JP2022161970A - Cleaning liquid for substrate of semiconductor device, cleaning method for substrate of semiconductor device, manufacturing method for substrate of semiconductor device, and substrate for semiconductor device - Google Patents
Cleaning liquid for substrate of semiconductor device, cleaning method for substrate of semiconductor device, manufacturing method for substrate of semiconductor device, and substrate for semiconductor device Download PDFInfo
- Publication number
- JP2022161970A JP2022161970A JP2022128053A JP2022128053A JP2022161970A JP 2022161970 A JP2022161970 A JP 2022161970A JP 2022128053 A JP2022128053 A JP 2022128053A JP 2022128053 A JP2022128053 A JP 2022128053A JP 2022161970 A JP2022161970 A JP 2022161970A
- Authority
- JP
- Japan
- Prior art keywords
- semiconductor device
- component
- cleaning
- mass
- cleaning liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 207
- 239000000758 substrate Substances 0.000 title claims abstract description 178
- 239000004065 semiconductor Substances 0.000 title claims abstract description 129
- 239000007788 liquid Substances 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 11
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 9
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 9
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 64
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 20
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 14
- 238000005498 polishing Methods 0.000 claims description 13
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 12
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 12
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 235000015165 citric acid Nutrition 0.000 claims description 7
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 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 5
- 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 5
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 23
- 239000002184 metal Substances 0.000 abstract description 23
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 46
- 238000011156 evaluation Methods 0.000 description 34
- 230000008569 process Effects 0.000 description 24
- 230000007547 defect Effects 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 12
- 238000011109 contamination Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 238000001139 pH measurement Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000010419 fine particle 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
- -1 hydroxyethyl group Chemical group 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 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
- 230000009471 action Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- RKTGAWJWCNLSFX-UHFFFAOYSA-M bis(2-hydroxyethyl)-dimethylazanium;hydroxide Chemical compound [OH-].OCC[N+](C)(C)CCO RKTGAWJWCNLSFX-UHFFFAOYSA-M 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 2
- 229960001231 choline Drugs 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000002410 histidine derivatives Chemical class 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- LSYBWANTZYUTGJ-UHFFFAOYSA-N 2-[2-(dimethylamino)ethyl-methylamino]ethanol Chemical compound CN(C)CCN(C)CCO LSYBWANTZYUTGJ-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- BDXGMDGYOIWKIF-UHFFFAOYSA-N 2-methylpropane-1,3-diamine Chemical compound NCC(C)CN BDXGMDGYOIWKIF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-MVHIGOERSA-N D-ascorbic acid Chemical compound OC[C@@H](O)[C@@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-MVHIGOERSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical class C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000005441 aurora Substances 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
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 235000010350 erythorbic acid Nutrition 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000004615 ingredient Substances 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
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004904 shortening 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage 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
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 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
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
Description
本発明は、半導体デバイス用基板の洗浄液に関する。また、本発明は、半導体デバイス用基板の洗浄方法、半導体デバイス用基板の製造方法及び半導体デバイス用基板にも関する。 The present invention relates to a cleaning liquid for semiconductor device substrates. The present invention also relates to a method for cleaning a semiconductor device substrate, a method for manufacturing a semiconductor device substrate, and a semiconductor device substrate.
半導体デバイス用基板は、シリコンウェハ基板の上に、配線となる金属膜や層間絶縁膜の堆積層を形成した後に、研磨微粒子を含む水系スラリーからなる研磨剤を使用する化学的機械的研磨（Ｃｈｅｍｉｃａｌ Ｍｅｃｈａｎｉｃａｌ Ｐｏｌｉｓｈｉｎｇ、以下、「ＣＭＰ」と称する。）工程によって表面の平坦化処理を行い、平坦となった面の上に新たな層を積み重ねていくことで製造される。半導体デバイス用基板の微細加工においては、各層における精度の高い平坦性が必要であり、ＣＭＰによる平坦化処理の重要性はますます高まっている。 Semiconductor device substrates are manufactured by chemical mechanical polishing (Chemical Polishing), which uses a polishing agent consisting of a water-based slurry containing polishing fine particles, after forming a deposited layer of a metal film and an interlayer insulating film on a silicon wafer substrate. Mechanical Polishing (hereinafter referred to as "CMP") is used to flatten the surface, and new layers are stacked on the flattened surface. 2. Description of the Related Art In microfabrication of substrates for semiconductor devices, high-precision flatness is required for each layer, and the importance of flattening processing by CMP is increasing more and more.
近年の半導体デバイス製造工程では、デバイスの高速化・高集積化のために抵抗値の低い銅（Ｃｕ）膜からなる配線（Ｃｕ配線）が導入されている。
Ｃｕは加工性がよいため微細加工に適するが、酸成分やアルカリ成分によって影響を受けやすいため、ＣＭＰ工程においてＣｕ配線の腐食や酸化状態の安定性が問題となっている。
2. Description of the Related Art In recent semiconductor device manufacturing processes, wiring (Cu wiring) made of a copper (Cu) film with a low resistance value has been introduced in order to increase the speed and integration of devices.
Cu has good workability and is suitable for microfabrication. However, since Cu is easily affected by acid and alkali components, corrosion of Cu wiring and stability of the oxidation state are problems in the CMP process.
また、ＣＭＰ工程後の半導体デバイス用基板表面には、ＣＭＰ工程で使用されたコロイダルシリカ等の砥粒や、スラリー中に含まれる防食剤由来の有機残渣等が多量に存在する。これらを除去するために、ＣＭＰ工程後の半導体デバイス用基板は洗浄工程に供される。 In addition, a large amount of abrasive grains such as colloidal silica used in the CMP process and organic residues derived from the anticorrosive agent contained in the slurry are present on the surface of the semiconductor device substrate after the CMP process. In order to remove these, the semiconductor device substrate after the CMP process is subjected to a cleaning process.
ＣＭＰ工程後の洗浄においては、酸性の洗浄液又はアルカリ性の洗浄液が用いられている。上記洗浄液の溶媒が共に水である場合、酸性の洗浄液については、その水溶液中で、コロイダルシリカが正に帯電し、基板表面は負に帯電し、電気的な引力が働き、コロイダルシリカの除去は困難となる。これに対し、アルカリ性の洗浄液については、その水溶液中ではＯＨ－が豊富に存在するため、コロイダルシリカと基板表面は共に負に帯電し、電気的な斥力が働き、コロイダルシリカの除去が行いやすくなる。 In cleaning after the CMP process, an acidic cleaning liquid or an alkaline cleaning liquid is used. When the solvent of the cleaning solution is water, colloidal silica is positively charged and the substrate surface is negatively charged in the aqueous solution of the acidic cleaning solution. becomes difficult. On the other hand, with an alkaline cleaning solution, since OH - is abundant in the aqueous solution, both the colloidal silica and the substrate surface are negatively charged, and an electrical repulsive force acts, facilitating the removal of the colloidal silica. .
一方で、Ｃｕは酸性水溶液中ではＣｕ２＋に酸化して液中に溶解するが、アルカリ性水溶液中ではＣｕ２ＯやＣｕＯといった不動態膜を表面に形成する。ＣＭＰ工程後の半導体デバイス用基板表面には、銅が露出していることから、酸性の洗浄液に比べてアルカリ性の洗浄液を用いた方が、ＣＭＰ工程後の洗浄工程における半導体デバイス用基板の銅の腐食を軽減すると考えられている。 On the other hand, Cu is oxidized to Cu 2+ in an acidic aqueous solution and dissolves in the liquid, but forms a passivation film such as Cu 2 O or CuO on the surface in an alkaline aqueous solution. Since copper is exposed on the surface of the semiconductor device substrate after the CMP process, it is better to use an alkaline cleaning liquid than an acidic cleaning liquid to remove copper from the semiconductor device substrate in the cleaning process after the CMP process. It is believed to reduce corrosion.
ここで、半導体デバイス用基板の洗浄液としては、例えば、特許文献１には、（Ａ）キレート剤、（Ｂ）ＮＨ２－Ｒ－ＮＨ２で表される化合物及び（Ｃ）水を含有する、ｐＨが８～１４の半導体デバイス用基板洗浄液が記載されている。 Here, as a cleaning liquid for semiconductor device substrates, for example, Patent Document 1 discloses (A) a chelating agent, (B) a compound represented by NH 2 —R—NH 2 and (C) water. A substrate cleaning liquid for semiconductor devices having a pH of 8 to 14 is described.
また、特許文献２には、（Ａ）ヒスチジン及び／又はヒスチジン誘導体、（Ｂ）アスコルビン酸、（Ｃ）没食子酸及び（Ｄ）水を含有するｐＨが８以上の半導体デバイス用基板洗浄液は、Ｃｕ表面にＣｕ２Ｏの酸化膜が安定的に存在し、Ｃｕ－ＢＴＡ錯体も除去しやすいと記載されている。また、（Ｂ）アスコルビン酸及び（Ｃ）没食子酸を含有せず、（Ａ）ヒスチジン及び/又はヒスチジン誘導体と（Ｄ）水のｐＨ８以上の半導体デバイス用基板の洗浄液は、Ｃｕ表面の酸化膜が不均一となる旨記載されている。 Further, in Patent Document 2, a semiconductor device substrate cleaning liquid having a pH of 8 or more containing (A) histidine and/or histidine derivatives, (B) ascorbic acid, (C) gallic acid and (D) water contains Cu It is described that an oxide film of Cu 2 O stably exists on the surface and that the Cu—BTA complex is also easily removed. In addition, a cleaning solution for semiconductor device substrates containing (B) ascorbic acid and (C) gallic acid and containing (A) histidine and/or histidine derivatives and (D) water with a pH of 8 or higher is used to remove an oxide film on the Cu surface. It is described that it becomes non-uniform.
さらに、特許文献３には、バリアメタル層を有する半導体デバイス用基板の洗浄液であって、半導体デバイス用基板のバリアメタル層がＴａ、Ｔｉ及びＲｕからなる群から選ばれた一つ以上の金属を含み、洗浄液が、ヒスチジン、ｐＨ調整剤及び水を含有し、洗浄液中のヒスチジンの濃度が０．０１２５質量％以上である洗浄液が記載されている。この洗浄液によって、ＣＭＰ工程後の半導体デバイス用基板を洗浄すると、洗浄性と防食性をバランスよく向上できることが記載されている。 Further, Patent Document 3 discloses a cleaning solution for a semiconductor device substrate having a barrier metal layer, wherein the barrier metal layer of the semiconductor device substrate contains one or more metals selected from the group consisting of Ta, Ti and Ru. The cleaning liquid contains histidine, a pH adjuster, and water, and the concentration of histidine in the cleaning liquid is 0.0125% by mass or more. It is described that cleaning a semiconductor device substrate after a CMP process with this cleaning solution can improve cleaning performance and anti-corrosion performance in a well-balanced manner.
特許文献１に代表されるように、アルカリ性の洗浄液は防食性に優れるが、ＣＭＰ工程後の半導体デバイス用基板上に残る有機残差（Ｃｕ－ＢＴＡ）除去に課題があった。一方、特許文献２及び３記載のアルカリ性の洗浄液は、ヒスチジンを含むことによって、ＣＭＰ工程後の半導体デバイス用基板上に残る有機残差（Ｃｕ－ＢＴＡ）を錯化して効率的に除去することが可能となった。 As typified by Patent Document 1, an alkaline cleaning solution has excellent anticorrosion properties, but has a problem in removing organic residue (Cu-BTA) remaining on a semiconductor device substrate after a CMP process. On the other hand, the alkaline cleaning solutions described in Patent Documents 2 and 3 contain histidine to complex and efficiently remove the organic residue (Cu—BTA) remaining on the semiconductor device substrate after the CMP process. It has become possible.
さらに、一般的な半導体デバイス用基板の製造では、ＣＭＰ工程後に行われる洗浄工程後の半導体デバイス用基板は、一定期間（数十分～１日以上）、大気中に放置されることがある。その間に、半導体デバイス用基板上に露出したＣｕ等の金属配線が酸化して微小異物が形成される問題があった。 Furthermore, in the general manufacture of semiconductor device substrates, the semiconductor device substrate after the cleaning process performed after the CMP process may be left in the atmosphere for a certain period of time (several tens of minutes to one day or more). In the meantime, there has been a problem that the metal wiring such as Cu exposed on the semiconductor device substrate is oxidized to form minute foreign matters.
また、特許文献２及び３に記載の半導体デバイス用基板の洗浄液は、上記微小異物の形成の回避と、ＣＭＰ工程後の基板表面上の有機残渣除去の両立という点で十分な機能を有する洗浄液とは言えず、特に、従来のアルカリ系の洗浄液において、これらの両立ができるものは見出されていなかった。 Further, the cleaning liquids for semiconductor device substrates described in Patent Documents 2 and 3 are cleaning liquids having sufficient functions in terms of both avoiding the formation of the above-described minute foreign matter and removing organic residues on the substrate surface after the CMP process. In particular, no conventional alkaline cleaning liquid has been found that can achieve both of these.
かかる状況下、本発明の目的は、半導体デバイス用基板の洗浄工程に用いられ、金属配線の酸化による微小異物の形成を抑制でき、かつ、基板表面上における有機残渣除去力の高い洗浄液を提供することにある。また、本発明の目的は、該洗浄液を用いた半導体デバイス用基板の洗浄方法、半導体デバイス用基板の製造方法及び半導体デバイス用基板を提供することにある。 Under such circumstances, an object of the present invention is to provide a cleaning liquid which is used in the cleaning process of substrates for semiconductor devices, which can suppress the formation of minute foreign matter due to oxidation of metal wiring, and which has a high ability to remove organic residues on the substrate surface. That's what it is. Another object of the present invention is to provide a method for cleaning a semiconductor device substrate using the cleaning liquid, a method for manufacturing a semiconductor device substrate, and a semiconductor device substrate.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、特定成分を含有するアルカリ性の洗浄液による半導体デバイス用基板の洗浄において、Ｃｕが露出している基板表面上に形成されるＣｕＯやＣｕ２Ｏの酸化膜が、上述の大気中での放置による基板表面上の微小異物の形成を制御できる点に着目し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors found that CuO formed on the substrate surface where Cu is exposed during cleaning of a semiconductor device substrate with an alkaline cleaning solution containing a specific component. The inventors have focused on the fact that the oxide film of Cu 2 O or Cu 2 O can control the formation of minute foreign matter on the substrate surface due to the above-described exposure to air, and have completed the present invention.
すなわち、本発明の要旨は以下の［１］～［１５］に存する。
［１］ｐＨが８以上１１．５以下で、以下の成分（Ａ）～（Ｅ）を含有する、半導体デバイス用基板の洗浄液。
成分（Ａ）：下記一般式（１）～（３）で表される化合物からなる群から選ばれる少なくとも１種を含有する化合物
That is, the gist of the present invention resides in the following [1] to [15].
[1] A cleaning liquid for semiconductor device substrates having a pH of 8 or more and 11.5 or less and containing the following components (A) to (E).
Component (A): a compound containing at least one selected from the group consisting of compounds represented by the following general formulas (1) to (3)
上記一般式（１）において、Ｒ１～Ｒ６はそれぞれ独立に水素原子、炭素数１～４のアルキル基、カルボキシル基、カルボニル基又はエステル結合を有する官能基を示す。 In the general formula (1), R 1 to R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group, or a functional group having an ester bond.
上記一般式（２）において、Ｒ１１～Ｒ１７はそれぞれ独立に水素原子、炭素数１～４のアルキル基、カルボキシル基、カルボニル基又はエステル結合を有する官能基を示す。 In the general formula (2), R 11 to R 17 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group, or a functional group having an ester bond.
上記一般式（３）において、Ｒ２１～Ｒ２８はそれぞれ独立に水素原子、炭素数１～４のアルキル基、カルボキシル基、カルボニル基又はエステル結合を有する官能基を示す。
成分（Ｂ）：アスコルビン酸
成分（Ｃ）：ポリカルボン酸又はヒドロキシカルボン酸
成分（Ｄ）：ｐＨ調整剤
成分（Ｅ）：水
［２］前記成分（Ａ）が下記一般式（１）～（２）で表される化合物からなる群から選ばれる少なくとも１種を含有する、［１］に記載の半導体デバイス用基板の洗浄液。
In the general formula (3), R 21 to R 28 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group, or a functional group having an ester bond.
Component (B): Ascorbic acid Component (C): Polycarboxylic acid or hydroxycarboxylic acid Component (D): pH adjuster Component (E): Water [2] The component (A) has the following general formulas (1) to ( 2) The cleaning liquid for semiconductor device substrates according to [1], containing at least one selected from the group consisting of the compounds represented by the following.
上記一般式（１）において、Ｒ１～Ｒ６はそれぞれ独立に水素原子又は炭素数１～４のアルキル基を示す。 In general formula (1) above, R 1 to R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
上記一般式（２）において、Ｒ１１～Ｒ１７はそれぞれ独立に水素原子又は炭素数１～４のアルキル基を示す。
［３］前記成分（Ａ）が、１，２－ジアミノプロパン、１，３－ジアミノプロパン及びＮ－メチル－１，３－ジアミノプロパンからなる群から選ばれる少なくとも１種を含有する、［１］又は［２］に記載の半導体デバイス用基板の洗浄液。
［４］前記成分（Ｃ）が、シュウ酸、クエン酸、酒石酸、リンゴ酸及び乳酸からなる群から選ばれる少なくとも１種を含有する、［１］～［３］のいずれか１つに記載の半導体デバイス用基板の洗浄液。
［５］前記成分（Ｄ）が、アルカリ金属を含む無機アルカリ化合物、アルカリ土類金属を含む無機アルカリ化合物及び下記一般式（４）で表される有機第４級アンモニウム水酸化物からなる群から選ばれる少なくとも１種である、［１］～［４］のいずれか１つに記載の半導体デバイス用基板の洗浄液。
（Ｒ３１）４Ｎ＋ＯＨ－・・・（４）
（上記一般式（４）中、Ｒ３１は、水酸基、アルコキシ基又はハロゲンにて置換されていてもよいアルキル基を示し、４個のＲ３１は、互いに同一でもよく異なっていてもよい。）
［６］前記ｐＨが、１０以上１１以下である、［１］～［５］のいずれか１つに記載の半導体デバイス用基板の洗浄液。
［７］ヒスチジンの含有率が、洗浄液全量１００質量％中、０質量％以上０．０１質量％以下である、［１］～［６］のいずれか１つに記載の半導体デバイス用基板の洗浄液。
［８］前記成分（Ａ）の含有率が、洗浄液全量１００質量％中、０．００１質量％以上２０質量％以下である、［１］～［７］のいずれか１つに記載の半導体デバイス用基板の洗浄液。
［９］前記成分（Ｂ）の含有率が、洗浄液全量１００質量％中、０．００１質量％以上２０質量％以下である、［１］～［８］のいずれか１つに記載の半導体デバイス用基板の洗浄液。
［１０］前記成分（Ｃ）の含有率が、洗浄液全量１００質量％中、０．００１質量％以上１０質量％以下である、［１］～［９］のいずれか１つに記載の半導体デバイス用基板の洗浄液。
［１１］［１］～［１０］のいずれか１つに記載の半導体デバイス用基板の洗浄液を用いて半導体デバイス用基板を洗浄する、半導体デバイス用基板の洗浄方法。
［１２］前記半導体デバイス用基板が、基板表面に銅配線と低誘電率絶縁膜とを含有する、［１１］に記載の半導体デバイス用基板の洗浄方法。
［１３］前記半導体デバイス用基板が、化学的機械的研磨を行った後の基板である、［１１］又は［１２］に記載の半導体デバイス用基板の洗浄方法。
［１４］［１］～［１０］のいずれか１つに記載の半導体デバイス用基板の洗浄液を用いて半導体デバイス用基板を洗浄する工程を含有する、半導体デバイス用基板の製造方法。
［１５］［１］～［１０］のいずれか１つに記載の半導体デバイス用基板の洗浄液を用いて半導体デバイス用基板を洗浄して得られた、半導体デバイス用基板。
In general formula (2) above, R 11 to R 17 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
[3] The component (A) contains at least one selected from the group consisting of 1,2-diaminopropane, 1,3-diaminopropane and N-methyl-1,3-diaminopropane, [1] Or the cleaning liquid for the semiconductor device substrate according to [2].
[4] Any one of [1] to [3], wherein the component (C) contains at least one selected from the group consisting of oxalic acid, citric acid, tartaric acid, malic acid and lactic acid. A cleaning solution for semiconductor device substrates.
[5] The component (D) is selected from the group consisting of an inorganic alkali compound containing an alkali metal, an inorganic alkali compound containing an alkaline earth metal, and an organic quaternary ammonium hydroxide represented by the following general formula (4). The cleaning liquid for semiconductor device substrates according to any one of [1] to [4], which is at least one selected.
(R 31 ) 4 N + OH - (4)
(In general formula (4) above, R 31 represents a hydroxyl group, an alkoxy group, or an alkyl group optionally substituted with halogen, and the four R 31 groups may be the same or different.)
[6] The cleaning liquid for semiconductor device substrates according to any one of [1] to [5], wherein the pH is 10 or more and 11 or less.
[7] The cleaning liquid for semiconductor device substrates according to any one of [1] to [6], wherein the histidine content is 0% by mass or more and 0.01% by mass or less in 100% by mass of the total amount of the cleaning liquid. .
[8] The semiconductor device according to any one of [1] to [7], wherein the content of component (A) is 0.001% by mass or more and 20% by mass or less in 100% by mass of the total amount of the cleaning liquid. substrate cleaning solution.
[9] The semiconductor device according to any one of [1] to [8], wherein the content of component (B) is 0.001% by mass or more and 20% by mass or less in 100% by mass of the total cleaning liquid. substrate cleaning solution.
[10] The semiconductor device according to any one of [1] to [9], wherein the content of component (C) is 0.001% by mass or more and 10% by mass or less in 100% by mass of the total amount of the cleaning liquid. substrate cleaning solution.
[11] A method for cleaning a semiconductor device substrate, comprising cleaning the semiconductor device substrate using the cleaning liquid for semiconductor device substrates according to any one of [1] to [10].
[12] The method for cleaning a semiconductor device substrate according to [11], wherein the semiconductor device substrate contains a copper wiring and a low dielectric constant insulating film on the substrate surface.
[13] The method for cleaning a semiconductor device substrate according to [11] or [12], wherein the semiconductor device substrate is a substrate after chemical mechanical polishing.
[14] A method for manufacturing a semiconductor device substrate, comprising a step of cleaning the semiconductor device substrate using the cleaning liquid for semiconductor device substrates according to any one of [1] to [10].
[15] A semiconductor device substrate obtained by cleaning a semiconductor device substrate with the cleaning liquid for a semiconductor device substrate according to any one of [1] to [10].
本発明の半導体デバイス用基板の洗浄液を用いることにより、半導体デバイス用基板の洗浄工程において、基板上の欠陥を抑制しつつ、洗浄後の基板への微小異物の形成を抑制でき、かつ、基板表面上における有機残渣を除去し、効率的な洗浄を行える。 By using the cleaning solution for semiconductor device substrates of the present invention, it is possible to suppress the formation of minute foreign matter on the substrate after cleaning while suppressing defects on the substrate in the step of cleaning the substrate for semiconductor devices, and to suppress the formation of minute foreign matter on the substrate surface. Removes organic residue on top and provides efficient cleaning.
以下、本発明の実施の形態を具体的に説明するが、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々に変更して実施することができる。 Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and can be carried out with various modifications within the scope of the gist thereof.
＜半導体デバイス用基板の洗浄液＞
本発明の半導体デバイス用基板の洗浄液（以下、「本発明の洗浄液」と称する場合がある。）は、半導体デバイス用基板の洗浄、好ましくは、半導体デバイス製造におけるＣＭＰ工程の後に行われる、半導体デバイス用基板の洗浄工程に用いられる洗浄液であって、ｐＨが８以上１１．５以下で、かつ、以下の成分（Ａ）～（Ｅ）を含有する。
<Washing solution for semiconductor device substrate>
The cleaning liquid for semiconductor device substrates of the present invention (hereinafter sometimes referred to as "the cleaning liquid of the present invention") is used for cleaning semiconductor device substrates, preferably after the CMP process in the manufacture of semiconductor devices. A cleaning solution used in a step of cleaning a substrate for printing, having a pH of 8 or more and 11.5 or less, and containing the following components (A) to (E).
成分（Ａ）：下記一般式（１）～（３）で表される化合物からなる群から選ばれる少なくとも１種を含有する化合物 Component (A): a compound containing at least one selected from the group consisting of compounds represented by the following general formulas (1) to (3)
上記一般式（１）において、Ｒ１～Ｒ６はそれぞれ独立に水素原子、炭素数１～４のアルキル基、カルボキシル基、カルボニル基又はエステル結合を有する官能基を示す。 In the general formula (1), R 1 to R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group, or a functional group having an ester bond.
上記一般式（２）において、Ｒ１１～Ｒ１７はそれぞれ独立に水素原子、炭素数１～４のアルキル基、カルボキシル基、カルボニル基又はエステル結合を有する官能基を示す。 In the general formula (2), R 11 to R 17 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group, or a functional group having an ester bond.
上記一般式（３）において、Ｒ２１～Ｒ２８はそれぞれ独立に水素原子、炭素数１～４のアルキル基、カルボキシル基、カルボニル基又はエステル結合を有する官能基を示す。 In the general formula (3), R 21 to R 28 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group, or a functional group having an ester bond.
成分（Ｂ）：アスコルビン酸
成分（Ｃ）：ポリカルボン酸又はヒドロキシカルボン酸
成分（Ｄ）：ｐＨ調整剤
成分（Ｅ）：水
Component (B): Ascorbic acid Component (C): Polycarboxylic acid or hydroxycarboxylic acid Component (D): pH adjuster Component (E): Water
［ヒスチジン］
本発明の洗浄液は、ヒスチジンの含有率が、洗浄液全量１００質量％中、０質量％以上５質量％以下であることが好ましく、０質量％以上０．０５質量％以下であることがより好ましく、０質量％以上０．０１質量％以下であることがさらに好ましい。
[Histidine]
In the cleaning liquid of the present invention, the histidine content is preferably 0% by mass or more and 5% by mass or less, more preferably 0% by mass or more and 0.05% by mass or less, based on 100% by mass of the total amount of the cleaning liquid. More preferably, it is 0% by mass or more and 0.01% by mass or less.
本発明の洗浄液を用いて半導体デバイス用基板を洗浄する際には、その洗浄液中のヒスチジンの含有率は少ない方がよく、０．０１質量％以下であれば、ヒスチジンの影響を大幅に抑制することができる。 When cleaning a semiconductor device substrate using the cleaning solution of the present invention, the content of histidine in the cleaning solution should be as low as possible. be able to.
また、本発明の洗浄液は、ヒスチジンの含有率が、洗浄液全量１００質量％中、０質量％以上０．０１質量％以下であると、ＣＭＰ工程後の半導体デバイス用基板の洗浄に用いても、微小異物が形成されにくくなる。その理由としては以下のことが推測される。 Further, when the cleaning liquid of the present invention has a histidine content of 0% by mass or more and 0.01% by mass or less in 100% by mass of the total amount of the cleaning liquid, It becomes difficult for minute foreign substances to be formed. The reason for this is presumed to be as follows.
ヒスチジンを含む洗浄液をＣＭＰ工程後の半導体デバイス用基板の洗浄に用いると、何らかの理由で、ヒスチジンが基板表面上の銅と強く結合し、基板上の露出した銅表面に残留すると推測される。そして、その結果、半導体デバイス用基板上に露出した銅の表面がヒスチジンで覆われるような形になり、大気中の酸素が、基板上の銅と結合しにくくなっていると推測される。 When a cleaning solution containing histidine is used to clean semiconductor device substrates after the CMP process, it is speculated that for some reason histidine strongly binds to copper on the substrate surface and remains on the exposed copper surface of the substrate. As a result, the surface of the copper exposed on the semiconductor device substrate is covered with histidine, presumably making it difficult for oxygen in the atmosphere to bond with the copper on the substrate.
本来であれば、大気中の酸素が基板表面上の銅と結合し、適切な厚みの酸化被膜を形成できるのであるが、ヒスチジンが一定量以上存在すると上記のような原因で、半導体デバイス用の基板表面上の銅露出部分に形成されるべき酸化膜（ＣｕＯやＣｕ２Ｏ）が形成されにくく、仮に形成したとしてもその酸化膜は薄いものとなっていると推測される。 Originally, oxygen in the atmosphere would combine with copper on the substrate surface to form an oxide film with an appropriate thickness. It is presumed that the oxide film (CuO or Cu 2 O) that should be formed on the copper-exposed portion on the substrate surface is difficult to form, and even if it is formed, the oxide film will be thin.
一方、ヒスチジンの含有率が、洗浄液全量１００質量％中、０質量％以上０．０１質量％以下である洗浄液で半導体デバイス用基板を洗浄すると、銅の酸化膜が形成しやすく、洗浄後大気下で半導体デバイス用基板を保管していても、基板表面上の銅露出部分が著しく酸化することはない。結果として、微小異物の形成は抑制できる。 On the other hand, when a semiconductor device substrate is washed with a cleaning liquid having a histidine content of 0% by mass or more and 0.01% by mass or less in 100% by mass of the total amount of the cleaning liquid, an oxide film of copper is likely to be formed. Even if the substrate for semiconductor devices is stored at room temperature, the exposed copper portion on the surface of the substrate is not significantly oxidized. As a result, the formation of minute foreign matter can be suppressed.
上記の推定メカニズムによれば、洗浄後の半導体デバイス用基板を大気雰囲気に放置した際に、異常酸化が起こるのは、洗浄液の成分として存在する一定量のヒスチジンが、酸化被膜の形成を阻害することが原因である、と推察される。 According to the above presumed mechanism, abnormal oxidation occurs when the semiconductor device substrate after cleaning is left in the air atmosphere because a certain amount of histidine present as a component of the cleaning liquid inhibits the formation of the oxide film. This is presumed to be the cause.
［ｐＨ］
本発明の洗浄液はｐＨが８以上１１．５以下である。洗浄液のｐＨが８以上であることにより、液中のコロイダルシリカ等のゼータ電位を低下させ、基板との電気的な反発力を稼ぐことができる。それにより、微小粒子の除去を容易にすることができ、かつ、除去した微小粒子が洗浄対象である基板表面に再付着することを抑制することができる。
[pH]
The cleaning liquid of the present invention has a pH of 8 or more and 11.5 or less. When the cleaning liquid has a pH of 8 or higher, the zeta potential of colloidal silica or the like in the liquid can be lowered, and the electrical repulsive force with the substrate can be increased. As a result, the microparticles can be easily removed, and the removed microparticles can be prevented from reattaching to the surface of the substrate to be cleaned.
ここで、ゼータ電位をより低下させるためには、本発明の洗浄液は、ｐＨが９以上であることが好ましく、ｐＨが１０以上であることがさらに好ましい。ｐＨを高くすればするほど、Ｃｕ表面が酸化膜で保護されるためエッチングされにくくなる。
また、洗浄性を担保しつつ、腐食を抑えるためには、ｐＨは１１．５以下であることが必要であり、１１．３以下であることが好ましく、１１以下であることがより好ましい。
なお、本発明の洗浄液におけるｐＨは、後述の成分（Ｄ）：ｐＨ調整剤やその他の成分の添加量等により上述のｐＨの範囲に調整することができる。
以下、本発明の洗浄液に含まれる各成分についてその作用と共に詳細に説明する。
Here, in order to further reduce the zeta potential, the cleaning liquid of the present invention preferably has a pH of 9 or higher, more preferably 10 or higher. The higher the pH, the more the Cu surface is protected by an oxide film, making it more difficult to etch.
Further, in order to suppress corrosion while ensuring detergency, the pH must be 11.5 or less, preferably 11.3 or less, and more preferably 11 or less.
The pH of the cleaning solution of the present invention can be adjusted to the pH range described above by adjusting the addition amounts of component (D): a pH adjuster and other components described later.
Hereinafter, each component contained in the cleaning liquid of the present invention will be described in detail together with its action.
［成分（Ａ）］
本発明の洗浄液に含まれる成分（Ａ）は、上述したとおり、上記一般式（１）～（３）で表される化合物からなる群から選ばれる少なくとも１種を含有する化合物である。
[Component (A)]
Component (A) contained in the cleaning liquid of the present invention is, as described above, a compound containing at least one selected from the group consisting of compounds represented by the general formulas (1) to (3).
上記一般式（１）～（３）で表される化合物は、分子内にアミノ基を２つ有する化合物であり、これらの化合物は、半導体デバイス用基板の洗浄液としては、キレート剤として機能する。具体的には、基板表面の金属配線に含まれる、タングステン等の不純物金属や、ＣＭＰ工程で使用されるバリアスラリー中に存在する防食剤と銅との不溶性金属錯体、ナトリウムやカリウム等のアルカリ金属をキレート作用により溶解、除去する作用を有するものである。 The compounds represented by the above general formulas (1) to (3) are compounds having two amino groups in the molecule, and these compounds function as chelating agents in cleaning liquids for semiconductor device substrates. Specifically, impurity metals such as tungsten contained in the metal wiring on the substrate surface, insoluble metal complexes between the anticorrosive agent and copper present in the barrier slurry used in the CMP process, and alkali metals such as sodium and potassium. It has the action of dissolving and removing by chelating action.
上述のように、上記一般式（１）において、Ｒ１～Ｒ６はそれぞれ独立に水素原子、炭素数１～４のアルキル基、カルボキシル基、カルボニル基又はエステル結合を有する官能基を示す。
炭素数１～４のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等が挙げられる。
As described above, in the general formula (1), R 1 to R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group, or a functional group having an ester bond.
Examples of alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group.
好ましくは、Ｒ１～Ｒ６はそれぞれ独立に水素原子又は炭素数１～４のアルキル基を示し、より好ましくは、Ｒ１～Ｒ６はそれぞれ独立に水素原子、メチル基又はエチル基を示し、さらに好ましくは、Ｒ１～Ｒ６はそれぞれ独立に水素原子又はメチル基を示す。 Preferably, R 1 to R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably R 1 to R 6 each independently represent a hydrogen atom, a methyl group or an ethyl group, More preferably, each of R 1 to R 6 independently represents a hydrogen atom or a methyl group.
上述のように、上記一般式（２）において、Ｒ１１～Ｒ１７はそれぞれ独立に水素原子、炭素数１～４のアルキル基、カルボキシル基、カルボニル基又はエステル結合を有する官能基を示す。
炭素数１～４のアルキル基としては、上記と同様である。
As described above, in the general formula (2), R 11 to R 17 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group, or a functional group having an ester bond.
The alkyl group having 1 to 4 carbon atoms is the same as described above.
好ましくは、Ｒ１１～Ｒ１７はそれぞれ独立に水素原子又は炭素数１～４のアルキル基を示し、より好ましくは、Ｒ１１～Ｒ１７はそれぞれ独立に水素原子、メチル基又はエチル基を示し、さらに好ましくは、Ｒ１１～Ｒ１７はそれぞれ独立に水素原子又はメチル基を示す。 Preferably, R 11 to R 17 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably R 11 to R 17 each independently represent a hydrogen atom, a methyl group or an ethyl group, More preferably, each of R 11 to R 17 independently represents a hydrogen atom or a methyl group.
上述のように、上記一般式（３）において、Ｒ２１～Ｒ２８はそれぞれ独立に水素原子、炭素数１～４のアルキル基、カルボキシル基、カルボニル基又はエステル結合を有する官能基を示す。
炭素数１～４のアルキル基としては、上記と同様である。
As described above, in the general formula (3), R 21 to R 28 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group, or a functional group having an ester bond.
The alkyl group having 1 to 4 carbon atoms is the same as described above.
好ましくは、Ｒ２１～Ｒ２８はそれぞれ独立に水素原子又は炭素数１～４のアルキル基を示し、より好ましくは、Ｒ２１～Ｒ２８はそれぞれ独立に水素原子、メチル基又はエチル基を示し、さらに好ましくは、Ｒ２１～Ｒ２８はそれぞれ独立に水素原子又はメチル基を示す。 Preferably, R 21 to R 28 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably R 21 to R 28 each independently represent a hydrogen atom, a methyl group or an ethyl group, More preferably, each of R 21 to R 28 independently represents a hydrogen atom or a methyl group.
また、成分（Ａ）としては、有機残渣除去の観点から、上記一般式（１）～（２）で表される化合物からなる群から選ばれる少なくとも１種を含有することが好ましく、上記一般式（２）で表される化合物を含有することがより好ましい。 In addition, from the viewpoint of removing organic residues, the component (A) preferably contains at least one compound selected from the group consisting of compounds represented by the general formulas (1) and (2). It is more preferable to contain the compound represented by (2).
成分（Ａ）は、より好ましくは、１，２－ジアミノエタン、１，２－ジアミノプロパン、１，３－ジアミノプロパン、１，４－ジアミノブタン、２－メチル－１，３－ジアミノプロパンからなる群から選ばれる少なくとも１種を含有し、さらに好ましくは、１，２－ジアミノプロパン、１，３－ジアミノプロパン、Ｎ－メチル－１，３－ジアミノプロパンからなる群から選ばれる少なくとも１種を含有し、特に好ましくは、１，３－ジアミノプロパン、Ｎ－メチル－１，３－ジアミノプロパンからなる群から選ばれる少なくとも１種を含有する。
成分（Ａ）は、１種を単独で使用してもよいし、２種以上を任意の割合で併用しても良い。
Component (A) more preferably consists of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2-methyl-1,3-diaminopropane Contains at least one selected from the group, more preferably contains at least one selected from the group consisting of 1,2-diaminopropane, 1,3-diaminopropane, and N-methyl-1,3-diaminopropane and particularly preferably at least one selected from the group consisting of 1,3-diaminopropane and N-methyl-1,3-diaminopropane.
Component (A) may be used alone or in combination of two or more in any ratio.
［成分（Ｂ）］
本発明の洗浄液に含まれる成分（Ｂ）のアスコルビン酸としては、Ｌ－アスコルビン酸、Ｄ－アスコルビン酸、イソアスコルビン酸が好ましいものとして挙げられ、また、これらの塩も好適に用いることができる。さらに好ましくはＬ－アスコルビン酸が用いられる。アスコルビン酸は水溶液の酸化還元電位を低下させ、銅等の金属の酸化状態を制御することができる。
[Component (B)]
Preferred examples of ascorbic acid, the component (B) contained in the cleaning solution of the present invention, include L-ascorbic acid, D-ascorbic acid, and isoascorbic acid, and salts thereof can also be suitably used. L-ascorbic acid is more preferably used. Ascorbic acid lowers the redox potential of aqueous solutions and can control the oxidation state of metals such as copper.
［成分（Ｃ）］
本発明の洗浄液に含まれる成分（Ｃ）は、ポリカルボン酸又はヒドロキシカルボン酸である。ポリカルボン酸とは、分子内に２以上のカルボキシル基を有する化合物であり、ヒドロキシカルボン酸とは、分子内に１以上のヒドロキシ基及び１以上のカルボキシル基を有する化合物である。
[Component (C)]
Component (C) contained in the cleaning solution of the present invention is polycarboxylic acid or hydroxycarboxylic acid. A polycarboxylic acid is a compound having two or more carboxyl groups in the molecule, and a hydroxycarboxylic acid is a compound having one or more hydroxy groups and one or more carboxyl groups in the molecule.
これらのうち、分子内に２以上のカルボキシル基と１以上のヒドロキシ基を有する化合物が好ましい。
成分（Ｃ）として、炭素数が比較的少ない化合物のほうが、入手や取り扱いが容易であるため、該化合物の炭素数は好ましくは２～１０であり、さらに好ましくは３～８であり、特に好ましくは３～６である。
Among these, compounds having two or more carboxyl groups and one or more hydroxy groups in the molecule are preferred.
As the component (C), a compound having a relatively small number of carbon atoms is easier to obtain and handle, so the compound preferably has 2 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and particularly preferably 3 to 8 carbon atoms. is 3-6.
成分（Ｃ）の好適な具体例としてはシュウ酸、クエン酸、酒石酸、リンゴ酸、乳酸が挙げられ、とりわけクエン酸が好ましい。
これらは、１種を単独で使用してもよいし、２種以上を任意の割合で併用しても良い。
また、本発明の効果を損なわない範囲で、成分（Ｃ）のカルボキシル基の一部が塩となったものを用いてもよい。
Preferred specific examples of component (C) include oxalic acid, citric acid, tartaric acid, malic acid and lactic acid, with citric acid being particularly preferred.
These may be used individually by 1 type, and may use 2 or more types together in arbitrary ratios.
Further, a salt in which a part of the carboxyl groups of the component (C) is converted may be used as long as the effects of the present invention are not impaired.
［成分（Ｄ）］
本発明の洗浄液の成分（Ｄ）のｐＨ調整剤は、その目的とするｐＨに調整できる成分であれば、特に限定されず、酸化合物又はアルカリ化合物を使用することができる。
酸化合物としては硫酸や硝酸等の無機酸及びその塩、又は、酢酸、乳酸、シュウ酸、酒石酸、クエン酸等の有機酸及びその塩が好適な例として挙げられる。なお、成分（Ｄ）は成分（Ｃ）と同じ化合物である場合もある。
[Component (D)]
The pH adjuster of the component (D) of the cleaning solution of the present invention is not particularly limited as long as it is a component capable of adjusting the desired pH, and an acid compound or an alkali compound can be used.
Preferred examples of the acid compound include inorganic acids such as sulfuric acid and nitric acid and salts thereof, and organic acids such as acetic acid, lactic acid, oxalic acid, tartaric acid and citric acid and salts thereof. In addition, the component (D) may be the same compound as the component (C).
また、アルカリ化合物については、有機アルカリ化合物と無機アルカリ化合物を用いることができ、有機アルカリ化合物としては、以下に示す有機第４級アンモニウム水酸化物等の四級アンモニウム及びその誘導体の塩、トリメチルアミン、トリエチルアミン等のアルキルアミン及びその誘導体の塩、モノエタノールアミン等のアルカノールアミン及びその誘導体が好適な具体例として挙げられる。 As for the alkali compound, organic alkali compounds and inorganic alkali compounds can be used. Examples of the organic alkali compounds include the following organic quaternary ammonium hydroxides and salts of quaternary ammonium and derivatives thereof, trimethylamine, Preferred specific examples include salts of alkylamines such as triethylamine and derivatives thereof, and alkanolamines such as monoethanolamine and derivatives thereof.
有機アルカリ化合物としての有機第４級アンモニウム水酸化物としては、下記一般式（４）で表されるものが挙げられる。
（Ｒ３１）４Ｎ＋ＯＨ－・・・（４）
（上記一般式（４）中、Ｒ３１は、水酸基、アルコキシ基又はハロゲンにて置換されていてもよいアルキル基を示し、４個のＲ３１は、互いに同一でもよく異なっていてもよい。）
Examples of the organic quaternary ammonium hydroxide as the organic alkali compound include those represented by the following general formula (4).
(R 31 ) 4 N + OH - (4)
(In general formula (4) above, R 31 represents a hydroxyl group, an alkoxy group, or an alkyl group optionally substituted with halogen, and the four R 31 groups may be the same or different.)
有機第４級アンモニウム水酸化物としては、上記一般式（４）において、Ｒ３１が、水酸基、炭素数１～４のアルコキシ基、又はハロゲンにて置換されていてもよい、直鎖又は分岐鎖の炭素数１～４のアルキル基であるものが好ましい。
上記アルキル基としては、特に直鎖の炭素数１～４のアルキル基及び／又は直鎖の炭素数１～４のヒドロキシアルキル基が好ましい。
As the organic quaternary ammonium hydroxide, in the above general formula (4), R 31 may be substituted with a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen, linear or branched is preferably an alkyl group having 1 to 4 carbon atoms.
As the alkyl group, a linear alkyl group having 1 to 4 carbon atoms and/or a linear hydroxyalkyl group having 1 to 4 carbon atoms are particularly preferred.
炭素数１～４のアルキル基としてはメチル基、エチル基、プロピル基、ブチル基等が挙げられる。
炭素数１～４のヒドロキシアルキル基としてはヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基等が挙げられる。
The alkyl group having 1 to 4 carbon atoms includes methyl group, ethyl group, propyl group, butyl group and the like.
A hydroxyalkyl group having 1 to 4 carbon atoms includes a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group and the like.
この有機第４級アンモニウム水酸化物としては具体的には、ビス（２－ヒドロキシエチル）ジメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、メチルトリエチルアンモニウムヒドロキシド、トリメチル（ヒドロキシエチル）アンモニウムヒドロキシド（通称：コリン）、トリエチル（ヒドロキシエチル）アンモニウムヒドロキシド等が挙げられる。 Specific examples of the organic quaternary ammonium hydroxide include bis(2-hydroxyethyl)dimethylammonium hydroxide, tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltriethyl ammonium hydroxide, trimethyl(hydroxyethyl)ammonium hydroxide (common name: choline), triethyl(hydroxyethyl)ammonium hydroxide and the like.
上述の有機第４級アンモニウム水酸化物の中でも、洗浄効果、金属の残留が少ないこと、経済性、洗浄液の安定性等の理由から、ビス（２－ヒドロキシエチル）ジメチルアンモニウムヒドロキシド、トリメチル（ヒドロキシエチル）アンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド等が特に好ましい。 Among the above organic quaternary ammonium hydroxides, bis(2-hydroxyethyl)dimethylammonium hydroxide, trimethyl(hydroxy Ethyl)ammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and the like are particularly preferred.
無機アルカリ化合物は、水溶液でアルカリ性を示すもののうち、アンモニア又は主にアルカリ金属若しくはアルカリ土類金属を含む無機化合物及びその塩のことであり、これらのうち、無機アルカリ化合物として、アルカリ金属を含む水酸化物を用いることが、安全性やコストの面で好ましい。具体的には、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム等が挙げられる。 Inorganic alkaline compounds refer to inorganic compounds and salts thereof containing ammonia or mainly alkali metals or alkaline earth metals, among those exhibiting alkalinity in an aqueous solution. The use of oxides is preferable in terms of safety and cost. Specific examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide.
これらの酸化合物又はアルカリ化合物は、本発明の洗浄液のｐＨを調整することを目的として用いられる場合は、１種を単独で使用してもよいし、２種以上を任意の割合で併用してもよい。
特に好ましい酸化合物又はアルカリ化合物としては、酢酸、シュウ酸、酒石酸、クエン酸等の有機酸及びその塩、水酸化ナトリウム、水酸化カリウム等の無機アルカリ化合物及びその塩、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリン等の四級アンモニウム及びその誘導体の塩が挙げられる。
When these acid compounds or alkali compounds are used for the purpose of adjusting the pH of the cleaning liquid of the present invention, one type may be used alone, or two or more types may be used in combination in an arbitrary ratio. good too.
Particularly preferred acid compounds or alkali compounds include organic acids such as acetic acid, oxalic acid, tartaric acid and citric acid and salts thereof, inorganic alkali compounds such as sodium hydroxide and potassium hydroxide and salts thereof, tetramethylammonium hydroxide and tetraethyl. Examples include ammonium hydroxide, quaternary ammonium such as choline, and salts of derivatives thereof.
［成分（Ｅ）］
本発明の洗浄液の成分（Ｅ）である水は、本発明の洗浄液の溶媒である。溶媒として使用される水としては、不純物を極力低減させた脱イオン水や超純水を用いることが好ましい。なお、本発明の洗浄液は、本発明の効果を損なわない範囲において、エタノール等の水以外の溶媒を含んでいてもよい。
[Component (E)]
Water, which is component (E) of the cleaning liquid of the present invention, is the solvent of the cleaning liquid of the present invention. As the water used as the solvent, it is preferable to use deionized water or ultrapure water in which impurities are reduced as much as possible. The cleaning liquid of the present invention may contain a solvent other than water, such as ethanol, as long as the effects of the present invention are not impaired.
＜洗浄液の製造方法＞
本発明の洗浄液の製造方法は、特に限定されず従来公知の方法によればよく、例えば、洗浄液の構成成分（成分（Ａ）～（Ｅ）、必要に応じて用いられるその他の成分）を混合することで製造することができる。通常、溶媒である成分（Ｅ）：水に、成分（Ａ）～（Ｄ）、必要に応じて用いられるその他の成分を添加することにより製造される。
<Method for producing cleaning solution>
The method for producing the cleaning solution of the present invention is not particularly limited and may be a conventionally known method. It can be manufactured by It is produced by adding components (A) to (D), and optionally other components, to component (E), which is usually a solvent: water.
その際の混合順序も、反応や沈殿物が発生する等特段の問題がない限り任意であり、洗浄液の構成成分のうち、何れか２成分又は３成分以上を予め配合し、その後に残りの成分を混合してもよいし、一度に全成分を混合してもよい。 The mixing order at that time is also arbitrary as long as there is no particular problem such as reaction or precipitation. may be mixed, or all ingredients may be mixed at once.
［本発明の洗浄液中の各成分の濃度］
本発明の洗浄液中、成分（Ａ）の濃度は通常０．００１～２０質量％、好ましくは０．００１～１０質量％、より好ましくは０．００１～０．８０質量％、更に好ましくは０．００１～０．４０質量％、特に好ましくは０．００２～０．３０質量％である。
[Concentration of each component in the cleaning liquid of the present invention]
In the cleaning liquid of the present invention, the concentration of component (A) is usually 0.001 to 20% by mass, preferably 0.001 to 10% by mass, more preferably 0.001 to 0.80% by mass, still more preferably 0.001 to 0.80% by mass. 001 to 0.40 mass %, particularly preferably 0.002 to 0.30 mass %.
本発明の洗浄液中、成分（Ａ）の濃度が０．００１質量％以上であると、半導体デバイス用基板の汚染の除去効果が充分に発揮され、２０質量％以下であると、Ｃｕ等の金属配線の腐食といった不具合を引き起こしにくい。 When the concentration of the component (A) in the cleaning liquid of the present invention is 0.001% by mass or more, the effect of removing contamination from the semiconductor device substrate is sufficiently exhibited, and when it is 20% by mass or less, metal such as Cu It is less likely to cause problems such as corrosion of wiring.
本発明の洗浄液中、成分（Ｂ）の濃度は通常０．００１～２０質量％、好ましくは０．００１～１０質量％、より好ましくは０．００１～０．８０質量％、更に好ましくは０．００５～０．４０質量％、特に好ましくは０．０１～０．３０質量％である。 In the cleaning liquid of the present invention, the concentration of component (B) is usually 0.001 to 20% by mass, preferably 0.001 to 10% by mass, more preferably 0.001 to 0.80% by mass, still more preferably 0.001 to 0.80% by mass. 005 to 0.40% by weight, particularly preferably 0.01 to 0.30% by weight.
本発明の洗浄液中、成分（Ｂ）の濃度が０．００１質量％以上であると、Ｃｕ等の金属配線の腐食といった不具合を引き起こしにくく、２０質量％以下であると、洗浄液のコストがあまりかからない。 When the concentration of the component (B) in the cleaning liquid of the present invention is 0.001% by mass or more, problems such as corrosion of metal wiring such as Cu are less likely to occur, and when it is 20% by mass or less, the cost of the cleaning liquid is not so high. .
本発明の洗浄液中、成分（Ｃ）の濃度は通常０．００１～１０質量％、好ましくは０．００１～７質量％、より好ましくは０．００１～０．４０質量％、更に好ましくは０．００２～０．２８質量％、特に好ましくは０．００５～０．２０質量％である。 In the cleaning liquid of the present invention, the concentration of component (C) is usually 0.001 to 10% by mass, preferably 0.001 to 7% by mass, more preferably 0.001 to 0.40% by mass, still more preferably 0.001 to 0.40% by mass. 002 to 0.28% by weight, particularly preferably 0.005 to 0.20% by weight.
本発明の洗浄液中、成分（Ｃ）の濃度が０．００１質量％以上であると、半導体デバイス用基板の汚染の除去効果が充分に発揮され、１０質量％以下であると、洗浄液のコストがあまりかからない。 When the concentration of the component (C) in the cleaning solution of the present invention is 0.001% by mass or more, the effect of removing contamination from the semiconductor device substrate is sufficiently exhibited, and when it is 10% by mass or less, the cost of the cleaning solution is reduced. It doesn't take much.
また、本発明の洗浄液中、成分（Ｄ）は、ｐＨを調整するために使用するので、成分（Ｄ）の濃度は、特に限定されないが、通常０．００２～３０質量％、好ましくは０．００２～２０質量％、より好ましくは０．００２～１質量％、更に好ましくは０．０１～０．５質量％、特に好ましくは０．１～０．３質量％である。 In the cleaning liquid of the present invention, the component (D) is used to adjust the pH, so the concentration of the component (D) is not particularly limited, but is usually 0.002 to 30% by mass, preferably 0.002% by mass. 002 to 20% by mass, more preferably 0.002 to 1% by mass, still more preferably 0.01 to 0.5% by mass, and particularly preferably 0.1 to 0.3% by mass.
本発明の洗浄液は、洗浄に適した濃度になるように、各成分の濃度を調整して製造することもできるが、輸送、保管時のコストを抑制する観点から、成分（Ｅ）：水以外のそれぞれの成分を高濃度で含有する洗浄液（以下、「洗浄原液」と称する場合がある。）を製造した後に成分（Ｅ）：水で希釈して使用されることも多い。 The cleaning solution of the present invention can be manufactured by adjusting the concentration of each component so that the concentration is suitable for cleaning. Component (E) is often diluted with water after manufacturing a cleaning solution containing each component in high concentration (hereinafter sometimes referred to as "cleaning stock solution").
成分（Ａ）と成分（Ｂ）の質量比（成分（Ｂ）の質量／成分（Ａ）の質量）は、半導体デバイス用基板の汚染の除去性とＣｕ等の金属配線の腐食の抑制との観点から、好ましくは０．０１～１００であり、より好ましくは０．１～２５であり、特に好ましくは０．５～１０である。 The mass ratio of the component (A) to the component (B) (mass of the component (B)/mass of the component (A)) determines the removability of the contamination of the semiconductor device substrate and the suppression of the corrosion of the metal wiring such as Cu. From the viewpoint, it is preferably 0.01 to 100, more preferably 0.1 to 25, and particularly preferably 0.5 to 10.
成分（Ａ）と成分（Ｃ）の質量比（成分（Ｃ）の質量／成分（Ａ）の質量）は、半導体デバイス用基板の汚染の除去性とＣｕ等の金属配線の腐食の抑制との観点から、好ましくは０．１～２００であり、より好ましくは０．５～５０であり、特に好ましくは１～２０である。 The mass ratio of the component (A) to the component (C) (mass of the component (C)/mass of the component (A)) determines the removability of the contamination of the semiconductor device substrate and the suppression of the corrosion of the metal wiring such as Cu. From the viewpoint, it is preferably 0.1 to 200, more preferably 0.5 to 50, and particularly preferably 1 to 20.
成分（Ａ）と成分（Ｄ）の質量比（成分（Ｄ）の質量／成分（Ａ）の質量）は、半導体デバイス用基板の汚染の除去性とＣｕ等の金属配線の腐食の抑制とｐＨの調整の観点から、好ましくは０．０５～５００であり、より好ましくは０．１～２００であり、特に好ましくは０．２～５０である。 The mass ratio of the component (A) to the component (D) (mass of the component (D)/mass of the component (A)) determines the removability of the semiconductor device substrate contamination, the suppression of the corrosion of the metal wiring such as Cu, and the pH From the viewpoint of adjustment of , it is preferably 0.05 to 500, more preferably 0.1 to 200, and particularly preferably 0.2 to 50.
成分（Ｂ）と成分（Ｃ）の質量比（成分（Ｃ）の質量／成分（Ｂ）の質量）は、半導体デバイス用基板の汚染の除去性の観点から、好ましくは０．２５～２０であり、より好ましくは０．５～１０であり、特に好ましくは０．１～５である。 The mass ratio of component (B) to component (C) (mass of component (C)/mass of component (B)) is preferably from 0.25 to 20 from the viewpoint of removability of contamination of substrates for semiconductor devices. Yes, more preferably 0.5 to 10, particularly preferably 0.1 to 5.
成分（Ｂ）と成分（Ｄ）の質量比（成分（Ｄ）の質量／成分（Ｂ）の質量）は、半導体デバイス用基板の汚染の除去性とｐＨの調整との観点から、好ましくは０．１～１００であり、より好ましくは０．５～５０であり、特に好ましくは１～１０である。 The mass ratio of the component (B) to the component (D) (mass of the component (D)/mass of the component (B)) is preferably 0 from the standpoint of removing contamination from the semiconductor device substrate and adjusting the pH. 0.1 to 100, more preferably 0.5 to 50, and particularly preferably 1 to 10.
成分（Ｃ）と成分（Ｄ）の質量比（成分（Ｄ）の質量／成分（Ｃ）の質量）は、半導体デバイス用基板の汚染の除去性とｐＨの調整との観点から、好ましくは０．１～１００であり、より好ましくは０．５～５０であり、特に好ましくは１～１０である。 The mass ratio of the component (C) to the component (D) (mass of the component (D)/mass of the component (C)) is preferably 0 from the standpoint of removing contamination from the semiconductor device substrate and adjusting the pH. 0.1 to 100, more preferably 0.5 to 50, and particularly preferably 1 to 10.
［洗浄原液中の各成分の濃度］
上記洗浄原液中、成分（Ａ）の濃度は通常０．１０～２０質量％、好ましくは０．１０～１０質量％、より好ましくは０．２０～７質量％である。
[Concentration of each component in the cleaning stock solution]
The concentration of the component (A) in the cleaning solution is usually 0.10 to 20% by mass, preferably 0.10 to 10% by mass, more preferably 0.20 to 7% by mass.
上記洗浄原液中、成分（Ｂ）の濃度は通常０．１０～２０質量％、好ましくは０．５０～１０質量％、より好ましくは１．００～７質量％である。 The concentration of the component (B) in the cleaning solution is usually 0.10 to 20% by mass, preferably 0.50 to 10% by mass, more preferably 1.00 to 7% by mass.
上記洗浄原液中、成分（Ｃ）の濃度は通常０．１０～１０質量％、好ましくは０．２０～７質量％、より好ましくは０．５０～５質量％である。 The concentration of the component (C) in the cleaning solution is usually 0.10 to 10% by mass, preferably 0.20 to 7% by mass, more preferably 0.50 to 5% by mass.
上記洗浄原液中、成分（Ｄ）の濃度は通常０．２０～３０質量％、好ましくは０．５０～２０質量％、より好ましくは１．００～１０質量％である。 The concentration of the component (D) in the cleaning solution is usually 0.20 to 30% by mass, preferably 0.50 to 20% by mass, more preferably 1.00 to 10% by mass.
上記洗浄原液中の成分（Ａ）～（Ｄ）の濃度がこのような範囲にあると、成分（Ａ）～（Ｄ）及び必要に応じて添加される他の成分並びにこれらの反応物が、輸送、保管時において、洗浄原液中で分離又は析出し難く、また、成分（Ｅ）：水を添加することにより容易に洗浄に適した濃度の洗浄液として好適に使用することができる。 When the concentrations of the components (A) to (D) in the cleaning stock solution are within this range, the components (A) to (D), other components added as necessary, and their reaction products are During transportation and storage, it is difficult to separate or precipitate in the washing stock solution, and by adding component (E): water, it can be easily used as a washing solution having a concentration suitable for washing.
なお、本発明の洗浄液は、洗浄対象となる半導体デバイス用基板に対して各成分の濃度が適切なものとなるように洗浄原液を希釈して製造してもよいし、その濃度になるように直接各成分を調整して製造してもよいが、好ましくは、洗浄原液を希釈して製造することである。 The cleaning solution of the present invention may be prepared by diluting the cleaning stock solution so that the concentration of each component is appropriate for the semiconductor device substrate to be cleaned. It may be produced by directly adjusting each component, but preferably, it is produced by diluting the undiluted washing solution.
洗浄原液を希釈して製造した本発明の洗浄液の希釈倍率としては、洗浄対象となる半導体デバイス用基板に応じて適宜決定されるが、好ましくは、４０～９０倍である。
なお、当該洗浄液中における上述の成分（Ａ）～（Ｄ）のそれぞれの濃度は、洗浄原液中の上述の成分（Ａ）～（Ｄ）のそれぞれの濃度を希釈倍率で割った値である。
The dilution ratio of the cleaning solution of the present invention, which is prepared by diluting the cleaning stock solution, is appropriately determined according to the semiconductor device substrate to be cleaned, but is preferably 40 to 90 times.
The concentration of each of the components (A) to (D) in the cleaning solution is a value obtained by dividing the concentration of each of the components (A) to (D) in the cleaning stock solution by the dilution ratio.
＜半導体デバイス用基板の洗浄方法＞
次いで、本発明の半導体デバイス用基板の洗浄方法（以下、「本発明の洗浄方法」と称する場合がある。）について説明する。
本発明の洗浄方法は、上述の本発明の洗浄液を半導体デバイス用基板に直接接触させる方法で行なわれる。
<Method for cleaning semiconductor device substrate>
Next, the method for cleaning a semiconductor device substrate of the present invention (hereinafter sometimes referred to as "the cleaning method of the present invention") will be described.
The cleaning method of the present invention is carried out by bringing the cleaning liquid of the present invention into direct contact with the semiconductor device substrate.
洗浄対象となる半導体デバイス用基板としては、半導体、ガラス、金属、セラミックス、樹脂、磁性体、超伝導体等の各種半導体デバイス用基板が挙げられる。
これらの中でも、本発明の洗浄液は、短時間のリンスで有機残渣及び砥粒の除去ができるため、配線等として表面に金属又は金属化合物を有する半導体デバイス用基板に対して特に好適であり、特に表面にＣｕ配線を有する半導体デバイス用基板に対して好適である。
Semiconductor device substrates to be cleaned include various semiconductor device substrates such as semiconductors, glass, metals, ceramics, resins, magnetic substances, and superconductors.
Among these, the cleaning solution of the present invention is particularly suitable for semiconductor device substrates having metals or metal compounds on the surface as wiring, etc., since it can remove organic residues and abrasive grains with a short-time rinse. It is suitable for semiconductor device substrates having Cu wiring on the surface.
ここで、半導体デバイス用基板に使用される上記金属としては、Ｗ、Ｃｕ、Ｔｉ、Ｃｒ、Ｃｏ、Ｚｒ、Ｈｆ、Ｍｏ、Ｒｕ、Ａｕ、Ｐｔ、Ａｇ等が挙げられ、半導体デバイス用基板に使用される上記金属化合物としては、上記金属の窒化物、酸化物、シリサイド等が挙げられる。
これらの中では、Ｃｕ及びＣｕを含有する化合物がより好適に半導体デバイス用基板に使用される。
また、本発明の洗浄方法は、疎水性の強い低誘電率絶縁材料に対しても洗浄効果が高いため、表面に低誘電率絶縁材料を有する半導体デバイス用基板に対しても好適である。
Here, examples of the metals used for semiconductor device substrates include W, Cu, Ti, Cr, Co, Zr, Hf, Mo, Ru, Au, Pt, and Ag. Examples of the metal compounds used include nitrides, oxides and silicides of the above metals.
Among these, Cu and compounds containing Cu are more preferably used for semiconductor device substrates.
Further, since the cleaning method of the present invention has a high cleaning effect even for a highly hydrophobic low dielectric constant insulating material, it is also suitable for a semiconductor device substrate having a low dielectric constant insulating material on its surface.
このような低誘電率絶縁材料としては、Ｐｏｌｙｉｍｉｄｅ、ＢＣＢ（Ｂｅｎｚｏｃｙｃｌｏｂｕｔｅｎｅ）、Ｆｌａｒｅ（商品名、Ｈｏｎｅｙｗｅｌｌ社製）、ＳｉＬＫ（商品名、Ｄｏｗ Ｃｈｅｍｉｃａｌ社製）等の有機ポリマー材料やＦＳＧ（Ｆｌｕｏｒｉｎａｔｅｄ ｓｉｌｉｃａｔｅ ｇｌａｓｓ）等の無機ポリマー材料、ＢＬＡＣＫ ＤＩＡＭＯＮＤ（商品名、Ａｐｐｌｉｅｄ Ｍａｔｅｒｉａｌｓ社製）、Ａｕｒｏｒａ（商品名、日本ＡＳＭ社製）等のＳｉＯＣ系材料が挙げられる。 Examples of such a low dielectric constant insulating material include organic polymer materials such as Polyimide, BCB (Benzocyclobutene), Flare (trade name, manufactured by Honeywell), SilK (trade name, manufactured by Dow Chemical), and FSG (Fluorinated Silicate Glass). SiOC-based materials such as inorganic polymer materials such as BLACK DIAMOND (trade name, manufactured by Applied Materials) and Aurora (trade name, manufactured by ASM Japan).
ここで、本発明の洗浄方法は、半導体デバイス用基板が、基板表面にＣｕ配線と低誘電率絶縁膜を有し、かつ、ＣＭＰ処理後に基板を洗浄する場合に特に好適に適用される。 Here, the cleaning method of the present invention is particularly suitably applied when a semiconductor device substrate has Cu wiring and a low dielectric constant insulating film on the substrate surface and the substrate is cleaned after CMP processing.
ＣＭＰ工程では、研磨剤を用いて基板をパッドに擦り付けて研磨が行われる。
研磨剤には、コロイダルシリカ（ＳｉＯ２）、フュームドシリカ（ＳｉＯ２）、アルミナ（Ａｌ２Ｏ３）、セリア（ＣｅＯ２）等の研磨粒子が含まれる。このような研磨粒子は、半導体デバイス用基板の微粒子汚染の主因となるが、本発明の洗浄液は、基板に付着した微粒子を除去して洗浄液中に分散させると共に該微粒子の再付着を防止する作用を有しているため、微粒子汚染に対して高い効果を示す。
In the CMP process, polishing is performed by rubbing the substrate against a pad using an abrasive.
Abrasives include abrasive particles such as colloidal silica ( SiO2 ), fumed silica ( SiO2 ), alumina ( Al2O3 ), ceria ( CeO2 ), and the like. Such abrasive particles are the main cause of particulate contamination of substrates for semiconductor devices, but the cleaning solution of the present invention has the effect of removing fine particles adhering to the substrate, dispersing them in the cleaning solution, and preventing redeposition of the fine particles. Therefore, it is highly effective against particulate contamination.
また、研磨剤には、酸化剤、分散剤等の研磨粒子以外の添加剤が含まれることがある。
特に、その表面に金属配線としてＣｕ膜を有する半導体デバイス用基板におけるＣＭＰ研磨では、Ｃｕ膜が腐食しやすいため、防食剤が添加されることが多い。
Moreover, the abrasive may contain additives other than the abrasive particles, such as an oxidizing agent and a dispersant.
In particular, in the CMP polishing of a semiconductor device substrate having a Cu film as a metal wiring on its surface, an anticorrosive agent is often added because the Cu film is easily corroded.
防食剤としては、防食効果の高いアゾール系防食剤が好ましく用いられる。より具体的には、へテロ原子が窒素原子のみの複素環を含むものとして、ジアゾール系やトリアゾール系、テトラゾール系が挙げられ、へテロ原子が窒素原子と酸素原子の複素環を含むものとして、オキサゾール系やイソオキサゾール系、オキサジアゾール系が挙げられ、へテロ原子が窒素原子と硫黄原子の複素環を含むものとして、チアゾール系やイソチアゾール系、チアジアゾール系が挙げられる。その中でも特に、防食効果に優れるベンゾトリアゾール（ＢＴＡ）系の防食剤が好ましく用いられている。 As the anticorrosion agent, an azole anticorrosion agent having a high anticorrosion effect is preferably used. More specifically, heteroatoms containing only nitrogen atoms include diazoles, triazoles, and tetrazoles. Examples include oxazole, isoxazole, and oxadiazole, and those containing a heterocyclic ring having a nitrogen atom and a sulfur atom as heteroatoms include thiazole, isothiazole, and thiadiazole. Among them, a benzotriazole (BTA)-based anticorrosive is particularly preferably used because of its excellent anticorrosion effect.
本発明の洗浄液は、このような防食剤を含んだ研磨剤で研磨した後の基板表面に適用すると、これら防食剤に由来した汚染を極めて効果的に除去できる点において優れている。
即ち、研磨剤中にこれらの防食剤が存在すると、Ｃｕ膜表面の腐食を抑える反面、研磨時に溶出したＣｕイオンと反応し、多量の不溶性析出物を生じる。本発明の洗浄液は、このような不溶性析出物を効率的に溶解除去することができ、さらに、金属表面に残りやすい界面活性剤を、短時間のリンスで除去することができ、スループットの向上が可能である。
The cleaning liquid of the present invention is excellent in that it can very effectively remove contamination caused by the anticorrosive when applied to the substrate surface after polishing with a polishing agent containing such an anticorrosive.
That is, when these anticorrosive agents are present in the polishing agent, they suppress the corrosion of the Cu film surface, but they react with the Cu ions eluted during polishing to produce a large amount of insoluble precipitates. The cleaning solution of the present invention can efficiently dissolve and remove such insoluble precipitates, and can remove surfactants that tend to remain on metal surfaces in a short time rinse, improving throughput. It is possible.
そのため、本発明の洗浄方法は、Ｃｕ膜と低誘電率絶縁膜が共存した表面をＣＭＰ処理した後の半導体デバイス用基板の洗浄に好適であり、特にアゾール系防食剤が入った研磨剤でＣＭＰ処理した上記基板の洗浄に好適である。
上述のように本発明の洗浄方法は、本発明の洗浄液を半導体デバイス用基板に直接接触させる方法で行われる。なお、洗浄対象となる半導体デバイス用基板の種類に合わせて、好適な成分濃度の洗浄液が選択される。
Therefore, the cleaning method of the present invention is suitable for cleaning semiconductor device substrates after CMP treatment of the surface on which a Cu film and a low dielectric constant insulating film coexist. Suitable for cleaning the above treated substrates.
As described above, the cleaning method of the present invention is performed by bringing the cleaning liquid of the present invention into direct contact with the semiconductor device substrate. A cleaning solution having a suitable component concentration is selected according to the type of semiconductor device substrate to be cleaned.
本発明の洗浄方法における洗浄液の基板への接触方法には、洗浄槽に洗浄液を満たして基板を浸漬させるディップ式、ノズルから基板上に洗浄液を流しながら基板を高速回転させるスピン式、基板に液を噴霧して洗浄するスプレー式等が挙げられる。この様な洗浄を行うための装置としては、カセットに収容された複数枚の基板を同時に洗浄するバッチ式洗浄装置、１枚の基板をホルダーに装着して洗浄する枚葉式洗浄装置等がある。 The method of contacting the substrate with the cleaning liquid in the cleaning method of the present invention includes a dipping method in which a cleaning tank is filled with the cleaning liquid and the substrate is immersed, a spin method in which the substrate is rotated at high speed while the cleaning liquid is poured onto the substrate from a nozzle, and a liquid is applied to the substrate. and a spray type for washing by spraying. Devices for performing such cleaning include a batch-type cleaning device that simultaneously cleans a plurality of substrates housed in a cassette, and a single-wafer cleaning device that cleans a single substrate after it is mounted on a holder. .
本発明の洗浄方法は、上記の何れの接触方法も適用できるが、短時間でより効率的な汚染除去ができる点から、スピン式やスプレー式の洗浄に好ましく使用される。この場合において、洗浄時間の短縮、洗浄液使用量の削減が望まれている枚葉式洗浄装置に適用するならば、これらの問題が解決されるので好ましい。 Although any of the contact methods described above can be applied to the cleaning method of the present invention, it is preferably used for spin-type or spray-type cleaning, since contaminants can be removed more efficiently in a short period of time. In this case, if it is applied to a single-wafer type cleaning apparatus in which it is desired to shorten the cleaning time and reduce the amount of cleaning liquid used, these problems can be solved, which is preferable.
また、本発明の洗浄方法は、物理力による洗浄方法、特に、洗浄ブラシを使用したスクラブ洗浄や周波数０．５メガヘルツ以上の超音波洗浄を併用すると、基板に付着した微粒子による汚染の除去性がさらに向上し、洗浄時間の短縮にも繋がるので好ましい。特に、ＣＭＰ工程後の洗浄においては、樹脂製ブラシを使用してスクラブ洗浄を行うのが好ましい。樹脂製ブラシの材質は、任意に選択し得るが、例えば、ＰＶＡ（ポリビニルアルコール）を使用するのが好ましい。 Further, the cleaning method of the present invention is effective in removing contamination caused by fine particles adhering to the substrate when scrub cleaning using a cleaning brush or ultrasonic cleaning with a frequency of 0.5 megahertz or more is used in combination. It is preferable because it further improves and leads to shortening of the cleaning time. In particular, in cleaning after the CMP process, it is preferable to perform scrub cleaning using a resin brush. Although the material of the resin brush can be selected arbitrarily, it is preferable to use, for example, PVA (polyvinyl alcohol).
さらに、本発明の洗浄方法による洗浄の前及び／又は後に、水による洗浄を行ってもよい。
本発明の洗浄方法において、洗浄液の温度は、通常は室温でよいが、性能を損なわない範囲で４０～７０℃程度に加温してもよい。
Furthermore, washing with water may be performed before and/or after washing by the washing method of the present invention.
In the cleaning method of the present invention, the temperature of the cleaning liquid is usually room temperature, but it may be heated to about 40 to 70° C. within a range that does not impair the performance.
＜半導体デバイス用基板＞
本発明の半導体デバイス用基板の製造方法は、本発明の洗浄液を用いて半導体デバイス用基板を洗浄する工程を含む。
また、本発明の半導体デバイス用基板は、本発明の洗浄液を用いて半導体デバイス用基板を洗浄して得られるものである。
本発明の洗浄液を用いた半導体デバイス用基板の洗浄については、＜半導体デバイス用基板の洗浄方法＞で上記したとおりである。
<Semiconductor device substrate>
The method for manufacturing a semiconductor device substrate of the present invention includes the step of cleaning the semiconductor device substrate using the cleaning liquid of the present invention.
Further, the semiconductor device substrate of the present invention is obtained by cleaning the semiconductor device substrate with the cleaning liquid of the present invention.
The cleaning of the semiconductor device substrate using the cleaning liquid of the present invention is as described above in <Method for cleaning semiconductor device substrate>.
以下、実施例により本発明をさらに詳細に説明するが、本発明は、その要旨を変更しない限り以下の実施例に限定されるものではない。 EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless the gist thereof is changed.
［実施例１］
＜洗浄液の調製＞
表１に示すように、成分（Ａ）として０．０４質量％の１，３－ジアミノプロパン（広栄化学株式会社製）、成分（Ｂ）として０．０６質量％のアスコルビン酸（扶桑化学工業株式会社製）、成分（Ｃ）として０．０９質量％のクエン酸（昭和化工株式会社製）、成分（Ｄ）として０．２２質量％のテトラエチルアンモニウムヒドロキシド（ＴＥＡＨ：セイケムジャパン合同会社製）を、成分（Ｅ）の超純水と混合して、半導体デバイス用基板の洗浄液を調製した。成分（Ｅ）の濃度は、成分（Ａ）、成分（Ｂ）、成分（Ｃ）、成分（Ｄ）、ヒスチジン及びその他の成分を除いた残余濃度とした。
[Example 1]
<Preparation of washing solution>
As shown in Table 1, 0.04% by mass of 1,3-diaminopropane (manufactured by Koei Chemical Co., Ltd.) as component (A) and 0.06% by mass of ascorbic acid (Fuso Chemical Industry Co., Ltd.) as component (B) company), 0.09% by mass of citric acid (manufactured by Showa Kako Co., Ltd.) as component (C), and 0.22% by mass of tetraethylammonium hydroxide (TEAH: Seichem Japan G.K.) as component (D). was mixed with ultrapure water of component (E) to prepare a cleaning liquid for semiconductor device substrates. The concentration of component (E) was the residual concentration after removing component (A), component (B), component (C), component (D), histidine and other components.
（ｐＨ測定）
実施例１で得られた洗浄液を、マグネティックスターラーを用いて攪拌しながら、ｐＨ計（株式会社堀場製作所「Ｄ－２４」）でｐＨの測定を行なった。測定サンプルは恒温槽中で２５℃に液温を保った。測定結果を表１に示す。
(pH measurement)
The pH of the washing liquid obtained in Example 1 was measured with a pH meter (Horiba Ltd. "D-24") while stirring with a magnetic stirrer. The liquid temperature of the measurement sample was kept at 25°C in a constant temperature bath. Table 1 shows the measurement results.
（欠陥評価）
Ｃｕ膜を成膜したシリコン基板のシリカスラリとＣＭＰ装置（ラップマスターＳＦＴ株式会社「ＬＧＰ－１５ＲＤ」）を用いてＣＭＰを実施した。その後、実施例１で得られた洗浄液を基板表面に導入しながら、ＰＶＡのブラシを用いて、ＣＭＰ工程後の基板表面の洗浄を行なった。
(defect evaluation)
CMP was performed using a silica slurry of the silicon substrate on which the Cu film was formed and a CMP apparatus (“LGP-15RD” from Lapmaster SFT Co., Ltd.). Thereafter, while introducing the cleaning liquid obtained in Example 1 onto the substrate surface, the substrate surface after the CMP process was cleaned using a PVA brush.
洗浄後の基板について、ウェハ表面検査装置（株式会社日立ハイテクフィールディング製「ＬＳ－６６００」）を用いて、基板上の０．３５μｍ以上の欠陥数を調べた。結果を表１に示す。 After cleaning, the number of defects of 0.35 μm or larger on the substrate was examined using a wafer surface inspection device (“LS-6600” manufactured by Hitachi High-Tech Fielding Co., Ltd.). Table 1 shows the results.
（有機物残留評価、酸化膜厚評価）
上記欠陥評価で使用した基板を、大気中に９０分放置した後、Ｘ線光電子分光分析法（ＸＰＳ）（ＰＨＩ社製「Ｑｕａｎｔｕｍ ２０００」）で表面分析を行った。取り出し角は４５°、測定領域は３００μｍで測定を行った。
(Evaluation of residual organic matter, evaluation of oxide film thickness)
After leaving the substrate used in the above defect evaluation in the atmosphere for 90 minutes, the surface was analyzed by X-ray photoelectron spectroscopy (XPS) (“Quantum 2000” manufactured by PHI). Measurement was performed with a take-out angle of 45° and a measurement area of 300 μm.
Ｃｕ２ｐ３／２に由来するピークが９３２．５ｅＶに、Ｎ１ｓに由来するピークが４００ｅＶに検出された。それぞれのピーク強度から検出されたＣｕとＮの量を測定し、原子量比（Ｎ／Ｃｕ）を求めた。結果を表１に示す。 A peak derived from Cu2p 3/2 was detected at 932.5 eV and a peak derived from N1s was detected at 400 eV. The amounts of Cu and N detected from the respective peak intensities were measured to determine the atomic weight ratio (N/Cu). Table 1 shows the results.
原子量比（Ｎ／Ｃｕ）が小さいと、Ｃｕ表面に残留するＮ含有有機物量が少ないことを示しているので、ＣＭＰ工程後の基板表面上の有機残渣が少ないといえる。 When the atomic weight ratio (N/Cu) is small, it indicates that the amount of N-containing organic substances remaining on the Cu surface is small, so it can be said that the organic residue on the substrate surface after the CMP process is small.
該原子量比が０．０５を超えるときＣｕ表面に残留するＮ含有有機物量が多いため、少なくとも０．０５以下、好ましくは０．０３以下にする必要がある。該原子量比が０．０５以下であれば、Ｃｕ表面に残留するＮ含有有機物量が少ないため、ＣＭＰ工程後の基板表面上の有機残渣が少ない。 When the atomic weight ratio exceeds 0.05, the amount of N-containing organic substances remaining on the Cu surface is large, so it should be at least 0.05 or less, preferably 0.03 or less. If the atomic weight ratio is 0.05 or less, the amount of N-containing organic substances remaining on the Cu surface is small, so that the amount of organic residue on the substrate surface after the CMP process is small.
また、Ｃｕ酸化膜に由来するピークが５６９ｅＶに検出され、Ｃｕメタルに由来するピークが５６７ｅＶに検出された。５６９ｅＶと５６７ｅＶの強度比（５６９ｅＶ／５６７ｅＶ）を求めた。結果を表１に示す。 A peak derived from Cu oxide film was detected at 569 eV, and a peak derived from Cu metal was detected at 567 eV. An intensity ratio of 569 eV and 567 eV (569 eV/567 eV) was obtained. Table 1 shows the results.
該強度比が０．９未満であるときＣｕ酸化膜が薄く、基板上の露出した銅表面の酸化が洗浄後に起こるため、少なくとも０．９以上、好ましくは１．０以上にする必要がある。該強度比が１．０以上であれば、銅表面の酸化が抑制されるため、Ｃｕ酸化膜が十分に形成され、基板表面上の微小異物の形成を抑制できる。 When the intensity ratio is less than 0.9, the Cu oxide film is thin and the exposed copper surface on the substrate is oxidized after cleaning. Therefore, it should be at least 0.9 or more, preferably 1.0 or more. If the intensity ratio is 1.0 or more, oxidation of the copper surface is suppressed, so that a Cu oxide film is sufficiently formed and the formation of minute foreign matter on the substrate surface can be suppressed.
［実施例２］
実施例１において、成分（Ａ）～（Ｄ）の配合割合を表１に示すものとした以外は同様にして、洗浄液を得た。
得られた洗浄液を用いて、実施例１と同様に、ｐＨ測定、欠陥評価、有機物残留評価、酸化膜厚評価を行なった。結果を表１に示す。
[Example 2]
A washing liquid was obtained in the same manner as in Example 1, except that the blending ratios of components (A) to (D) were changed to those shown in Table 1.
Similar to Example 1, pH measurement, defect evaluation, organic substance residual evaluation, and oxide film thickness evaluation were performed using the obtained cleaning liquid. Table 1 shows the results.
［実施例３］
実施例１において、成分（Ａ）を１，２－ジアミノプロパン（広栄化学株式会社製）とし、成分（Ａ）～（Ｄ）の配合割合を表１に示すものとした以外は同様にして、洗浄液を得た。
得られた洗浄液を用いて、実施例１に記載の方法で、ｐＨ測定、欠陥評価、有機物残留評価、酸化膜厚評価を行なった。結果を表１に示す。
[Example 3]
In the same manner as in Example 1, except that 1,2-diaminopropane (manufactured by Koei Chemical Co., Ltd.) was used as the component (A) and the blending ratios of the components (A) to (D) were as shown in Table 1. A washing solution was obtained.
Using the obtained cleaning solution, pH measurement, defect evaluation, organic substance residual evaluation, and oxide film thickness evaluation were performed by the method described in Example 1. Table 1 shows the results.
［実施例４］
実施例１において、成分（Ａ）を１，２－ジアミノプロパン（広栄化学株式会社製）とし、成分（Ａ）～（Ｄ）の配合割合を表１に示すものとし、０．０４質量％のヒスチジン（味の素株式会社製）を加えた以外は同様にして、洗浄液を得た。
得られた洗浄液を用いて、実施例１と同様に、ｐＨ測定、欠陥評価、有機物残留評価、酸化膜厚評価を行なった。結果を表１に示す。
[Example 4]
In Example 1, the component (A) is 1,2-diaminopropane (manufactured by Koei Chemical Co., Ltd.), and the blending ratios of the components (A) to (D) are shown in Table 1, and 0.04% by mass A washing liquid was obtained in the same manner except that histidine (manufactured by Ajinomoto Co., Inc.) was added.
Similar to Example 1, pH measurement, defect evaluation, organic substance residual evaluation, and oxide film thickness evaluation were performed using the obtained cleaning liquid. Table 1 shows the results.
［実施例５］
実施例１において、成分（Ａ）を１，２－ジアミノプロパン（広栄化学株式会社製）とし、成分（Ａ）～（Ｄ）の配合割合を表１に示すものとし、０．０９質量％のヒスチジン（味の素株式会社製）を加えた以外は同様にして、洗浄液を得た。
得られた洗浄液を用いて、実施例１と同様に、ｐＨ測定、欠陥評価、有機物残留評価、酸化膜厚評価を行なった。結果を表１に示す。
[Example 5]
In Example 1, the component (A) is 1,2-diaminopropane (manufactured by Koei Chemical Co., Ltd.), the blending ratio of the components (A) to (D) is shown in Table 1, and 0.09% by mass A washing liquid was obtained in the same manner except that histidine (manufactured by Ajinomoto Co., Inc.) was added.
Similar to Example 1, pH measurement, defect evaluation, organic substance residual evaluation, and oxide film thickness evaluation were performed using the obtained cleaning liquid. Table 1 shows the results.
［実施例６］
実施例１において、成分（Ａ）をＮ－メチル－１，３－ジアミノプロパン（広栄化学株式会社製）とし、成分（Ａ）～（Ｄ）の配合割合を表１に示すものとした以外は同様にして、洗浄液を得た。
得られた洗浄液を用いて、実施例１と同様に、ｐＨ測定、欠陥評価、有機物残留評価、酸化膜厚評価を行なった。結果を表１に示す。
[Example 6]
In Example 1, N-methyl-1,3-diaminopropane (manufactured by Koei Chemical Co., Ltd.) was used as component (A), and the blending ratios of components (A) to (D) were as shown in Table 1. A washing liquid was obtained in the same manner.
Similar to Example 1, pH measurement, defect evaluation, organic substance residual evaluation, and oxide film thickness evaluation were performed using the obtained cleaning liquid. Table 1 shows the results.
［比較例１］
実施例１において、成分（Ａ）を用いず、成分（Ｂ）～（Ｄ）の配合割合を表１に示すものとした以外は同様にして、洗浄液を得た。
得られた洗浄液を用いて、実施例１と同様に、ｐＨ測定、欠陥評価、有機物残留評価、酸化膜厚評価を行なった。結果を表１に示す。
[Comparative Example 1]
A washing liquid was obtained in the same manner as in Example 1, except that the component (A) was not used and the blending ratios of the components (B) to (D) were as shown in Table 1.
Similar to Example 1, pH measurement, defect evaluation, organic substance residual evaluation, and oxide film thickness evaluation were performed using the obtained cleaning liquid. Table 1 shows the results.
［比較例２］
実施例１において、成分（Ａ）～（Ｄ）の配合割合を表１に示すものとした以外は同様にして、洗浄液を得た。
得られた洗浄液を用いて、実施例１に記載の方法で、ｐＨ測定、欠陥評価を行なった。結果を表１に示す。なお、比較例２においては、基板上の欠陥数が多かったため、有機物残留評価、酸化膜厚評価は行わなかった。
[Comparative Example 2]
A washing liquid was obtained in the same manner as in Example 1, except that the blending ratios of components (A) to (D) were changed to those shown in Table 1.
pH measurement and defect evaluation were performed by the method described in Example 1 using the obtained cleaning liquid. Table 1 shows the results. In Comparative Example 2, since the number of defects on the substrate was large, evaluation of residual organic substances and evaluation of oxide film thickness were not performed.
［比較例３］
実施例１において、成分（Ａ）の代わりにＮ－（２－アミノエチル）ピペラジン（東京化成工業社製）を用い、Ｎ－（２－アミノエチル）ピペラジン及び成分（Ｂ）～（Ｄ）の配合割合を表１に示すものとした以外は同様にして、洗浄液を得た。
得られた洗浄液を用いて、実施例１に記載の方法で、ｐＨ測定、欠陥評価を行なった。結果を表１に示す。なお、比較例３においては、基板上の欠陥数が多かったため、有機物残留評価、酸化膜厚評価は行わなかった。
[Comparative Example 3]
In Example 1, N-(2-aminoethyl)piperazine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of component (A), and N-(2-aminoethyl)piperazine and components (B) to (D) were added. A washing liquid was obtained in the same manner, except that the blending ratio was as shown in Table 1.
pH measurement and defect evaluation were performed by the method described in Example 1 using the obtained cleaning liquid. Table 1 shows the results. In addition, in Comparative Example 3, since the number of defects on the substrate was large, the residual organic substance evaluation and oxide film thickness evaluation were not performed.
［比較例４］
実施例１において、成分（Ａ）の代わりに２－｛［２－（ジメチルアミノ）エチル］メチルアミノ｝エタノール（東京化成工業社製）を用い、２－｛［２－（ジメチルアミノ）エチル］メチルアミノ｝エタノール及び成分（Ｂ）～（Ｄ）の配合割合を表１に示すものとした以外は同様にして、洗浄液を得た。
得られた洗浄液を用いて、実施例１に記載の方法で、ｐＨ測定、欠陥評価を行なった。結果を表１に示す。なお、比較例４においては、基板上の欠陥数が多かったため、有機物残留評価、酸化膜厚評価は行わなかった。
[Comparative Example 4]
In Example 1, 2-{[2-(dimethylamino)ethyl]methylamino}ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of component (A), and 2-{[2-(dimethylamino)ethyl] A washing liquid was obtained in the same manner except that the mixing ratios of methylamino}ethanol and components (B) to (D) were as shown in Table 1.
pH measurement and defect evaluation were performed by the method described in Example 1 using the obtained cleaning liquid. Table 1 shows the results. Incidentally, in Comparative Example 4, since the number of defects on the substrate was large, the residual organic substance evaluation and oxide film thickness evaluation were not performed.
［比較例５］
実施例１において、成分（Ａ）の代わりにＮ，Ｎ，Ｎ’，Ｎ’－テトラキス（２－ヒドロキシプロピル）エチレンジアミン（東京化成工業社製）を用い、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラキス（２－ヒドロキシプロピル）エチレンジアミン及び成分（Ｂ）～（Ｄ）の配合割合を表１に示すものとした以外は同様にして、洗浄液を得た。
得られた洗浄液を用いて、実施例１に記載の方法で、ｐＨ測定、欠陥評価を行なった。結果を表１に示す。なお、比較例５においては、基板上の欠陥数が多かったため、有機物残留評価、酸化膜厚評価は行わなかった。
[Comparative Example 5]
In Example 1, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of component (A), and N,N,N',N'- A washing liquid was obtained in the same manner as above, except that the mixing ratios of tetrakis(2-hydroxypropyl)ethylenediamine and components (B) to (D) were as shown in Table 1.
pH measurement and defect evaluation were performed by the method described in Example 1 using the obtained cleaning liquid. Table 1 shows the results. Incidentally, in Comparative Example 5, since the number of defects on the substrate was large, the residual organic substance evaluation and oxide film thickness evaluation were not performed.
実施例１は、欠陥数が５と少なく、原子量比（Ｎ／Ｃｕ）が０．０２と低く、５６９ｅＶ／５６７ｅＶにおけるピーク強度比も１．０以上となっていることから、Ｃｕ表面には窒素を含んだ化合物はほとんど残留しておらず、またＣｕ酸化膜が厚く形成されており、大気に静置しておいた際に酸化も起こりにくい状況であることが分かった。
実施例２、実施例３及び実施例６も同様である。
In Example 1, the number of defects is as small as 5, the atomic weight ratio (N/Cu) is as low as 0.02, and the peak intensity ratio at 569 eV/567 eV is 1.0 or more. It was found that almost no compound containing was left, and a thick Cu oxide film was formed, so that oxidation would not easily occur when left standing in the air.
The same applies to Examples 2, 3 and 6.
実施例４及び実施例５は、実施例１の成分に加えて、ヒスチジンを含んでいるが、原子量比（Ｎ／Ｃｕ）がやや高いものの、欠陥数は少なかった。 Examples 4 and 5 contained histidine in addition to the components of Example 1, and although the atomic weight ratio (N/Cu) was slightly high, the number of defects was small.
一方、比較例１は、原子量比（Ｎ／Ｃｕ）は０．０１と低く、５６９ｅＶ／５６７ｅＶにおけるピーク強度比も１．４と高いが、成分（Ａ）を含有していないため、欠陥数が５５と多かった。
比較例２は、ｐＨが１１．９と高いため、欠陥数が多かった。
比較例３～比較例５は、成分（Ａ）の代わりに、上記一般式（１）～（３）で表される化合物と異なる成分を使用しているため、欠陥数が多かった。
On the other hand, Comparative Example 1 has a low atomic weight ratio (N/Cu) of 0.01 and a high peak intensity ratio of 1.4 at 569 eV/567 eV. It was as many as 55.
Comparative Example 2 had a large number of defects due to its high pH of 11.9.
Comparative Examples 3 to 5 used a component different from the compounds represented by the general formulas (1) to (3) instead of the component (A), and therefore had many defects.
本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は２０１７年３月２２日出願の日本特許出願（特願２０１７－０５６３７１）及び２０１７年１１月１日出願の日本特許出願（特願２０１７－２１１４９５）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on March 22, 2017 (Japanese patent application 2017-056371) and a Japanese patent application filed on November 1, 2017 (Japanese patent application 2017-211495). is taken as a reference to
Claims (15)
成分（Ａ）：下記一般式（１）～（３）で表される化合物からなる群から選ばれる少なくとも１種を含有する化合物
（上記一般式（１）において、Ｒ１～Ｒ６はそれぞれ独立に水素原子、炭素数１～４のアルキル基、カルボキシル基、カルボニル基又はエステル結合を有する官能基を示す。）
（上記一般式（２）において、Ｒ１１～Ｒ１７はそれぞれ独立に水素原子、炭素数１～４のアルキル基、カルボキシル基、カルボニル基又はエステル結合を有する官能基を示す。）
（上記一般式（３）において、Ｒ２１～Ｒ２８はそれぞれ独立に水素原子、炭素数１～４のアルキル基、カルボキシル基、カルボニル基又はエステル結合を有する官能基を示す。）
成分（Ｂ）：アスコルビン酸
成分（Ｃ）：ポリカルボン酸又はヒドロキシカルボン酸
成分（Ｄ）：ｐＨ調整剤
成分（Ｅ）：水 A cleaning liquid for semiconductor device substrates having a pH of 8 or more and 11.5 or less and containing the following components (A) to (E).
Component (A): a compound containing at least one selected from the group consisting of compounds represented by the following general formulas (1) to (3)
(In general formula (1) above, R 1 to R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group, or a functional group having an ester bond.)
(In general formula (2) above, R 11 to R 17 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group, or a functional group having an ester bond.)
(In general formula (3) above, R 21 to R 28 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, a carbonyl group, or a functional group having an ester bond.)
Component (B): Ascorbic acid Component (C): Polycarboxylic acid or hydroxycarboxylic acid Component (D): pH adjuster Component (E): Water
（上記一般式（１）において、Ｒ１～Ｒ６はそれぞれ独立に水素原子又は炭素数１～４のアルキル基を示す。）
（上記一般式（２）において、Ｒ１１～Ｒ１７はそれぞれ独立に水素原子又は炭素数１～４のアルキル基を示す。） 2. The cleaning liquid for semiconductor device substrates according to claim 1, wherein said component (A) contains at least one compound selected from the group consisting of compounds represented by the following general formulas (1) and (2).
(In general formula (1) above, R 1 to R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
(In general formula (2) above, R 11 to R 17 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
（Ｒ３１）４Ｎ＋ＯＨ－・・・（４）
（上記一般式（４）中、Ｒ３１は、水酸基、アルコキシ基又はハロゲンにて置換されていてもよいアルキル基を示し、４個のＲ３１は、互いに同一でもよく異なっていてもよい。） The component (D) is at least selected from the group consisting of an inorganic alkali compound containing an alkali metal, an inorganic alkali compound containing an alkaline earth metal, and an organic quaternary ammonium hydroxide represented by the following general formula (4) The cleaning liquid for semiconductor device substrates according to any one of claims 1 to 4, which is one type.
(R 31 ) 4 N + OH - (4)
(In general formula (4) above, R 31 represents a hydroxyl group, an alkoxy group, or an alkyl group optionally substituted with halogen, and the four R 31 groups may be the same or different.)
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017056371 | 2017-03-22 | ||
| JP2017056371 | 2017-03-22 | ||
| JP2017211495 | 2017-11-01 | ||
| JP2017211495 | 2017-11-01 | ||
| JP2019507709A JPWO2018174092A1 (en) | 2017-03-22 | 2018-03-20 | 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 |
| PCT/JP2018/011187 WO2018174092A1 (en) | 2017-03-22 | 2018-03-20 | Washing solution for substrates for semiconductor devices, method for washing substrate for semiconductor devices, method for producing substrate for semiconductor devices, and substrate for semiconductor devices |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019507709A Division JPWO2018174092A1 (en) | 2017-03-22 | 2018-03-20 | 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2022161970A true JP2022161970A (en) | 2022-10-21 |
| JP7400898B2 JP7400898B2 (en) | 2023-12-19 |
Family
ID=63586088
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019507709A Pending JPWO2018174092A1 (en) | 2017-03-22 | 2018-03-20 | 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 |
| JP2022128053A Active JP7400898B2 (en) | 2017-03-22 | 2022-08-10 | Cleaning liquid for semiconductor device substrate, method for cleaning semiconductor device substrate, method for manufacturing semiconductor device substrate, and semiconductor device substrate |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019507709A Pending JPWO2018174092A1 (en) | 2017-03-22 | 2018-03-20 | 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 |
Country Status (4)
| Country | Link |
|---|---|
| JP (2) | JPWO2018174092A1 (en) |
| CN (1) | CN110447090A (en) |
| TW (1) | TWI745569B (en) |
| WO (1) | WO2018174092A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210052445A (en) * | 2018-08-30 | 2021-05-10 | 미쯔비시 케미컬 주식회사 | Cleaning liquid, cleaning method, and manufacturing method of semiconductor wafer |
| JP7192461B2 (en) * | 2018-12-11 | 2022-12-20 | 三菱ケミカル株式会社 | Cleaning liquid, cleaning method, and semiconductor wafer manufacturing method |
| JP2020107641A (en) * | 2018-12-26 | 2020-07-09 | Jsr株式会社 | Composition for semiconductor surface treatment and method for treating semiconductor surface |
| WO2020213487A1 (en) * | 2019-04-15 | 2020-10-22 | 三菱ケミカル株式会社 | Cleaning fluid, cleaning method, and method for producing semiconductor wafer |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001071789A1 (en) * | 2000-03-21 | 2001-09-27 | Wako Pure Chemical Industries, Ltd. | Semiconductor wafer cleaning agent and cleaning method |
| JP2010287751A (en) * | 2009-06-12 | 2010-12-24 | Sanyo Chem Ind Ltd | Cleaning agent for copper-wired semiconductor |
| JP2014049521A (en) * | 2012-08-30 | 2014-03-17 | Advanced Technology Materials Inc | Cleaning agent for copper wiring semiconductor |
| JP2014170927A (en) * | 2013-02-06 | 2014-09-18 | Mitsubishi Chemicals Corp | Substrate cleaning solvent for semiconductor devices, and method for cleaning semiconductor device substrate |
| JP2014212262A (en) * | 2013-04-19 | 2014-11-13 | 関東化学株式会社 | Cleaning liquid composition |
| JP2015165562A (en) * | 2014-02-06 | 2015-09-17 | 三菱化学株式会社 | Substrate cleaning liquid for semiconductor devices and method for cleaning substrate for semiconductor devices |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI258504B (en) * | 2003-01-07 | 2006-07-21 | Tosoh Corp | Washing solution and washing method using the same |
| JP4277930B2 (en) * | 2005-12-21 | 2009-06-10 | 旭硝子株式会社 | Polishing composition, polishing method, and method for producing copper wiring for semiconductor integrated circuit |
| CN101755324B (en) * | 2007-07-26 | 2011-10-12 | 三菱瓦斯化学株式会社 | Composition for cleaning and rust prevention and process for producing semiconductor element or display element |
| KR101525275B1 (en) * | 2007-12-17 | 2015-06-02 | 산요가세이고교 가부시키가이샤 | Cleaning agent and cleaning method for electronic material |
| SG190444A1 (en) * | 2010-11-29 | 2013-06-28 | Wako Pure Chem Ind Ltd | Substrate cleaner for copper wiring, and method for cleaning copper wiring semiconductor substrate |
| US9862914B2 (en) * | 2013-11-08 | 2018-01-09 | Wako Pure Chemical Industries, Ltd. | Cleaning agent for semiconductor substrates and method for processing semiconductor substrate surface |
| KR102463341B1 (en) * | 2015-01-13 | 2022-11-04 | 씨엠씨 머티리얼즈, 인코포레이티드 | Cleaning composition and method for cleaning semiconductor wafers after CMP |
-
2018
- 2018-03-20 JP JP2019507709A patent/JPWO2018174092A1/en active Pending
- 2018-03-20 WO PCT/JP2018/011187 patent/WO2018174092A1/en active Application Filing
- 2018-03-20 CN CN201880019482.1A patent/CN110447090A/en active Pending
- 2018-03-22 TW TW107109799A patent/TWI745569B/en active
-
2022
- 2022-08-10 JP JP2022128053A patent/JP7400898B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001071789A1 (en) * | 2000-03-21 | 2001-09-27 | Wako Pure Chemical Industries, Ltd. | Semiconductor wafer cleaning agent and cleaning method |
| JP2010287751A (en) * | 2009-06-12 | 2010-12-24 | Sanyo Chem Ind Ltd | Cleaning agent for copper-wired semiconductor |
| JP2014049521A (en) * | 2012-08-30 | 2014-03-17 | Advanced Technology Materials Inc | Cleaning agent for copper wiring semiconductor |
| JP2014170927A (en) * | 2013-02-06 | 2014-09-18 | Mitsubishi Chemicals Corp | Substrate cleaning solvent for semiconductor devices, and method for cleaning semiconductor device substrate |
| JP2014212262A (en) * | 2013-04-19 | 2014-11-13 | 関東化学株式会社 | Cleaning liquid composition |
| JP2015165562A (en) * | 2014-02-06 | 2015-09-17 | 三菱化学株式会社 | Substrate cleaning liquid for semiconductor devices and method for cleaning substrate for semiconductor devices |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2018174092A1 (en) | 2020-01-30 |
| TW201840841A (en) | 2018-11-16 |
| WO2018174092A1 (en) | 2018-09-27 |
| TWI745569B (en) | 2021-11-11 |
| JP7400898B2 (en) | 2023-12-19 |
| CN110447090A (en) | 2019-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6711437B2 (en) | Semiconductor device substrate cleaning liquid and method for cleaning semiconductor device substrate | |
| JP7400898B2 (en) | Cleaning liquid for semiconductor device substrate, method for cleaning semiconductor device substrate, method for manufacturing semiconductor device substrate, and semiconductor device substrate | |
| JP6488740B2 (en) | Substrate cleaning liquid for semiconductor device and method for cleaning semiconductor device | |
| JP6123334B2 (en) | Cleaning device for semiconductor device and method for cleaning substrate for semiconductor device | |
| TWI648430B (en) | Cleaning solution for semiconductor device substrate and method for cleaning semiconductor device substrate | |
| JP7184044B2 (en) | Cleaning liquid, cleaning method, and semiconductor wafer manufacturing method | |
| JP7156266B2 (en) | Cleaning composition for semiconductor device substrate, method for cleaning semiconductor device substrate, method for producing semiconductor device substrate, and semiconductor device substrate | |
| JP5817310B2 (en) | Cleaning device and cleaning method for semiconductor device substrate | |
| JP2014036136A (en) | Substrate cleaning liquid for semiconductor device and cleaning method of substrate for semiconductor device | |
| JP2014154625A (en) | Cleaning solvent for semiconductor device substrate, and cleaning method | |
| JP2016086094A (en) | Cleaning liquid for semiconductor device substrate and cleaning method for semiconductor device substrate | |
| JP7276343B2 (en) | Cleaning liquid, cleaning method, and semiconductor wafer manufacturing method | |
| JP6635213B2 (en) | Semiconductor device substrate cleaning liquid and method for cleaning semiconductor device substrate | |
| JP7192461B2 (en) | Cleaning liquid, cleaning method, and semiconductor wafer manufacturing method | |
| JP2016178118A (en) | Substrate cleaning liquid for semiconductor device, and cleaning method of substrate for semiconductor device | |
| JP2012119513A (en) | Cleaning liquid and cleaning method of substrate for semiconductor device | |
| JP2015203047A (en) | Substrate cleaning liquid for semiconductor device and method for cleaning substrate for semiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220810 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220810 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20230619 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230704 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230807 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20231107 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20231120 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 7400898 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |