid (GA), all of the performance is excellent in spite of different kinds of additives, amount of ammonium hydroxide, and kind of secondary amine, ) Of about 3% by weight is used as the additive, the peeling performance, the copper corrosion inhibiting performance and the copper oxide film removing performance are excellent.
Comparing Examples 13 and 14, it can be seen that glycolic acid (GA) is used more than when using the same additive, 5-amine-1H-tetrazole (5-ATZ) and the same kind and amount of secondary amine and ammonium hydroxide, It is understood that the addition of an additive such as copper improves the removal performance of the copper oxide film. That is, it can be seen that when glycolic acid (GA) is used as an additive, the copper corrosion inhibiting performance and the copper oxide removing ability, particularly the copper oxide removing ability, are excellent without significantly deteriorating the peeling performance.
Meanwhile, in the case of Comparative Examples 1 to 3, 4 and 14, the time-dependent peeling performance, copper corrosion inhibition performance and copper oxide removal performance were measured.
[Table 3]
As can be seen from the above Table 3, as time elapses, the copper oxide film removal performance of Comparative Example 1 is lowered. In Comparative Example 2, the copper corrosion inhibition performance is almost independent of the time, It can be seen that the oxide film removing property is remarkably reduced with time. In the case of Comparative Example 3, the copper oxide film removal performance was almost not affected by the time, and the copper corrosion inhibition performance was not improved even after the elapse of time, and the peeling performance was deteriorated with time.
In addition, in Examples 4 and 14, it can be seen that the peeling performance, the copper corrosion inhibiting performance, and the copper oxide film removing performance are not reduced at all even after a lapse of time.
Accordingly, it can be seen that according to the embodiment of the present invention, the copper corrosion inhibiting performance and the copper oxide film removing performance as well as the peeling performance are kept good or excellent even if the time passes.
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.
Claims (7)
The amine is a secondary amine or a tertiary amine,
Wherein the additive comprises glycolic acid, glyconic acid, glyoxylic acid or sorbitol,
Wherein the amine and the additive are included in combination of one of the following combinations:
a) a combination of 1% by weight of the secondary amine relative to the total composition and 3% by weight of glycolic acid or 5% by weight of glycononic acid relative to the total composition;
b) a combination of 1-3% by weight of the tertiary amine relative to the total composition, and 0.1-5% by weight of the total composition (excluding 0.1% and 5% by weight) of glyoxylic acid; or
c) a combination of 1% by weight of secondary amine relative to the total composition and 3% by weight of sorbitol relative to the total composition, provided that the alkyl ammonium hydroxide is 10% by weight based on the total composition by weight of the 25% aqueous solution.
Wherein the amine and the additive are included in combination as a), wherein the additive is a glycolic acid.
Wherein the additive further comprises 3% by weight of sorbitol or 1% by weight of 5-amine-1H-tetrazole relative to the total composition.
When the sorbitol is further contained, the alkyl ammonium hydroxide is contained in an amount of 10% by weight based on the total composition based on 25% by weight aqueous solution,
Wherein the alkylammonium hydroxide is contained in an amount of 7% by weight based on the total composition based on 25% by weight aqueous solution when the 5-amine-1H-tetrazole is further included.
Wherein the secondary amine is diethanolamine or 2-methylamine ethanol, and the tertiary amine is dimethylethanolamine or triethanolamine.
The release liquid composition further comprises an aprotic polar solvent,
Wherein the aprotic polar solvent is dimethyl sulfoxide.
Wherein the alkyl ammonium hydroxide is tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrabutylammonium hydroxide.
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