TWI629349B - Grinding composition - Google Patents
Grinding composition Download PDFInfo
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- TWI629349B TWI629349B TW103123144A TW103123144A TWI629349B TW I629349 B TWI629349 B TW I629349B TW 103123144 A TW103123144 A TW 103123144A TW 103123144 A TW103123144 A TW 103123144A TW I629349 B TWI629349 B TW I629349B
- Authority
- TW
- Taiwan
- Prior art keywords
- polishing
- group
- polishing composition
- acid
- compound
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 123
- 238000000227 grinding Methods 0.000 title description 12
- 238000005498 polishing Methods 0.000 claims abstract description 218
- 229910052751 metal Inorganic materials 0.000 claims abstract description 55
- 239000002184 metal Substances 0.000 claims abstract description 55
- 239000004094 surface-active agent Substances 0.000 claims abstract description 40
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 29
- 239000007800 oxidant agent Substances 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 230000007797 corrosion Effects 0.000 claims abstract description 12
- 238000005260 corrosion Methods 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 12
- -1 polyoxyethylene group Polymers 0.000 claims description 76
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- 150000003839 salts Chemical class 0.000 claims description 24
- 239000006061 abrasive grain Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000005013 aryl ether group Chemical group 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 150000005215 alkyl ethers Chemical class 0.000 claims description 7
- 150000008378 aryl ethers Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 14
- 239000010410 layer Substances 0.000 description 47
- 239000003795 chemical substances by application Substances 0.000 description 28
- 230000000694 effects Effects 0.000 description 23
- 230000004888 barrier function Effects 0.000 description 21
- 125000000217 alkyl group Chemical group 0.000 description 20
- 239000010949 copper Substances 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 15
- 229910000420 cerium oxide Inorganic materials 0.000 description 14
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000003945 anionic surfactant Substances 0.000 description 10
- 150000007524 organic acids Chemical class 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 239000004020 conductor Substances 0.000 description 6
- 150000002391 heterocyclic compounds Chemical group 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 4
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229940024606 amino acid Drugs 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 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
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 2
- ZUHDIDYOAZNPBV-UHFFFAOYSA-N 2-[2-hydroxyethyl-[(4-methylbenzotriazol-1-yl)methyl]amino]ethanol Chemical compound CC1=CC=CC2=C1N=NN2CN(CCO)CCO ZUHDIDYOAZNPBV-UHFFFAOYSA-N 0.000 description 2
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 2
- MVPKIPGHRNIOPT-UHFFFAOYSA-N 5,6-dimethyl-2h-benzotriazole Chemical compound C1=C(C)C(C)=CC2=NNN=C21 MVPKIPGHRNIOPT-UHFFFAOYSA-N 0.000 description 2
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 2
- PWSZRRFDVPMZGM-UHFFFAOYSA-N 5-phenyl-1h-pyrazol-3-amine Chemical compound N1N=C(N)C=C1C1=CC=CC=C1 PWSZRRFDVPMZGM-UHFFFAOYSA-N 0.000 description 2
- ONYNOPPOVKYGRS-UHFFFAOYSA-N 6-methylindole Natural products CC1=CC=C2C=CNC2=C1 ONYNOPPOVKYGRS-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- YPWSLBHSMIKTPR-UHFFFAOYSA-N Cystathionine Natural products OC(=O)C(N)CCSSCC(N)C(O)=O YPWSLBHSMIKTPR-UHFFFAOYSA-N 0.000 description 2
- ILRYLPWNYFXEMH-UHFFFAOYSA-N D-cystathionine Natural products OC(=O)C(N)CCSCC(N)C(O)=O ILRYLPWNYFXEMH-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
- 239000004471 Glycine Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 2
- 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 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- FHQDWPCFSJMNCT-UHFFFAOYSA-N N(tele)-methylhistamine Chemical compound CN1C=NC(CCN)=C1 FHQDWPCFSJMNCT-UHFFFAOYSA-N 0.000 description 2
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 108010077895 Sarcosine Proteins 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 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
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 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
- 230000007423 decrease Effects 0.000 description 2
- 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 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 235000011187 glycerol 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
- 230000001965 increasing effect Effects 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 229940045996 isethionic acid Drugs 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- QMPFMODFBNEYJH-UHFFFAOYSA-N methyl 1h-1,2,4-triazole-5-carboxylate Chemical compound COC(=O)C1=NC=NN1 QMPFMODFBNEYJH-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000011146 organic particle Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 230000009467 reduction 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
- ZFRKQXVRDFCRJG-UHFFFAOYSA-N skatole Chemical compound C1=CC=C2C(C)=CNC2=C1 ZFRKQXVRDFCRJG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 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
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 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
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Classifications
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- 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
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- 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
-
- 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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]
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
本發明之課題係提供一種可減少有機殘留物、可提高半導體裝置之生產良率之研磨用組成物。
本發明提供一種研磨用組成物,其係用於研磨對象物之研磨的研磨用組成物,其含有金屬防腐蝕劑及界面活性劑之至少一者;氧化劑;及有機化合物;且前述有機化合物具有2~3個羥基。
Description
本發明係關於研磨用組成物。
近年來,隨著LSI之高積體化、高性能化已開發新的微細加工技術。化學機械研磨(以下亦簡稱為CMP)法亦為其一種,並已應用於LSI製造步驟,尤其係在多層配線形成步驟中之層間絕緣膜平坦化、金屬栓柱形成、埋入配線(鑲嵌配線)之形成中頻繁被利用之技術。
形成半導體裝置之配線時,一般首先於具有溝槽之絕緣膜上依序形成障壁層及導電性物質層。隨後,以化學機械研磨(CMP)至少去除位在溝槽外之導電性物質層之部分(導電性物質層之外側部分)及位在溝槽外之障壁層部分(障壁層之外側部分)。用於該至少去除導電性物質層之外側部分及障壁層之外側部分之研磨通常分為第1研磨步驟及第2研磨步驟進行。第1研磨步驟係為了使障壁層之上面露出,而去除導電性物質層之外側部分之一部分。接續之第2研磨步驟係為了使絕緣膜露出並且獲得平坦表面,而至少去除導電性物質層之外側部分之剩餘
部分及障壁層之外側部分。
用於形成該半導體裝置之配線之CMP一般係使用含有酸等研磨促進劑及氧化劑,進而視需要亦含有研磨粒之研磨用組成物。且,為了改善研磨後之研磨對象物之平坦性,亦即抑制配線部分過度研磨造成之凹陷,亦已提案使用進一步添加金屬防腐蝕劑之研磨用組成物。例如,專利文獻1中揭示使用含胺基乙酸及/或醯胺基硫酸、氧化劑、苯并三唑及水之研磨用組成物。專利文獻2中揭示於專利文獻1中揭示之研磨用組成物中進一步添加陰離子界面活性劑與非離子界面活性劑之研磨用組成物。
〔專利文獻1〕日本特開平8-83780號公報
〔專利文獻2〕日本特開2008-041781號公報
專利文獻1或專利文獻2中揭示之研磨用組成物中通常含有之成分的苯并三唑等之金屬防腐蝕劑或界面活性劑等存在有該等會附著於已研磨之研磨對象物上,即使經洗淨亦無法去除之所謂有機殘留物之問題。因此,存在有該有機殘留物時,會有使半導體裝置之生產良率下降之問題。
因此,本發明之目的係提供一種可減少有機殘留物且提高半導體裝置生產良率之研磨用組成物。
本發明人等為解決上述課題而進行積極檢討。
結果,藉由於研磨用組成物中含有具有2~3個羥基之有機化合物,出乎意料地發現可提供有機殘留物明顯降低之已研磨之研磨對象物。
亦即,本發明係一種研磨用組成物,其係用於研磨對象物之研磨之研磨用組成物,其含有金屬防腐蝕劑及界面活性劑之至少一者;氧化劑;與有機化合物,且前述有機化合物具有2~3個羥基。
本發明可提供可有機殘留物減少且提高半導體裝置之生產良率之研磨用組成物。且,依據本發明之研磨用組成物,可一面維持研磨速度,一面減少有機殘留物。
以下,說明本發明之實施形態。又,本發明並不僅限於以下之實施形態。此外,本說明書中,表示範圍之「X~Y」意指「不小於X且不大於Y」,「重量」與
「質量」、「重量%」與「質量%」及「重量份」與「質量份」係作為同義詞處理。且,若沒有特別指明,則操作及物性等之測定係在室溫(20~25℃)/相對濕度40~50%之條件測定。
本發明係一種研磨用組成物,其係用於研磨對象物之研磨的研磨用組成物,其含有金屬防腐蝕劑及界面活性劑之至少一者;氧化劑;與有機化合物,且前述有機化合物具有2~3個羥基。又,本說明書中,有時亦簡稱研磨組成物為「組成物」。
以下,針對本發明之研磨用組成物加以詳細說明。
本發明之研磨用組成物中含有機化合物,該有機化合物具有2~3個羥基。本說明書中,有時亦稱「有機化合物」為「含有羥基之有機化合物」。如上述,研磨用組成物中通常所含之成分的苯并三唑等金屬防腐蝕劑、或界面活性劑等係於研磨表面形成疏水性保護膜、抑制凹陷方面有用。然而,該等有機物會附著於研磨對象物(例如銅)上,而成為無法洗淨之有機殘留物。
為解決該問題,藉由使研磨用組成物成為含有具有2~3個羥基之有機化合物之構成,可抑制有機殘留物。且,依據本發明之研磨用組成物亦具有不抑制研磨速度,而可維持在高速之效果。
具有該效果之機制雖尚不明確,但本發明人等推測如下。但不用說本發明之技術範圍並不受以下機制之限制。
亦即,通常所含之成分的苯并三唑等金屬防腐蝕劑、或界面活性劑等,可於研磨表面形成疏水性之保護膜,且可抑制凹陷。然而,該有機物與溶解之研磨對象物(例如銅)同時形成不溶性錯體,該錯體會附著於疏水性保護膜上。該情況即使洗淨由於僅洗淨上層部,結果以有機殘留物殘留。因此認為含有具有2~3個羥基之有機化合物時,該有機化合物附著於疏水性保護膜上,藉由羥基使保護膜全體親水化。結果,可防止不溶性錯體之附著,故可藉洗淨而抑制包含保護膜之有機殘留物。
本發明之重點不僅如此。本發明亦具有之特徵為研磨用組成物中含有之有機化合物之羥基數。本發明之有機化合物之羥基為2~3個。羥基數為0個或1個時,無法抑制有機殘留物數。另一方面,羥基數為不小於4個時同樣亦無法抑制有機殘留物數。為何藉由將羥基數侷限在特定範圍能發揮本發明期望之效果之理由並不確定,換言之,堪稱本發明係超出熟習本技藝者之預測者。
另一方面,含有該含羥基之添加劑(含有羥基之有機化合物)時,由於吸附於研磨對象物上作為保護膜發揮功能,故認為亦使研磨速度降低。且亦認為藉由吸附於研磨粒上,引起研磨粒凝聚,使研磨速度降低。然而,與該預測相反,羥基數為2~3個時,發揮維持研磨速
度之驚人效果。就該點而言,本發明亦係超出熟習本技藝者之預測者。
據此本發明係發明人等之嘗試錯誤、積極研究下所創作者。
本發明中可使用之有機化合物只要羥基數為2~3個即可無特別限制地使用,但較好為以下述式1表示:【化1】HO-(XO)n-H‧‧‧(式1)
式1中,X為碳數1~3之伸烷基,n為1~100,但n為1時,前述伸烷基之1個氫原子可經羥基取代。
此處,碳數1~3之伸烷基之具體例亦無特別限制,可為直鏈狀或分支狀,列舉為例如亞甲基、伸乙基、三亞甲基、伸丙基等,尤其為伸乙基、伸丙基時,可有效發揮本發明期望之效果。
且,式1中,n為1~100,但較好為1~50,更好為1~30。藉由為該範圍而具有可一面維持研磨速度,一面減低有機殘留物之效果。
鑒於以上時,以式1表示之有機化合物之具體例列舉為聚乙二醇、聚丙二醇二醇、聚乙縮醛二醇。又,如上述,n為1時,伸烷基之1個氫原子可經羥基取代,該形態成為丙三醇。
研磨用組成物中之有機化合物之含量下限較好不小於0.0001(g/L),更好不小於0.001(g/L),又更好不小於0.01(g/L),最好不小於0.1(g/L)。且,研磨用組成物中之有機化合物含量上限較好不大於100(g/L),更好不大於50(g/L),又更好不大於10(g/L),最好不大於1(g/L)。若為該範圍,則可提高利用研磨用組成物之研磨對象物的研磨速度。且,若為該範圍,則可抑制有機殘留物。另外,僅對有機殘留物之去除有效,而具有例如不降低銅之研磨速度之優點。
本發明之研磨用組成物中,亦可含金屬防腐蝕劑(本說明書中,有時亦簡稱為「防腐蝕劑」)。本發明之研磨用組成物中不含界面活性劑時,金屬防腐蝕劑成為必要成分。當然,亦可與界面活性劑組合使用。藉由於研磨用組成物中添加金屬防腐蝕劑,可進一步抑制使用研磨用組成物之研磨而在配線之側邊產生凹陷。且,可更抑制在使用研磨用組成物研磨後之研磨對象物之表面產生凹陷等之階差缺陷。雖藉由該金屬防腐蝕劑而具有各種效果,但如上述,存在有附著於已研磨之研磨對象物上,即使洗淨亦無法去除之所謂有機殘留物之問題。若有機物殘留,則有半導體裝置生產良率降低之問題。相對於此,本發明之研磨用組成物由於含有具有2~3個羥基之有機化合物,故可減低有機殘留物(意指減少有機殘留物較多之異常品),可
提高半導體裝置之生產良率。此外,由於可簡化洗淨製程,故具有製程成本減低與製程時間縮短之雙重效果。
亦即,本發明之研磨用組成物含有具有2~3個羥基之有機化合物,藉由成為此構成而亦具有可簡單地洗淨有機殘留物之效果。亦即,亦可縮短洗淨之必要時間,亦可減低洗淨次數,再者亦關係到洗淨液減少,對環境而言亦較佳。
本發明中可使用之金屬防腐蝕劑並無特別限制,但較好為雜環式化合物。雜環式化合物對研磨對象物表面之化學或物理性吸附力高,故可進一步提高研磨對象物表面之撥水性,且形成牢固之保護膜。此就提高使用本發明之研磨用組成物研磨後之研磨對象物表面之平坦性有利。尤其,下述具體列舉之化合物之該等效果更為顯著。
本發明中可使用之金屬防腐蝕劑之一例的雜環式化合物中之雜環員數並無特別限制。而且,雜環式化合物可為單環化合物,亦可為具有縮合環之多環化合物。該金屬防腐蝕劑可單獨使用或混合2種以上使用。且,該金屬防腐蝕劑可使用市售品,亦可使用合成品。
可作為金屬防腐蝕劑使用之雜環化合物之具體例列舉為例如吡咯化合物、吡唑化合物、咪唑化合物、三唑化合物、四唑化合物、吡啶化合物、哌啶化合物、嗒嗪化合物、吡嗪化合物、吲哚嗪(indolizine)化合物、吲哚化合物、異吲哚化合物、吲唑化合物、嘌呤化合物、喹嗪(quinolizine)化合物、喹啉化合物、異喹啉化合
物、萘啶化合物、酞嗪化合物、喹喔啉化合物、喹唑啉化合物、噌啉化合物、喋啶化合物、噻唑化合物、異噻唑化合物、噁唑化合物、異噁唑化合物、呋咱化合物等含氮雜環化合物。其中,就提高研磨對象物之表面平坦性之觀點而言,較好為四唑化合物、吡唑化合物、三唑化合物,最好為三唑化合物。
三唑化合物中,具有至少一個之經羥基烷基取代之胺基之苯并三唑化合物就有效地發揮本發明之期望效果方面係較佳。此處,羥基烷基數亦無特別限制,但就研磨用組成物中之分散安定性之觀點而言,較好為1個或2個。且,羥基烷基中之烷基之碳數亦無特別限制,但就抑制研磨對象物(例如銅)之研磨速度降低之觀點而言,較好為1~5,更好為1~4,又更好為2~3。此外,羥基烷基數為2個以上時之烷基數可各自相同亦可不同,但就作為化合物之保存安定性之觀點或化合物之抗氧化觀點而言,較好為相同。若為具有該構造之三唑化合物,基於一面提高研磨速度,一面抑制凹陷之觀點而言係較佳。
三唑化合物較好為具有縮合環者,例如,與苯環、萘環、蒽環等縮合者,但就作為化合物之安定性之觀點而言,或就研磨用組成物之抗氧化之觀點而言較好為相同。且,三唑化合物亦可為具有碳數1~3之烷基、或羥基、或鹵原子等取代基者。
鑒於上述,三唑化合物之例較好為例如2,2’-[[(甲基-1H-苯并三唑-1-基)甲基]亞胺基]雙乙醇、1,2,3-
三唑、1,2,4-三唑、1-甲基-1,2,4-三唑、甲基-1H-1,2,4-三唑-3-羧酸酯、1,2,4-三唑-3-羧酸、1,2,4-三唑-3-羧酸甲酯、1H-1,2,4-三唑-3-硫醇、3,5-二胺基-1H-1,2,4-三唑、3-胺基-1,2,4-三唑-5-硫醇、3-胺基-1H-1,2,4-三唑、3-胺基-5-苄基-4H-1,2,4-三唑、3-胺基-5-甲基-4H-1,2,4-三唑、3-硝基-1,2,4-三唑、3-溴-5-硝基-1,2,4-三唑、4-(1,2,4-三唑-1-基)苯酚、4-胺基-1,2,4-三唑、4-胺基-3,5-二丙基-4H-1,2,4-三唑、4-胺基-3,5-二甲基-4H-1,2,4-三唑、4-胺基-3,5-二戊基-4H-1,2,4-三唑、5-甲基-1,2,4-三唑-3,4-二胺、1H-苯并三唑、1-羥基苯并三唑、1-胺基苯并三唑、1-羧基苯并三唑、5-氯-1H-苯并三唑、5-硝基-1H-苯并三唑、5-羧基-1H-苯并三唑、5-甲基-1H-苯并三唑、5,6-二甲基-1H-苯并三唑、1-(1’,2’-二羧基乙基)苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-5-甲基苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-4-甲基苯并三唑等。其中,就有效的發揮本發明期望之效果之觀點而言,且就可一面獲得研磨對象物(例如銅)之期望研磨速度一面實現低階差之觀點,以2,2’-[[(甲基-1H-苯并三唑-1-基)甲基]亞胺基]雙乙醇、1,2,3-三唑、1H-苯并三唑、5-甲基-1H-苯并三唑、5,6-二甲基-1H-苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-5-甲基苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-4-甲基苯并三唑、1,2,3-三唑及1,2,4-三唑較佳。
此外,吡唑化合物之例列舉為例如1H-吡唑、
4-硝基-3-吡唑羧酸、3,5-吡唑羧酸、3-胺基-5-苯基吡唑、5-胺基-3-苯基吡唑、3,4,5-三溴吡唑、3-胺基吡唑、3,5-二甲基吡唑、3,5-二甲基-1-羥基甲基吡唑、3-甲基吡唑、1-甲基吡唑、3-胺基-5-甲基吡唑、4-胺基-吡唑并[3,4-d]嘧啶、異嘌呤醇、4-氯-1H-吡唑并[3,4-D]嘧啶、3,4-二羥基-6-甲基吡唑并(3,4-B)-吡啶、6-甲基-1H-吡唑并[3,4-b]吡啶-3-胺等。
咪唑化合物之例列舉為例如咪唑、1-甲基咪唑、2-甲基咪唑、4-甲基咪唑、1,2-二甲基吡唑、2-乙基-4-甲基咪唑、2-異丙基咪唑、苯并咪唑、5,6-二甲基苯并咪唑、2-胺基苯并咪唑、2-氯苯并咪唑、2-甲基苯并咪唑、2-(1-羥基乙基)苯并咪唑、2-羥基苯并咪唑、2-苯基苯并咪唑、2,5-二甲基苯并咪唑、5-甲基苯并咪唑、5-硝基苯并咪唑、1H-嘌呤等。
四唑化合物之例列舉為例如1H-四唑、5-甲基四唑、5-胺基四唑、及5-苯基四唑等。
吲唑化合物之例列舉為例如1H-吲唑、5-胺基-1H-吲唑、5-硝基-1H-吲唑、5-羥基-1H-吲唑、6-胺基-1H-吲唑、6-硝基-1H-吲唑、6-羥基-1H-吲唑、3-羧基-5-甲基-1H-吲唑等。
吲哚化合物之例列舉為例如1H-吲哚、1-甲基-1H-吲哚、2-甲基-1H-吲哚、3-甲基-1H-吲哚、4-甲基-1H-吲哚、5-甲基-1H-吲哚、6-甲基-1H-吲哚、7-甲基-1H-吲哚、4-胺基-1H-吲哚、5-胺基-1H-吲哚、6-胺基-1H-吲
哚、7-胺基-1H-吲哚、4-羥基-1H-吲哚、5-羥基-1H-吲哚、6-羥基-1H-吲哚、7-羥基-1H-吲哚、4-甲氧基-1H-吲哚、5-甲氧基-1H-吲哚、6-甲氧基-1H-吲哚、7-甲氧基-1H-吲哚、4-氯-1H-吲哚、5-氯-1H-吲哚、6-氯-1H-吲哚、7-氯-1H-吲哚、4-羧基-1H-吲哚、5-羧基-1H-吲哚、6-羧基-1H-吲哚、7-羧基-1H-吲哚、4-硝基-1H-吲哚、5-硝基-1H-吲哚、6-硝基-1H-吲哚、7-硝基-1H-吲哚、4-腈-1H-吲哚、5-腈-1H-吲哚、6-腈-1H-吲哚、7-腈-1H-吲哚、2,5-二甲基-1H-吲哚、1,2-二甲基-1H-吲哚、1,3-二甲基-1H-吲哚、2,3-二甲基-1H-吲哚、5-胺基-2,3-二甲基-1H-吲哚、7-乙基-1H-吲哚、5-(胺基甲基)吲哚、2-甲基-5-胺基-1H-吲哚、3-羥基甲基-1H-吲哚、6-異丙基-1H-吲哚、5-氯-2-甲基-1H-吲哚等。
研磨用組成物中之金屬防腐蝕劑含量下限較好不小於0.001(g/L),更好不小於0.005(g/L),又更好不小於0.01(g/L),最好為不小於0.1(g/L)。又,研磨用組成物中之金屬防腐蝕劑含量之上限較好不大於10(g/L),更好不大於5(g/L),又更好不大於1(g/L)。若為該範圍,則可降低有機殘留物數。此外,可進一步抑制使用研磨用組成物研磨產生配線側邊之凹陷。且,可進一步抑制使用研磨用組成物研磨後之研磨對象物表面之凹陷等之階差缺陷。
本發明之研磨用組成物中含界面活性劑。本發明之研磨用組成物中不含金屬防腐蝕劑時,界面活性劑成為必要成分。但,亦可與金屬防腐蝕劑組合使用。藉由於研磨用組成物中添加界面活性劑,除了更不易因使用研磨用組成物研磨而於形成之配線側邊產生凹陷以外,亦有更不易於使用研磨用組成物研磨後之研磨對象物表面形成凹陷之優點。藉由含有該界面活性劑而有各種效果,但如上述,會有附著於已研磨之研磨對象物上,即使洗淨亦無法去除之所謂有機殘留物之問題。而且,存在該有機殘留物時,會有半導體裝置之生產良率下降之問題。相對於此,本發明之研磨用組成物由於含有具有2~3個羥基之有機化合物,故可減低有機殘留物,提高半導體裝置之生產良率。該機制同樣適用上述之說明。
本發明中使用之界面活性劑較好為陰離子性界面活性劑、陽離子性界面活性劑、兩性界面活性劑及非離子界面活性劑之任一種,但其中以陰離子性界面活性劑及非離子性界面活性劑較佳。亦可組合複數種之界面活性劑使用,就一面維持研磨速度,一面對於研磨後之研磨對象物表面更不易產生表面凹陷之觀點而言,最好組合陰離子性界面活性劑與非離子性界面活性劑使用。
陰離子性界面活性劑由於對於研磨對象物表面之化學或物理性吸附力高,故進一步提高研磨對象物之撥水性,且,可在研磨對象物表面形成更堅固之保護膜。此對於提高使用研磨用組成物研磨後之研磨對象物之表面
平坦性為有利。
陰離子性界面活性劑就防止氧化銅溶解之觀點而言,較好具有磷酸基、羧基、磺基(硫酸基)、聚氧伸烷基芳基醚基、單氧伸乙基或聚氧伸乙基。
陰離子性界面活性劑之具體例並無特別限制,列舉為例如聚氧伸烷基芳基磷酸、聚氧伸烷基芳基醚磷酸、醚聚氧伸乙基烷基醚乙酸、聚氧伸乙基烷基醚硫酸、烷基醚硫酸、聚氧伸乙基烷基硫酸酯、烷基硫酸酯、聚氧伸乙基烷基硫酸、烷基硫酸、烷基苯磺酸、烷基磷酸酯、聚氧伸乙基烷基磷酸酯、聚氧伸乙基磺基琥珀酸、烷基磺基琥珀酸、烷基萘磺酸、烷基二苯基醚二磺酸、及該等之鹽。
其中,就有效發揮本發明期望之效果之觀點,或一面獲得期望之研磨對象物(例如銅)之研磨速度一面實現低階差之觀點而言,以聚氧伸烷基芳基磷酸或其鹽、聚氧伸烷基芳基醚磷酸或其鹽、烷基硫酸或其鹽、聚氧伸乙基烷基醚乙酸或其鹽、聚氧伸乙基烷基醚硫酸或其鹽、烷基醚硫酸或其鹽及烷基苯磺酸或其鹽較佳。
此外,就提高研磨用組成物與研磨對象物間之撥水作用之觀點而言,研磨用組成物中所含之陰離子性界面活性劑較好具有烷基,更具體而言更好烷基之重複碳數為8個以上,又更具體而言較好為碳數8~14,更好為碳數10~14。亦即。上述列舉之陰離子性界面活性劑之具體例中含烷基時(例如烷基硫酸等),其烷基之碳數較好
為8~14個,更好碳數為10~14個。更具體而言,更好為辛基硫酸鹽、癸基硫酸鹽、月桂基(十二烷基)硫酸鹽、十八烷基硫酸鹽。
且其他具體例就一面獲得期望研磨對象物(例如銅)之研磨速度,一面可實現更低階差之觀點而言,研磨用組成物中所含陰離子性界面活性劑係如上述,較好具有聚氧伸烷基芳基醚基,更具體而言為以下述式2表示之化合物或其鹽:
式2中,A1~A3各獨立為氫原子、甲基、乙基或聚氧伸烷基芳基醚基,但,A1~A3中至少一個為聚氧伸烷基芳基醚基,前述聚氧伸烷基芳基醚基係:
式3中,Ar表示可具有取代基之碳數6~20之芳基,E為碳數1~3之伸烷基,n為1~100。
上述式2中,A1~A3各獨立為氫原子、甲基、乙基或聚氧伸烷基芳基醚基,但A1~A3中之至少一個為聚氧伸烷基芳基醚基。惟,基於金屬表面之蝕刻抑制效果之
觀點而言,A1~A3中之一個較好為聚氧伸烷基芳基醚基。且,基於界面活性劑之研磨用組成物中之分散性之觀點而言,A1~A3中至少一個較好為氫原子。又,就可一面維持高研磨速度一面實現低階差之觀點而言,A1~A3中,較好一個為具有後述之式4之聚氧伸烷基芳基醚基作為Ar,其餘部分為氫原子。為具有該構造之界面活性劑時,就一面維持研磨速度,一面抑制凹陷之觀點而言係較佳。又式2之化合物可為一種,亦可為兩種以上。另外,亦可併用單酯、二酯、三酯。
本發明之聚氧伸烷基芳基醚基,如上述,較好以下式表示:
式3中,Ar表示可具有取代基之碳數6~20之芳基,E為碳數1~3之伸烷基,n為1~100。
此處「Ar」中,芳基之碳數雖為碳數6~20,但較好為碳數6~15,更好為碳數6~13,又更好為碳數6~8。藉由使碳數落在該範圍,即使在研磨步驟中吸附於研磨對象物(例如銅)之表面,就親疏水(潤濕性)之觀點,仍可再脫離,且分散於研磨用組成物中。因此,不會成為研磨對象物(例如銅)表面之有機殘留物之原因,可有效發揮本發明期望之效果。且「Ar」之具體例並未特別限制,列舉為例如苯基、萘基或蒽基等,尤其為苯基時,
意味可降低於研磨對象物(例如Cu)上成為有機殘留物之顧慮,一面具有高研磨速度,一面實現低階差,故可有效發揮本發明之期望效果。
鑒於上述時,前述Ar較好以下述式4表示:
式4中,R1~R5各獨立為氫原子、經取代或未取代之碳數1~21之烷基或經取代或未經取代之碳數6~20之芳基。
經取代或未經取代之碳數1~21之烷基中之烷基的碳數,就分散安定性之觀點而言,較好為1~18,更好為1~10,又更好為1~5,最好為1~3。此外,烷基之具體例並無特別限制,可為直鏈亦可為分支,列舉為甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、第三戊基、新戊基、己基、異己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、2-乙基己基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基等。其中,就有效地發揮本發明期望之效果之觀點而言,以甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基較佳,更好為甲基、乙基、丙
基、異丙基,最好為甲基、乙基。
且經取代或未取代之碳數1~21之烷基中之取代基較好為芳基或鹵原子,至於芳基較好為苯基、萘基,鹵原子較好為氯、溴、碘等。尤其,具有芳基作為取代基時,吸附於研磨對象物(例如銅)表面時,研磨對象物(例如銅)之表面成為撥水性,使研磨粒或錯化劑難以與研磨對象物(例如銅)接液,因此,可防止障蔽膜露出後之過度研磨。
此外R1~R5中之「經取代或未取代之碳數1~21之烷基」或「經取代或未取代之碳數6~20之芳基」之數,就分散安定性之觀點而言,較好為1~3之整數。且R1~R5中之烷基之取代部位亦未特別限制,但就高研磨速度且實現低階差、蝕刻抑制效果之觀點而言,取代數為1時,較好為3位,取代數為3時較好為2位、4位、6位。
芳基係由芳香族烴衍生之官能基或取代基。芳基之碳數較好為6~21,但就分散安定性之觀點而言,更好為碳數6~14,又更好為碳數6~8。該芳基之具體例亦無特別限制,列舉為苯基、萘基或蒽基等。且經取代或未取代之碳數6~20之芳基中之取代基,較好為碳數1~21之烷基、或鹵原子等。碳數1~21之烷基之例亦可同樣應用上述之例。
鑒於上述時,前述Ar之具體例較好使用下述所示者:
此處,上述Ar1中,r為1~5之整數,就分散安定性之觀點而言,更好為1~3之整數;且,上述Ar2中,s為1~5之整數,就分散安定性之觀點而言,更好為1~3之整數,又更好為1~2之整數,最好為1。Ar1中之苯基上所取代之乙基之取代位置亦無特別限制,但r=1時,以3位或4位較佳,r=3時,就高研磨速度且實現低階差、蝕刻抑制效果之觀點,且能減低有機殘留物之觀點而
言,較好為2位、4位、6位。又,s=1時,以2位、3位或4位較佳,就蝕刻抑制效果之觀點而言,且減低有機殘留物之觀點而言,最好為3位。
此外,上述式3中之「E」中,碳數1~3之伸烷基之具體例亦無特別限制,可為直鏈狀、分支狀,列舉為例如亞甲基、伸乙基、三亞甲基、伸丙基等,尤其為伸乙基時,可有效發揮上述本發明之期望效果。且,n為1~100,但就分散安定性之觀點而言,較好為4~80之整數,更好為8~50之整數。
鑒於上述時,就有效發揮本發明之期望效果之觀點而言,可適當地使用以下述式5~7表示之化合物或其鹽之界面活性劑。
非離子性界面活性劑之具體例列舉為例如聚氧伸乙基烷基醚等聚氧伸烷基烷基醚、山梨糖醇酐脂肪酸酯、甘油脂肪酸酯、聚氧伸乙基脂肪酸酯、聚氧伸乙基烷基胺、及烷基烷醇醯胺。其中以聚氧伸烷基烷基醚較佳。聚氧伸烷基烷基醚由於對研磨對象物表面之化學或物理之吸附力高,故於研磨對象物表面形成更堅固之保護膜。此對於提高使用研磨用組成物研磨後之研磨對象物表面之平坦性有利。聚氧伸乙基烷基醚之重複單位(氧伸乙基)之數亦無特別限制,例如為1~20左右。且烷基之碳數亦無特別限制,例如為3~18左右。
陽離子性界面活性劑之具體例列舉為例如烷基三甲基銨鹽、烷基二甲基銨鹽、烷基苄基二甲基銨鹽、及烷基胺鹽。
兩性界面活性劑之具體例列舉為例如烷基甜菜鹼及烷基氧化胺。
如上述,本發明之界面活性劑亦可為鹽之形態。鹽之具體例列舉為一價或二價之金屬鹽,或銨鹽、胺鹽等。一價或二價之金屬鹽列舉為鋰鹽、鈉鹽、鉀鹽、鎂鹽、鈣鹽等。其中,基於半導體用之研磨用組成物之金屬
雜質之觀點,以胺鹽、銨鹽、鉀鹽較佳。此處,作為胺鹽具體列舉為三乙醇胺、三甲醇胺等,就研磨性能之觀點而言以三乙醇胺較適當。又,所謂鹽之形態,界面活性劑若以式2表示,則在A1~A3之一個或複數個為氫原子時,係指其一部分或全部氫原子經取代為上述列舉之鹽之形態。
研磨用組成物中之界面活性劑之含量較好為不小於0.01(g/L),更好不小於0.05(g/L),又更好為不小於0.1(g/L),最好不小於0.3(g/L)。隨著界面活性劑之含量變多會有提高使用研磨用組成物研磨後之研磨對象物表面之平坦性之優點。研磨用組成物中之界面活性劑之含量較好為不大於50(g/L),更好不大於25(g/L),又更好不大於5(g/L),最好不大於1(g/L)。隨著界面活性劑之含量減少,有提高利用研磨用組成物之研磨速度之優點。且,具有減低有機殘留物之效果。又尤其,不與金屬防腐蝕劑併用時,較好以容易增加界面活性劑在研磨用組成物中之含量之方式調節。又,研磨用組成物中之界面活性劑之含量在併用兩種以上之界面活性劑使用時,為其合計量。
此外,本發明之界面活性劑之數平均分子量(Mn)在使用高分子者時,較好為100~50000之範圍內,更好為250~1000之範圍內。又,本發明中,數平均分子量(Mn)係採用以GPC(凝膠滲透層析)法測定之聚苯乙烯換算之值者。
又,本發明之界面活性劑之HLB較好為6~16
之範圍內,更好為7~12之範圍內。
本發明之研磨用組成物之界面活性劑可購入市售品,亦可視需要參照過去習知之見解,或者組合進行合成。
本發明中,研磨用組成物含氧化劑。本說明書中之所謂氧化劑意指可對研磨對象物中所含之金屬發揮作為氧化劑功能之化合物。因此,氧化劑係依據是否為發揮該功能時具有充分之氧化還原電位者之基準進行選定。因此,氧化劑之延伸並非一定可統一明確定義者,但其一例列舉為例如過氧化氫、硝酸、亞氯酸、次氯酸、過碘酸、過硫酸鹽、氧化氫及其加成物,例如尿素過氧化氫及碳酸酯、有機過氧化物,例如苯甲醯、過乙酸及二第三丁基、硫氧化物(SO5)、硫氧化物(S5O8)、以及過氧化鈉。此外,列舉有過碘酸、亞碘酸、次碘酸、氫碘酸、過溴酸、亞溴酸、次溴酸、氫溴酸、過氯酸、氫氯酸、過氯酸、過硼酸、及該等之鹽等。尤其,就研磨速度之觀點或操作容易之觀點而言,以過氧化氫較佳。
本形態之研磨用組成物含氧化劑時,該研磨用組成物中之該氧化劑之含量下限較好不小於1g/L,更好不小於5g/L,又更好不小於10g/L。隨著氧化劑之含量變多,有利用研磨用組成物對研磨對象物之研磨速度提高之傾向。另一方面,本形態之研磨用組成物含氧化劑時,該
研磨用組成物中之該氧化劑之含量上限較好不大於100g/L,更好不大於50g/L。隨著氧化劑之含量變少,除了可抑制研磨用組成物之材料成本以外,可減輕研磨使用後之研磨用組成物之處理,亦即可減輕廢液處理之負荷。且,亦可獲得可防止因氧化劑所致之研磨對象物過度氧化之有利效果。
接著,說明本發明之研磨對象物及半導體配線製程之一例。半導體配線製程通常包含以下步驟,但本發明並不限於使用以下步驟。
在設於基板上之具有溝槽之絕緣體層上依序形成障壁層及金屬配線層。障壁層係在金屬配線層形成之前,以被覆絕緣體層表面之方式形成於絕緣體層上。障壁層之厚度比溝槽之深度及寬度小。金屬配線層係在形成障壁層之後,以至少埋入溝槽之方式形成於障壁層上。
藉由CMP,至少去除金屬配線層之外側部分及障壁層之外側部分時,首先,去除金屬配線層之外側部分之大部分。接著,為了使障壁層之外側部分之上面露出,而去除金屬配線層之外側部分之多餘部分。隨後,利用CMP去除至少位在溝槽外之金屬配線層之部分及位在溝槽外之障壁層之部分。結果,使位在溝槽中之障壁層之部分之至少一部分及位在溝槽中之金屬配線層之部分之至少一部分殘留在絕緣體層上。亦即,於溝槽之內側殘留障
壁層之一部分及金屬配線層之一部分。因此,殘留在溝槽內側之金屬配線層之部分係作為配線發揮功能。
本發明之研磨用組成物係使用於如上述之具有金屬配線層及障壁層之研磨對象物之研磨者。
金屬配線層中所含之金屬並無特別限制,列舉為例如銅、鋁、鉿、鈷、鎳、鈦、鎢等。該等金屬亦可以合金或金屬化合物之形態包含於金屬配線層中。就導電率之觀點而言,較好為銅、或銅合金。該等金屬可單獨使用或組合2種以上使用。
又,障壁層中所含金屬並無特限制,列舉為例如鈦、鉭之金屬及釕、銀、金、鈀、鉑、銠、銦及鋨等貴金屬。該等金屬及貴金屬亦可以合金或金屬化合物之形態包含於障壁層中,可單獨或組合2種以上使用。
接著,另外針對本發明之研磨用組成物中所含之各成分加以詳細說明。
本發明之研磨用組成物亦可含有水作為用以使各成分分散或溶解之分散介質或溶劑。就抑制阻礙其他成分之作用之觀點而言,較好為儘可能不含雜質之水,具體而言較好為以離子交換樹脂去除雜質離子後,通過過濾器去除異物之純水或超純水、或蒸餾水。
本發明之研磨用組成物亦可含錯化劑(本說明書中亦稱為「錯體形成劑」)。藉由於研磨用組成物中添加錯化劑,藉由錯化劑所具有之蝕刻作用,而有提高以研磨用組成物進行之研磨對象物之研磨速度的有利效果。
錯化劑係使用例如無機酸、有機酸、胺基酸、腈化合物及螯合劑等。無機酸之具體例列舉為硫酸、硝酸、硼酸、碳酸等。有機酸之具體例列舉為甲酸、乙酸、丙酸、丁酸、戊酸、2-甲基丁酸、正己酸、3,3-二甲基丁酸、2-乙基丁酸、4-甲基戊酸、正庚酸、2-甲基己酸、正辛酸、2-乙基己酸、苯甲酸、乙醇酸、水楊酸、甘油酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、馬來酸、鄰苯二甲酸、蘋果酸、酒石酸、檸檬酸、乳酸等。亦可使用甲烷磺酸、乙烷磺酸及羥乙磺酸等有機硫酸。亦可替代無機酸或有機酸或與無機酸或有機酸組合而使用無機酸或有機酸之鹼金屬鹽等之鹽。
胺基酸之具體例列舉為甘胺酸、α-丙胺酸、β-丙胺酸、N-甲基甘胺酸、N,N-二甲基甘胺酸、2-胺基丁酸、正纈胺酸、纈胺酸、亮胺酸、正亮胺酸、異亮胺酸、苯基丙胺酸、脯胺酸、肌胺酸、鳥胺酸、離胺酸、牛磺酸、絲胺酸、蘇胺酸、高絲胺酸、酪胺酸、N,N-二羥乙基甘胺酸(bicine)、N-叁羥甲基甲基甘胺酸(tricin)、3,5-二碘酪胺酸、β-(3,4-二羥基苯基)-丙胺酸、甲狀腺素(thyroxin)、4-羥基-脯胺酸、半胱胺酸、甲硫胺酸、乙硫胺酸、羊毛硫胺酸(lanthionine)、胱硫醚
(cystathionine)、胱胺酸、磺基丙胺酸(cysteic acid)、天門冬胺酸、穀胺酸、S-(羧基甲基)-半胱胺酸、4-胺基丁酸、天冬醯胺、穀醯胺、氮雜絲胺酸(azaserine)、精胺酸、刀豆胺酸(canavanine)、瓜胺酸、δ-羥基離胺酸、肌酸、組胺酸、1-甲基組胺酸、3-甲基組胺酸、色胺酸等。其中,自研磨速度之觀點而言,以甘胺酸、丙胺酸、蘋果酸、酒石酸、檸檬酸、乙醇酸、羥乙磺酸或該等之鹽較佳。又,關於「鹽」,於界面活性劑之說明中列舉者亦可同樣使用。
腈化合物之具體例列舉為例如乙腈、胺基乙腈、丙腈、丁腈、異丁腈、苄腈、戊二腈、甲氧基乙腈等。
螯合劑之具體例列舉為氮基三乙酸、二伸乙基三胺五乙酸、乙二胺四乙酸、N,N,N-三亞甲基膦酸、乙二胺-N,N,N’,N’-四亞甲基磺酸、反式環己烷二胺四乙酸、1,2-二胺基丙烷四乙酸、二醇醚二胺四乙酸、乙二胺鄰羥基苯基乙酸、乙二胺二琥珀酸(SS體)、N-(2-羧酸根乙基)-L-天門冬胺酸、β-丙胺酸二乙酸、2-膦醯丁烷-1,2,4-三羧酸、1-羥基亞乙基-1,1-二膦酸、N,N’-雙(2-羥基苄基)乙二胺-N,N’-二乙酸、1,2-二羥基苯-4,6-二磺酸等。
研磨用組成物之錯化劑之含量下限較好為不小於1(g/L),更好為不小於5(g/L)。隨著錯化劑之含量變多,研磨用組成物對研磨對象物之研磨速度提高。另一方面,基於減低因添加錯化劑而使研磨對象物容易接
受過度蝕刻之虞(防止過度蝕刻)之觀點而言,該研磨用組成物中之該錯化劑含量上限相對於組成物較好為不大於30(g/L),更好為不大於20(g/L)。
本發明之研磨用組成物亦可含研磨粒。研磨組成物中所含之研磨粒具有對研磨對象物機械研磨之作用,且可提高研磨用組成物對研磨對象物之研磨速度。
使用之研磨粒可為無機粒子、有機粒子及有機無機複合粒子之任一種。無機粒子之具體例列舉為例如由二氧化矽、氧化鋁、氧化鈰、氧化鈦等金屬氧化物所成之粒子,以及氮化矽粒子、碳化矽粒子、氮化硼粒子。有機粒子之具體例列舉為例如聚甲基丙烯酸甲酯(PMMA)粒子。該研磨粒可單獨使用或混合2種以上使用。另外,該研磨粒可使用市售品亦可使用合成品。
該等研磨粒中以二氧化矽較佳,最好為膠體二氧化矽。研磨粒亦可經表面修飾。通常之膠體二氧化矽由於在酸性條件下之Zeta電位值接近於零,故在酸性條件下二氧化矽粒子彼此間尤其最好為固定化有有機酸之膠體二氧化矽。有機酸對研磨用組成物中所含之膠體二氧化矽表面之固定化係藉由例如使有機酸之官能基化學鍵結於膠體二氧化矽表面而進行。僅單使膠體二氧化矽與有機酸共存,無法達到有機酸朝膠體二氧化矽之固定化。若使有機酸之一種的磺酸固定化於膠體二氧化矽上,則可藉例如
“Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups”,Chem.Commun.246-247(2003)中所記載之方法進行。具體而言,使3-巰丙基三甲氧基矽烷等之具有硫醇基之矽烷偶合劑偶合於膠體二氧化矽上後,以過氧化氫使硫醇基氧化,藉此可獲得磺酸固定化於表面之膠體二氧化矽。或者,若使羧酸固定化於膠體二氧化矽上,則可藉例如“Novel Silane Coupling Agents Containing a Photolabile 2-Nitrobenzyl Ester for Introduction of a Carboxy Group on the Surface of Silica Gel”,Chemistry Letters,3,228-229(2000)中所記載之方法進行。具體而言,在將含有光反應性2-硝基苄酯之矽烷偶合劑偶合於膠體二氧化矽後,藉由光照射,可獲得使羧酸固定化於表面之膠體二氧化矽。
研磨粒之平均一次粒徑之下限較好為不小於1nm,更好不小於3nm,又更好不小於5nm。且,研磨粒之平均一次粒徑之上限較好不大於500nm,更好不大於100nm,又更好不大於70nm。若為該範圍,則研磨用組成物對研磨對象物之研磨速度提高,且可進一步抑制使用研磨用組成物研磨後之研磨對象物表面產生凹陷等之階差缺陷。且易有防止研磨對象物表面產生刮痕等傷痕。又,研磨粒之平均一次粒徑係採用基於以BET法測定之研磨粒之比表面積而算出。此外,亦可使用具有不同兩種粒徑之研磨粒。使用具有不同兩種粒徑之研磨粒時具有可有效促進研磨速度之效果。
研磨用組成物中之研磨粒含量下限較好不小於0.01g/L,更好不小於0.03g/L,又更好不小於0.05g/L,最好不小於0.1g/L,又最好不小於1g/L。且,研磨用組成物中之研磨粒含量上限較好為不大於100g/L,更好不大於50g/L,又更好不大於25g/L,最好不大於10g/L。又,研磨用組成物中混合存在有具有兩種以上之平均一次粒徑之研磨粒時,含量為其合計量。若在該範圍,則可提高研磨對象物之研磨速度,且可抑制研磨用組成物之成本,可更抑制使用研磨用組成物研磨後之研磨對象物表面產生凹陷等之階差缺陷。
研磨用組成物之pH並無特別限制。但若不大於11.0,進而換言之不大於10.0之pH,則由於防止研磨粒溶解故而提高研磨用組成物之安定性。且,若不小於2.0,進而換言之不小於4.0,則研磨用組成物含研磨粒時可提高該研磨粒之分散性。
研磨用組成物之pH亦可使用pH調整劑調整至期望之值。使用之pH調整劑可為酸及鹼之任一種,且可為無機及有機化合物之任一種。該等pH調節劑可單獨使用或混合2種以上使用。又,本說明書中之「pH」係指液溫(25℃)下使用堀場製作所製造之型號F-72之pH計測定之值。
本發明之研磨用組成物之製造方法並未特別限制,但較佳之形態係一種研磨用組成物之製造方法,其係研磨對象物之研磨所用之研磨用組成物之製造方法,其係混合金屬防腐蝕劑及界面活性劑之至少一種;氧化劑;有機化合物,且前述有機化合物具有2~3個羥基。
依據更佳形態,本發明之研磨用組成物可藉由例如於水中攪拌混合構成本發明之研磨用組成物之各成分而得。此外,混合各成分時之溫度並無特別限制,但較好為10~40℃,亦可加熱以提高溶解速度。且,混合時間亦無特別限制。
如上述,本發明之研磨用組成物適用於具有金屬配線層之研磨對象物之研磨。因此,本發明提供以本發明之研磨用組成物或利用研磨用組成物之製造方法製造之研磨用組成物研磨研磨對象物之研磨方法。另外,本發明提供包含以前述研磨方法研磨研磨對象物之步驟之基板的製造方法。
研磨裝置可使用安裝有保持具有研磨對象物之基板等之載具與可改變轉數之馬達等,且具有可貼附研磨墊之研磨壓盤之一般研磨裝置。前述研磨墊可無特別限制的使用一般之不織布、聚胺基甲酸酯及多孔質氟樹脂等。研磨墊中較好施以可使研磨液積存之溝槽加工。
研磨條件亦無特別限制,例如研磨壓盤之轉
數較好為10~500rpm。此外,載具之轉數較好為20~110rpm。且,對具有研磨對象物之基板施加之壓力(研磨壓力)較好為0.5~10psi(3.45~69KPa)。將研磨用組成物供給於研磨墊之方法亦無特別限制,例如可採用泵等連續供給之方法。其供給量並無限制,但較好為100~500ml/min左右。此外,研磨時間亦無特別限制,但較好為30~120秒左右。研磨墊之表面較好隨時以本發明之研磨用組成物覆蓋。
研磨結束後,在水流中洗淨基板,以旋轉乾燥機等甩掉附著於基板上之水滴予以乾燥,而獲得具有金屬配線層及障壁層之基板。
以下,列舉實施例及比較例更詳細說明前述實施形態。
將表1中所示之研磨粒1、研磨粒2、氧化劑、錯體形成劑、金屬防腐蝕劑、界面活性劑1、界面活性劑2、含羥基之有機化合物以成為表1所示組成之方式,在水(超純水)中攪拌混合(混合溫度:約25℃,混合時間:約10分鐘),調製(25℃)實施例1~3、比較例1~6之研磨用組成物。又,研磨用組成物中之pH一律調製成7.0。又,表1中之「-」表示不含該成分。
研磨速率係測定使用所得研磨用組成物(實施例1~3、比較例1~6),以下述表2所示之研磨條件研磨銅無圖型晶圓(直徑:300mm)之表面60秒時之研磨速度。研磨速度[Å/min]係將使用以直流4探針法為原理之薄片電阻測定器測定之研磨前後之銅無圖型晶圓之厚度差除以研磨時間而求出。結果示於表1。
研磨速度考慮生產性時,愈快愈好,但鑒於實用速度,為不小於5650Å/min,較好不小於5700Å/min。
使用聚乙烯醇製刷且使用三菱化學股份有限公司製之液溫25℃之洗淨液“MCX-SDR4”作為洗淨藥劑,對已研磨之銅無圖型晶圓進行洗淨60秒。洗淨後,以光干涉式晶圓表面檢查裝置(SP-1,KLA-Tencor公司製),晶圓之整面(直徑300mm之圓)中,以檢測出0.16μm以上尺寸之條件進行測定,計算有機殘留物之數。結果示於表1。有機殘留物數考慮半導體裝置之生產良率時,愈少愈好,但鑒於實用數時,為10000個以下,更好為5000個以下,又更好為2500個以下。
又,本申請案係基於2013年9月13日申請之日本國專利申請案第2013-190788號,其揭示內容藉由參照全文被援用。
Claims (7)
- 一種研磨用組成物,其係用於研磨對象物之研磨的研磨用組成物,其含有界面活性劑;氧化劑;有機化合物,或含有界面活性劑;金屬防腐蝕劑;氧化劑;及有機化合物,前述有機化合物係以下述式1表示:【化1】HO-(XO)n-H‧‧‧(式1)式1中,X為碳數1~3之伸烷基,n為1~100,但n為1時,前述伸烷基之1個氫原子可經羥基取代,前述界面活性劑係選自由(i)碳數10~14之烷基硫酸或其鹽、(ii)聚氧伸乙基烷基醚、及(iii)以下述式2表示之化合物或其鹽所組成群之至少兩種:式2中,A1~A3各獨立為氫原子、甲基、乙基或聚氧伸烷基芳基醚基,但A1~A3中之至少一個為聚氧伸烷基芳基醚基,前述聚氧伸烷基芳基醚基係:式3中,Ar表示可具有取代基之碳數6~20之芳基,E為碳數1~3之伸烷基,n為1~100。
- 如請求項1之研磨用組成物,其中前述研磨對象物具有金屬配線層。
- 如請求項1或2之研磨用組成物,其中前述金屬防腐蝕劑係具有以至少1個經羥基烷基取代之胺基之苯并三唑化合物。
- 如請求項1之研磨用組成物,其係進一步含有研磨粒。
- 一種研磨用組成物之製造方法,其係用於研磨對象物之研磨的研磨用組成物之製造方法,其係混合界面活性劑;氧化劑;有機化合物,或混合含有界面活性劑;金屬防腐蝕劑;氧化劑;及有機化合物,前述有機化合物係以下述式1表示:【化1】HO-(XO)n-H‧‧‧(式1)式1中,X為碳數1~3之伸烷基,n為1~100,但n為1時,前述伸烷基之1個氫原子可經羥基取代,前述界面活性劑係選自由(i)碳數10~14之烷基硫酸或其鹽、(ii)聚氧伸乙基烷基醚、及(iii)以下述式2表示之化合物或其鹽所組成群之至少兩種:式2中,A1~A3各獨立為氫原子、甲基、乙基或聚氧伸烷基芳基醚基,但A1~A3中之至少一個為聚氧伸烷基芳基醚基,前述聚氧伸烷基芳基醚基係:式3中,Ar表示可具有取代基之碳數6~20之芳基,E為碳數1~3之伸烷基,n為1~100。
- 一種研磨方法,其係以如請求項1~4中任一項之研磨用組成物或以如請求項5之製造方法所得之研磨用組成物研磨前述研磨對象物。
- 一種基板之製造方法,其包含以如請求項6之研磨方法研磨前述研磨對象物之步驟。
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