KR102469936B1 - ETCHANT COMPOSITION FOR ETHCING TiN LAYER AND METHOD FOR FORMING METAL LINE USING THE SAME - Google Patents
ETCHANT COMPOSITION FOR ETHCING TiN LAYER AND METHOD FOR FORMING METAL LINE USING THE SAME Download PDFInfo
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- KR102469936B1 KR102469936B1 KR1020150116656A KR20150116656A KR102469936B1 KR 102469936 B1 KR102469936 B1 KR 102469936B1 KR 1020150116656 A KR1020150116656 A KR 1020150116656A KR 20150116656 A KR20150116656 A KR 20150116656A KR 102469936 B1 KR102469936 B1 KR 102469936B1
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- Prior art keywords
- ammonium
- film
- based alloy
- alloy film
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- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims description 19
- 239000000956 alloy Substances 0.000 claims abstract description 43
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 43
- 229910004349 Ti-Al Inorganic materials 0.000 claims abstract description 41
- 229910004692 Ti—Al Inorganic materials 0.000 claims abstract description 41
- 238000005530 etching Methods 0.000 claims abstract description 32
- -1 ammonium fluoride salt compound Chemical class 0.000 claims abstract description 13
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 11
- 150000007524 organic acids Chemical class 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910010041 TiAlC Inorganic materials 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- 229910010037 TiAlN Inorganic materials 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229910010038 TiAl Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical class N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims 1
- 235000011044 succinic acid Nutrition 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 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 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 230000021148 sequestering of metal ion Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- POSYVRHKTFDJTR-UHFFFAOYSA-M tetrapropylazanium;fluoride Chemical compound [F-].CCC[N+](CCC)(CCC)CCC POSYVRHKTFDJTR-UHFFFAOYSA-M 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
-
- 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
- C23F1/02—Local etching
-
- 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
- C23F1/20—Acidic compositions for etching aluminium 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
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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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- ing And Chemical Polishing (AREA)
Abstract
본 발명은 (A) 하기 화학식 1로 표시되는 불화암모늄염 화합물 1~10 중량%, (B) 2개 이상의 카르복실기를 포함하는 유기산 1~10 중량%, (C) 무기암모늄염 0.01~3 중량%, 및 (D) 잔량의 물을 포함하는 Ti-Al계 합금막 식각액 조성물 및 그 식각용 조성물을 이용하는 금속배선의 형성 방법을 제공한다.
[화학식 1]
[Formula 1]
Description
본 발명은 Ti-Al계 합금막의 식각액 조성물 및 그를 이용한 금속배선의 형성 방법에 관한 것이다. The present invention relates to an etchant composition for a Ti-Al-based alloy film and a method for forming a metal wire using the same.
전자재료분야에서 베리어 층(barrier layer)의 형성 등에 사용되는 Ti-Al계 합금막의 사용은 점차 확대되고 있다. 그러나, TiAl막, TiAlC막, TiAlN막, TiAlCr막 등의 Ti-Al계 합금막을 식각할 수 있는 효과적인 식각액 조성물은 알려져 있지 않다. 특히, W막이나 TiN막질을 손상시키지 않고 Ti-Al계 합금막을 선택적으로 식각할 수 있는 식각액 조성물의 개발은 시급히 요구되고 있다.In the field of electronic materials, the use of Ti-Al-based alloy films used in the formation of barrier layers and the like is gradually expanding. However, an effective etchant composition capable of etching a Ti-Al-based alloy film such as a TiAl film, a TiAlC film, a TiAlN film, or a TiAlCr film is not known. In particular, there is an urgent need to develop an etchant composition capable of selectively etching a Ti—Al-based alloy film without damaging W film or TiN film quality.
일본 특개 제2012-36488호Japanese Patent Laid-Open No. 2012-36488
본 발명은 Ti-Al계 합금막을 효과적으로 식각할 수 있는 Ti-Al계 합금막 식각액 조성물을 제공하는 것을 목적으로 한다. An object of the present invention is to provide a Ti-Al-based alloy film etchant composition capable of effectively etching the Ti-Al-based alloy film.
또한, 본 발명은 W막이나 TiN막질을 손상시키지 않고 Ti-Al계 합금막을 선택적으로 식각할 수 있는 Ti-Al계 합금막 식각액 조성물을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a Ti-Al-based alloy film etchant composition capable of selectively etching a Ti-Al-based alloy film without damaging the W film or TiN film quality.
조성물 총중량에 대하여,With respect to the total weight of the composition,
(A) 하기 화학식 1로 표시되는 불화암모늄염 화합물 1~10 중량%, (A) 1 to 10% by weight of an ammonium fluoride salt compound represented by Formula 1 below;
(B) 2개 이상의 카르복실기를 포함하는 유기산 1~10 중량%,(B) 1 to 10% by weight of an organic acid containing two or more carboxyl groups;
(C) 무기암모늄염 0.01~3 중량%, 및(C) 0.01 to 3% by weight of an inorganic ammonium salt, and
(D) 잔량의 물을 포함하는 Ti-Al계 합금막 식각액 조성물을 제공한다:(D) Provides a Ti-Al-based alloy film etchant composition containing a residual amount of water:
상기 식에서in the above formula
R1, R2, R3, 및 R4는 각각 독립적으로 수소 또는 탄소수 1 내지 10의 직쇄 또는 분지쇄의 알킬기이며,R1, R2, R3, and R4 are each independently hydrogen or a straight or branched chain alkyl group having 1 to 10 carbon atoms,
n은 0 또는 1이다.n is 0 or 1;
또한, 본 발명은In addition, the present invention
하부 금속막 또는 금속배선으로서 텅스텐(W) 또는 TiN을 포함하는 금속막 또는 금속배선을 포함하는 기판상에 Ti-Al계 합금막을 형성하는 방법에 있어서, A method of forming a Ti-Al-based alloy film on a substrate including a metal film or metal wiring containing tungsten (W) or TiN as a lower metal film or metal wiring,
상기 텅스텐(W) 또는 TiN을 포함하는 금속막 또는 금속배선에 대하여 상기 Ti-Al계 합금막을 선택적으로 식각하는 단계를 포함하며, 상기 식각단계는 청구항 1 내지 청구항 6 중 어느 한 항의 식각액을 사용하여 이루어지는 것을 특징으로 하는 금속배선의 형성 방법을 제공한다. and selectively etching the Ti-Al-based alloy film with respect to the metal film or metal wiring containing tungsten (W) or TiN, wherein the etching step is carried out using the etchant of any one of claims 1 to 6. It provides a method of forming a metal wiring, characterized in that made.
본 발명의 Ti-Al계 합금막 식각용 조성물은 Ti-Al계 합금막에 대한 효율적인 습식식각을 가능하게 하며, Ti-Al계 합금막의 식각시 W막이나 TiN막질을 손상시키지 않기 때문에 매우 유용하게 사용될 수 있다. The composition for etching a Ti-Al-based alloy film of the present invention enables efficient wet etching of a Ti-Al-based alloy film and is very useful because it does not damage the quality of a W film or TiN film during etching of a Ti-Al-based alloy film. can be used
본 발명은, 조성물 총중량에 대하여, (A) 하기 화학식 1로 표시되는 하기 화학식 1로 표시되는 불화암모늄염 화합물 1~10 중량%, (B) 2개 이상의 카르복실기를 포함하는 유기산 1~10 중량%, (C) 무기암모늄염 0.01~3 중량%, 및 (D) 잔량의 물을 포함하는 Ti-Al계 합금막 식각액 조성물에 관한 것이다:The present invention, based on the total weight of the composition, (A) 1 to 10% by weight of an ammonium fluoride salt compound represented by the following formula (1), (B) 1 to 10% by weight of an organic acid containing two or more carboxyl groups, (C) 0.01 to 3% by weight of an inorganic ammonium salt, and (D) a Ti-Al-based alloy film etchant composition containing the balance of water:
[화학식 1][Formula 1]
상기 식에서in the above formula
R1, R2, R3, 및 R4는 각각 독립적으로 수소 또는 탄소수 1 내지 10의 직쇄 또는 분지쇄의 알킬기이며,R1, R2, R3, and R4 are each independently hydrogen or a straight or branched chain alkyl group having 1 to 10 carbon atoms,
n은 0 또는 1이다.n is 0 or 1;
상기 Ti-Al계 합금막은 Ti 및 Al을 포함하는 합금으로 이루어진 막을 의미하며, 대표적인 예로는 TiAl막, TiAlC막, TiAlN막, TiAlCr막 등을 들 수 있다. 본 발명의 식각액은 이들 중에서 특히 TiAlC막, TiAlN막에 바람직하게 사용될 수 있다.The Ti-Al-based alloy film means a film made of an alloy including Ti and Al, and representative examples include a TiAl film, a TiAlC film, a TiAlN film, and a TiAlCr film. The etchant of the present invention can be particularly preferably used for TiAlC and TiAlN films.
상기 Ti-Al계 합금막 식각액 조성물은 특히, 텅스텐(W) 또는 TiN을 포함하는 금속막 또는 금속배선의 존재하에서 Ti-Al계 합금막의 선택적 식각을 위하여 유용하게 사용될 수 있다. The Ti-Al-based alloy film etchant composition may be usefully used for selective etching of a Ti-Al-based alloy film in the presence of a metal film or metal wiring containing tungsten (W) or TiN.
본 발명의 Ti-Al계 합금막 식각액 조성물에 있어서, 상기 (A) 화학식 1로 표시되는 불화암모늄염 화합물은 식각 기능을 수행한다:In the Ti-Al-based alloy film etchant composition of the present invention, the ammonium fluoride salt compound represented by Formula 1 (A) performs an etching function:
상기 화학식 1로 표시되는 불화암모늄염 화합물로는 불화암모늄염, 중불화암모늄염, 불화알킬암모늄염 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상을 조합하여 사용될 수 있다. Examples of the ammonium fluoride salt compound represented by Formula 1 include ammonium fluoride salts, ammonium bifluoride salts, and alkylammonium fluoride salts, which may be used alone or in combination of two or more.
상기 불화알킬암모늄염으로는 대표적으로 테트라메틸암모늄플루오라이드, 테트라에틸암모늄플루오라이드, 테트라프로필암모늄플루오라이드, 테트라부틸암모늄플루오라이드 등을 들 수 있다. Representative examples of the alkylammonium fluoride salt include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride.
상기 화학식 1로 표시되는 불화암모늄염 화합물로는 특히, 암모늄플루오라이드, 테트라메틸암모늄플루오라이드, 테트라부틸암모늄플루오라이드 등이 바람직하게 사용될 수 있다. As the ammonium fluoride salt compound represented by Formula 1, in particular, ammonium fluoride, tetramethylammonium fluoride, tetrabutylammonium fluoride and the like may be preferably used.
본 발명의 식각액 조성물에서 (A) 화학식 1로 표시되는 불화암모늄염은 조성물 총 중량에 대하여, 1 내지 10 중량%로 포함될 수 있으며, 더욱 바람직하게는 1 내지 8중량%로 포함되는 것이 좋다. 불화암모늄염 함량이 1 중량% 미만으로 포함되면 Ti-Al계 합금막의 식각속도가 감소되며, 10중량%를 초과하여 포함되면 보호막질인 W(tungsten)막 및 TiN(titanium nitride) 막질의 식각속도가 현저히 증가한다.In the etchant composition of the present invention, (A) the ammonium fluoride salt represented by Formula 1 may be included in an amount of 1 to 10% by weight, more preferably 1 to 8% by weight, based on the total weight of the composition. When the ammonium fluoride salt content is less than 1% by weight, the etching rate of the Ti-Al-based alloy film is reduced. increase markedly
본 발명의 식각액 조성물에서 상기 (B) 2개 이상의 카르복실기를 포함하는 유기산은 조성물의 pH를 조절함과 동시에 Ti-Al계 합금막의 식각 속도를 조절한다. In the etchant composition of the present invention, the (B) organic acid containing two or more carboxyl groups controls the pH of the composition and the etching rate of the Ti-Al-based alloy film.
상기 2개 이상의 카르복실기를 포함하는 유기산으로는 옥살산 (Oxalic acid), 시트르산 (Citric acid), 타타르산(Tartaric acid), 숙신산 (succinic acid) 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상을 조합하여 사용될 수 있다. 특히, 옥살산, 시트르산 등이 바람직하게 사용될 수 있다.Examples of the organic acid containing two or more carboxyl groups include oxalic acid, citric acid, tartaric acid, succinic acid, and the like, either alone or in combination of two or more. can be used in combination. In particular, oxalic acid, citric acid and the like can be preferably used.
본 발명의 식각액 조성물에서 2개 이상의 카르복실기를 포함하는 유기산은 조성물의 총 중량에 대하여, 1 내지 10 중량%로 포함될 수 있으며, 더욱 바람직하게는 2 내지 5 중량%로 포함되는 것이 좋다. 2개 이상의 카르복실기를 포함하는 유기산은 1 중량% 미만으로 포함되면 Ti-Al계 합금막의 식각속도가 감소되며, 10중량%를 초과하면 Ti-Al계 합금막의 식각속도가 증가하는 동시에 W(tungsten)의 식각이 현저히 증가한다.In the etchant composition of the present invention, the organic acid containing two or more carboxyl groups may be included in an amount of 1 to 10% by weight, more preferably 2 to 5% by weight, based on the total weight of the composition. When the amount of the organic acid containing two or more carboxyl groups is less than 1% by weight, the etching rate of the Ti-Al-based alloy film decreases, and when the content exceeds 10% by weight, the etching rate of the Ti-Al-based alloy film increases and W (tungsten) etching is significantly increased.
본 발명의 식각액 조성물에서 상기 (C) 무기암모늄염은 W막 및 TiN막질에 대한 식각을 억제하는 기능을 수행한다. In the etchant composition of the present invention, the inorganic ammonium salt (C) functions to inhibit etching of the W film and the TiN film.
상기 무기암모늄염으로는 인산암모늄, 황산암모늄, 초산암모늄, 질산암모늄, 붕산암모늄, 암모늄시트레이트, 암모늄옥살레이트, 암모늄포메이트, 암모늄카보네이트 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.Examples of the inorganic ammonium salt include ammonium phosphate, ammonium sulfate, ammonium acetate, ammonium nitrate, ammonium borate, ammonium citrate, ammonium oxalate, ammonium formate, ammonium carbonate, and the like, which can be used alone or in combination of two or more. Can be used in combination.
특히, 인산암모늄, 황산암모늄, 초산암모늄 등이 바람직하게 사용될 수 있다. In particular, ammonium phosphate, ammonium sulfate, ammonium acetate and the like can be preferably used.
상기 무기암모늄염은 상기 (A) 화학식 1로 표시되는 하기 화학식 1로 표시되는 불화암모늄염 화합물을 제외한 무기암모늄염을 의미한다.The inorganic ammonium salt means an inorganic ammonium salt other than the ammonium fluoride salt compound represented by the following Chemical Formula 1 represented by (A) Chemical Formula 1.
상기 무기암모늄염은 조성물 총 중량에 대하여, 0.01~3 중량%로 포함될 수 있으며, 더욱 바람직하게는 0.05 내지 1 중량%로 포함되는 것이 좋다. 무기암모늄염이 0.01 중량% 미만으로 포함되면 W막 및 TiN막질에 대한 식각억제 기능이 부족해지며, 3 중량%를 초과하면 Ti-Al계 합금막의 식각속도를 낮추는 문제를 야기할 수 있다.The inorganic ammonium salt may be included in an amount of 0.01 to 3% by weight, more preferably in an amount of 0.05 to 1% by weight, based on the total weight of the composition. If the inorganic ammonium salt is included in less than 0.01% by weight, the etching inhibitory function for the W film and TiN film quality is insufficient, and if it exceeds 3% by weight, the etching rate of the Ti-Al-based alloy film may be lowered.
본 발명의 조성물은 상기 기재된 성분을 이외에 (D)잔량의 물을 함유하는 것을 특징으로 한다. 물은 상기 화합물을 용해하는 역할을 한다.The composition of the present invention is characterized by containing (D) residual amount of water in addition to the components described above. Water serves to dissolve the compound.
본 발명의 조성물에는 전술한 성분 이외에 통상의 첨가제를 더 첨가할 수 있으며, 첨가제로는 부식방지제, 금속이온 봉쇄제, 계면활성제 등을 들 수 있다. 또한, 상기 첨가제는 이에만 한정되지 않으며, 발명의 효과를 더욱 양호하게 하기 위하여, 이 분야에 공지되어 있는 여러 다른 첨가제들을 선택하여 사용할 수도 있다.In addition to the components described above, conventional additives may be further added to the composition of the present invention, and examples of additives include corrosion inhibitors, metal ion sequestering agents, surfactants, and the like. In addition, the additive is not limited thereto, and in order to further improve the effect of the invention, several other additives known in the art may be selected and used.
본 발명에서 사용되는 (A) 화학식 1로 표시되는 불화암모늄염, (B) 2개 이상의 카르복실기를 포함하는 유기산, (C) 무기암모늄염, 첨가제 등은 통상적으로 공지된 방법에 의해서 제조가 가능하며, 본 발명의 식각용 조성물은 반도체 공정용의 순도를 가지는 것이 바람직하다. (A) the ammonium fluoride salt represented by Formula 1, (B) an organic acid containing two or more carboxyl groups, (C) an inorganic ammonium salt, additives, etc. used in the present invention can be prepared by a conventionally known method, and the present invention The etching composition of the present invention preferably has a purity suitable for semiconductor processing.
또한, 본 발명은 In addition, the present invention
하부 금속막 또는 금속배선으로서 텅스텐(W) 또는 TiN을 포함하는 금속막 또는 금속배선을 포함하는 기판상에 Ti-Al계 합금막을 형성하는 방법에 있어서, 상기 텅스텐(W) 또는 TiN을 포함하는 금속막 또는 금속배선에 대하여 상기 Ti-Al계 합금막을 선택적으로 식각하는 단계를 포함하며, 상기 식각단계는 상기 본 발명의 식각액을 사용하여 이루어지는 것을 특징으로 하는 금속배선의 형성 방법에 관한 것이다.A method of forming a Ti-Al-based alloy film on a substrate including a metal film or metal wiring containing tungsten (W) or TiN as a lower metal film or metal wiring, wherein the metal containing tungsten (W) or TiN and selectively etching the Ti-Al-based alloy film relative to the film or metal wiring, wherein the etching step is performed using the etchant of the present invention.
상기 Ti-Al계 합금막 식각액 조성물에 관하여 기술된 내용은 상기 금속배선의 형성 방법에 대하여 그대로 적용될 수 있다.The description of the Ti-Al-based alloy film etchant composition may be applied as it is to the method of forming the metal wiring.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다. Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples may be appropriately modified or changed by those skilled in the art within the scope of the present invention.
실시예Example 1~8 및 1-8 and 비교예comparative example 1~ 1~ 4: Ti4: Ti -- Al계Al-based 합금막alloy film 식각액etchant 조성물의 제조 preparation of the composition
하기 표 1에 기재된 성분들을 해당 성분으로 혼합하여 실시예 1~8 및 비교예 1~4의 Ti-Al계 합금막 식각액 조성물을 제조하였다. Ti-Al-based alloy film etchant compositions of Examples 1 to 8 and Comparative Examples 1 to 4 were prepared by mixing the components listed in Table 1 as the corresponding components.
(단위: 중량%)(Unit: % by weight)
1) A-1 : 암모늄플루라이드 (Ammonium fluoride)1) A-1: Ammonium fluoride
2) A-2 : 테트라부틸암모늄플루라이드 (Tetrabutylammonium fluoride)2) A-2: Tetrabutylammonium fluoride
3) B-1 : 옥살산 (Oxalic acid)3) B-1: Oxalic acid
4) B-2 : 시트르산 (Citric acid)4) B-2: Citric acid
5) B-3 : 아세트산 (Acetic acid)5) B-3: Acetic acid
6) C-1 : 암모늄 설페이트 (Ammonium sulfate)6) C-1: Ammonium sulfate
7) C-2 : 암모늄 포스페이트 (Ammonium phosphate)7) C-2: Ammonium phosphate
시험예test example : : 식각특성Etch characteristics 평가 evaluation
실리콘 웨이퍼 위에 TiAlC막, 텅스텐막(W), 질화티타늄막(TiN)이 각각 단일막으로 증착된 웨이퍼를 준비하였다. 상기의 웨이퍼 기판을 2x2cm 크기로 샘플링하여, 표 1의 식각액 조성물을 60℃로 승온시킨 후, 상기 기판을 상기 승온된 식각액 조성물에 1분간 침적하였다. 초순수(DIW)로 세정한 후 Ellipsometer(SE-MG-1000)와 SEM을 통해 막두께의 변화를 측정하여 식각 속도를 계산하고 그 결과를 하기 표 2에 나타냈다. A wafer in which a TiAlC film, a tungsten film (W), and a titanium nitride film (TiN) were respectively deposited as a single film was prepared on a silicon wafer. The wafer substrate was sampled in a size of 2x2 cm, the temperature of the etchant composition of Table 1 was raised to 60 ° C, and the substrate was immersed in the etchant composition for 1 minute. After washing with ultrapure water (DIW), the change in film thickness was measured using an ellipsometer (SE-MG-1000) and SEM to calculate the etching rate, and the results are shown in Table 2 below.
상기 표 2에 나타난 바와 같이, 본 발명의 식각액 조성물인 실시예 1 내지 8의 Ti-Al계 합금막 식각액 조성물은 TiAlC막에 대한 식각속도가 우수하였다. 또한, W막 및 TiN막에 대한 식각속도는 매우 느리기 때문에 TiAlC막의 식각시 W막 및 TiN막에 대한 손상은 무시할 정도임을 알 수 있었다. As shown in Table 2, the Ti-Al-based alloy film etchant compositions of Examples 1 to 8, which are the etchant compositions of the present invention, had excellent etching rates for TiAlC films. In addition, since the etching rate of the W film and the TiN film is very slow, it can be seen that the damage to the W film and the TiN film is negligible during the etching of the TiAlC film.
반면, 비교예 1 내지 4의 Ti-Al계 합금막 식각액 조성물은 TiAlC막에 대한 식각속도가 너무 느리거나, W막 또는 TiN막에 대한 식각속도는 너무 빠르기 때문에 TiAlC막의 식각에 적용하기 어려운 것을 확인하였다. On the other hand, it was confirmed that the Ti-Al-based alloy film etchant compositions of Comparative Examples 1 to 4 were difficult to apply to the etching of TiAlC films because the etching rates for TiAlC films were too slow or the etching rates for W films or TiN films were too fast. did
Claims (7)
(A) 하기 화학식 1로 표시되는 불화암모늄염 화합물 1~10 중량%,
(B) 2개 이상의 카르복실기를 포함하는 유기산 1~10 중량%,
(C) 무기암모늄염 0.01~3 중량%, 및
(D) 잔량의 물을 포함하고,
상기 (B) 2개 이상의 카르복실기를 포함하는 유기산은 옥살산(Oxalic acid), 시트르산(Citric acid), 타타르산(Tartaric acid) 및 숙신산 (succinic acid)으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는, Ti-Al계 합금막 식각액 조성물:
[화학식 1]
상기 식에서
R1, R2, R3, 및 R4는 각각 독립적으로 수소 또는 탄소수 1 내지 10의 직쇄 또는 분지쇄의 알킬기이며,
n은 0 또는 1이다.With respect to the total weight of the composition,
(A) 1 to 10% by weight of an ammonium fluoride salt compound represented by Formula 1 below;
(B) 1 to 10% by weight of an organic acid containing two or more carboxyl groups;
(C) 0.01 to 3% by weight of an inorganic ammonium salt, and
(D) contains a residual amount of water;
The (B) organic acid containing two or more carboxyl groups includes at least one selected from the group consisting of oxalic acid, citric acid, tartaric acid and succinic acid. Characterized in, Ti-Al-based alloy film etchant composition:
[Formula 1]
in the above formula
R1, R2, R3, and R4 are each independently hydrogen or a straight or branched chain alkyl group having 1 to 10 carbon atoms,
n is 0 or 1;
상기 Ti-Al계 합금막 식각액 조성물은 텅스텐(W) 또는 TiN을 포함하는 금속막 또는 금속배선의 존재하에서 Ti-Al계 합금막의 선택적 식각을 위하여 사용되는 것을 특징으로 하는 Ti-Al계 합금막 식각액 조성물. The method of claim 1,
The Ti-Al-based alloy film etchant composition is a Ti-Al-based alloy film etchant, characterized in that used for selective etching of the Ti-Al-based alloy film in the presence of a metal film or metal wiring containing tungsten (W) or TiN composition.
상기 (A) 화학식 1로 표시되는 불화암모늄염 화합물은 불화암모늄염, 중불화암모늄염 및 불화알킬암모늄염으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 Ti-Al계 합금막 식각액 조성물. The method of claim 1,
The (A) ammonium fluoride salt compound represented by Formula 1 comprises at least one selected from the group consisting of ammonium fluoride salts, ammonium bifluoride salts and alkylammonium fluoride salts Ti-Al-based alloy film etchant composition.
상기 (C) 무기암모늄염은 인산암모늄, 황산암모늄, 초산암모늄, 질산암모늄, 붕산암모늄, 암모늄시트레이트, 암모늄옥살레이트, 암모늄포메이트, 및 암모늄카보네이트로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 Ti-Al계 합금막 식각액 조성물.The method of claim 1,
The inorganic ammonium salt (C) includes at least one selected from the group consisting of ammonium phosphate, ammonium sulfate, ammonium acetate, ammonium nitrate, ammonium borate, ammonium citrate, ammonium oxalate, ammonium formate, and ammonium carbonate. Ti-Al-based alloy film etchant composition characterized by.
상기 Ti-Al계 합금막은 TiAl막, TiAlC막, TiAlN막, 및 TiAlCr막으로 이루어진 군으로부터 선택되는 것을 특징으로 하는 Ti-Al계 합금막 식각액 조성물.The method of claim 1,
The Ti-Al-based alloy film is a Ti-Al-based alloy film etchant composition, characterized in that selected from the group consisting of a TiAl film, a TiAlC film, a TiAlN film, and a TiAlCr film.
상기 텅스텐(W) 또는 TiN을 포함하는 금속막 또는 금속배선에 대하여 상기 Ti-Al계 합금막을 선택적으로 식각하는 단계를 포함하며, 상기 식각단계는 청구항 1 내지 3, 청구항 5 및 청구항 6 중 어느 한 항의 식각액을 사용하여 이루어지는 것을 특징으로 하는 금속배선의 형성 방법.A method of forming a Ti-Al-based alloy film on a substrate including a metal film or metal wiring containing tungsten (W) or TiN as a lower metal film or metal wiring,
and selectively etching the Ti-Al-based alloy film with respect to the metal film or metal wiring containing tungsten (W) or TiN, wherein the etching step is any one of claims 1 to 3, 5, and 6 A method of forming a metal wire, characterized in that it is made using the etchant of paragraph.
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