KR20160111649A - Etching composition for a metal - Google Patents
Etching composition for a metal Download PDFInfo
- Publication number
- KR20160111649A KR20160111649A KR1020150036535A KR20150036535A KR20160111649A KR 20160111649 A KR20160111649 A KR 20160111649A KR 1020150036535 A KR1020150036535 A KR 1020150036535A KR 20150036535 A KR20150036535 A KR 20150036535A KR 20160111649 A KR20160111649 A KR 20160111649A
- Authority
- KR
- South Korea
- Prior art keywords
- film
- etching
- titanium nitride
- etchant composition
- ether
- Prior art date
Links
- 238000005530 etching Methods 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 36
- 239000002184 metal Substances 0.000 title claims abstract description 36
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 45
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 40
- 239000010937 tungsten Substances 0.000 claims abstract description 40
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 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 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 22
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- -1 ammonium fluoride compound Chemical class 0.000 claims description 12
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 6
- NLCWFPMDXYWDOQ-UHFFFAOYSA-N 2-amino-1-methoxybutan-2-ol Chemical compound CCC(O)(N)COC NLCWFPMDXYWDOQ-UHFFFAOYSA-N 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- BPLPUJJTSPUWBQ-UHFFFAOYSA-N CCCCF.N Chemical compound CCCCF.N BPLPUJJTSPUWBQ-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 2
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 claims description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- PEWIGYIALNQNNY-UHFFFAOYSA-N 1-N-(2-aminoethyl)-3-methoxypropane-1,2-diamine Chemical compound COCC(N)CNCCN PEWIGYIALNQNNY-UHFFFAOYSA-N 0.000 claims 1
- CMZQPQQRGBOLHN-UHFFFAOYSA-N 1-methoxy-2-methylpropan-2-amine Chemical compound COCC(C)(C)N CMZQPQQRGBOLHN-UHFFFAOYSA-N 0.000 claims 1
- ZEHHJSJCLNQQRH-UHFFFAOYSA-N 2-amino-1-butoxybutan-2-ol Chemical compound CCC(O)(N)COCCCC ZEHHJSJCLNQQRH-UHFFFAOYSA-N 0.000 claims 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 21
- 239000000395 magnesium oxide Substances 0.000 abstract description 21
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 21
- 239000004065 semiconductor Substances 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000004210 ether based solvent Substances 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 128
- 230000000052 comparative effect Effects 0.000 description 35
- 230000008569 process Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 10
- 238000001039 wet etching Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229940043237 diethanolamine Drugs 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 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 2
- 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 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-N tetrabutylazanium;hydrofluoride Chemical compound F.CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 1
- CAQYAZNFWDDMIT-UHFFFAOYSA-N 1-ethoxy-2-methoxyethane Chemical compound CCOCCOC CAQYAZNFWDDMIT-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- GQCZPFJGIXHZMB-UHFFFAOYSA-N 1-tert-Butoxy-2-propanol Chemical compound CC(O)COC(C)(C)C GQCZPFJGIXHZMB-UHFFFAOYSA-N 0.000 description 1
- FGRBYDKOBBBPOI-UHFFFAOYSA-N 10,10-dioxo-2-[4-(N-phenylanilino)phenyl]thioxanthen-9-one Chemical compound O=C1c2ccccc2S(=O)(=O)c2ccc(cc12)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 FGRBYDKOBBBPOI-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- OHJYHAOODFPJOD-UHFFFAOYSA-N 2-(2-ethylhexoxy)ethanol Chemical compound CCCCC(CC)COCCO OHJYHAOODFPJOD-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- SDMNEUXIWBRMPK-UHFFFAOYSA-N 2-(2-methylpiperazin-1-yl)ethanol Chemical compound CC1CNCCN1CCO SDMNEUXIWBRMPK-UHFFFAOYSA-N 0.000 description 1
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LPZOCVVDSHQFST-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CC LPZOCVVDSHQFST-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZKCCKKDTLQTPKF-UHFFFAOYSA-N 2-ethoxy-1-methoxypropane Chemical compound CCOC(C)COC ZKCCKKDTLQTPKF-UHFFFAOYSA-N 0.000 description 1
- QVQDALFNSIKMBH-UHFFFAOYSA-N 2-pentoxyethanol Chemical compound CCCCCOCCO QVQDALFNSIKMBH-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- NTKBNCABAMQDIG-UHFFFAOYSA-N 3-butoxypropan-1-ol Chemical compound CCCCOCCCO NTKBNCABAMQDIG-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- VZKSLWJLGAGPIU-UHFFFAOYSA-N 3-morpholin-4-ylpropan-1-ol Chemical compound OCCCN1CCOCC1 VZKSLWJLGAGPIU-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- MGGVALXERJRIRO-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-2-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-1H-pyrazol-5-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)O MGGVALXERJRIRO-UHFFFAOYSA-N 0.000 description 1
- GXVDVJQTXFTVMP-UHFFFAOYSA-N 4-methoxypentan-2-ol Chemical compound COC(C)CC(C)O GXVDVJQTXFTVMP-UHFFFAOYSA-N 0.000 description 1
- QXDZKVUEOSMYRW-UHFFFAOYSA-N C(C)C(COCCO)CC.C(CO)O Chemical compound C(C)C(COCCO)CC.C(CO)O QXDZKVUEOSMYRW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 206010067482 No adverse event Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- AWXLLPFZAKTUCQ-UHFFFAOYSA-N [Sn].[W] Chemical compound [Sn].[W] AWXLLPFZAKTUCQ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
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Abstract
The present invention relates to a metal etchant composition, and more particularly, to a metal etchant composition comprising an ammonium fluoride-based compound, an alkanolamine, a glycol ether-based solvent, and water.
The metal etchant composition has an excellent etching speed for the titanium nitride film and the tungsten film, and also can protect the film quality without damaging the magnesium oxide (MgO) present on the pattern in the semiconductor manufacturing process. Thus, As a result, productivity and reliability can be greatly improved.
Description
The present invention relates to a metal etchant composition having selectively high etch rates for titanium nitride and tungsten films without damaging other films.
The tungsten or tungsten-based metal is used for a liquid crystal display, a gate electrode of a thin film transistor of a semiconductor device, a wiring, a barrier layer, a contact hole, and a buried hole. It is also used as a tungsten heater in the field of MEMS (Micro Electro Mechanical Systems)
A titanium nitride film (TiN, titanium nitride, or titanium nitride), which is a titanium-based metal, together with the tungsten or tungsten-based metal is used as a ground layer or a cap layer of a copper (Cu) wiring. Further, the semiconductor device may be used as a barrier metal or a gate metal.
The titanium nitride film or the tungsten film is present on the semiconductor substrate in a patterned state of a predetermined shape.
Patterning is usually done by a dry etch or wet etch process, using a gas or liquid etchant to selectively remove unwanted portions.
The etching process is divided according to the state of the substance causing the etching reaction, including wet etching using a soluble chemical and dry etching using an ionized gas. Wet etching is widely used because it has advantages of low cost and simple process compared to dry etching.
The etchant used for wet etching depends on the target to be etched.
For example, in connection with etching of a titanium nitride film, Korean Patent Laid-Open Publication No. 2014-0107602 proposes an etching solution composition composed of fluorine ions, a nitrogen-containing compound having two or more nitrogen-containing structural units, and water.
Korean Patent Publication No. 2007-0002946 discloses a method of fabricating a gate electrode of a semiconductor device capable of preventing the formation of an interfacial insulating film at an interface between tungsten and polysilicon in a tungsten poly metal gate electrode .
These etchants should not have an effect on the underlying film quality as well as an excellent etching effect on each film quality.
That is, a semiconductor having a titanium nitride film or a tungsten film pattern is used as an insulating film or a protective film of various materials for the purpose of short-circuiting or protecting the semiconductor thin film or the tungsten film pattern.
An inorganic oxide or an organic material is used for the insulating film or the protective film. Among them, a metal oxide film is used, and MgO material is generally used.
In the etching process, only the titanium nitride film or the tungsten film should be selectively etched. However, in the wet etching process such as immersion, damage is caused by the attack of the etchant, resulting in a significant deterioration of the quality of the film.
In the case of the insulating film or protective film, only the bulk etching was strictly controlled even if the film was removed by about 2 to 3 nm since the effect on the film dimension was not negligible . However, since the size of the semiconductor device is rapidly reduced, if the insulating film or the oxide film is removed to a certain level or more, the device performance may be seriously affected .
Therefore, it is required to produce a composition having an excellent etching performance for tungsten, tungsten alloy, and titanium nitride film without affecting other films in a semiconductor manufacturing process.
As a result of various studies on an etchant having an excellent etching performance for titanium nitride film and tungsten film without affecting other film quality, particularly, other film quality, the present applicant has found that fluorine based compounds, alkanolamine, glycol ether and water The present invention has been accomplished on the basis of the fact that the above-mentioned effects can be secured by performing wet etching for each film using the specific composition.
Accordingly, it is an object of the present invention to provide a metal etchant composition having an excellent etching performance selectively for a titanium nitride film and a tungsten film without affecting other films such as MgO.
In order to achieve the above object, the present invention provides a metal etchant composition comprising an ammonium fluoride-based compound, an alkanolamine, a glycol ether-based solvent, and water.
Wherein the metal etchant composition comprises 1 to 5% by weight of an ammonium fluoride compound, 5 to 30% by weight of an alkanolamine, 45 to 84% by weight of a glycol ether solvent, .
The metal etchant composition is characterized by selectively etching the titanium nitride film and the tungsten film without etching the underlying metal oxide film, for example, the magnesium oxide film.
The metal etchant composition according to the present invention has excellent etching speed for titanium nitride film and tungsten film and can protect the film quality without damaging the magnesium oxide (MgO) present on the pattern during semiconductor manufacturing process, And the productivity and reliability can be greatly improved by the improved etching characteristics.
The metal etchant composition according to the present invention has an excellent etching ability such as a rapid etching rate selectively only for a film to be etched without affecting other surrounding materials when wet etching is performed.
The metals mentioned in the specification of the present invention refer to titanium nitride (TiN, titanium nitride), or tungsten (W), which are deposited on a semiconductor substrate by vapor deposition or coating to form a thin film or a thick film, .
At this time, the film (or layer) made of titanium nitride (TiN) is defined as a titanium nitride film, and the film (or layer) made of tungsten is defined as a tungsten film.
Other films referred to in the specification of the present invention refer to films of materials other than the titanium nitride film and tungsten film existing on the pattern in the semiconductor manufacturing process and may be, for example, an insulating film, a protective film, or a sacrificial film. Magnesium oxide film (hereinafter referred to as " MgO film "). The MgO film may be positioned adjacent to the titanium nitride film or the tungsten film, and may be located on the lower side or the side surface of the film.
The wet etchant composition is selected in consideration of film uniformity, high etch rate, good selectivity, and profile, and is selected for other films No adverse effects should be or should be minimized. However, since the etchant composition used in the actual wet etching uses a material having a high acid or basicity, even if only the specific film is selectively etched, it attacks the adjacent film to cause damage to the film, Resulting in defective semiconductor products. Accordingly, the present invention provides an etchant composition capable of selectively etching only a specific film while minimizing the influence on other film quality.
Preferably, the metal etchant composition according to the present invention comprises an ammonium fluoride-based compound, an alkanolamine, a glycol ether-based solvent, and water. At this time, the respective contents and the ratio thereof greatly affect the etching rate for the metal film and the damage to the MgO film, and each composition will be described in detail below.
First, the ammonium fluoride compound constituting the metal etchant composition of the present invention serves to etch the surface of the metal film, and specifically, the titanium nitride film and / or the titanium nitride film by dissociating fluorine ions such as F - or HF 2 - Participates in the etch reaction of the tungsten film.
The kind of the ammonium fluoride compound is not particularly limited in the present invention, and any known one in this field can be used. (TbAHF), and combinations thereof, typically selected from the group consisting of ammonium fluoride (AF), ammonium butyl fluoride (ABF), tetramethylammonium fluoride (TMAF), tetrabutylammonium fluoride (TBAF), tetrabutylammonium hydrofluoride One species selected from the group is available, preferably ammonium fluoride.
The ammonium fluoride-based compound may be directly produced or commercially available.
Such an ammonium fluoride-based compound limits its content in order to sufficiently secure the etching effect of the titanium nitride film and / or the tungsten film. Preferably, 1 to 5% by weight, preferably 2 to 5% by weight, is used in the total etchant composition.
If the content is less than the above range, the etching effect on the metal film is insufficient. On the contrary, if the content is in the range above, the etching effect is greatly increased to cause damage (e.g., corrosion) or etching on the MgO film The removal of the etched residues is insufficient to cause bonding to the film due to residues remaining on the surface, which may adversely affect the characteristics of the device.
The etchant composition according to the present invention together with the ammonium fluoride-based compound uses an alkanolamine.
The alkanolamine is a substance having both a hydroxyl group and an amino group in the molecular structure and can control the pH (pH) of the hydrogen ion. That is, the hydrogen ion concentration (pH) is a measure of how much the hydrogen atoms are in the ion state. The hydrogen ion concentration is divided into 0 to 14, indicating how strong the acidity of the material is, ) Is 7, and if the hydrogen ion concentration is lower than 7, it is classified as an acid, and if it is higher, it can be classified as a base.
Accordingly, in the present invention, the alkanolamine is used to lower the hydrogen ion concentration, thereby enhancing the reactivity of the ammonium fluoride compound to improve the etching rate of the titanium nitride film and / or the tungsten film.
Specifically, the kind of the alkanolamine is not particularly limited in the present invention, and any known one in the field can be used. Typically, monoethanolamine, diethanolamine, triethanolamine, mono-propanol amine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N - methyl diethanol amine, N, N - dimethylethanolamine, N, N - diethylamino-ethanol, 2- (2-amino-ethylamino) -1-ethanol, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol (Methoxymethyl) aminoethanol, methyl (methoxymethyl) aminoethanol, methyl (methoxymethyl) aminoethanol, (2-hydroxyethyl) piperazine, 1- (2-hydroxyethyl) methylpiperazine, N - (2-aminoethoxy) -Hydroxyethyl) morpholine, N - (3-hydroxypropyl) morpholine, and combinations thereof. Preferably, one species selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, 2- (2-aminoethoxy) ethanol, N -methyldiethanolamine and combinations thereof can be used.
According to the experimental example of the present invention, when an alkylamine such as ethylenediamine or triethylamine is used instead of an alkanolamine (see Comparative Examples 11 and 12), the titanium nitride film is not etched and the tungsten film has poor etchability In addition, damage to the MgO film occurred.
The alkanolamine is preferably used in an amount of 5 to 30% by weight, more preferably 10 to 30% by weight, based on 100% by weight of the total composition. When the alkanolamine is used in an amount less than the above range, the above-mentioned effect (protection of the etching ability against the titanium nitride film and / or the tungsten film and protection of the MgO film) can not be ensured. On the other hand, There is a problem that the etching rate of the titanium nitride film and / or the tungsten film may be lowered due to excessive use, so that it is suitably used within the above range.
A glycol ether-based solvent is used together with the ammonium fluoride-based compound and the alkanolamine.
The glycol ether solvent is used to dissolve the metal film residue generated by the etching. The glycol ether solvent dissolves the particles or residue etched by the ammonium fluoride compound and is then easily removed by a process such as cleaning or scrubbing So that it can be removed. If the particles or residues remain as they are in the etching process, they may affect other patterns on the semiconductor substrate and short-circuit between the metal wirings may occur. Therefore, a glycol ether-based solvent which is a solvent having high solubility to particles or residues of titanium nitride and tungsten is used.
The glycol ether-based solvent is not particularly limited in its kind in the present invention, and any known one in this field can be used. Representative examples of the glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-pentyl ether, ethylene glycol mono- Ethylene glycol mono-2-ethylbutyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, and other ethylene glycol monoethers; Ethylene glycol diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether and ethylene glycol dibutyl ether; Propylene glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether and propylene glycol mono-t-butyl ether; Propylene glycol diethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether and propylene glycol methyl ethyl ether; Methyl-3-methoxy-1-butanol, 3-methoxy-1-butylacetate, 3-methoxy- Diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-n-butyl ether, and diethylene glycol mono-n-hexyl ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Ethyl glycol monoethers; Diethylene glycol diethyl ether such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Dipropylene glycol monomethyl ether such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monopropyl ether; Dipropylene glycol diethers such as dipropylene glycol dimethyl ether; And a combination thereof, and propylene glycol monomethyl is preferably used.
The glycol ether solvent is preferably used in an amount of 45 to 84% by weight, more preferably 50 to 75% by weight, based on 100% by weight of the total composition.
If the content is less than the above range, the dissolution of the particles and residues generated during the etching process is insufficient, so that it remains on the substrate after the etching process and can not cause short-circuiting of the metal wiring. Since there is no increase in the effect, it is suitably used within the above range.
The metal etchant composition of the present invention contains water, which is used for dissolving fluorine compounds and for mixing with other compounds.
In view of the application to the semiconductor process, which is a particularly suitable application for the present invention, the water is essentially required to be clean water. Specifically, it is preferable that the number of metals and other impurities that can affect the semiconductor is as small as possible. Examples of the method for obtaining such water include ion exchange method and the like.
The content of such water is not particularly limited, but may be included as a remainder to satisfy 100 wt% of the entire composition. The water content in the present invention can be varied depending on the concentration of the fluorine compound to be used, in a range capable of sufficiently dissolving the above-mentioned composition.
Further, the metal etchant composition according to the present invention may further include known additives. As the additive, a surfactant, a sequestering agent, and a corrosion inhibitor may be used.
For example, surfactants reduce surface tension and increase the uniformity of the etch. As such a surfactant, a surfactant which is resistant to an etching solution and has compatibility with the surfactant is preferable. Examples thereof include any of anionic, cationic, amphoteric or nonionic surfactants and the like. Further, a fluorine-based surfactant can be used as a surfactant.
The additive is not limited thereto, and various other additives known in the art can be selected and added for better effect of the present invention.
The metal etchant composition according to the present invention can be obtained by uniformly stirring each composition using a mixing apparatus.
Such a metal etchant composition can be applied to a patterning process of a titanium nitride film and / or a tungsten film in a semiconductor manufacturing process. According to a preferred embodiment of the present invention, the etch rate of the titanium nitride film is more than 2 Å / min, and the tungsten film etch rate is more than 8 Å / minute. .
In addition, it can be seen that the selective etching process can be performed by confirming that the MgO film has little influence on corrosion or cross section.
The etching method is not particularly limited in the present invention, and a wet etching process known in the art can be used.
For example, deposition, spraying, or a method using deposition and spray can be used.
As the etching conditions, the temperature is usually 30 to 80 캜, preferably 50 to 70 캜, and the deposition, spraying, or deposition and spraying time is usually 30 seconds to 10 minutes, preferably 1 to 5 minutes. However, these conditions are not strictly applied and can be selected by those skilled in the art as being convenient or suitable.
In the wet process, by treating with the etchant composition according to the present invention, it is possible to selectively remove only the film quality required to be removed.
Therefore, the metal etchant composition according to the present invention can improve the quality of a semiconductor device by improving the reliability of a wet process, and it can be used in a manufacturing process of a semiconductor device, a display device including the same, a MEMS device, and a printed wiring board Do.
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
Example 1 to 7 and Comparative Examples 1 to 14: Etchant Preparation of composition
The compositions shown in Table 1 were uniformly mixed at room temperature to prepare an etchant composition.
(weight%)
menstruum
week)
1) A-1: Ammonium fluoride (AF)
2) A-2: ammonium butyl fluoride (ABF),
3) A-3: tetramethylammonium fluoride (TMAF)
4) A-4: tetrabutylammonium fluoride (TBAHF)
5) A-5: tetrabutylammonium hydrofluoride (TbAHF)
6) B-1: monoethanolamine
7) B-2: Diethanolamine
8) B-3: Aminoethylethanolamine
9) C-1: Ethylenediamine
10) C-2: Triethylamine
11) D-1: Propylene glycol monomethyl ether
Experimental Example One: Etching Character rating
A wafer having a thickness of 1000 angstroms was prepared as a single film of a titanium nitride film, a tungsten film and a MgO film on a silicon wafer.
The titanium nitride film and the tungsten film were cut to a size of 2 x 2 cm and immersed in the etchant composition prepared in the above Examples and Comparative Examples at 30 DEG C for 30 minutes. Further, the MgO film was cut into a size of 2 x 2 cm and immersed in the etching composition prepared in the above Example and Comparative Example at 30 DEG C for 60 minutes.
The etching rates of the titanium nitride film and the tungsten film were determined by measuring the change in film thickness of each substrate through an Ellipsometer (SE-MG-1000) after cleaning each substrate with isopropyl alcohol. The results are shown in Table 2 Respectively. In addition, the change of the MgO film was observed with a scanning electron microscope (SEM), and the corrosion state was judged based on the following criteria, and the results are shown in Table 2.
<Standard>
(1) Titanium Of the nitride film (TiN) The etching rate (Å / min )
◎: TiN film etching rate> 2 Å / min
○: 1 Å / min <TiN film etching rate <2 Å / min
DELTA: TiN film etching rate <1 Å / min
×: No etching
(2) Of the tungsten film (W) The etching rate (Å / min )
◎: W film etching rate> 8 Å / min
○: 2 Å / <W film etching rate <8 Å / min
DELTA: W-film etching rate <2 Å / min ×: Not etched
(3) MoO Membrane change
◎: No corrosion at all
○: almost no corrosion
?: Surface roughness occurred
×: Etching occurrence
Referring to Table 2, the etchant compositions of Examples 1 to 7 of the present invention show that the etching rates of the titanium nitride film and the tungsten film are relatively fast, i.e., 2 to 8 Å or more per minute, as compared with Comparative Examples 1 to 4 Able to know.
Referring to Comparative Examples 1 to 10, it can be seen that the content ratio of each composition influences the etching rate of the titanium nitride film and the tungsten film and the corrosion of MgO.
In addition, in the case of Comparative Examples 11 and 12 using an alkylamine instead of an alkanolamine, the titanium nitride film could not be etched and the MgO film was rather etched.
From these results, it can be seen that the use of the content of the present invention minimizes the rapid etching rate and the influence on the MgO film on the titanium nitride film and the tungsten film.
The metal etchant composition of the present invention is applicable to a semiconductor manufacturing process.
Claims (5)
1 to 5% by weight of an ammonium fluoride compound,
5 to 30% by weight of an alkanolamine,
45 to 84% by weight of a glycol ether solvent, and
And water as the remainder.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20070002946A (en) | 2005-06-30 | 2007-01-05 | 주식회사 하이닉스반도체 | Poly-metal gate electrode and method for manufacturing the same |
| KR20110031233A (en) | 2008-09-09 | 2011-03-24 | 쇼와 덴코 가부시키가이샤 | Etchant for titanium-based metal, tungsten-based metal, titanium-tungsten-based metal or nitrides thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070002946A (en) | 2005-06-30 | 2007-01-05 | 주식회사 하이닉스반도체 | Poly-metal gate electrode and method for manufacturing the same |
| KR20110031233A (en) | 2008-09-09 | 2011-03-24 | 쇼와 덴코 가부시키가이샤 | Etchant for titanium-based metal, tungsten-based metal, titanium-tungsten-based metal or nitrides thereof |
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