US20210246334A1 - Polishing composition, method for producing polishing composition, polishing method, and method for producing semiconductor substrate - Google Patents
Polishing composition, method for producing polishing composition, polishing method, and method for producing semiconductor substrate Download PDFInfo
- Publication number
- US20210246334A1 US20210246334A1 US17/240,666 US202117240666A US2021246334A1 US 20210246334 A1 US20210246334 A1 US 20210246334A1 US 202117240666 A US202117240666 A US 202117240666A US 2021246334 A1 US2021246334 A1 US 2021246334A1
- Authority
- US
- United States
- Prior art keywords
- group
- acid
- polishing
- polishing composition
- soluble polymer
- 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.)
- Abandoned
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 201
- 239000000203 mixture Substances 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims description 24
- 239000000758 substrate Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000004065 semiconductor Substances 0.000 title claims description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 71
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 125000000129 anionic group Chemical group 0.000 claims abstract description 49
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 47
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 28
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 18
- 125000003277 amino group Chemical group 0.000 claims abstract description 15
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 73
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 39
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 39
- 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 24
- 229920002125 Sokalan® Polymers 0.000 claims description 23
- 239000004584 polyacrylic acid Substances 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 9
- 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 7
- 239000000178 monomer Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 229940120146 EDTMP Drugs 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 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 6
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 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 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002270 phosphoric acid ester group Chemical group 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 claims 1
- -1 for example Substances 0.000 description 17
- 239000003112 inhibitor Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 235000011007 phosphoric acid Nutrition 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 229940024606 amino acid Drugs 0.000 description 8
- 235000001014 amino acid Nutrition 0.000 description 8
- 150000001413 amino acids Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000003002 pH adjusting agent Substances 0.000 description 8
- 239000004475 Arginine Substances 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 7
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 7
- 229960003121 arginine Drugs 0.000 description 7
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000006061 abrasive grain Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 229940005657 pyrophosphoric acid Drugs 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000007517 polishing process Methods 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 2
- XYJLPCAKKYOLGU-UHFFFAOYSA-N 2-phosphonoethylphosphonic acid Chemical compound OP(O)(=O)CCP(O)(O)=O XYJLPCAKKYOLGU-UHFFFAOYSA-N 0.000 description 2
- IHCCAYCGZOLTEU-UHFFFAOYSA-N 3-furoic acid Chemical compound OC(=O)C=1C=COC=1 IHCCAYCGZOLTEU-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 2
- RHGKLRLOHDJJDR-BYPYZUCNSA-N L-citrulline Chemical compound NC(=O)NCCC[C@H]([NH3+])C([O-])=O RHGKLRLOHDJJDR-BYPYZUCNSA-N 0.000 description 2
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 2
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 2
- 239000004472 Lysine Substances 0.000 description 2
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 2
- SEQKRHFRPICQDD-UHFFFAOYSA-N N-tris(hydroxymethyl)methylglycine Chemical compound OCC(CO)(CO)[NH2+]CC([O-])=O SEQKRHFRPICQDD-UHFFFAOYSA-N 0.000 description 2
- RHGKLRLOHDJJDR-UHFFFAOYSA-N Ndelta-carbamoyl-DL-ornithine Natural products OC(=O)C(N)CCCNC(N)=O RHGKLRLOHDJJDR-UHFFFAOYSA-N 0.000 description 2
- 108010077895 Sarcosine Proteins 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- QWCKQJZIFLGMSD-UHFFFAOYSA-N alpha-aminobutyric acid Chemical compound CCC(N)C(O)=O QWCKQJZIFLGMSD-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 229960002173 citrulline Drugs 0.000 description 2
- 235000013477 citrulline Nutrition 0.000 description 2
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 2
- XVOYSCVBGLVSOL-UHFFFAOYSA-N cysteic acid Chemical compound OC(=O)C(N)CS(O)(=O)=O XVOYSCVBGLVSOL-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000000105 evaporative light scattering detection Methods 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-N isocaproic acid Chemical compound CC(C)CCC(O)=O FGKJLKRYENPLQH-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical compound OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- AGNGYMCLFWQVGX-AGFFZDDWSA-N (e)-1-[(2s)-2-amino-2-carboxyethoxy]-2-diazonioethenolate Chemical compound OC(=O)[C@@H](N)CO\C([O-])=C\[N+]#N AGNGYMCLFWQVGX-AGFFZDDWSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- UKAUYVFTDYCKQA-UHFFFAOYSA-N -2-Amino-4-hydroxybutanoic acid Natural products OC(=O)C(N)CCO UKAUYVFTDYCKQA-UHFFFAOYSA-N 0.000 description 1
- NYPYHUZRZVSYKL-UHFFFAOYSA-N -3,5-Diiodotyrosine Natural products OC(=O)C(N)CC1=CC(I)=C(O)C(I)=C1 NYPYHUZRZVSYKL-UHFFFAOYSA-N 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
- LUTLAXLNPLZCOF-UHFFFAOYSA-N 1-Methylhistidine Natural products OC(=O)C(N)(C)CC1=NC=CN1 LUTLAXLNPLZCOF-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- CFKBCVIYTWDYRP-UHFFFAOYSA-N 10-phosphonooxydecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCOP(O)(O)=O CFKBCVIYTWDYRP-UHFFFAOYSA-N 0.000 description 1
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 1
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 1
- CVKMFSAVYPAZTQ-UHFFFAOYSA-N 2-methylhexanoic acid Chemical compound CCCCC(C)C(O)=O CVKMFSAVYPAZTQ-UHFFFAOYSA-N 0.000 description 1
- MLMQPDHYNJCQAO-UHFFFAOYSA-N 3,3-dimethylbutyric acid Chemical compound CC(C)(C)CC(O)=O MLMQPDHYNJCQAO-UHFFFAOYSA-N 0.000 description 1
- NYPYHUZRZVSYKL-ZETCQYMHSA-N 3,5-diiodo-L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC(I)=C(O)C(I)=C1 NYPYHUZRZVSYKL-ZETCQYMHSA-N 0.000 description 1
- BRMWTNUJHUMWMS-UHFFFAOYSA-N 3-Methylhistidine Natural products CN1C=NC(CC(N)C(O)=O)=C1 BRMWTNUJHUMWMS-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- JIDDFPFGMDDOLO-UHFFFAOYSA-N 5-fluoro-1-(1-oxothiolan-2-yl)pyrimidine-2,4-dione Chemical compound O=C1NC(=O)C(F)=CN1C1S(=O)CCC1 JIDDFPFGMDDOLO-UHFFFAOYSA-N 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YPWSLBHSMIKTPR-UHFFFAOYSA-N Cystathionine Natural products OC(=O)C(N)CCSSCC(N)C(O)=O YPWSLBHSMIKTPR-UHFFFAOYSA-N 0.000 description 1
- ILRYLPWNYFXEMH-UHFFFAOYSA-N D-cystathionine Natural products OC(=O)C(N)CCSCC(N)C(O)=O ILRYLPWNYFXEMH-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- XUIIKFGFIJCVMT-GFCCVEGCSA-N D-thyroxine Chemical compound IC1=CC(C[C@@H](N)C(O)=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 XUIIKFGFIJCVMT-GFCCVEGCSA-N 0.000 description 1
- DIWVBIXQCNRCFE-UHFFFAOYSA-N DL-alpha-Methoxyphenylacetic acid Chemical compound COC(C(O)=O)C1=CC=CC=C1 DIWVBIXQCNRCFE-UHFFFAOYSA-N 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- PMMYEEVYMWASQN-DMTCNVIQSA-N Hydroxyproline Chemical compound O[C@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-DMTCNVIQSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SNDPXSYFESPGGJ-BYPYZUCNSA-N L-2-aminopentanoic acid Chemical compound CCC[C@H](N)C(O)=O SNDPXSYFESPGGJ-BYPYZUCNSA-N 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 description 1
- AHLPHDHHMVZTML-BYPYZUCNSA-N L-Ornithine Chemical compound NCCC[C@H](N)C(O)=O AHLPHDHHMVZTML-BYPYZUCNSA-N 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-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
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-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
- FSBIGDSBMBYOPN-VKHMYHEASA-N L-canavanine Chemical compound OC(=O)[C@@H](N)CCONC(N)=N FSBIGDSBMBYOPN-VKHMYHEASA-N 0.000 description 1
- ILRYLPWNYFXEMH-WHFBIAKZSA-N L-cystathionine Chemical compound [O-]C(=O)[C@@H]([NH3+])CCSC[C@H]([NH3+])C([O-])=O ILRYLPWNYFXEMH-WHFBIAKZSA-N 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- GGLZPLKKBSSKCX-YFKPBYRVSA-N L-ethionine Chemical compound CCSCC[C@H](N)C(O)=O GGLZPLKKBSSKCX-YFKPBYRVSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 1
- UKAUYVFTDYCKQA-VKHMYHEASA-N L-homoserine Chemical compound OC(=O)[C@@H](N)CCO UKAUYVFTDYCKQA-VKHMYHEASA-N 0.000 description 1
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 1
- DWPCPZJAHOETAG-IMJSIDKUSA-N L-lanthionine Chemical compound OC(=O)[C@@H](N)CSC[C@H](N)C(O)=O DWPCPZJAHOETAG-IMJSIDKUSA-N 0.000 description 1
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- SNDPXSYFESPGGJ-UHFFFAOYSA-N L-norVal-OH Natural products CCCC(N)C(O)=O SNDPXSYFESPGGJ-UHFFFAOYSA-N 0.000 description 1
- LRQKBLKVPFOOQJ-YFKPBYRVSA-N L-norleucine Chemical compound CCCC[C@H]([NH3+])C([O-])=O LRQKBLKVPFOOQJ-YFKPBYRVSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- JDHILDINMRGULE-LURJTMIESA-N N(pros)-methyl-L-histidine Chemical compound CN1C=NC=C1C[C@H](N)C(O)=O JDHILDINMRGULE-LURJTMIESA-N 0.000 description 1
- BRMWTNUJHUMWMS-LURJTMIESA-N N(tele)-methyl-L-histidine Chemical compound CN1C=NC(C[C@H](N)C(O)=O)=C1 BRMWTNUJHUMWMS-LURJTMIESA-N 0.000 description 1
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 1
- FSBIGDSBMBYOPN-UHFFFAOYSA-N O-guanidino-DL-homoserine Natural products OC(=O)C(N)CCON=C(N)N FSBIGDSBMBYOPN-UHFFFAOYSA-N 0.000 description 1
- AHLPHDHHMVZTML-UHFFFAOYSA-N Orn-delta-NH2 Natural products NCCCC(N)C(O)=O AHLPHDHHMVZTML-UHFFFAOYSA-N 0.000 description 1
- UTJLXEIPEHZYQJ-UHFFFAOYSA-N Ornithine Natural products OC(=O)C(C)CCCN UTJLXEIPEHZYQJ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- UZMAPBJVXOGOFT-UHFFFAOYSA-N Syringetin Natural products COC1=C(O)C(OC)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)O)=C1 UZMAPBJVXOGOFT-UHFFFAOYSA-N 0.000 description 1
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 1
- 239000004473 Threonine Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007997 Tricine buffer Substances 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- YRZBVIGIGZTWGT-UHFFFAOYSA-N [2-(diphosphonoamino)ethyl-phosphonoamino]phosphonic acid Chemical compound OP(O)(=O)N(P(O)(O)=O)CCN(P(O)(O)=O)P(O)(O)=O YRZBVIGIGZTWGT-UHFFFAOYSA-N 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 description 1
- LSYVCAOPFHHUHM-UHFFFAOYSA-N [hydroxy-[hydroxy-[hydroxy(phosphonooxy)phosphoryl]oxyphosphoryl]oxyphosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O LSYVCAOPFHHUHM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 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
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 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
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 235000009582 asparagine Nutrition 0.000 description 1
- 229960001230 asparagine Drugs 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 229950011321 azaserine Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 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
- 239000007998 bicine buffer Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- GBFLZEXEOZUWRN-UHFFFAOYSA-N carbocisteine Chemical compound OC(=O)C(N)CSCC(O)=O GBFLZEXEOZUWRN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229960003624 creatine Drugs 0.000 description 1
- 239000006046 creatine Substances 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 229960002433 cysteine Drugs 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 230000003247 decreasing effect 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
- KCFYHBSOLOXZIF-UHFFFAOYSA-N dihydrochrysin Natural products COC1=C(O)C(OC)=CC(C2OC3=CC(O)=CC(O)=C3C(=O)C2)=C1 KCFYHBSOLOXZIF-UHFFFAOYSA-N 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- 108700003601 dimethylglycine Proteins 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- PMMYEEVYMWASQN-UHFFFAOYSA-N dl-hydroxyproline Natural products OC1C[NH2+]C(C([O-])=O)C1 PMMYEEVYMWASQN-UHFFFAOYSA-N 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- YSMODUONRAFBET-UHNVWZDZSA-N erythro-5-hydroxy-L-lysine Chemical compound NC[C@H](O)CC[C@H](N)C(O)=O YSMODUONRAFBET-UHNVWZDZSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- 229960002743 glutamine Drugs 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ZUVCYFMOHFTGDM-UHFFFAOYSA-N hexadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCOP(O)(O)=O ZUVCYFMOHFTGDM-UHFFFAOYSA-N 0.000 description 1
- 229960002591 hydroxyproline Drugs 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229960003646 lysine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- DWPCPZJAHOETAG-UHFFFAOYSA-N meso-lanthionine Natural products OC(=O)C(N)CSCC(N)C(O)=O DWPCPZJAHOETAG-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 229960004452 methionine Drugs 0.000 description 1
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229940078490 n,n-dimethylglycine Drugs 0.000 description 1
- LYGCMUNBGIOQAB-UHFFFAOYSA-N naphthalen-1-ylmethylphosphonic acid Chemical compound C1=CC=C2C(CP(O)(=O)O)=CC=CC2=C1 LYGCMUNBGIOQAB-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229960003104 ornithine Drugs 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 229960005190 phenylalanine Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229960002429 proline Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- 229960001153 serine Drugs 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 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
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- KRIXEEBVZRZHOS-UHFFFAOYSA-N tetradecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCOP(O)(O)=O KRIXEEBVZRZHOS-UHFFFAOYSA-N 0.000 description 1
- UJJLJRQIPMGXEZ-UHFFFAOYSA-N tetrahydro-2-furoic acid Chemical compound OC(=O)C1CCCO1 UJJLJRQIPMGXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229960002898 threonine Drugs 0.000 description 1
- 229940034208 thyroxine Drugs 0.000 description 1
- XUIIKFGFIJCVMT-UHFFFAOYSA-N thyroxine-binding globulin Natural products IC1=CC(CC([NH3+])C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 XUIIKFGFIJCVMT-UHFFFAOYSA-N 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01G—WEIGHING
- G01G1/00—Weighing apparatus involving the use of a counterweight or other counterbalancing mass
- G01G1/02—Pendulum-weight apparatus
- G01G1/04—Pendulum-weight apparatus the pendulum having a fixed pivot axis
- G01G1/06—Pendulum-weight apparatus the pendulum having a fixed pivot axis with a plurality of pendulums
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
- G09G1/00—Control arrangements or circuits, of interest only in connection with cathode-ray tube indicators; General aspects or details, e.g. selection emphasis on particular characters, dashed line or dotted line generation; Preprocessing of data
- G09G1/04—Deflection circuits ; Constructional details not otherwise provided for
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
Definitions
- the present invention relates to a polishing composition, a method for producing a polishing composition, a polishing method, and a method for producing a semiconductor substrate.
- CMP chemical mechanical polishing
- CMP is used in processes such as shallow trench isolation (STI), flattening of interlayer insulating films (ILD films), formation of tungsten plugs, and formation of multilayer wires composed of copper and a low dielectric film.
- STI shallow trench isolation
- ILD films interlayer insulating films
- tungsten plugs formation of tungsten plugs
- multilayer wires composed of copper and a low dielectric film.
- an insulating film such as silicon nitride
- an electric conductive material such as titanium nitride
- a polishing speed of titanium nitride is suppressed.
- US 2015/221,521 A discloses that a polishing speed of titanium nitride is suppressed by using a polishing composition containing abrasive grains and a surfactant.
- the present invention is made in view of the above-described problems, and an object thereof is to provide a polishing composition having a sufficiently high polishing speed of silicon nitride with respect to a polishing speed of titanium nitride (that is, selectivity of silicon nitride/titanium nitride is high) even under a strong acidic condition (pH 2.5 or less).
- the present inventor has conducted intensive studies in view of the above-described problems. Consequently, the inventor found that the above-described problems can be solved by using a polishing composition including: silica;
- an anionic water-soluble polymer at least one compound selected from the group consisting of a phosphonate group-containing compound, a phosphate group-containing compound, and an amino group-containing compound; and a dispersing medium, and achieved the present invention.
- notation “(meth)acrylic” means “acrylic” and “methacrylic” and notation “(meth)acrylate” means “acrylate” and “methacrylate.”
- a polishing composition according to the present invention is expected to be also effective to a general object to be polished containing an insulating film and an electric conductive material.
- the insulating film include silicon oxide and silicon nitride.
- the electric conductive material include titanium, titanium nitride, tantalum, and tantalum nitride. Of them, an object to be polished containing silicon nitride (SiN) and titanium nitride (TiN) is preferable since the polishing composition exhibits significant effect with respect to the object to be polished.
- Specific examples of the object to be polished containing silicon nitride (SiN) and titanium nitride (TiN) include a semiconductor substrate having a structure in which a titanium nitride film is formed on a silicon nitride film and a semiconductor substrate having a structure in which all of a silicon nitride film and a titanium nitride film are exposed.
- the polishing composition according to an embodiment of the present invention is used in a step of polishing an object to be polished containing silicon nitride and titanium nitride.
- a polishing suppression action by the anionic water-soluble polymer along with at least one compound selected from the group consisting of a phosphonate group-containing compound, a phosphate group-containing compound, and an amino group-containing compound becomes stronger due to an action mechanism described below.
- the polishing composition according to the present invention has a function of suppressing the polishing speed of titanium nitride as a result of interaction between each component contained in the polishing composition and the object to be polished.
- the polishing composition according to the present invention contains silica, an anionic water-soluble polymer, at least one compound selected from the group consisting of a phosphonate group-containing compound, a phosphate group-containing compound, and an amino group-containing compound (hereinafter, simply also referred to as a TiN inhibitor), and a dispersing medium.
- the anionic water-soluble polymer is adsorbed to the titanium nitride film to form a protective film on the surface of the titanium nitride film so that polishing of titanium nitride can be suppressed.
- adsorption of the anionic water-soluble polymer to titanium nitride becomes weak, and thus the polishing speed of titanium nitride cannot be sufficiently suppressed.
- the present inventor has conducted intensive studies and found that the polishing speed of titanium nitride can be suppressed by further adding the TiN inhibitor. The reason for this is as follows.
- the TiN inhibitor is polarized into a part having a positive electric charge and a part having a negative electric charge.
- the part having a negative electric charge can be strongly adsorbed to the surface of the titanium nitride film even under the strong acidic condition, but has a small molecular weight and does not sufficiently coat the surface of titanium nitride.
- the anionic water-soluble polymer is further electrically adsorbed to the part having a positive electric charge of the TiN inhibitor.
- the polishing composition of the present invention can suppress the polishing speed of titanium nitride while polishing silicon nitride at a high speed, a high polishing selectivity between silicon nitride and titanium nitride can be realized.
- a polishing composition having a sufficiently high polishing speed of silicon nitride with respect to a polishing speed of titanium nitride (that is, selectivity of silicon nitride/titanium nitride is high) even under a strong acidic condition (pH 2.5 or less).
- the polishing composition according to the present invention contains silica.
- the silica contained in the polishing composition has an action of mechanically polishing an object to be polished.
- the type of silica is not particularly limited, and examples thereof include colloidal silica, fumed silica, and sol-gel method silica. Among these, from the viewpoint that solid-phase reaction between the polishing composition and the object to be polished can be efficiently exerted, colloidal silica is preferable.
- Examples of a method for producing colloidal silica include a silicate soda method and a sol-gel method, and colloidal silica produced by any production method may be used.
- examples of commercially available products of colloidal silica include colloidal silicas manufactured by Nissan Chemical Industries, Ltd., JGC Catalysts and Chemicals Ltd., NIPPON CHEMICAL INDUSTRIAL CO., LTD., FUSO CHEMICAL CO., LTD., ADEKA CORPORATION, Akzo Nobel Co., Ltd., AZ Electronic Materials, Nalco Chemical Company, and W. R. Grace & Co.—Conn.
- the lower limit of the average primary particle size of silica is preferably 6 nm or more, more preferably 8 nm or more, and further preferably 10 nm or more. With such a range, since a high polishing speed can be maintained, silica can be suitably used in a rough polishing process or the like.
- the upper limit of the average primary particle size of silica is preferably 200 nm or less, more preferably 100 nm or less, further preferably 50 nm or less, and particularly preferably 30 nm or less. With such a range, it is possible to further suppress occurrence of defects on the surface of the object to be polished after polishing.
- the average primary particle size of silica is calculated, for example, on the basis of a specific surface area of silica measured by a BET method.
- the lower limit of the average secondary particle size of silica is preferably 15 nm or more, more preferably 20 nm or more, and further preferably 25 nm or more. With such a range, since a high polishing speed can be maintained, silica can be suitably used in the rough polishing process.
- the upper limit of the average secondary particle size of silica is preferably 300 nm or less, more preferably 200 nm or less, further preferably 100 nm or less, and particularly preferably 50 nm or less. With such a range, it is possible to further suppress occurrence of defects on a surface of a silicon wafer after polishing.
- the average secondary particle size of silica can be measured, for example, by a dynamic light scattering method.
- the content of silica is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, and particularly preferably 1.4% by mass or more with respect to the polishing composition. With such a range, a high polishing speed can be maintained, and silica can be suitably used in the rough polishing process or the like.
- the content of silica is typically properly 10% by mass or less, preferably 5% by mass or less, more preferably 4% by mass or less, and particularly preferably 3% by mass or less. A smaller content of silica is preferable also from the viewpoint of economic efficiency.
- the polishing composition according to the present invention contains a dispersing medium for dispersing or dissolving each component.
- a dispersing medium for dispersing or dissolving each component.
- water does not contain impurities as much as possible from the viewpoint of inhibiting contamination of the object to be cleaned and action of other components.
- water for example, water in which the total content of transition metal ions is 100 ppb or less is preferable.
- the purity of water can be increased, for example, by an operation such as removing impurity ions using an ion exchange resin, removing foreign substances using a filter, or distillation.
- deionized water ion-exchanged water
- pure water, ultrapure water, distilled water, and the like are preferably used.
- the dispersing medium may be a mixed solvent of water and an organic solvent in order to disperse or dissolve each component.
- the organic solvent to be used include acetone, acetonitrile, ethanol, methanol, isopropanol, glycerin, ethylene glycol, and propylene glycol that are organic solvents mixing with water.
- these organic solvents may be used without being mixed with water, and may be mixed with water after each component is dispersed or dissolved. These organic solvents can be used either singly or in combination of two or more kinds thereof.
- the polishing composition according to the present invention contains an anionic water-soluble polymer.
- the anionic water-soluble polymer in the polishing composition is adsorbed to a surface of a titanium nitride layer when the polishing composition is used for polishing the object to be polished. According to this, the polishing composition according to the present invention can suppress the polishing speed of titanium nitride.
- an anionic group of the anionic water-soluble polymer examples include a carboxylic group (carboxyl group), a sulfonic group, a sulfuric acid ester group, a phosphoric acid ester group, and a phosphonate group, but from the viewpoint of reducing scratches and particles, the anionic water-soluble polymer preferably has a carboxylic group and more preferably has only a carboxylic group. That is, in the present invention, the anionic water-soluble polymer is preferably polycarboxylic acid. Incidentally, these anionic groups may be in the form of a neutralized salt.
- Examples of a water-soluble polymer having a carboxylic group include a (co) polymer having a constituent unit derived from a monomer having a carboxylic group and a salt thereof.
- Examples of the monomer having a carboxylic group include itaconic acid, (meth) acrylic acid, maleic acid, and salts thereof.
- the anionic water-soluble polymer two or more kinds of constituent unit derived from a monomer having a carboxylic group may be contained. Of them, as the anionic water-soluble polymer, poly (meth) acrylic acid, a (meth) acrylic acid-maleic acid copolymer, or a salt thereof is exemplified.
- the anionic water-soluble polymer may contain a constituent unit component derived from a monomer other than the anionic group-containing monomer within the range that the effect of the present invention is exhibited.
- the content of the anionic water-soluble polymer in the polishing composition is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more, further preferably 100 ppm by mass or more, even more preferably 1000 ppm by mass or more, and particularly preferably 2000 ppm by mass or more.
- the anionic water-soluble polymer adsorbed on the titanium nitride film increases so that the polishing speed of titanium nitride can be effectively suppressed.
- the content of the anionic water-soluble polymer in the polishing composition is also preferably 100000 ppm by mass or less, more preferably 10000 ppm by mass or less, further preferably 8000 ppm by mass or less, even more preferably 6000 ppm by mass or less, and particularly preferably 4000 ppm by mass or less.
- the abrasive grains in the polishing composition are less likely to aggregate. Thus, this provides an advantageous effect of improving the storage stability of the polishing composition.
- the weight average molecular weight (Mw) of the anionic water-soluble polymer in the polishing composition is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, further preferably 3000 or more, even more preferably 4000 or more, and particularly preferably 4500 or more. As the molecular weight of the anionic water-soluble polymer increases, the sufficient amount of the polymer to suppress the polishing speed of the titanium nitride layer by the polishing composition is easily adsorbed on the surface of the titanium nitride layer.
- the weight average molecular weight (Mw) of the anionic water-soluble polymer in the polishing composition is preferably 10000 or less, more preferably 6000 or less, further preferably 5500 or less, even more preferably 5400 or less, and particularly preferably 5300 or less.
- Mw weight average molecular weight
- the weight average molecular weight of the polymer compound a value of the weight average molecular weight (in terms of polyethyleneglycol) measured by gel permeation chromatography (GPC) was used. The weight average molecular weight was measured by the following apparatus and conditions.
- GPC apparatus manufactured by SHIMADZU CORPORATION
- Oven temperature 40° C.
- the polishing composition according to the present invention contains at least one compound selected from the group consisting of a phosphonate group-containing compound, a phosphate group-containing compound, and an amino group-containing compound as a TiN inhibitor.
- a phosphonate group-containing compound a phosphonate group-containing compound
- a phosphate group-containing compound a phosphate group-containing compound
- an amino group-containing compound as a TiN inhibitor.
- the pH of the polishing composition becomes more strongly acidic, even when only the anionic water-soluble polymer is used, the suppression of the polishing speed of titanium nitride is not sufficient.
- the TiN inhibitor and the anionic water-soluble polymer are concurrently used, the surface of the titanium nitride film can be sufficiently coated even under the strong acidic condition, and the polishing speed can be suppressed by forming a protective film.
- either only one or a plurality of kinds of the TiN inhibitor may be used.
- a compound having one to six phosphonate groups is preferably exemplified.
- examples of a compound having one phosphonate group include phosphonic acid, methyl phosphonic acid, phenyl phosphonic acid, and 1-naphthylmethyl phosphonic acid.
- examples of a compound having two phosphonate groups include methylene diphosphonic acid (MDPNA), ethylene diphosphonic acid (EDPNA), 1-hydroxyethane-1,1-diphosphonic acid (etidronic acid, HEDP), nitrilotris(methylenephosphonic acid) (NTMP), ethylenediamine tetraphosphonic acid, ethylenediamine tetramethylene phosphonic acid (EDTMP), and diethylenetriamine penta(methylenephosphonic acid) (DTPMP).
- MDPNA methylene diphosphonic acid
- EDPNA ethylene diphosphonic acid
- EDP 1-hydroxyethane-1,1-diphosphonic acid
- NTMP nitrilotris(methylenephosphonic acid)
- NTMP nitrilotris(methylenephosphonic acid)
- NTMP nitrilotris(methylenephosphonic acid)
- ETMP ethylenediamine tetraphosphonic acid
- ETMP
- the phosphonate group-containing compound is nitrilotris(methylenephosphonic acid) (NTMP), ethylenediamine tetramethylene phosphonic acid (EDTMP), and diethylenetriamine penta(methylenephosphonic acid) (DTPMP).
- NTMP nitrilotris(methylenephosphonic acid)
- ETMP ethylenediamine tetramethylene phosphonic acid
- DTPMP diethylenetriamine penta(methylenephosphonic acid)
- Examples of the phosphate group-containing compound which can be used as the TiN inhibitor include an inorganic phosphoric acid compound and an organic phosphoric acid compound.
- Specific examples of the inorganic phosphoric acid compound include monophosphoric acids such as phosphoric acid (orthophosphoric acid), phosphorous acid, and hypophosphorous acid, polyphosphoric acids such as pyrophosphoric acid, pyrophosphorous acid, triphosphoric acid, tetraphosphoric acid, hexaphosphoric acid, cyclophosphoric acid, metaphosphoric acid, and hexametaphosphoric acid, and salts thereof.
- organic phosphoric acid compound examples include alkyl phosphoric acid esters such as tetradecylphosphoric acid, hexadecylphosphoric acid, octadecylphosphoric acid, didecylphosphoric acid, 10-methacryloyloxy decyl dihydrogen phosphate, 12-acryloyloxy dodecyl dihydrogen phosphate, 12-methacryloyloxy dodecyl dihydrogen phosphate, 16-acryloyloxy hexadecyl dihydrogen phosphate, 16-methacryloyloxy hexadecyl dihydrogen phosphate, 20-acryloyloxy icosyl dihydrogen phosphate, 20-methacryloyloxy icosyl dihydrogen phosphate, bis[8-acryloyloxy octyl]hydrogen phosphate, bis[8-methacryloyloxy octyl]hydrogen phosphate, bis[8
- the content of the phosphonate group-containing compound or the phosphate group-containing compound in the polishing composition is preferably 50 ppm by mass or more, more preferably 100 ppm by mass or more, further preferably 120 ppm by mass or more, further preferably 150 ppm by mass or more, further preferably 220 ppm by mass or more, further preferably 240 ppm by mass or more, further preferably 260 ppm by mass or more, and particularly preferably 270 ppm by mass or more.
- the content of the phosphonate group-containing compound or the phosphate group-containing compound increases, the content of the TiN inhibitor to be adsorbed to the titanium nitride film increases, and thus the polishing speed of titanium nitride can be effectively suppressed.
- the content of the phosphonate group-containing compound or the phosphate group-containing compound in the polishing composition is also preferably 10000 ppm by mass or less, more preferably 1000 ppm by mass or less, further preferably 800 ppm by mass or less, further preferably 600 ppm by mass or less, further preferably 500 ppm by mass or less, further preferably 450 ppm by mass or less, and particularly preferably 400 ppm by mass or less.
- the polishing speed of the object to be polished particularly, silicon nitride contained in the object to be polished is less likely to decrease.
- the molecular weight of the phosphonate group-containing compound or the phosphate group-containing compound in the polishing composition is preferably less than 1000 and more preferably less than 600 from the viewpoint of the polishing speed of SiN.
- the phosphonate group-containing compound or the phosphate group-containing compound having a small molecular weight causes the polishing speed of SiN to be less likely to decrease.
- an amino acid is particularly preferable.
- the amino acid indicates an organic compound having both functional groups of an amino group and a carboxyl group.
- amino acid examples include glycine, ⁇ -alanine, ⁇ -alanine, N-methylglycine, N,N-dimethylglycine, 2-aminobutyric acid, norvaline, valine, leucine, norleucine, isoleucine, phenylalanine, proline, sarcosine, ornithine, lysine, taurine, serine, threonine, homoserine, tyrosine, bicine, tricine, 3,5-diiodo-tyrosine, ⁇ -(3,4-dihydroxyphenyl)-alanine, thyroxine, 4-hydroxy-proline, cysteine, methionine, ethionine, lanthionine, cystathionine, cystine, cysteic acid, aspartic acid, glutamic acid, S-(carboxymethyl)-cysteine, 4-aminobutyric acid, asparagine, glutamine,
- a basic amino acid is more preferable, and specifically, arginine, lysine, tryptophan, histidine, and citrulline are particularly preferable. Since the pH of the polishing composition of the present invention is lower than an isoelectric point (iso-electrostatic point) of the basic amino acid, regardless of the basic amino acid being positively charged or being not charged, the phosphonate group-containing compound or the phosphate group-containing compound causes the polishing speed of SiN to be less likely to decrease.
- the content of the amino group-containing compound in the polishing composition (in the case of containing two or more kinds, the total content thereof) is preferably 100 ppm by mass or more, more preferably 1000 ppm by mass or more, and further preferably 5000 ppm by mass or more. With such a range, SiN can be polished at a high polishing speed.
- the content of the amino group-containing compound in the polishing composition is preferably 100000 ppm by mass or less, more preferably 50000 ppm by mass or less, further preferably 20000 ppm by mass or less, and particularly preferably 10000 ppm by mass or less. With such a range, the amount of a pH adjusting agent used for adjusting pH to a target pH can be decreased, and the effect of slurry stability is obtainable.
- the pH of the polishing composition is also not particularly limited, but the lower limit thereof is preferably 1.0 or more, more preferably 1.5 or more, further preferably 1.7 or more, and particularly preferably 2.0 or more. Meanwhile, the upper limit thereof is preferably 7.0 or less, more preferably 5.0 or less, further preferably 3.0 or less, and further preferably 2.5 or less. Thus, according to an embodiment of the present invention, the pH of the polishing composition is 1.0 to 7.0. In view of the mechanism of the present invention, by employing such an embodiment, the effect of increasing selectivity during polishing is particularly significant.
- pH adjusting agent known acids, bases, and salts thereof can be used.
- acids which can be used as the pH adjusting agent include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, and phosphoric acid, and organic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, gluc
- an inorganic acid is used as the pH adjusting agent
- sulfuric acid, nitric acid, phosphoric acid, and the like are particularly preferable from the viewpoint of improving the polishing speed
- an organic acid is used as the pH adjusting agent
- glycolic acid, succinic acid, maleic acid, citric acid, tartaric acid, malic acid, gluconic acid, itaconic acid, and the like are preferable.
- bases which can be used as the pH adjusting agent include amines such as aliphatic amine and aromatic amine, organic bases such as quaternary ammonium hydroxide, hydroxides of alkali metal such as potassium hydroxide, hydroxides of alkaline-earth metal, tetramethylammonium hydroxide, and ammonia.
- amines such as aliphatic amine and aromatic amine
- organic bases such as quaternary ammonium hydroxide
- hydroxides of alkali metal such as potassium hydroxide
- hydroxides of alkaline-earth metal hydroxides of alkaline-earth metal
- tetramethylammonium hydroxide tetramethylammonium hydroxide
- ammonia potassium hydroxide or ammonia is preferable.
- the amount of the pH adjusting agent added is not particularly limited, and may be appropriately adjusted such that the polishing composition has a desired pH.
- a method for producing the polishing composition according to the present invention is not particularly limited.
- the polishing composition can be obtained by mixing and stirring silica, an anionic water-soluble polymer, a TiN inhibitor, and as necessary, other additives in a dispersant.
- a method for producing the polishing composition including mixing the silica, the anionic water-soluble polymer, the at least one compound selected from the group consisting of a phosphonate group-containing compound, a phosphate group-containing compound, and an amino group-containing compound, and the dispersing medium.
- a polishing method including a step of polishing an object to be polished by using the polishing composition according to the present invention.
- a working slurry containing the polishing composition according to the present invention is prepared.
- the polishing composition is supplied to an object to be polished and the object to be polished is polished by a general method.
- the object to be polished is set in a general polishing apparatus, and the polishing composition is supplied to the surface of the object to be polished (surface to be polished) through a polishing pad of the polishing apparatus.
- the polishing pad is pressed against the surface of the object to be polished and the polishing pad and the object to be polished are relatively moved (for example, rotationally moved).
- the object to be polished is subjected to this polishing step, whereby polishing of the object to be polished ends.
- the polishing pad used in the polishing step is not particularly limited.
- any polishing pad of a foamed polyurethane type, a non-woven fabric type, a suede type, including abrasive grains, and not including abrasive grains can be used.
- the polishing apparatus a double-side polishing apparatus which polishes both surfaces of the object to be polished may be used or a single-side polishing apparatus which polishes only one surface of the object to be polished may be used.
- the polishing composition may be used in an embodiment in which the polishing composition once used is discarded (so-called “discarded after single use”) or may be repeatedly used in recycle.
- One example of the method of using the polishing composition in recycle includes collecting the polishing composition after use, which is discharged from the polishing apparatus into a tank, and supplying the collected polishing composition to the polishing apparatus again.
- the amount of the polishing composition after use which is dealt with as wasted liquid, can be reduced as compared with the case of being discarded after single use, and thus environmental load can be reduced. Further, since the amount of the polishing composition used is reduced, the cost can be reduced.
- the object to be polished contains silicon nitride and titanium nitride.
- a method for producing a semiconductor substrate including a step of polishing an object to be polished by the polishing method.
- the present invention includes the following aspects and embodiments.
- Polishing compositions of respective Examples and Comparative Examples were prepared in the similar manner to preparation of the polishing composition of Example 1, except that the type and/or content of each component were changed as presented in the following Table 1. Incidentally, “-” in the table indicates that the corresponding component was not used.
- the silicon nitride substrate and the titanium nitride substrate serving as the semiconductor substrates were polished using the polishing composition of each of Examples 1 to 23 and Comparative Examples 1 to 4 under the following conditions.
- the silicon nitride substrate and the titanium nitride substrate a 300-mm wafer was used.
- Polishing apparatus FREX (registered trademark) 300E manufactured by EBARA CORPORATION
- Polishing pad Dow IC1400
- Polishing ⁇ ⁇ speed ⁇ ( nm/min ) [ Thickness ⁇ ( nm ) ⁇ ⁇ of ⁇ ⁇ substrate ⁇ ⁇ before ⁇ ⁇ polishing ] - [ Thickness ⁇ ( nm ) ⁇ ⁇ of ⁇ ⁇ substrate ⁇ ⁇ after ⁇ ⁇ polishing ] [ Treatment ⁇ ⁇ time ⁇ ( min ) ] Equation ⁇ ⁇ 1
Abstract
A polishing composition according to the present invention includes: silica; an anionic water-soluble polymer; at least one compound selected from the group consisting of a phosphonate group-containing compound, a phosphate group-containing compound, and an amino group-containing compound; and a dispersing medium.
Description
- The present invention relates to a polishing composition, a method for producing a polishing composition, a polishing method, and a method for producing a semiconductor substrate.
- In recent years, a so-called chemical mechanical polishing (CMP) technique for physically polishing and flattening a semiconductor substrate in producing a device is used in accordance with multilayer wiring on a surface of a semiconductor substrate. CMP is a method for flattening a surface of an object to be polished (material to be polished) such as a semiconductor substrate by using a polishing composition (slurry) containing abrasive grains of silica, alumina, ceria, or the like, an anti-corrosion agent, a surfactant, and the like. Specifically, CMP is used in processes such as shallow trench isolation (STI), flattening of interlayer insulating films (ILD films), formation of tungsten plugs, and formation of multilayer wires composed of copper and a low dielectric film. In such CMP, it is required that an insulating film (such as silicon nitride) and an electric conductive material (such as titanium nitride) are removed by polishing with a high polishing selectivity (that is, the insulating film such as silicon nitride is removed at a higher polishing speed than that of the electric conductive material such as titanium nitride).
- As a means for increasing polishing selectivity between silicon nitride and titanium nitride, it is considered that a polishing speed of titanium nitride is suppressed. For example, US 2015/221,521 A discloses that a polishing speed of titanium nitride is suppressed by using a polishing composition containing abrasive grains and a surfactant.
- However, the present inventor has found that when the object to be polished containing silicon nitride and titanium nitride is polished by using the polishing composition described in US 2015/221,521 A, a high polishing speed ratio between silicon nitride and titanium nitride is not still obtained particularly under a strong acidic condition (pH 2.5 or less).
- The present invention is made in view of the above-described problems, and an object thereof is to provide a polishing composition having a sufficiently high polishing speed of silicon nitride with respect to a polishing speed of titanium nitride (that is, selectivity of silicon nitride/titanium nitride is high) even under a strong acidic condition (pH 2.5 or less).
- The present inventor has conducted intensive studies in view of the above-described problems. Consequently, the inventor found that the above-described problems can be solved by using a polishing composition including: silica;
- an anionic water-soluble polymer; at least one compound selected from the group consisting of a phosphonate group-containing compound, a phosphate group-containing compound, and an amino group-containing compound; and a dispersing medium, and achieved the present invention.
- Hereinafter, the present invention will be described. Incidentally, the present invention is not limited only to the following embodiments. In addition, in the present specification, unless specifically described otherwise, operations and measurements of physical properties and the like are performed under conditions of room temperature (20° C. or higher and 25° C. or lower)/relative humidity of 40% RH or higher and 50% RH or lower.
- Incidentally, in the present specification, in specific compound names, notation “(meth)acrylic” means “acrylic” and “methacrylic” and notation “(meth)acrylate” means “acrylate” and “methacrylate.”
- A polishing composition according to the present invention is expected to be also effective to a general object to be polished containing an insulating film and an electric conductive material. Examples of the insulating film include silicon oxide and silicon nitride. Examples of the electric conductive material include titanium, titanium nitride, tantalum, and tantalum nitride. Of them, an object to be polished containing silicon nitride (SiN) and titanium nitride (TiN) is preferable since the polishing composition exhibits significant effect with respect to the object to be polished. Specific examples of the object to be polished containing silicon nitride (SiN) and titanium nitride (TiN) include a semiconductor substrate having a structure in which a titanium nitride film is formed on a silicon nitride film and a semiconductor substrate having a structure in which all of a silicon nitride film and a titanium nitride film are exposed.
- Herein, from the viewpoint of the effect exhibited by the present invention, it is preferable that the polishing composition according to an embodiment of the present invention is used in a step of polishing an object to be polished containing silicon nitride and titanium nitride. The reason for this is speculated that in such an object to be polished, a polishing suppression action by the anionic water-soluble polymer along with at least one compound selected from the group consisting of a phosphonate group-containing compound, a phosphate group-containing compound, and an amino group-containing compound becomes stronger due to an action mechanism described below.
- The present inventor speculates the mechanism that the above-described problems are solved by the present invention to be as follows. However, the following mechanism is merely speculation, and the scope of the invention is not intended to be limited by the mechanism.
- The polishing composition according to the present invention has a function of suppressing the polishing speed of titanium nitride as a result of interaction between each component contained in the polishing composition and the object to be polished. The polishing composition according to the present invention contains silica, an anionic water-soluble polymer, at least one compound selected from the group consisting of a phosphonate group-containing compound, a phosphate group-containing compound, and an amino group-containing compound (hereinafter, simply also referred to as a TiN inhibitor), and a dispersing medium. In a case where pH is acidic, since the surface of the titanium nitride film is positively charged, the anionic water-soluble polymer is adsorbed to the titanium nitride film to form a protective film on the surface of the titanium nitride film so that polishing of titanium nitride can be suppressed. However, as pH becomes more acidic, adsorption of the anionic water-soluble polymer to titanium nitride becomes weak, and thus the polishing speed of titanium nitride cannot be sufficiently suppressed. In this regard, the present inventor has conducted intensive studies and found that the polishing speed of titanium nitride can be suppressed by further adding the TiN inhibitor. The reason for this is as follows. The TiN inhibitor is polarized into a part having a positive electric charge and a part having a negative electric charge. The part having a negative electric charge can be strongly adsorbed to the surface of the titanium nitride film even under the strong acidic condition, but has a small molecular weight and does not sufficiently coat the surface of titanium nitride. However, when the TiN inhibitor and the anionic water-soluble polymer are concurrently used, the anionic water-soluble polymer is further electrically adsorbed to the part having a positive electric charge of the TiN inhibitor. Therefore, by concurrently using the TiN inhibitor and the anionic water-soluble polymer, the surface of the titanium nitride film can be sufficiently coated even under the strong acidic condition, the protective film is formed, and thus the polishing speed can be suppressed. In particular, such an effect is significantly exhibited under a strong acidic condition with pH of 2.5 or less. From the above description, it is considered that since the polishing composition of the present invention can suppress the polishing speed of titanium nitride while polishing silicon nitride at a high speed, a high polishing selectivity between silicon nitride and titanium nitride can be realized. Thus, according to the present invention, there is provided a polishing composition having a sufficiently high polishing speed of silicon nitride with respect to a polishing speed of titanium nitride (that is, selectivity of silicon nitride/titanium nitride is high) even under a strong acidic condition (pH 2.5 or less).
- (Silica)
- The polishing composition according to the present invention contains silica. The silica contained in the polishing composition has an action of mechanically polishing an object to be polished. The type of silica is not particularly limited, and examples thereof include colloidal silica, fumed silica, and sol-gel method silica. Among these, from the viewpoint that solid-phase reaction between the polishing composition and the object to be polished can be efficiently exerted, colloidal silica is preferable.
- Examples of a method for producing colloidal silica include a silicate soda method and a sol-gel method, and colloidal silica produced by any production method may be used. In addition, examples of commercially available products of colloidal silica include colloidal silicas manufactured by Nissan Chemical Industries, Ltd., JGC Catalysts and Chemicals Ltd., NIPPON CHEMICAL INDUSTRIAL CO., LTD., FUSO CHEMICAL CO., LTD., ADEKA CORPORATION, Akzo Nobel Co., Ltd., AZ Electronic Materials, Nalco Chemical Company, and W. R. Grace & Co.—Conn.
- The lower limit of the average primary particle size of silica is preferably 6 nm or more, more preferably 8 nm or more, and further preferably 10 nm or more. With such a range, since a high polishing speed can be maintained, silica can be suitably used in a rough polishing process or the like. In addition, the upper limit of the average primary particle size of silica is preferably 200 nm or less, more preferably 100 nm or less, further preferably 50 nm or less, and particularly preferably 30 nm or less. With such a range, it is possible to further suppress occurrence of defects on the surface of the object to be polished after polishing. Incidentally, the average primary particle size of silica is calculated, for example, on the basis of a specific surface area of silica measured by a BET method.
- The lower limit of the average secondary particle size of silica is preferably 15 nm or more, more preferably 20 nm or more, and further preferably 25 nm or more. With such a range, since a high polishing speed can be maintained, silica can be suitably used in the rough polishing process. In addition, the upper limit of the average secondary particle size of silica is preferably 300 nm or less, more preferably 200 nm or less, further preferably 100 nm or less, and particularly preferably 50 nm or less. With such a range, it is possible to further suppress occurrence of defects on a surface of a silicon wafer after polishing. The average secondary particle size of silica can be measured, for example, by a dynamic light scattering method.
- The content of silica is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, and particularly preferably 1.4% by mass or more with respect to the polishing composition. With such a range, a high polishing speed can be maintained, and silica can be suitably used in the rough polishing process or the like. In addition, from the viewpoint of scratch prevention or the like, the content of silica is typically properly 10% by mass or less, preferably 5% by mass or less, more preferably 4% by mass or less, and particularly preferably 3% by mass or less. A smaller content of silica is preferable also from the viewpoint of economic efficiency.
- (Dispersing Medium)
- The polishing composition according to the present invention contains a dispersing medium for dispersing or dissolving each component. As the dispersing medium, it is preferable that water does not contain impurities as much as possible from the viewpoint of inhibiting contamination of the object to be cleaned and action of other components. As such water, for example, water in which the total content of transition metal ions is 100 ppb or less is preferable. Herein, the purity of water can be increased, for example, by an operation such as removing impurity ions using an ion exchange resin, removing foreign substances using a filter, or distillation. Specifically, as water, for example, deionized water (ion-exchanged water) , pure water, ultrapure water, distilled water, and the like are preferably used.
- The dispersing medium may be a mixed solvent of water and an organic solvent in order to disperse or dissolve each component. In this case, examples of the organic solvent to be used include acetone, acetonitrile, ethanol, methanol, isopropanol, glycerin, ethylene glycol, and propylene glycol that are organic solvents mixing with water. In addition, these organic solvents may be used without being mixed with water, and may be mixed with water after each component is dispersed or dissolved. These organic solvents can be used either singly or in combination of two or more kinds thereof.
- (Anionic Water-Soluble Polymer)
- The polishing composition according to the present invention contains an anionic water-soluble polymer. The anionic water-soluble polymer in the polishing composition is adsorbed to a surface of a titanium nitride layer when the polishing composition is used for polishing the object to be polished. According to this, the polishing composition according to the present invention can suppress the polishing speed of titanium nitride.
- Examples of an anionic group of the anionic water-soluble polymer include a carboxylic group (carboxyl group), a sulfonic group, a sulfuric acid ester group, a phosphoric acid ester group, and a phosphonate group, but from the viewpoint of reducing scratches and particles, the anionic water-soluble polymer preferably has a carboxylic group and more preferably has only a carboxylic group. That is, in the present invention, the anionic water-soluble polymer is preferably polycarboxylic acid. Incidentally, these anionic groups may be in the form of a neutralized salt.
- Examples of a water-soluble polymer having a carboxylic group include a (co) polymer having a constituent unit derived from a monomer having a carboxylic group and a salt thereof. Examples of the monomer having a carboxylic group include itaconic acid, (meth) acrylic acid, maleic acid, and salts thereof. In the anionic water-soluble polymer, two or more kinds of constituent unit derived from a monomer having a carboxylic group may be contained. Of them, as the anionic water-soluble polymer, poly (meth) acrylic acid, a (meth) acrylic acid-maleic acid copolymer, or a salt thereof is exemplified.
- The anionic water-soluble polymer may contain a constituent unit component derived from a monomer other than the anionic group-containing monomer within the range that the effect of the present invention is exhibited.
- The content of the anionic water-soluble polymer in the polishing composition is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more, further preferably 100 ppm by mass or more, even more preferably 1000 ppm by mass or more, and particularly preferably 2000 ppm by mass or more. As the content of the anionic water-soluble polymer increases, the anionic water-soluble polymer adsorbed on the titanium nitride film increases so that the polishing speed of titanium nitride can be effectively suppressed.
- The content of the anionic water-soluble polymer in the polishing composition is also preferably 100000 ppm by mass or less, more preferably 10000 ppm by mass or less, further preferably 8000 ppm by mass or less, even more preferably 6000 ppm by mass or less, and particularly preferably 4000 ppm by mass or less. As the content of the water-soluble polymer decreases, the abrasive grains in the polishing composition are less likely to aggregate. Thus, this provides an advantageous effect of improving the storage stability of the polishing composition.
- The weight average molecular weight (Mw) of the anionic water-soluble polymer in the polishing composition is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, further preferably 3000 or more, even more preferably 4000 or more, and particularly preferably 4500 or more. As the molecular weight of the anionic water-soluble polymer increases, the sufficient amount of the polymer to suppress the polishing speed of the titanium nitride layer by the polishing composition is easily adsorbed on the surface of the titanium nitride layer.
- The weight average molecular weight (Mw) of the anionic water-soluble polymer in the polishing composition is preferably 10000 or less, more preferably 6000 or less, further preferably 5500 or less, even more preferably 5400 or less, and particularly preferably 5300 or less. As the molecular weight of the water-soluble polymer decreases, the abrasive grains in the polishing composition are less likely to aggregate. Thus, this provides an advantageous effect of improving the storage stability of the polishing composition. As the weight average molecular weight of the polymer compound, a value of the weight average molecular weight (in terms of polyethyleneglycol) measured by gel permeation chromatography (GPC) was used. The weight average molecular weight was measured by the following apparatus and conditions.
- GPC apparatus: manufactured by SHIMADZU CORPORATION
- Model: Prominence +ELSD detector (ELSD-LTII)
- Column: VP-ODS (manufactured by SHIMADZU CORPORATION)
- Mobile phase A: MeOH
-
- B: aqueous solution of 1% acetic acid
- Flow rate: 1 ml/min
- Detector: ELSD temp. 40° C., Gain 8, N2 GAS 350 kPa
- Oven temperature: 40° C.
- Injection amount: 40 μL
- (TiN Inhibitor)
- The polishing composition according to the present invention contains at least one compound selected from the group consisting of a phosphonate group-containing compound, a phosphate group-containing compound, and an amino group-containing compound as a TiN inhibitor. In addition, as described above, although the polishing speed of titanium nitride can be suppressed by addition of the anionic water-soluble polymer, the polishing speed of titanium nitride can be further suppressed by adding the TiN inhibitor.
- As the pH of the polishing composition becomes more strongly acidic, even when only the anionic water-soluble polymer is used, the suppression of the polishing speed of titanium nitride is not sufficient. In this regard, when the TiN inhibitor and the anionic water-soluble polymer are concurrently used, the surface of the titanium nitride film can be sufficiently coated even under the strong acidic condition, and the polishing speed can be suppressed by forming a protective film. Incidentally, either only one or a plurality of kinds of the TiN inhibitor may be used.
- As the phosphonate group-containing compound which can be used as the TiN inhibitor, a compound having one to six phosphonate groups is preferably exemplified. Specifically, examples of a compound having one phosphonate group include phosphonic acid, methyl phosphonic acid, phenyl phosphonic acid, and 1-naphthylmethyl phosphonic acid. In addition, examples of a compound having two phosphonate groups include methylene diphosphonic acid (MDPNA), ethylene diphosphonic acid (EDPNA), 1-hydroxyethane-1,1-diphosphonic acid (etidronic acid, HEDP), nitrilotris(methylenephosphonic acid) (NTMP), ethylenediamine tetraphosphonic acid, ethylenediamine tetramethylene phosphonic acid (EDTMP), and diethylenetriamine penta(methylenephosphonic acid) (DTPMP). Of the phosphonate group-containing compounds, compounds having two or more, preferably three to five phosphonate groups in one molecule are preferable. For example, it is particularly preferable that the phosphonate group-containing compound is nitrilotris(methylenephosphonic acid) (NTMP), ethylenediamine tetramethylene phosphonic acid (EDTMP), and diethylenetriamine penta(methylenephosphonic acid) (DTPMP).
- Examples of the phosphate group-containing compound which can be used as the TiN inhibitor include an inorganic phosphoric acid compound and an organic phosphoric acid compound. Specific examples of the inorganic phosphoric acid compound include monophosphoric acids such as phosphoric acid (orthophosphoric acid), phosphorous acid, and hypophosphorous acid, polyphosphoric acids such as pyrophosphoric acid, pyrophosphorous acid, triphosphoric acid, tetraphosphoric acid, hexaphosphoric acid, cyclophosphoric acid, metaphosphoric acid, and hexametaphosphoric acid, and salts thereof. Specific examples of the organic phosphoric acid compound include alkyl phosphoric acid esters such as tetradecylphosphoric acid, hexadecylphosphoric acid, octadecylphosphoric acid, didecylphosphoric acid, 10-methacryloyloxy decyl dihydrogen phosphate, 12-acryloyloxy dodecyl dihydrogen phosphate, 12-methacryloyloxy dodecyl dihydrogen phosphate, 16-acryloyloxy hexadecyl dihydrogen phosphate, 16-methacryloyloxy hexadecyl dihydrogen phosphate, 20-acryloyloxy icosyl dihydrogen phosphate, 20-methacryloyloxy icosyl dihydrogen phosphate, bis[8-acryloyloxy octyl]hydrogen phosphate, bis[8-methacryloyloxy octyl]hydrogen phosphate, bis[9-acryloyloxy nonyl]hydrogen phosphate, bis[9-methacryloyloxy nonyl]hydrogen phosphate, bis[10-acryloyloxy decyl]hydrogen phosphate, and bis[10-methacryloyloxy decyl]hydrogen phosphate; and pyrophosphoric acid esters such as pyrophosphoric acid bisoctyl, pyrophosphoric acid bis[8-acryloyloxy octyl], pyrophosphoric acid bis[8-methacryloyloxy octyl], pyrophosphoric acid bis[10-acryloyloxy decyl], and pyrophosphoric acid bis[10-methacryloyloxy decyl].
- The content of the phosphonate group-containing compound or the phosphate group-containing compound in the polishing composition (in the case of containing two or more kinds, the total content thereof) is preferably 50 ppm by mass or more, more preferably 100 ppm by mass or more, further preferably 120 ppm by mass or more, further preferably 150 ppm by mass or more, further preferably 220 ppm by mass or more, further preferably 240 ppm by mass or more, further preferably 260 ppm by mass or more, and particularly preferably 270 ppm by mass or more. As the content of the phosphonate group-containing compound or the phosphate group-containing compound increases, the content of the TiN inhibitor to be adsorbed to the titanium nitride film increases, and thus the polishing speed of titanium nitride can be effectively suppressed.
- The content of the phosphonate group-containing compound or the phosphate group-containing compound in the polishing composition (in the case of containing two or more kinds, the total content thereof) is also preferably 10000 ppm by mass or less, more preferably 1000 ppm by mass or less, further preferably 800 ppm by mass or less, further preferably 600 ppm by mass or less, further preferably 500 ppm by mass or less, further preferably 450 ppm by mass or less, and particularly preferably 400 ppm by mass or less. As the content of the phosphonate group-containing compound or the phosphate group-containing compound decreases, the polishing speed of the object to be polished, particularly, silicon nitride contained in the object to be polished is less likely to decrease.
- The molecular weight of the phosphonate group-containing compound or the phosphate group-containing compound in the polishing composition is preferably less than 1000 and more preferably less than 600 from the viewpoint of the polishing speed of SiN. The phosphonate group-containing compound or the phosphate group-containing compound having a small molecular weight causes the polishing speed of SiN to be less likely to decrease.
- Examples of the amino group-containing compound which can be used in the polishing composition include an amino acid, amino group-containing polyalkylene glycol, and aliphatic primary amine. Among these, an amino acid is particularly preferable. The amino acid indicates an organic compound having both functional groups of an amino group and a carboxyl group. Specific examples of the amino acid include glycine, α-alanine, β-alanine, N-methylglycine, N,N-dimethylglycine, 2-aminobutyric acid, norvaline, valine, leucine, norleucine, isoleucine, phenylalanine, proline, sarcosine, ornithine, lysine, taurine, serine, threonine, homoserine, tyrosine, bicine, tricine, 3,5-diiodo-tyrosine, β-(3,4-dihydroxyphenyl)-alanine, thyroxine, 4-hydroxy-proline, cysteine, methionine, ethionine, lanthionine, cystathionine, cystine, cysteic acid, aspartic acid, glutamic acid, S-(carboxymethyl)-cysteine, 4-aminobutyric acid, asparagine, glutamine, azaserine, arginine, canavanine, citrulline, δ-hydroxy-lysine, creatine, histidine, 1-methyl-histidine, 3-methyl-histidine, and tryptophan. Of them, from the viewpoint of the polishing speed of SiN, a basic amino acid is more preferable, and specifically, arginine, lysine, tryptophan, histidine, and citrulline are particularly preferable. Since the pH of the polishing composition of the present invention is lower than an isoelectric point (iso-electrostatic point) of the basic amino acid, regardless of the basic amino acid being positively charged or being not charged, the phosphonate group-containing compound or the phosphate group-containing compound causes the polishing speed of SiN to be less likely to decrease.
- The content of the amino group-containing compound in the polishing composition (in the case of containing two or more kinds, the total content thereof) is preferably 100 ppm by mass or more, more preferably 1000 ppm by mass or more, and further preferably 5000 ppm by mass or more. With such a range, SiN can be polished at a high polishing speed. In addition, the content of the amino group-containing compound in the polishing composition is preferably 100000 ppm by mass or less, more preferably 50000 ppm by mass or less, further preferably 20000 ppm by mass or less, and particularly preferably 10000 ppm by mass or less. With such a range, the amount of a pH adjusting agent used for adjusting pH to a target pH can be decreased, and the effect of slurry stability is obtainable.
- (pH and pH Adjusting Agent)
- According to an embodiment of the present invention, the pH of the polishing composition is also not particularly limited, but the lower limit thereof is preferably 1.0 or more, more preferably 1.5 or more, further preferably 1.7 or more, and particularly preferably 2.0 or more. Meanwhile, the upper limit thereof is preferably 7.0 or less, more preferably 5.0 or less, further preferably 3.0 or less, and further preferably 2.5 or less. Thus, according to an embodiment of the present invention, the pH of the polishing composition is 1.0 to 7.0. In view of the mechanism of the present invention, by employing such an embodiment, the effect of increasing selectivity during polishing is particularly significant.
- As the pH adjusting agent, known acids, bases, and salts thereof can be used.
- Specific examples of the acids which can be used as the pH adjusting agent include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, and phosphoric acid, and organic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, gluconic acid, itaconic acid, tartaric acid, citric acid, lactic acid, diglycolic acid, 2-furancarboxylic acid, 2,5-furandicarboxylic acid, 3-furancarboxylic acid, 2-tetrahydrofurancarboxylic acid, methoxyacetic acid, methoxyphenylacetic acid, and phenoxyacetic acid. In a case where an inorganic acid is used as the pH adjusting agent, particularly, sulfuric acid, nitric acid, phosphoric acid, and the like are particularly preferable from the viewpoint of improving the polishing speed, and in a case where an organic acid is used as the pH adjusting agent, glycolic acid, succinic acid, maleic acid, citric acid, tartaric acid, malic acid, gluconic acid, itaconic acid, and the like are preferable.
- Specific examples of the bases which can be used as the pH adjusting agent include amines such as aliphatic amine and aromatic amine, organic bases such as quaternary ammonium hydroxide, hydroxides of alkali metal such as potassium hydroxide, hydroxides of alkaline-earth metal, tetramethylammonium hydroxide, and ammonia. Among these, from the viewpoint of ease of availability, potassium hydroxide or ammonia is preferable.
- The amount of the pH adjusting agent added is not particularly limited, and may be appropriately adjusted such that the polishing composition has a desired pH.
- (Method for Producing Polishing Composition)
- A method for producing the polishing composition according to the present invention is not particularly limited. For example, the polishing composition can be obtained by mixing and stirring silica, an anionic water-soluble polymer, a TiN inhibitor, and as necessary, other additives in a dispersant. In an embodiment, there is provided a method for producing the polishing composition, the method including mixing the silica, the anionic water-soluble polymer, the at least one compound selected from the group consisting of a phosphonate group-containing compound, a phosphate group-containing compound, and an amino group-containing compound, and the dispersing medium.
- (Polishing Method)
- In an embodiment, there is provided a polishing method including a step of polishing an object to be polished by using the polishing composition according to the present invention.
- For example, a working slurry containing the polishing composition according to the present invention is prepared. Next, the polishing composition is supplied to an object to be polished and the object to be polished is polished by a general method. For example, the object to be polished is set in a general polishing apparatus, and the polishing composition is supplied to the surface of the object to be polished (surface to be polished) through a polishing pad of the polishing apparatus. Typically, while the polishing composition is continuously supplied, the polishing pad is pressed against the surface of the object to be polished and the polishing pad and the object to be polished are relatively moved (for example, rotationally moved). The object to be polished is subjected to this polishing step, whereby polishing of the object to be polished ends.
- The polishing pad used in the polishing step is not particularly limited. For example, any polishing pad of a foamed polyurethane type, a non-woven fabric type, a suede type, including abrasive grains, and not including abrasive grains can be used. In addition, as the polishing apparatus, a double-side polishing apparatus which polishes both surfaces of the object to be polished may be used or a single-side polishing apparatus which polishes only one surface of the object to be polished may be used.
- The polishing composition may be used in an embodiment in which the polishing composition once used is discarded (so-called “discarded after single use”) or may be repeatedly used in recycle. One example of the method of using the polishing composition in recycle includes collecting the polishing composition after use, which is discharged from the polishing apparatus into a tank, and supplying the collected polishing composition to the polishing apparatus again. In a case where the polishing composition is used in recycle, the amount of the polishing composition after use, which is dealt with as wasted liquid, can be reduced as compared with the case of being discarded after single use, and thus environmental load can be reduced. Further, since the amount of the polishing composition used is reduced, the cost can be reduced.
- Herein, in an embodiment, it is preferable that the object to be polished contains silicon nitride and titanium nitride.
- (Method for Producing Semiconductor Substrate)
- In an embodiment, there is provided a method for producing a semiconductor substrate, the method including a step of polishing an object to be polished by the polishing method.
- Although the embodiments of the present invention have been described in detail, these are descriptive and illustrative rather than limited, and it is apparent that the scope of the present invention has to be understood with the appended claims.
- The present invention includes the following aspects and embodiments.
- 1. A polishing composition containing:
- silica;
- an anionic water-soluble polymer;
- at least one compound selected from the group consisting of a phosphonate group-containing compound, a phosphate group-containing compound, and an amino group-containing compound; and
- a dispersing medium.
- 2. The polishing composition described in the item 1, in which pH is 1.0 to 7.0.
- 3. The polishing composition described in the item 1 or 2, in which the anionic water-soluble polymer is polycarboxylic acid.
- 4. The polishing composition described in any one of the items 1 to 3, in which the phosphonate group-containing compound has one to six phosphonate groups.
- 5. The polishing composition described in any one of the items 1 to 4, in which the phosphonate group-containing compound is at least one selected from the group consisting of nitrilotris(methylenephosphonic acid), ethylenediamine tetramethylene phosphoric acid, and diethylenetriamine penta(methylenephosphonic acid).
- 6. The polishing composition described in any one of the items 1 to 5, in which the phosphate group-containing compound is at least one selected from the group consisting of an inorganic phosphoric acid compound and an organic phosphoric acid compound.
- 7. The polishing composition described in any one of the items 1 to 6, in which the amino group-containing compound is an amino acid.
- 8. The polishing composition described in any one of the items 1 to 7, in which the polishing composition is used in a step of polishing an object to be polished containing silicon nitride and titanium nitride.
- 9. A method for producing the polishing composition described in anyone of the items 1 to 8, the method including mixing the silica, the anionic water-soluble polymer, the at least one compound selected from the group consisting of a phosphonate group-containing compound, a phosphate group-containing compound, and an amino group-containing compound, and the dispersing medium.
- 10. A polishing method including a step of polishing an object to be polished by using the polishing composition described in any one of the items 1 to 8.
- 11. The polishing method described in the item 10, in which the object to be polished contains silicon nitride and titanium nitride.
- 12. A method for producing a semiconductor substrate, the method including a step of polishing an object to be polished by the polishing method described in the item 10 or 11.
- The present invention will be described in more detail using the following Examples and Comparative Examples. However, the technical scope of the present invention is not intended to be limited only to the following Examples. Incidentally, unless specifically described otherwise, “ppm,” “%,” and “part(s)” mean “parts per million by mass,” “% by mass,” and “part(s) by mass,” respectively.
- (Preparation of Polishing Composition)
- Preparation of Polishing Composition of Example 1
- 2% by mass of colloidal silica (average primary particle size: 12 nm; average secondary particle size: 30 nm) with respect to the final polishing composition, 3200 ppm of polyacrylic acid (Mw=5000) with respect to the final polishing composition, and 50 ppm of diethylenetriamine penta(methylenephosphonic acid) (DTPMP) with respect to the final polishing composition were added and an aqueous solution of nitric acid (70%) and water (ultrapure water) were added such that a pH of the polishing composition would be 2.2, thereby preparing a polishing composition of Example 1. The pH value of the polishing composition of Example 1 (liquid temperature: 25° C.) was confirmed by a pH meter (model: LAQUA (registered trademark) manufactured by HORIBA, Ltd.).
- Preparation of Polishing Compositions of Examples 2 to 23 and Comparative Examples 1 to 4
- Polishing compositions of respective Examples and Comparative Examples were prepared in the similar manner to preparation of the polishing composition of Example 1, except that the type and/or content of each component were changed as presented in the following Table 1. Incidentally, “-” in the table indicates that the corresponding component was not used.
- (CMP Process)
- The silicon nitride substrate and the titanium nitride substrate serving as the semiconductor substrates were polished using the polishing composition of each of Examples 1 to 23 and Comparative Examples 1 to 4 under the following conditions. Herein, as the silicon nitride substrate and the titanium nitride substrate, a 300-mm wafer was used.
- (Polishing Apparatus and Polishing Conditions)
- Polishing apparatus: FREX (registered trademark) 300E manufactured by EBARA CORPORATION
- Polishing pad: Dow IC1400
- Polishing pressure: 2.0 psi (1 psi=6894.76 Pa, the same applies hereafter)
- Rotation number of polishing table: 60 rpm
- Rotation number of head: 61 rpm
- Supply of polishing composition: discarded after single use
- Supply amount of polishing composition: 300 ml/min
- Polishing time: for 30 seconds
- (Polishing Speed Evaluation)
- The polishing speed of each object to be polished after polishing described above was obtained using the following Equation 1. The evaluation results are collectively presented in Table 1.
-
- In addition, in Examples, evaluation was performed using each of the silicon nitride substrate and the titanium nitride substrate, but even in the case of using a substrate containing silicon nitride and titanium nitride, or the like, it is speculated that the same result as described above is obtained.
-
TABLE 1 TiN inhibitor SiN TiN Anionic water-soluble polymer Number of polishing polishing Content phosphate Content speed speed SiN/TiN Type Mw (ppm) Type groups (ppm) (nm/min) (nm/min) selectivity Example 1 Polyacrylic acid 5000 3200 DTPMP 5 50 503 438 1.15 Example 2 Polyacrylic acid 5000 3200 DTPMP 5 100 479 358 1.34 Example 3 Polyacrylic acid 5000 3200 DTPMP 5 150 457 13 35.15 Example 4 Polyacrylic acid 5000 3200 DTPMP 5 180 444 11 40.36 Example 5 Polyacrylic acid 5000 3200 DTPMP 5 210 434 9 48.22 Example 6 Polyacrylic acid 5000 3200 DTPMP 5 240 426 7 60.86 Example 7 Polyacrylic acid 5000 3200 DTPMP 5 270 419 4 104.75 Example 8 Polyacrylic acid 5000 3200 DTPMP 5 300 417 2.3 181.30 Example 9 Polyacrylic acid 5000 3200 DTPMP 5 400 360 2.8 130.27 Example 10 Polyacrylic acid 5000 3200 DTPMP 5 500 341 3.5 98.94 Example 11 Polyacrylic acid 2000 3200 DTPMP 5 300 356 99 3.60 Example 12 Sodium 3000 3200 DTPMP 5 300 377 174 2.17 polyacrylate Example 13 Ammonium 6000 3200 DTPMP 5 300 353 98 3.60 polyacrylate Example 14 Ammonium 10000 3200 DTPMP 5 300 359 193 1.86 polyacrylate Example 15 (Acrylic 2800 3200 DTPMP 5 300 325 18 18.06 acid-maleic acid) salt copolymer Example 16 Polyacrylic acid 5000 3200 EDTMP 4 300 379 26 14.85 Example 17 Polyacrylic acid 5000 3200 NTMP 3 1550 366 73 5.03 Example 18 Polyacrylic acid 5000 3200 HEDP 2 1730 427 79 5.39 Example 19 Polyacrylic acid 5000 3200 Phenyl 1 1860 541 283 1.91 phosphonic acid Example 20 Polyacrylic acid 5000 3200 Arginine — 9900 442 52 8.45 Example 21 Polyacrylic acid 5000 1600 Arginine — 8000 476 72 6.61 Example 22 Polyacrylic acid 5000 1600 Arginine — 4000 548 134 4.09 Example 23 Polyacrylic acid 5000 1600 Arginine — 2000 519 214 2.42 Comparative Polyacrylic acid 5000 3200 — — — 535 542 0.99 Example 1 Comparative — — — DTPMP 5 300 309 480 0.64 Example 2 Comparative — — — Arginine — 8000 408 545 0.75 Example 3 Comparative — — — — — — 456 665 0.69 Example 4 - From the results of Table 1, it was found that in Examples 1 to 23 using the polishing composition of the present invention, the polishing speed of silicon nitride with respect to the polishing speed of titanium nitride (SiN/TiN selectivity) is sufficiently high. On the other hand, in Comparative Examples 1 to 4 not having at least one of the anionic water-soluble polymer and the TiN inhibitor, the SiN/TiN selectivity was low. In addition, it was found that among Examples, the result of Example 8 using DTPMP is extremely excellent.
- The present application is based on Japanese Patent Application No. 2017-185460 filed on Sep. 26, 2017, and a disclosed content thereof is incorporated herein as a whole by reference.
Claims (14)
1.-12. (canceled)
13. A polishing composition comprising:
silica;
an anionic water-soluble polymer;
at least one compound selected from the group consisting of a phosphonate group-containing compound, a phosphate group-containing compound, and an amino group-containing compound; and
a dispersing medium,
wherein an anionic group of the anionic water-soluble polymer is selected from the group consisting of a carboxylic group (carboxyl group), a sulfonic group, a sulfuric acid ester group, a phosphoric acid ester group, and a phosphonate group, and a content of the anionic water-soluble polymer is 1600 ppm or more.
14. The polishing composition according to claim 13 , wherein the anionic water-soluble polymer comprises a (co)polymer having a constituent unit derived from a monomer having a carboxylic group and a salt thereof.
15. The polishing composition according to claim 14 , wherein the monomer having a carboxylic group is selected from the group consisting of itaconic acid, (meth)acrylic acid, maleic acid and a salt thereof.
16. The polishing composition according to claim 13 , wherein the anionic water-soluble polymer is selected from the group consisting of polyacrylic acid, polyacrylic acid salt, (acrylic acid-maleic acid) copolymer and (acrylic acid-maleic acid) salt copolymer.
17. The polishing composition according to claim 13 , wherein a weight average molecular weight of the anionic water-soluble polymer is 1000 or more.
18. The polishing composition according to claim 13 , wherein the phosphonate group-containing compound has one to six phosphonate groups.
19. The polishing composition according to claim 13 , wherein the phosphonate group-containing compound is at least one selected from the group consisting of 1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediamine tetramethylene phosphonic acid, and diethylenetriamine penta(methylenephosphonic acid).
20. The polishing composition according to claim 13 , wherein a pH of the polishing composition is 2.5 or less.
21. The polishing composition according to claim 13 , wherein the polishing composition is used in a step of polishing an object to be polished containing silicon nitride and titanium nitride.
22. A method for producing the polishing composition according to claim 13 , the method comprising mixing the silica, the anionic water-soluble polymer, the at least one compound selected from the group consisting of a phosphonate group-containing compound having one to six phosphonate groups, and the dispersing medium,
wherein an anionic group of the anionic water-soluble polymer is selected from the group consisting of a carboxylic group (carboxyl group), a sulfonic group, a sulfuric acid ester group, a phosphoric acid ester group, and a phosphonate group, and a content of the anionic water-soluble polymer is 1600 ppm or more.
23. A polishing method comprising a step of polishing an object to be polished by using the polishing composition according to claim 13 .
24. The polishing method according to claim 23 , wherein the object to be polished contains silicon nitride and titanium nitride.
25. A method for producing a semiconductor substrate, the method comprising a step of polishing an object to be polished by the polishing method according to claim 23 .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/240,666 US20210246334A1 (en) | 2017-09-26 | 2021-04-26 | Polishing composition, method for producing polishing composition, polishing method, and method for producing semiconductor substrate |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017185460A JP2019062078A (en) | 2017-09-26 | 2017-09-26 | Polishing composition, manufacturing method thereof, polishing method and manufacturing method of semiconductor substrate |
JP2017-185460 | 2017-09-26 | ||
US16/133,686 US11015087B2 (en) | 2017-09-26 | 2018-09-17 | Polishing composition, method for producing polishing composition, polishing method, and method for producing semiconductor substrate |
US17/240,666 US20210246334A1 (en) | 2017-09-26 | 2021-04-26 | Polishing composition, method for producing polishing composition, polishing method, and method for producing semiconductor substrate |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/133,686 Division US11015087B2 (en) | 2017-09-26 | 2018-09-17 | Polishing composition, method for producing polishing composition, polishing method, and method for producing semiconductor substrate |
Publications (1)
Publication Number | Publication Date |
---|---|
US20210246334A1 true US20210246334A1 (en) | 2021-08-12 |
Family
ID=65808650
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/133,686 Active US11015087B2 (en) | 2017-09-26 | 2018-09-17 | Polishing composition, method for producing polishing composition, polishing method, and method for producing semiconductor substrate |
US17/240,666 Abandoned US20210246334A1 (en) | 2017-09-26 | 2021-04-26 | Polishing composition, method for producing polishing composition, polishing method, and method for producing semiconductor substrate |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/133,686 Active US11015087B2 (en) | 2017-09-26 | 2018-09-17 | Polishing composition, method for producing polishing composition, polishing method, and method for producing semiconductor substrate |
Country Status (3)
Country | Link |
---|---|
US (2) | US11015087B2 (en) |
JP (1) | JP2019062078A (en) |
TW (1) | TWI791585B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023140049A1 (en) * | 2022-01-24 | 2023-07-27 | 富士フイルム株式会社 | Polishing solution and polishing method |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003277734A (en) | 2001-12-31 | 2003-10-02 | Hynix Semiconductor Inc | Cmp (chemical mechanical polishing) slurry for metal and method for forming metal wiring contact plug of semiconductor element using the same |
US7427362B2 (en) * | 2005-01-26 | 2008-09-23 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Corrosion-resistant barrier polishing solution |
TWI506621B (en) * | 2005-12-22 | 2015-11-01 | Kao Corp | Polishing composition for hard disk substrate |
US8163049B2 (en) * | 2006-04-18 | 2012-04-24 | Dupont Air Products Nanomaterials Llc | Fluoride-modified silica sols for chemical mechanical planarization |
JP2008135452A (en) * | 2006-11-27 | 2008-06-12 | Fujimi Inc | Polishing composition and polishing method |
JP2008192930A (en) * | 2007-02-06 | 2008-08-21 | Fujifilm Corp | Metal polishing composition and chemical mechanical polishing method using the same |
TW200936749A (en) * | 2007-10-29 | 2009-09-01 | Ekc Technology Inc | Process of purification of amidoxime containing cleaning solutions and their use |
JP5698989B2 (en) * | 2011-01-07 | 2015-04-08 | 花王株式会社 | Method for producing polishing composition |
CN103119122B (en) | 2010-09-24 | 2014-10-08 | 花王株式会社 | Manufacturing method of polishing liquid composition |
JP6028432B2 (en) * | 2012-07-17 | 2016-11-16 | 日立化成株式会社 | Polishing liquid for CMP, storage liquid for polishing liquid for CMP, and polishing method |
US9752057B2 (en) | 2014-02-05 | 2017-09-05 | Cabot Microelectronics Corporation | CMP method for suppression of titanium nitride and titanium/titanium nitride removal |
US9803109B2 (en) * | 2015-02-03 | 2017-10-31 | Cabot Microelectronics Corporation | CMP composition for silicon nitride removal |
US9481811B2 (en) * | 2015-02-20 | 2016-11-01 | Cabot Microelectronics Corporation | Composition and method for polishing memory hard disks exhibiting reduced edge roll-off |
-
2017
- 2017-09-26 JP JP2017185460A patent/JP2019062078A/en active Pending
-
2018
- 2018-08-08 TW TW107127584A patent/TWI791585B/en active
- 2018-09-17 US US16/133,686 patent/US11015087B2/en active Active
-
2021
- 2021-04-26 US US17/240,666 patent/US20210246334A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
JP2019062078A (en) | 2019-04-18 |
US20190092974A1 (en) | 2019-03-28 |
US11015087B2 (en) | 2021-05-25 |
TW201915131A (en) | 2019-04-16 |
TWI791585B (en) | 2023-02-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2977418B1 (en) | Chemical mechanical polishing (cmp) of cobalt-containing substrate | |
US6428721B1 (en) | Polishing composition and polishing method employing it | |
EP2614123B1 (en) | Aqueous polishing composition and process for chemically mechanically polishing substrate materials for electrical, mechanical and optical devices | |
KR101473501B1 (en) | Aqueous dispersion for chemical mechanical polishing and method of chemical mechanical polishing of semiconductor device | |
EP2035523B1 (en) | Compositions and methods for polishing silicon nitride materials | |
US20090289217A1 (en) | Polishing composition | |
US20090004863A1 (en) | Polishing liquid and polishing method using the same | |
JP6029916B2 (en) | Polishing composition | |
US10093834B2 (en) | Polishing composition and polishing method | |
EP1894978A2 (en) | Polishing composition and polishing process | |
KR20200077373A (en) | Polishing compositions and methods of using same | |
JP2016069535A (en) | Polishing composition and producing method thereof and polishing method | |
KR20230022939A (en) | Polishing compositions and methods of using same | |
KR102498069B1 (en) | Composition for surface treatment and method for surface treatment using the same | |
KR20190035490A (en) | Surface treatment composition, preparation method thereof, surface treatment method using the same | |
WO2019190730A2 (en) | Barrier ruthenium chemical mechanical polishing slurry | |
JP2008227098A (en) | Metal polishing solution | |
JP2009123880A (en) | Polishing composition | |
US20190301028A1 (en) | Composition for surface treatment, and method for surface treatment and method for producing semiconductor substrate using the same | |
US20210246334A1 (en) | Polishing composition, method for producing polishing composition, polishing method, and method for producing semiconductor substrate | |
US10954479B2 (en) | Composition for surface treatment and surface treatment method using the same | |
EP3792327A1 (en) | Polishing composition, polishing method and method for manufacturing semiconductor substrate | |
US20190085208A1 (en) | Polishing composition, method for producing same, polishing method, and method for producing substrate | |
US10851266B2 (en) | Slurry composition for polishing and method for polishing semiconductor thin film with steps of a high aspect ratio | |
KR20170072524A (en) | Chemical Mechanical Polishing Slurry and POLISHING METHOD USING THE SAME |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STPP | Information on status: patent application and granting procedure in general |
Free format text: APPLICATION DISPATCHED FROM PREEXAM, NOT YET DOCKETED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |