TW202035794A - Etching composition and etching method using the same - Google Patents
Etching composition and etching method using the same Download PDFInfo
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- TW202035794A TW202035794A TW109109110A TW109109110A TW202035794A TW 202035794 A TW202035794 A TW 202035794A TW 109109110 A TW109109110 A TW 109109110A TW 109109110 A TW109109110 A TW 109109110A TW 202035794 A TW202035794 A TW 202035794A
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- etching
- weight
- film
- compound
- metal film
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- 238000005530 etching Methods 0.000 title claims abstract description 258
- 239000000203 mixture Substances 0.000 title claims abstract description 134
- 238000000034 method Methods 0.000 title claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 81
- 239000002184 metal Substances 0.000 claims abstract description 81
- -1 amine compound Chemical class 0.000 claims abstract description 71
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003112 inhibitor Substances 0.000 claims abstract description 44
- 239000000654 additive Substances 0.000 claims abstract description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000000996 additive effect Effects 0.000 claims abstract description 23
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 229960000643 adenine Drugs 0.000 claims abstract description 8
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- 229910052750 molybdenum Inorganic materials 0.000 claims description 32
- 239000011733 molybdenum Substances 0.000 claims description 31
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
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- 239000011701 zinc Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229910052757 nitrogen Chemical group 0.000 claims description 3
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Chemical group 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 135
- 230000000052 comparative effect Effects 0.000 description 25
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 239000000758 substrate Substances 0.000 description 14
- 229910052723 transition metal Inorganic materials 0.000 description 13
- 150000003624 transition metals Chemical class 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
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- 239000002253 acid Substances 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 3
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- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 2
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
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- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 150000001412 amines Chemical class 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
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- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
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- 150000002739 metals Chemical class 0.000 description 2
- DTSBBUTWIOVIBV-UHFFFAOYSA-N molybdenum niobium Chemical compound [Nb].[Mo] DTSBBUTWIOVIBV-UHFFFAOYSA-N 0.000 description 2
- JZLMRQMUNCKZTP-UHFFFAOYSA-N molybdenum tantalum Chemical compound [Mo].[Ta] JZLMRQMUNCKZTP-UHFFFAOYSA-N 0.000 description 2
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
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- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- QFKJQDAZSYZAOM-UHFFFAOYSA-N (1-oxidanyl-1-phosphono-ethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O.OP(=O)(O)C(O)(C)P(O)(O)=O QFKJQDAZSYZAOM-UHFFFAOYSA-N 0.000 description 1
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
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- ZYVAQZSGKALVEU-UHFFFAOYSA-N 2-[2-[bis(2-hydroxy-2-oxoethyl)amino]ethyl-(2-hydroxy-2-oxoethyl)amino]ethanoic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O ZYVAQZSGKALVEU-UHFFFAOYSA-N 0.000 description 1
- KQLXBKWUVBMXEM-UHFFFAOYSA-N 2-amino-3,7-dihydropurin-6-one;7h-purin-6-amine Chemical compound NC1=NC=NC2=C1NC=N2.O=C1NC(N)=NC2=C1NC=N2 KQLXBKWUVBMXEM-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
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- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 229940087646 methanolamine Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- 125000002950 monocyclic group Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
- C23F11/165—Heterocyclic compounds containing sulfur as hetero atom
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- 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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Abstract
Description
本發明涉及蝕刻組合物及利用其的蝕刻方法，更詳細而言，涉及一種蝕刻組合物、利用其的金屬膜的蝕刻方法以及包括利用本發明蝕刻組合物而進行的製程的半導體元件製造方法。The present invention relates to an etching composition and an etching method using the same. More specifically, it relates to an etching composition, a metal film etching method using the same, and a semiconductor device manufacturing method including a process performed using the etching composition of the present invention.
半導體裝置及TFT-LCD等微電路是經過如下的一系列光微影製程而完成的。即，將光阻劑均勻塗布於形成在基板上的鋁、鋁合金、銅及銅合金等導電性金屬膜或矽氧化膜、矽氮化膜等絕緣膜，然後藉由刻有圖案的光罩照射光後，藉由顯影而形成所需圖案的光阻，藉由乾式或濕式蝕刻對存在於光阻下部的金屬膜或絕緣膜轉印圖案後，藉由剝離製程，將不需要的光阻去除。Microcircuits such as semiconductor devices and TFT-LCDs are completed through a series of photolithography processes as follows. That is, the photoresist is uniformly coated on conductive metal films such as aluminum, aluminum alloy, copper, and copper alloys or insulating films such as silicon oxide films, silicon nitride films, etc., formed on the substrate, and then the patterned photomask After irradiating light, the photoresist with the desired pattern is formed by developing, and the pattern is transferred to the metal film or insulating film existing under the photoresist by dry or wet etching, and then the unwanted light is removed by the peeling process. Block removal.
為了製造半導體裝置及TFT-LCD的基板，作為TFT的柵極及數據線電極用配線材料，經常使用鋁、鋁合金層及鉻，但為了實現大型顯示器，需要減少電極用配線的電阻，為此正在嘗試將電阻低的金屬銅用於形成配線。In order to manufacture semiconductor devices and TFT-LCD substrates, aluminum, aluminum alloy layers, and chromium are often used as wiring materials for TFT gate and data line electrodes. However, in order to realize large-scale displays, it is necessary to reduce the resistance of electrode wiring. Attempts are being made to use low-resistance metal copper to form wiring.
但是，由於銅存在與玻璃基板及矽絕緣膜的附著力低且會向矽膜擴散的問題，因而將鈦、鉬等用作銅膜的下部阻隔金屬。However, because copper has the problem of low adhesion to the glass substrate and silicon insulating film and diffusion into the silicon film, titanium, molybdenum, etc. are used as the lower barrier metal of the copper film.
由此，正在針對用於下部阻隔金屬膜與銅膜之蝕刻的蝕刻組合物進行積極研究。Therefore, active research is being conducted on etching compositions used for etching of the lower barrier metal film and the copper film.
當阻隔金屬為鈦、鉬合金時，蝕刻製程由於鈦的化學性質而具有只能以特定離子或特定條件進行蝕刻的缺點；當阻隔金屬為鉬時，蝕刻製程具有銅膜與鉬膜的附著力降低的缺點。特別是在銅膜與鉬膜的附著力降低的情況下，蝕刻組合物因滲透而導致的過蝕刻現象很嚴重。When the barrier metal is titanium or molybdenum alloy, the etching process has the disadvantage that it can only be etched with specific ions or specific conditions due to the chemical properties of titanium; when the barrier metal is molybdenum, the etching process has the adhesion of the copper film and the molybdenum film Reduce the disadvantages. Especially when the adhesion between the copper film and the molybdenum film is reduced, the over-etching phenomenon caused by the penetration of the etching composition is very serious.
進而，利用具有強氧化性的蝕刻溶液對銅鉬膜進行蝕刻時，由於蝕刻速度過快而在製程寬容度方面存在問題，錐形輪廓（taper profile）中錐角（taper angle）具有90度或更大的值而使後續製程變得困難，圖案的直線性也不好。Furthermore, when the copper-molybdenum film is etched with a strong oxidizing etching solution, there is a problem in the process latitude due to the excessively fast etching speed. In the tapered profile (taper profile), the taper angle is 90 degrees or A larger value makes the subsequent manufacturing process difficult, and the linearity of the pattern is not good.
作為一個例子，當同時蝕刻銅／鉬合金時，為了提高鉬合金的蝕刻速度並去除鉬合金的殘渣，銅／鉬合金蝕刻液包含氟化合物。這種氟化合物存在如下問題：不僅蝕刻鉬合金，還蝕刻作為銅／鉬合金柵極配線之下部膜的玻璃基板以及作為源極汲極配線之下部膜的SiNx。下部膜的蝕刻增加會使得後續製程及再處理（rework）製程中因蝕刻污漬而導致的不良以及減薄製程中因蝕刻污漬而導致的不良增加。As an example, when etching the copper/molybdenum alloy at the same time, in order to increase the etching speed of the molybdenum alloy and remove the residue of the molybdenum alloy, the copper/molybdenum alloy etching solution contains a fluorine compound. Such fluorine compounds have the following problems: not only etching the molybdenum alloy, but also etching the glass substrate as the lower film of the copper/molybdenum alloy gate wiring and the SiNx as the lower film of the source drain wiring. The increase in the etching of the lower film will increase the defects caused by the etching stains in the subsequent process and the rework process and the defects caused by the etching stains in the thinning process.
各種傳統蝕刻組合物除了上述記載的問題以外，依然具有降低蝕刻特性的問題，因此需要針對能夠顯著改善這種問題的蝕刻組合物進行研究。In addition to the problems described above, various conventional etching compositions still have the problem of reducing the etching characteristics. Therefore, it is necessary to study etching compositions that can significantly improve this problem.
現有技術文獻[01] 專利文獻[02] 韓國公開專利第10-2010-0040352號Prior Art Literature [01] Patent Literature [02] Korean Patent Publication No. 10-2010-0040352
本發明提供一種蝕刻組合物，特別是將銅等金屬的單一膜或包含銅等金屬的多重金屬膜有效地進行蝕刻，而能夠顯著提高蝕刻特性的蝕刻組合物及利用其的蝕刻方法。The present invention provides an etching composition, particularly an etching composition that effectively etches a single film of a metal such as copper or a multiple metal film containing a metal such as copper, and can significantly improve the etching characteristics, and an etching method using the same.
另外，本發明提供一種包括利用本發明蝕刻組合物而進行的製程的半導體元件製造方法。In addition, the present invention provides a method for manufacturing a semiconductor device including a process performed using the etching composition of the present invention.
本發明提供可驚人地提高蝕刻性能的蝕刻組合物，本發明的蝕刻組合物包含過氧化氫、蝕刻添加劑、pH調節劑、氟化合物、底切抑制劑、胺化合物、以及餘量的水，該蝕刻添加劑為磷酸系化合物及硫酸系化合物，該底切抑制劑為腺嘌呤、鳥嘌呤或其混合物，該底切抑制劑與該胺化合物的重量比為1：5至10。The present invention provides an etching composition that can surprisingly improve etching performance. The etching composition of the present invention includes hydrogen peroxide, an etching additive, a pH adjuster, a fluorine compound, an undercut inhibitor, an amine compound, and the balance of water. The etching additives are phosphoric acid compounds and sulfuric acid compounds, the undercutting inhibitor is adenine, guanine or a mixture thereof, and the weight ratio of the undercutting inhibitor to the amine compound is 1:5-10.
較佳地，根據本發明之一實施態樣的胺化合物可為C4至C10的烷基胺、C3至C10的環烷基胺或其混合物，更佳地，可為直鏈或支鏈的己胺。Preferably, the amine compound according to one embodiment of the present invention may be a C4 to C10 alkylamine, a C3 to C10 cycloalkylamine or a mixture thereof, and more preferably, it may be a linear or branched hexylamine. amine.
根據本發明之一實施態樣的蝕刻組合物中，pH調節劑與蝕刻添加劑的重量比可為1：1至4。In the etching composition according to an embodiment of the present invention, the weight ratio of the pH adjuster to the etching additive may be 1:1 to 4.
根據本發明之一實施態樣的磷酸系化合物可為磷酸、磷酸鹽或其混合物，硫酸系化合物可為硫酸、硫酸鹽或其混合物。The phosphoric acid compound according to an embodiment of the present invention may be phosphoric acid, phosphate or a mixture thereof, and the sulfuric acid compound may be sulfuric acid, a sulfate or a mixture thereof.
根據本發明之一實施態樣的蝕刻組合物相對於蝕刻組合物之總重量可包含10至30重量%的過氧化氫、0.01至5重量%的蝕刻添加劑、0.1至3重量%的pH調節劑、0.01至1重量%的氟化合物、0.01至2重量%的底切抑制劑、0.1至5重量%的胺化合物、以及餘量的水。The etching composition according to one embodiment of the present invention may contain 10 to 30% by weight of hydrogen peroxide, 0.01 to 5% by weight of etching additives, and 0.1 to 3% by weight of pH regulator relative to the total weight of the etching composition. , 0.01 to 1% by weight of fluorine compound, 0.01 to 2% by weight of undercut inhibitor, 0.1 to 5% by weight of amine compound, and the balance of water.
根據本發明之一實施態樣的氟化合物可為選自HF、NaF、KF、AlF3 、HBF4 、NH4 F、NH4 HF2 、NaHF2 、KHF2 、及NH4 BF4 的任一種或二種以上。The fluorine compound according to an embodiment of the present invention may be any one selected from HF, NaF, KF, AlF 3 , HBF 4 , NH 4 F, NH 4 HF 2 , NaHF 2 , KHF 2 , and NH 4 BF 4 Or two or more.
根據本發明之一實施態樣的蝕刻組合物還可以包含選自蝕刻抑制劑及螯合劑的一種或二種以上。The etching composition according to an embodiment of the present invention may further include one or more selected from an etching inhibitor and a chelating agent.
根據本發明之一實施態樣的蝕刻抑制劑是分子內包含選自氧、硫及氮之一種或二種以上的雜原子的雜環化合物，The etching inhibitor according to an embodiment of the present invention is a heterocyclic compound containing one or more heteroatoms selected from oxygen, sulfur and nitrogen in the molecule,
螯合劑可為分子內包含胺基及羧酸基或膦酸基的化合物。The chelating agent may be a compound containing an amine group and a carboxylic acid group or a phosphonic acid group in the molecule.
另外，本發明提供一種金屬膜的蝕刻方法，包括使根據本發明之一實施態樣的蝕刻組合物與金屬膜接觸而對金屬膜進行蝕刻的步驟。In addition, the present invention provides a method for etching a metal film, including the step of contacting the etching composition according to an embodiment of the present invention with the metal film to etch the metal film.
根據本發明之一實施態樣的金屬膜可包含選自銅、鉬、鈦、銦、鋅、錫、及鈮的一種或二種以上。The metal film according to one embodiment of the present invention may include one or more selected from copper, molybdenum, titanium, indium, zinc, tin, and niobium.
另外，根據本發明之一實施態樣的金屬膜可選自包含銅的單一金屬膜、包含銅合金膜的合金膜、以及包含含銅之上部膜與鉬膜或鉬合金膜的多重膜。In addition, the metal film according to an embodiment of the present invention may be selected from a single metal film including copper, an alloy film including a copper alloy film, and a multiple film including a copper-containing upper film and a molybdenum film or a molybdenum alloy film.
另外，本發明提供一種半導體元件的製造方法，包括利用根據本發明之一實施態樣的蝕刻組合物而進行的蝕刻製程。In addition, the present invention provides a method for manufacturing a semiconductor device, including an etching process performed by using the etching composition according to one embodiment of the present invention.
本發明的蝕刻組合物的穩定性非常優異，即使處理張數及處理時間增加，蝕刻速度、蝕刻均勻性及不發生底切等蝕刻特性也不會發生變化，因而具有優異的蝕刻性能。The etching composition of the present invention has excellent stability. Even if the number of processed sheets and processing time increase, the etching characteristics such as etching speed, etching uniformity, and no undercutting will not change, and thus have excellent etching performance.
另外，本發明的蝕刻組合物不僅蝕刻速度優異，而且具有如下顯著提高的蝕刻特性：不殘留下部膜的金屬等殘渣，蝕刻時不產生熱量，因而不會發生底切，具有低錐角等。In addition, the etching composition of the present invention not only has excellent etching speed, but also has significantly improved etching characteristics: no residues such as metal of the underlying film remain, no heat is generated during etching, no undercut occurs, and low taper angle.
因此，利用本發明蝕刻組合物的金屬膜的蝕刻方法能夠將金屬單一膜或包含金屬等的多重金屬膜以優異的蝕刻速度有效地進行蝕刻。Therefore, the method for etching a metal film using the etching composition of the present invention can efficiently etch a single metal film or a multiple metal film containing metal or the like at an excellent etching rate.
另外，包括利用本發明蝕刻組合物而進行的製程的半導體元件製造方法由於利用本發明蝕刻組合物，從而能夠實現具有提高之性能的半導體元件的製造。In addition, the semiconductor device manufacturing method including the process performed by using the etching composition of the present invention can realize the manufacture of semiconductor devices with improved performance due to the use of the etching composition of the present invention.
本發明說明書中記載的「烷基」是指僅由碳及氫原子構成，並具有1至20個碳原子（C1-C20烷基）、1至15個碳原子（C1-C15烷基）、4至10個碳原子（C4-C10烷基）、較佳為4至8個碳原子（C4-C8烷基），且藉由單鍵附著於分子之其他部分的飽和直鏈型或支鏈型烴鏈原子團。作為具體例的烷基包含甲基、乙基、正丙基、1-甲基乙基（異丙基）、正丁基、正戊基、1,1-二甲基乙基（三級丁基）、3-甲基己基、2-甲基己基等。The "alkyl group" described in the specification of the present invention is composed of only carbon and hydrogen atoms, and has 1 to 20 carbon atoms (C1-C20 alkyl), 1 to 15 carbon atoms (C1-C15 alkyl), 4 to 10 carbon atoms (C4-C10 alkyl group), preferably 4 to 8 carbon atoms (C4-C8 alkyl group), and is attached to the other part of the molecule by a single bond saturated linear or branched Type hydrocarbon chain radicals. Specific examples of alkyl groups include methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, n-pentyl, 1,1-dimethylethyl (tertiary butyl) Group), 3-methylhexyl, 2-methylhexyl, etc.
本說明書中記載的「環烷基」是指僅由碳原子及氫原子構成，並且可包含具有3至15個碳原子、較佳為3至10個碳原子、3至9個碳原子、3至8個碳原子、3至7個碳原子、3至6個碳原子、3至5個碳原子的稠合或橋連的環系、具有4個碳原子的環、或者具有3個碳原子的環的穩定的非芳香族單環或多環烴原子團。環烷基環可為飽和或不飽和，可以藉由單鍵附著於分子之其他部分。單環原子團例如包含環丙基、環丁基、環戊基、環己基、環庚基、及環辛基。多環原子團例如包含金剛烷基、降莰基、十氫萘基、7,7-二甲基-雙環[2.2.1]庚基等。The "cycloalkyl group" described in this specification means only composed of carbon atoms and hydrogen atoms, and may include 3 to 15 carbon atoms, preferably 3 to 10 carbon atoms, 3 to 9 carbon atoms, 3 A fused or bridged ring system of to 8 carbon atoms, 3 to 7 carbon atoms, 3 to 6 carbon atoms, 3 to 5 carbon atoms, a ring with 4 carbon atoms, or 3 carbon atoms The stable non-aromatic monocyclic or polycyclic hydrocarbon radicals of the ring. The cycloalkyl ring can be saturated or unsaturated, and can be attached to other parts of the molecule by a single bond. The monocyclic atom group includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. The polycyclic atom group includes, for example, adamantyl, norbornyl, decahydronaphthyl, 7,7-dimethyl-bicyclo[2.2.1]heptyl and the like.
本發明提供一種蝕刻組合物，特別是提供一種顯著提高含銅等單一或多重金屬膜之蝕刻特性且蝕刻時不發熱的蝕刻組合物。The present invention provides an etching composition, in particular, an etching composition that significantly improves the etching characteristics of single or multiple metal films containing copper and the like and does not generate heat during etching.
本發明的蝕刻組合物包含過氧化氫、蝕刻添加劑、pH調節劑、氟化合物、底切抑制劑、胺化合物、以及餘量的水，該蝕刻添加劑為磷酸系化合物及硫酸系化合物，該底切抑制劑為腺嘌呤、鳥嘌呤或其混合物，該底切抑制劑與該胺化合物的重量比為1：5至10。The etching composition of the present invention contains hydrogen peroxide, an etching additive, a pH adjuster, a fluorine compound, an undercut inhibitor, an amine compound, and the balance of water. The etching additive is a phosphoric acid compound and a sulfuric acid compound. The inhibitor is adenine, guanine or a mixture thereof, and the weight ratio of the undercutting inhibitor to the amine compound is 1:5-10.
本發明的蝕刻組合物藉由如上所述之成分的組合，特別是藉由過氧化氫、pH調節劑、氟化合物、特定化合物之混合物的蝕刻添加劑、特定化合物的底切抑制劑、及胺化合物的組合，且同時具有受控制的底切抑制劑與胺化合物的重量比，從而驚人地提高蝕刻特性。The etching composition of the present invention is based on the combination of the above-mentioned components, especially by hydrogen peroxide, a pH adjuster, a fluorine compound, an etching additive of a mixture of a specific compound, an undercut inhibitor of a specific compound, and an amine compound It also has a controlled weight ratio of undercut inhibitor to amine compound, which surprisingly improves etching characteristics.
具體而言，具有如上所述之成分的組合及特定成分之受控制的重量比的本發明蝕刻組合物，其穩定性非常優異、可保護被蝕刻的單一或多重金屬膜的介面、不發熱，從而極度提高蝕刻特性。Specifically, the etching composition of the present invention having the above-mentioned combination of components and a controlled weight ratio of specific components has excellent stability, can protect the interface of the etched single or multiple metal films, and does not generate heat. Thereby greatly improving the etching characteristics.
較佳地，本發明藉由於蝕刻組合物中混合使用屬於特定化合物的磷酸系化合物與硫酸系化合物作為蝕刻添加劑，從而具有進一步提高的蝕刻特性。本發明的磷酸系化合物可為磷酸、磷酸鹽或其混合物，硫酸系化合物可為硫酸、硫酸鹽或其混合物。較佳地，本發明的蝕刻組合物藉由使用硫酸與磷酸鹽的混合物作為蝕刻添加劑，從而藉由與蝕刻添加劑以外的其它組合物的組合，而在蝕刻特性方面具有協同效果。Preferably, in the present invention, the etching composition has further improved etching characteristics by mixing phosphoric acid-based compounds and sulfuric acid-based compounds belonging to specific compounds as etching additives in the etching composition. The phosphoric acid compound of the present invention may be phosphoric acid, phosphate or a mixture thereof, and the sulfuric acid compound may be sulfuric acid, a sulfate or a mixture thereof. Preferably, the etching composition of the present invention uses a mixture of sulfuric acid and phosphate as an etching additive, and thus has a synergistic effect in terms of etching characteristics by combining with other compositions other than the etching additive.
根據本發明之一實施態樣的胺化合物可以是C4至C10的烷基胺、C3至C10的環烷基胺或其混合物，較佳地，可以是C4至C8的烷基胺、C3至C8的環烷基胺或其混合物。The amine compound according to one embodiment of the present invention may be a C4 to C10 alkyl amine, a C3 to C10 cycloalkyl amine or a mixture thereof, preferably, it may be a C4 to C8 alkyl amine, C3 to C8 Of cycloalkylamines or mixtures thereof.
較佳地，根據本發明之一實施態樣的胺化合物可為直鏈或支鏈的C5-C7烷基胺，更佳地，可為直鏈或支鏈的己胺。Preferably, the amine compound according to an embodiment of the present invention may be a linear or branched C5-C7 alkylamine, more preferably, it may be a linear or branched hexylamine.
根據本發明之一實施態樣的底切抑制劑與胺化合物的重量比可為1：5至10。The weight ratio of the undercut inhibitor to the amine compound according to an embodiment of the present invention may be 1:5-10.
相對於根據本發明之一實施態樣的蝕刻組合物之總重量，可包含10至30重量%的過氧化氫、0.01至5重量%的蝕刻添加劑、0.1至3重量%的pH調節劑、0.01至1重量%的氟化合物、0.01至2重量%的底切抑制劑、0.1至5重量%的胺化合物、以及餘量的水，較佳地，可以是15至25重量%的過氧化氫、0.1至3重量%的蝕刻添加劑、0.1至3重量%的pH調節劑、0.05至0.5重量的氟化合物、0.05至1重量%的底切抑制劑、0.1至1重量%的胺化合物、以及餘量的水。Relative to the total weight of the etching composition according to one embodiment of the present invention, it may contain 10 to 30% by weight of hydrogen peroxide, 0.01 to 5% by weight of etching additives, 0.1 to 3% by weight of pH adjuster, 0.01 To 1% by weight of fluorine compound, 0.01 to 2% by weight of undercut inhibitor, 0.1 to 5% by weight of amine compound, and the balance of water, preferably 15 to 25% by weight of hydrogen peroxide, 0.1 to 3% by weight of etching additives, 0.1 to 3% by weight of pH adjusters, 0.05 to 0.5% by weight of fluorine compounds, 0.05 to 1% by weight of undercut inhibitors, 0.1 to 1% by weight of amine compounds, and the balance Of water.
下面，對於根據本發明之一實施態樣的蝕刻組合物的各個構成成分更詳細地進行說明。Hereinafter, each constituent component of the etching composition according to one embodiment of the present invention will be described in more detail.
（a）過氧化氫(A) Hydrogen peroxide
本發明的蝕刻組合物中，過氧化氫作為金屬或金屬膜的過渡金屬或金屬的主要氧化劑而發揮作用。In the etching composition of the present invention, hydrogen peroxide functions as a transition metal of a metal or a metal film, or a main oxidizing agent of the metal.
相對於蝕刻組合物總重量，根據本發明之一實施態樣的過氧化氫可包含10至30重量%。當過氧化氫以小於10重量%包含時，由於過渡金屬的氧化性不充分而可能無法完成蝕刻，當以超過30重量%包含時，存在由於蝕刻速度過快而製程控制變得困難的問題。針對可實現較佳蝕刻速度而能夠防止蝕刻殘渣及蝕刻不良，並且減少CD損失（CD loss）且容易調節製程的方面而言，較佳可包含15至25重量%。Relative to the total weight of the etching composition, the hydrogen peroxide according to an embodiment of the present invention may contain 10 to 30% by weight. When hydrogen peroxide is contained at less than 10% by weight, etching may not be completed due to insufficient oxidation of the transition metal, and when it is contained at more than 30% by weight, there is a problem that process control becomes difficult due to an excessively fast etching rate. In terms of achieving a better etching rate, preventing etching residues and etching defects, reducing CD loss, and easily adjusting the process, it is preferable to include 15 to 25% by weight.
（b）蝕刻添加劑(B) Etching additives
本發明的蝕刻添加劑針對過渡金屬或金屬發揮輔助氧化劑的作用，並且改善錐形輪廓，本發明的蝕刻添加劑使用特定無機酸的混合物。The etching additive of the present invention acts as an auxiliary oxidant for transition metals or metals and improves the tapered profile. The etching additive of the present invention uses a mixture of specific inorganic acids.
本發明的無機酸可為磷酸系化合物及硫酸系化合物，磷酸系化合物只要是包含磷酸的化合物，則均可使用，可為磷酸、磷酸鹽、或其混合物，另外，硫酸系化合物只要是包含硫酸的無機酸，則均可使用，作為實例，可為硫酸、硫酸鹽、或其混合物，上述硫酸鹽可為硫酸銨、過硫酸銨、硫酸鈉、過硫酸鈉、硫酸鉀、或過硫酸鉀，但並不限於此。The inorganic acid of the present invention may be a phosphoric acid compound or a sulfuric acid compound. As long as the phosphoric acid compound is a compound containing phosphoric acid, any phosphoric acid compound may be used. It may be phosphoric acid, phosphate, or a mixture thereof. In addition, the sulfuric acid compound may contain sulfuric acid. Any inorganic acid can be used. As an example, it can be sulfuric acid, sulfate, or a mixture thereof. The aforementioned sulfate can be ammonium sulfate, ammonium persulfate, sodium sulfate, sodium persulfate, potassium sulfate, or potassium persulfate, But it is not limited to this.
較佳地，根據本發明之一實施態樣的磷酸系化合物可為選自磷酸、磷酸氫鉀、磷酸氫鈉、磷酸氫銨、磷酸鈉、過磷酸鈉、磷酸鉀、過磷酸鉀、磷酸銨、以及過磷酸銨的一種或二種以上，硫酸系化合物可為選自硫酸、硫酸氫銨、硫酸銨、過硫酸銨、硫酸鈉、過硫酸鈉、硫酸鉀、及過硫酸鉀的一種或二種以上。Preferably, the phosphoric acid compound according to one embodiment of the present invention may be selected from phosphoric acid, potassium hydrogen phosphate, sodium hydrogen phosphate, ammonium hydrogen phosphate, sodium phosphate, sodium superphosphate, potassium phosphate, potassium superphosphate, and ammonium phosphate. , And one or more of ammonium perphosphate, the sulfuric acid compound can be one or two selected from sulfuric acid, ammonium bisulfate, ammonium sulfate, ammonium persulfate, sodium sulfate, sodium persulfate, potassium sulfate, and potassium persulfate More than species.
較佳地，根據本發明之一實施態樣的蝕刻添加劑可為硫酸及磷酸鹽的組合。Preferably, the etching additive according to an embodiment of the present invention may be a combination of sulfuric acid and phosphate.
根據本發明之一實施態樣的蝕刻添加劑相對於蝕刻組合物之總重量可包含0.01至5重量%，針對使用蝕刻添加劑的錐形輪廓改善效果及抑制蝕刻特性的降低的方面而言，較佳可包含0.1至3重量%，更佳可包含1至3重量%。The etching additive according to an embodiment of the present invention may contain 0.01 to 5% by weight relative to the total weight of the etching composition. It is preferable to use the etching additive to improve the tapered profile effect and suppress the degradation of etching characteristics It may contain 0.1 to 3% by weight, more preferably 1 to 3% by weight.
（c）pH調節劑(C) pH regulator
根據本發明之一實施態樣的pH調節劑可為選自氫氧化鈉、氫氧化鉀、碳酸鈉、及氫氧化銨的一種或二種以上，較佳可為氫氧化鈉。可將上述蝕刻液組合物的pH調節為3至5。當上述蝕刻液組合物的pH具有如上所述的範圍時，氧化物半導體不會被蝕刻，並且能夠順利地進行銅與鉬合金的蝕刻。上述pH調節劑相對於組合物的總重量較佳包含0.1至3重量%。The pH adjusting agent according to an embodiment of the present invention may be one or two or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, and ammonium hydroxide, and preferably may be sodium hydroxide. The pH of the etchant composition can be adjusted to 3 to 5. When the pH of the etching solution composition has the above range, the oxide semiconductor is not etched, and the copper and molybdenum alloy can be etched smoothly. The aforementioned pH adjuster preferably contains 0.1 to 3% by weight relative to the total weight of the composition.
pH調節劑與蝕刻添加劑的重量比可為1：1至4。The weight ratio of the pH adjuster to the etching additive may be 1:1 to 4.
蝕刻添加劑的重量比無法滿足上述的範圍時，蝕刻速度顯著減少，在處理張數增加時可能會發熱及發生底切，且抑制鉬蝕刻，從而可能導致殘膜發生。If the weight ratio of the etching additive does not satisfy the above range, the etching rate is significantly reduced, and when the number of processed sheets increases, heat generation and undercutting may occur, and molybdenum etching may be suppressed, which may cause film residue.
（d）氟化合物(D) Fluorine compounds
本發明的蝕刻組合物所包含的氟化合物在同時蝕刻作為雙重金屬膜之實例的銅／鉬膜時，發揮提高鉬膜的蝕刻速度而使尾部長度減少，並去除蝕刻時必然產生的鉬殘渣的作用。鉬的尾部增加可能會減少亮度，當殘渣殘留於基板及下部膜時，會發生電器短路、配線不良以及減少亮度，因此必須去除。When the fluorine compound contained in the etching composition of the present invention simultaneously etches a copper/molybdenum film as an example of a dual metal film, it can increase the etching speed of the molybdenum film to reduce the length of the tail and remove the molybdenum residue inevitably generated during etching. effect. The increase in the tail of molybdenum may reduce the brightness. When the residue remains on the substrate and the lower film, electrical short circuits, poor wiring, and reduced brightness will occur, so it must be removed.
根據本發明之一實施態樣的氟化合物只要是可以解離而生成F- 或HF2 - 的化合物，則均可使用，但作為具體例，可為選自HF、NaF、KF、AlF3 、HBF4 、NH4 F、NH4 HF2 、NaHF2 、KHF2 、及NH4 BF4 的一種或二種以上，較佳地，可為選自HF、AlF3 、HBF4 、NH4 F、及NH4 HF2 的一種或二種以上。氟化合物相對於蝕刻組合物之總重量可包含0.01至1重量%，針對從銅／鉬膜有效地去除作為金屬殘渣之實例的鉬殘渣，以及抑制玻璃基板等下部膜之蝕刻的方面而言，較佳可包含0.05至0.5重量%。According to an embodiment of the present invention, the fluorine compound can be used as long as it can be dissociated to produce F - or HF 2 - , but as a specific example, it can be selected from HF, NaF, KF, AlF 3 , and HBF 4. One or two or more of NH 4 F, NH 4 HF 2 , NaHF 2 , KHF 2 , and NH 4 BF 4 , preferably selected from HF, AlF 3 , HBF 4 , NH 4 F, and One or more of NH 4 HF 2 . The fluorine compound may contain 0.01 to 1% by weight with respect to the total weight of the etching composition. In terms of effectively removing molybdenum residues, which are examples of metal residues, from the copper/molybdenum film and suppressing the etching of lower films such as glass substrates, Preferably, it may contain 0.05 to 0.5% by weight.
（e）底切抑制劑(E) Undercut inhibitor
根據本發明之一實施態樣的蝕刻組合物所包含的底切抑制劑係使用作為特定之化合物的腺嘌呤（adenine）、鳥嘌呤（guanine）、或其混合物，是作為與本發明特定之蝕刻添加劑及胺化合物的最佳組合而特意採用的化合物。The undercut inhibitor contained in the etching composition according to one embodiment of the present invention uses adenine, guanine, or a mixture thereof as a specific compound, and is used as a specific etching compound of the present invention. A compound specially used for the best combination of additives and amine compounds.
藉由本發明的這種組合，本發明蝕刻組合物的蝕刻速度不會降低，蝕刻時不會產生熱量，不會產生金屬的殘渣，從而驚人地提高蝕刻特性。With this combination of the present invention, the etching speed of the etching composition of the present invention will not be reduced, heat will not be generated during etching, and metal residue will not be generated, thereby surprisingly improving the etching characteristics.
特別是在同時蝕刻金屬雙重膜時，例如同時蝕刻銅／鉬膜時，不會降低蝕刻速度，並且防止鉬膜的鉬殘渣，可以抑制底切發生。Especially when the metal double film is etched at the same time, for example, when the copper/molybdenum film is etched at the same time, the etching rate is not reduced, and molybdenum residue of the molybdenum film is prevented, and the occurrence of undercut can be suppressed.
考慮到產生鉬殘渣的可能性、銅的蝕刻速度減少、以及抑制底切等，本發明的底切抑制劑的含量最好是相對於組合物之總重量可包含0.01至2重量%，較佳包含0.05至1重量%。Taking into account the possibility of generating molybdenum residue, the reduction of copper etching rate, and the suppression of undercutting, the content of the undercutting inhibitor of the present invention is preferably 0.01 to 2% by weight relative to the total weight of the composition, preferably Contains 0.05 to 1% by weight.
（f）胺化合物(F) Amine compounds
就本發明的蝕刻組合物中所包含的胺化合物而言，在蝕刻製程時，蝕刻組合物內的金屬離子濃度增加，這種金屬離子發揮分解作為氧化劑的過氧化氫的催化劑作用，從而導致蝕刻製程整體的經時變化，但是藉由含有胺化合物，從而抑制這種過氧化氫的分解，進而抑制整體蝕刻製程的經時變化，提高蝕刻特性。Regarding the amine compound contained in the etching composition of the present invention, during the etching process, the concentration of metal ions in the etching composition increases, and this metal ion acts as a catalyst for decomposing hydrogen peroxide as an oxidizing agent, thereby causing etching The overall process changes over time, but by containing amine compounds, the decomposition of hydrogen peroxide is suppressed, thereby suppressing changes over time in the overall etching process and improving etching characteristics.
較佳地，本發明的胺化合物可為C4至C10的烷基胺、C3至C10的環烷基胺、或其混合物，較佳可為C4至C8的烷基胺、C3至C8的環烷基胺、或其混合物，較佳可為直鏈或支鏈的具有5至7個碳原子數的己胺，更佳可為直鏈或支鏈的己胺，己胺可選自下列化合物，但並不限於此。[01] 
考量為了具有優異的效果，根據本發明之一實施態樣的胺化合物較佳可為選自正己胺、異己胺、及新己胺的一種或二種以上。Considering that in order to have an excellent effect, the amine compound according to an embodiment of the present invention may preferably be one or two or more selected from n-hexylamine, isohexylamine, and neohexylamine.
根據本發明之一實施態樣的胺化合物可為0.1至5重量%，較佳為0.1至1重量%。The amine compound according to an embodiment of the present invention may be 0.1 to 5% by weight, preferably 0.1 to 1% by weight.
就根據本發明之一實施態樣的胺化合物及底切抑制劑而言，具體地，作為特定胺化合物的己胺：作為特定底切抑制劑的腺嘌呤、鳥嘌呤、或其混合物的重量比可為5至10：1。Regarding the amine compound and the undercutting inhibitor according to one embodiment of the present invention, specifically, the weight ratio of hexylamine as a specific amine compound: adenine, guanine, or a mixture thereof as a specific undercutting inhibitor It can be 5 to 10:1.
胺化合物的比例低於上述胺化合物與底切抑制劑的重量比時，過氧化氫分解抑制效果減少，處理張數增加時可能發生底切及發熱。此外，胺化合物的比例高於上述胺化合物與底切抑制劑的重量比時，則抑制鉬蝕刻，從而可能導致殘膜發生。When the ratio of the amine compound is lower than the weight ratio of the above-mentioned amine compound to the undercut inhibitor, the hydrogen peroxide decomposition inhibitory effect is reduced, and undercut and heat generation may occur when the number of processed sheets increases. In addition, when the ratio of the amine compound is higher than the weight ratio of the above-mentioned amine compound to the undercut inhibitor, molybdenum etching is suppressed, which may cause film residue.
（g）蝕刻抑制劑(G) Etching inhibitor
根據本發明之一實施態樣的蝕刻組合物還可包含蝕刻抑制劑，蝕刻抑制劑調節過渡金屬的蝕刻速度而減少圖案的CD損失（CD loss），提高製程寬容度，使其成為具有適當的錐角的蝕刻輪廓，蝕刻抑制劑可為分子內包含選自氧、硫、及氮的一種或二種以上的雜原子的雜環化合物，本發明的雜環化合物包含單環式雜環化合物以及具有單環式雜環及苯環之稠合結構的多環式雜環化合物。The etching composition according to an embodiment of the present invention may further include an etching inhibitor. The etching inhibitor adjusts the etching speed of the transition metal to reduce the CD loss of the pattern, increase the process latitude, and make it suitable The etching profile of the cone angle. The etching inhibitor may be a heterocyclic compound containing one or two or more heteroatoms selected from oxygen, sulfur, and nitrogen in the molecule. The heterocyclic compound of the present invention includes a monocyclic heterocyclic compound and A polycyclic heterocyclic compound with a condensed structure of a monocyclic heterocyclic ring and a benzene ring.
根據本發明之一實施態樣的雜環化合物的具體例可為噁唑（oxazole）、咪唑（imidazole）、吡唑（pyrazole）、三唑（triazole）、四唑（tetrazole）、5-胺基四唑（5-aminotetrazole）、甲基四唑（methyltetrazole）、呱嗪（piperazine）、甲基呱嗪（methylpiperazine）、羥基乙基呱嗪（hydroxyethylpiperazine）、苯並咪唑（benzimidazole）、苯並吡唑（benzpyrazole）、甲苯三唑（tolutriazole）、氫化甲苯三唑（hydrotolutriazole）、或羥基甲苯三唑（hydroxytolutriazole），較佳為選自四唑、5-胺基四唑、及甲基四唑的一種或二種以上。Specific examples of the heterocyclic compound according to an embodiment of the present invention may be oxazole, imidazole, pyrazole, triazole, tetrazole, 5-amino group Tetrazole (5-aminotetrazole), methyltetrazole (methyltetrazole), piperazine (methylpiperazine), hydroxyethylpiperazine (hydroxyethylpiperazine), benzimidazole (benzimidazole), benzopyrazole (Benzpyrazole), tolutriazole (tolutriazole), hydrogenated tolutriazole (hydrotolutriazole), or hydroxytolutriazole (hydroxytolutriazole), preferably one selected from the group consisting of tetrazole, 5-aminotetrazole, and methyltetrazole Or two or more.
相對於蝕刻組合物之總重量，本發明的蝕刻抑制劑可包含0.01至5重量%、較佳包含0.05至2重量%。蝕刻抑制劑以小於0.01重量%包含時，不容易調節蝕刻速度，調節錐角的能力降低，且製程寬容度少，存在批量生產能力降低的問題，當以超過5重量%包含時，蝕刻速度減少而存在低效率的問題。Relative to the total weight of the etching composition, the etching inhibitor of the present invention may contain 0.01 to 5% by weight, preferably 0.05 to 2% by weight. When the etching inhibitor is contained in less than 0.01% by weight, it is difficult to adjust the etching speed, the ability to adjust the taper angle is reduced, and the process latitude is small, and there is a problem of reduced mass production capacity. When it is contained in more than 5% by weight, the etching speed is reduced And there is a problem of low efficiency.
（h）螯合劑(H) Chelating agent
根據本發明之一實施態樣的蝕刻組合物還可包含螯合劑，螯合劑與在蝕刻進行過程中所產生的金屬離子形成螯合物而使其失活，從而防止發生由這些金屬離子導致的副反應，其結果使得在重複的蝕刻製程中也能夠維持蝕刻特性。特別是在銅層的情況下，存在如下問題：蝕刻組合物中大量殘留銅離子形成鈍化膜而被氧化，無法進行蝕刻，但投入螯合劑時，可防止形成銅離子的鈍化膜。此外，螯合劑防止過氧化氫自身的分解反應，從而可增加蝕刻組合物的穩定性。因此，如果在蝕刻組合物中未添加螯合劑時，在進行蝕刻的過程中被氧化的金屬離子被活化，從而使蝕刻組合物的蝕刻特性容易發生變化，還會促進過氧化氫的分解反應而可能發生發熱及爆炸。The etching composition according to one embodiment of the present invention may further include a chelating agent. The chelating agent forms a chelate compound with the metal ions generated during the etching process to deactivate it, thereby preventing the occurrence of these metal ions. As a result of side reactions, the etching characteristics can be maintained even in repeated etching processes. Particularly in the case of the copper layer, there is a problem that a large amount of copper ions remain in the etching composition to form a passivation film and are oxidized and cannot be etched. However, when a chelating agent is added, the formation of a passivation film of copper ions can be prevented. In addition, the chelating agent prevents the decomposition reaction of hydrogen peroxide itself, thereby increasing the stability of the etching composition. Therefore, if a chelating agent is not added to the etching composition, the oxidized metal ions are activated during the etching process, so that the etching characteristics of the etching composition are easily changed, and the decomposition reaction of hydrogen peroxide is also promoted. Heat and explosion may occur.
即，根據本發明實施態樣的螯合劑發揮與蝕刻製程時產生的金屬離子螯合而抑制過氧化氫的分解、在保存蝕刻组合物時也提高穩定性的作用。螯合劑沒有特別限定，但可以在分子內包含胺基及羧酸基或膦酸基，具體而言，可為選自亞胺基二乙酸（iminodiacetic acid）、次氮基三乙酸（nitrilotriacetic acid）、乙二胺四乙酸（ethylenediaminetetraacetic acid）、二伸乙基三腈五乙酸（diethylenetrinitril pentaacetic acid）、胺基三（伸甲基膦酸）（aminotris(methylenephosphonic acid)）、（1-羥基乙烷-1,1-二基）雙 （膦酸）（(1-hydroxyethane-1,1-diyl)bis(phosphonic acid)）、乙二胺四(伸甲基膦酸)（ethylenediamine tetra(methylene phosphonic acid)）、二伸乙基三胺五（伸甲基膦酸）（Diethylenetri amine penta(methylenephosphonic acid) ）、丙胺酸（alanine）、麩胺酸（glutamic acid）、胺基丁酸（aminobutyric acid）、及甘胺酸（glycin）的一種或二種以上，較佳可為選自亞胺基二乙酸、次氮基三乙酸、乙二胺四乙酸、及二伸乙基三腈五乙酸的一種或二種以上。That is, the chelating agent according to the embodiment of the present invention chelates with the metal ions generated during the etching process to suppress the decomposition of hydrogen peroxide, and also improves the stability when the etching composition is stored. The chelating agent is not particularly limited, but it may contain an amine group and a carboxylic acid group or a phosphonic acid group in the molecule. Specifically, it may be selected from iminodiacetic acid and nitrilotriacetic acid. , Ethylenediaminetetraacetic acid (ethylenediaminetetraacetic acid), diethylenetrinitril pentaacetic acid (diethylenetrinitril pentaacetic acid), aminotris (methylenephosphonic acid), (1-hydroxyethane- 1,1-diyl) bis(phosphonic acid) ((1-hydroxyethane-1,1-diyl)bis(phosphonic acid)), ethylenediamine tetra(methylene phosphonic acid) ), Diethylenetri amine penta(methylenephosphonic acid), alanine, glutamic acid, aminobutyric acid, and One or two or more kinds of glycin, preferably one or two selected from iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, and diethylenetrinitrile pentaacetic acid More than species.
根據本發明之一實施態樣的螯合劑相對於蝕刻組合物之總重量可包含0.1至5重量%、較佳包含0.1至3重量%。當螯合劑以小於0.1重量%包含時，可使金屬離子失活的量過少而使得抑制過氧化氫分解反應的能力降低，當以超過5重量%包含時，由於進一步形成螯合而無法期待使金屬失活的作用，可能產生低效的問題。The chelating agent according to an embodiment of the present invention may contain 0.1 to 5% by weight, preferably 0.1 to 3% by weight, relative to the total weight of the etching composition. When the chelating agent is contained in less than 0.1% by weight, the amount that can deactivate the metal ions is too small to reduce the ability to inhibit the decomposition reaction of hydrogen peroxide. When it is contained in more than 5% by weight, it cannot be expected to cause further chelation. The effect of metal inactivation may cause inefficiency.
（i）水(I) Water
在根據本發明之一實施態樣的蝕刻組合物中，水沒有特別限定，但較佳為去離子水，更佳為水中的離子被去除的程度以電阻率值表示為18MQ/cm以上的去離子水。In the etching composition according to an embodiment of the present invention, the water is not particularly limited, but it is preferably deionized water, and more preferably, the degree of ion removal in the water is expressed as a resistivity value of 18MQ/cm or more. Ionized water.
上述水可以使蝕刻組合物之總重量成為100重量%的量包含。The above-mentioned water may be contained in such an amount that the total weight of the etching composition becomes 100% by weight.
（j）其它添加劑(J) Other additives
為了提高蝕刻性能，本發明的金屬膜的蝕刻組合物還可包含通常用於蝕刻組合物的任何添加劑。作為上述添加劑，可舉出追加的蝕刻穩定劑、玻璃蝕刻抑制劑、二元醇系高分子等。它們可單獨使用一種或者混合二種以上使用。In order to improve the etching performance, the etching composition of the metal film of the present invention may further include any additives commonly used in etching compositions. Examples of the above additives include additional etching stabilizers, glass etching inhibitors, glycol-based polymers, and the like. These can be used alone or in combination of two or more.
根據本發明之一實施態樣的蝕刻穩定劑可為同時具有醇基及胺基的化合物。作為具體例，可為選自甲醇胺、乙醇胺、丙醇胺、丁醇胺、二乙醇胺、三乙醇胺、二甲基乙醇胺、及N-甲基乙醇胺的任意一種或二種以上的混合物，但並不限於此。The etching stabilizer according to an embodiment of the present invention may be a compound having both an alcohol group and an amine group. As a specific example, it may be any one or a mixture of two or more selected from methanolamine, ethanolamine, propanolamine, butanolamine, diethanolamine, triethanolamine, dimethylethanolamine, and N-methylethanolamine, but not Not limited to this.
以蝕刻組合物的總重量為基準，上述蝕刻穩定劑可添加0.01至10重量%、較佳添加0.05至7重量%、更佳添加0.1至5重量%。在上述範圍內，蝕刻穩定劑可有效抑制金屬殘渣的產生。Based on the total weight of the etching composition, the above-mentioned etching stabilizer may be added at 0.01 to 10% by weight, preferably at 0.05 to 7% by weight, more preferably at 0.1 to 5% by weight. Within the above range, the etching stabilizer can effectively suppress the generation of metal residues.
根據本發明之一實施態樣的玻璃蝕刻抑制劑可為選自硼氟酸或硼氟酸鹽的任一種以上的混合物。作為具體例，可為選自HBF4 、NaBF4 、KBF4 、及NH4 BF4 等的任一種或二種以上的混合物，但並不限於此。The glass etching inhibitor according to an embodiment of the present invention may be a mixture of at least one selected from borofluoric acid or borofluoride. As a specific example, it may be any one or a mixture of two or more selected from HBF 4 , NaBF 4 , KBF 4 , and NH 4 BF 4 , but it is not limited thereto.
就上述玻璃蝕刻抑制劑的含量而言，以蝕刻組合物的總重量為基準，較佳添加0.01至10重量%、更佳添加0.05至7重量%、進一步較佳添加0.1至5重量%。在上述範圍內，玻璃蝕刻抑制效果優異，蝕刻速度不會減少而較佳。Regarding the content of the glass etching inhibitor, based on the total weight of the etching composition, 0.01 to 10% by weight is preferred, 0.05 to 7% by weight is more preferred, and 0.1 to 5% by weight is further preferred. Within the above range, the glass etching suppression effect is excellent, and the etching rate is not reduced, which is preferable.
根據本發明之一實施態樣的蝕刻组合物還可包含二元醇系高分子，作為具體實例，可包含聚乙二醇（polyethlene glycol）等，但並不限於此。根據本發明之一實施態樣的二元醇系高分子以蝕刻組合物的總重量為基準可添加0.1至30重量%、更佳添加1至20重量%、進一步較佳添加5至15重量%。在上述範圍內，二元醇系高分子對於過氧化氫分解反應的控制效果優異，不會降低蝕刻性能而較佳。The etching composition according to an embodiment of the present invention may further include a glycol-based polymer. As a specific example, it may include polyethylene glycol (polyethlene glycol), but is not limited thereto. According to one embodiment of the present invention, the glycol-based polymer can be added at 0.1 to 30% by weight, more preferably at 1 to 20% by weight, and further preferably at 5 to 15% by weight based on the total weight of the etching composition. . Within the above range, the glycol-based polymer has an excellent control effect on the decomposition reaction of hydrogen peroxide and does not reduce the etching performance, which is preferable.
根據本發明之一實施態樣的蝕刻組合物在金屬或金屬膜的蝕刻時，容易調節蝕刻速度，並且蝕刻輪廓（etch profile）優異，配線的直線性優異。此外，可完全去除殘渣，從而能夠非常有用地作為TFT-LCD柵極及源／汲極電極的過渡金屬膜、特別是包含銅的膜的蝕刻組合物。The etching composition according to one embodiment of the present invention can easily adjust the etching rate during the etching of a metal or a metal film, and has an excellent etch profile and excellent wiring linearity. In addition, residues can be completely removed, so that it can be very useful as an etching composition for transition metal films of TFT-LCD gates and source/drain electrodes, particularly films containing copper.
另外，根據本發明之一實施態樣的蝕刻組合物用於雙重金屬膜、特別是銅／鉬膜或銅／鈦膜的蝕刻製程時，具有上述提及的優點且能保護金屬膜的介面，抑制介面過蝕刻，穩定性優異，能夠改善錐角、CD損失及蝕刻直線性等蝕刻特性。In addition, when the etching composition according to one embodiment of the present invention is used in the etching process of a double metal film, especially a copper/molybdenum film or a copper/titanium film, it has the above-mentioned advantages and can protect the interface of the metal film. It suppresses interface over-etching, has excellent stability, and can improve the etching characteristics such as taper angle, CD loss, and etching straightness.
由此，作為構成液晶顯示裝置的TFT（Thin Film Transistor，薄膜電晶體）的柵極、源極、或汲極電極用金屬配線材料而使用雙重金屬膜或多重金屬膜，特別是使用銅／鉬膜時，根據本發明之一實施態樣的蝕刻組合物可有用地作為用於形成金屬配線圖案的蝕刻組合物。Therefore, as the metal wiring material for the gate, source, or drain electrode of the TFT (Thin Film Transistor) constituting the liquid crystal display device, a double metal film or a multiple metal film is used, especially copper/molybdenum. When filming, the etching composition according to one embodiment of the present invention can be useful as an etching composition for forming metal wiring patterns.
根據本發明之一實施態樣的蝕刻組合物是可用於金屬膜的蝕刻的組合物，記載於本發明中的金屬膜是指包含金屬、非金屬或過渡金屬，較佳可為過渡金屬，可單獨包含金屬或過渡金屬，或者可為金屬或過渡金屬的混合金屬。The etching composition according to one embodiment of the present invention is a composition that can be used for the etching of metal films. The metal film described in the present invention refers to containing metal, non-metal or transition metal, preferably a transition metal, The metal or transition metal is included alone, or may be a mixed metal of the metal or the transition metal.
具體而言，可為單一金屬膜、金屬合金膜或金屬氧化膜，作為金屬氧化膜之實例，可舉出ITO、IZO、IGZO等。Specifically, it may be a single metal film, a metal alloy film, or a metal oxide film. Examples of the metal oxide film include ITO, IZO, IGZO, and the like.
可適用根據本發明之一實施態樣的蝕刻組合物的過渡金屬或金屬膜可為包含選自銅、鉬、鈦、銦、鋅、錫、鎢、銀、金、鉻、錳、鐵、鈷、鎳、及鈮的一種或二種以上的金屬或過渡金屬的膜，作為具體例，可為銅膜、銅／鉬膜、銅／鈦膜、銅／鉬合金膜、銅／銦合金膜，較佳可為銅／鉬合金膜。The transition metal or metal film applicable to the etching composition according to one embodiment of the present invention can be selected from copper, molybdenum, titanium, indium, zinc, tin, tungsten, silver, gold, chromium, manganese, iron, and cobalt. Films of one or two or more metals such as, nickel, and niobium or transition metals, as specific examples, may be copper films, copper/molybdenum films, copper/titanium films, copper/molybdenum alloy films, copper/indium alloy films, Preferably, it may be a copper/molybdenum alloy film.
根據本發明之一實施態樣的銅／鉬膜或銅／鉬合金膜可為一個以上的銅（Cu）膜與一個以上的鉬（Mo）膜及／或鉬合金膜（Mo-alloy）相互層疊而成的多重膜，上述多重膜可以包含Cu／Mo（Mo-alloy）雙重膜、Cu／Mo（Mo-alloy）／Cu或Mo（Mo-alloy）／Cu／Mo（alloy）的三重膜。上述膜的順序可根據基板的物質、接合性而適當地調節。The copper/molybdenum film or copper/molybdenum alloy film according to an embodiment of the present invention may be more than one copper (Cu) film and more than one molybdenum (Mo) film and/or molybdenum alloy film (Mo-alloy) mutual Laminated multiple films, the above multiple films may include Cu/Mo (Mo-alloy) double film, Cu/Mo (Mo-alloy)/Cu or Mo (Mo-alloy)/Cu/Mo (alloy) triple film . The order of the above-mentioned films can be appropriately adjusted according to the substance and bonding properties of the substrate.
根據本發明之一實施態樣的鉬合金膜可由鉬-鎢（Mo-W）、鉬-鈦（Mo-Ti）、鉬-鈮（Mo-Nb）、鉬-鉻（Mo-Cr）、或鉬-鉭（Mo-Ta）構成，針對實施無殘渣且有效蝕刻的方面而言，上述鉬膜或鉬合金膜為100至500Å，上述銅膜可以具有1000至10000Å的厚度的方式進行蒸鍍。The molybdenum alloy film according to one embodiment of the present invention can be made of molybdenum-tungsten (Mo-W), molybdenum-titanium (Mo-Ti), molybdenum-niobium (Mo-Nb), molybdenum-chromium (Mo-Cr), or With regard to the molybdenum-tantalum (Mo-Ta) structure, the molybdenum film or the molybdenum alloy film is 100 to 500 Å, and the copper film may be vapor-deposited with a thickness of 1,000 to 10,000 Å in terms of residue-free and effective etching.
另外，本發明提供一種金屬膜的蝕刻方法，包括使本發明的蝕刻組合物與金屬膜接觸而對金屬膜進行蝕刻的步驟。In addition, the present invention provides a method for etching a metal film, including the step of contacting the etching composition of the present invention with the metal film to etch the metal film.
利用本發明蝕刻組合物的金屬膜的蝕刻方法係利用本發明的蝕刻組合物，除此以外，可藉由本領域技術人員能夠認知的習知方法實施。The etching method of the metal film using the etching composition of the present invention uses the etching composition of the present invention. In addition, it can be implemented by a conventional method that can be recognized by those skilled in the art.
具體而言，可藉由包含如下步驟的方法對金屬膜進行蝕刻：在基板上蒸鍍金屬膜的步驟；在上述金屬膜上形成光阻膜後圖案化的步驟；以及使用本發明的蝕刻組合物對形成有上述圖案化光阻膜的金屬膜進行蝕刻的步驟，此時形成在上述基板上的金屬膜可為單一膜、雙重金屬膜或多重金屬膜（多層金屬膜），在雙重金屬膜或多重金屬膜的情況下層疊順序沒有特別限定。Specifically, the metal film can be etched by a method including the following steps: a step of vaporizing a metal film on a substrate; a step of patterning after forming a photoresist film on the metal film; and using the etching combination of the present invention The step of etching the metal film on which the patterned photoresist film is formed. At this time, the metal film formed on the substrate can be a single film, a double metal film or a multiple metal film (multilayer metal film). Or in the case of multiple metal films, the stacking order is not particularly limited.
另外，上述蝕刻方法還可包括如下步驟：在基板與過渡金屬膜之間，即，作為基板與過渡金屬膜之間的一個例子，在銅／鉬膜的情況下，在基板與銅膜之間或基板與鉬膜之間，形成半導體結構體。In addition, the above-mentioned etching method may further include the following steps: between the substrate and the transition metal film, that is, as an example between the substrate and the transition metal film, in the case of a copper/molybdenum film, between the substrate and the copper film Or between the substrate and the molybdenum film, a semiconductor structure is formed.
根據本發明之一實施態樣的金屬膜的蝕刻方法中所用的金屬膜可包含選自銅、鉬、鈦、銦、鋅、錫、及鈮的一種或二種以上，如上述記載，金屬膜可選自包含銅的單一金屬膜、包含銅合金膜的合金膜、以及包含含銅之上部膜與鉬膜或鉬合金膜的多重膜，較佳可包含含銅之上部膜與鉬膜或鉬合金膜的多重膜。The metal film used in the metal film etching method according to one embodiment of the present invention may include one or more selected from copper, molybdenum, titanium, indium, zinc, tin, and niobium. As described above, the metal film It can be selected from a single metal film containing copper, an alloy film containing a copper alloy film, and a multiple film containing a copper-containing upper film and a molybdenum film or a molybdenum alloy film, and preferably may include a copper-containing upper film and a molybdenum film or molybdenum Multiple films of alloy films.
另外，本發明提供一種半導體元件的製造方法，包括利用本發明的蝕刻組合物而進行的蝕刻製程。In addition, the present invention provides a method for manufacturing a semiconductor device, including an etching process using the etching composition of the present invention.
根據本發明之一實施態樣的半導體元件可為液晶顯示裝置、電漿顯示器面板等顯示裝置用半導體結構體。具體而言，上述半導體結構體可包含選自介電膜、導電膜、以及非晶或多晶等的矽膜的一層以上的膜，這些半導體結構體可藉由習知的方法製造。The semiconductor element according to an embodiment of the present invention may be a semiconductor structure for a display device such as a liquid crystal display device and a plasma display panel. Specifically, the above-mentioned semiconductor structure may include one or more films selected from a dielectric film, a conductive film, and an amorphous or polycrystalline silicon film, and these semiconductor structures can be manufactured by a conventional method.
下面，藉由實施例對本發明詳細地進行說明。但是下述實施例只是例示本發明，本發明的內容並不限於下述實施例。Hereinafter, the present invention will be described in detail with examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited to the following examples.
[實施例1][Example 1]
將過氧化氫20重量%、5-胺基四唑（ATZ）0.5重量%、亞胺基二琥珀酸（Iminodisuccinic acid，IDA）3重量%、氟化銨（Ammonium fluoride，AF）0.1重量%、下表1中記載的成分、以及餘量的水進行混合而製造蝕刻組合物。20% by weight of hydrogen peroxide, 0.5% by weight of 5-aminotetrazole (ATZ), 3% by weight of iminodisuccinic acid (IDA), 0.1% by weight of ammonium fluoride (AF), The components described in Table 1 below and the balance of water were mixed to produce an etching composition.
[實施例2至6及比較例1至2][Examples 2 to 6 and Comparative Examples 1 to 2]
在實施例1中，除了改變下表1中記載的成分及含量以外，藉由與實施例1相同的方法實施，從而製造蝕刻組合物。In Example 1, the etching composition was manufactured by the same method as Example 1, except that the components and contents described in Table 1 below were changed.
[比較例3][Comparative Example 3]
在實施例1中，除了改變下表1中記載的成分及含量及未包含氟化合物以外，藉由與實施例1相同的方法實施，從而製造蝕刻組合物。In Example 1, the etching composition was produced by the same method as Example 1, except that the components and contents described in Table 1 below were changed and the fluorine compound was not included.
[比較例4][Comparative Example 4]
在實施例1中，除了改變下表1中記載的成分及含量及未包含胺化合物以外，藉由與實施例1相同的方法實施，從而製造蝕刻組合物。In Example 1, the etching composition was produced by the same method as Example 1, except that the components and contents described in Table 1 below were changed and the amine compound was not included.
[比較例5][Comparative Example 5]
在實施例1中，除了改變下表1中記載的成分及含量及未包含蝕刻添加劑以外，藉由與實施例1相同的方法實施，從而製造蝕刻組合物。In Example 1, the etching composition was produced by the same method as Example 1, except that the components and contents described in Table 1 below were changed and the etching additive was not included.
[比較例6至7][Comparative Examples 6 to 7]
在實施例1中，除了改變下表1中記載的蝕刻添加劑的成分及含量以外，藉由與實施例1相同的方法實施，從而製造蝕刻組合物。In Example 1, the etching composition was produced by the same method as Example 1, except that the components and content of the etching additives described in Table 1 below were changed.
[比較例8][Comparative Example 8]
在實施例1中，除了改變下表1中記載的底切抑制劑、蝕刻添加劑、胺化合物的含量及未添加pH調節劑以外，藉由與實施例1相同的方法實施，從而製造蝕刻組合物。[03]
[表1]
在玻璃基板上分別依次蒸鍍厚度4500Å的銅膜及鉬膜而製造試片。對於上述試片進行光微影製程而形成圖案化的光阻膜，分別利用上述實施例1至6及比較例1至5的蝕刻組合物實施對於銅及鉬膜的蝕刻。此時，上述蝕刻製程係使用可噴塗設備（Mini-etcher ME-001）以在32℃下所測定的終點檢測（EPD，end point detection）加上50%的過度蝕刻而進行蝕刻。關於EPD測定，在進行蝕刻時用肉眼觀察試片的顏色變化而測定，利用掃描式電子顯微鏡（Hitachi公司，S-4800）觀察是否發生錐角、鉬殘渣、及根據處理張數的底切。A copper film and a molybdenum film with a thickness of 4500 Å were sequentially deposited on the glass substrate to produce test pieces. A photolithography process was performed on the test piece to form a patterned photoresist film, and the copper and molybdenum films were etched using the etching compositions of the foregoing Examples 1 to 6 and Comparative Examples 1 to 5, respectively. At this time, the above-mentioned etching process uses sprayable equipment (Mini-etcher ME-001) to perform etching with end point detection (EPD) measured at 32°C plus 50% over-etching. Regarding the EPD measurement, the color change of the test piece was observed with the naked eye during etching, and the measurement was performed using a scanning electron microscope (Hitachi, S-4800) to observe whether the taper angle, molybdenum residue, and undercut according to the number of processed sheets occurred.
如下測定是否發生蝕刻發熱：在作為蝕刻液處理張數之極限值的7000 ppm濃度下，將試片在32℃下恆溫保存，對蝕刻液測定發熱時間。It is determined whether etching heat generation occurs as follows: at a concentration of 7000 ppm, which is the limit value of the number of etching solutions processed, the test piece is stored at a constant temperature at 32°C, and the heat generation time of the etching solution is measured.
開始測定後在24小時內若因溫度升高而觀察到發熱時則視為發熱，若直至24小時都沒有升溫時則判斷為不發熱。If fever is observed due to a temperature rise within 24 hours after the start of the measurement, it is regarded as fever, and if there is no temperature rise up to 24 hours, it is judged as no fever.
將其結果記載於下表2。[06]
[表2]
如表2所示，本發明實施例1至6的蝕刻組合物與比較例1至8的蝕刻組合物相比，蝕刻速度非常優異，蝕刻時不產生熱量。As shown in Table 2, compared with the etching compositions of Comparative Examples 1 to 8, the etching compositions of Examples 1 to 6 of the present invention have a very excellent etching rate, and no heat is generated during etching.
另外，本發明的蝕刻組合物即使處理張數增加也不會發生底切，不會殘留鉬殘渣物而具有優異的蝕刻特性。In addition, the etching composition of the present invention does not cause undercuts even if the number of processed sheets increases, does not leave molybdenum residues, and has excellent etching characteristics.
判斷為這是本發明的蝕刻組合物因如下特定成分的組合而顯示的蝕刻特性：過氧化氫；磷酸系化合物及硫酸系化合物的蝕刻添加劑；pH調節劑；氟化合物；腺嘌呤、鳥嘌呤或其混合物的底切抑制劑；胺化合物；以及餘量的水的。特別是判斷為這是如下組合所帶來的效果：作為特定的蝕刻添加劑的硫酸及磷酸鹽、作為特定之底切抑制劑的腺嘌呤、鳥嘌呤或其混合物、以及胺化合物。It is judged that this is the etching characteristic exhibited by the etching composition of the present invention due to the combination of the following specific components: hydrogen peroxide; etching additives for phosphoric acid compounds and sulfuric acid compounds; pH adjusters; fluorine compounds; adenine, guanine or The undercut inhibitor of its mixture; amine compound; and the balance of water. In particular, it is judged that this is the effect of the combination of sulfuric acid and phosphate as a specific etching additive, adenine, guanine or a mixture thereof as a specific undercut inhibitor, and an amine compound.
進而，在胺化合物與底切抑制劑的重量比在5至10：1範圍之外的比較例1至2的情況下，產生殘渣及發熱，並發生底切的問題，因此，可知胺化合物與底切抑制劑的重量比對蝕刻特性產生重要影響。Furthermore, in the case of Comparative Examples 1 to 2 in which the weight ratio of the amine compound to the undercut inhibitor is outside the range of 5 to 10:1, residues and heat are generated, and the problem of undercut occurs. Therefore, it can be seen that the amine compound and the undercut The weight ratio of the undercut inhibitor has an important influence on the etching characteristics.
另外，可知蝕刻添加劑與pH調節劑的重量比相當於1至4：1的範圍時，在產生殘渣、發熱及發生底切等方面顯示出進一步提高的蝕刻特性。In addition, it can be seen that when the weight ratio of the etching additive to the pH adjuster is in the range of 1 to 4:1, the etching characteristics are further improved in terms of generation of residue, heat generation, and undercut generation.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113969403A (en) * | 2021-10-27 | 2022-01-25 | 湖南工程学院 | Etching solution and method for nickel and titanium high-temperature alloy |
| CN113969403B (en) * | 2021-10-27 | 2023-10-31 | 湖南工程学院 | Etching solution and method for nickel-titanium superalloy |
| CN114164003A (en) * | 2021-12-06 | 2022-03-11 | Tcl华星光电技术有限公司 | Etchant composition for display panel and etching method of display panel |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102619627B1 (en) | 2024-01-04 |
| KR20200112673A (en) | 2020-10-05 |
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