JP4374989B2 - Cleaning liquid and cleaning method using the same - Google Patents
Cleaning liquid and cleaning method using the same Download PDFInfo
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- JP4374989B2 JP4374989B2 JP2003382738A JP2003382738A JP4374989B2 JP 4374989 B2 JP4374989 B2 JP 4374989B2 JP 2003382738 A JP2003382738 A JP 2003382738A JP 2003382738 A JP2003382738 A JP 2003382738A JP 4374989 B2 JP4374989 B2 JP 4374989B2
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- cleaning liquid
- liquid according
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- copper
- semiconductor substrate
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- 238000004140 cleaning Methods 0.000 title claims description 55
- 239000007788 liquid Substances 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 19
- 239000004065 semiconductor Substances 0.000 claims description 33
- 238000005530 etching Methods 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 230000007797 corrosion Effects 0.000 claims description 18
- 238000005260 corrosion Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- -1 polyoxyethylene Polymers 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 150000007514 bases Chemical class 0.000 claims description 9
- 238000001312 dry etching Methods 0.000 claims description 9
- 150000002222 fluorine compounds Chemical class 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 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 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 3
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims 2
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- HNXQXTQTPAJEJL-UHFFFAOYSA-N 2-aminopteridin-4-ol Chemical class C1=CN=C2NC(N)=NC(=O)C2=N1 HNXQXTQTPAJEJL-UHFFFAOYSA-N 0.000 description 2
- OBMBUODDCOAJQP-UHFFFAOYSA-N 2-chloro-4-phenylquinoline Chemical compound C=12C=CC=CC2=NC(Cl)=CC=1C1=CC=CC=C1 OBMBUODDCOAJQP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 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
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- YHAPLSJUSDORPR-UHFFFAOYSA-N 2-(dimethylamino)ethane-1,1-diol Chemical compound CN(C)CC(O)O YHAPLSJUSDORPR-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- RJFMDYQCCOOZHJ-UHFFFAOYSA-L 2-hydroxyethyl(trimethyl)azanium dihydroxide Chemical compound [OH-].[OH-].C[N+](C)(C)CCO.C[N+](C)(C)CCO RJFMDYQCCOOZHJ-UHFFFAOYSA-L 0.000 description 1
- FHCUSSBEGLCCHQ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CCO FHCUSSBEGLCCHQ-UHFFFAOYSA-M 0.000 description 1
- ZLRANBHTTCVNCE-UHFFFAOYSA-N 2-phenyl-3-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CN=C1C1=CC=CC=C1 ZLRANBHTTCVNCE-UHFFFAOYSA-N 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- MCGBIXXDQFWVDW-UHFFFAOYSA-N 4,5-dihydro-1h-pyrazole Chemical compound C1CC=NN1 MCGBIXXDQFWVDW-UHFFFAOYSA-N 0.000 description 1
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005229 chemical vapour deposition 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
- 239000011651 chromium Substances 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- HQLZFBUAULNEGP-UHFFFAOYSA-N hexan-3-amine Chemical compound CCCC(N)CC HQLZFBUAULNEGP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- OQNCIVCOTSERAJ-UHFFFAOYSA-N methyl(2,2,2-trihydroxyethyl)azanium;hydroxide Chemical compound [OH-].C[NH2+]CC(O)(O)O OQNCIVCOTSERAJ-UHFFFAOYSA-N 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- WJKYOQDIQYJXSD-UHFFFAOYSA-N propan-1-imine Chemical compound CCC=N WJKYOQDIQYJXSD-UHFFFAOYSA-N 0.000 description 1
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 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
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ASVMCHUOIVTKQQ-UHFFFAOYSA-M triethyl(methyl)azanium;fluoride Chemical compound [F-].CC[N+](C)(CC)CC ASVMCHUOIVTKQQ-UHFFFAOYSA-M 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Detergent Compositions (AREA)
- Weting (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Description
本発明は、半導体基体表面の付着物を除去する洗浄液および該洗浄液を用いる洗浄方法に関し、詳しくは半導体基体表面の強固な付着物を半導体基体上の金属配線、層間絶縁膜などにダメージを与えずに除去できる洗浄液および該洗浄液を用いる洗浄方法に関するものである。 The present invention relates to a cleaning liquid for removing deposits on the surface of a semiconductor substrate and a cleaning method using the cleaning liquid. More specifically, the solid deposits on the surface of a semiconductor substrate do not damage metal wirings, interlayer insulating films, etc. on the semiconductor substrate. And a cleaning method using the cleaning liquid.
今日、高集積化されたLSIなどの半導体素子の製造方法としては、一般にリソグラフィー法が採用されている。このリソグラフィー法により半導体素子を製造する場合には、通常シリコンウェハーなどの基板上に、導電用配線素材となる金属膜などの導電薄膜や、導電薄膜や配線間の絶縁を行う目的のシリコン酸化膜などの層間絶縁膜を形成した後、その表面にフォトレジストを均質に塗布して感光層を設け、これに選択的露光および現像処理を施して所望のレジストパターンを形成する。次いで、このレジストパターンをマスクとして下層部の薄膜に選択的エッチング処理を施すことにより、該薄膜に所望のレジストパターンを形成する。そして、その後このレジストパターンを完全に除去するという一連の工程がとられている。 Today, a lithography method is generally employed as a method for manufacturing a highly integrated semiconductor device such as an LSI. When a semiconductor element is manufactured by this lithography method, a conductive thin film such as a metal film, which is a conductive wiring material, or a silicon oxide film for the purpose of insulation between the conductive thin film and the wiring is usually formed on a substrate such as a silicon wafer. After forming an interlayer insulating film such as the above, a photoresist is uniformly applied to the surface to provide a photosensitive layer, which is subjected to selective exposure and development treatment to form a desired resist pattern. Next, a selective resist pattern is formed on the thin film by subjecting the thin film in the lower layer portion to selective etching using the resist pattern as a mask. Thereafter, a series of steps of completely removing the resist pattern is taken.
ところで、近年、半導体素子は高集積化が進み、0.18μm以下のパターン形成が必要となってきており、この加工寸法の超微細化に伴い、上記選択的エッチング処理においてはドライエッチング法が主流となってきている。ドライエッチング処理においては、形成されたパターン周辺部に、ドライエッチングガス、レジスト、被加工膜およびドライエッチング装置内の処理室部材などに起因する残渣(以下、これらをエッチング残渣という)が生成することが知られている。エッチング残渣が、特にビアホール内部およびその周辺部に残存すると、高抵抗化を招いたり、電気的に短絡が生じたりするなどの好ましくない事態を招くおそれがある。 By the way, in recent years, semiconductor elements have been highly integrated, and pattern formation of 0.18 μm or less has become necessary. With the miniaturization of the processing dimensions, dry etching is the mainstream in the selective etching process. It has become. In the dry etching process, a residue (hereinafter referred to as an etching residue) due to a dry etching gas, a resist, a film to be processed, a processing chamber member in the dry etching apparatus, and the like is generated around the formed pattern. It has been known. If the etching residue remains inside and around the via hole, in particular, there is a possibility of causing an undesirable situation such as an increase in resistance or an electrical short circuit.
従来、半導体素子等に金属配線を形成する工程においてエッチング残渣を除去するための洗浄液として、例えば、特許文献1、特許文献2等には、アルカノールアミンと有機溶剤の混合系からなる有機アミン系剥離液が開示されている。
これら有機アミン系剥離液は、エッチング残渣およびレジスト等の除去後に水洗を行った場合には、吸湿した水分によりアミンの解離が起こり、アルカリ性となる結果、微細配線加工の配線材料に使用される金属薄膜等を腐食するおそれがある。そのため、上記腐食を避けるためには、リンス液にアルコール等の有機溶剤を使用しなければならないという問題点がある。
Conventionally, as a cleaning liquid for removing an etching residue in a process of forming a metal wiring on a semiconductor element or the like, for example,
These organic amine-based stripping solutions, when washed with water after removal of etching residues and resists, cause dissociation of amines due to moisture absorbed and become alkaline, resulting in the metal used for wiring materials for fine wiring processing. There is a risk of corrosion of thin films. Therefore, in order to avoid the corrosion, there is a problem that an organic solvent such as alcohol must be used for the rinse liquid.
また、有機アミン系剥離液よりもエッチング残渣、レジスト硬化層の除去能力が高い洗浄剤として、例えば、特許文献3、特許文献4等にはフッ素化合物、有機溶剤および防食剤等からなるフッ素系洗浄液が開示されているが、近年、半導体素子の製造工程におけるドライエッチングの条件が厳しくなり、ドライエッチングの際に使用するガスや温度条件によりレジスト自体が変質され易くなり、上記の有機アミン系剥離液やフッ素系水溶液ではエッチング残渣の完全な除去ができなくなっている。 Further, as a cleaning agent having a higher ability to remove etching residues and resist cured layers than organic amine-based stripping solutions, for example, Patent Document 3, Patent Document 4 and the like include a fluorine-based cleaning liquid composed of a fluorine compound, an organic solvent, an anticorrosive, and the like. However, in recent years, the conditions for dry etching in semiconductor device manufacturing processes have become stricter, and the resist itself is likely to be altered by the gas and temperature conditions used during dry etching. Etching residues cannot be completely removed with fluorinated aqueous solutions.
また、配線素材として従来多用されていたアルミニウムを主成分とする素材では、電気抵抗が高すぎて回路を高速で動作させることが困難となってきており、配線素材として銅単体の利用が高まりつつある。そこで、このような配線素材にダメージを与えることなくエッチング残渣を効率良く除去することが、高品質の半導体素子を製造するために極めて重要な課題となってきている。 In addition, aluminum-based materials, which have been widely used as wiring materials, have become too difficult to operate circuits at high speed due to too high electrical resistance, and the use of copper alone as wiring materials is increasing. is there. Thus, efficient removal of etching residues without damaging such wiring materials has become an extremely important issue for manufacturing high-quality semiconductor elements.
さらに、有機溶剤を多量に含む有機アミン系洗浄液やフッ素系洗浄液は、どちらも半導体製造プロセスにおいて安全対策や廃液処理などの環境面の負荷が大きく、その対策が重要となっており、例えば、特許文献5には有機酸の水溶液である酸系洗浄剤が、また特許文献6には、硝酸と、硫酸およびリン酸の水溶液である酸系洗浄剤が開示されている。しかしながら、何れも、より強固となっているエッチング残渣、特に層間絶縁膜成分を含んだエッチング残渣に対しては除去能力が不充分である。
従って、半導体製造プロセスにおいて、配線素材にダメージを与えることなくエッチング残渣を完全に除去でき、かつ、半導体製造プロセスにおける安全および環境面の負荷が小さい洗浄液が強く要望されている。
In addition, organic amine cleaning liquids and fluorine-based cleaning liquids containing a large amount of organic solvents both have significant environmental impacts such as safety measures and waste liquid treatment in the semiconductor manufacturing process, and such measures are important. Document 5 discloses an acid detergent that is an aqueous solution of an organic acid, and Patent Document 6 discloses an acid detergent that is an aqueous solution of nitric acid, sulfuric acid, and phosphoric acid. However, in any case, the removal capability is insufficient with respect to the etching residue that is stronger, particularly the etching residue containing the interlayer insulating film component.
Accordingly, there is a strong demand for a cleaning solution that can completely remove etching residues without damaging the wiring material in the semiconductor manufacturing process and that has a small safety and environmental burden in the semiconductor manufacturing process.
本発明は、半導体基体のドライエッチング後に残存するエッチング残渣を短時間で除去でき、かつ、銅配線材料や絶縁膜材料等を酸化または腐食しない洗浄液を提供すること、および該洗浄液を用いる金属配線が施された半導体基体の洗浄方法を提供することを目的とする。 The present invention provides a cleaning solution that can remove etching residues remaining after dry etching of a semiconductor substrate in a short time and that does not oxidize or corrode copper wiring materials, insulating film materials, etc., and a metal wiring using the cleaning solution. An object is to provide a method for cleaning an applied semiconductor substrate.
本発明者らは、上記課題を解決するために鋭意研究した結果、硝酸、硫酸、フッ素化合物および塩基性化合物に、腐食防止剤を組合わせて使用することにより、優れた洗浄液が得られることを見出した。
すなわち、本発明は、
(1)硝酸、硫酸、フッ素化合物および腐食防止剤を含有し、塩基性化合物を添加してpHが3〜7に調整され、水の濃度が80重量%以上であることを特徴とする半導体基体用洗浄液、および
(2)上記(1)に記載の洗浄液を用いることを特徴とする金属配線が施された半導体基体の洗浄方法
を提供するものである。
As a result of diligent research to solve the above problems, the present inventors have found that an excellent cleaning solution can be obtained by using a combination of a corrosion inhibitor with nitric acid, sulfuric acid, a fluorine compound and a basic compound. I found it.
That is, the present invention
(1) A semiconductor substrate comprising nitric acid, sulfuric acid, a fluorine compound and a corrosion inhibitor, adjusted to pH 3 to 7 by adding a basic compound, and having a water concentration of 80% by weight or more And (2) a method for cleaning a semiconductor substrate provided with metal wiring, characterized by using the cleaning liquid described in (1) above.
本発明の洗浄液は、安全および環境面の負荷が小さい洗浄液である。本発明の洗浄剤を使用することにより、半導体基体上のエッチング残渣を短時間で容易に除去することができるため、配線材料を全く腐食せずに半導体基体の微細加工が可能となる。さらに、リンス液としてアルコールのような有機溶剤を使用する必要がなく、水のみでリンスすることができるので、高精度、高品質の回路配線製造が可能となる。 The cleaning liquid of the present invention is a cleaning liquid with a small safety and environmental load. Since the etching residue on the semiconductor substrate can be easily removed in a short time by using the cleaning agent of the present invention, the semiconductor substrate can be finely processed without corroding the wiring material at all. Furthermore, it is not necessary to use an organic solvent such as alcohol as the rinsing liquid, and rinsing can be performed only with water, so that high-precision and high-quality circuit wiring can be manufactured.
本発明で用いられる洗浄液中の硝酸および硫酸の濃度は、好ましくは0.001〜10重量%、特に好ましくは0.005〜8重量%である。
硝酸と硫酸の濃度は同じでも良いし、各々異なっていても良いが、硫酸/硝酸の重量比は、0.1〜1000重量比が好ましく、1.0〜100重良比がより好ましく、1〜60重量比が更に好ましい。
また、該洗浄液中での水の濃度は、80重量%以上、好ましくは85重量%以上である。
洗浄液中の硝酸濃度、硫酸濃度、および水の濃度を前記範囲とすることで、エッチング残渣が効率良く除去でき、かつ配線材料等の腐食を効果的に押さえることができる。
The concentration of nitric acid and sulfuric acid in the cleaning liquid used in the present invention is preferably 0.001 to 10% by weight, particularly preferably 0.005 to 8% by weight.
The concentration of nitric acid and sulfuric acid may be the same or different, but the weight ratio of sulfuric acid / nitric acid is preferably 0.1 to 1000 weight ratio, more preferably 1.0 to 100 weight ratio, A 60 weight ratio is more preferred.
The concentration of water in the cleaning liquid is 80% by weight or more, preferably 85% by weight or more.
By setting the nitric acid concentration, sulfuric acid concentration, and water concentration in the cleaning liquid within the above ranges, etching residues can be efficiently removed, and corrosion of the wiring material and the like can be effectively suppressed.
一方、本発明で用いられるフッ素化合物としては、フッ化水素酸、フッ化アンモニウム、酸性フッ化アンモニウム、および下記の一般式(1)で示されるフッ化第四級アンモニウム等が挙げられる。 On the other hand, examples of the fluorine compound used in the present invention include hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, and quaternary ammonium fluoride represented by the following general formula (1).
(式中、R1、R2、R3およびR4は、各々独立して、炭素数が1〜6のアルキル基、ヒドロキシアルキル基、アルコキシアルキル基、またはアルケニル基および炭素数が6〜12のアリール基、アラルキル基を示す。)
一般式(1)で表されるフッ化第四級アンモニウムの具体例としては、フッ化テトラメチルアンモニウム、フッ化テトラエチルアンモニウム、フッ化トリエチルメチルアンモニウム、フッ化トリメチルヒドロキシエチルアンモニウム、フッ化テトラエタノールアンモニウム、フッ化メチルトリエタノールアンモニウム等が挙げられる。これらの中ではフッ化アンモニウムおよびフッ化テトラメチルアンモニウムが好ましい。
Wherein R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group, an alkoxyalkyl group, or an alkenyl group and 6 to 12 carbon atoms. An aryl group or an aralkyl group of
Specific examples of the quaternary ammonium fluoride represented by the general formula (1) include tetramethylammonium fluoride, tetraethylammonium fluoride, triethylmethylammonium fluoride, trimethylhydroxyethylammonium fluoride, and tetraethanolammonium fluoride. And methyltriethanolammonium fluoride. Of these, ammonium fluoride and tetramethylammonium fluoride are preferred.
本発明に用いられる上記のフッ素化合物は、単独でも2種類以上組み合わせて用いてもよい。また、本発明の洗浄液中のフッ素化合物の濃度は、好ましくは0.001〜15重量%であり、特に好ましくは0.005〜10重量%である。
フッ素化合物の濃度が0.001重量%以上でエッチング残渣を効率良く除去でき、15重量%を越えると配線材料等への腐食の問題が生じるおそれがある。
The above fluorine compounds used in the present invention may be used alone or in combination of two or more. The concentration of the fluorine compound in the cleaning liquid of the present invention is preferably 0.001 to 15% by weight, and particularly preferably 0.005 to 10% by weight.
Etching residues can be efficiently removed when the concentration of the fluorine compound is 0.001% by weight or more, and if it exceeds 15% by weight, there is a possibility that a problem of corrosion of the wiring material or the like may occur.
本発明で用いられる腐食防止剤としては、特に制限はなく、燐酸系、カルボン酸系、アミン系、オキシム系、芳香族ヒドロキシ化合物、トリアゾ-ル化合物、糖アルコ-ル等、各種のものを使用することができる。好ましい腐食防止剤としては、分子内に少なくとも1つのアミノ基またはチオール基を含むポリエチレンイミン、3−アミノトリアゾールなどのトリアゾール類、2,4−ジアミノ−6−メチル−1,3,5−トリアジン等のトリアジン誘導体、2−アミノ−4−ヒドロキシプテリン、2−アミノ−4,6−ジヒドロキシプテリン等のプテリン誘導体、ポリアミンスルホンが挙げられる。これらの中では、下記の式(2)の構造を有する、平均分子量が200〜100,000、好ましくは1,000〜80,000のポリエチレンイミン(PEI)が特に好ましい。 The corrosion inhibitor used in the present invention is not particularly limited, and various types such as phosphoric acid-based, carboxylic acid-based, amine-based, oxime-based, aromatic hydroxy compound, triazole compound, sugar alcohol and the like are used. can do. Preferred corrosion inhibitors include polyethyleneimine containing at least one amino group or thiol group in the molecule, triazoles such as 3-aminotriazole, 2,4-diamino-6-methyl-1,3,5-triazine, and the like. Triazine derivatives, pterin derivatives such as 2-amino-4-hydroxypterin and 2-amino-4,6-dihydroxypterin, and polyamine sulfone. Among these, polyethyleneimine (PEI) having the structure of the following formula (2) and having an average molecular weight of 200 to 100,000, preferably 1,000 to 80,000 is particularly preferable.
本発明で用いられる塩基性化合物としては、無金属イオン塩基が好ましく、例えば、アンモニア、第1アミン、第2アミン、第3アミン、イミン、アルカノールアミン、炭素数1〜8のアルキル基を有していてもよい窒素原子を有する複素環式化合物、および下記の一般式(3)で示される水酸化第四級アンモニウム類が挙げられる。 As the basic compound used in the present invention, a metal-free ion base is preferable, for example, ammonia, primary amine, secondary amine, tertiary amine, imine, alkanolamine, and an alkyl group having 1 to 8 carbon atoms. And a heterocyclic compound having a nitrogen atom which may be present, and quaternary ammonium hydroxides represented by the following general formula (3).
(式中、R5、R6、R7およびR8は、各々独立して炭素数が1〜6のアルキル基、ヒドロキシアルキル基、アルコキシアルキル基、またはアルケニル基および炭素数が6〜12のアリール基、アラルキル基を示す。) Wherein R 5 , R 6 , R 7 and R 8 are each independently an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group, an alkoxyalkyl group, or an alkenyl group and 6 to 12 carbon atoms. An aryl group and an aralkyl group are shown.)
第1アミンの具体例としては、エチルアミン、n−プロピルアミン、ブチルアミン、1−エチルブチルアミン、1,3−ジアミノプロパン、シクロヘキシルアミン等が挙げられる。
第2アミンとしては、ジエチルアミン、ジ−n−プロピルアミン、ジ−n−ブチルアミン、4,4'−ジアミノジフェニルアミン等が挙げられる。
第3アミンとしては、ジメチルエチルアミン、ジエチルメチルアミン、トリエチルアミン、トリブチルアミン等が挙げられる。
イミンとしては、1−プロパンイミン、ビス−(ジアルキルアミノ)イミン等が挙げられる。
アルカノールアミンとしては、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジエチルエタノールアミン、プロパノールアミン等が挙げられる。
炭素数1〜8のアルキル基を有していてもよい窒素原子を有する複素環式化合物としては、ピロール、イミダゾール、ピラゾール、ピリジン、ピロリジン、2−ピロリン、イミダゾリジン、2−ピラゾリン、ピラソリジン、ピペリジン、ピペラジン、モルホリン等が挙げられる。
Specific examples of the primary amine include ethylamine, n-propylamine, butylamine, 1-ethylbutylamine, 1,3-diaminopropane, cyclohexylamine and the like.
Examples of the secondary amine include diethylamine, di-n-propylamine, di-n-butylamine, 4,4′-diaminodiphenylamine and the like.
Examples of the tertiary amine include dimethylethylamine, diethylmethylamine, triethylamine, and tributylamine.
Examples of the imine include 1-propaneimine and bis- (dialkylamino) imine.
Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, diethylethanolamine, and propanolamine.
Examples of the heterocyclic compound having a nitrogen atom which may have an alkyl group having 1 to 8 carbon atoms include pyrrole, imidazole, pyrazole, pyridine, pyrrolidine, 2-pyrroline, imidazolidine, 2-pyrazoline, pyrazolidine, piperidine , Piperazine, morpholine and the like.
一般式(3)で表される水酸化第四級アンモニウム類の具体例としては、水酸化テトラメチルアンモニウム(TMAH)、水酸化トリメチルヒドロキシエチルアンモニウム(コリン)、水酸化メチルトリヒドロキシエチルアンモニウム、水酸化ジメチルジヒドロキシエチルアンモニウム、水酸化トリメチルエチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラブチルアンモニウム、水酸化テトラエタノールアンモニウム等が挙げられる。これらの塩基性化合物の中では、強塩基である水酸化テトラメチルアンモニウム、および水酸化トリメチルヒドロキシエチルアンモニウム(コリン)が好ましい。 Specific examples of the quaternary ammonium hydroxide represented by the general formula (3) include tetramethylammonium hydroxide (TMAH), trimethylhydroxyethylammonium hydroxide (choline), methyltrihydroxyethylammonium hydroxide, water Examples thereof include dimethyldihydroxyethylammonium oxide, trimethylethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and tetraethanolammonium hydroxide. Among these basic compounds, tetramethylammonium hydroxide, which is a strong base, and trimethylhydroxyethylammonium hydroxide (choline) are preferable.
本発明に用いられる上記の塩基性化合物は、単独でも2種類以上適宜組み合わせて用いてもよい。また、洗浄液中の塩基性化合物の濃度は、通常0.01〜15重量%の濃度で使用されるが、塩基性化合物の濃度については、洗浄液のpHが3〜7の範囲になるように適宜決定すればよい。 The basic compounds used in the present invention may be used alone or in combination of two or more. Further, the concentration of the basic compound in the cleaning solution is usually 0.01 to 15% by weight, but the concentration of the basic compound is suitably set so that the pH of the cleaning solution is in the range of 3 to 7. Just decide.
本発明の洗浄剤には、その濡れ性を向上させるために、界面活性剤を添加して使用することができる。界面活性剤としては、陽イオン性、陰イオン性、非イオン性およびフッ素系界面活性剤の何れの界面活性剤も使用することができる。これらの中で、特に陰イオン性界面活性剤が好ましく、さらにポリオキシエチレンアルキルエーテルのリン酸エステル、またはポリオキシエチレンアルキルアリールエーテルのリン酸エステルがより好ましい。ポリオキシエチレンアルキルエーテルのリン酸エステルとしては、例えば、第一工業製薬(株)製の商品名:プライサーフA215C、東邦化学工業(株)製の商品名:フォスファノールRS-710が市販されている。また、ポリオキシエチレンアルキルアリールエーテルのリン酸エステルとしては、例えば、第一工業製薬(株)製の商品名:プライサーフA212E、A217Eが市販されている。
本発明に用いられる界面活性剤は、単独でも2種類以上適宜組み合わせて用いてもよい。洗浄液中の界面活性剤の濃度は、好ましくは0.0001〜5重量%、より好ましくは0.001〜0.1重量%である。
また、本発明の洗浄液には、所望により本発明の目的を損なわない範囲で、従来から洗浄液に使用されている他の添加剤を配合してもよい。
In order to improve the wettability of the cleaning agent of the present invention, a surfactant can be added and used. As the surfactant, any of cationic, anionic, nonionic, and fluorosurfactants can be used. Of these, anionic surfactants are particularly preferred, and polyoxyethylene alkyl ether phosphates or polyoxyethylene alkyl aryl ether phosphates are more preferred. Examples of the phosphoric acid ester of polyoxyethylene alkyl ether are commercially available from Daiichi Kogyo Seiyaku Co., Ltd. under the trade name: Prisurf A215C and Toho Chemical Co., Ltd. under the trade name: Phosphanol RS-710. ing. Moreover, as a phosphoric ester of polyoxyethylene alkyl aryl ether, for example, trade names: Prisurf A212E and A217E manufactured by Daiichi Kogyo Seiyaku Co., Ltd. are commercially available.
The surfactants used in the present invention may be used alone or in combination of two or more. The concentration of the surfactant in the cleaning liquid is preferably 0.0001 to 5% by weight, more preferably 0.001 to 0.1% by weight.
Moreover, you may mix | blend with the cleaning liquid of this invention the other additive conventionally used for the cleaning liquid in the range which does not impair the objective of this invention if desired.
本発明の洗浄液のpHは3〜7の範囲であり、より好ましくは4〜6の範囲である。 洗浄液のpHが3〜7の範囲でエッチング残渣が効率良く除去できるので、この範囲でエッチングの条件や使用される半導体基体によりpHを適宜選択すればよい。
本発明の洗浄方法を実施する際の温度は、通常、常温から90℃の範囲であり、エッチングの条件や使用される半導体基体により適宜選択すればよい。
The pH of the cleaning liquid of the present invention is in the range of 3-7, more preferably in the range of 4-6. Since the etching residue can be efficiently removed when the pH of the cleaning liquid is in the range of 3 to 7, the pH may be appropriately selected depending on the etching conditions and the semiconductor substrate used.
The temperature for carrying out the cleaning method of the present invention is usually in the range from room temperature to 90 ° C., and may be appropriately selected depending on the etching conditions and the semiconductor substrate used.
本発明の洗浄法が適用される半導体基体としては、シリコン、非晶性シリコン、ポリシリコン、シリコン酸化膜、シリコン窒化膜、銅、チタン、チタン−タングステン、窒化チタン、タングステン、タンタル、タンタル化合物、クロム、クロム酸化物、クロム合金等の金属配線材料あるいはガリウム−砒素、ガリウム−リン、インジウム−リン等の化合物半導体等が施された半導体基板、ポリイミド樹脂等のプリント基板、LCD等に使用されるガラス基板等が挙げられる。
本発明の洗浄液は、前記半導体基体の中でも、金属配線が施された半導体素子または表示素子における回路を高速で動作させるために、銅単体又は銅とバリアメタル(境界金属層)の積層構造を含む金属配線が施された半導体基体に対しより効果的に使用することができる。
As the semiconductor substrate to which the cleaning method of the present invention is applied, silicon, amorphous silicon, polysilicon, silicon oxide film, silicon nitride film, copper, titanium, titanium-tungsten, titanium nitride, tungsten, tantalum, tantalum compound, Used for metal wiring materials such as chromium, chromium oxide, chromium alloy, semiconductor substrates coated with compound semiconductors such as gallium-arsenic, gallium-phosphorus, indium-phosphorus, printed circuit boards such as polyimide resin, LCD, etc. A glass substrate etc. are mentioned.
The cleaning liquid of the present invention includes a copper single body or a laminated structure of copper and a barrier metal (boundary metal layer) in order to operate a circuit in a semiconductor element or display element provided with metal wiring at a high speed among the semiconductor substrates. It can be used more effectively for a semiconductor substrate provided with metal wiring.
本発明の洗浄方法においては、必要に応じて超音波による洗浄を併用することができる。半導体基体上のエッチング残渣を除去した後のリンスとしては、アルコールのような有機溶剤、アルコールと超純水との混合物を使用することもできるが、本発明の洗浄方法によれば、超純水でリンスするだけで十分である。 In the cleaning method of the present invention, ultrasonic cleaning can be used in combination as necessary. As the rinsing after removing the etching residue on the semiconductor substrate, an organic solvent such as alcohol or a mixture of alcohol and ultrapure water can be used. However, according to the cleaning method of the present invention, ultrapure water is used. It is enough to rinse with.
以下、実施例および比較例により本発明をより具体的に説明するが、本発明はこれら実施例により何ら限定されるものではない。
実施例1〜7、および比較例1〜5
図1に、下層銅配線体1上にCVD法によりシリコン窒化膜2とシリコン酸化膜3を順に堆積させた後、レジストを塗布し、通常のフォト技術を用いてレジストを加工し、その後ドライエッチング技術を使用して前記シリコン酸化膜を所望のパターンにエッチング加工し、残存したレジストを除去した半導体素子の一部断面図を示す。図1に示すように、エッチング加工した側壁にエッチング残渣4が残存している。
上記銅回路素子を表1−1、1−2及び表2−1、2−2に示す洗浄液を用いて、所定の条件で洗浄した後、超純水でリンスして乾燥した。しかる後に、走査型電子顕微鏡(SEM)で表面状態を観察し、エッチング残渣の除去状態および銅配線体の腐食状態について評価した。その結果を第1表−1、第1表−2(実施例)及び第2表−1、第2表−2(比較例)に示した。
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not limited at all by these Examples.
Examples 1-7 and Comparative Examples 1-5
In FIG. 1, a silicon nitride film 2 and a silicon oxide film 3 are sequentially deposited on the lower
The copper circuit elements were washed under predetermined conditions using the cleaning solutions shown in Table 1-1, 1-2 and Tables 2-1 and 2-2, rinsed with ultrapure water and dried. Thereafter, the surface state was observed with a scanning electron microscope (SEM), and the removal state of the etching residue and the corrosion state of the copper wiring body were evaluated. The results are shown in Table 1, Table 1, Table 2 (Example), Table 2, and Table 2 (Comparative Example).
なお、評価基準は次の通りである。
(1)エッチング残渣の除去状態について
◎:エッチング残渣が完全に除去された。
○:エッチング残渣がほぼ完全に除去された。
△:エッチング残渣が一部残存していた。
×:エッチング残渣が大部分残存していた。
(2)銅の腐食状態について
◎:腐食が全く認められられなかった。
○:腐食が殆ど認められられなかった。
△:クレーター状あるいはピット状の腐食が認められた。
×:銅層の全面に「荒れ」が認められ、更に銅層の後退が認められた。
The evaluation criteria are as follows.
(1) About the removal state of an etching residue (double-circle): The etching residue was removed completely.
○: Etching residue was almost completely removed.
Δ: Some etching residue remained.
X: Most etching residue remained.
(2) About the corrosion state of copper (double-circle): Corrosion was not recognized at all.
○: Almost no corrosion was observed.
Δ: Crater-like or pit-like corrosion was observed.
X: “Roughness” was observed on the entire surface of the copper layer, and further receding of the copper layer was observed.
第1表−1及び第1表−2に示したように、本発明の洗浄液および洗浄方法を適用した実施例1〜7においては、銅を全く腐食することなく、エッチング残渣の除去性も優れていた。また、実施例3のように洗浄条件を実施例2より高温、長時間としても、銅を腐食することはないが、ポリエチレンイミン(腐食防止剤)未添加の場合(比較例2)には、銅の腐食が認められた。その他の比較例においても、いずれもエッチング残渣の除去が不完全であったか、または銅の腐食が生じていた。
As shown in Table 1 and Table 1, in Examples 1 to 7 to which the cleaning liquid and the cleaning method of the present invention were applied, the etching residue was excellently removed without corroding copper at all. It was. Further, even if the cleaning conditions are higher than that of Example 2 for a long time as in Example 3, copper is not corroded, but when polyethyleneimine (corrosion inhibitor) is not added (Comparative Example 2), Copper corrosion was observed. Also in other comparative examples, the removal of etching residues was incomplete or copper corrosion occurred.
1:下層銅配線体
2:シリコン窒化膜
3:シリコン酸化膜
4:エッチング残渣
1: Lower copper wiring body 2: Silicon nitride film 3: Silicon oxide film 4: Etching residue
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US10/777,085 US20040224866A1 (en) | 2003-02-19 | 2004-02-13 | Cleaning solution and cleaning process using the solution |
TW093103739A TWI403579B (en) | 2003-02-19 | 2004-02-17 | Cleaning solution and cleaning process using the solution |
KR1020040010288A KR101047776B1 (en) | 2003-02-19 | 2004-02-17 | Cleaning solution and cleaning method using the same |
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US8772214B2 (en) * | 2005-10-14 | 2014-07-08 | Air Products And Chemicals, Inc. | Aqueous cleaning composition for removing residues and method using same |
JP2008153272A (en) * | 2006-12-14 | 2008-07-03 | Tosoh Corp | Method of cleaning semiconductor device manufacturing component, and cleaning solution composition |
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CN101657887B (en) | 2007-04-13 | 2012-02-01 | 大金工业株式会社 | Etching solution |
JP2011517328A (en) * | 2008-03-07 | 2011-06-02 | アドバンスド テクノロジー マテリアルズ,インコーポレイテッド | Non-selective oxide etching wet cleaning composition and method of use |
KR101486116B1 (en) * | 2008-10-09 | 2015-01-28 | 아반토르 퍼포먼스 머티리얼스, 인크. | Aqueous acidic formulations for copper oxide etch residue removal and prevention of copper electrodeposition |
JP5519728B2 (en) * | 2011-05-17 | 2014-06-11 | 富士フイルム株式会社 | Etching method, etching solution used therefor, and method for manufacturing semiconductor device using the same |
JP6110814B2 (en) | 2013-06-04 | 2017-04-05 | 富士フイルム株式会社 | Etching solution and kit thereof, etching method using them, method for producing semiconductor substrate product, and method for producing semiconductor element |
CN113382554A (en) * | 2021-06-04 | 2021-09-10 | 广东工业大学 | Cleaning method of laser forming metal circuit |
JP7145351B1 (en) | 2022-03-25 | 2022-09-30 | 富士フイルム株式会社 | Composition, method for producing semiconductor device |
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