WO2019167970A1 - アルミナのダメージを抑制した組成物及びこれを用いた半導体基板の製造方法 - Google Patents
アルミナのダメージを抑制した組成物及びこれを用いた半導体基板の製造方法 Download PDFInfo
- Publication number
- WO2019167970A1 WO2019167970A1 PCT/JP2019/007408 JP2019007408W WO2019167970A1 WO 2019167970 A1 WO2019167970 A1 WO 2019167970A1 JP 2019007408 W JP2019007408 W JP 2019007408W WO 2019167970 A1 WO2019167970 A1 WO 2019167970A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- barium
- semiconductor substrate
- alumina
- composition according
- dry etching
- Prior art date
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 87
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 239000000758 substrate Substances 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000001312 dry etching Methods 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 35
- 150000001553 barium compounds Chemical class 0.000 claims abstract description 13
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims description 46
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 46
- 229910017052 cobalt Inorganic materials 0.000 claims description 45
- 239000010410 layer Substances 0.000 claims description 39
- 239000011229 interlayer Substances 0.000 claims description 33
- -1 barium tetrafluoroborate Chemical compound 0.000 claims description 17
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 13
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 239000012964 benzotriazole Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 7
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 7
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 6
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 6
- 229910001626 barium chloride Inorganic materials 0.000 claims description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 150000004673 fluoride salts Chemical class 0.000 claims description 6
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 claims description 3
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 claims description 3
- 229910001620 barium bromide Inorganic materials 0.000 claims description 3
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 claims description 3
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 claims description 3
- 229940083898 barium chromate Drugs 0.000 claims description 3
- UNLSXXHOHZUADN-UHFFFAOYSA-N barium cyanide Chemical compound [Ba+2].N#[C-].N#[C-] UNLSXXHOHZUADN-UHFFFAOYSA-N 0.000 claims description 3
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 claims description 3
- 229940075444 barium iodide Drugs 0.000 claims description 3
- 229910001638 barium iodide Inorganic materials 0.000 claims description 3
- OOULUYZFLXDWDQ-UHFFFAOYSA-L barium perchlorate Chemical compound [Ba+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O OOULUYZFLXDWDQ-UHFFFAOYSA-L 0.000 claims description 3
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 claims description 3
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 3
- ARSLNKYOPNUFFY-UHFFFAOYSA-L barium sulfite Chemical compound [Ba+2].[O-]S([O-])=O ARSLNKYOPNUFFY-UHFFFAOYSA-L 0.000 claims description 3
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 3
- 239000010408 film Substances 0.000 description 60
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 38
- 235000012431 wafers Nutrition 0.000 description 32
- 229910000531 Co alloy Inorganic materials 0.000 description 30
- 238000011156 evaluation Methods 0.000 description 19
- 239000010936 titanium Substances 0.000 description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 17
- 229910052719 titanium Inorganic materials 0.000 description 17
- 239000000463 material Substances 0.000 description 12
- 238000011282 treatment Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052581 Si3N4 Inorganic materials 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 150000004761 hexafluorosilicates Chemical class 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- ZUHDIDYOAZNPBV-UHFFFAOYSA-N 2-[2-hydroxyethyl-[(4-methylbenzotriazol-1-yl)methyl]amino]ethanol Chemical compound CC1=CC=CC2=C1N=NN2CN(CCO)CCO ZUHDIDYOAZNPBV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- JZKFIPKXQBZXMW-UHFFFAOYSA-L beryllium difluoride Chemical compound F[Be]F JZKFIPKXQBZXMW-UHFFFAOYSA-L 0.000 description 1
- 229910001633 beryllium fluoride Inorganic materials 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical class O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XQMTUIZTZJXUFM-UHFFFAOYSA-N tetraethoxy silicate Chemical compound CCOO[Si](OOCC)(OOCC)OOCC XQMTUIZTZJXUFM-UHFFFAOYSA-N 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
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/105—Nitrates; Nitrites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3281—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
-
- 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02178—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing aluminium, e.g. Al2O3
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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
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Definitions
- the present invention relates to a composition capable of suppressing damage of alumina in a manufacturing process of a semiconductor integrated circuit and removing a dry etching residue existing on the surface of the semiconductor integrated circuit, and a method of manufacturing a semiconductor substrate using the composition.
- a residue (referred to as a dry etching residue) derived from an etching gas component, a layer to be etched, a mask layer (resist, hard mask, etc.), and the like is generated. If the process proceeds to the next step without removing the dry etching residue, the yield decreases, and therefore a step of removing the dry etching residue is required.
- the dry etching residue is removed with oxygen plasma, the material exposed to oxygen plasma or the like is damaged, resulting in a problem that the electrical characteristics are remarkably deteriorated. Therefore, there is a need for a method that removes dry etching residues to the same extent as in the oxygen plasma process and does not damage other materials.
- etch stop layer is provided on the cobalt, and vias are formed by dry etching until the etch stop layer is reached.Then, the etch stop layer at the bottom of the via is removed by a method having a small influence on cobalt, and the cobalt is removed.
- An exposure process is conceivable.
- a fluorine-based gas is selected.
- alumina is highly resistant to fluorine-based gases, so even a thin film is etched.
- Nonpatent literature 1 There exists an advantage which functions as a stop layer (nonpatent literature 1).
- alumina As the etch stop layer, it is necessary to suppress damage to the alumina at the same time in the step of removing the dry etching residue, and there is a demand for a chemical that can achieve this.
- a hard mask used as a mask at the time of dry etching a silicon-based or titanium-based hard mask is generally used.
- a zirconia-based hard mask is also used (Non-patent Document 2). Therefore, when a zirconia hard mask is used, zirconia is included in the dry etching residue.
- An object of the present invention is to provide a composition capable of suppressing damage to alumina and removing a dry etching residue, and a method for producing a semiconductor substrate using the composition.
- the present invention is as follows.
- the barium compound (A) is barium nitrate, barium acetate, barium chloride, barium hydroxide, barium sulfite, barium chlorate, barium perchlorate, barium peroxide, barium chromate, barium oxide, barium cyanide,
- the composition according to [1] comprising one or more selected from the group consisting of barium bromide, barium carbonate, barium metaborate, barium iodide, barium tetrafluoroborate, barium sulfate and barium sulfide.
- an etching rate of alumina at 50 ° C. is 40 ⁇ / min (4.0 ⁇ 10 ⁇ 9 nm / min) or less.
- composition according to any one of [1] to [9] wherein an etching rate of cobalt at 50 ° C.
- the production method of the present invention includes a step of removing a dry etching residue using the composition according to any one of [1] to [12].
- the composition of the present invention by using the composition of the present invention, it is possible to remove the dry etching residue on the surface of the object to be processed while suppressing the damage of alumina in the manufacturing process of the semiconductor circuit.
- a high-precision and high-quality semiconductor substrate can be manufactured with a high yield.
- composition in the present invention contains a barium compound (A) and a fluorine compound (B). These will be described in detail below.
- the barium compound (A) of the present application is an inorganic substance containing barium and has an effect of preventing corrosion of alumina.
- Specific examples of the barium compound (A) include barium nitrate, barium acetate, barium chloride, barium hydroxide, barium sulfite, barium chlorate, barium perchlorate, barium peroxide, barium chromate, barium oxide, barium cyanide, Examples include barium bromide, barium carbonate, barium metaborate, barium iodide, barium tetrafluoroborate, barium sulfate, barium sulfide, and salts obtained by reacting barium hydroxide with an acid.
- barium nitrate, barium acetate, barium chloride, and barium hydroxide are preferable because of their high water solubility and availability.
- the concentration (content) of the barium compound (A) in the composition is 0.00005 to 1% by mass, preferably 0.00025 to 0.75% by mass, more preferably 0.001 to 0.1% by mass, especially The amount is preferably 0.004 to 0.06% by mass. By being in this range, damage to alumina can be effectively suppressed.
- the fluorine compound (B) in the present invention is a compound containing a fluorine atom (excluding those having a carbon-fluorine (C—F) bond).
- a fluorine atom excluding those having a carbon-fluorine (C—F) bond.
- Specific examples thereof include hydrofluoric acid, fluoride salt, tetrafluoro Examples thereof include boric acid, tetrafluoroborate, hexafluorosilicate, hexafluorosilicate, hexafluorophosphate, and hexafluorophosphate.
- the fluoride salt is not particularly limited as long as it is a salt of hydrofluoric acid with an inorganic alkali or an organic alkali.
- fluoride salts include ammonium fluoride, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, beryllium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, fluorine Preferred examples include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride.
- the fluorine compound (B) has an effect of removing dry etching residues. Of these, hydrofluoric acid and fluoride salts, which have high removability of dry etching residues and are easily available, are preferable.
- the concentration (content) of the fluorine compound (B) in the composition is 0.01 to 20% by mass, preferably 0.02 to 17.5% by mass, more preferably 0.03 to 15.0% by mass, particularly Preferably, the content is 0.05 to 10.0% by mass. By being in this range, damage to alumina can be effectively suppressed.
- a benzotriazole compound (C) may be added to enhance the corrosion resistance to cobalt or a cobalt alloy.
- the benzotriazole compound (C) is a compound having a benzotriazole skeleton. Specific examples thereof include benzotriazole, 5-methyl-1H-benzotriazole, and 2,2 ′-[[(methyl-1H-benzotriazole- 1-yl) methyl] imino] bisethanol and the like.
- any compound having a benzotriazole skeleton can be used. These can be used alone or in combination of two or more.
- the concentration (content) of the benzotriazole compound (C) in the composition is usually 0.01 to 10% by mass, preferably 0.025 to 7.5% by mass, More preferably, it is 0.05 to 5.0% by mass, and particularly preferably 0.1 to 1.0% by mass. By being in this range, damage to cobalt or a cobalt alloy can be effectively suppressed.
- a compound (D) having a pyrrolidone structure may be added in order to improve the corrosion resistance to the low dielectric constant interlayer insulating film and cobalt or cobalt alloy.
- the compound (D) having a pyrrolidone structure used in the present invention is an oligomer or polymer containing a pyrrolidone unit as a repeating unit.
- a polyvinyl pyrrolidone a random copolymer containing a pyrrolidone unit, An alternating copolymer containing units, a block copolymer containing pyrrolidone units, and a branched polymer containing pyrrolidone units.
- the weight average molecular weight of the compound (D) having a pyrrolidone structure is usually 1000 to 5000000, preferably 1300 to 3500000, more preferably 1600 to 2800000, and particularly preferably 2000 to 1200000.
- the ratio of the repeating unit of the pyrrolidone unit is usually 50% or more, preferably 60% or more, more preferably 65% or more, and particularly preferably 70% or more. By being in these ranges, damage to the low dielectric constant interlayer insulating film and cobalt or cobalt alloy can be effectively suppressed.
- the compound (D) having a pyrrolidone structure for example, Pitzkor (trademark) series manufactured by Daiichi Kogyo Seiyaku Co., Ltd. is available and can be preferably used.
- the concentration (content) of the compound (D) having a pyrrolidone structure in the composition is usually 0.0005 to 1% by mass, preferably 0.001 to 0.75. % By mass, more preferably 0.002 to 0.5% by mass, particularly preferably 0.003 to 0.1% by mass.
- composition of the present invention may be blended with components conventionally used in semiconductor compositions as long as the object of the present invention is not impaired.
- diethylene glycol monobutyl ether can be added as a solvent, and alkalis, acids, chelating agents, surfactants, antifoaming agents, oxidizing agents, reducing agents, metal anticorrosives, water-soluble organic solvents, and the like can be added as additives.
- the balance of the composition of the present invention is water.
- the water that can be used in the present invention is not particularly limited, but water from which metal ions, organic impurities, particles, and the like have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, and the like is preferable, and pure water is more preferable. Ultrapure water is particularly preferable.
- the concentration (content) of water in the composition is preferably 45 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
- the composition of the present invention is prepared by adding water (preferably ultrapure water) to the barium compound (A), the fluorine compound (B) and other components as necessary, and stirring until uniform.
- the pH range of the composition is 2.5 to 8.0, preferably 2.7 to 7.8, more preferably 2.9 to 7.6, particularly preferably 3.1 to 7.4, It is preferably less than 7.0, and more preferably 3.1 to 6.5.
- dry etching residues can be removed while effectively suppressing damage to cobalt or a cobalt alloy, alumina, a low dielectric constant interlayer insulating film, and silicon nitride.
- the composition of this invention does not contain hydrogen peroxide substantially, and it is more preferable that the density
- the temperature at which the composition of the present invention is used is usually 20 to 70 ° C., preferably 30 to 60 ° C., particularly preferably 40 to 55 ° C. What is necessary is just to select suitably by the conditions of dry etching and the structure of the semiconductor substrate to be used.
- the time for using the composition of the present invention is usually 0.2 to 60 minutes. What is necessary is just to select suitably by the conditions of dry etching and the structure of the semiconductor substrate to be used.
- the composition of the present invention can be used, for example, in contact with the surface of a semiconductor substrate.
- the dry etching residue can be removed from the surface of the semiconductor substrate by bringing the composition of the present invention into contact with the surface of the semiconductor substrate.
- the dry etching residue is removed from the surface of the semiconductor substrate while suppressing damage to the alumina contained in the alumina layer. Can do.
- the method for bringing the composition of the present invention into contact with the surface of the semiconductor substrate is not particularly limited.
- the method of bringing the composition of the present invention into contact with the surface of the semiconductor substrate by a method such as dropping (single-leaf spin treatment) or spraying, or A method of immersing a semiconductor substrate in the composition of the present invention can be employed. Any method may be employed in the present invention.
- the rinsing liquid after using the composition of the present invention both an organic solvent and water can be used.
- semiconductor substrate As a semiconductor substrate in which the composition of the present invention can be suitably used, Substrate materials such as silicon, amorphous silicon, polysilicon, glass; Insulating materials such as silicon oxide, silicon nitride, silicon carbide and their derivatives; Materials such as cobalt, cobalt alloy, tungsten, titanium-tungsten; Substrates using compound semiconductors such as gallium-arsenide, gallium-phosphorus, indium-phosphorus, indium-gallium-arsenic, indium-aluminum-arsenic, and oxide semiconductors such as chromium oxide, particularly low dielectric constant interlayer insulating films
- the semiconductor substrate having any material preferably has an alumina layer containing alumina.
- an alumina layer is provided as an etch stop layer.
- the content of alumina in the alumina layer is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass.
- Examples of the dry etching residue to be removed in the present invention include those generated when a via or trench is formed in a low dielectric constant interlayer insulating film by dry etching using a titanium or zirconia hard mask as a mask. In this case, a part of the dry etching residue is generated when the etching gas comes into contact with the titanium hard mask or the zirconia hard mask. Therefore, the dry etching residue to be removed usually contains titanium or zirconium.
- the composition of this invention can fully suppress the damage of an alumina in the process of removing a dry etching residue.
- the etching rate of alumina when the semiconductor substrate is immersed in the composition of the present invention and measured at 50 ° C. is preferably 40 ⁇ / min (4.0 ⁇ 10 ⁇ 9 nm / min) or less, more preferably 35 ⁇ / min (3.5 ⁇ 10 -9 nm / min) or less, more preferably 33 ⁇ / min (3.3 ⁇ 10 -9 nm / min) or less, particularly preferably 15 ⁇ / min (1.5 ⁇ 10 - 9 nm / min) or less.
- the cobalt etching rate when the semiconductor substrate is immersed in the composition of the present invention and measured at 50 ° C. is preferably 5.0 ⁇ / min (5.0 ⁇ 10 ⁇ 10 nm) or less, more preferably 3.0 kg / min (3.0 ⁇ 10 ⁇ 10 nm / min) or less, more preferably 1.0 kg / min (1.0 ⁇ 10 ⁇ 10 nm / min) or less, and even more preferably 0.5 kg / min.
- the semiconductor substrate is immersed in the composition of the present invention, and the etching rate of the low dielectric constant interlayer insulating film when measured at 50 ° C. is 5.0 ⁇ / min (5.0 ⁇ 10 ⁇ 10 nm) or less, More preferably, 3.0 ⁇ / min (3.0 ⁇ 10 ⁇ 10 nm / min) or less, still more preferably 1.0 ⁇ / min (1.0 ⁇ 10 ⁇ 10 nm / min), and still more preferably 0.5 ⁇ / min. /min(0.5 ⁇ 10 -10 nm / min) or less, particularly preferably 0.2 ⁇ / min (0.2 ⁇ 10 -10 nm / min) or less.
- the manufacturing method of the semiconductor substrate of this invention includes the process of removing a dry etching residue using the composition of this invention. For example, after a via or trench is formed by dry etching, a semiconductor substrate having an alumina layer before removing the dry etching residue is brought into contact with the composition of the present invention to remove the dry etching residue from the surface of the semiconductor substrate. Process.
- the use temperature and use time of the composition of the present invention are as described in the above-mentioned “Method of using composition”.
- the semiconductor substrate having the alumina layer is as described in the above “semiconductor substrate”.
- the method for bringing the composition of the present invention into contact with the surface of the semiconductor substrate having an alumina layer is not particularly limited.
- the composition of the present invention is brought into contact with the surface of the semiconductor substrate by a method such as dropping (single wafer spin treatment) or spraying.
- a method of immersing a semiconductor substrate in the composition of the present invention can be employed. Any method may be employed in the present invention.
- 1 to 4 show an example of a cross-sectional structure of a semiconductor substrate having an alumina layer after a via is formed by dry etching and before a dry etching residue is removed.
- FIG. 1 shows an embodiment of a semiconductor substrate having a structure of a low dielectric constant interlayer insulating film, cobalt or a cobalt alloy, alumina, and a titanium-based hard mask in a semiconductor substrate before dry etching residue removal when the bottom of the via is alumina.
- FIG. 1 cobalt or a cobalt alloy 3 as a wiring material and alumina 4 as an etch stop layer are stacked on a semiconductor substrate, and a low dielectric constant interlayer insulating film 5 and a titanium hard mask 2 are stacked in this order. doing.
- the bottom of the via is alumina 4, and the titanium dry etching residue 1 is attached to the surface of the via and the titanium hard mask 2.
- FIG. 2 shows a semiconductor substrate having a structure of a low dielectric constant interlayer insulating film, cobalt or cobalt alloy, alumina, titanium hard mask in a semiconductor substrate before dry etching residue removal when the bottom of the via is made of cobalt or a cobalt alloy.
- FIG. 2 cobalt or cobalt alloy 3 as a wiring material and alumina 4 as an etch stop layer are laminated on a semiconductor substrate, and further a low dielectric constant interlayer insulating film 5 and a titanium hard mask 2 are laminated in this order. doing.
- the bottom of the via is made of cobalt or a cobalt alloy 3, and the titanium dry etching residue 1 is attached to the surface of the via and the titanium hard mask 2.
- FIG. 3 shows an embodiment of a semiconductor substrate having a structure of a low dielectric constant interlayer insulating film, cobalt or a cobalt alloy, alumina, or a zirconia-based hard mask in a semiconductor substrate before dry etching residue removal when the bottom of the via is alumina.
- FIG. 3 cobalt or cobalt alloy 3 as a wiring material and alumina 4 as an etch stop layer are laminated on a semiconductor substrate, and a low dielectric constant interlayer insulating film 5 and a zirconia hard mask 7 are laminated in this order. doing.
- the bottom of the via is alumina 4, and a zirconia dry etching residue 6 is attached to the surface of the via and the zirconia hard mask 7.
- FIG. 4 shows a semiconductor substrate having a structure of a low dielectric constant interlayer insulating film, cobalt or cobalt alloy, alumina, or zirconia hard mask in a semiconductor substrate before dry etching residue removal when the bottom of the via is made of cobalt or a cobalt alloy.
- FIG. 4 cobalt or a cobalt alloy 3 as a wiring material and alumina 4 as an etch stop layer are laminated on a semiconductor substrate, and further a low dielectric constant interlayer insulating film 5 and a zirconia hard mask 7 are laminated in this order. doing.
- the bottom of the via is cobalt or a cobalt alloy 3, and zirconia dry etching residue 6 is attached to the surface of the via and the zirconia hard mask 7.
- the dry etching residue is removed from the surface of the semiconductor substrate by contacting the semiconductor substrate having the alumina layer before removing the dry etching residue and the composition of the present invention. Can be removed. Thereby, a semiconductor substrate can be manufactured with a high yield. According to the preferred embodiment of the present invention, damage to the alumina contained in the alumina layer can be sufficiently suppressed in the step of removing the dry etching residue. In one embodiment of the present invention, in the case where the semiconductor substrate has cobalt or a cobalt alloy, and further, a low dielectric constant interlayer insulating film in addition to alumina, the damage can be suppressed. Thereby, a semiconductor substrate can be manufactured without affecting electrical characteristics.
- the method for cleaning a semiconductor substrate of the present invention includes a step of removing a dry etching residue using the composition of the present invention. For example, after a via or trench is formed by dry etching, a semiconductor substrate having an alumina layer before removing the dry etching residue is brought into contact with the composition of the present invention to remove the dry etching residue from the surface of the semiconductor substrate. Process.
- the use temperature and use time of the composition of the present invention are as described in the above-mentioned “Method of using composition”.
- the method of bringing the composition of the present invention into contact with the surface of a semiconductor substrate having an alumina layer is also as described in the above-mentioned “Method for producing a semiconductor substrate having an alumina layer”.
- the semiconductor substrate having the alumina layer to be cleaned is also as described in the “semiconductor substrate” and the “method for manufacturing a semiconductor substrate having an alumina layer”.
- etching residues can be removed from the surface of the semiconductor substrate.
- alumina damage can be sufficiently suppressed in the step of removing the dry etching residue.
- those damages can be sufficiently suppressed. Thereby, a semiconductor substrate can be manufactured without affecting electrical characteristics.
- ⁇ Wafer with film> For evaluation of damage to alumina, cobalt, and low dielectric constant interlayer insulating film by composition Alumina, cobalt, and low dielectric constant interlayer insulating film (TEOS “Tetraethoxysilicate”) are formed into respective films.
- TEOS low dielectric constant interlayer insulating film
- Each wafer with a film (a wafer with an alumina film, a wafer with a cobalt film, a wafer with a wafer film with a TEOS film) was used.
- Each film-coated wafer is treated with a composition at 50 ° C., and the difference in film thickness before and after the treatment is divided by the treatment time. R. was calculated.
- the film thickness of the film-coated wafer is measured using a fluorescent X-ray apparatus SEA1200VX (film thickness measuring apparatus A) manufactured by SII Nano Technology, Inc. or an optical film thickness meter n & k 1280 (film thickness measuring apparatus B) manufactured by n & k Technology. It was measured.
- the film thickness was measured using the film thickness measuring apparatus A for the wafer with the cobalt film, and the film thickness measuring apparatus B for the wafer with the alumina film and the wafer film with the TEOS film.
- Alumina is an E.I. R. Is 40 ⁇ / min or less.
- TEOS is 1.0 ⁇ / min or less.
- Examples 1 to 8 and Comparative Examples 1 to 12 In the test, an evaluation wafer A, an evaluation wafer B, and a wafer with an alumina film were used. It was immersed in the composition described in Table 1 at 50 ° C., and then rinsed with ultrapure water and dried by spraying dry nitrogen gas. All of the evaluation wafer A and the evaluation wafer B were subjected to an immersion process for 1 minute, and the processed wafer was observed with an SEM. A wafer with an alumina film is immersed for 5 minutes. R. (In the comparative example, since the alumina film was completely dissolved in the immersion treatment for 5 minutes, the ER was calculated by performing immersion treatment for 30 seconds except for Comparative Example 11).
- Example 9 to 13 Evaluation in the composition of Table 2 which used together the benzotriazole compound (C) and the compound (D) which has a pyrrolidone structure was performed.
- an evaluation wafer A, an evaluation wafer B, a wafer with an alumina film, a wafer with a cobalt film, and a wafer with a film of TEOS were used. It was immersed in the composition described in Table 2 at 50 ° C., and then rinsed with ultrapure water and dried by spraying dry nitrogen gas.
- the immersion treatment was performed for 1 minute in the same manner as in Examples 1 to 8, and the processed wafer was observed with an SEM.
- the wafer with an alumina film was subjected to an immersion treatment for 5 minutes in the same manner as in Examples 1 to 8.
- R. was calculated.
- Each of the wafers with a film of cobalt and TEOS is immersed for 30 minutes.
- R. was calculated. It can be seen that in Examples 9 and 10, the dry etching residue was completely removed while preventing damage to alumina and cobalt. Further, in Examples 11 to 13, it can be seen that the dry etching residue is completely removed while preventing damage to the alumina, cobalt, and the low dielectric constant interlayer insulating film.
- Titanium-based dry etching residue 2 Titanium-based hard mask 3: Cobalt or cobalt alloy 4: Alumina 5: Low dielectric constant interlayer insulating film 6: Zirconia-based dry etching residue 7: Zirconia-based hard mask
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Abstract
Description
ドライエッチング残渣を酸素プラズマで除去する場合、酸素プラズマなどに曝された材質がダメージを受け、電気特性が著しく劣化するという問題が生じる。そのため、酸素プラズマ工程と同程度にドライエッチング残渣を除去し、その他の材質にはダメージを与えない方法が求められる。
配線材料であるコバルトに達するまでドライエッチングを行う場合、コバルトがドライエッチングのガスに晒され変質し、電気特性に影響を与える場合がある。そのため、コバルトの上にエッチストップ層を設け、ドライエッチングでエッチストップ層に到達するまでビアを形成し、次いでコバルトへの影響が少ない方法で、ビアの底のエッチストップ層を除去し、コバルトを露出させる工程が考えられる。
一般的に、ドライエッチングでビアを形成する際は、フッ素系のガスが選択されるが、エッチストップ層としてアルミナを選択すると、アルミナはフッ素系のガスへの耐性が高いため、薄い膜でもエッチストップ層として機能する利点がある(非特許文献1)。
エッチストップ層としてアルミナを選択する場合、このドライエッチング残渣を除去する工程では、同時にアルミナへのダメージを抑制する必要があり、これを達成可能な薬液が求められている。
また、アルミナだけでなくコバルトや低誘電率層間絶縁膜のダメージの抑制も基板の構成によっては必要になってくる。
また、ドライエッチング時にマスクとして使用されるハードマスクはシリコン系やチタン系が一般的に用いられるが、近年ジルコニア系のハードマスクも使用される例もある(非特許文献2)。そのため、ジルコニア系ハードマスクが使用される場合は、ドライエッチング残渣にジルコニアが含まれることになる。
[2] バリウム化合物(A)が、硝酸バリウム、酢酸バリウム、塩化バリウム、水酸化バリウム、亜硫酸バリウム、塩素酸バリウム、過塩素酸バリウム、過酸化バリウム、クロム酸バリウム、酸化バリウム、シアン化バリウム、臭化バリウム、炭酸バリウム、メタホウ酸バリウム、ヨウ化バリウム、テトラフルオロホウ酸バリウム、硫酸バリウム及び硫化バリウムからなる群より選択される1以上を含有する[1]に記載の組成物。
[3] バリウム化合物(A)が、硝酸バリウム、酢酸バリウム、塩化バリウム及び水酸化バリウムからなる群より選択される1以上を含有する[1]に記載の組成物。
[4] フッ素化合物(B)が、フッ酸又はフッ化物塩を含有する[1]~[3]のいずれか一項に記載の組成物。
[5] pHが3.1~7.4の範囲にある、[1]~[4]のいずれか一項に記載の組成物。
[6] 過酸化水素の含有量が0.002質量%未満である、[1]~[5]のいずれか一項に記載の組成物。
[7] ベンゾトリアゾール化合物(C)を更に0.01~10質量%含有する、[1]~[6]のいずれか一項に記載の組成物。
[8] ピロリドン構造を有する化合物(D)を更に0.0005~1質量%含有する、[1]~[7]のいずれか一項に記載の組成物。
[9] 50℃におけるアルミナのエッチングレートが、40Å/min(4.0×10-9nm/min)以下である、[1]~[8]のいずれか一項に記載の組成物。
[10] 50℃におけるコバルトのエッチングレートが、1.0Å/min(1.0×10-10nm/min)以下である、[1]~[9]のいずれか一項に記載の組成物。
[11] 50℃における低誘電率層間絶縁膜のエッチングレートが、1.0Å/min(1.0×10-10nm/min)以下である、[1]~[10]のいずれか一項に記載の組成物。
[12] アルミナ層を有する半導体基板のドライエッチング残渣除去に使用される、[1]~[11]のいずれか一項に記載の組成物。
[13] [1]~[12]のいずれか一項に記載の組成物を用いた、アルミナ層を有する半導体基板の製造方法。なお、本発明の製造方法は、[1]~[12]のいずれか一項に記載の組成物を用いてドライエッチング残渣を除去する工程を含む。
[14] [1]~[12]のいずれか一項に記載の組成物を用いてドライエッチング残渣を除去する工程を含む、アルミナ層を有する半導体基板の洗浄方法。
本願のバリウム化合物(A)はバリウムを含有する無機物であり、アルミナを防食する効果がある。
バリウム化合物(A)の具体例として、硝酸バリウム、酢酸バリウム、塩化バリウム、水酸化バリウム、亜硫酸バリウム、塩素酸バリウム、過塩素酸バリウム、過酸化バリウム、クロム酸バリウム、酸化バリウム、シアン化バリウム、臭化バリウム、炭酸バリウム、メタホウ酸バリウム、ヨウ化バリウム、テトラフルオロホウ酸バリウム、硫酸バリウム、硫化バリウム、及び水酸化バリウムと酸を反応させた塩が挙げられ、これらは単独または2種類以上を組み合わせて使用できる。
これらの中で硝酸バリウム、酢酸バリウム、塩化バリウム及び水酸化バリウムが高い水溶性があり、入手が容易なため好ましい。
バリウム化合物(A)の組成物中の濃度(含有量)は0.00005~1質量%、好ましくは0.00025~0.75質量%、さらに好ましくは0.001~0.1質量%、特に好ましくは0.004~0.06質量%である。この範囲にあることでアルミナへのダメージを効果的に抑制できる。
本発明におけるフッ素化合物(B)は、フッ素原子を含有する化合物(ただし、炭素-フッ素(C-F)結合を有するものを除く)であり、具体例として、フッ酸、フッ化物塩、テトラフルオロホウ酸、テトラフルオロホウ酸塩、ヘキサフルオロケイ酸、ヘキサフルオロケイ酸塩、ヘキサフルオロリン酸及びヘキサフルオロリン酸塩などが挙げられる。
ここでフッ化物塩は、フッ酸と、無機アルカリ又は有機アルカリとの塩であれば特に限定されない。フッ化物塩の具体例としては、フッ化アンモニウム、フッ化リチウム、フッ化ナトリウム、フッ化カリウム、フッ化ルビジウム、フッ化セシウム、フッ化ベリリウム、フッ化マグネシウム、フッ化カルシウム、フッ化ストロンチウム、フッ化テトラメチルアンモニウム、フッ化テトラエチルアンモニウム、フッ化テトラプロピルアンモニウム及びフッ化テトラブチルアンモニウムなどが好ましく挙げられる。
フッ素化合物(B)は、ドライエッチング残渣を除去する効果がある。これらの中でドライエッチング残渣の除去性が高く、入手が容易なフッ酸及びフッ化物塩が好ましい。また、これらは単独または2種類以上を組み合わせて使用できる。
フッ素化合物(B)の組成物中の濃度(含有量)は0.01~20質量%、好ましくは0.02~17.5質量%、さらに好ましくは0.03~15.0質量%、特に好ましくは0.05~10.0質量%である。この範囲にあることでアルミナへのダメージを効果的に抑制できる。
本発明では、コバルトまたはコバルト合金への防食性を高めるためにベンゾトリアゾール化合物(C)を加えても良い。
ベンゾトリアゾール化合物(C)とは、ベンゾトリアゾール骨格を有する化合物であり、具体例として、ベンゾトリアゾール、5-メチル-1H-ベンゾトリアゾール、及び2,2’―[[(メチル―1H―ベンゾトリアゾール―1―イル)メチル]イミノ]ビスエタノールなどが挙げられる。他にも、ベンゾトリアゾール骨格を有する化合物であれば使用できる。これらは単独または2種類以上を組み合わせて使用できる。
ベンゾトリアゾール化合物(C)を使用する場合、ベンゾトリアゾール化合物(C)の組成物中の濃度(含有量)は、通常0.01~10質量%、好ましくは0.025~7.5質量%、さらに好ましくは0.05~5.0質量%、特に好ましくは0.1~1.0質量%である。この範囲にあることでコバルトまたはコバルト合金へのダメージを効果的に抑制できる。
本発明では、低誘電率層間絶縁膜及びコバルトまたはコバルト合金への防食性を高めるためにピロリドン構造を有する化合物(D)を加えても良い。
本発明に使用されるピロリドン構造を有する化合物(D)とは、繰り返し単位にピロリドンのユニットを含むオリゴマーあるいはポリマーであり、具体的にはポリビニルピロリドン、ピロリドンのユニットを含むランダム共重合体、ピロリドンのユニットを含む交互共重合体、ピロリドンのユニットを含むブロック共重合体、ピロリドンのユニットを含む分岐ポリマーである。
ピロリドン構造を有する化合物(D)の重量平均分子量は、通常1000~5000000、好ましくは1300~3500000、さらに好ましくは1600~2800000、特に好ましくは2000~1200000であり、ピロリドン構造を有する化合物(D)中のピロリドンのユニットの繰り返し単位の比率は、通常50%以上、好ましくは60%以上、さらに好ましくは65%以上、特に好ましくは70%以上である。これらの範囲内にあることで低誘電率層間絶縁膜と、コバルトまたはコバルト合金へのダメージを効果的に抑制できる。
ピロリドン構造を有する化合物(D)としては、例えば第一工業製薬株式会社製のピッツコール(商標)シリーズが入手可能であり、好適に使用可能である。
ピロリドン構造を有する化合物(D)を使用する場合、ピロリドン構造を有する化合物(D)の組成物中の濃度(含有量)は通常0.0005~1質量%、好ましくは0.001~0.75質量%、さらに好ましくは0.002~0.5質量%、特に好ましくは0.003~0.1質量%である。上記範囲内であると低誘電率層間絶縁膜と、コバルトまたはコバルト合金へのダメージを効果的に抑制できる。
本発明の組成物には、所望により本発明の目的を損なわない範囲で従来から半導体用組成物に使用されている成分を配合してもよい。
例えば、溶剤としてジエチレングリコールモノブチルエーテル、添加剤として、アルカリ、酸、キレート剤、界面活性剤、消泡剤、酸化剤、還元剤、金属防食剤及び水溶性有機溶剤などを添加することができる。
本発明の組成物の残部は水である。本発明に使用できる水としては、特に限定されないが、蒸留、イオン交換処理、フイルター処理、各種吸着処理などによって、金属イオンや有機不純物、パーテイクルなどが除去されたものが好ましく、純水がより好ましく、超純水が特に好ましい。
組成物中の水の濃度(含有量)は、45~100質量%が好ましく、より好ましくは90~100質量%、さらに好ましくは95~100質量%である。
本発明の組成物は、バリウム化合物(A)、フッ素化合物(B)及び必要に応じてその他の成分に水(好ましくは超純水)を加えて均一になるまで攪拌することで調製される。
組成物のpHの範囲は、2.5~8.0、好ましくは2.7~7.8、さらに好ましくは2.9~7.6、特に好ましくは3.1~7.4であり、なお好ましくは7.0未満、さらになお好ましくは3.1~6.5である。pHがこの範囲であることにより、コバルトまたはコバルト合金、アルミナ、低誘電率層間絶縁膜、窒化シリコンへのダメージを効果的に抑制しつつ、ドライエッチング残渣を除去できる。
なお、本発明の組成物は、過酸化水素を実質的に含まないことが好ましく、過酸化水素の組成物中の濃度(含有量)は0.002質量%未満とすることがより好ましい。
本発明の組成物を使用する温度は、通常20~70℃、好ましくは30~60℃、特に好ましくは40~55℃である。ドライエッチングの条件や使用される半導体基板の構成により適宜選択すればよい。
本発明の組成物を使用する時間は、通常0.2~60分である。ドライエッチングの条件や使用される半導体基板の構成により適宜選択すればよい。
本発明の組成物は、例えば、半導体基板の表面に接触させて使用することができる。本発明の好ましい態様によれば、本発明の組成物を半導体基板の表面に接触させることにより、半導体基板の表面からドライエッチング残渣を除去することができる。本発明の特に好ましい態様によれば、半導体基板がアルミナを含有するアルミナ層を有する場合に、アルミナ層に含有されるアルミナのダメージを抑制しながら、半導体基板の表面からドライエッチング残渣を除去することができる。
半導体基板の表面に本発明の組成物を接触させる方法は特に制限されなく、例えば滴下(枚葉スピン処理)またはスプレーなどの形式により半導体基板の表面に本発明の組成物を接触させる方法、または半導体基板を本発明の組成物に浸漬させる方法などを採用することができる。本発明においては、いずれの方法を採用してもよい。
本発明の組成物を使用した後のリンス液としては、有機溶剤も水もどちらも使用できる。
本発明の組成物が好適に使用できる半導体基板としては、
シリコン、非晶質シリコン、ポリシリコン、ガラスなどの基板材料;
酸化シリコン、窒化シリコン、炭化シリコン及びこれらの誘導体などの絶縁材料;
コバルト、コバルト合金、タングステン、チタン-タングステンなどの材料;
ガリウム-砒素、ガリウム-リン、インジウム-リン、インジウム-ガリウム-砒素、インジウム-アルミニウム-砒素などの化合物半導体及びクロム酸化物などの酸化物半導体、特に低誘電率層間絶縁膜を使用している基板であり、いずれの材料を有する半導体基板も、アルミナを含有するアルミナ層を有することが好ましい。具体的には、例えば、エッチストップ層などとしてアルミナ層を有する。
アルミナ層におけるアルミナの含有量は、好ましくは30質量%以上、より好ましくは50質量%以上、さらに好ましくは70質量%以上、さらにより好ましくは90質量%以上、特に好ましくは100質量%である。
また、本発明の一態様において、半導体基板が、アルミナに加えて、コバルトまたはコバルト合金、さらには低誘電率層間絶縁膜を有する場合は、それらのダメージを抑制できることがより好ましい。
例えば、本発明の組成物に前記半導体基板を浸漬し、50℃で測定したときのコバルトのエッチングレートは、好ましくは5.0Å/min(5.0×10-10nm)以下、より好ましくは3.0Å/min(3.0×10-10nm/min)以下、さらに好ましくは1.0Å/min(1.0×10-10nm/min)以下、さらにより好ましくは0.5Å/min(0.5×10-10nm/min)以下、特に好ましくは0.3Å/min(0.3×10-10nm/min)以下である。
また、本発明の組成物に前記半導体基板を浸漬し、50℃で測定したときの低誘電率層間絶縁膜のエッチングレートが、5.0Å/min(5.0×10-10nm)以下、より好ましくは3.0Å/min(3.0×10-10nm/min)以下、さらに好ましくは1.0Å/min(1.0×10-10nm/min)、さらにより好ましくは0.5Å/min(0.5×10-10nm/min)以下、特に好ましくは0.2Å/min(0.2×10-10nm/min)以下である。
本発明の半導体基板の製造方法は、本発明の組成物を用いてドライエッチング残渣を除去する工程を含む。例えば、ドライエッチングによりビアやトレンチを形成した後、ドライエッチング残渣を除去する前のアルミナ層を有する半導体基板を、本発明の組成物と接触させて、半導体基板の表面からドライエッチング残渣を除去する工程を含む。
本発明の半導体基板の洗浄方法は、本発明の組成物を用いてドライエッチング残渣を除去する工程を含む。例えば、ドライエッチングによりビアやトレンチを形成した後、ドライエッチング残渣を除去する前のアルミナ層を有する半導体基板を、本発明の組成物と接触させて、半導体基板の表面からドライエッチング残渣を除去する工程を含む。
尚、特に指定しない限り%は質量%を意味する。
<評価ウェハA>:チタン(Ti)系残渣の除去評価用
下層から、窒化シリコン、層間絶縁膜、窒化シリコン、酸化チタン、フォトレジストを製膜し、次いでフォトレジストをパターニングした。
フォトレジストをマスクとしてハードマスクの所定の箇所をドライエッチングで除去し、酸素プラズマによるアッシングでフォトレジストを除去した。さらにハードマスクをマスクとして、ドライエッチングにより窒化シリコン、層間絶縁膜にビアを形成した。
<評価ウェハB>:ジルコニア(Zr)系残渣の除去評価用
下層から、窒化シリコン、層間絶縁膜、窒化シリコン、ジルコニア、フォトレジストを製膜し、次いでフォトレジストをパターニングした。
フォトレジストをマスクとしてハードマスクの所定の箇所をドライエッチングで除去し、酸素プラズマによるアッシングでフォトレジストを除去した。さらにハードマスクをマスクとして、ドライエッチングにより窒化シリコン、層間絶縁膜にビアを形成した。
アルミナ、コバルト、低誘電率層間絶縁膜(TEOS「テトラエトキシシリケート」)のそれぞれの材質が製膜された各膜付きウェハ(アルミナ膜付きウェハ、コバルト膜付きウェハ、TEOS膜付きウェハ膜付きウェハ)を用いた。
<残渣の除去評価>
各種組成物で処理した後の評価ウェハA及び評価ウェハBについてSEM観察を行った。
測定機器;株式会社日立ハイテクノロジーズ社製、超高分解能電界放出形走査電子顕微鏡SU9000(倍率10万倍)
判定方法:
E:ドライエッチング残渣が完全に除去された。
G:ドライエッチング残渣が概ね完全に除去された。
P:ドライエッチング残渣の除去が不十分であった。
E、G判定を合格とした。
それぞれの膜付きウェハを50℃の組成物で処理し、処理前後の膜厚差を処理時間で除することでE.R.を算出した。膜付きウェハの膜厚は、エスアイアイ・ナノテクノロジー株式会社製 蛍光X線装置SEA1200VX(膜厚測定装置A)、あるいはn&kテクノロジー社製光学式膜厚計n&k1280(膜厚測定装置B)を用いて測定した。コバルト膜付きウェハは膜厚測定装置Aを、アルミナ膜付きウェハ、TEOS膜付きウェハ膜付きウェハは膜厚測定装置Bを用いて膜厚を測定した。
アルミナはE.R.が40Å/min以下
コバルトはE.R.が1.0Å/min以下
TEOSは1.0Å/min以下 の場合を良品とした。
試験には、評価ウェハA、評価ウェハBおよびアルミナ膜付きウェハを使用した。表1に記した組成物に50℃で浸漬し、その後、超純水によるリンス、乾燥窒素ガス噴射による乾燥を行った。評価ウェハAおよび評価ウェハBに関しては、全て1分間浸漬処理を行い、処理後のウェハをSEMで観察した。
アルミナ膜付きウェハに対しては5分間浸漬処理を行い、処理前後の膜厚からE.R.を算出した(比較例では、5分間の浸漬処理ではアルミナ膜が完全に溶解したため、比較例11以外は30秒間浸漬処理を行いE.R.を算出した)。
各組成物のpHは、25℃にてpHメーター(株式会社堀場製作所製pHメーターF-52)を使用して測定した。
実施例1~8においては、アルミナのダメージを防ぎながら、ドライエッチング残渣を完全に除去していることがわかる。
一方、比較例においては、アルミナのダメージを抑制し、被処理物表面のドライエッチング残渣を除去する目的には使用できないことがわかる。特に、比較例4~10においては、バリウムと同族のBe、Mg、Ca、Srにカチオンを変更したものを使用しているが、バリウム塩と同様の効果が得られていないことが分かる。
ベンゾトリアゾール化合物(C)及びピロリドン構造を有する化合物(D)を併用した表2の組成における評価を行った。試験には、評価ウェハA、評価ウェハB、アルミナ膜付きウェハ、コバルト膜付きウェハ及びTEOSの膜付きウェハを使用した。表2に記した組成物に50℃で浸漬し、その後、超純水によるリンス、乾燥窒素ガス噴射による乾燥を行った。評価ウェハA及び評価ウェハBに関しては、実施例1~8と同様に1分間浸漬処理を行い、処理後のウェハをSEMで観察した。アルミナ膜付きウェハに対しては、実施例1~8と同様に5分間浸漬処理を行い、E.R.を算出した。コバルトとTEOSの膜付きウェハに対してはそれぞれ30分間浸漬処理を行い、E.R.を算出した。実施例9,10においては、アルミナ、コバルトのダメージを防ぎながら、ドライエッチング残渣を完全に除去していることがわかる。さらに、実施例11~13においては、アルミナ、コバルト、低誘電率層間絶縁膜のダメージを防ぎながら、ドライエッチング残渣を完全に除去していることがわかる。
2:チタン系ハードマスク
3:コバルトまたはコバルト合金
4:アルミナ
5:低誘電率層間絶縁膜
6:ジルコニア系ドライエッチング残渣
7:ジルコニア系ハードマスク
Claims (14)
- バリウム化合物(A)を0.00005~1質量%及びフッ素化合物(B)を0.01~20質量%で含有し、pHが2.5~8.0の範囲にある組成物。
- バリウム化合物(A)が、硝酸バリウム、酢酸バリウム、塩化バリウム、水酸化バリウム、亜硫酸バリウム、塩素酸バリウム、過塩素酸バリウム、過酸化バリウム、クロム酸バリウム、酸化バリウム、シアン化バリウム、臭化バリウム、炭酸バリウム、メタホウ酸バリウム、ヨウ化バリウム、テトラフルオロホウ酸バリウム、硫酸バリウム及び硫化バリウムからなる群より選択される1以上を含有する、請求項1に記載の組成物。
- バリウム化合物(A)が、硝酸バリウム、酢酸バリウム、塩化バリウム及び水酸化バリウムからなる群より選択される1以上を含有する、請求項1に記載の組成物。
- フッ素化合物(B)が、フッ酸又はフッ化物塩を含有する、請求項1~3のいずれか一項に記載の組成物。
- pHが3.1~7.4の範囲にある、請求項1~4のいずれか一項に記載の組成物。
- 過酸化水素の含有量が0.002質量%未満である、請求項1~5のいずれか一項に記載の組成物。
- ベンゾトリアゾール化合物(C)を0.01~10質量%更に含有する、請求項1~6のいずれか一項に記載の組成物。
- ピロリドン構造を有する化合物(D)を0.0005~1質量%更に含有する、請求項1~7のいずれか一項に記載の組成物。
- 50℃におけるアルミナのエッチングレートが、40Å/min(4.0×10-9nm/min)以下である、請求項1~8のいずれか一項に記載の組成物。
- 50℃におけるコバルトのエッチングレートが、1.0Å/min(1.0×10-10nm/min)以下である、請求項1~9のいずれか一項に記載の組成物。
- 50℃における低誘電率層間絶縁膜のエッチングレートが、1.0Å/min(1.0×10-10nm/min)以下である、請求項1~10のいずれか一項に記載の組成物。
- アルミナ層を有する半導体基板のドライエッチング残渣除去に使用される、請求項1~11のいずれか一項に記載の組成物。
- 請求項1~12のいずれか一項に記載の組成物を用いてドライエッチング残渣を除去する工程を含む、アルミナ層を有する半導体基板の製造方法。
- 請求項1~12のいずれか一項に記載の組成物を用いてドライエッチング残渣を除去する工程を含む、アルミナ層を有する半導体基板の洗浄方法。
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KR1020207019597A KR20200127151A (ko) | 2018-03-02 | 2019-02-27 | 알루미나의 데미지를 억제한 조성물 및 이것을 이용한 반도체기판의 제조방법 |
EP19761160.1A EP3761345A4 (en) | 2018-03-02 | 2019-02-27 | COMPOSITION WITH SUPPRESSED ALUMINUM DAMAGE AND PROCESS FOR MANUFACTURING A SEMICONDUCTOR SUBSTRATE THEREFORE |
JP2020503538A JP7294315B2 (ja) | 2018-03-02 | 2019-02-27 | アルミナのダメージを抑制した組成物及びこれを用いた半導体基板の製造方法 |
CN201980014145.8A CN111742392A (zh) | 2018-03-02 | 2019-02-27 | 抑制了氧化铝的损伤的组合物及使用了其的半导体基板的制造方法 |
US16/976,614 US11479744B2 (en) | 2018-03-02 | 2019-02-27 | Composition having suppressed alumina damage and production method for semiconductor substrate using same |
IL277045A IL277045B1 (en) | 2018-03-02 | 2019-02-27 | Preparations for protecting alumina from damage and processes for the production of semiconductor substrates using these preparations |
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US20220044941A1 (en) * | 2019-09-25 | 2022-02-10 | Taiwan Semiconductor Manufacturing Co., Ltd. | Methods Of Etching Metals In Semiconductor Devices |
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WO2019026677A1 (ja) * | 2017-07-31 | 2019-02-07 | 三菱瓦斯化学株式会社 | コバルト、アルミナ、層間絶縁膜、窒化シリコンのダメージを抑制した組成液及びこれを用いた洗浄方法 |
WO2019208686A1 (ja) * | 2018-04-27 | 2019-10-31 | 三菱瓦斯化学株式会社 | 水性組成物及びこれを用いた洗浄方法 |
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US11479744B2 (en) | 2022-10-25 |
IL277045B1 (en) | 2024-05-01 |
TW201938767A (zh) | 2019-10-01 |
JP7294315B2 (ja) | 2023-06-20 |
CN111742392A (zh) | 2020-10-02 |
EP3761345A4 (en) | 2021-04-28 |
IL277045A (en) | 2020-10-29 |
KR20200127151A (ko) | 2020-11-10 |
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US20210002591A1 (en) | 2021-01-07 |
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