TWI648430B - Cleaning solution for semiconductor device substrate and method for cleaning semiconductor device substrate - Google Patents
Cleaning solution for semiconductor device substrate and method for cleaning semiconductor device substrate Download PDFInfo
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- TWI648430B TWI648430B TW103103877A TW103103877A TWI648430B TW I648430 B TWI648430 B TW I648430B TW 103103877 A TW103103877 A TW 103103877A TW 103103877 A TW103103877 A TW 103103877A TW I648430 B TWI648430 B TW I648430B
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- Prior art keywords
- substrate
- semiconductor device
- acid
- component
- cleaning
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- 238000004140 cleaning Methods 0.000 title claims abstract description 184
- 239000000758 substrate Substances 0.000 title claims abstract description 138
- 239000004065 semiconductor Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 28
- 239000002738 chelating agent Substances 0.000 claims description 27
- 239000004094 surface-active agent Substances 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 15
- 125000005647 linker group Chemical group 0.000 claims description 15
- -1 sulfosuccinic acid diester Chemical class 0.000 claims description 15
- 239000003945 anionic surfactant Substances 0.000 claims description 14
- 239000003002 pH adjusting agent Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 12
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 11
- 235000015165 citric acid Nutrition 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 7
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- 239000004471 Glycine Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 5
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 229940000635 beta-alanine Drugs 0.000 claims description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims 1
- 235000003704 aspartic acid Nutrition 0.000 claims 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 51
- 230000007797 corrosion Effects 0.000 abstract description 49
- 229910052751 metal Inorganic materials 0.000 abstract description 26
- 239000002184 metal Substances 0.000 abstract description 26
- 239000000243 solution Substances 0.000 description 78
- 239000010949 copper Substances 0.000 description 58
- 239000007788 liquid Substances 0.000 description 57
- 238000005406 washing Methods 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 25
- 239000003085 diluting agent Substances 0.000 description 25
- 239000011550 stock solution Substances 0.000 description 23
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 19
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 19
- 229910052802 copper Inorganic materials 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 239000003112 inhibitor Substances 0.000 description 16
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 15
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 239000004615 ingredient Substances 0.000 description 12
- 235000015073 liquid stocks Nutrition 0.000 description 10
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 229940075614 colloidal silicon dioxide Drugs 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 6
- 239000012964 benzotriazole Substances 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 229960002449 glycine Drugs 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 235000010323 ascorbic acid Nutrition 0.000 description 4
- 229960005070 ascorbic acid Drugs 0.000 description 4
- 239000011668 ascorbic acid Substances 0.000 description 4
- 150000004699 copper complex Chemical class 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- 229940093915 gynecological organic acid Drugs 0.000 description 4
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- 235000005985 organic acids Nutrition 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- 230000009471 action Effects 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- RKTGAWJWCNLSFX-UHFFFAOYSA-M bis(2-hydroxyethyl)-dimethylazanium;hydroxide Chemical compound [OH-].OCC[N+](C)(C)CCO RKTGAWJWCNLSFX-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
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- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
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- 238000005530 etching Methods 0.000 description 2
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- 125000005843 halogen group Chemical group 0.000 description 2
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- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- BCWOCGQNLLUTOG-UHFFFAOYSA-N acetic acid;1-tridecoxytridecane Chemical compound CC(O)=O.CCCCCCCCCCCCCOCCCCCCCCCCCCC BCWOCGQNLLUTOG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229960005305 adenosine Drugs 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 150000004716 alpha keto acids Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 229960001230 asparagine Drugs 0.000 description 1
- 235000009582 asparagine Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000005441 aurora Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- RGTXVXDNHPWPHH-UHFFFAOYSA-N butane-1,3-diamine Chemical compound CC(N)CCN RGTXVXDNHPWPHH-UHFFFAOYSA-N 0.000 description 1
- GHWVXCQZPNWFRO-UHFFFAOYSA-N butane-2,3-diamine Chemical group CC(N)C(C)N GHWVXCQZPNWFRO-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940097043 glucuronic acid Drugs 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229960005489 paracetamol Drugs 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- WTSXICLFTPPDTL-UHFFFAOYSA-N pentane-1,3-diamine Chemical compound CCC(N)CCN WTSXICLFTPPDTL-UHFFFAOYSA-N 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003212 purines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- GRNRCQKEBXQLAA-UHFFFAOYSA-M triethyl(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CCO GRNRCQKEBXQLAA-UHFFFAOYSA-M 0.000 description 1
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- 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
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- 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
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- C11D2111/22—
Abstract
本發明所提供的洗淨液，係在半導體裝置用基板，特別係表面具有金屬佈線的半導體裝置用基板，於CMP步驟後的洗淨步驟中所使用，對金屬佈線具有充分防蝕性，可抑制殘渣產生及殘渣附著於基板表面。 The cleaning solution provided by the present invention is a substrate for a semiconductor device, particularly a substrate for a semiconductor device having a metal wiring on its surface. It is used in the cleaning step after the CMP step, and has sufficient corrosion resistance to the metal wiring, and can be suppressed. Residue generation and residue adhere to the substrate surface.
Description
本發明係關於半導體裝置用基板洗淨液及半導體裝置用基板之洗淨方法，詳言之係關於用於將經施行化學性機械研磨後，在表面上露出Cu等金屬的半導體裝置用基板表面有效施行洗淨的洗淨液、及使用該洗淨液的洗淨方法。 The present invention relates to a substrate cleaning solution for a semiconductor device and a method for cleaning a substrate for a semiconductor device. More specifically, the present invention relates to a surface of a substrate for a semiconductor device for exposing a metal such as Cu to the surface after chemical mechanical polishing is performed. The washing liquid and the washing method using the washing liquid are effectively performed.
半導體裝置用基板係在矽晶圓基板上，形成成為佈線的金屬膜或層間絕緣膜之沉積層後，再使用由含有研磨微粒子的水系漿料所構成之研磨劑的化學性機械研磨(Chemical Mechanical Polishing，以下稱「CMP」)，施行表面的平坦化處理，藉由在成為平坦的面上積層重疊著新的層而進行製造。在半導體裝置用基板的細微加工時，各層需要高精度平坦性，利用CMP施行平坦化處理的重要性越益提高。 The substrate for a semiconductor device is formed on a silicon wafer substrate. After forming a deposition layer of a metal film or an interlayer insulating film for wiring, chemical mechanical polishing using an abrasive composed of an aqueous slurry containing abrasive particles is performed. Polishing (hereinafter referred to as "CMP") is performed by flattening the surface and manufacturing by laminating a new layer on a flat surface. During the microfabrication of a substrate for a semiconductor device, high precision flatness is required for each layer, and the importance of performing planarization by CMP is increasing.
近年的半導體裝置製造步驟，由於裝置的高速化．高積體化，因而導入由電阻值較低之銅(Cu)膜所構成的佈線(Cu佈線)。由於Cu的加工性佳，因而適於細微加工，但在水中容易氧化劣化，且因酸成分或鹼成分而易腐蝕，因而在CMP步驟中，Cu佈線的氧化或腐蝕便成為問題。 In recent years, the manufacturing steps of semiconductor devices are due to the high speed of the devices. Since it is highly integrated, a wiring (Cu wiring) composed of a copper (Cu) film having a low resistance value is introduced. Cu has good processability and is suitable for fine processing. However, Cu is easily oxidized and deteriorated in water and is easily corroded by acid or alkali components. Therefore, in the CMP step, oxidation or corrosion of Cu wiring becomes a problem.
因此，習知具有Cu佈線的半導體裝置用基板的CMP，係於研磨劑中添加苯并***、甲苯基***或該等的衍生物等防蝕劑，藉由該防蝕劑強力吸附於Cu表面並形成保護膜，而抑制CMP時Cu 佈線之腐蝕。 Therefore, it is known that the CMP of a substrate for a semiconductor device having Cu wiring is based on the addition of an anti-corrosive such as benzotriazole, tolyl triazole, or a derivative thereof to the abrasive, and the anti-corrosive agent strongly adsorbs on the surface of Cu. And form a protective film to suppress Cu during CMP Corrosion of wiring.
在CMP步驟後的半導體裝置用基板表面上，大量存在CMP步驟中所使用的膠體二氧化矽等磨粒、因CMP而產生源自Cu佈線或層間絕緣膜的微小粒子、在漿料中所含有源自防蝕劑的有機殘渣等，因而為去除該等，便將CMP步驟後的半導體裝置用基板提供至洗淨步驟。 On the surface of the substrate for a semiconductor device after the CMP step, a large amount of abrasive particles such as colloidal silicon dioxide used in the CMP step are present, minute particles derived from Cu wiring or an interlayer insulating film are generated by the CMP, and are contained in the paste. Since organic residues and the like derived from the corrosion inhibitor are removed, the substrate for a semiconductor device after the CMP step is provided to a cleaning step.
作為CMP後洗淨步驟中之洗淨液，若大致區分，則主要係使用酸性洗淨液與鹼性洗淨液。在酸性水溶液中，膠體二氧化矽係帶正帶，基板表面係帶負電，因電性吸引力的作用，導致膠體二氧化矽較難除去。相對於此，在鹼性水溶液中，由於OH-豐富存在，因而膠體二氧化矽與基板表面均帶負電，且因電性排斥力的作用，而可輕易地施行膠體二氧化矽的除去。 As the cleaning solution in the post-CMP cleaning step, if it is roughly distinguished, an acidic cleaning solution and an alkaline cleaning solution are mainly used. In an acidic aqueous solution, colloidal silicon dioxide is positively banded, and the substrate surface is negatively charged. Due to the effect of electrical attraction, colloidal silica is difficult to remove. On the other hand, in alkaline aqueous solution, since the OH - rich presence, and thus the colloidal silicon dioxide and the substrate surfaces are negatively charged, and the electrical repulsive force due to the action of, and can be easily removed purposes of colloidal silicon dioxide.
另一方面，Cu在酸性水溶液中會氧化成Cu2+而溶解於溶液中，但在鹼性水溶液中會在表面上形成Cu2O或CuO之類的鈍化膜。因此，相較於酸性洗淨液之下，使用鹼性洗淨液可將洗淨步驟中的腐蝕現象減輕到一定程度，但會有Cu表面的氧化膜均勻性較低的情形，或因洗淨條件、基板細微加工(Cu佈線)之狀態而引發腐蝕的可能性。 On the other hand, Cu is oxidized to Cu 2+ in an acidic aqueous solution and dissolved in the solution, but a passivation film such as Cu 2 O or CuO is formed on the surface in an alkaline aqueous solution. Therefore, compared with the acidic cleaning solution, the use of alkaline cleaning solution can reduce the corrosion phenomenon in the cleaning step to a certain extent, but the uniformity of the oxide film on the Cu surface may be lower, or due to the cleaning Possibility to cause corrosion due to net conditions and fine substrate processing (Cu wiring).
為了防止此種具有Cu佈線的基板在CMP後的洗淨步驟中Cu的氧化劣化或腐蝕，便有在洗淨步驟所使用的洗淨液中添加防蝕劑之方法的各種提案。 In order to prevent the oxidation degradation or corrosion of Cu in such a substrate having a Cu wiring in a cleaning step after CMP, various proposals have been made for a method of adding an anticorrosive agent to a cleaning solution used in the cleaning step.
例如，專利文獻1所記載的洗淨液，係作為CMP後的洗淨步驟所使用之洗淨液，其含有以具有某特定結構的苯并***衍生物為防蝕劑，其中亦記載有：可輕佳地使用以有機酸為主成分，且含 有四級銨氫氧化物、胺類所代表的有機鹼成分、或磺酸型陰離子性界面活性劑的酸性洗淨液。 For example, the cleaning liquid described in Patent Document 1 is a cleaning liquid used as a cleaning step after CMP, and contains a benzotriazole derivative having a specific structure as an anticorrosive agent. It also describes: Can be used lightly based on organic acids There are quaternary ammonium hydroxides, organic alkali components represented by amines, or acidic cleaning solutions of sulfonic acid anionic surfactants.
專利文獻2所記載的洗淨組成物，係含有溶劑、以及以伸乙二胺及烷醇胺所代表之胺的洗淨劑；其中，作為腐蝕防止劑係含有從三聚氰酸、巴比妥酸及其衍生物、葡萄醣醛酸、方酸、α-酮酸、腺核苷及其衍生物、嘌呤化合物及其衍生物、膦酸衍生物、啡啉/抗壞血酸、甘胺酸/抗壞血酸、菸醯胺及其衍生物、黃酮醇及其衍生物、花青苷(anthocyanin)及其衍生物、黃酮醇/花青苷、以及該等的組合所構成群組中選擇的化學種；並記載有：在含有氫氧化三甲基銨(TMAH)及1-胺基-2-丙醇的鹼性溶液中，改變該等腐蝕防止劑的種類及含有量而使用時，將Cu的腐蝕速度計算出之實施例。 The cleaning composition described in Patent Document 2 is a cleaning agent containing a solvent and an amine represented by ethylenediamine and an alkanolamine. Among them, as a corrosion inhibitor, it contains cyanuric acid, barbie Turonic acid and its derivatives, glucuronic acid, cubic acid, α-keto acid, adenosine and its derivatives, purine compounds and its derivatives, phosphonic acid derivatives, morpholine / ascorbic acid, glycine / ascorbic acid, smoke Chondramine and its derivatives, flavonols and its derivatives, anthocyanin and its derivatives, flavonols / anthocyanins, and combinations of these; selected species : Calculate the corrosion rate of Cu when it is used in an alkaline solution containing trimethylammonium hydroxide (TMAH) and 1-amino-2-propanol while changing the type and content of these corrosion inhibitors. Of an embodiment.
專利文獻3所揭示的半導體加工物洗淨用組成物，係含有：洗淨劑、螯合劑、及阻止腐食化合物；其中，洗淨劑係從氫氧化銨及四烷基氫氧化銨(tetraalkylammonium hydroxide)群組中選擇的化合物；螯合劑係從檸檬酸銨及草酸銨等所構成群組中選擇的化合物；阻止腐食化合物係從乙醯胺酚、胺苯酚及苯并***等所構成群組中選擇的化合物。 The semiconductor composition cleaning composition disclosed in Patent Document 3 contains a detergent, a chelating agent, and a carrion-preventing compound, and the detergent is composed of ammonium hydroxide and tetraalkylammonium hydroxide. ) Compounds selected from the group; Chelating agents are compounds selected from the group consisting of ammonium citrate and ammonium oxalate; block carrion compounds are selected from the group consisting of acetaminophen, aminephenol, and benzotriazole. Compound.
專利文獻1：日本專利特開2012-44118號公報 Patent Document 1: Japanese Patent Laid-Open No. 2012-44118
專利文獻2：日本專利特表2010-527405號公報 Patent Document 2: Japanese Patent Publication No. 2010-527405
專利文獻3：日本專利特表2007-525836號公報 Patent Document 3: Japanese Patent Publication No. 2007-525836
習知，可用於CMP後的洗淨所使用的洗淨液中之防蝕劑，會與從Cu佈線溶出的Cu離子形成錯合物，而有產生對基板具有附著性之殘渣的問題。又，若使用截至目前已知之殘渣生成較少的防蝕劑，雖不會產生上述之殘渣，但會有抑制Cu佈線的氧化劣化或腐蝕變得不足的問題。 It is known that the corrosion inhibitor in the cleaning solution used for cleaning after CMP may form a complex with Cu ions eluted from the Cu wiring, and there is a problem that residues having adhesion to the substrate are generated. In addition, if an anticorrosive agent that generates less residues using conventionally known residues is used, although the above residues are not generated, there is a problem that oxidative degradation or insufficient corrosion of the Cu wiring is suppressed.
在此狀況下，本發明目的在於提供：半導體裝置用基板，特別係表面具有金屬佈線的半導體裝置用基板，於CMP步驟後的洗淨步驟中所使用，對金屬佈線具有充分的防蝕性，且可抑制殘渣產生及殘渣於基板表面附著的洗淨液、及洗淨方法。 Under these circumstances, an object of the present invention is to provide a substrate for a semiconductor device, particularly a substrate for a semiconductor device having a metal wiring on its surface, which is used in a cleaning step after the CMP step, and has sufficient corrosion resistance to the metal wiring, and Cleaning solution and method for suppressing generation of residue and adhesion of residue on substrate surface.
本發明者等人為解決上述問題經反複深入鑽研，結果發現藉由併用螯合劑、與具有某特定結構的化合物，便可在未添加習知防蝕劑之情況下，抑制腐蝕發生、且亦可減輕腐蝕進行，故可解決因使用防蝕劑而衍生的殘渣產生、及殘渣於基板表面附著的問題，遂完成本發明。 The present inventors and others have repeatedly researched in order to solve the above problems, and found that by using a chelating agent and a compound having a specific structure in combination, the occurrence of corrosion can be suppressed without the addition of a conventional anticorrosive agent, and it can also be reduced. The corrosion progresses, so that the problems of residue generation due to the use of the corrosion inhibitor and the adhesion of the residue on the substrate surface can be solved, and the present invention is completed.
即，本發明係關於以下的發明。 That is, the present invention relates to the following inventions.
1.一種半導體裝置用基板洗淨液，係含有以下成分(A)~(C)，且pH為8~14： 1. A substrate cleaning solution for a semiconductor device, which contains the following components (A) to (C) and has a pH of 8 to 14:
(A)螯合劑 (A) Chelating agent
(B)以下述一般式(1)所示之化合物：NH2-R-NH2．．．(1)(上述一般式(1)中的連接基R係表示以下述一般式(2)所示之脂肪族烴基。) (B) A compound represented by the following general formula (1): NH 2 -R-NH 2 . ． ． (1) (The linking group R in the above general formula (1) represents an aliphatic hydrocarbon group represented by the following general formula (2).)
-(CX1X2)n-．．．(2)(上述一般式(2)中，n係表示3以上的整數；X1、X2係表示各自獨立的氫原子或烷基。n個CX1X2係相互可為相同亦可為不同。) -(CX 1 X 2 ) n-. ． ． (2) (In the above general formula (2), n represents an integer of 3 or more; X 1 and X 2 represent independent hydrogen atoms or alkyl groups. The n CX 1 X 2 systems may be the same as each other or may be different.)
(C)水 (C) Water
2.如前項1所記載的半導體裝置用基板洗淨液，其中，上述成分(B)係上述一般式(1)的連接基R為以上述一般式(2)所示之脂肪族烴基、n為3~10的整數，且X1、X2均為氫原子的化合物。 2. The substrate cleaning solution for a semiconductor device according to the preceding paragraph 1, wherein the component (B) is a linking group R of the general formula (1), and is an aliphatic hydrocarbon group represented by the general formula (2), n A compound having an integer of 3 to 10, and X 1 and X 2 are both hydrogen atoms.
3.如前項1或2所記載的半導體裝置用基板洗淨液，其中，更進一步含有成分(D)界面活性劑。 3. The substrate cleaning liquid for a semiconductor device according to the above item 1 or 2, further comprising a component (D) surfactant.
4.如前項1至3中任一項所記載的半導體裝置用基板洗淨液，其中，更進一步含有成分(E)pH調整劑。 4. The substrate cleaning liquid for a semiconductor device according to any one of the preceding paragraphs 1 to 3, further comprising a component (E) pH adjuster.
5.如前項3或4所記載的半導體裝置用基板洗淨液，其中，上述成分(D)係陰離子性界面活性劑。 5. The substrate cleaning liquid for a semiconductor device according to the above item 3 or 4, wherein the component (D) is an anionic surfactant.
6.如前項3至5中任一項所記載的半導體裝置用基板洗淨液，其中，上述成分(D)係從烷基磺酸及其鹽、烷基苯磺酸及其鹽、烷基二苯基醚二磺酸及其鹽、烷基甲基牛磺酸及其鹽、以及磺基琥珀酸二酯及其鹽所構成群組中選擇至少1種。 6. The substrate cleaning liquid for a semiconductor device according to any one of 3 to 5, wherein the component (D) is selected from alkylsulfonic acid and a salt thereof, alkylbenzenesulfonic acid and a salt thereof, and an alkyl group. At least one selected from the group consisting of diphenyl ether disulfonic acid and its salts, alkylmethyltaurine and its salts, and sulfosuccinic acid diester and its salts.
7.如前項1至6中任一項所記載的半導體裝置用基板洗淨液，其中，上述成分(A)係從草酸、檸檬酸、酒石酸、蘋果酸、吡啶羧酸、伸乙二胺、1,2-二胺基丙烷、甘胺酸及亞胺基二醋酸所構成群組中選擇至少1種。 7. The substrate cleaning liquid for a semiconductor device according to any one of the foregoing paragraphs 1 to 6, wherein the component (A) is selected from oxalic acid, citric acid, tartaric acid, malic acid, pyridinecarboxylic acid, ethylenediamine, At least one kind is selected from the group consisting of 1,2-diaminopropane, glycine, and iminodiacetic acid.
8.一種半導體裝置用基板之洗淨方法，係使用前項1至7中任一項所記載的半導體裝置用基板洗淨液，施行半導體裝置用基板洗淨。 8. A method for cleaning a substrate for a semiconductor device, which comprises cleaning the substrate for a semiconductor device using the substrate cleaning liquid for a semiconductor device according to any one of 1 to 7 above.
9.如前項8所記載的半導體裝置用基板之洗淨方法，其中，半導體 裝置用基板係在基板表面上具有Cu佈線與低介電常數絕緣膜，且經施行化學性機械研磨後的基板。 9. The method for cleaning a substrate for a semiconductor device according to the above item 8, wherein the semiconductor The device substrate is a substrate having a Cu wiring and a low dielectric constant insulating film on the surface of the substrate and subjected to chemical mechanical polishing.
藉由使用本發明的半導體裝置用基板洗淨液，在CMP步驟後的半導體裝置用基板之洗淨步驟中，可防止金屬佈線的腐蝕，並可抑制殘渣產生及殘渣附著於基板表面，俾可施行有效的洗淨。 By using the substrate cleaning solution for a semiconductor device of the present invention, in the step of cleaning the substrate for a semiconductor device after the CMP step, the metal wiring can be prevented from being corroded, and residue generation and residue adhesion on the substrate surface can be suppressed. Perform effective washing.
圖1係在實施例1之洗淨液(稀釋液)中浸漬30分鐘後，圖案化基板的SEM圖(照片)。 FIG. 1 is an SEM image (photograph) of a patterned substrate after being immersed in the cleaning solution (diluent) of Example 1 for 30 minutes.
圖2係在實施例2之洗淨液(稀釋液)中浸漬30分鐘後，圖案化基板的SEM圖(照片)。 FIG. 2 is an SEM image (photograph) of a patterned substrate after being immersed in a cleaning solution (diluent) of Example 2 for 30 minutes.
圖3係在實施例3之洗淨液(稀釋液)中浸漬30分鐘後，圖案化基板的SEM圖(照片)。 FIG. 3 is an SEM image (photograph) of the patterned substrate after being immersed in the cleaning solution (diluent) of Example 3 for 30 minutes.
圖4係在實施例4之洗淨液(稀釋液)中浸漬30分鐘後，圖案化基板的SEM圖(照片)。 FIG. 4 is an SEM image (photograph) of the patterned substrate after being immersed in the cleaning solution (diluent) of Example 4 for 30 minutes.
圖5係在比較例1之洗淨液(稀釋液)中浸漬30分鐘後，圖案化基板的SEM圖(照片)。 FIG. 5 is an SEM image (photograph) of a patterned substrate after being immersed in a cleaning solution (diluent) of Comparative Example 1 for 30 minutes.
圖6係在比較例2之洗淨液(稀釋液)中浸漬30分鐘後，圖案化基板的SEM圖(照片)。 FIG. 6 is an SEM image (photograph) of a patterned substrate after being immersed in a cleaning solution (diluent) of Comparative Example 2 for 30 minutes.
圖7係在比較例3之洗淨液(稀釋液)中浸漬30分鐘後，圖案化基板的SEM圖(照片)。 FIG. 7 is an SEM image (photograph) of a patterned substrate after being immersed in a cleaning solution (diluent) of Comparative Example 3 for 30 minutes.
圖8係在比較例4之洗淨液(稀釋液)中浸漬30分鐘後，圖案化基板的SEM圖(照片)。 FIG. 8 is an SEM image (photograph) of a patterned substrate after being immersed in a cleaning solution (diluent) of Comparative Example 4 for 30 minutes.
以下，針對本發明實施形態進行具體地說明，惟本發明並不僅侷限於以下的實施形態，在其主旨範圍內可進行各種變更而實施。 Hereinafter, the embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof.
本發明的半導體裝置用基板洗淨液(以下有時亦稱「本發明之洗淨液」)，係半導體裝置用基板之洗淨，較佳係在半導體裝置製造的化學性機械研磨(CMP)步驟後，才實施的半導體裝置用基板之洗淨步驟中所使用的洗淨液，其特徵在於：含有以下成分(A)~(C)作為必要成分，且pH為8~14的洗淨液。 The substrate cleaning solution for a semiconductor device of the present invention (hereinafter sometimes referred to as "the cleaning solution of the present invention") is a method for cleaning a substrate for a semiconductor device, and is preferably a chemical mechanical polishing (CMP) process for manufacturing a semiconductor device. The cleaning liquid used in the step of cleaning the substrate for a semiconductor device, which is performed after the step, is characterized in that it contains the following components (A) to (C) as essential components and has a pH of 8 to 14 .
(A)螯合劑 (A) Chelating agent
(B)以下述一般式(1)所示之化合物：NH2-R-NH2．．．(1)(上述一般式(1)中的連接基R係表示以下述一般式(2)所示之脂肪族烴基。) (B) A compound represented by the following general formula (1): NH 2 -R-NH 2 . ． ． (1) (The linking group R in the above general formula (1) represents an aliphatic hydrocarbon group represented by the following general formula (2).)
-(CX1X2)n-．．．(2)(上述一般式(2)中，n係表示3以上的整數；X1、X2係表示各自獨立的氫原子或烷基。n個CX1X2係相互可為相同亦可為不同。) -(CX 1 X 2 ) n-. ． ． (2) (In the above general formula (2), n represents an integer of 3 or more; X 1 and X 2 represent independent hydrogen atoms or alkyl groups. The n CX 1 X 2 systems may be the same as each other or may be different.)
(C)水 (C) Water
本發明中藉由將上述成分(B)化合物與成分(A)螯合劑一起使用，便使成分(B)發揮作為防蝕劑之機能，俾可提升洗淨液的防蝕性能。此項作用機構的詳細內容雖尚未明確，但可推定如下述。 In the present invention, by using the component (B) compound and the component (A) chelating agent together, the component (B) can function as an anticorrosive agent, and the anticorrosive performance of the cleaning solution can be improved. Although the details of this mechanism are not clear, it can be presumed as follows.
例如，為了使防蝕劑對銅發揮防蝕性能，一般係在佈線 表面上形成銅-防蝕劑錯合物的膜，且要求該膜的水溶性較低。然而，若銅-防蝕劑錯合物的溶解度過低，便無法利用洗淨步驟除去，會有在銅佈線上形成結晶或殘留有機殘渣的問題。 For example, in order for corrosion inhibitors to exert anti-corrosive properties on copper, A film of a copper-corrosion inhibitor complex is formed on the surface, and the water solubility of the film is required to be low. However, if the solubility of the copper-corrosion inhibitor complex is too low, it cannot be removed by a washing step, and there is a problem that crystals or organic residues remain on the copper wiring.
本發明成分(B)之以一般式(1)所示之化合物，由於在分子內具有2個胺基，因而該2個胺基會分別配位於銅而形成銅錯合物。此處藉由所形成之銅錯合物的水溶性差異，該化合物若發揮作為螯合劑的能力、或發揮作為防蝕劑的能力，推測可成為表現出不同的機能者。 Since the compound represented by the general formula (1) of the component (B) of the present invention has two amine groups in the molecule, the two amine groups are respectively coordinated with copper to form a copper complex. Here, due to the difference in water solubility of the copper complex formed, if the compound exhibits its ability to function as a chelating agent or its ability to act as an anticorrosive agent, it is estimated that it can exhibit different functions.
在該推測的基礎下，若使用習知洗淨劑所廣泛使用的伸乙二胺(即，若使用以一般式(1)所示之結構式，在屬於交聯基的R係-CH2CH2-之情況下(即，一般式(2)中，n為2，X1、X2為氫原子的情況))，便發揮作為螯合劑的作用，因而本發明者等人發現將胺基彼此間予以連結的交聯基R(本發明中，交聯基R亦稱「連接基R」)，關聯著錯合物的水溶性。 Based on this assumption, if ethylenediamine, which is widely used in conventional detergents, is used (that is, if a structural formula represented by the general formula (1) is used, R-CH 2 which is a crosslinking group is used. In the case of CH 2- (that is, in the general formula (2), n is 2, and X 1 and X 2 are hydrogen atoms), it functions as a chelating agent. Therefore, the present inventors have found that the amine The cross-linking group R (the cross-linking group R is also referred to as "linking group R" in the present invention) to which the groups are linked to each other is related to the water solubility of the complex.
即，在該連接基R自體的疏水性較低的情況下，所形成銅錯合物的水溶性較高，推測該化合物具有作為螯合劑的機能。另一方面，在連接基R自體的疏水性較高的情況下，因所形成之銅錯合物的水溶性降低，該錯合物會覆蓋銅表面，推測該化合物具有作為防蝕劑的機能。 That is, when the hydrophobicity of the linker R itself is low, the water solubility of the copper complex formed is high, and it is estimated that the compound has a function as a chelating agent. On the other hand, when the linker R itself is highly hydrophobic, the copper complex formed will have a reduced water solubility, and the complex will cover the copper surface. It is estimated that the compound has a function as an anticorrosive. .
再者，雖利用連接基R的種類便能調整2個胺基間的距離，但當連接基R過短時，銅佈線會遭腐蝕。反之，當連接基R過長時，由於在銅表面上會大量殘留該化合物，因而無法發揮充分的洗淨效果。 Furthermore, although the distance between the two amine groups can be adjusted by the type of the linking group R, if the linking group R is too short, the copper wiring will be corroded. On the other hand, when the linking group R is too long, since a large amount of the compound remains on the copper surface, a sufficient cleaning effect cannot be exhibited.
因此，為了使以一般式(1)所示之化合物能兼顧防蝕性與洗淨性，認為較佳係選擇2個胺基間的距離能保持適當長度的交聯結 構。 Therefore, in order for the compound represented by the general formula (1) to have both corrosion resistance and detergency, it is considered to be preferable to select a distance between two amine groups to maintain a cross-linking of an appropriate length. 结构。 Structure.
再者，本發明的洗淨液中，由於成分(A)亦作為螯合劑存在，因而認為較佳係亦考慮因螯合劑造成的銅溶解作用，再選擇呈現適度防蝕效果的成分(B)之化合物。 Furthermore, since the component (A) also exists as a chelating agent in the cleaning solution of the present invention, it is considered that it is better to consider the dissolution of copper due to the chelating agent, and then select the component (B) that exhibits a moderate anticorrosive effect. Compound.
由此種現象得知，本發明中，成分(B)係使用上述一般式(1)的連接基R為以上述一般式(2)所示之脂肪族烴基或芳香族烴基的化合物，藉由成分(A)之螯合劑與成分(B)之化合物的共存，便可兼顧對金屬佈線的充分洗淨性與充分防蝕性，俾能抑制殘渣產生、及殘渣於基板表面的附著。 From this phenomenon, it is known that in the present invention, the component (B) is a compound using the linking group R of the general formula (1) as an aliphatic hydrocarbon group or an aromatic hydrocarbon group represented by the general formula (2). The coexistence of the chelating agent of the component (A) and the compound of the component (B) can achieve sufficient cleaning and corrosion resistance of the metal wiring, and can suppress the generation of residues and the adhesion of the residues to the substrate surface.
本發明的洗淨液係pH8~14。藉由洗淨液的pH達8以上，便會使溶液中的膠體二氧化矽等之ξ電位降低，藉由與基板間之電性排斥力作用，便可輕易地去除微小粒子。又，可抑制經除去的微小粒子再附著屬於洗淨對象的基板表面上。 The cleaning liquid of the present invention has a pH of 8 to 14. When the pH of the cleaning solution reaches 8 or more, the ξ potential of colloidal silicon dioxide in the solution will be reduced, and the small particles can be easily removed by the electric repulsive force with the substrate. In addition, the removed fine particles can be prevented from re-adhering to the surface of the substrate belonging to the cleaning target.
此處，為了更降低ξ電位，本發明的洗淨液較佳係pH9以上、更佳係pH10以上。 Here, in order to further reduce the zeta potential, the cleaning liquid of the present invention is preferably at least pH 9 and more preferably at least pH 10.
再者，關於本發明洗淨液的pH上限，較佳係13以下。 The upper limit of the pH of the cleaning solution of the present invention is preferably 13 or less.
另外，本發明洗淨液的pH係利用後述成分(E)pH調整劑或其他成分的添加量等，便可調整於上述pH範圍內。 In addition, the pH of the cleaning liquid of the present invention can be adjusted within the above-mentioned pH range by using a component (E) pH adjuster described later or the addition amount of other components and the like.
以下，針對本發明洗淨液中所含之各成分，與其作用一併進行詳細地說明。 Hereinafter, each component contained in the cleaning liquid of the present invention will be described in detail together with its action.
本發明洗淨劑中所含之成分(A)螯合劑，係具有將基板表面的金屬佈線中所含有之鎢等雜質金屬、CMP步驟所使用之障壁漿(barrier slurry)中存在之防蝕劑與銅的不溶性金屬錯合物、以及鈉或鉀等鹼金屬，利用螯合作用予以溶解、除去的作用。 The chelating agent of the component (A) contained in the cleaning agent of the present invention is a barrier slurry (impurity metal such as tungsten contained in the metal wiring on the substrate surface and used in the CMP step). The insoluble metal complex of the corrosion inhibitor and copper present in the slurry), and alkali metals such as sodium or potassium are dissolved and removed by chelation.
螯合劑係可使用具有上述作用的有機酸、胺類及其鹽或其衍生物，可單獨使用1種，亦可依任意比例併用2種以上。 As the chelating agent, organic acids, amines, and salts or derivatives thereof having the above-mentioned effects may be used, and they may be used alone or in combination of two or more at any ratio.
成分(A)特佳係從草酸、檸檬酸、酒石酸、蘋果酸、吡啶羧酸、伸乙二胺、1,2-二胺基丙烷、伸乙二胺四醋酸、甘胺酸、天冬胺酸、亞胺基二醋酸、丙胺酸及β-丙胺酸所構成群組中選擇至少1種。又，該等的鹽亦可適宜地使用。 Ingredient (A) is particularly preferred from oxalic acid, citric acid, tartaric acid, malic acid, pyridinecarboxylic acid, ethylenediamine, 1,2-diaminopropane, ethylenediaminetetraacetic acid, glycine, and asparagine At least one member is selected from the group consisting of acids, iminodiacetic acid, alanine, and β-alanine. Such salts can also be suitably used.
該等之中，就螯合效果強度、品質安定性或取得容易度的觀點而言，可適宜地使用從草酸、檸檬酸、酒石酸、蘋果酸、吡啶羧酸、伸乙二胺、1,2-二胺基丙烷、甘胺酸及亞胺基二醋酸所構成群組中選擇至少1種，特別係可適宜地使用從草酸、檸檬酸、酒石酸、吡啶羧酸、伸乙二胺、1,2-二胺基丙烷、甘胺酸及亞胺基二醋酸所構成群組中選擇至少1種。 Among these, from the viewpoints of strength of chelating effect, quality stability, and ease of acquisition, from oxalic acid, citric acid, tartaric acid, malic acid, pyridinecarboxylic acid, ethylenediamine, 1,2 -At least one selected from the group consisting of diaminopropane, glycine, and iminodiacetic acid. In particular, oxalic acid, citric acid, tartaric acid, pyridinecarboxylic acid, ethylenediamine, and 1, At least one member is selected from the group consisting of 2-diaminopropane, glycine, and iminodiacetic acid.
另外，本發明洗淨劑中所含的成分(A)螯合劑，係以下述一般式(1)所示之化合物除外。 In addition, the component (A) chelating agent contained in the detergent of the present invention is excluding a compound represented by the following general formula (1).
NH2-R-NH2．．．(1)(上述一般式(1)中的連接基R係表示以下述一般式(2)所示之脂肪族烴基。) NH 2 -R-NH 2 . ． ． (1) (The linking group R in the above general formula (1) represents an aliphatic hydrocarbon group represented by the following general formula (2).)
-(CX1X2)n-．．．(2)(上述一般式(2)中，n係表示3以上的整數；X1、X2係表示各自獨立的氫原子或烷基。n個CX1X2係相互可為相同亦可為不同。) -(CX 1 X 2 ) n-. ． ． (2) (In the above general formula (2), n represents an integer of 3 or more; X 1 and X 2 represent independent hydrogen atoms or alkyl groups. The n CX 1 X 2 systems may be the same as each other or may be different.)
本發明洗淨液中所含成分(B)，係以下述一般式(1)所示之化合物，但該成分(B)係利用連接基R為以下述一般式(2)所示之脂肪族烴基，降低親水性，而達成主要對Cu之腐蝕抑制效果的防蝕劑機能。 The component (B) contained in the cleaning solution of the present invention is a compound represented by the following general formula (1), but the component (B) is a aliphatic compound represented by the following general formula (2) using a linking group R Hydrocarbon group reduces the hydrophilicity and achieves the function of an anticorrosive agent which mainly inhibits the corrosion of Cu.
NH2-R-NH2．．．(1)(上述一般式(1)中的連接基R係表示以下述一般式(2)所示之脂肪族烴基。) NH 2 -R-NH 2 . ． ． (1) (The linking group R in the above general formula (1) represents an aliphatic hydrocarbon group represented by the following general formula (2).)
-(CX1X2)n-．．．(2)(上述一般式(2)中，n係表示3以上的整數；X1、X2係表示各自獨立的氫原子或烷基。n個CX1X2係相互可為相同亦可為不同。) -(CX 1 X 2 ) n-. ． ． (2) (In the above general formula (2), n represents an integer of 3 or more; X 1 and X 2 represent independent hydrogen atoms or alkyl groups. The n CX 1 X 2 systems may be the same as each other or may be different.)
上述一般式(1)中，當連接基R係以上述一般式(2)所示之脂肪族烴基時，X1、X2的烷基係可為直鏈，亦可為具有分支鏈者，亦可為環狀，但較佳係碳數1~12的直鏈烷基，且n係3以上的整數，較佳係n為3~10的整數，更佳係n為3~8的整數、特佳係n為3~6的整數。 In the above general formula (1), when the linking group R is an aliphatic hydrocarbon group represented by the above general formula (2), the alkyl system of X 1 and X 2 may be a straight chain or a branched chain. It may also be cyclic, but is preferably a linear alkyl group having 1 to 12 carbon atoms, and n is an integer of 3 or more, preferably n is an integer of 3 to 10, and more preferably n is an integer of 3 to 8 In particular, n is an integer from 3 to 6.
X1、X2的烷基之碳數過多、或n過大者，水溶性降低，導致成分(B)析出，而無法發揮充分的洗淨效果。因此，上述一般式(2)中，較佳係X1、X2均為氫原子，且更佳係n為3~8、特佳係n為3~6。 If the number of carbons in the alkyl groups of X 1 and X 2 is too large or n is too large, the water solubility is reduced, and the component (B) is precipitated, so that a sufficient cleaning effect cannot be exhibited. Therefore, in the above general formula (2), it is preferable that X 1 and X 2 are both hydrogen atoms, and a more preferable system n is 3 to 8 and a particularly preferable system n is 3 to 6.
以一般式(1)所示之化合物的具體例，較適宜之例係可列舉例如：1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷及1,8-二胺基辛烷。 Specific examples of the compound represented by the general formula (1) may include, for example, 1,3-diaminopropane, 1,4-diaminobutane, and 1,5-diaminopentane. Alkanes, 1,6-diaminohexane and 1,8-diaminooctane.
其中，就品質安定性或取得容易度的觀點而言，成分(B)可適宜地使用1,3-二胺基丙烷、1,4-二胺基丁烷及1,6-二胺基己烷。 Among these, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexan are suitably used as a component (B) from a viewpoint of quality stability or ease of acquisition. alkyl.
成分(B)係可單獨使用式(1)之化合物1種，亦可依任意比例併用2種以上。 As the component (B), one kind of the compound of the formula (1) may be used alone, or two or more kinds may be used in combination at any ratio.
本發明洗淨液中所含之成分(C)水，較佳係使用經盡力減少雜質的脫離子水或超純水。 The component (C) water contained in the cleaning solution of the present invention is preferably deionized water or ultrapure water that has been used to reduce impurities as much as possible.
本發明洗淨液中，除上述成分(A)~(C)外，較佳係更進一步含有成分(D)界面活性劑。界面活性劑係當於層間絕緣膜使用疏水性材料時，以水為基本組成的洗淨液變得較難施行洗淨。成分(D)的界面活性劑係具有提升疏水性基板表面與洗淨液之親和性的作用。藉由摻合界面活性劑而提升與基板表面間之親和性，就連與基板上所存在之粒子等之間亦可發揮洗淨液的作用，對殘渣的除去具有貢獻。特別係當對疏水性較強的基板表面施行洗淨時，未含界面活性劑的洗淨液中由於洗淨液與基板表面間之親和性低，因而洗淨效果變得不足。 In the cleaning solution of the present invention, in addition to the above-mentioned components (A) to (C), it is preferable that the component (D) further contains a surfactant. When a surfactant is used for an interlayer insulating film, a washing | cleaning liquid which consists of water becomes difficult to wash | clean. The surfactant of the component (D) has a function of improving the affinity between the surface of the hydrophobic substrate and the cleaning solution. By blending a surfactant, the affinity with the substrate surface is enhanced, and even with particles and the like existing on the substrate, the cleaning liquid can also play a role and contribute to the removal of the residue. In particular, when a highly hydrophobic substrate surface is cleaned, a cleaning solution that does not contain a surfactant has a low affinity for the cleaning liquid and the substrate surface, and thus the cleaning effect becomes insufficient.
成分(D)的界面活性劑並無特別的限制，可使用陰離子性界面活性劑、陽離子性界面活性劑、非離子性界面活性劑及兩性界面活性劑中之任一者。 The surfactant of the component (D) is not particularly limited, and any one of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used.
本發明洗淨液中可適宜地使用的成分(D)界面活性劑，係陰離子性界面活性劑。陰離子性界面活性劑之例係可列舉：烷基磺酸及其鹽、烷基苯磺酸及其鹽、烷基二苯基醚二磺酸及其鹽、烷基甲基牛磺酸及其鹽、以及磺基琥珀酸二酯及其鹽，特佳的磺酸型陰離子性界面活性劑係可列舉：十二烷基苯磺酸(DBS)、十二烷基磺酸及該等的鹼金屬鹽等。其中，就品質安定性或取得容易度的觀點而言，特佳係十二烷基苯磺酸及其鹼金屬鹽。 The component (D) surfactant which can be suitably used in the cleaning liquid of the present invention is an anionic surfactant. Examples of the anionic surfactant include alkylsulfonic acid and its salts, alkylbenzenesulfonic acid and its salts, alkyldiphenyl ether disulfonic acid and its salts, alkylmethyltaurine and its salts. Salts, and sulfosuccinic acid diesters and salts thereof. Particularly preferred sulfonic acid type anionic surfactants are: dodecylbenzenesulfonic acid (DBS), dodecylsulfonic acid, and the like. Metal salts, etc. Among these, particularly preferred is dodecylbenzenesulfonic acid and its alkali metal salt from the viewpoint of quality stability or ease of acquisition.
其他陰離子性界面活性劑之例係可列舉羧酸型陰離子性界面活性劑。羧酸型陰離子性界面活性劑係分子內含有羧基的陰離子性界面活性劑，其中較佳係以下述一般式(4)所示之化合物：R2-O-(AO)a-(CH2)b-COOH (4) Examples of other anionic surfactants include carboxylic acid-type anionic surfactants. The carboxylic acid type anionic surfactant is an anionic surfactant having a carboxyl group in the molecule. Among them, a compound represented by the following general formula (4) is preferred: R 2 -O- (AO) a- (CH 2 ) b -COOH (4)
上述一般式(4)中，R2係直鏈或分支鏈的烷基，其碳數係8~15，較佳係10~13。又，AO係氧化伸乙基及/或氧化伸丙基，a係3~30，較佳係4~20，更佳係4.5~10。又，b係1~6，較佳係1~3。 In the above general formula (4), R 2 is a linear or branched alkyl group, and its carbon number is 8 to 15, preferably 10 to 13. In addition, the AO-based oxyethylidene and / or oxy-propylidene, the a-based is 3 to 30, preferably 4 to 20, and more preferably 4.5 to 10. In addition, b is 1 to 6, preferably 1 to 3.
以上述一般式(4)所示之羧酸型陰離子性界面活性劑，具體而言，係可列舉：聚氧化伸乙基月桂基醚醋酸、聚氧化伸乙基十三烷基醚醋酸及聚氧化伸乙基烷基醚醋酸等。 Specific examples of the carboxylic acid type anionic surfactant represented by the general formula (4) include polyoxyethylene lauryl ether acetic acid, polyoxyethylene tridecyl ether acetic acid, and poly (ethylene tridecyl ether acetic acid). Oxidized ethyl alkyl ether acetic acid and the like.
該等陰離子性界面活性劑等界面活性劑，可單獨使用1種，亦可依任意比例併用2種以上。 These anionic surfactants, such as a surfactant, may be used individually by 1 type, and may use 2 or more types together by arbitrary ratios.
另外，界面活性劑就通常市售的形態，有含有1~數千質量ppm程度之Na、K及Fe等金屬雜質的情況，此情況下，界面活性劑便成為金屬污染源。因此，當成分(D)中含有金屬雜質時，較佳係依各個金屬雜質的含有量通常在10ppm以下、較佳係1ppm以下、更佳係0.3ppm以下的方式，將成分(D)施行精製後才使用。該精製方法較佳係例如將成分(D)溶解於水中之後，通液於離子交換樹脂，使金屬雜質被捕捉於樹脂中的方法。藉由使用依此所精製的界面活性劑，便可獲得盡力降低金屬雜質含有量的洗淨液。 In addition, the surfactant is generally commercially available, and may contain metal impurities such as Na, K, and Fe in the range of 1 to several thousand ppm by mass. In this case, the surfactant becomes a source of metal contamination. Therefore, when a metal impurity is contained in the component (D), the component (D) is preferably refined in such a manner that the content of each metal impurity is usually 10 ppm or less, preferably 1 ppm or less, and more preferably 0.3 ppm or less. Only use it later. This purification method is preferably, for example, a method in which the component (D) is dissolved in water, and then the solution is passed through an ion exchange resin to trap metal impurities in the resin. By using the surfactant thus purified, a cleaning solution that minimizes the content of metal impurities can be obtained.
本發明洗淨液中，除上述成分(A)~(C)外，較佳係更進一步含有成分(E)的pH調整劑。pH調整劑係在其目的為可調整pH之成分的前提 下，並無特別的限定，可使用氧化合物或鹼化合物。氧化合物的較適宜之例係可列舉：硫酸及硝酸等無機酸及其鹽；或醋酸、乳酸、草酸、酒石酸及檸檬酸等有機酸及其鹽。 In the cleaning liquid of the present invention, in addition to the above-mentioned components (A) to (C), it is preferred that the pH-adjusting agent further contains the component (E). The pH adjusting agent is a premise that the purpose is to adjust pH Hereinafter, there is no particular limitation, and an oxygen compound or a basic compound can be used. Preferable examples of the oxygen compound include inorganic acids and salts thereof such as sulfuric acid and nitric acid; and organic acids and salts thereof such as acetic acid, lactic acid, oxalic acid, tartaric acid, and citric acid.
再者，關於鹼化合物係可使用有機鹼化合物及無機鹼化合物，有機鹼化合物的較適宜之例係可列舉以下所示之有機四級銨氫氧化物等四級銨及其衍生物的鹽、三甲胺及三乙胺等烷基胺及其衍生物的鹽、單乙醇胺等烷醇胺及其衍生物。 In addition, as the base compound, an organic base compound and an inorganic base compound can be used. Examples of suitable organic base compounds include salts of quaternary ammonium and derivatives thereof such as organic quaternary ammonium hydroxides, Salts of alkylamines and their derivatives such as trimethylamine and triethylamine, and alkanolamines and their derivatives such as monoethanolamine.
作為有機鹼化合物的有機四級銨氫氧化物，係可列舉以以下一般式(3)所示者：(R1)4N+OH- (3)(上述一般式(3)中，R1係表示羥基、烷氧基、或亦可被鹵取代的烷基；4個R1係可全部相同，亦可相異。) As the organic quaternary ammonium hydroxide, an organic base compound include lines to that shown in the following general formula (3): (R 1) 4 N + OH - (3) ( the general formula (3), R 1 is Represents a hydroxyl group, an alkoxy group, or an alkyl group which may be substituted by halogen; the four R 1 systems may be all the same or different.)
有機四級銨氫氧化物在上述一般式(3)中，R1係羥基、碳數1~4之烷氧基、或亦可係被鹵取代的直鏈或分支鏈的碳數1~4之烷基，特佳係直鏈的碳數1~4之烷基及/或直鏈的碳數1~4之羥烷基。R1的烷基係可列舉例如：甲基、乙基、丙基及丁基等碳數1~4的低級烷基。羥烷基係可列舉例如：羥甲基、羥乙基、羥丙基及羥丁基等碳數1~4的低級羥烷基。 Organic quaternary ammonium hydroxide In the above general formula (3), R 1 is a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a straight or branched chain carbon number 1 to 4 which may be substituted with halogen. The alkyl group is particularly preferably a linear alkyl group having 1 to 4 carbon atoms and / or a linear alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group of R 1 include lower alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl. Examples of the hydroxyalkyl system include lower hydroxyalkyl groups having 1 to 4 carbon atoms such as hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl.
該有機四級銨氫氧化物具體而言係可列舉例如：氫氧化雙(2-羥乙基)二甲銨、氫氧化四乙銨(TEAH)、氫氧化四丙銨、氫氧化四丁銨、氫氧化甲基三乙銨、氫氧化三甲基(羥乙基)銨(通稱：膽)及氫氧化三乙基(羥乙基)銨等。 Specific examples of the organic quaternary ammonium hydroxide include bis (2-hydroxyethyl) dimethylammonium hydroxide, tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , Methyltriethylammonium hydroxide, trimethyl (hydroxyethyl) ammonium hydroxide (commonly known as bile ) And triethyl (hydroxyethyl) ammonium hydroxide.
上述有機四級銨氫氧化物中，就洗淨效果、金屬殘留較少、經濟性及洗淨液安定性等理由而言，特佳係氫氧化雙(2-羥乙基) 二甲銨、氫氧化三甲基(羥乙基)銨、氫氧化四乙銨及氫氧化四丁銨等。 The above-mentioned organic quaternary ammonium hydroxide is particularly preferably bis (2-hydroxyethyl) hydroxide for reasons of cleaning effect, less metal residue, economy, and stability of the cleaning solution. Dimethylammonium, trimethyl (hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide.
無機鹼化合物係在水溶液中呈鹼性者之中，含有氨、或主要為鹼金屬或鹼土族金屬的無機化合物及其鹽，該等之中，就安全性及成本的觀點而言，無機鹼較佳係使用含有鹼金屬的氫氧化物。具體而言，係可列舉例如：氫氧化鋰、氫氧化鈉、氫氧化鉀、氫氧化銣及氫氧化銫等。 Inorganic alkali compounds are those which are alkaline in an aqueous solution, and which contain ammonia, or an inorganic compound mainly composed of an alkali metal or an alkaline earth metal, and salts thereof. Among these, from the viewpoints of safety and cost, inorganic alkalis Preferably, an alkali metal-containing hydroxide is used. Specific examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide.
該等氧化合物或鹼化合物係當以調整本發明洗淨液之pH為目的而使用時，可單獨使用1種，亦可依任意比例併用2種以上。 When the oxygen compound or the alkali compound is used for the purpose of adjusting the pH of the cleaning solution of the present invention, it may be used alone, or two or more kinds may be used in combination at any ratio.
特佳的酸或鹼係可列舉：醋酸、草酸、酒石酸及檸檬酸等有機酸及其鹽；氫氧化鈉及氫氧化鉀等無機鹼及其鹽；以及氫氧化四甲銨、氫氧化四乙銨及膽等四級銨及其衍生物的鹽。 Particularly preferred acids or bases are: organic acids and salts thereof such as acetic acid, oxalic acid, tartaric acid and citric acid; inorganic bases and salts thereof such as sodium hydroxide and potassium hydroxide; and tetramethylammonium hydroxide and tetraethyl hydroxide Ammonium and bile And other salts of quaternary ammonium and its derivatives.
本發明的洗淨液中，在不損及其性能之範圍內，亦可依任意比例含有上述成分(A)~(E)以外的成分。 The cleaning liquid of the present invention may contain components other than the above-mentioned components (A) to (E) in an arbitrary ratio within a range that does not impair its performance.
其他成分係可列舉例如下述者。 Examples of the other component systems include the following.
亦可含有：苯并***、3-胺基***、N(R3)3(R3係相互可為相同，亦可為不同的碳數1~4之烷基及/或碳數1~4之羥烷基)、氨、脲及硫脲等含氮有機化合物；聚乙二醇及聚乙烯醇等水溶性聚合物；R4OH(R4係碳數1~4之烷基)等烷基醇系化合物等防蝕劑；氫、氬、氮、二氧化碳及氨等溶存氣體；氫氟酸、氟化銨及BHF(緩衝氫氟酸)等可期待在乾式蝕刻後將牢固附著的聚合物等予以除去效果的蝕刻促進劑；抗壞血酸、沒食子酸及肼等還原劑；過氧化氫、臭氧及氧等氧化劑；單乙醇胺；精胺酸等胺基酸；以及作為溶劑的乙醇等除水以外的 成分。 May also contain: benzotriazole, 3-aminotriazole, N (R 3 ) 3 (R 3 series may be the same as each other, or may be different alkyl groups having 1 to 4 carbon atoms and / or carbon numbers 1 ~ 4 hydroxyalkyl), nitrogen-containing organic compounds such as ammonia, urea, and thiourea; water-soluble polymers such as polyethylene glycol and polyvinyl alcohol; R 4 OH (R 4 is an alkyl group having 1 to 4 carbon atoms) Corrosion inhibitors such as alkyl alcohol compounds; dissolved gases such as hydrogen, argon, nitrogen, carbon dioxide, and ammonia; hydrofluoric acid, ammonium fluoride, and BHF (buffered hydrofluoric acid), etc. Polymers that are expected to adhere firmly after dry etching Removal agents such as ascorbic acid, gallic acid and hydrazine; reducing agents such as ascorbic acid, gallic acid and hydrazine; oxidizing agents such as hydrogen peroxide, ozone and oxygen; monoethanolamine; amino acids such as arginine; and ethanol, etc. as solvents Ingredients other than water.
本發明洗淨液的製造方法並無特別的限定，只要依照習知公知方法便可，例如將洗淨液的構成成分(含有成分(A)~(C)，以及該等之外較佳的成分(D)及/或成分(E)，以及視需要使用的其他成分)予以混合便可製造。通常藉由在屬於溶劑的成分(C)水中，添加成分(A)~(B)，較佳係含有成分(D)及/或成分(E)，以及視需要使用的其他成分而製造。 The manufacturing method of the washing | cleaning liquid of this invention is not specifically limited, As long as it is based on a conventionally well-known method, for example, the constituent components of a washing | cleaning liquid (containing components (A)-(C), and other than these are preferable) Ingredient (D) and / or ingredient (E), and other ingredients used as needed) can be produced by mixing. Generally, it is manufactured by adding components (A) to (B) to the component (C) water which is a solvent, preferably containing the component (D) and / or the component (E), and other components used as necessary.
上述混合的順序亦係在不會產生反應或沉澱物等特殊問題之前提下可為任意，洗淨液的構成成分中，係可預先摻合任2成分或3成分以上，其後再混合其餘的成分，亦可一次將所有成分混合。 The order of the above mixing is also arbitrary before mentioning that there are no special problems such as reaction or precipitation. Among the constituents of the cleaning liquid, any two or more components can be blended in advance, and then the rest are mixed. Ingredients, or mix all ingredients at once.
本發明的洗淨液亦可依成為適於洗淨的濃度之方式，調整各成分的濃度而進行製造，就抑制輸送、保管時的成本之觀點而言，大多係製造以高濃度含有各成分的洗淨液(以下有時稱「洗淨原液」)後，利用水稀釋而使用。 The cleaning liquid of the present invention can also be manufactured by adjusting the concentration of each component to a concentration suitable for washing. From the viewpoint of suppressing costs during transportation and storage, most of them are manufactured by containing each component at a high concentration. After using a cleaning solution (hereinafter sometimes referred to as "cleaning solution"), it is diluted with water and used.
洗淨原液的各成分濃度並無特別的限制，較佳係所含有的成分(A)~(C)，以及該等之外較佳的成分(D)及/或成分(E)，以及視需要使用的其他成分及該等的反應物，在洗淨原液中不會分離、或析出的範圍。 The concentration of each component of the washing stock solution is not particularly limited, and it is preferably the components (A) to (C) contained therein, and other preferable components (D) and / or (E), and Other components to be used and such reactants are in a range that will not be separated or precipitated in the washing stock solution.
具體而言，洗淨原液的濃度範圍，較佳係成分(A)為0.01~10質量%、成分(B)為0.01~10質量%、成分(D)為0.01~10質量%。 Specifically, the concentration range of the washing stock solution is preferably that the component (A) is 0.01 to 10% by mass, the component (B) is 0.01 to 10% by mass, and the component (D) is 0.01 to 10% by mass.
若在上述濃度範圍內，則於輸送及保管時，不易引發含有成分的分離，且藉由添加成分(C)的水，可適宜地使用作為適於輕易洗淨之濃度的洗淨液。 When the concentration is within the above-mentioned concentration range, separation of the contained components is unlikely to occur during transportation and storage, and the water containing the component (C) can be suitably used as a cleaning solution having a concentration suitable for easy cleaning.
施行半導體裝置用基板之洗淨時，洗淨液的各成分濃度係配合成為洗淨對象的半導體裝置用基板再行適當決定。 When the semiconductor device substrate is cleaned, the concentration of each component of the cleaning solution is determined in accordance with the semiconductor device substrate that is the object of cleaning.
另外，供洗淨用的洗淨液，係可依對成為洗淨對象的半導體裝置用基板，各成分濃度成為適當者之方式稀釋洗淨原液而製造，亦可依成為該濃度的方式直接調整各成分而製造。 In addition, the cleaning liquid for cleaning can be manufactured by diluting the cleaning stock solution so that the concentration of each component becomes appropriate for the semiconductor device substrate to be cleaned, or it can be adjusted directly as the concentration. Each component.
本發明洗淨液的各成分濃度，即作為洗淨液使用時的本發明洗淨液中之各成分濃度，係如下。 The concentration of each component of the cleaning liquid of the present invention, that is, the concentration of each component in the cleaning liquid of the present invention when used as a cleaning liquid, is as follows.
成分(A)在洗淨液中的濃度較佳係0.0001~1質量%，更佳係0.001~1質量%。若成分(A)的濃度過低，則會有半導體裝置用基盤的污染除去變得不足的情況。即便超過1質量%，除無法獲得更佳的效果之外，會變得更加耗費洗淨液成本。又，若成分(A)的濃度超過1質量%，亦會有引發Cu等金屬佈線腐蝕之類的不良情況。 The concentration of the component (A) in the cleaning solution is preferably 0.0001 to 1% by mass, and more preferably 0.001 to 1% by mass. If the concentration of the component (A) is too low, contamination removal of the substrate for a semiconductor device may become insufficient. Even if it exceeds 1% by mass, in addition to failing to obtain better results, the cost of the cleaning solution becomes more expensive. Further, if the concentration of the component (A) exceeds 1% by mass, problems such as corrosion of metal wiring such as Cu may be caused.
成分(B)在洗淨液中的濃度較佳係0.0001~1質量%，更佳係0.0001~0.5質量%。若成分(B)的濃度達0.0001質量%以上，便可充分發揮其防蝕性。若成分(B)的濃度在1質量%以下，可防止作為殘渣之成分(B)與Cu的不溶性錯合物大量產生的情況，亦可防止基板表面未被洗淨的情況。又，亦可防止引發Cu等金屬佈線腐蝕的不良情況。 The concentration of the component (B) in the cleaning solution is preferably 0.0001 to 1% by mass, and more preferably 0.0001 to 0.5% by mass. When the concentration of the component (B) is 0.0001% by mass or more, its corrosion resistance can be fully exhibited. When the concentration of the component (B) is 1% by mass or less, it is possible to prevent a large amount of insoluble complexes of the component (B) and Cu, which are residues, and prevent the surface of the substrate from being cleaned. In addition, it is also possible to prevent defects that cause corrosion of metal wiring such as Cu.
另外，本發明的洗淨液中，為了更有效發揮因成分(A)螯合劑與成分(B)的共存而造成的防蝕性及洗淨性之效果，成分(A)與成分(B)係依質量比使用成分(A)：成分(B)=1：0.01~100，較佳係1：0.1~50之範圍。 In addition, in the cleaning liquid of the present invention, in order to more effectively exert the effects of the corrosion prevention and cleaning properties caused by the coexistence of the chelating agent of the component (A) and the component (B), the component (A) and the component (B) are The component (A) is used in accordance with the mass ratio: the component (B) = 1: 0.01 to 100, preferably in the range of 1: 0.1 to 50.
成分(D)界面活性劑在洗淨液中的濃度較佳係0.0001~1 質量%，更佳係0.0003~0.1質量%，特佳係0.001~0.1質量%。若成分(D)的濃度過低，則有界面活性劑的添加效果變得不足之情況，即便成分(D)的濃度過高，亦無法獲得更佳的效果，而有發生過度起泡、或增加廢液處理負擔的情況。 The concentration of the component (D) surfactant in the cleaning solution is preferably 0.0001 to 1 Mass%, more preferably 0.0003 to 0.1% by mass, and particularly good 0.001 to 0.1% by mass. If the concentration of the component (D) is too low, the effect of adding a surfactant may be insufficient. Even if the concentration of the component (D) is too high, a better effect may not be obtained, and excessive foaming may occur, or Increasing the burden of waste liquid treatment.
本發明半導體裝置用基板之洗淨方法(以下有時稱「本發明之洗淨方法」)，係如下。 The method for cleaning a substrate for a semiconductor device of the present invention (hereinafter sometimes referred to as the "cleaning method of the present invention") is as follows.
本發明的洗淨方法係利用使上述本發明洗淨液，直接接觸半導體裝置用基板的方法而實施。 The cleaning method of the present invention is implemented by a method in which the cleaning solution of the present invention is brought into direct contact with a substrate for a semiconductor device.
成為洗淨對象的半導體裝置用基板係可列舉例如：半導體、玻璃、金屬、陶瓷、樹脂、磁性體及超導體等各種半導體裝置用基板。 Examples of substrates for semiconductor devices to be cleaned include various semiconductor device substrates such as semiconductors, glass, metals, ceramics, resins, magnetic bodies, and superconductors.
若使用本發明的洗淨液，由於短時間的沖洗便可洗淨，因而對於作為佈線等於表面上具有金屬或金屬化合物的半導體裝置用基板特別適宜，特別適宜於表面上具有Cu佈線的半導體裝置用基板。 If the cleaning solution of the present invention is used, it can be cleaned in a short time. Therefore, it is particularly suitable as a substrate for a semiconductor device having a wiring having a metal or a metal compound on the surface, and particularly suitable for a semiconductor device having a Cu wiring on the surface With substrate.
此處半導體裝置用基板所使用的上述金屬，係可列舉例如：W、Cu、Ti、Cr、Co、Zr、Hf、Mo、Ru、Au、Pt及Ag等。金屬化合物係可列舉例如上述金屬的氮化物、氧化物及矽化物等。特別係Cu及含有該等的化合物屬於較適宜的洗淨對象。 Examples of the metal used in the substrate for a semiconductor device include W, Cu, Ti, Cr, Co, Zr, Hf, Mo, Ru, Au, Pt, and Ag. Examples of the metal compound system include nitrides, oxides, and silicides of the above metals. In particular, Cu and compounds containing these are suitable cleaning targets.
再者，本發明的洗淨方法係即便對於疏水性強的低介電常數絕緣材料亦具有高的洗淨效果，因而亦適宜於具有低介電常數絕緣材料的半導體裝置用基板。 Furthermore, the cleaning method of the present invention has a high cleaning effect even on a low-dielectric-constant insulating material having high hydrophobicity, and is therefore suitable for a substrate for a semiconductor device having a low-dielectric-constant insulating material.
此種低介電常數材料係可列舉例如：Polyimide(聚亞醯胺)、BCB(Benzocyclobutene，苯并環丁烯)、Flare(Honeywell公司)及 SiLK(Dow Chemical公司)等有機聚合物材料；FSG(Fluorinated silicate glass，氟化矽酸鹽玻璃)等無機聚合物材料；BLACK DIAMOND(黑鑽)(Applied Materials公司)及Aurora(日本ASM公司)等SiOC系材料。 Examples of such a low dielectric constant material system include: Polyimide (Polyimide), BCB (Benzocyclobutene, benzocyclobutene), Flare (Honeywell), and Organic polymer materials such as SiLK (Dow Chemical); inorganic polymer materials such as FSG (Fluorinated silicate glass); BLACK DIAMOND (Applied Materials) and Aurora (Japan ASM) SiOC-based materials.
此處，本發明的洗淨方法特別適宜於半導體裝置用基板係在基板表面上具有Cu佈線與低介電常數絕緣膜，且對經CMP處理後的基板施行洗淨之情況。 Here, the cleaning method of the present invention is particularly suitable when the substrate for a semiconductor device has a Cu wiring and a low dielectric constant insulating film on the surface of the substrate, and the substrate after CMP treatment is cleaned.
CMP步驟係使用研磨劑，將基板在墊上搓擦而施行研磨。 In the CMP step, the substrate is polished by rubbing the substrate with a polishing agent.
研磨劑中係含有例如：膠體二氧化矽(SiO2)、燻矽(SiO2)、氧化鋁(Al2O3)及氧化鈰(CeO2)等研磨粒子。該研磨粒子雖會成為半導體裝置用基板的微粒子污染之主因，但本發明的洗淨液會將在基板上所附著之微粒子除去，並使分散於洗淨液中，且具有防止再附著的作用，因而對於微粒子污染的除去呈現高效果。 The abrasive contains abrasive particles such as colloidal silicon dioxide (SiO 2 ), fumed silica (SiO 2 ), aluminum oxide (Al 2 O 3 ), and cerium oxide (CeO 2 ). Although the abrasive particles may be a major cause of contamination of fine particles on a substrate for a semiconductor device, the cleaning liquid of the present invention removes the fine particles adhering to the substrate, disperses them in the cleaning liquid, and has a function of preventing re-adhesion. Therefore, it exhibits a high effect on the removal of particulate contamination.
再者，研磨劑中含有氧化劑及分散劑等研磨粒子以外的添加劑。特別係在表面上具有作為金屬佈線的Cu膜之半導體裝置用基板，在CMP研磨時由於Cu膜較容易腐蝕，因而大多添加有防蝕劑。 The abrasive contains additives other than abrasive particles such as an oxidizing agent and a dispersant. In particular, a substrate for a semiconductor device having a Cu film as a metal wiring on the surface thereof. Since the Cu film is easily corroded during CMP polishing, an anticorrosive agent is often added.
作為防蝕劑而使用者較佳係防蝕效果高的唑系防蝕劑。更具體而言，作為含有雜原子僅為氮原子的雜環者係可列舉例如：二唑系、***系及四唑系；作為含有氮原子及氧原子的雜環者係可列舉例如：唑系、異唑系及二唑系；作為含有氮原子及硫原子的雜環者係可列舉例如：噻唑系、異噻唑系及噻二唑系。特佳係防蝕效果優異的苯并***(BTA)系防蝕劑。 As the corrosion inhibitor, the user is preferably an azole-based corrosion inhibitor having a high corrosion resistance. More specifically, examples of the heterocyclic ring system containing a hetero atom containing only a nitrogen atom include diazole, triazole, and tetrazole systems; and examples of the heterocyclic ring system containing a nitrogen atom and oxygen atom include: Azole, iso Azole series and Diazole system; Examples of the heterocyclic system containing a nitrogen atom and a sulfur atom include a thiazole system, an isothiazole system, and a thiadiazole system. A benzotriazole (BTA) corrosion inhibitor with excellent corrosion resistance.
本發明的洗淨液係若使用於利用含有上述防蝕劑的研磨劑施行研磨後之基板表面，就可極有效去除源自該等防蝕劑的污染 之觀點而言，係屬優異。 If the cleaning liquid of the present invention is used on the surface of a substrate that has been polished with an abrasive containing the above-mentioned corrosion inhibitor, the pollution from these corrosion inhibitors can be effectively removed. From a viewpoint, it is excellent.
即，若研磨劑中存在有該等防蝕劑，雖能抑制Cu膜表面之腐蝕，但另一方面會與在研磨時溶出的Cu離子產生反應，生成大量的不溶性析出物。本發明的洗淨液可有效率地溶解除去上述不溶性析出物，且利用短時間的沖洗便可除去在金屬表面上容易殘留的界面活性劑，而可提升產能。 That is, if such an anticorrosive agent is present in the polishing agent, although the corrosion of the surface of the Cu film can be suppressed, on the other hand, it will react with Cu ions eluted during polishing to generate a large amount of insoluble precipitates. The cleaning liquid of the present invention can efficiently dissolve and remove the insoluble precipitates described above, and can easily remove the surfactant remaining on the metal surface by short-time washing, thereby improving the productivity.
因此，本發明的洗淨方法係適宜於將Cu膜與低介電常數絕緣膜共存的表面，施行CMP處理後的半導體裝置用基板之洗淨，特別適宜於經利用摻入唑系防蝕劑的研磨劑，施行CMP處理過的上述基板之洗淨。 Therefore, the cleaning method of the present invention is suitable for cleaning the surface of a Cu film and a low-dielectric-constant insulating film coexisting with the semiconductor device substrate after the CMP treatment, and is particularly suitable for the use of azole-based corrosion inhibitors. The polishing agent is used to clean the substrate after the CMP treatment.
如上述本發明的洗淨方法，係利用使本發明洗淨液直接接觸半導體裝置用基板的方法實施。另外，配合成為洗淨對象的半導體裝置用基板種類，選擇適宜成分濃度的洗淨液。 As described above, the cleaning method of the present invention is implemented by a method of directly bringing the cleaning solution of the present invention into contact with a substrate for a semiconductor device. In addition, a cleaning liquid having an appropriate component concentration is selected in accordance with the type of the semiconductor device substrate to be cleaned.
洗淨液對基板的接觸方法係可列舉例如：在洗淨槽中裝滿洗淨液再浸漬基板的浸漬式；一邊從噴嘴朝基板上流出洗淨液一邊使基板高速旋轉的旋轉式；及朝基板噴霧出洗淨液而施行洗淨的噴霧式等。作為施行上述洗淨用的裝置，係例如：將收容盒中所收容之複數片基板同時施行洗淨的批次式洗淨裝置，以及將1片基板安裝於支架上而施行洗淨的單片式洗淨裝置等。 Examples of the method for contacting the cleaning solution with the substrate include: an immersion method in which a cleaning tank is filled with the cleaning solution and then immersing the substrate; a rotary method in which the substrate is rotated at a high speed while the cleaning solution flows out of the nozzle onto the substrate; A cleaning method such as spraying a cleaning solution onto a substrate is performed. As the device for performing the above cleaning, for example, a batch-type cleaning device that simultaneously cleans a plurality of substrates contained in a storage box, and a single piece that is mounted on a bracket to perform cleaning Type washing device.
本發明的洗淨液係可適用於上述任何方法，但就利用短時間便可更有效率去除污染的觀點而言，較佳係使用旋轉式及噴霧式洗淨。在此情況下，若適用於期待縮短洗淨時間及削減洗淨液使用量的單片式洗淨裝置，便可解決上述問題，故屬較佳。 The cleaning liquid system of the present invention can be applied to any of the above methods, but from the viewpoint of more efficient removal of contamination in a short period of time, it is preferable to use rotary and spray cleaning. In this case, if it is applied to a single-piece cleaning device that is expected to shorten the cleaning time and reduce the amount of cleaning liquid used, the above problems can be solved, which is preferable.
再者，本發明的洗淨方法若併用利用物理力的洗淨方 法，特別係使用清洗刷的洗滌洗淨、或頻率0.5百萬赫茲以上的超音波洗淨，便可更加提升因基板上所附著之微粒子而造成之污染的除去性，亦關聯於洗淨時間的縮短，故屬較佳。特別係在CMP後的洗淨，較佳係使用樹脂製刷施行洗滌洗淨。樹脂製刷的材質係可任意選擇，較佳係使用例如PVA(聚乙烯醇)。又，在利用本發明洗淨方法進行洗淨的前及/或後，亦可利用水施行洗淨。 Furthermore, if the washing method of the present invention is used in combination with a washing method using physical force The method, especially the cleaning using a cleaning brush, or the ultrasonic cleaning with a frequency above 0.5 megahertz, can further improve the removability of contamination caused by the particles attached to the substrate, and it is also related to the cleaning time. Shortened, it is better. In particular, the washing is performed after CMP, and the washing and washing are preferably performed using a resin brush. The material of the resin brush can be arbitrarily selected, and for example, PVA (polyvinyl alcohol) is preferably used. Moreover, before and / or after washing | cleaning by the washing method of this invention, you may wash with water.
本發明的洗淨方法中，洗淨液的溫度通常係室溫便可，但在不損及性能的範圍內，亦可加溫至40~70℃左右。 In the cleaning method of the present invention, the temperature of the cleaning solution is usually room temperature, but it can also be heated to about 40 to 70 ° C. within a range that does not impair performance.
以下，利用實施例針對本發明進行更詳細地說明，惟本發明在不變更其主旨的前提下，並不侷限於以下之實施例。 Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to the following examples without changing the gist thereof.
將作為成分(A)螯合劑的0.5質量%檸檬酸、作為成分(B)化合物的0.5質量%1,3-二胺基丙烷、成分(C)的水、作為成分(D)界面活性劑的0.5質量%十二烷基苯磺酸(DBS)、及作為成分(E)pH調整劑的5質量%氫氧化雙(2-羥乙基)二甲銨(AH212、四日市合成股份有限公司)予以混合，調製成表1所示組成的實施例1之半導體裝置用基板洗淨液的原液。接著，在該洗淨液原液中添加水稀釋為40倍，便調製得實施例1的洗淨液(稀釋液)。 0.5% by mass of citric acid as a chelating agent of component (A), 0.5% by mass of 1,3-diaminopropane as a compound of component (B), water of component (C), and surfactant of component (D) 0.5% by mass of dodecylbenzenesulfonic acid (DBS) and 5% by mass of bis (2-hydroxyethyl) dimethylammonium hydroxide (AH212, Yokkaichi Synthesis Co., Ltd.) as a component (E) pH adjuster Mix and prepare a stock solution of the substrate cleaning liquid for a semiconductor device of Example 1 having the composition shown in Table 1. Next, water was added to this washing liquid stock solution and diluted 40-fold, and the washing liquid (diluent) of Example 1 was prepared.
將經稀釋40倍的洗淨液，一邊使用電磁攪拌器施行攪拌，一邊利 用pH計(堀場製作所(股)「D-24」)施行pH測定。測定樣品係在恆溫槽中，將液溫保持在25℃。將測定結果示於表1。 The washing liquid diluted 40 times was stirred while using an electromagnetic stirrer. The pH measurement was performed using a pH meter (Horiba Seisakusho Co., Ltd. "D-24"). The measurement sample was placed in a thermostatic bath, and the liquid temperature was kept at 25 ° C. The measurement results are shown in Table 1.
準備將含有線寬/線距=180nm/180nm之Cu佈線梳齒形圖案的圖案基板(SEMATECH854)，切斷為1cm方塊者，在經稀釋為40倍的洗淨液中，於40℃下浸漬30分鐘。取出浸漬後的基板並馬上利用超純水洗淨，再利用送風使乾燥。 Prepare a pattern substrate (SEMATECH854) containing Cu wiring comb-tooth pattern with line width / space = 180nm / 180nm, cut into 1cm squares, and dip it in a washing solution diluted 40 times at 40 ° 30 minutes. The immersed substrate was taken out and immediately washed with ultrapure water, and then dried by air supply.
經浸漬結束的基板利用場發射掃描式電子顯微鏡(日本電子股份有限公司製「JSM-6320F」)觀察，施行防蝕性評價。另外，防蝕性係利用Cu佈線圖案的腐蝕進行情況判斷，依據以下的評價基準進行評價。將評價結果示於表1。 The substrate after the immersion was observed with a field emission scanning electron microscope ("JSM-6320F" manufactured by Japan Electronics Co., Ltd.), and corrosion resistance was evaluated. In addition, the corrosion resistance was judged by the corrosion of the Cu wiring pattern, and was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 1.
○：未發現有腐蝕。 ○: No corrosion was found.
×：發現有腐蝕。 ×: Corrosion was found.
再者，圖1所示係在實施例1的洗淨液(稀釋液)中浸漬30分鐘後的圖案化基板之SEM照片。 In addition, FIG. 1 is a SEM photograph of the patterned substrate after being immersed in the cleaning solution (diluent) of Example 1 for 30 minutes.
將利用PVD製膜的銅種子基板(市售品)裁剪為2.5cm方塊。利用X射線螢光分析儀(XRF)(日本電子(股)R1X-3000)測定經切斷的基板之銅膜厚(nm)。使該銅基板在洗淨液(稀釋液)中浸漬120分鐘。浸漬後的基板利用超純水充分沖洗，再利用送風使乾燥後，再度利用XRF測定銅膜厚(nm)。蝕刻速率係依下述(5)式計算出。 A copper seed substrate (commercial product) formed by PVD film was cut into 2.5 cm squares. The thickness of the copper film (nm) of the cut substrate was measured by an X-ray fluorescence analyzer (XRF) (Japan Electronics Co., Ltd. R1X-3000). This copper substrate was immersed in a cleaning solution (diluent) for 120 minutes. After the immersion, the substrate was sufficiently rinsed with ultrapure water, and then dried by blowing air, and the copper film thickness (nm) was measured again by XRF. The etching rate is calculated by the following formula (5).
[(浸漬前的膜厚(nm))-(浸漬後的膜厚(nm))]/120分 (5) [(Film thickness (nm) before immersion)-(Film thickness (nm) after immersion)] / 120 minutes (5)
將評價結果示於表1。 The evaluation results are shown in Table 1.
在利用PVD法使Cu膜成膜的矽基板(Advantech(股))上，注入0.1質量%苯并***水溶液200mL，接著注入0.01質量%膠體二氧化矽水溶液(扶桑化學(股)「PL-10H」)200mL，接著注入超純水1L後，將基板利用「複旋轉機KSSP-201」(KAIJO(股))，使用上述經稀釋40倍的洗淨液施行洗淨後，利用晶圓表面檢查裝置「LS-6600」(日立高科技(股))調查0.23μm以上的缺陷數。將評價結果示於表1。 200 mL of a 0.1% by mass benzotriazole aqueous solution was injected onto a silicon substrate (Advantech (stock)) where a Cu film was formed by the PVD method, and then a 0.01% by mass colloidal silicon dioxide aqueous solution (Fusang Chemical Co., Ltd. "PL- 10H ") 200mL, followed by injecting 1L of ultrapure water, the substrate was cleaned with a" multi-rotor KSSP-201 "(KAIJO (shares)) using the cleaning solution diluted 40 times, and then the wafer surface was used. The inspection device "LS-6600" (Hitachi Hi-Tech Co., Ltd.) investigates the number of defects above 0.23 μm. The evaluation results are shown in Table 1.
將作為成分(A)螯合劑的0.05質量%伸乙二胺、作為成分(B)的0.5質量%1,3-二胺基丙烷、成分(C)的水、作為成分(D)界面活性劑的0.5質量%十二烷基苯磺酸(DBS)、及作為成分(E)pH調整劑的8質量%氫氧化四乙銨(TEAH)予以混合，調製成表1所示組成的實施例2之半導體裝置用基板洗淨液的原液。接著，在該洗淨液原液中添加水稀釋為40倍，便調製得實施例2的洗淨液(稀釋液)。 0.05% by mass of ethylenediamine as the chelating agent of component (A), 0.5% by mass of 1,3-diaminopropane as component (B), water of component (C), and surfactant as component (D) 0.5% by mass of dodecylbenzenesulfonic acid (DBS) and 8% by mass of tetraethylammonium hydroxide (TEAH) as a component (E) pH adjuster were mixed to prepare Example 2 having a composition shown in Table 1. Stock solution of substrate cleaning solution for semiconductor devices. Next, water was added to this washing liquid stock solution and diluted 40-fold, and the washing liquid (diluent) of Example 2 was prepared.
針對該洗淨液，將施行與實施例1同樣評價的結果示於表1。 Table 1 shows the results of the same evaluation as in Example 1 for this cleaning solution.
再者，圖2所示係在實施例2的洗淨液(稀釋液)中浸漬30分鐘後的圖案化基板之SEM照片。 In addition, FIG. 2 is an SEM photograph of the patterned substrate after being immersed in the cleaning solution (diluent) of Example 2 for 30 minutes.
將作為成分(A)螯合劑的0.5質量%檸檬酸、作為成分(B)的0.5質 量%1,3-二胺基丁烷、成分(C)的水、作為成分(D)界面活性劑的0.5質量%十二烷基苯磺酸(DBS)、及作為成分(E)pH調整劑的8質量%氫氧化四乙銨(TEAH)予以混合，調製成表1所示組成的實施例3之半導體裝置用基板洗淨液的原液。接著，在該洗淨液原液中添加水稀釋為40倍，便調製得實施例3的洗淨液(稀釋液)。 0.5% by mass of citric acid as the chelating agent of the component (A) and 0.5% by mass of the citric acid as the component (B) Amount of 1,3-diaminobutane, water of component (C), 0.5% by mass of dodecylbenzenesulfonic acid (DBS) as component (D) surfactant, and pH adjustment as component (E) 8 mass% of tetraethylammonium hydroxide (TEAH) of the agent was mixed to prepare a stock solution of a substrate cleaning solution for a semiconductor device of Example 3 having a composition shown in Table 1. Next, water was added to this washing liquid stock solution and diluted 40-fold, and the washing liquid (diluent) of Example 3 was prepared.
針對該洗淨液，將施行與實施例1同樣評價的結果示於表1。 Table 1 shows the results of the same evaluation as in Example 1 for this cleaning solution.
再者，圖3所示係在實施例3的洗淨液(稀釋液)中浸漬30分鐘後的圖案化基板之SEM照片。 3 is a SEM photograph of the patterned substrate after being immersed in the cleaning solution (diluent) of Example 3 for 30 minutes.
將作為成分(A)螯合劑的0.05質量%伸乙二胺、作為成分(B)的0.5質量%1,3-二胺基戊烷、成分(C)的水、作為成分(D)界面活性劑的0.5質量%十二烷基苯磺酸(DBS)、及作為成分(E)pH調整劑的8質量%氫氧化四乙銨(TEAH)予以混合，調製成表1所示組成的實施例4之半導體裝置用基板洗淨液的原液。接著，在該洗淨液原液中添加水稀釋為40倍，便調製得實施例4的洗淨液(稀釋液)。 0.05% by mass of ethylenediamine as the chelating agent of component (A), 0.5% by mass of 1,3-diaminopentane as component (B), water of component (C), and interface activity as component (D) 0.5% by mass of dodecylbenzenesulfonic acid (DBS) and 8% by mass of tetraethylammonium hydroxide (TEAH) as a component (E) pH adjuster were mixed to prepare an example having the composition shown in Table 1. Stock solution of substrate cleaning liquid for semiconductor device 4. Next, water was added to this washing liquid stock solution and diluted 40-fold, and the washing liquid (diluent) of Example 4 was prepared.
針對該洗淨液，將施行與實施例1同樣評價的結果示於表1。 Table 1 shows the results of the same evaluation as in Example 1 for this cleaning solution.
再者，圖4所示係在實施例4的洗淨液(稀釋液)中浸漬30分鐘後的圖案化基板之SEM照片。 In addition, FIG. 4 is an SEM photograph of the patterned substrate after being immersed in the cleaning solution (diluent) of Example 4 for 30 minutes.
將作為成分(D)界面活性劑的0.5質量%十二烷基苯磺酸(DBS)、作為成分(E)pH調整劑的8質量%氫氧化四乙銨(TEAH)、及成分(C)的水予以混合，調製成表1所示組成的比較例1之半導體裝置用基板洗淨 液的原液。接著，在該洗淨液原液中添加水稀釋為40倍，便調製得比較例1的洗淨液(稀釋液)。 0.5% by mass of dodecylbenzenesulfonic acid (DBS) as the component (D) surfactant, 8% by mass of tetraethylammonium hydroxide (TEAH) as the component (E) pH adjuster, and component (C) Water was mixed to prepare a substrate for a semiconductor device of Comparative Example 1 having a composition shown in Table 1. Liquid stock solution. Next, the washing liquid stock solution was diluted by 40 times by adding water to prepare a washing liquid (diluent) of Comparative Example 1.
針對該洗淨液，將施行與實施例1同樣評價的結果示於表1。 Table 1 shows the results of the same evaluation as in Example 1 for this cleaning solution.
再者，圖5所示係在比較例1的洗淨液(稀釋液)中浸漬30分鐘後的圖案化基板之SEM照片。 5 is a SEM photograph of the patterned substrate after being immersed in the cleaning solution (diluent) of Comparative Example 1 for 30 minutes.
將作為成分(A)螯合劑的0.05質量%伸乙二胺、成分(C)的水、作為成分(D)界面活性劑的0.5質量%十二烷基苯磺酸(DBS)、及作為成分(E)pH調整劑的8質量%氫氧化四乙銨(TEAH)予以混合，調製成表1所示組成的比較例2之半導體裝置用基板洗淨液的原液。接著，在該洗淨液原液中添加水稀釋為40倍，便調製得比較例2的洗淨液(稀釋液)。 0.05% by mass of ethylenediamine as component (A) chelating agent, water of component (C), 0.5% by mass of dodecylbenzenesulfonic acid (DBS) as component (D) surfactant, and as components (E) 8% by mass of tetraethylammonium hydroxide (TEAH) as a pH adjuster was mixed to prepare a stock solution of a semiconductor device substrate cleaning solution of Comparative Example 2 having a composition shown in Table 1. Next, water was added to this washing liquid stock solution and diluted 40-fold to prepare a washing liquid (diluent) of Comparative Example 2.
針對該洗淨液，將施行與實施例1同樣評價的結果示於表1。 Table 1 shows the results of the same evaluation as in Example 1 for this cleaning solution.
再者，圖6所示係在比較例2的洗淨液(稀釋液)中浸漬30分鐘後的圖案化基板之SEM照片。 6 is a SEM photograph of the patterned substrate after being immersed in the cleaning solution (diluent) of Comparative Example 2 for 30 minutes.
將作為成分(A)螯合劑的0.05質量%伸乙二胺、成分(C)的水、作為成分(D)界面活性劑的0.5質量%十二烷基苯磺酸(DBS)、以及作為成分(E)pH調整劑的8質量%氫氧化四乙銨(TEAH)與0.5質量%的1,2-二胺基丙烷予以混合，調製成表1所示組成的比較例3之半導體裝置用基板洗淨液的原液。接著，在該洗淨液原液中添加水稀釋為40倍，便調製得比較例3的洗淨液(稀釋液)。 0.05% by mass of ethylenediamine as component (A) chelating agent, water of component (C), 0.5% by mass of dodecylbenzenesulfonic acid (DBS) as component (D) surfactant, and as components (E) 8% by mass of tetraethylammonium hydroxide (TEAH) as a pH adjuster and 0.5% by mass of 1,2-diaminopropane were mixed to prepare a substrate for a semiconductor device of Comparative Example 3 having a composition shown in Table 1. Stock solution of washing liquid. Next, water was added to this washing liquid stock solution and diluted 40-fold to prepare a washing liquid (diluent) of Comparative Example 3.
針對該洗淨液，將施行與實施例1同樣評價的結果示於表1。 Table 1 shows the results of the same evaluation as in Example 1 for this cleaning solution.
再者，圖7所示係在比較例3的洗淨液(稀釋液)中浸漬30分鐘後的圖案化基板之SEM照片。 7 is a SEM photograph of the patterned substrate after being immersed in the cleaning solution (diluent) of Comparative Example 3 for 30 minutes.
將作為成分(B)的0.5質量%1,3-二胺基丙烷、成分(C)的水、作為成分(D)界面活性劑的0.5質量%十二烷基苯磺酸(DBS)、作為成分(E)pH調整劑的5質量%氫氧化雙(2-羥乙基)二甲銨(AH212、四日市合成股份有限公司)予以混合，調製成表1所示組成的比較例4之半導體裝置用基板洗淨液的原液。接著，在該洗淨液原液中添加水稀釋為40倍，便調製得比較例4的洗淨液(稀釋液)。 0.5% by mass of 1,3-diaminopropane as component (B), water of component (C), and 0.5% by mass of dodecylbenzenesulfonic acid (DBS) as component (D) surfactant, as 5 mass% bis (2-hydroxyethyl) dimethylammonium hydroxide (AH212, Yokkaichi Synthetic Co., Ltd.) of the component (E) pH adjuster was mixed and prepared into a semiconductor device of Comparative Example 4 having the composition shown in Table 1. Stock solution of substrate washing liquid. Next, water was added to this washing liquid stock solution and diluted 40-fold to prepare a washing liquid (diluent) of Comparative Example 4.
針對該洗淨液，將施行與實施例1同樣評價的結果示於表1。 Table 1 shows the results of the same evaluation as in Example 1 for this cleaning solution.
再者，圖8所示係在比較例4的洗淨液(稀釋液)中浸漬30分鐘後的圖案化基板之SEM照片。 8 is a SEM photograph of the patterned substrate after being immersed in the cleaning solution (diluent) of Comparative Example 4 for 30 minutes.
另外，實施例1~實施例4、比較例1~比較例4各洗淨液原液中所含成分(C)水的量，係各洗淨液原液中所含成分(C)以外的成分含有量(質量%)的其餘部分(質量%)。 In addition, the amounts of the component (C) water contained in each of the cleaning solution stock solutions of Examples 1 to 4, and Comparative Examples 1 to 4 are those other than the component (C) contained in each cleaning solution stock solution. Amount (mass%) of the remainder (mass%).
實施例1至實施例4的洗淨液，藉由成分(A)與成分(B)的摻合，基板上並沒有二胺基烷殘留，且Cu佈線並沒有發現有腐蝕。由該等結果可確認，實施例1至實施例4藉由選擇適度強度與量的成分(A)螯合劑、與呈現適度強度防蝕性的成分(B)化合物，便可適當地發揮本發明之效果。 In the cleaning liquids of Examples 1 to 4, by blending the component (A) and the component (B), no diaminoalkane remained on the substrate, and no corrosion was found in the Cu wiring. From these results, it was confirmed that Examples 1 to 4 can appropriately exert the present invention by selecting a component (A) chelating agent having a suitable strength and amount and a component (B) compound having a moderate strength and corrosion resistance. effect.
另一方面，比較例1並未含成分(A)螯合劑與成分(B)二胺基烷，得知Cu佈線表面粗糙。 On the other hand, Comparative Example 1 did not contain the component (A) chelating agent and component (B) diaminoalkane, and found that the surface of the Cu wiring was rough.
比較例2中，並未含有成分(B)化合物，會因成分(A)螯合劑的作用而導致Cu佈線溶解，發現有明顯的腐蝕。 In Comparative Example 2, the compound of component (B) was not contained, and the Cu wiring was dissolved by the action of the chelating agent of component (A), and significant corrosion was found.
比較例3中，相較於成分(B)之下，使用一般式NH2-(CX1X2)n-NH2，n=2、且X1、X2中之其中一者為氫原子、而另一者為甲基的1,2-二胺基丙烷，並未發揮充分的防蝕性，銅佈線發現有明顯的腐蝕。 In Comparative Example 3, compared with the component (B), the general formula NH 2- (CX 1 X 2 ) n -NH 2 is used , n = 2, and one of X 1 and X 2 is a hydrogen atom. The other is methyl 1,2-diaminopropane, which does not exhibit sufficient corrosion resistance, and obvious corrosion was found in the copper wiring.
比較例4中並未含有成分(A)，未發揮充分的防蝕性，銅佈線發現有明顯的腐蝕。 Comparative Example 4 did not contain component (A), did not exhibit sufficient corrosion resistance, and noticeable corrosion was found in the copper wiring.
由以上的結果得知，藉由使用本發明的洗淨液，便可在不致引發Cu佈線腐蝕的情況下，施行有效果的洗淨，且藉由Cu佈線表面的防蝕，便可達半導體裝置用基板的優異洗淨效果。 From the above results, it is known that by using the cleaning liquid of the present invention, effective cleaning can be performed without causing corrosion of the Cu wiring, and the semiconductor device can be reached by the corrosion prevention of the surface of the Cu wiring. Excellent cleaning effect with substrate.
本發明的半導體裝置用基板洗淨液係可在不致使半導體裝置用基板表面引發腐蝕的情況下，施行有效率地洗淨，且由於水沖洗性亦良好，因而本發明半導體裝置或顯示器裝置等的製造步驟 中，作為污染半導體裝置用基板的洗淨處理技術係屬工業性非常有用。 The substrate cleaning liquid for a semiconductor device of the present invention can be efficiently cleaned without causing corrosion on the surface of the substrate for the semiconductor device, and also has good water flushing properties. Therefore, the semiconductor device or display device of the present invention Manufacturing steps Among them, industrial cleaning is very useful as a cleaning treatment technique for contaminated semiconductor device substrates.
雖針對本發明使用特定態樣進行了詳細地說明，惟在不致脫逸本發明意圖與範圍之前提下，可進行各種變更及變化，此係熟習相關技術者可輕易思及。另外，本申請案係以2013年2月6日所提出申請的日本專利申請案(特願2013-021241)為基礎，並爰引其全體內容融入於本案中。 Although the present invention has been described in detail using specific aspects, various changes and modifications can be made without departing from the intention and scope of the present invention, which can be easily considered by those skilled in the relevant art. In addition, this application is based on the Japanese Patent Application (Japanese Patent Application No. 2013-021241) filed on February 6, 2013, and the entire contents of which are incorporated herein.
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| KR101638467B1 (en) * | 2014-10-07 | 2016-07-12 | 한국생산기술연구원 | Composition for cleaning after jet scrubbing process |
| TWI726859B (en) * | 2015-01-05 | 2021-05-11 | 美商恩特葛瑞斯股份有限公司 | Post chemical mechanical polishing formulations and method of use |
| EP3245668B1 (en) * | 2015-01-13 | 2021-06-30 | CMC Materials, Inc. | Cleaning composition and method for cleaning semiconductor wafers after cmp |
| JP6824719B2 (en) * | 2015-12-28 | 2021-02-03 | 花王株式会社 | Cleaning agent composition for removing negative resin mask |
| JP6602720B2 (en) * | 2016-04-04 | 2019-11-06 | グローバルウェーハズ・ジャパン株式会社 | Method for forming protective film on semiconductor substrate |
| JP6847657B2 (en) * | 2016-12-28 | 2021-03-24 | 花王株式会社 | Cleaning agent composition for substrates for semiconductor devices |
| JPWO2018174092A1 (en) | 2017-03-22 | 2020-01-30 | 三菱ケミカル株式会社 | Cleaning solution for substrate for semiconductor device, method for cleaning substrate for semiconductor device, method for manufacturing substrate for semiconductor device, and substrate for semiconductor device |
| US10106705B1 (en) * | 2017-03-29 | 2018-10-23 | Fujifilm Planar Solutions, LLC | Polishing compositions and methods of use thereof |
| US11085011B2 (en) * | 2018-08-28 | 2021-08-10 | Entegris, Inc. | Post CMP cleaning compositions for ceria particles |
| JP7230621B2 (en) * | 2019-03-25 | 2023-03-01 | 三菱ケミカル株式会社 | Semiconductor wafer cleaning method and semiconductor wafer manufacturing method |
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