JP2016178118A - Semiconductor device substrate cleaning liquid and semiconductor device substrate cleaning method - Google Patents
Semiconductor device substrate cleaning liquid and semiconductor device substrate cleaning method Download PDFInfo
- Publication number
- JP2016178118A JP2016178118A JP2015055079A JP2015055079A JP2016178118A JP 2016178118 A JP2016178118 A JP 2016178118A JP 2015055079 A JP2015055079 A JP 2015055079A JP 2015055079 A JP2015055079 A JP 2015055079A JP 2016178118 A JP2016178118 A JP 2016178118A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- semiconductor device
- cleaning liquid
- cleaning
- component
- 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.)
- Pending
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 178
- 239000000758 substrate Substances 0.000 title claims abstract description 124
- 239000007788 liquid Substances 0.000 title claims abstract description 93
- 239000004065 semiconductor Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 58
- 230000004888 barrier function Effects 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 11
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims description 26
- -1 sulfosuccinic acid diester Chemical class 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000003945 anionic surfactant Substances 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 11
- 150000002739 metals Chemical class 0.000 claims description 11
- 238000005498 polishing Methods 0.000 claims description 11
- 239000002738 chelating agent Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000004615 ingredient Substances 0.000 claims description 8
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 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 4
- 239000004471 Glycine Substances 0.000 claims description 4
- 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 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229940081066 picolinic acid Drugs 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 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
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000000524 functional 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
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000001629 suppression Effects 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 36
- 239000000243 solution Substances 0.000 description 20
- 239000010408 film Substances 0.000 description 18
- 230000008569 process Effects 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000010936 titanium Substances 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 7
- 239000012964 benzotriazole Substances 0.000 description 7
- 239000012459 cleaning agent Substances 0.000 description 7
- 239000008119 colloidal silica Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 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
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 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
- 230000006866 deterioration Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001139 pH measurement Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000005441 aurora Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002337 glycosamines Chemical class 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant 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
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 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
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
本発明は、半導体デバイス用基板洗浄液及び半導体デバイス用基板の洗浄方法に係り、詳しくは化学的機械的研磨を行った後の、表面にＣｕ等の金属が露出した半導体デバイス用基板表面を効果的に洗浄するための洗浄液とこの洗浄液を用いた洗浄方法に関する。 The present invention relates to a semiconductor device substrate cleaning liquid and a method for cleaning a semiconductor device substrate, and more particularly, after a chemical mechanical polishing, an effective surface of a semiconductor device substrate having a metal such as Cu exposed on the surface. The present invention relates to a cleaning liquid for cleaning and a cleaning method using the cleaning liquid.
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。）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行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。 A semiconductor device substrate is a chemical mechanical polishing (chemical) that uses a polishing slurry made of a water-based slurry containing abrasive fine particles after forming a metal film or interlayer insulating film deposition layer on a silicon wafer substrate. Mechanical polishing (hereinafter, referred to as “CMP”). The surface is planarized by a process, and a new layer is stacked on the flattened surface. In microfabrication of a substrate for a semiconductor device, high-precision flatness in each layer is required, and the importance of planarization by CMP is increasing.
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。また、Ｃｕが層間絶縁膜中に拡散することを防ぐという目的で、それらの間にバリアメタル層が利用されている。バリアメタルとしては、タンタル（Ｔａ）やタンタル化合物、チタン（Ｔｉ）やチタン化合物、ルテニウム（Ｒｕ）やルテニウム化合物、コバルト（Ｃｏ）やコバルト化合物などが主としてバリアメタルに使用されることが多い。 In the semiconductor device manufacturing process, a wiring (Cu wiring) made of a copper (Cu) film having a low resistance value is introduced to increase the speed and integration of the device. In addition, a barrier metal layer is used between them for the purpose of preventing Cu from diffusing into the interlayer insulating film. As the barrier metal, tantalum (Ta), a tantalum compound, titanium (Ti), a titanium compound, ruthenium (Ru), a ruthenium compound, cobalt (Co), a cobalt compound, or the like is often used as the barrier metal.
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腐食しやすいことから、ＣＭＰ工程において、Ｃｕ配線の酸化や腐食が問題となっている。 Cu is suitable for microfabrication because of its good workability. However, since Cu is easily corroded by an acid component or an alkali component, oxidation and corrosion of Cu wiring are problematic in the CMP process.
そのため、従来、Ｃｕ配線を有する半導体デバイス用基板のＣＭＰにおいて、研磨剤にはベンゾトリアゾール、トリルトリアゾールやそれらの誘導体等の防食剤が添加されており、この防食剤がＣｕ酸化膜に強く配位して保護膜を形成することにより、ＣＭＰにおけるＣｕ配線の腐食を抑制している（例えば特許文献１）。 Therefore, conventionally, in CMP of a semiconductor device substrate having Cu wiring, anticorrosive agents such as benzotriazole, tolyltriazole and their derivatives are added to the polishing agent, and this anticorrosive agent is strongly coordinated to the Cu oxide film. By forming a protective film, corrosion of Cu wiring in CMP is suppressed (for example, Patent Document 1).
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などの砥粒や、スラリー中に含まれる防食剤由来の有機残渣などが多量に存在することから、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。 A large amount of abrasive grains such as colloidal silica used in the CMP process and organic residues derived from anticorrosive agents contained in the slurry are removed on the surface of the semiconductor device substrate after the CMP process. Therefore, the semiconductor device substrate after the CMP process is subjected to a cleaning process.
ＣＭＰ後の洗浄においては、酸性洗浄液とアルカリ性洗浄液が用いられている。酸性水溶液中では、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。しかし、一方で、Ｃｕ表面が酸化されるという欠点も存在する。 In the cleaning after CMP, an acidic cleaning solution and an alkaline cleaning solution are used. In an acidic aqueous solution, colloidal silica is positively charged, the substrate surface is negatively charged, and an electric attractive force acts, making it difficult to remove the colloidal silica. On the other hand, since OH − is abundant in the alkaline aqueous solution, both the colloidal silica and the substrate surface are negatively charged, an electric repulsion acts, and the colloidal silica can be easily removed. However, on the other hand, there is a drawback that the Cu surface is oxidized.
この酸化劣化や腐食を防止するために、洗浄工程に用いる洗浄液に防食剤を添加する方法が提案されているが、従来、ＣＭＰに使用されている防食剤は、Ｃｕ配線から溶出したＣｕイオンと錯体を形成して基板への付着性を有する残渣を発生させるという問題があった。また、これまでに知られている残渣生成の少ない防食剤を使用すると、上述の残渣は生成しないが、Ｃｕ配線の酸化劣化や腐食の抑制が不十分になるという問題があった。 In order to prevent this oxidative degradation and corrosion, a method of adding an anticorrosive to the cleaning liquid used in the cleaning process has been proposed. Conventionally, the anticorrosive used in CMP is a Cu ion eluted from the Cu wiring. There is a problem in that a complex is formed and a residue having adhesion to the substrate is generated. Moreover, when the anticorrosive agent with little residue production | generation known until now is used, the above-mentioned residue will not be produced | generated, but there existed a problem that suppression of oxidation deterioration and corrosion of Cu wiring became inadequate.
特許文献２〜５には、このようなＣｕ配線を有する半導体の洗浄液に関連する技術が開示されている。特許文献２は、水酸化アンモニウム等の洗浄剤と、キレート剤と、腐食阻止化合物を含む半導体加工物洗浄用組成物が開示するものである。特許文献３は、アミノ糖、脂肪族アミンおよび水を必須成分とする洗浄剤を開示するものである。特許文献４は、腐食防止剤、アミン４級塩基を含む洗浄組成物を開示するものである。特許文献５は、４級アンモニウム水酸化物、界面活性剤、キレート剤、側鎖に芳香環を有するアミノ酸、水を含有する所定のｐＨの半導体デバイス用基板洗浄液が開示するものである。これらは、ＣＭＰ後の金属などの残渣を除去することに適したものである。 Patent Documents 2 to 5 disclose techniques related to a semiconductor cleaning liquid having such a Cu wiring. Patent Document 2 discloses a semiconductor workpiece cleaning composition containing a cleaning agent such as ammonium hydroxide, a chelating agent, and a corrosion inhibiting compound. Patent Document 3 discloses a cleaning agent containing amino sugar, aliphatic amine and water as essential components. Patent Document 4 discloses a cleaning composition containing a corrosion inhibitor and an amine quaternary base. Patent Document 5 discloses a substrate cleaning solution for a semiconductor device having a predetermined pH containing a quaternary ammonium hydroxide, a surfactant, a chelating agent, an amino acid having an aromatic ring in a side chain, and water. These are suitable for removing residues such as metals after CMP.
上記特許文献２〜５に記載の半導体デバイス用基板洗浄液は、ＣＭＰ後の洗浄液に関するものであり、いずれにもヒスチジンを含み得るものが開示されているが、銅の腐食の抑制（＝Ｃｕエッチングレート）及び基板表面の残渣（Ｃｕ−ＢＴＡ）の低減の両立という点で十分な機能を有する洗浄液とは考えられていなかった。
これは、バリアメタル層として最も汎用されているＣｏ系のバリアメタルに対して、洗浄液中のヒスチジン濃度を高くするとＣｏの腐食が著しく、洗浄液による洗浄欠陥が生じるため、他のバリアメタルに対しても有効ではないと考えられる傾向にあったためである。
また、ヒスチジン等を用いるアルカリ水溶液系の洗浄液を用いる場合、アルカリ性を高くするほど、洗浄剤を供給する配管やバルブなどの設備の劣化が進行しやすいため、ｐＨ８〜９程度で効果を示す洗浄液が選択されやすかったためである。
The semiconductor device substrate cleaning liquids described in Patent Documents 2 to 5 described above relate to cleaning liquids after CMP, and any one that may contain histidine has been disclosed, but suppression of copper corrosion (= Cu etching rate) ) And a residue on the substrate surface (Cu-BTA) has not been considered as a cleaning liquid having a sufficient function.
This is because, compared to Co-based barrier metals, which are most widely used as barrier metal layers, when the histidine concentration in the cleaning liquid is increased, the corrosion of Co becomes remarkable and cleaning defects are caused by the cleaning liquid. This is because there was a tendency to be considered ineffective.
In addition, when using an alkaline aqueous cleaning solution that uses histidine or the like, the higher the alkalinity, the easier the deterioration of equipment such as piping and valves for supplying the cleaning agent, so a cleaning solution that is effective at about pH 8-9 is available. This is because it was easy to be selected.
かかる状況下、本発明の目的は、半導体デバイス用基板、特にバリアメタルがＴｉ，Ｔａ，Ｒｕなどの金属を有する半導体デバイス用基板におけるＣＭＰ工程後の洗浄工程に用いられ、金属配線に対する十分な防食性を有し、残渣の発生及び基板表面への残渣の付着を抑制することができる洗浄液及び洗浄方法を提供することにある。 Under such circumstances, an object of the present invention is to provide a sufficient anticorrosion for metal wiring, which is used in a cleaning process after a CMP process in a semiconductor device substrate, particularly a semiconductor device substrate in which the barrier metal includes a metal such as Ti, Ta, Ru. It is an object of the present invention to provide a cleaning liquid and a cleaning method that can prevent generation of residues and adhesion of residues to the substrate surface.
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、下記の発明が上記目的に合致することを見出し、本発明に至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the following inventions meet the above object, and have reached the present invention.
本発明者らは、これまで洗浄液の成分としての例示こそあるものの十分な活用がされていたとは言えなかったヒスチジン系のキレートの利用に着目した。前述したようにＣｏ系のバリアメタルに対してヒスチジンを用いる洗浄液は採用されにくい。しかしながら、本発明者らが検討した結果、Ｔａ、ＴｉおよびＲｕ系のバリアメタルに対しては腐食が生じにくいことがわかった。その推定メカニズムとしては、まず、基板（バリアメタル）と洗浄剤とが接触すると、基板の表面に酸化被膜が形成される。すなわち、Ｔａ、Ｔｉの場合はＴａ2Ｏ5、ＴｉＯ2がそれぞれ酸化被膜となり、基板表面を非常に薄い膜で覆っている状態となる。Ｃｏ系のバリアメタルはキレート（例えば、ヒスチジンのような成分（Ａ）で示すもの）の濃度が高いと、コバルトが溶けてしまい、結果として、基板への腐食が進行する。一方で、Ｔｉ、Ｔａの酸化被膜は極めて安定（キレートが高くても酸化被膜が溶けない）である。以上の点で、Ｃｏには適用が困難であったが、Ｔａ，Ｔｉには適用可能であり、洗浄効果を多く発現することが可能となった。また、本発明者らが検討した結果、高いｐＨでも銅の浸食を抑えながら、十分な洗浄効果を発揮することができることを見出した。 The present inventors paid attention to the use of histidine-based chelates that have been used as examples of the components of the cleaning liquid but have not been fully utilized. As described above, it is difficult to employ a cleaning liquid that uses histidine for a Co-based barrier metal. However, as a result of studies by the present inventors, it has been found that corrosion is unlikely to occur with respect to Ta, Ti and Ru-based barrier metals. As an estimation mechanism, first, when the substrate (barrier metal) comes into contact with the cleaning agent, an oxide film is formed on the surface of the substrate. That is, in the case of Ta and Ti, Ta 2 O 5 and TiO 2 are oxide films, respectively, and the substrate surface is covered with a very thin film. When the Co-based barrier metal has a high concentration of chelate (for example, a component (A) such as histidine), cobalt is dissolved, and as a result, corrosion of the substrate proceeds. On the other hand, Ti and Ta oxide films are extremely stable (the oxide film does not dissolve even if the chelate is high). From the above points, it was difficult to apply to Co, but it could be applied to Ta and Ti, and a lot of cleaning effects could be expressed. Further, as a result of investigations by the present inventors, it has been found that a sufficient cleaning effect can be exhibited while suppressing copper erosion even at a high pH.
すなわち、本発明の要旨は以下の発明に係るものである。
＜１＞ 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、
前記半導体デバイス用基板のバリアメタル層がＴａ、ＴｉおよびＲｕからなる群から選ばれた１以上の金属を含み、
前記洗浄液が、以下の成分（Ａ）〜（Ｃ）を含有し、前記洗浄液のｐＨの値が１０〜１４であり、該洗浄液中の成分（Ａ）の濃度が０．０１２５質量％以上である半導体デバイス用基板洗浄液。
成分（Ａ）：下記一般式（１）で示される化合物
That is, the gist of the present invention relates to the following invention.
<1> A cleaning liquid for a substrate for a semiconductor device having a barrier metal layer,
The barrier metal layer of the semiconductor device substrate includes one or more metals selected from the group consisting of Ta, Ti and Ru,
The cleaning liquid contains the following components (A) to (C), the pH value of the cleaning liquid is 10 to 14, and the concentration of the component (A) in the cleaning liquid is 0.0125% by mass or more. Substrate cleaning solution for semiconductor devices.
Component (A): Compound represented by the following general formula (1)
成分（Ｂ）：ｐＨ調整剤
成分（Ｃ）：水
＜２＞ 前記成分（Ａ）の一般式（１）で示される化合物がヒスチジン及びその誘導体またはその塩である前記＜１＞に記載の半導体デバイス用基板洗浄液。
＜３＞ 前記成分（Ｂ）のｐＨ調整剤が、下記一般式（２）で示される有機第４級アンモニウム水酸化物を含む前記＜１＞または＜２＞に記載の半導体デバイス用基板洗浄液。
（Ｒ4）4Ｎ+ＯＨ- ・・・（２）
（上記式（２）において、Ｒ4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Ｒ4は全て同一でもよく、互いに異なっていてもよい。）
＜４＞ 更に成分（Ｄ）：キレート剤を含む前記＜１＞〜＜３＞のいずれかに記載の半導体デバイス用基板洗浄液。
＜５＞ 前記成分（Ｄ）のキレート剤が、ジアミノプロパン、シュウ酸、クエン酸、酒石酸、リンゴ酸、ピコリン酸、グリシン及びイミノジ酢酸からなる群から選ばれた少なくとも１種以上である前記＜４＞に記載の半導体デバイス用基板洗浄液。
＜６＞ 更に成分（Ｅ）：界面活性剤を含む前記＜１＞〜＜５＞のいずれかに記載の半導体デバイス用基板洗浄液。
＜７＞ 前記成分（Ｅ）の界面活性剤が、アニオン性界面活性剤である前記＜６＞に記載の半導体デバイス用基板洗浄液。
＜８＞ 前記アニオン性界面活性剤が、アルキルスルホン酸及びその塩、アルキルベンゼンスルホン酸及びその塩、アルキルジフェニルエーテルジスルホン酸及びその塩、アルキルメチルタウリン酸及びその塩、並びにスルホコハク酸ジエステル及びその塩からなる群から選ばれた少なくとも１種である前記＜７＞に記載の半導体デバイス用基板洗浄液。
＜９＞ 前記成分（Ｅ）として、少なくとも、ドデシルベンゼンスルホン酸を用い、当該ドデシルベンゼンスルホン酸濃度が、２．５×１０-3質量％未満である前記＜８＞に記載の半導体デバイス用基板洗浄液。
＜１０＞ 前記＜１＞〜＜９＞のいずれかに記載の半導体デバイス用基板洗浄液を用いて、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。
＜１１＞ 半導体デバイス用基板が、基板表面にＣｕ配線とバリアメタルを有し、かつ、化学的機械的研磨を行った後の基板である前記＜１０＞に記載の半導体デバイス用基板の洗浄方法。
Component (B): pH adjuster Component (C): Water <2> The semiconductor according to <1>, wherein the compound represented by the general formula (1) of the component (A) is histidine, a derivative thereof, or a salt thereof. Substrate cleaning solution for devices.
<3> The semiconductor device substrate cleaning solution according to <1> or <2>, wherein the pH adjuster of the component (B) includes an organic quaternary ammonium hydroxide represented by the following general formula (2).
(R 4 ) 4 N + OH − (2)
(In the above formula (2), R 4 represents a hydroxyl group, an alkoxy group, or an alkyl group which may be substituted with a halogen, and all four R 4 s may be the same or different from each other. )
<4> The semiconductor device substrate cleaning liquid according to any one of <1> to <3>, further comprising component (D): a chelating agent.
<5> The above-mentioned <4>, wherein the chelating agent of component (D) is at least one selected from the group consisting of diaminopropane, oxalic acid, citric acid, tartaric acid, malic acid, picolinic acid, glycine and iminodiacetic acid. > Substrate cleaning liquid for semiconductor devices.
<6> The substrate cleaning solution for a semiconductor device according to any one of <1> to <5>, further comprising a component (E): a surfactant.
<7> The substrate cleaning solution for a semiconductor device according to <6>, wherein the surfactant of the component (E) is an anionic surfactant.
<8> The anionic surfactant comprises alkyl sulfonic acid and its salt, alkyl benzene sulfonic acid and its salt, alkyl diphenyl ether disulfonic acid and its salt, alkyl methyl tauric acid and its salt, and sulfosuccinic acid diester and its salt. The substrate cleaning solution for a semiconductor device according to <7>, which is at least one selected from the group.
<9> The substrate for a semiconductor device according to <8>, wherein at least dodecylbenzenesulfonic acid is used as the component (E), and the dodecylbenzenesulfonic acid concentration is less than 2.5 × 10 −3 mass%. Cleaning liquid.
<10> A method for cleaning a semiconductor device substrate, wherein the semiconductor device substrate is cleaned using the semiconductor device substrate cleaning liquid according to any one of <1> to <9>.
<11> The method for cleaning a semiconductor device substrate according to <10>, wherein the semiconductor device substrate has a Cu wiring and a barrier metal on the substrate surface, and is a substrate after chemical mechanical polishing. .
本発明の半導体デバイス用基板洗浄液を用いることにより、ＣＭＰ工程後の半導体デバイス用基板の洗浄工程において、金属配線の銅配線の腐食を防止し、残渣の発生及び基板表面への残渣の付着を抑制して、効率的なＣＭＰ工程の後洗浄を行える。 By using the semiconductor device substrate cleaning liquid of the present invention, the copper wiring of the metal wiring is prevented from corroding in the cleaning process of the semiconductor device substrate after the CMP process, and the generation of residues and the adhesion of the residues to the substrate surface are suppressed. Thus, an efficient post-CMP cleaning can be performed.
以下、本発明の実施の形態を具体的に説明するが、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。 Hereinafter, embodiments of the present invention will be specifically described. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist.
［半導体デバイス用基板洗浄液］
本発明の半導体デバイス用基板洗浄液（以下、「本発明の洗浄液」と称す場合がある。）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る。これは、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化学的機械的研磨（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、前記半導体デバイス用基板のバリアメタル層がＴａ、ＴｉおよびＲｕからなる群から選ばれた１以上の金属を含むものに用いられる。この前記洗浄液は、以下の成分（Ａ）〜（Ｃ）を含有し、前記洗浄液のｐＨの値が１０〜１４であり、該洗浄液中の成分（Ａ）の濃度が０．０１２５質量（ｗｔ）％以上である半導体デバイス用基板洗浄液である。
[Substrate cleaning solution for semiconductor devices]
The semiconductor device substrate cleaning liquid of the present invention (hereinafter sometimes referred to as “the cleaning liquid of the present invention”) is a cleaning liquid for a semiconductor device substrate having a barrier metal layer. This is a cleaning liquid used for a semiconductor device substrate cleaning process performed after a semiconductor device substrate cleaning, preferably a chemical mechanical polishing (CMP) process in semiconductor device manufacturing, and for the semiconductor device The barrier metal layer of the substrate is used for one containing one or more metals selected from the group consisting of Ta, Ti and Ru. This cleaning liquid contains the following components (A) to (C), the pH value of the cleaning liquid is 10 to 14, and the concentration of the component (A) in the cleaning liquid is 0.0125 mass (wt) % Of the semiconductor device substrate cleaning solution.
成分（Ａ）：下記一般式（１）で示される化合物 Component (A): Compound represented by the following general formula (1)
（上記式（１）において、Ｒ1は水素原子、炭素数１〜４のアルキル基を示す。Ｒ2はカルボキシル基、カルボニル基、エステル結合を有する官能基、炭素数１〜４のアルキル基又は水素原子を示す。Ｒ3は水素原子、アセチル基、炭素数１〜４のアルキル基を示す。） (In the above formula (1), R 1 represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. R 2 represents a carboxyl group, a carbonyl group, a functional group having an ester bond, an alkyl group having 1 to 4 carbon atoms, or R 3 represents a hydrogen atom, an acetyl group, or an alkyl group having 1 to 4 carbon atoms.
成分（Ｂ）：ｐＨ調整剤
成分（Ｃ）：水
Component (B): pH adjuster component (C): Water
前述のように、アルカリ性水溶液中では、ＯＨ-が豊富に存在するため、コロイダルシリカ等のパーティクル表面が負に帯電し、洗浄対象となる基板表面も同様に負に帯電する。液中のゼータ電位が同符号に制御されることにより、電気的な反発力が発生する。その結果、基板表面からの前記パーティクルの除去を容易にすることができ、また、一度除去したパーティクルが基板表面に再付着することを防ぐこともできる。
本発明の洗浄液のｐＨは１０以上であり、好ましくはｐＨ１１以上である。また、その上限については、水溶液であることから、ｐＨの上限は通常１４以下であり、さらに好ましくは１３以下である。なお、本発明の洗浄液の使用時のｐＨは、洗浄液に含まれる各成分の添加量により調整することができる。
As described above, since OH − is abundant in the alkaline aqueous solution, the particle surface such as colloidal silica is negatively charged, and the substrate surface to be cleaned is similarly negatively charged. When the zeta potential in the liquid is controlled to the same sign, an electric repulsive force is generated. As a result, the removal of the particles from the substrate surface can be facilitated, and the particles once removed can be prevented from reattaching to the substrate surface.
The pH of the cleaning liquid of the present invention is 10 or more, preferably pH 11 or more. Moreover, about the upper limit, since it is aqueous solution, the upper limit of pH is 14 or less normally, More preferably, it is 13 or less. In addition, pH at the time of use of the washing | cleaning liquid of this invention can be adjusted with the addition amount of each component contained in a washing | cleaning liquid.
<成分（Ａ）：一般式（１）で示される化合物＞
本発明の洗浄液に含まれる成分（Ａ）は、下記一般式（１）で示される化合物である。この成分（Ａ）は、基板表面の金属配線に含まれる、タングステンやコバルトなどの不純物金属や、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。
<Component (A): Compound represented by the general formula (1)>
The component (A) contained in the cleaning liquid of the present invention is a compound represented by the following general formula (1). This component (A) chelates an insoluble metal complex of copper and an anticorrosive agent present in an impurity metal such as tungsten or cobalt contained in the metal wiring on the substrate surface or a barrier slurry used in the CMP process. It has an action of dissolving and removing.
（上記式（１）において、Ｒ1は水素原子、炭素数１〜４のアルキル基を示す。Ｒ2はカルボキシル基、カルボニル基、エステル結合を有する官能基、炭素数１〜４のアルキル基又は水素原子を示す。Ｒ3は水素原子、アセチル基、炭素数１〜４のアルキル基を示す。）
式（１）において、Ｒ1、Ｒ3は好ましくは水素原子であり、Ｒ2は好ましくは、カルボキシル基である。
(In the above formula (1), R 1 represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. R 2 represents a carboxyl group, a carbonyl group, a functional group having an ester bond, an alkyl group having 1 to 4 carbon atoms, or R 3 represents a hydrogen atom, an acetyl group, or an alkyl group having 1 to 4 carbon atoms.
In the formula (1), R 1 and R 3 are preferably hydrogen atoms, and R 2 is preferably a carboxyl group.
成分（Ａ）の式（１）で示される化合物の中でも、具体的に好ましくは、ヒスチジン及び／若しくはその誘導体、又はそれらの塩である。 Among the compounds represented by the formula (1) of the component (A), histidine and / or a derivative thereof, or a salt thereof is particularly preferable.
＜成分（Ｂ）：ｐＨ調整剤＞
本発明の洗浄液において含まれる成分（Ｂ）のｐＨ調整剤は、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などの無機酸及びその塩、又は、酢酸、乳酸などの有機酸及びその塩が好適な例として挙げられる。
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る。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など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、トリエチルアミンなど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などのアルカノールアミン及びその誘導体が好適な例として挙げられる。
<Component (B): pH adjuster>
The pH adjuster of component (B) contained in the cleaning liquid of the present invention is not particularly limited as long as it is a component that can be adjusted to the target 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, or organic acids such as acetic acid and lactic acid and salts thereof.
Moreover, about an alkali compound, an organic alkali compound and an inorganic alkali compound can be used. Examples of the organic alkali compound include salts of quaternary ammonium such as organic quaternary ammonium hydroxides and derivatives thereof, alkylamines such as trimethylamine and triethylamine and salts thereof, alkanolamines such as monoethanolamine, and the like. Derivatives are preferred examples.
本発明の洗浄剤において、使用される成分（Ｂ）のｐＨ調整剤として、好ましくは、アルカリ金属及び／若しくはアルカリ土類金属を含む無機アルカリ化合物又は下記式（２）で示される有機第４級アンモニウム水酸化物である。
（Ｒ4）4Ｎ+ＯＨ- ・・・（２）
（上記式（２）において、Ｒ4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Ｒは全て同一でもよく、互いに異なっていてもよい。）
上記一般式（２）において、Ｒ4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、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であるものが好ましい。Ｒ4のアルキル基としてはメチル基、エチル基、プロピル基、ブチル基等の炭素数１〜４の低級アルキル基が挙げられる。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の炭素数１〜４の低級ヒドロキシアルキル基が挙げられる。
In the cleaning agent of the present invention, the pH adjuster for the component (B) used is preferably an inorganic alkali compound containing an alkali metal and / or an alkaline earth metal or an organic quaternary compound represented by the following formula (2). Ammonium hydroxide.
(R 4 ) 4 N + OH − (2)
(In the above formula (2), R 4 represents a hydroxyl group, an alkoxy group, or an alkyl group which may be substituted with a halogen, and all four Rs may be the same or different from each other.)
In the general formula (2), R 4 is a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen, particularly a straight chain. What is a C1-C4 alkyl group of a chain | strand and / or a linear C1-C4 hydroxyalkyl group is preferable. Examples of the alkyl group for R 4 include lower alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the hydroxyalkyl group include lower hydroxyalkyl groups having 1 to 4 carbon atoms such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group.
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、テトラメチルアンモニウムヒドロキシド（“ＴＭＡＨ”と略記することがある。）、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”と略記することがある。）、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、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 tetramethylammonium hydroxide (sometimes abbreviated as “TMAH”), bis (2-hydroxyethyl) dimethylammonium hydroxide, and tetraethylammonium hydroxide. (May be abbreviated as “TEAH”), tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethyl (hydroxyethyl) ammonium hydroxide (common name: choline), triethyl (hydroxyethyl) ammonium hydroxide, and the like. It is done.
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、洗浄液の安定性などの理由から、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、テトラブチルアンモニウムヒドロキシドが特に好ましい。
これらの有機第４級アンモニウム水酸化物は、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。
Among the organic quaternary ammonium hydroxides described above, bis (2-hydroxyethyl) dimethylammonium hydroxide, trimethyl (hydroxy) are used for reasons such as cleaning effect, low metal residue, economy, and stability of the cleaning solution. Ethyl) ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide are particularly preferred.
These organic quaternary ammonium hydroxides may be used individually by 1 type, and may use 2 or more types together by arbitrary ratios.
＜成分（Ｃ）：水＞
本発明の洗浄液において使用される成分（Ｃ）の水は、主に溶媒としての役割を果たし、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。
<Ingredient (C): Water>
The component (C) water used in the cleaning liquid of the present invention mainly serves as a solvent, and it is preferable to use deionized water or ultrapure water in which impurities are reduced as much as possible.
＜成分（Ｄ）：キレート剤＞
本発明の洗浄剤において、上述の成分（Ａ）〜（Ｃ）に加えて、好ましくは、更に成分（Ｄ）として成分（Ａ）以外のキレート剤を含んでいても良い。
<Component (D): Chelating agent>
In the cleaning agent of the present invention, in addition to the components (A) to (C) described above, a chelating agent other than the component (A) may be further included as the component (D).
キレート剤は基板表面の金属配線に含まれる、タングステンやコバルトなどの不純物金属や、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。
キレート剤としては、上記作用を有する有機酸、無機酸、アミン類及びその塩若しくはその誘導体を使用することができ、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。
The chelating agent dissolves and removes insoluble metal complexes of copper and anticorrosive agents present in the barrier slurry used in the CMP process, including impurity metals such as tungsten and cobalt, contained in the metal wiring on the substrate surface. It has an action.
As the chelating agent, organic acids, inorganic acids, amines and salts thereof or derivatives thereof having the above-described action can be used, and one kind may be used alone, or two or more kinds may be used in an arbitrary ratio. You may use together.
成分（Ｄ）として、特にシュウ酸、クエン酸、酒石酸、リンゴ酸、ピコリン酸、エチレンジアミン、アミノエタノール、エチレンジアミン四酢酸、アンモニア、グリシン、アスパラギン酸、イミノジ酢酸、アラニン及びβ−アラニンからなる群から選ばれた少なくとも１種であることが好ましい。また、これらの塩も好適に用いることができる。 Component (D) is selected from the group consisting of oxalic acid, citric acid, tartaric acid, malic acid, picolinic acid, ethylenediamine, aminoethanol, ethylenediaminetetraacetic acid, ammonia, glycine, aspartic acid, iminodiacetic acid, alanine and β-alanine. Preferably, at least one selected from the above is used. Moreover, these salts can also be used suitably.
これらのうち、キレート効果の強度、品質の安定性や入手のしやすさにおいて、シュウ酸、クエン酸、酒石酸、ピコリン酸、グリシン及びイミノジ酢酸からなる群から選ばれた少なくとも１種を好適に用いることができる。 Of these, at least one selected from the group consisting of oxalic acid, citric acid, tartaric acid, picolinic acid, glycine and iminodiacetic acid is preferably used in terms of chelate effect strength, quality stability, and availability. be able to.
＜成分（Ｅ）：界面活性剤＞
本発明の洗浄剤において、上述の成分（Ａ）〜（Ｄ）に加えて、更に成分（Ｅ）として界面活性剤を含んでいてもよい。層間絶縁膜表面は疎水性であるため、水をベース組成とする洗浄液では洗浄が困難である。成分（Ｅ）の界面活性剤は、疎水性基板表面の親水性を向上させる作用を有するものである。界面活性剤を配合して基板表面との親和性を向上させることで、基板上に存在するパーティクルなどとの間にも洗浄液の作用を及ぼすことができ、残渣の除去に貢献することができる。界面活性剤を含まない洗浄液では、洗浄液と疎水性基板表面との親和性が低いために、洗浄効果が低くなる。
<Component (E): Surfactant>
In the cleaning agent of the present invention, in addition to the components (A) to (D) described above, a surfactant may further be included as the component (E). Since the surface of the interlayer insulating film is hydrophobic, it is difficult to clean with a cleaning liquid having a water-based composition. The component (E) surfactant has an action of improving the hydrophilicity of the hydrophobic substrate surface. By adding a surfactant to improve the affinity with the substrate surface, it is possible to act on the cleaning liquid between particles present on the substrate and contribute to the removal of residues. In the case of the cleaning liquid not containing the surfactant, the cleaning effect is low because the affinity between the cleaning liquid and the hydrophobic substrate surface is low.
成分（Ｅ）の界面活性剤としては特に制限はなく、アニオン性界面活性剤、カチオン性界面活性剤、非イオン性界面活性剤、両性界面活性剤のいずれも使用することができる。 There is no restriction | limiting in particular as surfactant of a component (E), Any of anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used.
本発明の洗浄液において好適に用いることができる界面活性剤として、アニオン性界面活性剤がある。アニオン性界面活性剤の例として、アルキルスルホン酸及びその塩、アルキルベンゼンスルホン酸及びその塩、アルキルジフェニルエーテルジスルホン酸及びその塩、アルキルメチルタウリン酸及びその塩、並びにスルホコハク酸ジエステル及びその塩が挙げられ、特に好ましいスルホン酸型アニオン性界面活性剤として、ドデシルベンゼンスルホン酸（“ＤＢＳ”と略記することがある）、ドデカンスルホン酸及びこれらのアルカリ金属塩等が挙げられる。この中でも、品質の安定性や入手のしやすさから、ドデシルベンゼンスルホン酸及びそのアルカリ金属塩が好適に用いられる。この成分（Ｅ）としてＤＢＳやそのアルカリ金属塩等を用いる場合、洗浄液中のＤＢＳやそのアルカリ金属塩の濃度は、２．５×１０-3質量％未満が好ましく、更に２．５×１０-4質量％未満であることが好ましい。ＤＢＳやそのアルカリ金属塩の濃度がこの範囲から外れるとき、Ｃｕ−ＢＴＡが悪くなる、すなわち洗浄性が低下する。また、泡立ちが生じたり、白濁が生じるおそれがある。また、ＤＢＳやそのアルカリ金属塩を用いると、Ｃｏは腐食するが、Ｔａ，Ｔｉは腐食しないため、本発明の洗浄液が適用されるバリアメタル層を有する基板に対して適した特性を有している。 An example of a surfactant that can be suitably used in the cleaning liquid of the present invention is an anionic surfactant. Examples of anionic surfactants include alkyl sulfonic acids and salts thereof, alkyl benzene sulfonic acids and salts thereof, alkyl diphenyl ether disulfonic acids and salts thereof, alkyl methyl tauric acids and salts thereof, and sulfosuccinic acid diesters and salts thereof. Particularly preferred sulfonic acid type anionic surfactants include dodecylbenzenesulfonic acid (sometimes abbreviated as “DBS”), dodecanesulfonic acid, and alkali metal salts thereof. Among these, dodecylbenzenesulfonic acid and its alkali metal salt are preferably used because of the stability of quality and availability. If this the as component (E) used DBS or its alkali metal salts, DBS and concentration of the alkali metal salt in the cleaning liquid is preferably less than 2.5 × 10 -3 wt%, further 2.5 × 10 - It is preferably less than 4 % by mass. When the concentration of DBS or its alkali metal salt is out of this range, Cu-BTA deteriorates, that is, the detergency deteriorates. In addition, foaming may occur or white turbidity may occur. Further, when DBS or an alkali metal salt thereof is used, Co is corroded, but Ta and Ti are not corroded. Therefore, it has characteristics suitable for a substrate having a barrier metal layer to which the cleaning liquid of the present invention is applied. Yes.
別のアニオン性界面活性剤の例として、カルボン酸型アニオン性界面活性剤が挙げられる。カルボン酸型アニオン性界面活性剤は、分子内にカルボキシル基を含むアニオン性界面活性剤であり、その中でも下記一般式（３）で表される化合物が好適である。
Ｒ5−Ｏ−（ＡＯ）m−（ＣＨ2）n−ＣＯＯＨ （３）
Another example of the anionic surfactant is a carboxylic acid type anionic surfactant. The carboxylic acid type anionic surfactant is an anionic surfactant containing a carboxyl group in the molecule, and among them, a compound represented by the following general formula (3) is preferable.
R 5 -O- (AO) m - (CH 2) n -COOH (3)
上記式（３）において、Ｒ5は直鎖若しくは分岐鎖のアルキル基であり、その炭素数は８〜１５、好ましくは１０〜１３である。また、ＡＯはオキシエチレン基及び／又はオキシプロピレン基であり、ｍは３〜３０、好ましくは４〜２０、より好ましくは４．５〜１０である。また、ｎは１〜６、好ましくは１〜３である。 In the above formula (3), R 5 is an alkyl group of straight or branched chain, the number of carbon atoms is 8-15, preferably 10-13. AO is an oxyethylene group and / or oxypropylene group, and m is 3 to 30, preferably 4 to 20, and more preferably 4.5 to 10. N is 1 to 6, preferably 1 to 3.
上記一般式（３）で表されるカルボン酸型アニオン性界面活性剤として、具体的には、ポリオキシエチレンラウリルエーテル酢酸、ポリオキシエチレントリデシルエーテル酢酸、ポリオキシエチレンアルキルエーテル酢酸などを挙げることができる。これらのアニオン性界面活性剤等の界面活性剤は、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。 Specific examples of the carboxylic acid type anionic surfactant represented by the general formula (3) include polyoxyethylene lauryl ether acetic acid, polyoxyethylene tridecyl ether acetic acid, polyoxyethylene alkyl ether acetic acid and the like. Can do. These surfactants such as anionic surfactants may be used alone or in combination of two or more at any ratio.
なお、界面活性剤は、通常市販されている形態において１〜数千質量ｐｐｍ程度のＮａ、Ｋ、Ｆｅ等の金属不純物を含有している場合があり、この場合には、界面活性剤が金属汚染源となる。そのため、成分（Ｅ）に金属不純物が含まれる場合には、各々の金属不純物の含有量が、通常１０ｐｐｍ以下、好ましくは１ｐｐｍ以下、更に好ましくは０．３ｐｐｍ以下となるように、成分（Ｅ）を精製して使用することが好ましい。この精製方法としては、例えば、成分（Ｅ）を水に溶解した後、イオン交換樹脂に通液し、樹脂に金属不純物を捕捉させる方法が好適である。このようにして精製された界面活性剤を使用することで、金属不純物含有量が極めて低減された洗浄液を得ることができる。 In addition, the surfactant may contain metal impurities such as Na, K, and Fe of about 1 to several thousand mass ppm in a commercially available form. In this case, the surfactant is a metal. It becomes a pollution source. Therefore, when the component (E) contains metal impurities, the component (E) is such that the content of each metal impurity is usually 10 ppm or less, preferably 1 ppm or less, more preferably 0.3 ppm or less. Is preferably used after purification. As the purification method, for example, a method in which the component (E) is dissolved in water and then passed through an ion exchange resin to capture metal impurities in the resin is suitable. By using the surfactant thus purified, it is possible to obtain a cleaning liquid in which the content of metal impurities is extremely reduced.
＜その他の成分＞
本発明の洗浄液には、その性能を損なわない範囲において、上記成分（Ａ）〜（Ｃ）（さらに、適宜成分（Ｄ），（Ｅ））以外の成分を任意の割合で含有していてもよい。
その他の成分としては、次のようなものが挙げられる。
成分（Ｂ）の効果を補完するパラトルエンスルホン酸及びその塩やナフタレンスルホン酸及びその塩；ベンゾトリアゾール、３−アミノトリアゾール、Ｎ（Ｒ3）3（Ｒ3は互いに同一であっても異なっていてもよい炭素数１〜４のアルキル基及び／又は炭素数１〜４のヒドロキシアルキル基）、ウレア、チオウレア等の含窒素有機化合物；ポリエチレングリコール、ポリビニルアルコール等の水溶性ポリマー；Ｒ4ＯＨ（Ｒ4は炭素数１〜４のアルキル基）等のアルキルアルコール系化合物；等の防食剤：
水素、アルゴン、窒素、二酸化炭素、アンモニア等の溶存ガス：
フッ酸、フッ化アンモニウム、ＢＨＦ（バッファードフッ酸）等のドライエッチング後に強固に付着したポリマー等の除去効果が期待できるエッチング促進剤：
過酸化水素、オゾン、酸素等の酸化剤：
また、溶媒として、エタノールなど水以外の成分を含んでいてもよい。
<Other ingredients>
The cleaning liquid of the present invention may contain components other than the above components (A) to (C) (further appropriate components (D) and (E)) at an arbitrary ratio within a range not impairing the performance. Good.
Examples of other components include the following.
P-Toluenesulfonic acid and its salt or naphthalenesulfonic acid and its salt to complement the effect of component (B); benzotriazole, 3-aminotriazole, N (R 3 ) 3 (R 3 is the same or different from each other) A nitrogen-containing organic compound such as urea and thiourea; a water-soluble polymer such as polyethylene glycol and polyvinyl alcohol; R 4 OH ( R 4 is an alkyl alcohol compound such as an alkyl group having 1 to 4 carbon atoms;
Dissolved gases such as hydrogen, argon, nitrogen, carbon dioxide and ammonia:
Etching accelerators that can be expected to remove polymers such as hydrofluoric acid, ammonium fluoride, BHF (buffered hydrofluoric acid), etc. that adhere firmly after dry etching:
Oxidants such as hydrogen peroxide, ozone, oxygen:
Moreover, components other than water, such as ethanol, may be included as a solvent.
＜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）〜（Ｃ）に、必要に応じて用いられるその他の成分（Ｄ）、（Ｅ）等）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（Ｃ）水に、成分（Ａ）、（Ｂ）、必要に応じて用いられるその他の成分（Ｄ）、（Ｅ）等を混合することにより製造される。
<Manufacturing method of cleaning liquid>
The method for producing the cleaning liquid of the present invention is not particularly limited, and may be a conventionally known method. For example, other components (D used as necessary for the components of the cleaning liquid (components (A) to (C)) ), (E), etc.) can be mixed. Usually, it is produced by mixing the components (A) and (B) and other components (D) and (E) used as necessary with water (C) as a solvent.
その際の混合順序も、反応や沈殿物が発生するなど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、一度に成分を混合してもよい。 The mixing order at that time is arbitrary as long as there is no particular problem such as reaction or precipitation, and any two components or three or more components are pre-blended among the components of the cleaning liquid, and then the remaining components May be mixed, or the components may be mixed at once.
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、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。）を製造した後に水で希釈して使用されることも多い。この洗浄原液における各成分の濃度は、特に制限はないが、成分（Ａ）、（Ｂ）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、洗浄原液中で分離したり、析出しない範囲であることが好ましい。具体的には、洗浄原液の好適な濃度範囲は、成分（Ａ）が、０．１〜１０．０質量％の濃度であり、成分（Ｂ）はｐＨ調整剤として用いるものによって適宜調整される。このような濃度範囲であると、輸送、保管時において、含有成分の分離を抑制でき、また、（Ｃ）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。 The cleaning liquid of the present invention can be manufactured by adjusting the concentration of each component so that the concentration is suitable for cleaning. However, from the viewpoint of reducing the cost during transportation and storage, each component is highly concentrated. In many cases, it is used after the preparation of the contained cleaning liquid (hereinafter referred to as “cleaning stock solution”) after dilution with water. The concentration of each component in this washing stock solution is not particularly limited, but components (A), (B) and other components added as necessary, and these reactants may be separated in the washing stock solution, It is preferable that it is the range which does not precipitate. Specifically, the preferred concentration range of the cleaning stock solution is that the component (A) is 0.1 to 10.0% by mass, and the component (B) is appropriately adjusted depending on what is used as a pH adjuster. . In such a concentration range, separation of contained components can be suppressed during transportation and storage, and (C) it can be suitably used as a cleaning solution having a concentration suitable for easy cleaning by adding water. it can.
成分（Ａ）の洗浄液中の好適な濃度範囲としては、０．０１２５質量％以上、より好適な範囲は０．０２０質量％以上であり、さらに好ましくは０．０２５質量％以上である。この濃度が０．０１２５質量％未満の場合、スラリー由来の不溶性析出物を除去できないおそれがある。また、成分（Ｂ）の濃度は、０．００１〜０．５質量％であることが好ましい。 A preferred concentration range of the component (A) in the cleaning liquid is 0.0125% by mass or more, a more preferred range is 0.020% by mass or more, and further preferably 0.025% by mass or more. When this concentration is less than 0.0125% by mass, insoluble precipitates derived from the slurry may not be removed. Moreover, it is preferable that the density | concentration of a component (B) is 0.001-0.5 mass%.
＜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。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、超伝導体などの各種半導体デバイス用基板が挙げられる。この中でも、本発明の洗浄液は、Ｔａ、ＴｉおよびＲｕからなる群から選ばれた１以上の金属を含むバリアメタルに腐食を引き起こすことなく効果的な洗浄を行えることができ、配線など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。
<Cleaning method of semiconductor device substrate>
Next, a method for cleaning a substrate for a semiconductor device of the present invention (hereinafter sometimes referred to as “the cleaning method of the present invention”) will be described.
The cleaning method of the present invention is performed by a method in which the above-described cleaning liquid of the present invention is brought into direct contact with a semiconductor device substrate. Examples of semiconductor device substrates to be cleaned include various semiconductor device substrates such as semiconductors, glasses, metals, ceramics, resins, magnetic materials, and superconductors. Among these, the cleaning liquid of the present invention can perform effective cleaning without causing corrosion to a barrier metal containing one or more metals selected from the group consisting of Ta, Ti and Ru, and can be used as a wiring on the surface. It is suitable for a semiconductor device substrate having a metal or a metal compound, and particularly suitable for a semiconductor device substrate having Cu wiring on the surface.
ここで、具体的に配線などとして半導体デバイス用基板の表面に使用される金属としては、バリアメタル層が前述したものであれば、Ｗ、Ｃｕ、Ｔａ、Ｔｉ、Ａｌ、Ｃｒ、Ｃｏ、Ｚｒ、Ｈｆ、Ｍｏ、Ｒｕ、Ａｕ、Ｐｔ、Ａｇ等が挙げられ、金属化合物としては、これらの金属の窒化物、酸化物、シリサイド等が挙げられる。これらの中では、Ｗ、Ｃｕ、Ａｌ、Ａｕ、Ｐｔ、Ａｇ並びにこれらを含有する金属化合物を使用したものが好適な洗浄対象である。 Here, as a metal specifically used for the surface of the substrate for a semiconductor device as a wiring or the like, if the barrier metal layer is as described above, W, Cu, Ta, Ti, Al, Cr, Co, Zr, Hf, Mo, Ru, Au, Pt, Ag, and the like can be given, and examples of the metal compound include nitrides, oxides, silicides, and the like of these metals. Among these, W, Cu, Al, Au, Pt, Ag, and those using a metal compound containing these are suitable cleaning objects.
本発明の洗浄液による洗浄は、Ｔａ、ＴｉおよびＲｕからなる群から選ばれた１以上の金属を含むバリアメタル層を有する半導体デバイス用基板の洗浄に用いられる。ここで、バリアメタル層は、通常、単独の金属あるいは、その金属の窒化物や酸化物、シリサイド等の金属化合物を主たる成分とするものから構成され、これらの金属または金属化合物の金属として、Ｔａ、ＴｉおよびＲｕのいずれかが用いられたものが洗浄対象となる。 The cleaning with the cleaning liquid of the present invention is used for cleaning a substrate for a semiconductor device having a barrier metal layer containing one or more metals selected from the group consisting of Ta, Ti and Ru. Here, the barrier metal layer is generally composed of a single metal or a metal compound such as a nitride, oxide, or silicide of the metal as a main component. , Ti and Ru are used for cleaning.
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、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。 Further, the cleaning method of the present invention is suitable for a semiconductor device substrate having a low dielectric constant insulating material because the cleaning effect is high even for a low dielectric constant insulating material having strong hydrophobicity.
このような低誘電率材料としては、Ｐｏｌｙｉｍｉｄｅ、ＢＣＢ（Ｂｅｎｚｏｃｙｃｌｏｂｕｔｅｎｅ）、Ｆｌａｒｅ（Ｈｏｎｅｙｗｅｌｌ社）、ＳｉＬＫ（Ｄｏｗ Ｃｈｅｍｉｃａｌ社）等の有機ポリマー材料やＦＳＧ（Ｆｌｕｏｒｉｎａｔｅｄ ｓｉｌｉｃａｔｅ ｇｌａｓｓ）などの無機ポリマー材料、ＢＬＡＣＫ ＤＩＡＭＯＮＤ（Ａｐｐｌｉｅｄ Ｍａｔｅｒｉａｌｓ社）、Ａｕｒｏｒａ（日本ＡＳＭ社）等のＳｉＯＣ系材料が挙げられる。 Examples of such a low dielectric constant material include organic polymer materials such as Polyimide, BCB (Benzocycle), Flare (Honeywell), SiLK (Dow Chemical), FSG (Fluorinated silicate glass), and BLACK AM (Dlack AM). Examples thereof include SiOC-based materials such as Applied Materials) and Aurora (Japan ASM).
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配線とバリアメタルを有し、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 preferably applied when the semiconductor device substrate has Cu wiring and a barrier metal on the substrate surface, and the substrate is cleaned after the CMP process.
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）など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再付着を防止する作用を有しているため、微粒子汚染の除去に対して高い効果を示す。 In the CMP process, polishing is performed by rubbing the substrate against the pad using an abrasive. The abrasive includes abrasive particles such as colloidal silica (SiO 2 ), fumed silica (SiO 2 ), alumina (Al 2 O 3 ), and ceria (CeO 2 ). Such abrasive particles are a major cause of particulate contamination of the substrate for semiconductor devices. However, the cleaning liquid of the present invention has an action of removing the fine particles adhering to the substrate and dispersing them in the cleaning liquid and preventing re-adhesion. Therefore, it has a high effect on removing fine particle 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。 Further, the abrasive may contain additives other than abrasive particles such as an oxidizing agent and a dispersant. In particular, in CMP polishing on 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 tends to corrode.
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、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、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 anticorrosive, an azole anticorrosive having a high anticorrosive effect is preferably used. More specifically, examples of the hetero atom containing a heterocyclic ring containing only a nitrogen atom include a diazole type, a triazole type, and a tetrazole type, and those containing a heterocyclic ring of a nitrogen atom and an oxygen atom, An oxazole type and an oxadiazole type are mentioned, As a thing containing the heterocyclic ring of a nitrogen atom and a sulfur atom, a thiazole type, an isothiazole type, and a thiadiazole type are mentioned. Among them, a benzotriazole (BTA) anticorrosive having an excellent anticorrosion effect is particularly preferably used.
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、スループットの向上が可能である。 When the cleaning liquid of the present invention is applied to the surface of a substrate after being polished with an abrasive containing such an anticorrosive, it is excellent in that the contamination derived from the anticorrosive can be removed extremely effectively. That is, when these anticorrosives are present in the abrasive, the corrosion of the surface of the Cu film is suppressed, but on the other hand, it reacts with Cu ions eluted during polishing to produce a large amount of insoluble precipitates. The cleaning liquid of the present invention can efficiently dissolve and remove such insoluble precipitates, and can improve the throughput.
そのため、本発明の洗浄方法は、Ｃｕ膜とバリアメタルが共存した表面を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。 Therefore, the cleaning method of the present invention is suitable for cleaning a substrate for a semiconductor device after the CMP treatment on the surface on which the Cu film and the barrier metal coexist, and in particular, the above CMP treatment with an abrasive containing an azole anticorrosive Suitable for cleaning the substrate.
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。 As described above, the cleaning method of the present invention is performed by a method in which the cleaning liquid of the present invention is brought into direct contact with the semiconductor device substrate. A cleaning liquid having a suitable component concentration is selected according to the type of the semiconductor device substrate to be cleaned.
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などが挙げられる。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などがある。 The contact method of the cleaning liquid to the substrate is a dip type in which the cleaning tank is filled with the cleaning liquid and the substrate is immersed, a spin type in which the substrate is rotated at high speed while flowing the cleaning liquid from the nozzle onto the substrate, and the substrate is cleaned by spraying the liquid on the substrate. A spray type etc. are mentioned. As an apparatus for performing such cleaning, there are a batch-type cleaning apparatus that simultaneously cleans a plurality of substrates housed in a cassette, a single-wafer cleaning apparatus that mounts and cleans a single substrate in a holder, and the like. .
本発明の洗浄液は、上記の何れの方法にも適用できるが、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。 The cleaning liquid of the present invention can be applied to any of the above-described methods, but is preferably used for spin-type or spray-type cleaning because it allows more efficient decontamination in a short time. In this case, it is preferable to apply to a single wafer cleaning apparatus in which the cleaning time and the amount of cleaning liquid used are desired, since these problems can be solved.
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更に向上し、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）やその変性物であるＰＶＦ（ポリビニルホルマール）を使用するのが好ましい。 In addition, the cleaning method of the present invention is capable of removing contamination caused by fine particles adhering to the substrate when used in combination with a cleaning method based on physical force, particularly scrub cleaning using a cleaning brush or ultrasonic cleaning with a frequency of 0.5 MHz or higher. This is preferable because it further improves and shortens the cleaning time. In particular, in the cleaning after CMP, it is preferable to perform scrub cleaning using a resin brush. The material of the resin brush can be selected arbitrarily, but for example, PVA (polyvinyl alcohol) or its modified product PVF (polyvinyl formal) is preferably used.
更に、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３０〜７０℃程度に加温してもよい。 Furthermore, you may perform the washing | cleaning by water before and / or after the washing | cleaning by the washing | cleaning method of this invention. In the cleaning method of the present invention, the temperature of the cleaning liquid is usually room temperature, but may be heated to about 30 to 70 ° C. within a range not impairing the performance.
以下、実施例により本発明を更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 Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is changed.
＜洗浄液原液の調製＞
成分（Ａ）：ヒスチジン、成分（Ｂ）：テトラエチルアンモニウムヒドロキシド（ＴＥＡＨ：四日市合成株式会社）、成分（Ｃ）：水、及び成分（Ｄ）：クエン酸を混合して、表１および表２に示す組成の実施例１〜２１、比較例１〜７の半導体デバイス用基板洗浄液の原液を調製した。次いで、該洗浄液原液に、さらに水を加えて４０倍希釈して表１および表２に示す組成の実施例および比較例の洗浄液（希釈液）を調製した。
<Preparation of washing solution stock solution>
Ingredient (A): Histidine, Ingredient (B): Tetraethylammonium hydroxide (TEAH: Yokkaichi Gosei Co., Ltd.), Ingredient (C): Water, and Ingredient (D): Citric acid are mixed, Tables 1 and 2 The stock solutions of the substrate cleaning liquids for semiconductor devices of Examples 1 to 21 and Comparative Examples 1 to 7 having the compositions shown in FIG. Next, water was further added to the cleaning solution stock and diluted 40 times to prepare cleaning solutions (diluted solutions) of Examples and Comparative Examples having the compositions shown in Tables 1 and 2.
＜ｐＨ測定＞
４０倍に希釈し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）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および２に示した。
<PH measurement>
While the cleaning liquid diluted 40 times was stirred using a magnetic stirrer, the pH was measured with a pH meter (Horiba, Ltd. “D-24”). The measurement sample kept the liquid temperature at 25 degreeC in the thermostat. The measurement results are shown in Tables 1 and 2.
＜ｐＨ測定＞
実施例１の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）堀場製作所製 商品名「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。実施例および比較例の各洗浄液の測定結果を表１および表２に示した。
<PH measurement>
While stirring the cleaning liquid of Example 1 using a magnetic stirrer, pH was measured with a pH meter (trade name “D-24” manufactured by Horiba, Ltd.). The measurement sample kept the liquid temperature at 25 degreeC in the thermostat. Tables 1 and 2 show the measurement results of the cleaning liquids of Examples and Comparative Examples.
＜Ｃｕエッチレートの測定（防食性の評価）＞
Ｃｕ膜を成膜したシリコン基板を２５ｍｍ角にカットし、蛍光Ｘ線分析装置（Ｒｉｇａｋｕ社製 型式：「ＲＩＸ３０００」）を用いて基板の膜厚を測定した。続いて、実施例および比較例の洗浄液中に２５℃に所定の時間１時間浸漬させた。浸漬後の基板を取り出してすぐに超純水で洗浄し、エアーブローで乾燥させた。
浸漬乾燥後の基板を再度、最初の測定条件と同様に蛍光Ｘ線分析装置で膜厚を測定し、Ｃｕ基板の溶解した膜厚量（膜厚減少量）を測定し、Ｃｕエッチレート［ｎｍ／ｍｉｎ］を求めた。結果を表１および表２に「Ｃｕ−Ｅｔｃｈ」として示した。
<Measurement of Cu etch rate (evaluation of corrosion resistance)>
The silicon substrate on which the Cu film was formed was cut into 25 mm square, and the film thickness of the substrate was measured using a fluorescent X-ray analyzer (model name: “RIX3000” manufactured by Rigaku). Subsequently, it was immersed in the cleaning liquids of Examples and Comparative Examples at 25 ° C. for a predetermined time of 1 hour. The substrate after immersion was taken out, immediately washed with ultrapure water, and dried by air blow.
The substrate after immersion drying was measured again with a fluorescent X-ray analyzer in the same manner as the first measurement conditions, the amount of film thickness dissolved (thickness reduction) of the Cu substrate was measured, and the Cu etch rate [nm / Min]. The results are shown in Tables 1 and 2 as “Cu-Etch”.
＜Ｃｕ−ＢＴＡ溶解度測定＞
酢酸銅（ＩＩ）（無水）を超純水で溶解し１．５質量％の水溶液（酢酸銅水溶液）を作製した。続いて、ベンゾトリアゾールを超純水で溶解し１．０質量％の水溶液（ＢＴＡ水溶液）を作製した。酢酸銅水溶液に対し、２倍の重量のＢＴＡ水溶液を加え撹拌し、０．９質量％Ｃｕ−ＢＴＡ水溶液を作製した。洗浄液４０ｇに対して、Ｃｕ−ＢＴＡ水溶液を１００μＬ加え、２分間撹拌し、溶解の有無を目視で確認した。不溶物が観察されるまで、０．９％Ｃｕ−ＢＴＡ水溶液を加え続けた。不溶物が観察されるまでの０．９％Ｃｕ−ＢＴＡ水溶液の添加液量からＣｕ−ＢＴＡ溶解度［ｍｇ／Ｌ］を求めた。結果を表１および表２に「Ｃｕ-ＢＴＡ」として示した。
<Cu-BTA solubility measurement>
Copper (II) acetate (anhydrous) was dissolved in ultrapure water to prepare a 1.5 mass% aqueous solution (copper acetate aqueous solution). Subsequently, benzotriazole was dissolved in ultrapure water to prepare a 1.0 mass% aqueous solution (BTA aqueous solution). A double weight BTA aqueous solution was added to the copper acetate aqueous solution and stirred to prepare a 0.9 mass% Cu-BTA aqueous solution. To 40 g of the cleaning liquid, 100 μL of Cu-BTA aqueous solution was added and stirred for 2 minutes, and the presence or absence of dissolution was visually confirmed. The 0.9% Cu-BTA aqueous solution was added continuously until insoluble material was observed. Cu-BTA solubility [mg / L] was determined from the amount of 0.9% Cu-BTA aqueous solution added until insoluble matter was observed. The results are shown in Tables 1 and 2 as “Cu-BTA”.
［考察］
Ｃｕ−Ｅｔｃｈの評価結果をもとに、防食性を評価した。Ｃｕ−Ｅｔｃｈが、０．１００（ｎｍ／ｍｉｎ）以下のとき、防食性を〇とした。一方、０．１００（ｎｍ／ｍｉｎ）を超えるとき、防食性を×とした。
Ｃｕ−ＢＴＡの評価結果をもとに、洗浄性を評価した。Ｃｕ-ＢＴＡが、３００ｍｇ／Ｌ以上のとき、洗浄性を〇とした。一方、３００（ｍｇ／Ｌ）未満のとき、洗浄性を×とした。
実施例１〜２１にかかる洗浄液は、防食性、洗浄性ともに〇であった。一方、比較例１、６にかかる洗浄液は、成分（Ａ）のヒスチジン濃度が低く、洗浄性が×であった。また、比較例２〜５、７〜８にかかる洗浄液は、ｐＨが１０未満であり、防食性が×であった。
[Discussion]
The anticorrosion property was evaluated based on the evaluation result of Cu-Etch. When Cu-Etch was 0.100 (nm / min) or less, the anticorrosion property was evaluated as “good”. On the other hand, when it exceeded 0.100 (nm / min), anticorrosion property was set to x.
The detergency was evaluated based on the evaluation result of Cu-BTA. When Cu-BTA was 300 mg / L or more, the detergency was evaluated as ◯. On the other hand, when it was less than 300 (mg / L), the detergency was evaluated as x.
The cleaning liquid concerning Examples 1-21 was (circle) in both anticorrosion property and detergency. On the other hand, the cleaning liquids according to Comparative Examples 1 and 6 had a low histidine concentration of the component (A) and the cleaning property was x. Moreover, the cleaning liquid concerning Comparative Examples 2-5, 7-8 was pH less than 10, and anticorrosion property was x.
本発明の半導体デバイス用基板洗浄液は、半導体デバイス用基板表面に腐食を起こすことなく、効率的に洗浄を行うことが可能であり、本発明は、半導体デバイスやディスプレイデバイスなどの製造工程における汚染半導体デバイス用基板の洗浄処理技術として、工業的に非常に有用である。 The substrate cleaning solution for a semiconductor device of the present invention can be efficiently cleaned without causing corrosion on the surface of the substrate for a semiconductor device, and the present invention is a contaminated semiconductor in a manufacturing process of a semiconductor device, a display device, etc. This is industrially very useful as a cleaning technology for device substrates.
Claims (11)
前記半導体デバイス用基板のバリアメタル層がＴａ、ＴｉおよびＲｕからなる群から選ばれた１以上の金属を含み、
前記洗浄液が、以下の成分（Ａ）〜（Ｃ）を含有し、前記洗浄液のｐＨの値が１０〜１４であり、該洗浄液中の成分（Ａ）の濃度が０．０１２５質量％以上であることを特徴とする半導体デバイス用基板洗浄液。
成分（Ａ）：下記一般式（１）で示される化合物
成分（Ｂ）：ｐＨ調整剤
成分（Ｃ）：水 A cleaning liquid for a semiconductor device substrate having a barrier metal layer,
The barrier metal layer of the semiconductor device substrate includes one or more metals selected from the group consisting of Ta, Ti and Ru,
The cleaning liquid contains the following components (A) to (C), the pH value of the cleaning liquid is 10 to 14, and the concentration of the component (A) in the cleaning liquid is 0.0125% by mass or more. A substrate cleaning solution for a semiconductor device.
Component (A): Compound represented by the following general formula (1)
Ingredient (B): pH adjuster Ingredient (C): Water
（Ｒ4）4Ｎ+ＯＨ- ・・・（２）
（上記式（２）において、Ｒ4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Ｒ4は全て同一でもよく、互いに異なっていてもよい。） The substrate cleaning solution for a semiconductor device according to claim 1 or 2, wherein the pH adjuster of the component (B) contains an organic quaternary ammonium hydroxide represented by the following general formula (2).
(R 4 ) 4 N + OH − (2)
(In the above formula (2), R 4 represents a hydroxyl group, an alkoxy group, or an alkyl group which may be substituted with a halogen, and all four R 4 s may be the same or different from each other. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015055079A JP2016178118A (en) | 2015-03-18 | 2015-03-18 | Semiconductor device substrate cleaning liquid and semiconductor device substrate cleaning method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015055079A JP2016178118A (en) | 2015-03-18 | 2015-03-18 | Semiconductor device substrate cleaning liquid and semiconductor device substrate cleaning method |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019056832A Division JP6635213B2 (en) | 2019-03-25 | 2019-03-25 | Semiconductor device substrate cleaning liquid and method for cleaning semiconductor device substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2016178118A true JP2016178118A (en) | 2016-10-06 |
Family
ID=57070286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015055079A Pending JP2016178118A (en) | 2015-03-18 | 2015-03-18 | Semiconductor device substrate cleaning liquid and semiconductor device substrate cleaning method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2016178118A (en) |
Cited By (1)
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004217814A (en) * | 2003-01-16 | 2004-08-05 | Nec Corp | Washing composition for device substrate and washing method and washing apparatus each using the same composition |
| JP2013229569A (en) * | 2012-02-17 | 2013-11-07 | Mitsubishi Chemicals Corp | Semiconductor device cleaning liquid and method for cleaning semiconductor device substrate |
| JP2014036136A (en) * | 2012-08-09 | 2014-02-24 | Mitsubishi Chemicals Corp | Substrate cleaning liquid for semiconductor device and cleaning method of substrate for semiconductor device |
| WO2014168166A1 (en) * | 2013-04-10 | 2014-10-16 | 和光純薬工業株式会社 | Cleaning agent for metal wiring substrate, and method for cleaning semiconductor substrate |
-
2015
- 2015-03-18 JP JP2015055079A patent/JP2016178118A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004217814A (en) * | 2003-01-16 | 2004-08-05 | Nec Corp | Washing composition for device substrate and washing method and washing apparatus each using the same composition |
| JP2013229569A (en) * | 2012-02-17 | 2013-11-07 | Mitsubishi Chemicals Corp | Semiconductor device cleaning liquid and method for cleaning semiconductor device substrate |
| JP2014036136A (en) * | 2012-08-09 | 2014-02-24 | Mitsubishi Chemicals Corp | Substrate cleaning liquid for semiconductor device and cleaning method of substrate for semiconductor device |
| WO2014168166A1 (en) * | 2013-04-10 | 2014-10-16 | 和光純薬工業株式会社 | Cleaning agent for metal wiring substrate, and method for cleaning semiconductor substrate |
Cited By (2)
| 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 |
| US11597896B2 (en) | 2018-08-30 | 2023-03-07 | Mitsubishi Chemical Corporation | Cleaning liquid, cleaning method, and method for producing semiconductor wafer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6711437B2 (en) | Semiconductor device substrate cleaning liquid and method for cleaning 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 | |
| JP5948758B2 (en) | Substrate cleaning solution for semiconductor device and cleaning method | |
| TWI648430B (en) | Cleaning solution for semiconductor device substrate and method for cleaning semiconductor device substrate | |
| JP6014985B2 (en) | Substrate cleaning solution for semiconductor device and cleaning method | |
| JP7400898B2 (en) | Cleaning liquid for semiconductor device substrate, method for cleaning semiconductor device substrate, method for manufacturing semiconductor device substrate, and semiconductor device substrate | |
| WO2019073931A1 (en) | Cleaning fluids, cleaning method, and production method for semiconductor wafer | |
| US11066627B2 (en) | Cleaning agent composition for semiconductor device substrate, method of cleaning semiconductor device substrate, method of manufacturing semiconductor device substrate, and semiconductor device substrate | |
| JP2016086094A (en) | Cleaning liquid for semiconductor device substrate and cleaning method for 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 | |
| JP6635213B2 (en) | Semiconductor device substrate cleaning liquid and method for cleaning semiconductor device substrate | |
| JP2016178118A (en) | Semiconductor device substrate cleaning liquid and semiconductor device substrate cleaning method | |
| JP2012044118A (en) | Cleaning fluid and cleaning method for substrate for semiconductor device | |
| JP2012119513A (en) | Cleaning liquid and cleaning method of substrate for semiconductor device | |
| JP2015203047A (en) | Semiconductor device substrate cleaning liquid and semiconductor device substrate cleaning method | |
| JP2012049387A (en) | Cleaning fluid and cleaning method of substrate for semiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20170508 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20171026 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180611 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180717 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180827 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20190108 |