TW202009326A - 組成物及蝕刻方法 - Google Patents
組成物及蝕刻方法 Download PDFInfo
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- TW202009326A TW202009326A TW108121022A TW108121022A TW202009326A TW 202009326 A TW202009326 A TW 202009326A TW 108121022 A TW108121022 A TW 108121022A TW 108121022 A TW108121022 A TW 108121022A TW 202009326 A TW202009326 A TW 202009326A
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- Prior art keywords
- composition
- mass
- etching
- copper
- general formula
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 238000005530 etching Methods 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 13
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 4
- -1 methyl ethylidene Chemical group 0.000 claims description 25
- CWYNVVGOOAEACU-UHFFFAOYSA-N iron (II) ion Substances [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract 1
- 229910001447 ferric ion Inorganic materials 0.000 abstract 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- 125000003342 alkenyl group Chemical group 0.000 description 10
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 9
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 7
- 229910000881 Cu alloy Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 239000002738 chelating agent Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 235000016068 Berberis vulgaris Nutrition 0.000 description 4
- 241000335053 Beta vulgaris Species 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 150000003385 sodium Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 description 1
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- LNQQBMJYPYXJBH-UHFFFAOYSA-N 1-(dibutylamino)butan-2-ol Chemical compound CCCCN(CCCC)CC(O)CC LNQQBMJYPYXJBH-UHFFFAOYSA-N 0.000 description 1
- ICMJHPBQTVWCNT-UHFFFAOYSA-N 1-(dibutylamino)propan-2-ol Chemical compound CCCCN(CC(C)O)CCCC ICMJHPBQTVWCNT-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- RAEOEMDZDMCHJA-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl]amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CCN(CC(O)=O)CC(O)=O)CC(O)=O RAEOEMDZDMCHJA-UHFFFAOYSA-N 0.000 description 1
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XNSPQPOQXWCGKC-UHFFFAOYSA-N C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.[N] Chemical compound C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.[N] XNSPQPOQXWCGKC-UHFFFAOYSA-N 0.000 description 1
- 0 CC(*O)N(*)* Chemical compound CC(*O)N(*)* 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical class CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021576 Iron(III) bromide Inorganic materials 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XJUDXRXKBMGKAV-UHFFFAOYSA-N [Cl].[Mn] Chemical compound [Cl].[Mn] XJUDXRXKBMGKAV-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 1
- 229960001950 benzethonium chloride Drugs 0.000 description 1
- 210000000941 bile Anatomy 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical class CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
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- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 150000002537 isoquinolines Chemical class 0.000 description 1
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- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N n-butyl carbinol Natural products CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- LRWJZGCOPMDWFZ-UHFFFAOYSA-N phthalic acid;hydrochloride Chemical compound Cl.OC(=O)C1=CC=CC=C1C(O)=O LRWJZGCOPMDWFZ-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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Abstract
本發明所提供的組成物,係可在抑制殘膜發生之下,形成直線性高、尺寸精度優異的微細圖案,可使用於銅系層等金屬層蝕刻的組成物。本發明的組成物係含有:(A)從銅(II)離子與鐵(II)離子中選擇之至少1種成分0.1~25質量%;(B)氯化物離子0.1~30質量%;(C)下述一般式(1)(R1係單鍵等;R2與R3係碳原子數1~4之伸烷基;R4與R5係氫原子等;n係使數量平均分子量成為550~1,400的數值)所示,且數量平均分子量550~1,400的化合物0.01~10質量%;(D)下述一般式(2)(R6係正丁基;R7係碳原子數2~4之伸烷基;m係1~3之整數)所示化合物0.01~10質量%;以及水;的水溶液。
Description
本發明係關於含有特定構造化合物的組成物、及使用其之蝕刻方法。
印刷基板、半導體封裝基板等的電路形成法,已知有:事後對基板附加電路圖案的添加法、從基板上的金屬箔除去不需要部分而形成電路圖案的移除法(蝕刻法)。目前在印刷基板製造時一般係採取製造成本較低的移除法(蝕刻法)。而且,近年隨電子裝置的高度化與小型化,針對能在印刷基板上形成高直線性微細圖案的蝕刻液的開發演進。
例如專利文獻1所揭示的蝕刻液,係含有:氯化鐵、草酸、及伸乙二胺四聚氧乙烯聚氧丙烯的銅或銅合金用蝕刻液。又,專利文獻2所揭示的含銅材料用蝕刻液,係含有:氯化鐵(II)、二醇醚類化合物、伸乙二胺四聚氧乙烯聚氧丙烯、磷酸、及鹽酸。
[專利文獻1]日本專利特開2012-107286號公報
[專利文獻2]日本專利特開2009-167459號公報
然而,上述專利文獻所揭示的蝕刻液,存在有難以形成具有高直線性與所需尺寸精度的微細圖案、或者容易發生成為斷線或短路肇因的殘膜等問題。
緣是,本發明為了解決上述問題而完成,其課題在於提供:可在抑制殘膜發生之下,形成直線性高、尺寸精度優異的微細圖案,並可使用於銅系層等金屬層之蝕刻的組成物。又,本發明課題在於提供:使用上述組成物的蝕刻方法。
本發明人等為了解決上述課題經深入鑽研,結果發現含有特定成分的組成物可解決上述問題,遂完成本發明。
即,根據本發明所提供的組成物,係含有:(A)從銅(II)離子與鐵(II)離子中選擇之至少1種成分0.1~25質量%、(B)氯化物離子0.1~30質量%、(C)下述一般式(1)所示數量平均分子量550~1,400的化合物0.01~10質量%、(D)下述一般式(2)所示化合物0.01~10質量%、及水的水溶液。
(上述一般式(1)中,R1係表示單鍵、或碳原子數1~4之直鏈或分支狀伸烷基;R2與R3係各自獨立表示碳原子數1~4之直鏈或分支狀伸烷基;R4與R5係各自獨立表示氫原子、或碳原子數1~4之直鏈或分支狀烷基;n係各自獨立表示使上述一般式(1)所示化合物的數量平均分子量成為550~1,400的數值;)
(上述一般式(2)中,R6係表示正丁基;R7係表示碳原子數2~4之直鏈狀或分支狀伸烷基;m係表示1~3之整數)
再者,根據本發明提供一種蝕刻方法,係包括有:使用上述組成物進行蝕刻的步驟。
根據本發明可提供能在抑制殘膜發生之下,形成直線性高、尺寸精度優異之微細圖案,並可使用於銅系層等金屬層之蝕刻的組成物。又,根據本發明可提供使用上述組成物的蝕刻方法。
1‧‧‧銅箔
2‧‧‧光阻
3‧‧‧樹脂基體
4‧‧‧細線上部寬度
5‧‧‧細線下部寬度
6‧‧‧光阻線寬
圖1係蝕刻後的試驗基板之示意剖視圖。
以下,針對本發明實施形態進行詳細說明。本發明的組成物係含有:(A)從銅(II)離子與鐵(II)離子中選擇之至少1種成分(以下亦稱「(A)成分」);(B)氯化物離子(以下亦稱「(B)成分」);(C)一般式(1)所示化合物(以下亦稱「(C)成分」);(D)一般式(2)所示化合物(以下亦稱「(D)成分」);及水作為必須成分的水溶液。本發明的組成物係適合作為用於對銅系層等金屬層施行蝕刻的蝕刻液組成物。銅系層係可例如含有:銀銅合金、鋁銅合金等銅合金;及銅等的層。其中,本發明組成物適合作為用於對含銅之銅系層進行蝕刻的蝕刻液組成物。
(A)成分係可分別單獨或組合使用銅(II)離子與鐵(II)離子。藉由摻合銅(II)化合物,可使組成物含有銅(II)離子。即,銅(II)離子的供應源係可使用銅(II)化合物。又,藉由摻合鐵(III)化合物,可使組成物含有鐵(II)離子。即,鐵(II)離子的供應源係可使用鐵(III)化合物。
銅(II)化合物係可舉例如:氯化銅(II)、溴化銅(II)、硫酸銅(II)、及氫氧化銅(II)等。鐵(III)化合物係可舉例如:氯化鐵(III)、溴化鐵(III)、碘化鐵(III)、硫酸鐵(III)、硝酸鐵(III)、及醋酸鐵(III)等。該等化合物中,較佳係氯化銅(II)與氯化鐵(III)、更佳係氯化銅(II)。該等化合物係可單獨使用一種、或組合使用二種以上。
本發明組成物中的(A)成分濃度係0.1~25質量%、較佳係0.5~23質量%、更佳係1~20質量%。(A)成分的濃度係可配合被蝕刻物的 厚度、寬度等再行適當調整。(A)成分的濃度係當單獨使用銅(II)離子或鐵(II)離子的情況,意指銅(II)離子的濃度、或鐵(II)離子的濃度。又,當組合(混合)使用銅(II)離子與鐵(II)離子的情況,意指銅(II)離子濃度與鐵(II)離子濃度的合計。例如氯化銅(II)含有10質量%時,(A)成分的濃度約4.7質量%。又,當氯化銅(II)含有10質量%、氯化鐵(III)含有10質量%時,(A)成分的濃度約8.2質量%。又,鐵(II)離子的濃度較佳係未滿5質量%。
作為(B)成分的供應源係可使用例如:氯化氫、氯化鈉、氯化鈣、氯化鉀、氯化鋇、氯化銨、氯化鐵(III)、氯化銅(II)、氯化錳(II)、氯化鈷(II)、氯化鈰(III)、及氯化鋅(II)等。其中,從蝕刻速度容易控制、及配線圖案形狀容易控制等理由而言,較佳係氯化氫、氯化鐵(III)、氯化銅(II),更佳係氯化氫。
本發明組成物中的(B)成分濃度係0.1~30質量%、較佳係0.5~28質量%、更佳係1~25質量%。(B)成分的濃度係可配合被蝕刻物的厚度、寬度等再行適當調整。若(B)成分的濃度未滿0.1質量%,則有蝕刻速度不足的情況。另一方面,即使(B)成分的濃度超過30質量%,仍不易更加提升蝕刻速度,且反而容易發生裝置構件遭腐蝕等不良情況。
(C)成分係下述一般式(1)所示數量平均分子量550~1,400的化合物。
(上述一般式(1)中,R1係表示單鍵、或碳原子數1~4之直鏈或分支狀伸烷基;R2與R3係各自獨立表示碳原子數1~4之直鏈或分支狀伸烷基;R4與R5係各自獨立表示氫原子、或碳原子數1~4之直鏈或分支狀烷基;n係各自獨立表示使上述一般式(1)所示化合物的數量平均分子量成為550~1,400的數值)
R1、R2、及R3所示碳原子數1~4之直鏈或分支狀伸烷基,係可舉例如:亞甲基、伸乙基、伸丙基、甲基伸乙基、伸丁基、乙基伸乙基、1-甲基伸丙基、及2-甲基伸丙基。R4與R5所示碳原子數1~4之直鏈或分支狀烷基係可舉例如:甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基。
(C)成分係從蝕刻速度容易控制、容易抑制側蝕刻方面而言,較佳係一般式(1)中的R1為伸乙基、R2與R3為甲基伸乙基、R4與R5為氫原子、且數量平均分子量650~1,300的化合物。其中,(C)成分的數量平均分子量更佳係750~1,200。
一般式(1)所示化合物的較佳具體例係可舉例如下述化學式No.1~No.36所示化合物。下述化學式No.1~No.36中,「Me」係表示甲基,「Et」係表示乙基,「iPr」係表示異丙基。又,n係表示各自獨立使化學式No.1~No.36所示化合物的數量平均分子量成為550~1,400之數值。
製造(C)成分的方法並無特別的限定,可應用周知反應進行製造。例如將伸乙二胺與環氧丙烷使用為原料,依照下述式(3)所示反應進行製造。下述式(3)中的「Me」係表示甲基。
本發明組成物中的(C)成分濃度係0.01~10質量%、較佳係0.05~8質量%、更佳係0.1~5質量%。若(C)成分的濃度未滿0.01質量%,無法獲得藉由摻合(C)成分所造成的所需效果。另一方面,若(C)成分的濃度超過10質量%,當將本發明組成物使用為蝕刻液組成物時,容易導致蝕刻速度降低。又,蝕刻液組成物容易滲透至銅系層等金屬層與光阻的界面處,有容易發生圖案形狀不良等情況。
(D)成分係下述一般式(2)所示化合物。
(上述一般式(2)中,R6係表示正丁基;R7係表示碳原子數2~4之直鏈狀或分支狀伸烷基;m係表示1~3之整數)
R7所示碳原子數2~4之直鏈或分支狀伸烷基,係可舉例如:伸乙基、伸丙基、甲基伸乙基、伸丁基、乙基伸乙基、1-甲基伸丙基、及2-甲基伸丙基。為使細線下部的直線性良好,R7較佳係伸乙基, m較佳係1。
一般式(2)所示化合物的較佳具體例係可舉例如:下述式No.37~No.42所示化合物。下述式No.37~No.42中,「Me」係表示甲基,「Et」係表示乙基,「nBu」係表示正丁基。
(D)成分可根據公知方法進行製造,亦可使用市售物。市售物係可舉例如:2-(二丁胺基)乙醇(產品型號:550035)、1-二丁胺基-2-丙醇(產品型號:S348856)、1-二丁胺基-2-丁醇(產品型號:S619973)等(均為SIGMA-ALDRICH公司製)。
本發明組成物中的(D)成分濃度係0.01~10質量%、較佳係0.05~8質量%、更佳係0.1~5質量%。若(D)成分濃度未滿0.01質量 %,則即使將本發明組成物使用為蝕刻液組成物,仍無法形成高直線性圖案。
本發明的組成物係含有水作為必需成分,屬於各成分溶解於水中的水溶液。水較佳係使用例如:離子交換水、純水、及超純水等經除去離子性物質與雜質的水。
本發明的組成物可適用為例如:用於對銅系層等金屬層施行蝕刻的蝕刻劑(蝕刻液)、無電解電鍍液用添加劑、金屬電解精煉用添加劑、農藥、及殺蟲劑等。尤佳係使用為用於對金屬層施行蝕刻的蝕刻劑組成物。
在本發明組成物係蝕刻液組成物的情況,在該蝕刻液組成物中,除(A)成分、(B)成分、(C)成分、(D)成分及水以外的成分,在不致損及本發明效果之範圍內,亦可摻合周知的添加劑。添加劑係可舉例如:蝕刻液組成物的安定化劑、各成分的可溶化劑、消泡劑、pH調節劑、比重調節劑、黏度調節劑、潤濕性改善劑、螯合劑、氧化劑、還原劑、界面活性劑等。該等添加劑的濃度若分別設在0.001~50質量%範圍內即可。
pH調節劑係可舉例如:硫酸、硝酸等無機酸及該等的鹽;水溶性有機酸、及其鹽;氫氧化鋰、氫氧化鈉、氫氧化鉀等氫氧化鹼金屬類;氫氧化鈣、氫氧化鍶、氫氧化鋇等氫氧化鹼土族金屬類;碳酸銨、碳酸鋰、碳酸鈉、碳酸鉀等鹼金屬的碳酸鹽類;碳酸氫鈉、 碳酸氫鉀等鹼金屬的碳酸氫鹽類;氫氧化四甲銨、膽等四級銨氫氧化物類;乙胺、二乙胺、三乙胺、羥乙胺等有機胺類;碳酸氫銨;氨等。該等pH調節劑係可單獨使用一種、或組合使用二種以上。pH調節劑的含有量係只要設為使蝕刻液組成物的pH成為所需pH的量即可。
螯合劑係可舉例如:伸乙二胺四醋酸、二伸乙三胺五醋酸、三伸乙四胺六醋酸、四伸乙五胺七醋酸、五伸乙六胺八醋酸、氮基三醋酸、及該等的鹼金屬(較佳係鈉)鹽等胺基羧酸系螯合劑;羥基亞乙基二膦酸、氮基三亞甲基膦酸、膦醯基丁烷三羧酸、及該等的鹼金屬(較佳係鈉)鹽等膦酸系螯合劑;草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、順丁烯二酸、反丁烯二酸、蘋果酸、酒石酸、檸檬酸、該等的酐、及該等的鹼金屬(較佳係鈉)鹽等二元以上的羧酸化合物;以及由二元以上羧酸化合物經脫水的單酐、二酐。蝕刻液組成物中的螯合劑濃度一般係0.01~40質量%範圍、較佳係0.05~30質量%範圍。
界面活性劑係可使用例如:非離子性界面活性劑、陽離子性活性劑、及兩性界面活性劑。非離子性界面活性劑係可舉例如:聚氧伸烷基烷醚、聚氧伸烷基烯醚、聚氧乙烯聚氧丙烯烷醚(環氧乙烷與環氧丙烷的加成形態係可為無規狀或嵌段狀之任一種)、聚乙二醇環氧丙烷加成物、聚丙二醇環氧乙烷加成物、甘油脂肪酸酯及其環氧乙烷加成物;山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇酐脂肪酸酯、烷基聚葡萄糖苷、脂肪酸單乙醇醯胺及其環氧乙烷加成物; 脂肪酸-N-甲基單乙醇醯胺及其環氧乙烷加成物;脂肪酸二乙醇醯胺及其環氧乙烷加成物;蔗糖脂肪酸酯、烷基(聚)甘油醚、聚甘油脂肪酸酯、聚乙二醇脂肪酸酯、脂肪酸甲酯乙氧化物、N-長鏈烷基二甲基氧化胺等。陽離子性界面活性劑係可舉例如:烷基(烯基)三甲銨鹽、二烷基(烯基)二甲銨鹽、烷基(烯基)四級銨鹽、含有醚基、酯基或醯胺基的單或二烷基(烯基)四級銨鹽;烷基(烯基)吡啶鎓鹽、烷基(烯基)二甲基苄銨鹽、烷基(烯基)異喹啉鎓鹽、二烷基(烯基)味啉鎓鹽、聚氧乙烯烷基(烯基)胺、烷基(烯基)胺鹽、聚胺脂肪酸衍生物、戊醇脂肪酸酯衍生物、氯化苯二甲烴銨、氯化本索寧(benzethonium chloride)等。兩性界面活性劑係可舉例如:羧基甜菜、磺甜菜、磷酸酯甜菜、醯胺胺基酸、咪唑鎓甜菜系界面活性劑等。蝕刻液組成物中的界面活性劑濃度,一般係0.001~10質量%範圍。
本發明的蝕刻方法係包括有:使用上述本發明組成物(蝕刻液組成物)進行蝕刻的步驟。除使用上述蝕刻液組成物之外,其餘本發明的蝕刻方法係可採用周知一般蝕刻方法的步驟。被蝕刻物係於金屬層中,較佳為銅系層。銅系層可舉例如含有:銀銅合金、鋁銅合金等銅合金;及銅等的層。其中更佳係銅。具體的蝕刻方法係可採用例如:浸漬法、噴霧法等。相關蝕刻條件係只要配合所使用蝕刻液組成物的組成與蝕刻方法再行適當調整即可。又,亦可採用例如:批次式、流動式、以及利用蝕刻液的氧化還原電位、比重、酸濃度進行的自動控制式等周知各種方式。
蝕刻條件並無特別的限定,可配合被蝕刻物的形狀與膜厚等再行任意設定。例如較佳係將蝕刻液組成物依0.01~0.2MPa施行噴霧、更佳係依0.01~0.1MPa施行噴霧。又,蝕刻溫度較佳係10~50℃、更佳係20~50℃。因為蝕刻液組成物的溫度會因反應熱而上升,因而視需要為了使其維持於上述溫度範圍內,亦可利用公知手段進行溫度控制。蝕刻時間係只要設定為被蝕刻物能被充分蝕刻的時間即可。例如針對膜厚1μm左右、線寬10μm左右、及開口部100μm左右的被蝕刻物,依上述溫度範圍施行蝕刻時,蝕刻時間只要設定在10~300秒左右即可。
根據使用本發明蝕刻液組成物進行的蝕刻方法,可在抑制產生殘膜情況下,形成具高直線性微細圖案。所以,除印刷配線基板之外,亦可適用於要求具高直線性之微細間距的封裝用基板、COF、TAB用途之移除法。
以下,利用實施例與比較例,針對本發明進行詳細說明,惟本發明並不因該等而受限定。
實施例及比較例所使用(C)成分的數量平均分子量,如表1所示。表1中的c-1~c-4係化學式No.17所示化合物,化學式No.17中的n係使化學式No.17所示化合物的數量平均分子量成為表1所示值的數值。
(D)成分係準備以下所示的d-1~d-5。
d-1:化合物No.37
d-2:比較化合物1
d-3:比較化合物2
d-4:比較化合物3
d-5:比較化合物4
比較化合物1~4的構造式係如下示:
(實施例1及比較例1)
依成為表2所示組成的方式,將氯化銅(II)、鹽酸、(C)成分、及(D)成分混合,獲得蝕刻液組成物No.1~17。另外,該等蝕刻液組成物中之其餘部分為水。
(實施例2及比較例2)
準備在樹脂基體上積層了厚度8μm銅箔的基體。在該基體的銅箔上形成線寬10μm、開口部6μm之圖案的光阻,而製得試驗基板。針對所製得試驗基板,使用所製備的蝕刻液組成物,於處理溫度45℃、處理壓力0.05MPa條件下,施行恰當蝕刻時間(50~95秒)噴霧的濕式蝕刻。所謂恰當蝕刻時間係指從蝕刻速度計算出直到細線下部寬度成為8μm為止的時間。然後,使用剝離液除去光阻圖案,形 成圖案(細線)。
針對所形成的細線,施行以下所示(1)~(4)項評價。評價結果如表3所示。另外,沒有殘膜(蝕刻部分之殘餘)意味著不易發生斷線、短路。又,單邊側蝕刻幅度越小,則表示側蝕刻越受抑制。蝕刻後的試驗基板之示意剖視圖係如圖1所示。
(1)有無形成細線
使用雷射顯微鏡施行截面觀察而測定。形成有細線的情況評為「++」,未形成細線的情況評為「--」。
(2)有無殘膜
使用雷射顯微鏡施行截面觀察而測定。沒有殘膜的情況評為「++」,有殘膜的情況評為「--」。
(3)細線之直線性
使用雷射顯微鏡觀察細線形狀,細線偏移未滿0.5μm者評為「+++」,0.5μm以上且未滿1.0μm者評為「++」,1.0μm以上者評為「--」。其中,於有殘膜時,由於並無法測定細線偏移,因而記為「無法測定」。
(4)單側側蝕刻寬
由下式計算出。單位係「μm」。其中,在未形成細線時,由於無法測定細線上部的寬度,因而記為「無法測定」。
「單邊側蝕刻寬度」={「光阻線寬」-「細線上部之寬度測定值」}/2
如表3所示,可知實施例2-1~2-9係可在抑制殘膜發生之下,形成直線性高、單側側蝕刻幅度小的圖案。可得知尤其實施例2-1~2-5可形成直線性更高的圖案。另一方面,得知比較例2-3~2-7係形成直線性低的圖案。又,比較例2-1~2-2均觀察到殘膜,同時比較例2-7~2-8並未形成圖案。如上述,根據本發明,可提供不易發生成為斷線與短路肇因的殘膜,能形成具有所需直線性及尺寸精度之微細圖案的蝕刻用組成物及蝕刻方法。
Claims (8)
- 一種組成物,係含有下述者之水溶液:(A)從銅(II)離子與鐵(II)離子中選擇之至少1種成分0.1~25質量%;(B)氯化物離子0.1~30質量%;(C)下述一般式(1)所示數量平均分子量550~1,400的化合物0.01~10質量%;(D)下述一般式(2)所示化合物0.01~10質量%;以及(上述一般式(1)中,R 1係表示單鍵、或碳原子數1~4之直鏈或分支狀伸烷基;R 2與R 3係各自獨立表示碳原子數1~4之直鏈或分支狀伸烷基;R 4與R 5係各自獨立表示氫原子、或碳原子數1~4之直鏈或分支狀烷基;n係各自獨立表示使上述一般式(1)所示化合物的數量平均分子量成為550~1,400的數值);(上述一般式(2)中,R 6係表示正丁基;R 7係表示碳原子數2~4之直鏈狀或分支狀伸烷基;m係表示1~3之整數)。
- 如請求項1之組成物,其中,上述一般式(1)中,R 1係伸乙基,R 2與R 3係甲基伸乙基。
- 如請求項1或2之組成物,其中,上述一般式(2)中,R 7係伸乙基,m係1。
- 如請求項1或2之組成物,係用於對金屬層施行蝕刻的蝕刻液組成物。
- 如請求項4之組成物,其中,上述金屬層係銅系層。
- 如請求項3之組成物,係用於對金屬層施行蝕刻的蝕刻液組成物。
- 如請求項6之組成物,其中,上述金屬層係銅系層。
- 一種蝕刻方法,係包括有:使用請求項4至7中任一項之組成物進行蝕刻的步驟。
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