TWI808161B - 水性組成物及使用此組成物之清洗方法 - Google Patents
水性組成物及使用此組成物之清洗方法 Download PDFInfo
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- TWI808161B TWI808161B TW108114402A TW108114402A TWI808161B TW I808161 B TWI808161 B TW I808161B TW 108114402 A TW108114402 A TW 108114402A TW 108114402 A TW108114402 A TW 108114402A TW I808161 B TWI808161 B TW I808161B
- Authority
- TW
- Taiwan
- Prior art keywords
- acid
- alkyl
- phosphoric acid
- aqueous composition
- phosphonate
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 117
- 238000004140 cleaning Methods 0.000 title claims description 37
- 238000000034 method Methods 0.000 title claims description 16
- -1 alkyl phosphonic acid Chemical compound 0.000 claims abstract description 74
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000002253 acid Substances 0.000 claims abstract description 54
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 50
- 150000003839 salts Chemical class 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 235000011007 phosphoric acid Nutrition 0.000 claims description 49
- 125000000217 alkyl group Chemical group 0.000 claims description 42
- 125000005600 alkyl phosphonate group Chemical group 0.000 claims description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000005530 etching Methods 0.000 claims description 11
- 150000001553 barium compounds Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 5
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 5
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 claims description 4
- OZFLRNPZLCUVFP-UHFFFAOYSA-N 8-methylnonyl dihydrogen phosphate Chemical compound CC(C)CCCCCCCOP(O)(O)=O OZFLRNPZLCUVFP-UHFFFAOYSA-N 0.000 claims description 4
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 4
- 229910001626 barium chloride Inorganic materials 0.000 claims description 4
- SCIGVHCNNXTQDB-UHFFFAOYSA-N decyl dihydrogen phosphate Chemical compound CCCCCCCCCCOP(O)(O)=O SCIGVHCNNXTQDB-UHFFFAOYSA-N 0.000 claims description 4
- DZQISOJKASMITI-UHFFFAOYSA-N decyl-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound CCCCCCCCCCP(O)(O)=O DZQISOJKASMITI-UHFFFAOYSA-N 0.000 claims description 4
- SVMUEEINWGBIPD-UHFFFAOYSA-N dodecylphosphonic acid Chemical compound CCCCCCCCCCCCP(O)(O)=O SVMUEEINWGBIPD-UHFFFAOYSA-N 0.000 claims description 4
- GGKJPMAIXBETTD-UHFFFAOYSA-N heptyl dihydrogen phosphate Chemical compound CCCCCCCOP(O)(O)=O GGKJPMAIXBETTD-UHFFFAOYSA-N 0.000 claims description 4
- VAJFLSRDMGNZJY-UHFFFAOYSA-N heptylphosphonic acid Chemical compound CCCCCCCP(O)(O)=O VAJFLSRDMGNZJY-UHFFFAOYSA-N 0.000 claims description 4
- PHNWGDTYCJFUGZ-UHFFFAOYSA-N hexyl dihydrogen phosphate Chemical compound CCCCCCOP(O)(O)=O PHNWGDTYCJFUGZ-UHFFFAOYSA-N 0.000 claims description 4
- GJWAEWLHSDGBGG-UHFFFAOYSA-N hexylphosphonic acid Chemical compound CCCCCCP(O)(O)=O GJWAEWLHSDGBGG-UHFFFAOYSA-N 0.000 claims description 4
- WYAKJXQRALMWPB-UHFFFAOYSA-N nonyl dihydrogen phosphate Chemical compound CCCCCCCCCOP(O)(O)=O WYAKJXQRALMWPB-UHFFFAOYSA-N 0.000 claims description 4
- OLGGYSFJQGDOFX-UHFFFAOYSA-N nonylphosphonic acid Chemical compound CCCCCCCCCP(O)(O)=O OLGGYSFJQGDOFX-UHFFFAOYSA-N 0.000 claims description 4
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 claims description 4
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical compound CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 claims description 4
- NVTPMUHPCAUGCB-UHFFFAOYSA-N pentyl dihydrogen phosphate Chemical compound CCCCCOP(O)(O)=O NVTPMUHPCAUGCB-UHFFFAOYSA-N 0.000 claims description 4
- CKVICYBZYGZLLP-UHFFFAOYSA-N pentylphosphonic acid Chemical compound CCCCCP(O)(O)=O CKVICYBZYGZLLP-UHFFFAOYSA-N 0.000 claims description 4
- VAIOGRPEROWKJX-UHFFFAOYSA-N undecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCOP(O)(O)=O VAIOGRPEROWKJX-UHFFFAOYSA-N 0.000 claims description 4
- GKIQHTGBORJXKZ-UHFFFAOYSA-N undecylphosphonic acid Chemical compound CCCCCCCCCCCP(O)(O)=O GKIQHTGBORJXKZ-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 claims description 3
- UOKRBSXOBUKDGE-UHFFFAOYSA-N butylphosphonic acid Chemical compound CCCCP(O)(O)=O UOKRBSXOBUKDGE-UHFFFAOYSA-N 0.000 claims description 3
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- GAJQCIFYLSXSEZ-UHFFFAOYSA-N tridecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCOP(O)(O)=O GAJQCIFYLSXSEZ-UHFFFAOYSA-N 0.000 claims description 3
- KREGXBHGJXTOKZ-UHFFFAOYSA-N tridecylphosphonic acid Chemical compound CCCCCCCCCCCCCP(O)(O)=O KREGXBHGJXTOKZ-UHFFFAOYSA-N 0.000 claims description 3
- FRCRFINDRJFEFN-UHFFFAOYSA-N CCCCCCCCCCCCCOP(O)=O Chemical compound CCCCCCCCCCCCCOP(O)=O FRCRFINDRJFEFN-UHFFFAOYSA-N 0.000 claims description 2
- MGJJRXIEFROZLZ-UHFFFAOYSA-N CCCCCCCCCCCCOP(O)=O Chemical compound CCCCCCCCCCCCOP(O)=O MGJJRXIEFROZLZ-UHFFFAOYSA-N 0.000 claims description 2
- DEKOLWKUSOWLMN-UHFFFAOYSA-N CCCCCCCCCCCOP(O)=O Chemical compound CCCCCCCCCCCOP(O)=O DEKOLWKUSOWLMN-UHFFFAOYSA-N 0.000 claims description 2
- ZBEKPPVMYNVMQO-UHFFFAOYSA-N CCCCCCCCCCOP(O)=O Chemical compound CCCCCCCCCCOP(O)=O ZBEKPPVMYNVMQO-UHFFFAOYSA-N 0.000 claims description 2
- OCLUUUROQDRUIU-UHFFFAOYSA-N CCCCCCCCCOP(O)=O Chemical compound CCCCCCCCCOP(O)=O OCLUUUROQDRUIU-UHFFFAOYSA-N 0.000 claims description 2
- XJKCIKMIYBWISX-UHFFFAOYSA-N CCCCCCCCOP(O)=O Chemical compound CCCCCCCCOP(O)=O XJKCIKMIYBWISX-UHFFFAOYSA-N 0.000 claims description 2
- DEVJMJPPUVBPOV-UHFFFAOYSA-N CCCCCCCOP(O)=O Chemical compound CCCCCCCOP(O)=O DEVJMJPPUVBPOV-UHFFFAOYSA-N 0.000 claims description 2
- OEODWKRQWJHQSK-UHFFFAOYSA-N CCCCCCOP(O)=O Chemical compound CCCCCCOP(O)=O OEODWKRQWJHQSK-UHFFFAOYSA-N 0.000 claims description 2
- WMFDLEFIURCJJE-UHFFFAOYSA-N CCCCCOP(O)=O Chemical compound CCCCCOP(O)=O WMFDLEFIURCJJE-UHFFFAOYSA-N 0.000 claims description 2
- WCJLOEFXANROAO-UHFFFAOYSA-N CCCCOP(O)=O Chemical compound CCCCOP(O)=O WCJLOEFXANROAO-UHFFFAOYSA-N 0.000 claims 1
- 150000007513 acids Chemical class 0.000 abstract description 12
- 239000010408 film Substances 0.000 description 39
- 238000001312 dry etching Methods 0.000 description 37
- 235000012431 wafers Nutrition 0.000 description 26
- 239000010941 cobalt Substances 0.000 description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 25
- 229910017052 cobalt Inorganic materials 0.000 description 24
- 125000004432 carbon atom Chemical group C* 0.000 description 19
- 150000002148 esters Chemical group 0.000 description 19
- 239000004065 semiconductor Substances 0.000 description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 229910000531 Co alloy Inorganic materials 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000011282 treatment Methods 0.000 description 8
- 229910052581 Si3N4 Inorganic materials 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 229940024606 amino acid Drugs 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- PPYIVKOTTQCYIV-UHFFFAOYSA-L beryllium;selenate Chemical compound [Be+2].[O-][Se]([O-])(=O)=O PPYIVKOTTQCYIV-UHFFFAOYSA-L 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003297 rubidium Chemical class 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 159000000008 strontium salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical class C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical class CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- HBUXNNBOWNIKNE-UHFFFAOYSA-N 4-(3-carboxypropylamino)butanoic acid Chemical compound OC(=O)CCCNCCCC(O)=O HBUXNNBOWNIKNE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
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- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
- H01L21/76814—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics post-treatment or after-treatment, e.g. cleaning or removal of oxides on underlying conductors
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- C11D2111/22—
Abstract
根據本發明可提供一種水性組成物,包含:
(A)以組成物總量基準計為0.0001~10質量%之選自於C4-13
烷基膦酸、C4-13
烷基膦酸酯、C4-13
烷基磷酸、及它們的鹽中之1種以上之化合物,及
(B)以組成物總量基準計為0.0001~50質量%之除C4-13
烷基膦酸與C4-13
烷基膦酸酯與C4-13
烷基磷酸以外之酸或其鹽。
Description
本發明關於水性組成物及使用此組成物之清洗方法,例如關於電子器件(例如半導體元件)之製造步驟中所使用的清洗用組成物、及使用此組成物之清洗方法。
如半導體元件等,在製造電子器件的過程中形成半導體積體電路時,通常會採用乾蝕刻步驟。在該乾蝕刻步驟中,會產生乾蝕刻殘渣(鋯系殘渣、鈦系殘渣、聚合物殘渣等),而必須將其去除。用以去除該乾蝕刻殘渣之清洗劑宜為不會對係成為清洗對象之半導體積體電路所使用的配線用金屬材料(例如:銅、鈦、鈷、鎢等)造成不良影響(例如侵蝕)。
考慮如此的觀點,已開發出各種清洗劑。例如日本特表2013-533631號公報(專利文獻1)、日本特開2016-171294號公報(專利文獻2)、日本特開2006-83376號公報(專利文獻3)等已揭示用以去除乾蝕刻後所產生的乾蝕刻殘渣之清洗用組成物、使用該組成物之清洗方法等。
在形成半導體積體電路的過程有時會有使用硬遮罩的情況。就硬遮罩的材料而言,以往係使用矽系、鈦系材料,但近年也有人提出氧化鋯系之硬遮罩(非專利文獻1:M Padmanaban et al, J. Photopolym.Sci.Technol.,27(2014)503)。
又,以乾蝕刻形成導孔時,會選擇氟系氣體。若選擇氧化鋁作為蝕刻停止層的話,由於氧化鋁對氟系氣體之耐性高,故有即使為薄膜仍可發揮作為蝕刻停止層之功能的優點,並於近年已有人提出氧化鋁系之蝕刻停止層(非專利文獻2:16th MME workshop, Goeteborg, Sweden, 2005 “Etch stop materials for release by vapor HF etching”)。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特表2013-533631號公報
[專利文獻2]日本特開2016-171294號公報
[專利文獻3]日本特開2006-83376號公報
[非專利文獻]
[非專利文獻1]M Padmanaban et al, J. Photopolym.Sci.Technol.,27(2014)503
[非專利文獻2]16th MME workshop, Goeteborg, Sweden, 2005 “Etch stop materials for release by vapor HF etching”
[發明所欲解決之課題]
電子器件所使用的配線用之金屬材料、或乾蝕刻時所使用的遮蔽材料有各種種類,其組合也很多樣。因此,考慮乾蝕刻殘渣之去除效率、對配線用之金屬材料的抗腐蝕效果等之觀點,要求新穎的清洗用組成物之開發。
[解決課題之手段]
本發明提供如下之水性組成物、使用該水性組成物之清洗方法等。
[1]一種水性組成物,包含:
(A)以組成物總量基準計為0.0001~10質量%之選自於C4-13
烷基膦酸、C4-13
烷基膦酸酯、C4-13
烷基磷酸、及它們的鹽中之1種以上之化合物,及
(B)以組成物總量基準計為0.0001~50質量%之除C4-13
烷基膦酸與C4-13
烷基膦酸酯與C4-13
烷基磷酸以外之酸或其鹽。
[2]如上述[1]所記載之組成物,其pH落在0~7(例如:0~6、0~5、0~4或0~3)之範圍內。
[3]如上述[1]或[2]所記載之組成物,其中,前述(B)成分之酸或其鹽係氫氟酸、硝酸、硫酸、鹽酸、磷酸、乙酸或它們的鹽。
[4]如上述[3]所記載之組成物,其中,前述酸係氫氟酸。
[5]如上述[1]~[4]中任一項所記載之組成物,其中,前述水性組成物包含選自於下列中之至少任一者:
作為前述烷基膦酸之正丁基膦酸、正戊基膦酸、正己基膦酸、正庚基膦酸、正辛基膦酸、正壬基膦酸、正癸基膦酸、正十一烷基膦酸、正十二烷基膦酸、正十三烷基膦酸、或它們的混合物,
作為前述烷基膦酸酯之膦酸正丁酯、膦酸正戊酯、膦酸正己酯、膦酸正庚酯、膦酸正辛酯、膦酸正壬酯、膦酸正癸酯、膦酸正十一酯、膦酸正十二酯、膦酸正十三酯、或它們的混合物,及
前述烷基膦酸及前述烷基膦酸酯的鹽。
[5a]如上述[1]~[5]中任一項所記載之組成物,其中,前述烷基膦酸係C5-12
烷基膦酸(宜為C5-11
烷基膦酸,為C5-9
烷基膦酸更佳,為C6-8
烷基膦酸再更佳),
前述烷基膦酸酯係這些烷基膦酸的酯。
[6]如上述[1]~[4]中任一項所記載之組成物,其中,前述水性組成物包含選自於下列中之至少任一者:
作為前述烷基磷酸之正丁基磷酸、正戊基磷酸、正己基磷酸、正庚基磷酸、正辛基磷酸、正壬基磷酸、正癸基磷酸、正十一烷基磷酸、正十二烷基磷酸、正十三烷基磷酸、磷酸-2-乙基己酯、磷酸異癸酯、或它們的混合物,以及
前述烷基磷酸的鹽。
[6a]如上述[1]~[6]中任一項所記載之組成物,其中,前述烷基磷酸係C4-13
烷基磷酸(宜為C5-11
烷基磷酸,為C5-9
烷基磷酸更佳,為C6-8
烷基磷酸再更佳)。
[7]如上述[1]~[6]中任一項所記載之組成物,其中,前述烷基膦酸、前述烷基膦酸酯及前述烷基磷酸中,烷基鏈之數量為2以下。
[8]如上述[7]所記載之組成物,其中,前述烷基膦酸、前述烷基膦酸酯及前述烷基磷酸中,烷基鏈之數量為1。
[9]如上述[1]~[8]中任一項所記載之組成物,其中,前述烷基膦酸、前述烷基膦酸酯及前述烷基磷酸中,烷基鏈為直鏈狀。
[10]如上述[1]~[9]中任一項所記載之組成物,更含有鋇化合物。
[11]如上述[10]所記載之組成物,其中,前述鋇化合物包含選自於硝酸鋇、乙酸鋇、氯化鋇及氫氧化鋇中之至少任一者。
[11a]如上述[1]~[11]中任一項所記載之組成物,其係用以去除乾蝕刻後之殘渣(例如:氧化鋯系乾蝕刻殘渣)之乾蝕刻殘渣去除用組成物。
[11b]如上述[1]~[11]中任一項所記載之組成物,其係用以防止係成為清洗對象之電子器件的配線材料(例如:鈷或鈷合金等)腐蝕之組成物。
[11c]如上述[1]~[11]中任一項所記載之組成物,其係自前述烷基膦酸排除十二烷基膦酸。
[12]一種電子器件之清洗方法,包含下列步驟:
使如上述[1]~[11]中任一項所記載之組成物與電子器件接觸。
[13]一種電子器件之製造方法,包含下列步驟:
使如上述[1]~[11]中任一項所記載之組成物與電子器件接觸。
[14]一種蝕刻液,包含如上述[1]~[11]中任一項所記載之組成物。
[15]一種清洗液,包含如上述[1]~[11]中任一項所記載之組成物。
[發明之效果]
有關本發明之理想態樣之水性組成物,即使在低pH區域(例如4以下),仍會對鈷或鈷合金發揮良好的抗腐蝕效果。
又,有關本發明之另一理想態樣之水性組成物(例如摻合有氟化氫之組成物),對鈷或鈷合金發揮良好的抗腐蝕效果,同時蝕刻殘渣的去除性也良好。
根據有關本發明之理想態樣之清洗方法,由於對鈷等配線材料之抗腐蝕效果、乾蝕刻殘渣去除性良好,故能在半導體元件等電子器件之製造步驟中,以良好產率製造高精度、高品質的電子器件。
本發明中的水性組成物包含:
(A)以組成物總量基準計為0.0001~10質量%之選自於C4-13
烷基膦酸、C4-13
烷基膦酸酯、C4-13
烷基磷酸、及它們的鹽中之1種以上之化合物,及
(B)以組成物總量基準計為0.0001~50質量%之除(A)成分以外之酸,亦即除C4-13
烷基膦酸與C4-13
烷基膦酸酯與C4-13
烷基磷酸以外之酸,或這些酸的鹽。
另外,本說明書中,各成分之含量的範圍包含上限值與下限值,例如上述(A)成分之含量的範圍包含0.0001質量%與10質量%。
以下,針對有關本發明之水性組成物進行詳細地說明。
[(A)成分:烷基膦酸或烷基磷酸等]
(A1)烷基膦酸以及烷基膦酸酯
本發明所使用的烷基膦酸係具有4~13個碳原子之C4-13
烷基膦酸(具有4~13個碳原子之烷基膦酸)。如此的烷基膦酸係為公知,且能於商業上取得(例如能從東京化成工業公司取得)。烷基膦酸宜為C5-11
烷基膦酸,為C5-9
烷基膦酸更佳,為C6-8
烷基膦酸再更佳。烷基膦酸的烷基部分可為直鏈,也可分支,但直鏈較佳。烷基膦酸的烷基部分若分支時,支鏈的數量宜為5以下,為3以下更佳,為1特佳。
本發明之水性組成物中也可使用上述烷基膦酸的酯。亦即,也可使用上述C4-13
烷基膦酸(具有4~13個碳原子之烷基膦酸)之烷基酯。
若烷基膦酸通常以通式R1
P(=O)(OH)2
(R1
為烷基)表示時,通式R1
P(=O)(OR2
)2
(R1
為烷基,R2
為烷基或氫原子:惟,2個R2
中之至少一個為烷基)表示之烷基膦酸酯也能使用於水性組成物中。
又,本說明書所記載之烷基膦酸酯也包含亞磷酸之烷基酯(亞磷酸酯)。亦即,通式R1
P(=O)(OR2
)2
(R1
為氫原子,R2
為烷基或氫原子:惟,2個R2
中之至少一個為烷基)表示之亞磷酸酯也能在本說明書中作為烷基膦酸酯而使用於水性組成物中。
由上可知,水性組成物中可使用如下通式(A)表示之化合物作為烷基膦酸或烷基膦酸酯。
R1
P(=O)(OR2
)2
・・・(A)
通式(A)中,R1
以及R2
分別獨立地為烷基或氫原子:惟,R1
及2個R2
之中,至少一個為烷基。
本發明所使用的烷基膦酸酯係合計具有4~13個碳原子之C4-13
烷基膦酸酯(合計具有4~13個碳原子之烷基膦酸酯)。烷基膦酸酯宜為C5-11
烷基膦酸酯,為C5-9
烷基膦酸酯更佳,為C6-8
烷基膦酸酯再更佳。又,上述通式(A)中的R1
及R2
之烷基鏈分別獨立地具有4~12個碳原子為佳,具有6~11個碳原子更佳,具有8~10個碳原子再更佳。
烷基膦酸酯之烷基,亦即上述通式(A)之R1
及R2
可為直鏈,也可分支,但宜包含直鏈狀之烷基。
又,上述通式(A)中的烷基鏈之數量,亦即R1
及R2
之烷基鏈的合計數量宜為2以下。亦即,就烷基膦酸酯而言,可使用上述通式(A)之R1
P(=O)(OR2
)2
之中,R1
及R2
均為烷基者,可使用R1
為烷基且R2
中之一個以下為烷基者、或R1
為氫原子,且R2
中之二個以下為烷基者等。再更佳為僅具有單一烷基鏈之烷基膦酸,亦即,使用上述通式(A)之R1
P(=O)(OR2
)2
之R1
及2個R2
之中,僅任一個為烷基者較理想。使用上述通式(A)之僅R1
為烷基者特佳。
本發明所使用的烷基膦酸的鹽為上述烷基膦酸的鹽,可列舉例如:銨鹽、四甲基銨鹽、四乙基銨鹽、四丙基銨鹽、四丁基銨鹽、鋰鹽、鈉鹽、鉀鹽、銣鹽、銫鹽、鈹鹽、鎂鹽、鈣鹽、鍶鹽、鋇鹽等。
就本發明所使用的烷基膦酸或其鹽而言,理想可列舉:正丁基膦酸、正戊基膦酸、正己基膦酸、正庚基膦酸、正辛基膦酸、正壬基膦酸、正癸基膦酸、正十一烷基膦酸、正十二烷基膦酸、正十三烷基膦酸、它們的鹽或它們的混合物。
就更理想使用的烷基膦酸或其鹽而言,係正戊基膦酸、正己基膦酸、正庚基膦酸、正辛基膦酸、正壬基膦酸、正癸基膦酸、正十一烷基膦酸、它們的鹽或它們的混合物。
又,本發明之水性組成物中也可使用上述烷基膦酸酯的鹽。例如可列舉對應於上述烷基膦酸的鹽者作為烷基膦酸酯的鹽。
烷基膦酸、烷基膦酸酯、或它們的鹽在水性組成物中的濃度可考慮為蝕刻對象或清洗對象之電子器件的配線材料之種類、蝕刻步驟所使用的遮蔽材料之種類等而適當地變更。理想的烷基膦酸、烷基膦酸酯、或其鹽之濃度以組成物總量基準計為0.0003~5質量%,為0.0006~1質量%再更佳,為0.001~0.5質量%或0.01~0.1質量%特佳。
(A2)烷基磷酸
本發明所使用的烷基磷酸係具有4~13個碳原子之C4-13
烷基磷酸(具有4~13個碳原子之烷基磷酸)。如此的烷基磷酸係為公知,且能於商業上取得(例如能從東京化成工業公司取得)。烷基磷酸宜為C5-11
烷基磷酸,為C5-9
烷基磷酸更佳,為C6-8
烷基磷酸再更佳。烷基磷酸的烷基部分可為直鏈,也可分支,但直鏈較佳。烷基磷酸的烷基部分若分支時,支鏈的數量宜為5以下,為3以下更佳,為1特佳。
本發明之水性組成物中,就烷基磷酸而言,除可使用磷酸之單烷基酯以外,還可使用二烷基酯及三烷基酯。亦即,不僅可使用通式P(=O)(OR3
)3
(R3
均為氫原子)表示之磷酸之R3
之中僅1個被取代為烷基而成的磷酸之單烷基酯,也可將R3
之中2個被取代為烷基而成的二烷基酯以及R3
均被取代為烷基而成的三烷基酯使用於本發明之水性組成物中。惟,就烷基磷酸而言,烷基鏈之數量為2以下之二烷基酯(上述通式P(=O)(OR3
)3
之R3
中的2個為烷基者)及單烷基酯(上述通式P(=O)(OR3
)3
之R3
中僅1個為烷基者)較理想,烷基鏈之數量為1之單烷基酯更佳。亦即,烷基磷酸宜僅具有單個烷基鏈(以上述R3
表示之烷基)。
烷基磷酸不考慮酯鍵之數量,合計具有4~13個碳原子。烷基磷酸不考慮酯鍵之數量,宜使用C5-11
烷基磷酸,使用C5-9
烷基磷酸更佳,使用C6-8
烷基磷酸再更佳。
又,上述通式P(=O)(OR3
)3
之R3
之烷基鏈宜具有4~12個碳原子,具有6~11個碳原子更佳,具有8~10個碳原子再更佳。烷基磷酸之烷基,亦即,上述通式P(=O)(OR3
)3
之R3
可為直鏈,也可分支,但宜包含直鏈狀之烷基。
本發明所使用的烷基磷酸的鹽係上述磷酸之單烷基酯或二烷基酯的鹽,可列舉例如:銨鹽、四甲基銨鹽、四乙基銨鹽、四丙基銨鹽、四丁基銨鹽、鋰鹽、鈉鹽、鉀鹽、銣鹽、銫鹽、鈹鹽、鎂鹽、鈣鹽、鍶鹽、鋇鹽等。
就本發明所使用的烷基磷酸或其鹽而言,理想可列舉:正丁基磷酸、正戊基磷酸、正己基磷酸、正庚基磷酸、正辛基磷酸、正壬基磷酸、正癸基磷酸、正十一烷基磷酸、正十二烷基磷酸、正十三烷基磷酸、磷酸-2-乙基己酯、磷酸異癸酯、它們的鹽或它們的混合物。
就更理想使用的烷基磷酸或其鹽而言,係正戊基磷酸、正己基磷酸、正庚基磷酸、正辛基磷酸、正壬基磷酸、正癸基磷酸、正十一烷基磷酸、磷酸-2-乙基己酯、磷酸異癸酯、它們的鹽或它們的混合物。
烷基磷酸或其鹽在水性組成物中的濃度可考慮為蝕刻對象或清洗對象之電子器件的配線材料之種類、蝕刻步驟所使用的遮蔽材料之種類等而適當地變更。理想的烷基磷酸或其鹽之濃度以組成物總量基準計為0.0003~5質量%,為0.0006~1質量%再更佳,為0.001~0.5質量%或0.01~0.1質量%之範圍特佳。
[(B)成分:除(A)成分以外之酸]
就本發明之水性組成物所使用的酸而言,除(A)成分以外之無機酸、有機酸均可使用。亦即,就水性組成物所使用的酸而言,可列舉除C4-13
烷基膦酸、為部分酯亦歸類在酸之C4-13
烷基膦酸酯、以及C4-13
烷基磷酸以外之酸。又,也可將除(A)成分以外之酸的鹽使用於水性組成物中。
就能在本發明使用的無機酸而言,可列舉例如:氫氟酸、硝酸、硫酸、鹽酸、磷酸等。其中,宜為氫氟酸,使用氫氟酸時,在pH低的區域會改善乾蝕刻殘渣之去除性。
就能在本發明使用的有機酸而言,可列舉例如:碳數1~18之脂肪族羧酸、碳數6~10之芳香族羧酸,此外還可列舉碳數1~10之胺基酸等。
就碳數1~18之脂肪族羧酸而言,宜列舉:甲酸、乙酸、丙酸、乳酸、乙醇酸、二乙醇酸、丙酮酸、丙二酸、丁酸、羥基丁酸、酒石酸、琥珀酸、蘋果酸、馬來酸、富馬酸、戊酸、戊二酸、伊康酸、己二酸、己酸、己二酸、檸檬酸、丙三羧酸、反烏頭酸、庚酸、羊脂酸(caprylic acid)、月桂酸、肉荳蔻酸、棕櫚酸、硬脂酸、油酸、亞麻油酸、次亞麻油酸等。
就碳數6~10之芳香族羧酸而言,宜列舉:苯甲酸、水楊酸、杏仁酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸等。
又,就碳數1~10之胺基酸而言,宜列舉:胺甲酸、丙胺酸、甘胺酸、天冬醯胺酸(asparagine)、天冬胺酸(aspartic acid)、肌胺酸、絲胺酸、麩醯胺酸(glutamine)、麩胺酸(glutamic acid)、4-胺基丁酸、亞胺基二丁酸、精胺酸、白胺酸、異白胺酸、氮基三乙酸等。
本組成物中之酸的含量為0.0001~50質量%,宜為0.0005~20質量%,為0.001~10質量%更佳,為0.01~1質量%再更佳,為0.02~1質量%特佳。
[(C)成分:水]
本發明之組成物為水性,包含水作為稀釋劑。本發明之水並無特別限制,宜為利用蒸餾、離子交換處理、過濾器處理、各種吸附處理等已將金屬離子、有機雜質、微粒粒子等予以去除而得者,為純水或超純水特佳。
本組成物中之水的含量通常為40~99.9998質量%,宜為89.5~99.998質量%。
[(D)成分:鋇化合物]
有關本發明之水性組成物也可含有鋇化合物。本發明所使用的鋇化合物係含有鋇之無機物,具有防止氧化鋁腐蝕之效果。
就鋇化合物而言,可列舉例如:硝酸鋇、乙酸鋇、氯化鋇、氫氧化鋇、亞硫酸鋇、氯酸鋇、過氯酸鋇、過氧化鋇、鉻酸鋇、氧化鋇、氰化鋇、溴化鋇、碳酸鋇、偏硼酸鋇、碘化鋇、四氟硼酸鋇、硫酸鋇、硫化鋇、及氫氧化鋇與酸反應而得的鹽,它們可單獨使用或將2種以上組合使用。
它們之中,硝酸鋇、乙酸鋇、氯化鋇及氫氧化鋇為高水溶性,且取得容易,故較理想。
鋇化合物在組成物中的濃度為0.00005~10質量%,宜為0.00025~5質量%,為0.001~2質量%再更佳,為0.002~1質量%特佳。落在此範圍內可有效地抑制對氧化鋁之損壞。
[其他成分]
本發明之水性組成物中,也可依期望在不損及本發明之目的的範圍內摻合以往使用於半導體用水性組成物中之添加劑。
例如可添加鹼(例如氨)、螯合劑、界面活性劑、消泡劑、氧化劑、還原劑、金屬抗腐蝕劑、水溶性有機溶劑等作為添加劑。這些添加劑係為公知,例如記載於日本特表2013-533631號公報中。
[水性組成物(液狀組成物)之調製方法]
本發明之水性組成物(液狀組成物)係藉由將上述(A)成分、上述(B)成分、水、因應需要添加之上述(D)成分、上述其他成分予以攪拌直到均勻而製得。
本發明之水性組成物之pH的範圍並無特別限制,通常為0~7,宜為0~6,為0~5更佳,為0~4再更佳。
根據有關理想態樣之本發明之水性組成物,可防止鈷、氧化鋁等腐蝕,同時能有效率地去除乾蝕刻殘渣。
[水性組成物之使用方法:電子器件之清洗/製造方法]
有關本發明之水性組成物係藉由以清洗用水性組成物(以下也稱為「清洗液」)之形式,於濕式蝕刻步驟(或其前後之步驟)中,與電子器件(例如半導體元件)接觸,而可將乾蝕刻殘渣予以去除。就接觸的方法而言,例如藉由將清洗液容納於清洗用容器中,並將係成為清洗對象之電子器件浸漬於清洗液,可去除乾蝕刻殘渣,清洗電子器件。或藉由利用單片清洗方式處理電子器件,可去除乾蝕刻殘渣,清洗電子器件。清洗用水性組成物除可使用作為乾蝕刻殘渣去除液(清洗液)以外,也適合使用作為蝕刻液。又,也可將水性組成物使用作為化學機械研磨(CMP)步驟後用來清洗電子器件之清洗液。
如上所述,有關本發明之水性組成物能適於使用在具有清洗電子器件之步驟的清洗方法以及包含如此步驟之電子器件之製造方法中。
使用本發明之清洗液的溫度通常為10~80℃,宜為15~70℃,為20℃~65℃再更佳,為20℃~60℃特佳。溫度可依清洗的條件、所使用的電子器件(例如半導體元件)而適當地選擇。
使用本發明之清洗液的時間通常為0.2~60分鐘。時間可依清洗的條件、所使用的電子器件(例如半導體元件)而適當地選擇。可使用有機溶劑、或水、碳酸水、氨水作為使用本發明之清洗液後的淋洗液。
[成為清洗對象/製造對象之電子器件]
就作為本發明可適合使用的清洗對象以及製造對象之電子器件而言,例如係半導體元件及顯示元件,通常,乾蝕刻步驟後的中間產品係成為清洗的對象。半導體元件及顯示元件為:矽、非晶矽、多晶矽、玻璃等基板材料;氧化矽、氮化矽、碳化矽及它們的衍生物等絕緣材料;鈷、鈷合金、鎢、鈦-鎢等材料;鎵-砷、鎵-磷、銦-磷、銦-鎵-砷、銦-鋁-砷等化合物半導體及氧化鉻等氧化物半導體。就作為本發明之清洗對象之電子器件而言,特佳可列舉:使用有鈷或鈷合金配線材料、氧化鋯系硬遮罩、低介電常數層間絕緣膜之元件。
在本發明中,成為對象之乾蝕刻殘渣例如係將氧化鋯系之硬遮罩作為遮罩,並利用乾蝕刻在低介電常數層間絕緣膜上形成導孔、或溝時所產生者。乾蝕刻殘渣有部分係由於蝕刻氣體與氧化鋯系硬遮罩接觸而產生。因此,此時對象之乾蝕刻殘渣包含鋯。
[實施例]
以下,利用實施例具體地說明本發明,但只要能發揮本發明的效果,則可將實施形態適當地予以變化。
另外,若無特別指定,則%意指質量%。
[評價用晶圓]
>評價晶圓A>:用以評價乾蝕刻殘渣的去除狀態
從下層開始將氮化矽、層間絕緣膜、氮化矽、氧化鋯、進一步將光阻進行製膜,然後使光阻圖案化。
以光阻作為遮罩,利用乾蝕刻去除硬遮罩之預定的位置,並利用氧電漿所為之灰化將光阻去除。再以硬遮罩作為遮罩,利用乾蝕刻於氮化矽、層間絕緣膜上形成導孔。
>設有膜之晶圓>:用以評價鈷及氧化鋁的損壞
分別以如下的製膜條件製得分別將鈷、氧化鋁之材質製膜而得的設有膜之晶圓。
(1)鈷:利用物理氣相沉積法進行製膜,以2000Å之厚度於Si上進行製膜。
(2)氧化鋁:利用物理氣相沉積法進行製膜,以1000Å之厚度於Si上進行製膜。
[評價方法]
>乾蝕刻殘渣之去除狀態>
針對以各種水性組成物(清洗液)處理後之評價晶圓A實施SEM觀察。
測定設備:日立先端科技股份有限公司製之超高解析度場發射型掃描式電子顯微鏡SU9000(倍率10萬倍)
判定方法:
E:乾蝕刻殘渣完全被去除。
G:乾蝕刻殘渣幾乎完全被去除。
P:乾蝕刻殘渣之去除不足。
E、G判定為合格。
>膜厚>
使用SII NanoTechnology股份有限公司製之螢光X射線裝置SEA1200VX(膜厚測定裝置A)、或n&k Technology公司製光學式膜厚計n&k1280(膜厚測定裝置B)測定設有膜之晶圓之膜厚。設有鈷膜之晶圓係使用膜厚測定裝置A測定膜厚,設有氧化鋁膜之晶圓係使用膜厚測定裝置B測定膜厚。
>E.R.(蝕刻速率)>
以清洗液處理設有各種膜之晶圓,並藉由將處理前後之膜厚差除以處理時間來算出E.R.。
鈷的情況之E.R.為1Å/min以下、氧化鋁的情況之E.R.為25Å/min以下時為優良。
>pH值之測定>
各實施例以及參考例之水性組成物的pH值,係於25℃使用pH計(堀場製作所股份有限公司製之pH計F-52)進行測定。
[實施例1~31]
試驗中使用評價晶圓A及設有各種膜之晶圓。將前述晶圓以表1、表2所記載之處理溫度浸漬於表1、表2所記載之清洗液中,其後實施利用超純水所為之淋洗、利用乾燥氮氣噴射所為之乾燥。針對評價晶圓A係實施5分鐘之處理,並以SEM觀察處理後之晶圓。
針對設有各種膜之晶圓而言,設有鈷膜之晶圓係實施30分鐘之處理,設有氧化鋁膜之晶圓係實施5分鐘之處理。從處理前後之膜厚算出E.R.。
[實施例1~31及參考例1~23]
試驗中使用評價晶圓A及設有鈷膜之晶圓、設有氧化鋁膜之晶圓。將前述晶圓以20℃或50℃浸漬(參照表中處理溫度之欄位)於表1、表2、表3所記載之水性組成物(清洗液)中,其後實施利用超純水所為之淋洗、利用乾燥氮氣噴射所為之乾燥。針對評價晶圓A係全部實施5分鐘之浸漬處理,並以SEM觀察處理後之晶圓。
設有鈷膜之晶圓係實施30分鐘之浸漬處理,設有氧化鋁膜之晶圓係實施5分鐘之浸漬處理,並從處理前後之膜厚算出E.R.。
由實施例1~31中可得知防止了鈷的損壞。
另一方面,由表3之參考例中可得知其並不能稱得上是很適合於抑制鈷的損壞之目的。
又,由表1、表2之含有HF之組成物中可得知能去除評價晶圓A所含的乾蝕刻殘渣。
此外,由表2之實施例中可得知含有鋇化合物之組成物防止了氧化鋁的損壞。
[表1]
[表2]
[表3]
[產業上利用性]
有關本發明之理想態樣之水性組成物,即使在低pH區域(例如4以下),仍會對鈷或鈷合金發揮良好的抗腐蝕效果。
又,有關本發明之另一理想態樣之水性組成物(例如摻合有氟化氫之組成物),對鈷或鈷合金發揮良好的抗腐蝕效果,同時乾蝕刻殘渣的去除性也良好。
而且,根據有關本發明之理想態樣之蝕刻液、清洗液以及清洗方法,由於對鈷等配線材料之抗腐蝕效果、乾蝕刻殘渣去除性良好,故能在半導體元件等電子器件之製造步驟中,以良好產率製造高精度、高品質的電子器件。
1‧‧‧氧化鋯系乾蝕刻殘渣
2‧‧‧氧化鋯系硬遮罩
3‧‧‧鈷或鈷合金
4‧‧‧氧化鋁
5‧‧‧低介電常數層間絕緣膜
6‧‧‧氮化矽(SiN)
[圖1]係導孔的底部為氧化鋁,且係去除乾蝕刻殘渣1前的半導體元件之具有氧化鋯系硬遮罩2、鈷或鈷合金3、氧化鋁4、低介電常數層間絕緣膜5、氮化矽6之結構之半導體元件之一形態之剖面圖之示意圖。
[圖2]係導孔的底部為鈷或鈷合金,且係去除乾蝕刻殘渣1前的半導體元件之具有氧化鋯系硬遮罩2、鈷或鈷合金3、氧化鋁4、低介電常數層間絕緣膜5、氮化矽6之結構之半導體元件之一形態之剖面圖之示意圖。
Claims (15)
- 一種水性組成物,包含:(A)以該組成物總量基準計為0.0001~10質量%之選自於C4-13烷基膦酸、C4-13烷基膦酸酯、C4-13烷基磷酸、及它們的鹽中之1種以上之化合物,(B)以該組成物總量基準計為0.0001~10質量%之除C4-13烷基膦酸與C4-13烷基膦酸酯與C4-13烷基磷酸以外之酸或其鹽,及以該組成物總量基準計為89.5~99.9998質量%之水。
- 如申請專利範圍第1項之水性組成物,其pH落在0~7之範圍內。
- 如申請專利範圍第1或2項之水性組成物,其中,該(B)成分之酸或其鹽係氫氟酸、硝酸、硫酸、鹽酸、磷酸、乙酸、或它們的鹽。
- 如申請專利範圍第3項之水性組成物,其中,該酸係氫氟酸。
- 如申請專利範圍第1或2項之水性組成物,其中,該水性組成物包含選自於下列中之至少任一者:作為該烷基膦酸之正丁基膦酸、正戊基膦酸、正己基膦酸、正庚基膦酸、正辛基膦酸、正壬基膦酸、正癸基膦酸、正十一烷基膦酸、正十二烷基膦酸、正十三烷基膦酸、或它們的混合物, 作為該烷基膦酸酯之膦酸正丁酯、膦酸正戊酯、膦酸正己酯、膦酸正庚酯、膦酸正辛酯、膦酸正壬酯、膦酸正癸酯、膦酸正十一酯、膦酸正十二酯、膦酸正十三酯、或它們的混合物,及該烷基膦酸及該烷基膦酸酯的鹽。
- 如申請專利範圍第1或2項之水性組成物,其中,該水性組成物包含選自於下列中之至少任一者:作為該烷基磷酸之正丁基磷酸、正戊基磷酸、正己基磷酸、正庚基磷酸、正辛基磷酸、正壬基磷酸、正癸基磷酸、正十一烷基磷酸、正十二烷基磷酸、正十三烷基磷酸、磷酸-2-乙基己酯、磷酸異癸酯、或它們的混合物,以及該烷基磷酸的鹽。
- 如申請專利範圍第1或2項之水性組成物,其中,該烷基膦酸、該烷基膦酸酯及該烷基磷酸中,烷基鏈之數量為2以下。
- 如申請專利範圍第7項之水性組成物,其中,該烷基膦酸、該烷基膦酸酯及該烷基磷酸中,烷基鏈之數量為1。
- 如申請專利範圍第1或2項之水性組成物,其中,該烷基膦酸、該烷基膦酸酯及該烷基磷酸中,烷基鏈為直鏈狀。
- 如申請專利範圍第1或2項之水性組成物,更含有鋇化合物。
- 如申請專利範圍第10項之水性組成物,其中,該鋇化合物包含選自於硝酸鋇、乙酸鋇、氯化鋇及氫氧化鋇中之至少任一者。
- 一種電子器件之清洗方法,包含下列步驟:使如申請專利範圍第1至11項中任一項之水性組成物與電子器件接觸。
- 一種電子器件之製造方法,包含下列步驟:使如申請專利範圍第1至11項中任一項之水性組成物與電子器件接觸。
- 一種蝕刻液,包含如申請專利範圍第1至11項中任一項之水性組成物。
- 一種清洗液,包含如申請專利範圍第1至11項中任一項之水性組成物。
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TW201945529A (zh) | 2019-12-01 |
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