CN113969215A - 洗涤液组合物及使用其的洗涤方法 - Google Patents
洗涤液组合物及使用其的洗涤方法 Download PDFInfo
- Publication number
- CN113969215A CN113969215A CN202110832189.0A CN202110832189A CN113969215A CN 113969215 A CN113969215 A CN 113969215A CN 202110832189 A CN202110832189 A CN 202110832189A CN 113969215 A CN113969215 A CN 113969215A
- Authority
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- China
- Prior art keywords
- acid
- sulfonate
- cleaning composition
- fluoride
- composition according
- 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
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- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 238000004140 cleaning Methods 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 title abstract description 31
- -1 fluoride compound Chemical class 0.000 claims abstract description 51
- 238000005406 washing Methods 0.000 claims abstract description 47
- 150000007524 organic acids Chemical class 0.000 claims abstract description 42
- 239000002738 chelating agent Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims description 38
- 229910019142 PO4 Inorganic materials 0.000 claims description 31
- 239000010452 phosphate Substances 0.000 claims description 31
- 238000005498 polishing Methods 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 17
- 239000004065 semiconductor Substances 0.000 claims description 14
- 239000003945 anionic surfactant Substances 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003002 pH adjusting agent Substances 0.000 claims description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 12
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 claims description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 7
- 150000005215 alkyl ethers Chemical class 0.000 claims description 7
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 7
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 6
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 6
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 6
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 6
- 229940043276 diisopropanolamine Drugs 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 6
- HOXINJBQVZWYGZ-UHFFFAOYSA-N fenbutatin oxide Chemical compound C=1C=CC=CC=1C(C)(C)C[Sn](O[Sn](CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C1=CC=CC=C1 HOXINJBQVZWYGZ-UHFFFAOYSA-N 0.000 claims description 6
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 6
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 claims description 6
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 claims description 6
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000005228 aryl sulfonate group Chemical group 0.000 claims description 5
- HJIDCURXVDBWEO-UHFFFAOYSA-N benzene;phosphoric acid Chemical compound OP(O)(O)=O.C1=CC=CC=C1 HJIDCURXVDBWEO-UHFFFAOYSA-N 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 5
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 5
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 5
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004711 α-olefin Substances 0.000 claims description 5
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 4
- XHAZMZWXAOBLQG-UHFFFAOYSA-N (1-hydroxy-1-phosphonopropyl)phosphonic acid Chemical compound CCC(O)(P(O)(O)=O)P(O)(O)=O XHAZMZWXAOBLQG-UHFFFAOYSA-N 0.000 claims description 3
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 claims description 3
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- KQIXMZWXFFHRAQ-UHFFFAOYSA-N 1-(2-hydroxybutylamino)butan-2-ol Chemical compound CCC(O)CNCC(O)CC KQIXMZWXFFHRAQ-UHFFFAOYSA-N 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 3
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- MSAHCLIFKYIZKK-UHFFFAOYSA-N 2-[2-[bis(2-phosphonoethyl)amino]ethyl-(2-phosphonoethyl)amino]ethylphosphonic acid Chemical compound OP(O)(=O)CCN(CCP(O)(O)=O)CCN(CCP(O)(O)=O)CCP(O)(O)=O MSAHCLIFKYIZKK-UHFFFAOYSA-N 0.000 claims description 3
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 claims description 3
- QZXIXSZVEYUCGM-UHFFFAOYSA-N 2-aminopropan-2-ol Chemical compound CC(C)(N)O QZXIXSZVEYUCGM-UHFFFAOYSA-N 0.000 claims description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 3
- XYJLPCAKKYOLGU-UHFFFAOYSA-N 2-phosphonoethylphosphonic acid Chemical compound OP(O)(=O)CCP(O)(O)=O XYJLPCAKKYOLGU-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 claims description 3
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 claims description 3
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 claims description 3
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- 239000004135 Bone phosphate Substances 0.000 claims description 3
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- ODBLHEXUDAPZAU-ZAFYKAAXSA-N D-threo-isocitric acid Chemical compound OC(=O)[C@H](O)[C@@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-ZAFYKAAXSA-N 0.000 claims description 3
- 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 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- ODBLHEXUDAPZAU-FONMRSAGSA-N Isocitric acid Natural products OC(=O)[C@@H](O)[C@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-FONMRSAGSA-N 0.000 claims description 3
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- TXXHDPDFNKHHGW-CCAGOZQPSA-N Muconic acid Natural products OC(=O)\C=C/C=C\C(O)=O TXXHDPDFNKHHGW-CCAGOZQPSA-N 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- HMNDRWDQGZZYIC-UHFFFAOYSA-N [2-(phosphonomethylamino)ethylamino]methylphosphonic acid Chemical compound OP(O)(=O)CNCCNCP(O)(O)=O HMNDRWDQGZZYIC-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 229940091181 aconitic acid Drugs 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000003704 aspartic acid Nutrition 0.000 claims description 3
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 3
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C—CHEMISTRY; METALLURGY
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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Abstract
本发明涉及一种洗涤液组合物及使用其的洗涤方法。根据本发明的一方面,提供一种洗涤液组合物,其包括:螯合剂,其包括第一有机酸及第二有机酸;以及蚀刻剂,其包括氟化物化合物。
Description
技术领域
本发明涉及一种洗涤液组合物及使用其的洗涤方法。
背景技术
近年来,随着半导体器件小型化的发展,人们对基板各层的平坦度提出更高的要求。此外,为了提高生产效率,需要同时对不同硬度或性能的不同类型的表面进行平坦化处理。
化学机械抛光(CMP)是一种保证半导体器件基板的平坦度的技术。化学机械抛光在提供含有抛光粒子的抛光剂的同时,使用抛光垫对基板表面进行抛光及平坦。作为抛光剂,以二氧化硅粒子为抛光粒子的二氧化硅浆料和以氧化铈粒子为抛光粒子的氧化铈浆料得到了广泛的应用。二氧化硅浆料主要用于铜等金属及二氧化硅的抛光,氧化铈浆料用于二氧化硅及氮化硅的抛光。
在使用诸如二氧化硅浆料或氧化铈浆料之类的抛光剂执行抛光工艺之后,需要一种洗涤过程以去除残留在基板表面上的抛光碎屑、颗粒、有机残留物、副产物等。
在使用二氧化铈浆料执行CMP工艺之后,通常执行氢氟酸洗涤以去除残留在基板表面上的二氧化铈(一种抛光粒子)。然而,在氢氟酸洗涤中,由于对热氧化膜的溶解性过强,因此会产生划痕或表面缺陷,导致影响洗涤后的工艺,还会降低半导体器件的成品率及质量。另外,当使用稀氟化氢(dHF)时,对氧化膜的刻蚀作用不大。
因此,需要开发一种既能替代氟化氢,又能有效地去除CMP工艺后的残留物,并可减少缺陷发生的洗涤液。
上述描述已经在构思本公开的过程中被发明人所拥有或获取,并且,不一定是在提出本申请之前公知的技术。
发明内容
要解决的技术问题
本发明的目的在于解决上述问题,为此提供一种洗涤液组合物及使用其的洗涤方法,其中所述洗涤液组合物能够减少表面缺陷的发生,同时有效地去除使用氧化铈粒子进行抛光过程后的洗涤过程中的残留物。
然而,本发明要解决的问题并非受限于上述言及的问题,未言及的其他问题将通过下面的记载由本领域普通技术人员所明确理解。
解决问题的技术方法
根据本发明的一方面,提供一种洗涤液组合物,其包括:螯合剂,其包括第一有机酸及第二有机酸;以及蚀刻剂,其包括氟化物化合物。
根据一实施例,所述第一有机酸可以包括羧基或砜基,所述第二有机酸可以包括磷酸基。
根据一实施例,所述第一有机酸的含量可以为1重量%至10重量%,所述第二有机酸的含量可以为0.01重量%至5重量%。
根据一实施例,所述第一有机酸可以包括从由苹果酸、丙二酸、己二酸、琥珀酸、酒石酸、戊二酸、乙醇酸、天冬氨酸、衣康酸、谷氨酸、丙三羧酸、庚二酸、辛二酸、癸二酸、硬脂酸、丙酮酸、乙酰乙酸、乙醛酸、壬二酸、富马酸、戊烯二酸、创伤酸、粘康酸、乌头酸、丙三羧酸(carballylic acid)、三元酸、苯六甲酸、异柠檬酸、柠檬酸、乳酸、葡萄糖酸、马来酸、抗坏血酸、亚氨基乙酸、草酸、焦性没食子酸、甲酸、乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、十一酸、月桂酸、十三酸、肉豆蔻酸、十五酸、棕榈酸、氨基磺酸、水杨酸、对甲苯磺酸、聚苯乙烯磺酸、2-萘磺酸、聚乙烯磺酸、十二烷基苯磺酸、对羟基苯磺酸、甲基磺酸及硝基苯磺酸组成的组中选择的一种以上。
根据一实施例,所述第二有机酸可以包括从由亚乙基二膦酸、1-羟基亚乙基-1,1'-二膦酸(HEDP)、1-羟基亚丙基-1,1'-二膦酸、1-羟基丁烯基-1,1'-二膦酸、乙氨基双(亚甲基膦酸)、十二烷基氨基双(亚甲基膦酸)、2-膦酰基-丁烷-1,2,4-三羧酸(PBTC)、次氨基三(亚甲基膦酸)(NTPO)、乙二胺双(亚甲基膦酸)(EDDPO)、1,3-丙二胺双(亚甲基膦酸)、乙二胺四(亚甲基膦酸)(EDTPO)、乙二胺四(亚乙基膦酸)、1,3-丙二胺四(亚甲基膦酸)(PDTMP)、1,2-二氨基丙烷四(亚甲基膦酸)、1,6-己二胺四(亚甲基膦酸)、己烯二胺四(亚甲基膦酸)、二乙烯三胺五(亚甲基膦酸)(DEPPO)、二乙烯三胺五亚(diethylenetriaminepentakis)(甲基膦酸)、N,N,N',N'-乙二胺四(亚甲基膦酸)、二乙烯三胺五(亚乙基膦酸)、三乙烯四胺六(亚甲基膦酸)及三乙烯四胺六(亚乙基膦酸)组成的组中选择的一种以上。
根据一实施例,所述氟化物化合物可以包括从由氟化氢铵、氟化铵、氟化钠、氟化钡、氟化钙、氟化镁、氟化钾、氟化铝、三氟化氨基苯甲酸酯、三氟化硼及氟化钴组成的组中选择的一种以上。
根据一实施例,所述蚀刻剂的含量可以为0.1重量%至15重量%。
根据一实施例,还包括阴离子表面活性剂,其包括磺酸盐或磷酸盐,并且,所述阴离子表面活性剂的含量可以为0.01重量%至10重量%。
根据一实施例,所述磺酸盐可以包括从由烷基芳基磺酸盐(alkyl arylsulfonate)、烷基醚磺酸盐(alkyl ether sulfonate)、烷基磺酸盐(alkyl sulfonate)、芳基磺酸盐(aryl sulfonate)、聚苯乙烯磺酸盐(polystyrene sulfonate)、烷烃磺酸盐(alkane sulfonate)、α-烯烃磺酸盐(α-olefin sulfonate)、十二烷基苯磺酸盐(dodecylbenzene sulfonate)及烷基苯磺酸盐(alkylbenzene sulfonate)组成的组中选择的一种以上。
根据一实施例,所述磷酸盐可以包括从由烷基芳基磷酸盐(alkyl arylphosphate)、烷基醚磷酸盐(alkyl ether phosphate)、芳基醚磷酸盐(aryl etherphosphate)、烷基磷酸盐(alkyl phosphate)、芳基磷酸盐(aryl phosphate)及苯磷酸盐(benzene phosphate)组成的组中选择的一种以上。
根据一实施例,还包括pH调节剂,并且,所述pH调节剂可以包括烷醇胺、氢氧化胺或两者。
根据一实施例,所述pH调节剂可以包括从由单乙醇胺(MEA)、单正丙醇胺、单异丙醇胺、单正丁醇胺、单戊醇胺、单己醇胺、单庚醇胺、单辛醇胺、单壬醇胺、单癸醇胺、二乙醇胺(DEA)、二丙醇胺、二异丙醇胺(DIPA)、二丁醇胺、二戊醇胺、二己醇胺、二庚醇胺、二辛醇胺、二壬醇胺、二癸醇胺、N-甲基二乙醇胺(MDEA)、三乙醇胺(TEA)、三异丙醇胺(TIPA)、三戊醇胺、三己醇胺、三庚醇胺、三辛醇胺、三壬醇胺、三癸醇胺、2-氨基-2-甲基-丙醇(AMP)、1-氨基异丙醇(AIP)、2-氨基-1-丙醇、N-甲基氨基乙醇(N-MAE)、3-氨基-1-丙醇、4-氨基-1-丁醇、2-(2-氨基乙氧基)-1-乙醇(AEE)及2-(2-氨乙基氨基)-1-乙醇组成的组中选择的一种以上。
根据一实施例,所述洗涤液组合物的pH可以为2至7。
根据一实施例,可以在抛光包括氮化硅膜、氧化硅膜或两者的用于半导体器件的晶圆表面之后进行洗涤。
根据一实施例,可以用于在使用含有二氧化铈的CMP浆料进行抛光之后进行洗涤。
根据本发明的另一方面,提供一种洗涤方法,包括以下步骤:使用所述洗涤液组合物,在用于半导体器件的晶圆的化学机械抛光之后洗涤用于半导体器件的晶圆。
根据一实施例,所述洗涤液组合物可以为无(free)氟化氢。
发明的效果
根据本发明的洗涤液组合物包括含有氟化物化合物的蚀刻剂,从而在抛光过程之后进行洗涤时再次对表面给予蚀刻效果,由此可以最大化洗涤能力,还可以减少膜受损及表面缺陷。
此外,根据本发明的洗涤方法具有减少膜受损及表面缺陷的效果,同时表现出比通过使用通常使用的氢氟酸及SC1洗涤液执行洗涤过程获得的洗涤能力更优的洗涤能力。
附图说明
图1为显示根据5重量%的氟化氢铵(ABF)溶液及本发明一实施例的洗涤液组合物(实施例1-3)的室温条件下稀释比的蚀刻量的曲线图。
图2为显示根据5重量%的氟化氢铵(ABF)溶液及本发明一实施例的洗涤液组合物(实施例1-3)的60℃条件下稀释比的蚀刻量的曲线图。
具体实施方式
以下,将参照附图对实施例进行详细说明。
能够对实施例进行多种变更,本发明的权利范围并非受到实施例的限制或限定。对于实施例的全部应变、等同物或替代物均包括在权利范围内。
实施例中使用的术语仅用于说明特定实施例,并非用于限定实施例。在内容中没有特别说明的情况下,单数表达包括复数含义。在本说明书中,“包括”或者“具有”等术语用于表达存在说明书中所记载的特征、数字、步骤、操作、构成要素、配件或其组合,并不排除还具有一个或以上的其他特征、数字、步骤、操作、构成要素、配件或其组合,或者附加功能。
在没有其他定义的情况下,包括技术或者科学术语在内的在此使用的全部术语,都具有本领域普通技术人员所理解的通常的含义。通常使用的与词典定义相同的术语,应理解为与相关技术的通常的内容相一致的含义,在本申请中没有明确言及的情况下,不能过度理想化或解释为形式上的含义。
并且,在参照附图进行说明的过程中,与附图标记无关,相同的构成要素赋予相同的附图标记,并省略对此的重复的说明。在说明实施例的过程中,当判断对于相关公知技术的具体说明会不必要地混淆实施例时,省略对其详细说明。
此外,在对实施例的组件的描述中,可以使用第一、第二、A、B、(a)、(B)等术语。这些术语仅用于区分其构成元素和另一构成元素,该元素的性质、序列或顺序不受这些术语的限制。当一构成元素被描述为“连接”、“结合”或“接触”到另一构成元素时,应理解为其构成元素可以直接连接或附加到另一构成元素,也可以理解为另一构成元素“连接”、“结合”或“接触”到各构成元素之间。
对于包括在某一实施例的构成要素和具有公共功能的元素,可以在另一实施例中使用相同的名称来描述。除非另外提及,关于某一实施例的描述可以适用于其他实施例,在重复的范围内,将省略其详细描述。
根据本发明的一方面,提供一种洗涤液组合物,其包括:螯合剂,其包括第一有机酸及第二有机酸;以及蚀刻剂,其包括氟化物化合物。
根据本发明的洗涤液组合物包括含有氟化物化合物的蚀刻剂,从而在抛光过程之后进行洗涤时再次对表面给予蚀刻效果,由此可以最大化洗涤能力,还可以减少膜受损及表面缺陷。
在根据本发明的洗涤液组合物中,所述螯合剂(chelate agent)可以用于防止来自抛光浆料或抛光粒子的金属污染。即,通过将来自抛光浆料或抛光粒子的金属污染物与螯合剂进行反应并由此形成络合物,可以有效地去除用于半导体器件的晶圆表面上的金属污染。
例如,通过与所述螯合剂进行反应来形成络合物,可以有效地去除在使用包括铈粒子的抛光浆料来执行CMP工艺之后剩余的铈离子。
所述螯合剂包括两种以上的有机酸,从而有助于与残留在表面的金属离子形成络合物,并由此有效地去除金属污染物。
根据一实施例,所述第一有机酸可以包括羧基或砜基,所述第二有机酸可以包括磷酸基。
根据一实施例,所述第一有机酸的含量可以为1重量%至10重量%,所述第二有机酸的含量可以为0.01重量%至5重量%。
优选地,所述第一有机酸的含量可以为2重量%至8重量%;优选地,所述第二有机酸的含量可以为0.1重量%至3重量%。
所述第一有机酸:第二有机酸的含量比可以为2:1至10:1。
当所述第一有机酸及所述第二有机酸小于上述范围时,可能无法充分进行与残留金属离子形成络合物的过程,从而会降低金属污染物的去除效果;当当所述第一有机酸及所述第二有机酸超过上述范围时,过量添加的有机酸可能残留在晶圆表面并导致缺陷。
此外,所述第一有机酸和所述第二有机酸均被包括在上述含量范围内,由此可以优化与金属离子的络合物形成反应。
即,所述第一有机酸和第二有机酸具有不同的官能团,同时或分别与剩余的金属离子反应形成络合物,从而有效地形成络合物。
根据一实施例,所述第一有机酸可以包括从由苹果酸、丙二酸、己二酸、琥珀酸、酒石酸、戊二酸、乙醇酸、天冬氨酸、衣康酸、谷氨酸、丙三羧酸、庚二酸、辛二酸、癸二酸、硬脂酸、丙酮酸、乙酰乙酸、乙醛酸、壬二酸、富马酸、戊烯二酸、创伤酸、粘康酸、乌头酸、丙三羧酸(carballylic acid)、三元酸、苯六甲酸、异柠檬酸、柠檬酸、乳酸、葡萄糖酸、马来酸、抗坏血酸、亚氨基乙酸、草酸、焦性没食子酸、甲酸、乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、十一酸、月桂酸、十三酸、肉豆蔻酸、十五酸、棕榈酸、氨基磺酸、水杨酸、对甲苯磺酸、聚苯乙烯磺酸、2-萘磺酸、聚乙烯磺酸、十二烷基苯磺酸、对羟基苯磺酸、甲基磺酸及硝基苯磺酸组成的组中选择的一种以上。
根据一实施例,所述第二有机酸可以包括从由亚乙基二膦酸、1-羟基亚乙基-1,1'-二膦酸(HEDP)、1-羟基亚丙基-1,1'-二膦酸、1-羟基丁烯基-1,1'-二膦酸、乙氨基双(亚甲基膦酸)、十二烷基氨基双(亚甲基膦酸)、2-膦酰基-丁烷-1,2,4-三羧酸(PBTC)、次氨基三(亚甲基膦酸)(NTPO)、乙二胺双(亚甲基膦酸)(EDDPO)、1,3-丙二胺双(亚甲基膦酸)、乙二胺四(亚甲基膦酸)(EDTPO)、乙二胺四(亚乙基膦酸)、1,3-丙二胺四(亚甲基膦酸)(PDTMP)、1,2-二氨基丙烷四(亚甲基膦酸)、1,6-己二胺四(亚甲基膦酸)、己烯二胺四(亚甲基膦酸)、二乙烯三胺五(亚甲基膦酸)(DEPPO)、二乙烯三胺五亚(diethylenetriaminepentakis)(甲基膦酸)、N,N,N',N'-乙二胺四(亚甲基膦酸)、二乙烯三胺五(亚乙基膦酸)、三乙烯四胺六(亚甲基膦酸)及三乙烯四胺六(亚乙基膦酸)组成的组中选择的一种以上。
包括所述氟化物化合物的蚀刻剂可以在抛光过程之后进行洗涤时再次对已抛光的表面给予蚀刻效果,从而具有促进缺陷去除的功能。
此外,与使用氟化氢(HF)的情况相比,可以减少膜受损。
例如,在使用氧化铈粒子的CMP工艺之后的洗涤过程中,作为待抛光膜的氧化硅膜的表面被再次蚀刻并被洗涤,从而可以在减少膜受损的同时有效地去除表面缺陷。
根据一实施例,所述氟化物化合物可以包括从由氟化氢铵、氟化铵、氟化钠、氟化钡、氟化钙、氟化镁、氟化钾、氟化铝、三氟化氨基苯甲酸酯、三氟化硼及氟化钴组成的组中选择的一种以上。
根据一实施例,所述蚀刻剂的含量可以为0.1重量%至15重量%。
优选地,所述蚀刻剂的含量可以为0.5重量%至10重量%。
当所述蚀刻剂的含量小于上述范围时,洗涤时的蚀刻效果可能不显著,并降低去除表面缺陷的功能;当超过上述范围时,可能会发生膜受损或由于残留的蚀刻剂而增加表面缺陷。
根据一实施例,所述洗涤液组合物还包括阴离子表面活性剂,其包括磺酸盐或磷酸盐,并且,所述阴离子表面活性剂的含量可以为0.01重量%至10重量%。
包括所述磺酸盐或磷酸盐的阴离子表面活性剂通过降低ζ电位并电吸附到颗粒粒子的机制,可以从基板中去除粒子,并防止在基板表面重新吸附,由此可以发挥良好的洗涤效果。尤其,可以改善对氮化硅膜及氧化硅膜等亲水膜的洗涤和缺陷。
根据一实施例,所述阴离子表面活性剂的含量可以为0.01重量%至10重量%。
优选地,所述阴离子表面活性剂的含量可以为0.05重量%至8重量%;更优选地,所述阴离子表面活性剂的含量可以为0.05重量%至7重量%。
当所述阴离子表面活性剂的含量小于上述范围时,颗粒粒子可能未被充分吸附并且粒子可能未被电去除;当超过上述范围时,即使过量使用也无法获得超过一定效果的效果,因此不经济,且可能会产生残留在表面的问题。
根据一实施例,所述磺酸盐可以包括从由烷基芳基磺酸盐(alkyl arylsulfonate)、烷基醚磺酸盐(alkyl ether sulfonate)、烷基磺酸盐(alkyl sulfonate)、芳基磺酸盐(aryl sulfonate)、聚苯乙烯磺酸盐(polystyrene sulfonate)、烷烃磺酸盐(alkane sulfonate)、α-烯烃磺酸盐(α-olefin sulfonate)、十二烷基苯磺酸盐(dodecylbenzene sulfonate)及烷基苯磺酸盐(alkylbenzene sulfonate)组成的组中选择的一种以上。
根据一实施例,所述磷酸盐可以包括从由烷基芳基磷酸盐(alkyl arylphosphate)、烷基醚磷酸盐(alkyl ether phosphate)、芳基醚磷酸盐(aryl etherphosphate)、烷基磷酸盐(alkyl phosphate)、芳基磷酸盐(aryl phosphate)及苯磷酸盐(benzene phosphate)组成的组中选择的一种以上。
根据一实施例,还包括pH调节剂,并且,所述pH调节剂可以包括烷醇胺、氢氧化胺或两者。
所述pH调节剂是用于调节所述洗涤液组合物的pH值的材料。
根据一实施例,所述pH调节剂可以包括烷醇胺、氢氧化胺或两者。
根据一实施例,所述pH调节剂可以包括从由单乙醇胺(MEA)、单正丙醇胺、单异丙醇胺、单正丁醇胺、单戊醇胺、单己醇胺、单庚醇胺、单辛醇胺、单壬醇胺、单癸醇胺、二乙醇胺(DEA)、二丙醇胺、二异丙醇胺(DIPA)、二丁醇胺、二戊醇胺、二己醇胺、二庚醇胺、二辛醇胺、二壬醇胺、二癸醇胺、N-甲基二乙醇胺(MDEA)、三乙醇胺(TEA)、三异丙醇胺(TIPA)、三戊醇胺、三己醇胺、三庚醇胺、三辛醇胺、三壬醇胺、三癸醇胺、2-氨基-2-甲基-丙醇(AMP)、1-氨基异丙醇(AIP)、2-氨基-1-丙醇、N-甲基氨基乙醇(N-MAE)、3-氨基-1-丙醇、4-氨基-1-丁醇、2-(2-氨基乙氧基)-1-乙醇(AEE)及2-(2-氨乙基氨基)-1-乙醇组成的组中选择的一种以上。
可以适量使用所述pH调节剂,以调节所需pH。
根据一实施例,所述洗涤液组合物的pH可以为2至7。
所述洗涤液组合物的pH范围是在所述洗涤液组合物中能够充分发挥螯合剂、蚀刻剂及阴离子表面活性剂的功能,从而使洗涤能力和缺陷去除效果最大化的范围。此外,其还作用于氧化铈粒子与晶圆表面之间的电斥力,由于粒子的斥力特性,可以起到防止再吸附的作用。
根据实施例,所述洗涤液组合物可以包括溶剂,所述溶剂可以包括水、有机溶剂或两者。洗涤液组合物中的水用于溶解或分散洗涤液组合物中的其他组分。水最好尽可能少含杂质,以抑制其他成分的作用。具体地,优选地,可以是在使用离子交换树脂去除杂质离子之后通过过滤器去除杂质离子的离子交换水、纯水、超纯水、去离子水或蒸馏水。
根据一实施例,可以在抛光包括氮化硅膜、氧化硅膜或两者的用于半导体器件的晶圆表面之后进行洗涤。
所述蚀刻率可以指将氧化硅膜在所述洗涤液组合物中浸渍60分钟后,所述洗涤液组合物处理前后的厚度差除以处理时间而获得之值。
根据一实施例,以已使用常规氢氟酸和SC1来进行洗涤的晶圆(氮化硅膜、氧化硅膜)的缺陷为基准,使用所述洗涤液组合物进行洗涤后的氧化硅膜的缺陷比基准减少50%以上,最多减少76%以上;氮化硅膜的缺陷比基准减少10%以上,最多减少87%以上。
所述SC1是一般使用的洗涤液,指标准洗涤液(SC1,Standard Cleaning1),是氨水、过氧化氢及水的混合洗涤液。
根据一实施例,可以用于在使用含有二氧化铈的CMP浆料进行抛光之后进行洗涤。
即,在使用含有氧化铈粒子的CMP浆料进行抛光工艺之后,其可作为后续工艺用于洗涤残留物的工艺。
根据一实施例,所述残留物可以是来自CMP抛光浆料的粒子、存在于CMP抛光浆料中的化学物质、CMP抛光浆料的反应副产物、富碳粒子、抛光垫粒子、刷卸载粒子、组成粒子的设备材料,金属、金属氧化物或其组合。
根据本发明的另一方面,提供一种洗涤方法,包括以下步骤:使用所述洗涤液组合物,在用于半导体器件的晶圆的化学机械抛光之后洗涤用于半导体器件的晶圆。
根据一实施例,可以单独使用本发明的洗涤液组合物执行一次或多次,并且,可以在使用稀氟化氢(dHF)进行预处理之后,使用所述洗涤液组合物执行所述洗涤方法。
根据一实施例,可以通过在与通常的晶圆洗涤中使用的设备和条件相同的设备和条件下将所述洗涤液组合物与半导体器件晶圆直接接触来进行洗涤。
根据本发明的洗涤方法具有减少膜受损及表面缺陷的效果,同时表现出比通过使用通常使用的氢氟酸及SC1洗涤液执行洗涤过程获得的洗涤能力更优的洗涤能力。
根据一实施例,所述洗涤液组合物可以为无(free)氟化氢。
根据本发明的洗涤方法使用无氟化氢的洗涤液组合物,与使用氟化氢作为洗涤液的现有情况相比可以减少膜受损和表面缺陷,同时确保相同或更高的洗涤能力。
下面,将通过实施例及比较例来更详细地描述本发明。
然而,以下实施例仅用于说明本发明,本发明的内容并不限于以下实施例。
实验例1、蚀刻率评估
1)根据蚀刻剂的蚀刻率评估
将含有羧酸基(柠檬酸)作为螯合剂的有机酸的3重量%、含有磷酸基(HEDP,1-羟基亚乙基-1,1’-二磷酸,羟乙磷酸)的有机酸的1重量%、氟化氢铵(ABF)作为蚀刻剂的进行混合,并以单乙醇胺作为pH调节剂,将pH值调整为5,由此制备了洗涤液组合物。
作为比较例,准备了使用氟化四铵(TMAF)作为蚀刻剂的洗涤液组合物和无添加蚀刻剂的洗涤液组合物。
使用所准备的每个洗涤液组合物,对氧化硅膜(TEO)的蚀刻率进行了评估。
首先,使用DIW对面积为2×2cm的氧化物晶圆(Oxide wafer)进行洗涤并干燥,再使用反射计(Reflectometer)(Filmmetrics公司)来测量预厚度(PRE thickness)。在测量预厚度之后,在每个温度和浓度条件下将每个洗涤液组合物浸渍(dipping)60分钟,之后进行洗涤及干燥,然后测量后厚度(POST thickness)。
蚀刻率(Etchrate)由下式1计算。
[式1]
表1示出了各个洗涤液组合物的蚀刻剂的类型和含量、温度条件以及所评估的蚀刻率。
[表1]
参照表1可以看出,当不使用蚀刻剂(比较例1-1至1-3)或使用TMAF作为蚀刻剂(比较例1-4至1-6)时,根据温度或蚀刻剂的含量的蚀刻率变化并不显著。另外,在实施例1-1至1-9的情况下,即,当使用本发明的蚀刻剂时,可以看出,蚀刻率随着温度或蚀刻剂的含量的增加而显著增加。
2)根据稀释比的蚀刻率趋势评估
在室温(RT)和60℃的温度下分别测量根据5重量%氟化氢铵(ABF)溶液和实施例1-3的洗涤液组合物的稀释比的蚀刻程度,测量结果见表2。
[表2]
图1为显示根据5重量%的氟化氢铵(ABF)溶液及本发明一实施例的洗涤液组合物(实施例1-3)的室温条件下稀释比的蚀刻量的曲线图。
图2为显示根据5重量%的氟化氢铵(ABF)溶液及本发明一实施例的洗涤液组合物(实施例1-3)的60℃条件下稀释比的蚀刻量的曲线图。
参照表2及图1和图2可以看出,在室温和60℃的温度条件下,随着5重量%氟化氢铵(ABF)溶液及本发明一实施例的洗涤液组合物(实施例1-3)的稀释比增加,蚀刻量的减少程度相似。由此可知,当在洗涤液组合物中添加氟化氢铵(ABF)时,在稳定性不变的情况下维持氧化膜蚀刻性能。
实验例2、缺陷(Defect)去除效果
使用含有直径为100nm的氧化铈粒子的抛光浆料,在2psi压力下对晶圆进行CMP抛光10秒。使用根据实施例和比较例的洗涤液组合物,将刷(Brush)1及刷2分别应用于已抛光完的晶圆上,从而进行洗涤。
洗涤晶圆后,使用缺陷测量装置(KLA-Tencor公司)对其进行测量,确认其缺陷,并使用下面式2来计算缺陷去除率。
[式2]
缺陷去除率(%)={1-(缺陷数/比较例1缺陷数)}*100
表3及表4示出了所使用的实施例及比较例的组合物的组成以及所测量的缺陷去除率。
[表3]
[表4]
参照表3及表4可以看出,在实施例2-1至2-4的情况下,基于使用SC1的比较例2-1所测量的缺陷去除率相对于氮化膜和氧化膜显著增加;在实施例2-1的情况下,氮化膜的缺陷去除率提高到76.7%,氧化膜的缺陷去除率提高到87.4%。
相比之下,可以看出,在使用TMAF作为蚀刻剂的比较例2-2至2-4的情况下,基于使用SC1的比较例2-1所测量的缺陷增加率并未显著增加,氧化膜的缺陷反而有所增加。
综上,通过有限的附图对实施例进行了说明,本领域普通技术人员能够基于所述记载进行多种更改与变形。例如,所说明的技术按照与说明的方法不同的顺序执行,和/或所说明的构成要素按照与说明的方法不同的形态进行结合或组合,或者由其他构成要素或者等同物置换或代替,也能得到适当的结果。
由此,其他体现,其他实施例以及权利要求范围的等同物,均属于本发明的权利要求范围。
Claims (17)
1.一种洗涤液组合物,其特征在于,
包括:
螯合剂,其包括第一有机酸及第二有机酸;以及
蚀刻剂,其包括氟化物化合物。
2.根据权利要求1所述的洗涤液组合物,其特征在于,
所述第一有机酸包括羧基或砜基,
所述第二有机酸包括磷酸基。
3.根据权利要求1所述的洗涤液组合物,其特征在于,
所述第一有机酸的含量为1重量%至10重量%,
所述第二有机酸的含量为0.01重量%至5重量%。
4.根据权利要求1所述的洗涤液组合物,其特征在于,
所述第一有机酸包括从由苹果酸、丙二酸、己二酸、琥珀酸、酒石酸、戊二酸、乙醇酸、天冬氨酸、衣康酸、谷氨酸、丙三羧酸、庚二酸、辛二酸、癸二酸、硬脂酸、丙酮酸、乙酰乙酸、乙醛酸、壬二酸、富马酸、戊烯二酸、创伤酸、粘康酸、乌头酸、丙三羧酸(carballylic acid)、三元酸、苯六甲酸、异柠檬酸、柠檬酸、乳酸、葡萄糖酸、马来酸、抗坏血酸、亚氨基乙酸、草酸、焦性没食子酸、甲酸、乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、十一酸、月桂酸、十三酸、肉豆蔻酸、十五酸、棕榈酸、氨基磺酸、水杨酸、对甲苯磺酸、聚苯乙烯磺酸、2-萘磺酸、聚乙烯磺酸、十二烷基苯磺酸、对羟基苯磺酸、甲基磺酸及硝基苯磺酸组成的组中选择的一种以上。
5.根据权利要求1所述的洗涤液组合物,其特征在于,
所述第二有机酸包括从由亚乙基二膦酸、1-羟基亚乙基-1,1'-二膦酸(HEDP)、1-羟基亚丙基-1,1'-二膦酸、1-羟基丁烯基-1,1'-二膦酸、乙氨基双(亚甲基膦酸)、十二烷基氨基双(亚甲基膦酸)、2-膦酰基-丁烷-1,2,4-三羧酸(PBTC)、次氨基三(亚甲基膦酸)(NTPO)、乙二胺双(亚甲基膦酸)(EDDPO)、1,3-丙二胺双(亚甲基膦酸)、乙二胺四(亚甲基膦酸)(EDTPO)、乙二胺四(亚乙基膦酸)、1,3-丙二胺四(亚甲基膦酸)(PDTMP)、1,2-二氨基丙烷四(亚甲基膦酸)、1,6-己二胺四(亚甲基膦酸)、己烯二胺四(亚甲基膦酸)、二乙烯三胺五(亚甲基膦酸)(DEPPO)、二乙烯三胺五亚(diethylenetriaminepentakis)(甲基膦酸)、N,N,N',N'-乙二胺四(亚甲基膦酸)、二乙烯三胺五(亚乙基膦酸)、三乙烯四胺六(亚甲基膦酸)及三乙烯四胺六(亚乙基膦酸)组成的组中选择的一种以上。
6.根据权利要求1所述的洗涤液组合物,其特征在于,
所述氟化物化合物包括从由氟化氢铵、氟化铵、氟化钠、氟化钡、氟化钙、氟化镁、氟化钾、氟化铝、三氟化氨基苯甲酸酯、三氟化硼及氟化钴组成的组中选择的一种以上。
7.根据权利要求1所述的洗涤液组合物,其特征在于,
所述蚀刻剂的含量为0.1重量%至15重量%。
8.根据权利要求1所述的洗涤液组合物,其特征在于,
还包括:
阴离子表面活性剂,其包括磺酸盐或磷酸盐,
所述阴离子表面活性剂的含量为0.01重量%至10重量%。
9.根据权利要求8所述的洗涤液组合物,其特征在于,
所述磺酸盐包括从由烷基芳基磺酸盐、烷基醚磺酸盐、烷基磺酸盐、芳基磺酸盐、聚苯乙烯磺酸盐、烷烃磺酸盐、α-烯烃磺酸盐、十二烷基苯磺酸盐及烷基苯磺酸盐组成的组中选择的一种以上。
10.根据权利要求8所述的洗涤液组合物,其特征在于,
所述磷酸盐包括从由烷基芳基磷酸盐、烷基醚磷酸盐、芳基醚磷酸盐、烷基磷酸盐、芳基磷酸盐及苯磷酸盐组成的组中选择的一种以上。
11.根据权利要求1所述的洗涤液组合物,其特征在于,
还包括:
pH调节剂,
所述pH调节剂包括烷醇胺、氢氧化胺或两者。
12.根据权利要求11所述的洗涤液组合物,其特征在于,
所述pH调节剂包括从由单乙醇胺(MEA)、单正丙醇胺、单异丙醇胺、单正丁醇胺、单戊醇胺、单己醇胺、单庚醇胺、单辛醇胺、单壬醇胺、单癸醇胺、二乙醇胺(DEA)、二丙醇胺、二异丙醇胺(DIPA)、二丁醇胺、二戊醇胺、二己醇胺、二庚醇胺、二辛醇胺、二壬醇胺、二癸醇胺、N-甲基二乙醇胺(MDEA)、三乙醇胺(TEA)、三异丙醇胺(TIPA)、三戊醇胺、三己醇胺、三庚醇胺、三辛醇胺、三壬醇胺、三癸醇胺、2-氨基-2-甲基-丙醇(AMP)、1-氨基异丙醇(AIP)、2-氨基-1-丙醇、N-甲基氨基乙醇(N-MAE)、3-氨基-1-丙醇、4-氨基-1-丁醇、2-(2-氨基乙氧基)-1-乙醇(AEE)及2-(2-氨乙基氨基)-1-乙醇组成的组中选择的一种以上。
13.根据权利要求1所述的洗涤液组合物,其特征在于,
pH为2至7。
14.根据权利要求1所述的洗涤液组合物,其特征在于,
在抛光包括氮化硅膜、氧化硅膜或两者的用于半导体器件的晶圆表面之后进行洗涤。
15.根据权利要求1所述的洗涤液组合物,其特征在于,
用于在使用含有二氧化铈的CMP浆料进行抛光之后进行洗涤。
16.一种洗涤方法,其特征在于,
包括以下步骤:
使用权利要求1至15中任一项所述的洗涤液组合物,在用于半导体器件的晶圆的化学机械抛光之后洗涤用于半导体器件的晶圆。
17.根据权利要求16所述的洗涤方法,其特征在于,
所述洗涤液组合物为无氟化氢。
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