CN107078043B - 抑制了包含钽的材料的损伤的半导体元件的清洗液、及使用其的清洗方法 - Google Patents
抑制了包含钽的材料的损伤的半导体元件的清洗液、及使用其的清洗方法 Download PDFInfo
- Publication number
- CN107078043B CN107078043B CN201580056375.2A CN201580056375A CN107078043B CN 107078043 B CN107078043 B CN 107078043B CN 201580056375 A CN201580056375 A CN 201580056375A CN 107078043 B CN107078043 B CN 107078043B
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- Prior art keywords
- tantalum
- cleaning
- mass
- film
- semiconductor element
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Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 110
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000004065 semiconductor Substances 0.000 title claims abstract description 38
- 239000007788 liquid Substances 0.000 title claims description 41
- 230000006378 damage Effects 0.000 title description 29
- 238000001312 dry etching Methods 0.000 claims abstract description 40
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 40
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 14
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 5
- 150000001553 barium compounds Chemical class 0.000 claims description 5
- 229940043430 calcium compound Drugs 0.000 claims description 5
- 150000001674 calcium compounds Chemical class 0.000 claims description 5
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 5
- 235000011056 potassium acetate Nutrition 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 235000011181 potassium carbonates Nutrition 0.000 claims description 5
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 5
- 235000011009 potassium phosphates Nutrition 0.000 claims description 5
- 150000003438 strontium compounds Chemical class 0.000 claims description 5
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 5
- 239000010408 film Substances 0.000 description 55
- 239000000243 solution Substances 0.000 description 27
- 238000004519 manufacturing process Methods 0.000 description 13
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- 239000010949 copper Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
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- 239000002184 metal Substances 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 7
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- 239000000203 mixture Substances 0.000 description 5
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- -1 hexafluorosilicic acid Chemical compound 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 2
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- 239000000654 additive Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 2
- 229910001620 barium bromide Inorganic materials 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 2
- 229910001632 barium fluoride Inorganic materials 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 2
- 229910001638 barium iodide Inorganic materials 0.000 description 2
- 229940075444 barium iodide Drugs 0.000 description 2
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- FCKYPQBAHLOOJQ-NXEZZACHSA-N 2-[[(1r,2r)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)[C@@H]1CCCC[C@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-NXEZZACHSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- 244000132059 Carica parviflora Species 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000005441 aurora Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
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- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
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- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
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- 235000011010 calcium phosphates Nutrition 0.000 description 1
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- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- YJPVTCSBVRMESK-UHFFFAOYSA-L strontium bromide Chemical compound [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 description 1
- 229910001625 strontium bromide Inorganic materials 0.000 description 1
- 229940074155 strontium bromide Drugs 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 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
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- KRIJWFBRWPCESA-UHFFFAOYSA-L strontium iodide Chemical compound [Sr+2].[I-].[I-] KRIJWFBRWPCESA-UHFFFAOYSA-L 0.000 description 1
- 229910001643 strontium iodide Inorganic materials 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/08—Liquid soap, e.g. for dispensers; capsuled
-
- 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
-
- 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
- C11D7/06—Hydroxides
-
- 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
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
-
- G—PHYSICS
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Abstract
根据本发明,可以提供一种去除半导体元件表面的光致抗蚀剂和干蚀刻残渣的清洗方法,其特征在于,所述半导体元件具有Low‑k膜和包含10原子%以上的钽的材料,所述清洗方法使用包含过氧化氢0.002~50质量%、碱土金属化合物0.001~1质量%、碱和水的清洗液。
Description
技术领域
本发明涉及:在半导体元件的制造工序中抑制低介电常数膜和包含钽的材料的损伤、去除被处理物表面的光致抗蚀剂和干蚀刻残渣的清洗液、及使用其的清洗方法。
背景技术
经过高集成化的半导体元件的制造通常如下:在硅晶圆等元件上形成作为导电用布线原材料的金属膜等导电薄膜、用于进行导电薄膜间的绝缘的层间绝缘膜,然后在其表面上均匀地涂布光致抗蚀剂而设置光敏层,并对其实施选择性地曝光、显影处理,制作期望的光致抗蚀剂图案。接着,以该光致抗蚀剂图案作为掩模,对层间绝缘膜实施干刻蚀处理,从而在该薄膜上形成期望的图案。而且,一般采用的是,将光致抗蚀剂图案和通过干刻蚀处理而产生的残渣物(以下,称为“干蚀刻残渣”)等利用基于氧等离子体的灰化、使用清洗液的清洗等完全去除之类的一系列工序。
近年来,设计规则的微细化推进,信号传导延迟逐渐支配高速度演算处理的限度。因此,导电用布线原材料从铝向电阻更低的铜转移,层间绝缘膜从硅氧化膜向低介电常数膜(相对介电常数小于3的膜。以下,称为“Low-k膜”)的转移正在推进。铜与层间绝缘膜的密合性不充分,而且若铜与层间绝缘膜相接,则铜向层间绝缘膜经时地扩散。为了改善这些问题,通常采用如下方法:在铜与层间绝缘膜之间插入包含被称为势垒金属的钽的材料的膜。另外,随着设计规则的微细化,晶体管的栅极的构成从氧化硅和多晶硅的组合逐渐变更为高介电常数材料和金属的组合。作为该金属,有时使用包含钽的材料。
利用氧等离子体去除光致抗蚀剂、干蚀刻残渣的情况下,发生Low-k膜被暴露于氧等离子体等而受到损伤、电特性明显劣化的问题。另外,包含钽的材料被暴露于氧等离子体等而受到损伤,在之后的制造工序发生不良情况。因此,在使用Low-k膜和包含钽的材料的半导体元件(图1)的制造中,要求抑制Low-k膜和包含钽的材料的损伤的同时,与氧等离子体工序同等程度地去除光致抗蚀剂和干蚀刻残渣。
已知利用清洗液的处理中,通过使用含过氧化氢且强碱性的清洗液可以去除光致抗蚀剂和干蚀刻残渣。含过氧化氢且强碱性的清洗液去除光致抗蚀剂和干蚀刻残渣的去除性优异,但与包含钽的材料接液时,导致包含钽的材料激烈地受到损伤。因此,期望能够有效地去除光致抗蚀剂和干蚀刻残渣、包含钽的材料不受到损伤的、含过氧化氢且强碱性的清洗液、及使用其的清洗方法。
专利文献1中提出了,利用包含碱、WzMXy(式中,M为选自由Si、Ge、Sn、Pt、P、B、Au、Ir、Os、Cr、Ti、Zr、Rh、Ru和Sb组成的组中的金属;X为选自由F、Cl、Br和I组成的组中的卤化物;W为选自H、碱或碱土金属和不含金属离子的氢氧化物碱基部分;y相对应金属卤化物而为4~6的数;而且z为1、2或3的数)的清洗液的布线形成方法。专利文献1记载的清洗方法中,既无法去除光致抗蚀剂,也无法抑制Low-k膜的损伤,因此不能在本目的中使用(参照比较例8)。另外,本发明的清洗方法所使用的清洗液中,专利文献1记载的配混有WzMXy的清洗液代替为了抑制包含钽的材料的损伤而配混的碱土金属化合物,会导致包含钽的材料和Low-k膜受到损伤(参照比较例9)。
现有技术文献
专利文献
专利文献1:日本特表2007-510307号公报
发明内容
发明要解决的问题
本发明的目的在于,提供在半导体元件的制造工序中抑制低介电常数膜和包含钽的材料的损伤、去除被处理物表面的光致抗蚀剂和干蚀刻残渣的清洗液、及使用其的清洗方法。
用于解决问题的方案
根据本发明,可以解决上述课题。即,本发明如以下。
<1>一种去除半导体元件表面的光致抗蚀剂和干蚀刻残渣的清洗方法,其特征在于,所述半导体元件具有Low-k膜和包含10原子%以上的钽的材料,所述清洗方法使用包含过氧化氢0.002~50质量%、碱土金属化合物0.001~1质量%、碱和水的清洗液。
<2>根据上述<1>所述的清洗方法,其中,前述清洗液的pH值为7~14。
<3>根据上述<1>或<2>所述的清洗方法,其中,前述包含10原子%以上的钽的材料为选自由氧化钽、氮化钽和钽组成的组中的至少1种。
<4>根据上述<1>~<3>中任一项所述的清洗方法,其中,前述碱土金属化合物为选自由钙化合物、锶化合物和钡化合物组成的组中的至少1种。
<5>根据上述<1>~<4>中任一项所述的清洗方法,其中,前述碱的含量为0.1~20质量%。
<6>根据上述<1>~<5>中任一项所述的清洗方法,其中,前述碱为选自由氢氧化钾、乙酸钾、碳酸钾、磷酸钾、氨、四甲基氢氧化铵、三乙胺、乙醇胺和1-氨基-2-丙醇组成的组中的至少1种。
<7>一种去除半导体元件表面的光致抗蚀剂和干蚀刻残渣的清洗液,其特征在于,所述半导体元件具有Low-k膜和包含10原子%以上的钽的材料,所述清洗液包含过氧化氢0.002~50质量%、碱土金属化合物0.001~1质量%、碱和水。
<8>根据上述<7>所述的清洗液,所述清洗液的pH值为7~14。
<9>根据上述<7>或<8>所述的清洗液,其中,前述包含10原子%以上的钽的材料为选自由氧化钽、氮化钽和钽组成的组中的至少1种。
<10>根据上述<7>~<9>中任一项所述的清洗液,其中,前述碱土金属化合物为选自由钙化合物、锶化合物和钡化合物组成的组中的至少1种。
<11>根据上述<7>~<10>中任一项所述的清洗液,其中,前述碱的含量为0.1~20质量%。
<12>根据上述<7>~<11>中任一项所述的清洗液,其中,前述碱为选自由氢氧化钾、乙酸钾、碳酸钾、磷酸钾、氨、四甲基氢氧化铵、三乙胺、乙醇胺和1-氨基-2-丙醇组成的组中的至少1种。
发明的效果
根据本发明的清洗液及使用其的清洗方法,在半导体元件的制造工序中抑制Low-k膜和包含钽的材料的损伤、选择性地去除被处理物表面的光致抗蚀剂和干蚀刻残渣成为可能,可以成品率良好地制造高精度、高品质的半导体元件。
附图说明
图1为示出光致抗蚀剂和干蚀刻残渣去除前的半导体元件的包含铜和铜的势垒金属钽的结构的一例的示意性剖视图。
图2为示出光致抗蚀剂和干蚀刻残渣去除前的半导体元件的一例的示意性剖视图。
具体实施方式
本发明的清洗液及使用其的清洗方法在制造半导体元件的清洗工序中使用,此时,能够以充分满足的程度清洗、去除光致抗蚀剂和干蚀刻残渣,并且可以抑制Low-k膜和包含钽的材料的损伤。
本发明的清洗液所应用的半导体元件中所含的包含钽的材料为包含10原子%以上的钽的材料,该钽的原子组成百分率优选为15原子%以上、更优选为20原子%以上、进一步优选为25原子%以上、特别优选为30原子%以上。包含钽的材料的具体例为氧化钽、氮化钽、钽等。然而,包含钽的材料只要为包含10原子%以上的钽的材料,就不限定于这些。
本发明中,钽的含量利用X射线光电子能谱法(XPS)的离子溅射法,测定作为对象的包含钽的材料的钽原子的构成比,从而可以进行考察。有时因包含钽的材料的表面附近被氧化,而使氧原子的构成比高于材料的内部。因此,可以利用离子溅射对包含钽的材料的表面进行蚀刻直至钽和氧的原子的构成比达到一定,测定因离子溅射而露出的包含钽的材料的内部的钽原子的构成比。作为测定装置,可以使用全自动XPS分析装置K-Alpha(ThermoFisher Scientific Co.,Ltd.制)。
本发明的清洗液所含的碱土金属化合物的浓度范围为0.001~1质量%、优选为0.002~0.5质量%、进一步优选为0.003~0.2质量%、特别优选为0.005~0.1质量%。若为上述范围内则可以有效地防止包含钽的材料的腐蚀。若浓度范围超过1质量%则有时干蚀刻残渣的去除性降低。
本发明人等首次发现清洗液所含的碱土金属化合物对于包含钽的材料显示出防腐蚀的效果。其机理尚未明确,但认为是碱土金属化合物吸附于钽的表面,防止清洗液所含的过氧化氢、碱对钽的侵蚀。
碱土金属化合物的具体例为钙化合物、锶化合物和钡化合物。更具体而言,可例示出硝酸钡、氢氧化钡、氯化钡、乙酸钡、氧化钡、溴化钡、碳酸钡、氟化钡、碘化钡、硫酸钡、磷酸钡、硝酸钙、氢氧化钙、氯化钙、乙酸钙、氧化钙、溴化钙、碳酸钙、氟化钙、碘化钙、硫酸钙、磷酸钙、硝酸锶、氢氧化锶、碳酸锶、氯化锶、乙酸锶、氧化锶、溴化锶、氟化锶、碘化锶、硫酸锶、磷酸锶等,但不限定于这些。
它们之中,优选硝酸钡、氢氧化钡、氯化钡、乙酸钡、氧化钡、溴化钡、碳酸钡、氟化钡、碘化钡、硫酸钡、磷酸钡、硝酸钙和硝酸锶。
这些碱土金属化合物可以单独或组合2种以上而配混。
本发明的清洗液所含的过氧化氢的浓度范围为0.002~50质量%、优选为0.01~40质量%、更优选为0.01~30质量%、进一步优选为0.1~30质量%、特别优选为0.5~25质量%。若为上述范围内则可以有效地去除干蚀刻残渣。
本发明的清洗液所含的碱是为了调整pH而加入的。因此,碱的种类没有限制,而且可以以任意的浓度加入。碱的浓度范围优选为0.1~20质量%、更优选为0.3~15质量%、进一步优选为0.5~12质量%、特别优选为0.6~10.4质量%。若为上述范围内则可以有效地防止包含钽的材料的腐蚀。若浓度范围超过20质量%则有时Low-k膜受到损伤。
本发明所使用的碱可以使用氢氧化钾、乙酸钾、碳酸钾、磷酸钾、氨、四甲基氢氧化铵、三乙胺、乙醇胺、1-氨基-2-丙醇等,但不限定于这些。
它们之中,优选氢氧化钾、氨和四甲基氢氧化铵。
这些碱可以单独或组合2种以上而配混。
本发明的清洗液的pH值可以在7~14的任意范围使用。优选的pH值为7.5~14、更优选为8~13.8、进一步优选为8.5~13.5。若为该范围的pH值则可以抑制Low-k膜和包含钽的材料的损伤、选择性地去除被处理物表面的光致抗蚀剂和干蚀刻残渣。
本发明的清洗液所含的水优选由蒸馏、离子交换处理、过滤器处理、各种吸附处理等将金属离子、有机杂质、微粒等去除后的水,特别优选为纯水、超纯水。此时,水的浓度为除去各种试剂后的余量部分。
本发明的清洗液中,根据期望在不有损本发明的目的的范围内可以配混一直以来在半导体用清洗液中所使用的添加剂。例如,作为添加剂,可以添加酸、金属防腐剂、水溶性有机溶剂、氟化合物、氧化剂、还原剂、螯合剂、表面活性剂、消泡剂等。
使用本发明的清洗液的温度为20~80℃、优选为50~70℃的范围,根据蚀刻的条件、所使用的半导体元件而适宜选择即可。
本发明的清洗方法根据需要可以组合使用超声波。
使用本发明的清洗液的时间为0.3~120分钟、优选为0.5~60分钟的范围,根据蚀刻的条件、所使用的半导体元件而适宜选择即可。
作为使用本发明的清洗液之后的冲洗液,也可以使用如醇那样的有机溶剂,但用水进行冲洗就足够。
作为本发明的清洗液所应用的半导体元件中含有的通常的Low-k膜,使用羟基倍半硅氧烷(HSQ)系、甲基倍半硅氧烷(MSQ)系的OCD(商品名,东京应化工业株式会社制)、碳掺杂氧化硅(SiOC)系的Black Diamond(商品名、Applied Materials株式会社制)、Aurora(商品名、ASM International株式会社制)、Coral(商品名、Novellus Systems株式会社制)、以及无机系的Orion(商品名、Trikon Tencnlogies株式会社制)。Low-k膜不限定于这些。
本发明的清洗液所应用的半导体元件可以包含阻隔绝缘膜和/或硬掩模。
实施例
接着,通过实施例和比较例进一步具体说明本发明。但是,本发明不受这些实施例的任何限制。
钽膜厚测定:
带有膜的晶圆的膜厚使用SII Nano Technology Co.,Ltd.制荧光X射线装置SEA1200VX进行测定。
钽的蚀刻速率的测定和判断:
包含钽的材料的蚀刻速率的评价使用包含30原子%的钽的带有氮化钽膜的晶圆(Advantec株式会社制)。将所述带有膜的晶圆的清洗液处理前后的膜厚除以处理时间而得的值定义为蚀刻速率并算出。
蚀刻速率以下为合格。
SEM观察:
半导体元件的清洗、去除处理前后的状况观察使用以下的SEM(扫描型电子显微镜)装置,以倍率10万倍观察。
测定设备:Hitachi High-Technologies Corporation制、超高分辨率场发射扫描电子显微镜SU9000
判断:
I.光致抗蚀剂的去除状态
E:光致抗蚀剂完全被去除。
G:光致抗蚀剂基本被去除。
P:光致抗蚀剂的去除不充分。
E和G判断为合格。
II.干蚀刻残渣的去除状态
E:干蚀刻残渣完全被去除。
G:干蚀刻残渣基本被去除。
P:干蚀刻残渣的去除不充分。
E和G判断为合格。
III.Low-k膜的损伤
E:与清洗前相比Low-k膜未见变化。
G:与清洗前相比Low-k膜可见稍有变化。
P:Low-k膜可见形状的变化。
E和G判断为合格。
实施例1~11
使用具有光致抗蚀剂2和Low-k膜4的具有如图2所示的截面的布线结构的半导体元件,调查去除干蚀刻残渣3的清洗效果。使用表1所示的清洗液,以表2所示的温度、时间进行浸渍,然后进行基于超纯水的冲洗、基于干燥氮气喷射的干燥。通过将清洗后的半导体元件用SEM观察,判断光致抗蚀剂2和干蚀刻残渣3(图2)的去除状态和Low-k膜4(图2)的损伤。
使用包含钽的材料的上述带有膜的晶圆(Advantec株式会社制),考察包含钽的材料的损伤。在表1所示的清洗液中以表2所示的温度、时间进行浸渍,然后进行基于超纯水的冲洗、基于干燥氮气喷射的干燥。浸渍前后的膜厚利用上述荧光X射线装置SEA1200VX求得,算出蚀刻速率。
可知在应用表2所示的本发明的清洗液、及使用其的清洗方法的实施例1~11中,防止Low-k膜4的损伤、并且完全去除光致抗蚀剂2和干蚀刻残渣3。另外,还可知氮化钽的蚀刻速率为以下,对包含钽的材料的损伤小。
比较例1~7(无碱土金属化合物)
利用实施例1、3~7所使用的清洗液(表1,清洗液1A、1C~1G)中不添加硝酸钡的清洗液(表3,清洗液2A、2C~2G)来清洗图2所示的半导体元件。另外,测定氮化钽的蚀刻速率。表5中示出清洗条件和清洗结果。与在比较例1~7所示的清洗液2A、2C~2G中加入有硝酸钡的清洗液(表1,清洗液1A、1C~1G)相比,Low-k膜4的损伤以及光致抗蚀剂2和干蚀刻残渣3的去除性方面没有差异,但氮化钽的蚀刻速率变高。因此,使用2A、2C~2G的清洗液的清洗方法在作为本发明的对象的半导体元件的制造工序中可以抑制Low-k膜的损伤、去除被处理物表面的光致抗蚀剂和干蚀刻残渣,但是对包含钽的材料的损伤大,因此不能在本申请的目的中使用(表5)。另外,由这些和实施例8~11可知碱土金属化合物不会使光致抗蚀剂和干蚀刻残渣的去除性恶化,抑制包含钽的材料的损伤是有用的。
比较例8(专利文献1中记载的发明)
利用包含TMAH 3.35质量%、CyDTA 0.11质量%、过氧化氢1.64质量%、六氟硅酸0.23质量%和水94.67质量%的清洗液(表4,清洗液2H)清洗图1所示的半导体元件。表5中示出清洗条件和评价结果。该清洗液可以去除干蚀刻残渣、氮化钽的蚀刻速率低,但是无法去除光致抗蚀剂,Low-k膜受到损伤。因此,可知使用2H的清洗液的清洗方法不能在作为本发明的对象的半导体元件的制造工序中抑制包含钽的材料和Low-k膜的损伤、去除被处理物表面的光致抗蚀剂和干蚀刻残渣的目的中使用。
比较例9
利用包含KOH 4.5质量%、过氧化氢0.01质量%、六氟硅酸0.01质量%和水95.48质量%的清洗液(表4,清洗液2I)清洗图1所示的半导体元件。表5中示出清洗条件和评价结果。使用该清洗液的清洗方法中,可以去除光致抗蚀剂和干蚀刻残渣,但氮化钽的蚀刻速率高、Low-k膜受到损伤。另外,可知与比较例3的清洗方法所使用的包含KOH 4.5质量%、过氧化氢0.01质量%和水95.49质量%的清洗液(表4,清洗液2C)相比,氮化钽的蚀刻速率相同,加入六氟硅酸后,从而Low-k膜受到损伤。由以上可知,使用2I的清洗液的清洗方法不能在作为本发明的对象的半导体元件的制造工序中抑制包含钽的材料和Low-k膜的损伤、去除被处理物表面的光致抗蚀剂和干蚀刻残渣的目的中使用。
[表1]
KOH:氢氧化钾
TMAH:四甲基氢氧化铵
[表2]
去除状态I:光致抗蚀剂2的去除状态
去除状态II:干蚀刻残渣3的去除状态
损伤I:Low-k膜4的损伤
TaN ER:氮化钽的蚀刻速率(包含钽的材料的损伤)
[表3]
KOH:氢氧化钾
TMAH:四甲基氢氧化铵
[表4]
TMAH:四甲基氢氧化铵
CyDTA:反式-1,2-二氨基环己烷-N,N,N’,N’-四乙酸1水合物
KOH:氢氧化钾
[表5]
去除状态I:光致抗蚀剂2的去除状态
去除状态II:干蚀刻残渣3的去除状态
损伤I:Low-k膜4的损伤
TaN ER:氮化钽的蚀刻速率(包含钽的材料的损伤)
产业上的可利用性
根据本发明的清洗液和清洗方法,在半导体元件的制造工序中抑制包含钽的材料和Low-k膜的损伤、去除被处理物表面的光致抗蚀剂和干蚀刻残渣成为可能,可以成品率良好地制造高精度、高品质的半导体元件,在工业上有用。
附图标记说明
1:包含钽的材料
2:光致抗蚀剂
3:干蚀刻残渣
4:Low-k膜
5:铜
Claims (8)
1.一种去除半导体元件表面的光致抗蚀剂和干蚀刻残渣的清洗方法,其特征在于,所述半导体元件具有Low-k膜和包含10原子%以上的钽的材料,
所述清洗方法使用包含过氧化氢0.002~50质量%、碱土金属化合物0.001~1质量%、碱和水、且pH值为7.9~14的清洗液,
所述碱土金属化合物为选自由钙化合物、锶化合物和钡化合物组成的组中的至少1种。
2.根据权利要求1所述的清洗方法,其中,所述包含10原子%以上的钽的材料为选自由氧化钽、氮化钽和钽组成的组中的至少1种。
3.根据权利要求1或2所述的清洗方法,其中,所述碱的含量为0.1~20质量%。
4.根据权利要求1或2所述的清洗方法,其中,所述碱为选自由氢氧化钾、乙酸钾、碳酸钾、磷酸钾、氨、四甲基氢氧化铵、三乙胺、乙醇胺和1-氨基-2-丙醇组成的组中的至少1种。
5.一种去除半导体元件表面的光致抗蚀剂和干蚀刻残渣的清洗液,其特征在于,所述半导体元件具有Low-k膜和包含10原子%以上的钽的材料,
所述清洗液包含过氧化氢0.002~50质量%、碱土金属化合物0.001~1质量%、碱和水,且pH值为7.9~14,
所述碱土金属化合物为选自由钙化合物、锶化合物和钡化合物组成的组中的至少1种。
6.根据权利要求5所述的清洗液,其中,所述包含10原子%以上的钽的材料为选自由氧化钽、氮化钽和钽组成的组中的至少1种。
7.根据权利要求5或6所述的清洗液,其中,所述碱的含量为0.1~20质量%。
8.根据权利要求5或6所述的清洗液,其中,所述碱为选自由氢氧化钾、乙酸钾、碳酸钾、磷酸钾、氨、四甲基氢氧化铵、三乙胺、乙醇胺和1-氨基-2-丙醇组成的组中的至少1种。
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