TWI595058B - Cmp slurry composition for organic film and polishing method using the same - Google Patents
Cmp slurry composition for organic film and polishing method using the same Download PDFInfo
- Publication number
- TWI595058B TWI595058B TW105114483A TW105114483A TWI595058B TW I595058 B TWI595058 B TW I595058B TW 105114483 A TW105114483 A TW 105114483A TW 105114483 A TW105114483 A TW 105114483A TW I595058 B TWI595058 B TW I595058B
- Authority
- TW
- Taiwan
- Prior art keywords
- substituted
- organic film
- unsubstituted
- slurry composition
- film
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 105
- 238000005498 polishing Methods 0.000 title claims description 80
- 239000002002 slurry Substances 0.000 title claims description 70
- 238000000034 method Methods 0.000 title claims description 15
- 238000000227 grinding Methods 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 27
- 229910044991 metal oxide Inorganic materials 0.000 claims description 22
- 150000004706 metal oxides Chemical class 0.000 claims description 22
- 229920002125 Sokalan® Polymers 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 17
- 239000004584 polyacrylic acid Substances 0.000 claims description 16
- 239000007800 oxidant agent Substances 0.000 claims description 14
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000013522 chelant Substances 0.000 claims description 7
- 239000012454 non-polar solvent Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- FZIZEIAMIREUTN-UHFFFAOYSA-N azane;cerium(3+) Chemical compound N.[Ce+3] FZIZEIAMIREUTN-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 description 34
- 125000004429 atom Chemical group 0.000 description 33
- 125000003118 aryl group Chemical group 0.000 description 30
- 125000000524 functional group Chemical group 0.000 description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 13
- 125000000753 cycloalkyl group Chemical group 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 125000003710 aryl alkyl group Chemical group 0.000 description 8
- 125000000392 cycloalkenyl group Chemical group 0.000 description 8
- 125000001072 heteroaryl group Chemical group 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 125000003282 alkyl amino group Chemical group 0.000 description 7
- 125000000304 alkynyl group Chemical group 0.000 description 7
- 125000004104 aryloxy group Chemical group 0.000 description 7
- 125000001188 haloalkyl group Chemical group 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 125000004404 heteroalkyl group Chemical group 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product 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
- 125000004093 cyano group Chemical group *C#N 0.000 description 6
- 125000004446 heteroarylalkyl group Chemical group 0.000 description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 5
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 5
- -1 iron halide salt Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000005011 alkyl ether group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000005275 alkylenearyl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000004405 heteroalkoxy group Chemical group 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-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
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000005907 alkyl ester group Chemical group 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 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
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- MCVVDMSWCQUKEV-UHFFFAOYSA-N (2-nitrophenyl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1=CC=CC=C1[N+]([O-])=O MCVVDMSWCQUKEV-UHFFFAOYSA-N 0.000 description 1
- DLDWUFCUUXXYTB-UHFFFAOYSA-N (2-oxo-1,2-diphenylethyl) 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 DLDWUFCUUXXYTB-UHFFFAOYSA-N 0.000 description 1
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 1
- DAJPMKAQEUGECW-UHFFFAOYSA-N 1,4-bis(methoxymethyl)benzene Chemical compound COCC1=CC=C(COC)C=C1 DAJPMKAQEUGECW-UHFFFAOYSA-N 0.000 description 1
- MVFYNVDEWCIFFY-UHFFFAOYSA-N 1-methoxyanthracene Chemical compound C1=CC=C2C=C3C(OC)=CC=CC3=CC2=C1 MVFYNVDEWCIFFY-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-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
- NJQJGRGGIUNVAB-UHFFFAOYSA-N 2,4,4,6-tetrabromocyclohexa-2,5-dien-1-one Chemical compound BrC1=CC(Br)(Br)C=C(Br)C1=O NJQJGRGGIUNVAB-UHFFFAOYSA-N 0.000 description 1
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 1
- SHOANEAFHGLDHL-UHFFFAOYSA-N 2-(2-nitrophenyl)-1-phenylethanesulfonic acid Chemical compound C=1C=CC=CC=1C(S(=O)(=O)O)CC1=CC=CC=C1[N+]([O-])=O SHOANEAFHGLDHL-UHFFFAOYSA-N 0.000 description 1
- MXVMRHIWTSFDPU-UHFFFAOYSA-N 2-chlorobenzenecarboximidamide Chemical compound NC(=N)C1=CC=CC=C1Cl MXVMRHIWTSFDPU-UHFFFAOYSA-N 0.000 description 1
- NXKOSHBFVWYVIH-UHFFFAOYSA-N 2-n-(butoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound CCCCOCNC1=NC(N)=NC(N)=N1 NXKOSHBFVWYVIH-UHFFFAOYSA-N 0.000 description 1
- KFVIYKFKUYBKTP-UHFFFAOYSA-N 2-n-(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCNC1=NC(N)=NC(N)=N1 KFVIYKFKUYBKTP-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- JZTPOMIFAFKKSK-UHFFFAOYSA-N O-phosphonohydroxylamine Chemical compound NOP(O)(O)=O JZTPOMIFAFKKSK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 101100107923 Vitis labrusca AMAT gene Proteins 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WTHXTWHYLIZJBH-UHFFFAOYSA-N acetic acid;azane Chemical compound N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O WTHXTWHYLIZJBH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005227 alkyl sulfonate group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 230000004075 alteration Effects 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
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 description 1
- 150000001576 beta-amino acids Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 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
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001297 coherence probe microscopy Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- RVOJTCZRIKWHDX-UHFFFAOYSA-N cyclohexanecarbonyl chloride Chemical compound ClC(=O)C1CCCCC1 RVOJTCZRIKWHDX-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- WCQOBLXWLRDEQA-UHFFFAOYSA-N ethanimidamide;hydrochloride Chemical compound Cl.CC(N)=N WCQOBLXWLRDEQA-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000001046 glycoluril group Chemical class [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JOAJYEIQYSPWHF-UHFFFAOYSA-N naphthalene-1,4-dione;hydrochloride Chemical compound Cl.C1=CC=C2C(=O)C=CC(=O)C2=C1 JOAJYEIQYSPWHF-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- 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
- H01L21/302—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
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Description
本發明是有關於一種用於有機膜的化學機械研磨(CMP)漿料組成物及使用其的研磨方法。 The present invention relates to a chemical mechanical polishing (CMP) slurry composition for an organic film and a polishing method using the same.
用於製造半導體的方法包含在經圖案化的矽晶圓上形成無機膜(例如氧化矽膜或氮化矽膜)的製程及間隙填充在無機膜中形成的通孔的製程。使用有機膜材料執行間隙填充製程以填充通孔。在間隙填充製程之後，執行平坦化製程以移除過量有機膜。對於平坦化，化學機械研磨(chemical mechanical polishing，CMP)在此項技術中引起注意。 A method for fabricating a semiconductor includes a process of forming an inorganic film (for example, a hafnium oxide film or a tantalum nitride film) on a patterned germanium wafer and a process of filling a via hole formed in the inorganic film. A gap filling process is performed using the organic film material to fill the via holes. After the gap fill process, a planarization process is performed to remove excess organic film. For planarization, chemical mechanical polishing (CMP) has attracted attention in the art.
典型的用於有機膜的CMP漿料組成物包含聚合物研磨粒子，以便使得有機膜可在高研磨速率下研磨而無表面條件劣化，諸如刮痕。然而，由於所有有機膜並非由同一材料形成，故此類典型CMP漿料組成物相對於一些種類的有機膜未能在經研磨表面上增強平坦程度的同時達成所需研磨速率。此外，當在有機 膜研磨中使用用於研磨金屬膜的金屬氧化物磨蝕劑(諸如矽及其類似物)時，相對於某些種類的有機膜難以達成所需研磨量，及/或因刮痕及其類似物而降低經研磨表面上的平坦程度。 A typical CMP slurry composition for an organic film comprises polymer abrasive particles such that the organic film can be ground at high polishing rates without surface condition degradation, such as scratches. However, since all organic films are not formed of the same material, such typical CMP slurry compositions fail to achieve a desired degree of polishing while maintaining a flatness on the ground surface relative to some types of organic films. Also, when in organic When a metal oxide abrasive for polishing a metal film, such as ruthenium and the like, is used in film polishing, it is difficult to achieve a desired amount of polishing with respect to certain kinds of organic films, and/or due to scratches and the like. The flatness on the ground surface is reduced.
相關技術的一個實例揭示於韓國專利公開案第2007-0057009A號中。 An example of the related art is disclosed in Korean Patent Publication No. 2007-0057009A.
本發明的一個態樣為提供用於有機膜的CMP漿料組成物，其在研磨具有高碳含量、高膜密度以及高硬度的有機膜時具有優良效應。 One aspect of the present invention is to provide a CMP slurry composition for an organic film which has an excellent effect in grinding an organic film having a high carbon content, a high film density, and a high hardness.
本發明的另一個態樣為提供用於有機膜的CMP漿料組成物，其在研磨有機膜時具有比在研磨無機膜時更佳的效應。 Another aspect of the present invention is to provide a CMP slurry composition for an organic film which has a better effect when the organic film is ground than when the inorganic film is ground.
本發明的另一個態樣為提供用於有機膜的CMP漿料組成物，其在研磨具有高碳含量、高膜密度以及高硬度的有機膜之後在經研磨表面上提供良好平坦性，且其藉由容易自研磨停止膜移除殘餘有機膜材料而使得研磨更均一。 Another aspect of the present invention is to provide a CMP slurry composition for an organic film which provides good flatness on an abrasive surface after grinding an organic film having a high carbon content, a high film density, and a high hardness, and The grinding is more uniform by easily removing the residual organic film material from the polishing stop film.
根據本發明的一個態樣，用於研磨碳含量為約50原子%至約99原子%的有機膜的CMP漿料組成物包含：極性溶劑及非極性溶劑中的至少一者；金屬氧化物磨蝕劑；氧化劑；以及分子量為約3500公克/莫耳或小於3500公克/莫耳的聚丙烯酸。 According to one aspect of the present invention, a CMP slurry composition for milling an organic film having a carbon content of from about 50 at% to about 99 at% comprises: at least one of a polar solvent and a non-polar solvent; metal oxide abrasion An oxidizing agent; and a polyacrylic acid having a molecular weight of about 3500 g/m or less than 3500 g/m.
所述有機膜可具有約0.5公克/立方公分至約2.5公克/立方公分的膜密度及約0.4GPa或大於0.4GPa的硬度。 The organic film may have a film density of from about 0.5 g/cm 3 to about 2.5 g/cm 3 and a hardness of about 0.4 GPa or greater than 0.4 GPa.
所述有機膜可具有約0.5公克/立方公分至約2.5公克/立方公分的膜密度及約0.4GPa至約1.5GPa的硬度。 The organic film may have a film density of from about 0.5 g/cm 3 to about 2.5 g/cm 3 and a hardness of from about 0.4 GPa to about 1.5 GPa.
所述有機膜可具有約0.5公克/立方公分至約2.5公克/立方公分的膜密度及約0.6GPa至約1.5GPa的硬度。 The organic film may have a film density of from about 0.5 g/cm 3 to about 2.5 g/cm 3 and a hardness of from about 0.6 GPa to about 1.5 GPa.
所述有機膜可具有約1.0公克/立方公分至約2.0公克/立方公分的膜密度及約0.6GPa至1.5GPa的硬度。 The organic film may have a film density of from about 1.0 g/cm 3 to about 2.0 g/cm 3 and a hardness of from about 0.6 GPa to 1.5 GPa.
所述有機膜可具有約1.0公克/立方公分至約2.5公克/立方公分的膜密度及約0.6GPa至1.5GPa的硬度。 The organic film may have a film density of from about 1.0 g/cm 3 to about 2.5 g/cm 3 and a hardness of from about 0.6 GPa to 1.5 GPa.
所述有機膜可具有約1.0公克/立方公分至約2.0公克/立方公分的膜密度及約1.0GPa或大於1.0GPa的硬度。 The organic film may have a film density of from about 1.0 g/cm 3 to about 2.0 g/cm 3 and a hardness of about 1.0 GPa or more.
所述金屬氧化物磨蝕劑可包含二氧化矽、氧化鋁、二氧化鈰、二氧化鈦以及二氧化鋯中的至少一者。 The metal oxide abrasive may include at least one of cerium oxide, aluminum oxide, cerium oxide, titanium oxide, and zirconium dioxide.
所述金屬氧化物磨蝕劑可以約0.1重量%至約20重量%的量存在於所述組成物中。 The metal oxide abrasive may be present in the composition in an amount from about 0.1% to about 20% by weight.
所述聚丙烯酸可以約0.01重量%至約5重量%的量存在於所述組成物中。 The polyacrylic acid may be present in the composition in an amount from about 0.01% to about 5% by weight.
所述氧化劑可包含多價氧化態金屬鹽及過渡金屬螯合物中的至少一者。 The oxidizing agent may comprise at least one of a polyvalent oxidation state metal salt and a transition metal chelate compound.
所述氧化劑可以約0.001重量%至約15重量%的量存在於所述組成物中。 The oxidizing agent may be present in the composition in an amount from about 0.001% to about 15% by weight.
所述多價氧化態金屬鹽可包含鈰銨鹽、硝酸鐵以及氯化鐵中的至少一者。 The multivalent oxidation state metal salt may comprise at least one of a cerium ammonium salt, iron nitrate, and ferric chloride.
所述有機膜的酸值可為約0mg KOH/g。 The organic film may have an acid value of about 0 mg KOH/g.
根據本發明的另一個態樣，用於研磨有機膜的方法包含：使用如以上所述的用於有機膜的CMP漿料組成物研磨有機膜，所述有機膜具有約50原子%至約99原子%的碳含量、約0.5公克/立方公分至約2.5公克/立方公分的膜密度以及約0.4GPa或大於0.4GPa的硬度。 According to another aspect of the present invention, a method for polishing an organic film includes: grinding an organic film using a CMP slurry composition for an organic film as described above, the organic film having from about 50 atom% to about 99 Atomic % carbon content, a film density of from about 0.5 g/cm to about 2.5 g/cm and a hardness of about 0.4 GPa or greater than 0.4 GPa.
根據本發明，所述CMP漿料組成物在研磨具有高碳含量、高膜密度以及高硬度的有機膜時提供優良效應，在研磨有機膜時具有比在研磨無機膜時更佳的研磨速率，在研磨有機膜之後在經研磨表面上提供良好平坦性，以及藉由容易自研磨停止膜移除殘餘有機膜材料而使得研磨更均一。 According to the present invention, the CMP slurry composition provides an excellent effect in grinding an organic film having a high carbon content, a high film density, and a high hardness, and has a higher polishing rate when the organic film is ground than when the inorganic film is polished. Good flatness is provided on the ground surface after grinding the organic film, and grinding is more uniform by easily removing the residual organic film material from the polishing stop film.
100‧‧‧矽晶圓 100‧‧‧矽 wafer
110‧‧‧無機膜 110‧‧‧Inorganic film
120‧‧‧有機碳膜 120‧‧‧Organic carbon film
T‧‧‧研磨停止線 T‧‧‧ grinding stop line
圖1(a)及圖1(b)為根據本發明的一個實施例的用於研磨有機膜的方法的圖式。 1(a) and 1(b) are diagrams of a method for polishing an organic film according to an embodiment of the present invention.
有機膜CMP漿料組成物Organic film CMP slurry composition
根據本發明的一個實施例，用於有機膜的CMP漿料組成物可包含：極性溶劑及非極性溶劑中的至少一者；金屬氧化物磨蝕劑；氧化劑；以及聚丙烯酸(PAA)。所述CMP漿料組成物相對於作 為研磨目標的有機膜增加研磨速率，而相對於二氧化矽降低研磨速率，由此確保對有機膜的優良選擇率。 According to an embodiment of the present invention, the CMP slurry composition for an organic film may include: at least one of a polar solvent and a non-polar solvent; a metal oxide abrasive; an oxidizing agent; and polyacrylic acid (PAA). The CMP slurry composition is relative to The polishing rate is increased for the organic film of the polishing target, and the polishing rate is lowered with respect to the cerium oxide, thereby ensuring an excellent selectivity for the organic film.
當使用金屬氧化物磨蝕劑研磨具有高碳含量的有機膜時，極性溶劑及/或非極性溶劑用於減小摩擦力且可包含例如水(諸如超純水)、有機胺、有機醇、有機醇胺、有機醚、有機酮及其類似物。舉例而言，極性溶劑及/或非極性溶劑可為超純水。極性溶劑及/或非極性溶劑可以余量存在於所述CMP漿料組成物中。 When an organic film having a high carbon content is ground using a metal oxide abrasive, a polar solvent and/or a non-polar solvent is used to reduce friction and may include, for example, water (such as ultrapure water), organic amines, organic alcohols, organic Alcoholamines, organic ethers, organic ketones and the like. For example, the polar solvent and/or the non-polar solvent can be ultrapure water. A polar solvent and/or a non-polar solvent may be present in the CMP slurry composition in the balance.
金屬氧化物磨蝕劑可在高研磨速率下研磨具有高碳含量、高膜密度以及高硬度的有機膜。具體言之，當研磨根據本發明的有機膜時，金屬氧化物磨蝕劑不產生刮痕，由此改良經研磨表面上的平坦性。特定言之，金屬氧化物磨蝕劑可包含選自二氧化矽、氧化鋁、二氧化鈰、二氧化鈦以及二氧化鋯當中的至少一者。具體言之，二氧化矽可提供更佳的分散穩定性，且二氧化鈰即使當氧化劑不存在或以痕量(trace amount)存在時仍可提供較高研磨速率。 The metal oxide abrasive can grind an organic film having a high carbon content, a high film density, and a high hardness at a high polishing rate. Specifically, when the organic film according to the present invention is ground, the metal oxide abrasive does not cause scratches, thereby improving the flatness on the ground surface. In particular, the metal oxide abrasive may comprise at least one selected from the group consisting of cerium oxide, aluminum oxide, cerium oxide, titanium dioxide, and zirconium dioxide. In particular, cerium oxide provides better dispersion stability, and cerium oxide provides a higher polishing rate even when the oxidizing agent is absent or present in a trace amount.
金屬氧化物磨蝕劑可為球狀粒子且具有10奈米至150奈米、例如30奈米至70奈米的平均粒子直徑。在此範圍內，金屬氧化物磨蝕劑可相對於有機膜提供足夠研磨速率，不產生刮痕且可改良平坦性。 The metal oxide abrasive can be spherical particles and have an average particle diameter of from 10 nanometers to 150 nanometers, such as from 30 nanometers to 70 nanometers. Within this range, the metal oxide abrasive can provide a sufficient polishing rate with respect to the organic film, does not cause scratches, and can improve flatness.
金屬氧化物磨蝕劑可以約0.1重量%(wt%)至約20重量%、例如約0.1重量%至約15重量%的量存在。在此範圍內，金屬氧化物磨蝕劑可相對於有機膜提供足夠研磨速率，不產生刮痕 且可顯示出良好分散穩定性。用於有機膜的CMP漿料組成物可藉由增加金屬氧化物磨蝕劑的平均粒子直徑及降低漿料組成物中金屬氧化物磨蝕劑的量而具有相對於有機膜的改良研磨速率及相對於無機膜的低研磨速率。 The metal oxide abrasive can be present in an amount from about 0.1% by weight (wt%) to about 20% by weight, such as from about 0.1% to about 15% by weight. Within this range, the metal oxide abrasive provides sufficient polishing rate relative to the organic film without scratches And can show good dispersion stability. The CMP slurry composition for an organic film can have an improved polishing rate relative to the organic film and increase relative to the organic oxide film by increasing the average particle diameter of the metal oxide abrasive and reducing the amount of the metal oxide abrasive in the slurry composition. Low polishing rate of inorganic film.
氧化劑藉由氧化有機膜的表面層而有助於研磨具有高碳含量、高膜密度以及高硬度的有機膜。此外，當無機膜因研磨而暴露時，氧化劑有助於移除無機膜上的殘餘有機膜，由此使得有機膜可均一地研磨且因此能夠改良經研磨表面的表面粗糙度。特定言之，氧化劑可包含多價氧化態金屬鹽及過渡金屬螯合物中的至少一者。本文中所用的術語「多價」是指二價或高於二價，例如三價或高於三價，例如四價或高於四價。 The oxidizing agent contributes to grinding an organic film having a high carbon content, a high film density, and a high hardness by oxidizing a surface layer of the organic film. Further, when the inorganic film is exposed by grinding, the oxidizing agent helps to remove the residual organic film on the inorganic film, thereby allowing the organic film to be uniformly ground and thus capable of improving the surface roughness of the ground surface. In particular, the oxidizing agent may comprise at least one of a polyvalent oxidation state metal salt and a transition metal chelate compound. The term "multivalent" as used herein refers to divalent or higher than divalent, such as trivalent or higher than trivalent, such as tetravalent or higher.
多價氧化態金屬鹽能夠相對於有機膜增加研磨速率，而相對於無機膜降低研磨速率。金屬鹽可包含諸如過渡金屬、鑭系元素及其類似物的金屬，且可另外包含鹵素、銨、硝酸鹽及其類似物。特定言之，金屬鹽可包含鈰銨鹽、鐵鹵鹽、硝酸鐵及其類似物，且可包含例如硝酸鈰銨、硝酸鐵、氯化鐵及其類似物。 The multivalent oxidation state metal salt is capable of increasing the polishing rate relative to the organic film while reducing the polishing rate relative to the inorganic film. The metal salt may contain a metal such as a transition metal, a lanthanide element, and the like, and may additionally contain a halogen, an ammonium, a nitrate, and the like. Specifically, the metal salt may contain a cerium ammonium salt, an iron halide salt, iron nitrate, and the like, and may include, for example, cerium ammonium nitrate, iron nitrate, iron chloride, and the like.
過渡金屬螯合物可相對於有機膜增加研磨速率，而相對於無機膜降低研磨速率。 The transition metal chelate can increase the polishing rate relative to the organic film while reducing the polishing rate relative to the inorganic film.
在過渡金屬螯合物中，過渡金屬可包含通常已知的第III族至第XII族過渡金屬，例如鐵、銅、錳以及鉻。螯合物可包含乙二酸、經胺基取代的羧酸(例如胺基聚羧酸酯，諸如亞胺基二乙酸、乙二胺二丁二酸、亞胺基二丁二酸、乙二胺四乙酸以及氮 基三乙酸；諸如甘胺酸的α-胺基酸；以及β-胺基酸)、經羥基取代的羧酸(例如乙醇酸、乳酸以及含有羥基的多羧酸，諸如蘋果酸、檸檬酸以及酒石酸)、膦醯基羧酸、胺基磷酸及其組合。舉例而言，過渡金屬螯合物可包含含有Fe的化合物(包含丙二胺四乙酸-Fe)及含有Mn的化合物(包含丙二胺四乙酸-Mn)中的至少一者，但不限於此。 In the transition metal chelate, the transition metal may comprise generally known Group III to Group XII transition metals such as iron, copper, manganese and chromium. The chelate may comprise oxalic acid, an amine-substituted carboxylic acid (eg, an amine polycarboxylate such as iminodiacetic acid, ethylenediamine disuccinic acid, imidodisuccinic acid, ethylene) Amine tetraacetic acid and nitrogen a triacetic acid; an α-amino acid such as glycine; and a β-amino acid), a hydroxy-substituted carboxylic acid (such as glycolic acid, lactic acid, and a polycarboxylic acid having a hydroxyl group such as malic acid, citric acid, and the like) Tartaric acid), phosphinium carboxylic acid, aminophosphoric acid, and combinations thereof. For example, the transition metal chelate may include at least one of a Fe-containing compound (including propylenediaminetetraacetic acid-Fe) and a Mn-containing compound (including propylenediaminetetraacetic acid-Mn), but is not limited thereto. .
氧化劑可以約0.001重量%至約15重量%、例如約0.01重量%至約5重量%、例如約0.05重量%至約3重量%的量存在於CMP漿料組成物中。在此範圍內，CMP漿料組成物可相對於有機膜保持適當蝕刻特性。就氧化劑的穩定性而言，CMP漿料組成物可為酸性。在此情況下，CMP漿料組成物可增加相對於有機膜的研磨速率，改良經研磨表面上的平坦程度以及增加對無機膜的研磨選擇率。 The oxidizing agent may be present in the CMP slurry composition in an amount from about 0.001% to about 15% by weight, such as from about 0.01% to about 5% by weight, such as from about 0.05% to about 3% by weight. Within this range, the CMP slurry composition can maintain suitable etching characteristics relative to the organic film. The CMP slurry composition can be acidic in terms of the stability of the oxidizing agent. In this case, the CMP slurry composition can increase the polishing rate with respect to the organic film, improve the flatness on the ground surface, and increase the polishing selectivity to the inorganic film.
聚丙烯酸(PAA)是指包含由式1表示的重複單元(n為重複單元的數目)的聚合物化合物及其衍生物。 Polyacrylic acid (PAA) refers to a polymer compound and a derivative thereof comprising a repeating unit represented by Formula 1 (n is the number of repeating units).
(其中n為重複單元的數目) (where n is the number of repeating units)
聚丙烯酸的分子量可為約3,500公克/莫耳或小於3,500公克/莫耳。特定言之，聚丙烯酸的分子量可為約1,000公克/莫耳 至約3,000公克/莫耳。在此範圍內，CMP漿料組成物可確保優良的有機膜研磨速率及對有機膜的高選擇率。 The polyacrylic acid may have a molecular weight of about 3,500 grams per mole or less than 3,500 grams per mole. In particular, polyacrylic acid may have a molecular weight of about 1,000 grams per mole. To about 3,000 grams per mole. Within this range, the CMP slurry composition ensures excellent organic film polishing rate and high selectivity to organic films.
聚丙烯酸可以約0.01重量%至約5重量%、例如約0.05重量%至約3重量%的量存在於CMP漿料組成物中。在此範圍內，CMP漿料組成物可相對於有機膜確保優良的研磨速率及選擇率。 The polyacrylic acid may be present in the CMP slurry composition in an amount from about 0.01% to about 5% by weight, such as from about 0.05% to about 3% by weight. Within this range, the CMP slurry composition can ensure excellent polishing rates and selectivity with respect to the organic film.
CMP漿料組成物的pH可為約6或小於6，例如約5或小於5。舉例而言，藉由pH調節劑可將CMP漿料組成物調節至如以上所述範圍內的pH。舉例而言，pH調節劑可包含氫氧化鉀、氫氧化鈉以及氫氧化銨中的至少一者，但不限於此。 The pH of the CMP slurry composition can be about 6 or less, such as about 5 or less than 5. For example, the CMP slurry composition can be adjusted to a pH within the range as described above by a pH adjusting agent. For example, the pH adjuster may include at least one of potassium hydroxide, sodium hydroxide, and ammonium hydroxide, but is not limited thereto.
CMP漿料組成物可更包含如以上所述的pH調節劑以具有酸性pH 。pH調節劑可包含在CMP漿料組成物中，以將總體組成物的pH調節至適當水準，由此進一步改良對有機膜的研磨選擇率。 The CMP slurry composition may further comprise a pH adjusting agent as described above to have an acidic pH. A pH adjusting agent may be included in the CMP slurry composition to adjust the pH of the overall composition to an appropriate level, thereby further improving the grinding selectivity of the organic film.
CMP漿料組成物可更包含添加劑。舉例而言，CMP漿料組成物可更包含研磨促進劑。CMP漿料組成物更包含研磨促進劑，由此藉由抑制相對於無機膜的研磨速率而增加對無機膜的研磨選擇率。研磨促進劑可包含以下有機酸中的至少一者：例如蘋果酸、檸檬酸、甲酸、戊二酸、乙二酸、鄰苯二甲酸、丁二酸、酒石酸、順丁烯二酸以及丙二酸。研磨促進劑可以約0.02重量%至約0.5重量%的量存在於CMP漿料組成物中。在此範圍內，研磨促進劑不具有對研磨速率、漿料的分散穩定性以及有機碳膜的表面特性的不利影響。 The CMP slurry composition may further comprise an additive. For example, the CMP slurry composition can further comprise a polishing accelerator. The CMP slurry composition further includes a polishing accelerator, thereby increasing the polishing selectivity to the inorganic film by suppressing the polishing rate with respect to the inorganic film. The polishing accelerator may comprise at least one of the following organic acids: for example, malic acid, citric acid, formic acid, glutaric acid, oxalic acid, phthalic acid, succinic acid, tartaric acid, maleic acid, and propylene acid. The grinding accelerator may be present in the CMP slurry composition in an amount from about 0.02% to about 0.5% by weight. Within this range, the polishing accelerator does not have an adverse effect on the polishing rate, the dispersion stability of the slurry, and the surface characteristics of the organic carbon film.
根據本發明的一個實施例，CMP漿料組成物相對於有機膜可具有約500埃/分鐘至約10000埃/分鐘、尤其約500埃/分鐘至約5000埃/分鐘的研磨速率。根據本發明的實施例，CMP漿料組成物可具有約300或大於300、尤其約350至約700的選擇率，如藉由方程式1所計算： 選擇率=α/β---方程式1， 其中α為相對於有機膜的研磨速率且β為相對於二氧化矽膜的研磨速率)。 In accordance with an embodiment of the present invention, the CMP slurry composition can have a polishing rate of from about 500 angstroms per minute to about 10,000 angstroms per minute, especially from about 500 angstroms per minute to about 5,000 angstroms per minute, relative to the organic film. According to an embodiment of the invention, the CMP slurry composition may have a selectivity of about 300 or greater than 300, especially from about 350 to about 700, as calculated by Equation 1: Selection rate = α / β - Equation 1, Wherein α is the polishing rate with respect to the organic film and β is the polishing rate with respect to the cerium oxide film).
CMP漿料組成物的研磨目標Grinding target of CMP slurry composition
在下文中，將詳細描述作為根據本發明的CMP漿料組成物的研磨目標的有機膜。 Hereinafter, an organic film which is an abrasive target of the CMP slurry composition according to the present invention will be described in detail.
本文所用術語「經取代或未經取代的」中的術語「經取代」意指官能基中的至少一個氫原子經羥基、鹵素原子、亞硫醯基、硫醇基、氰基、胺基、C1至C30烷基、C2至C30烯基、C2至C30炔基、C3至C30環烷基、C3至C30環烯基、C6至C30芳基、C7至C30芳基烷基、C1至C20雜烷基、C2至C30雜環烷基、C2至C30雜環烯基、C2至C30雜芳基、C2至C30雜芳基烷基、C1至C20烷基胺基、C1至C30烷氧基、C6至C30芳氧基、C1至C20醛基、C1至C40烷基醚基、C7至C20芳基伸烷基醚基、C1至C30鹵烷基、含P官能基、含B官能基或其組合取代。 The term "substituted" as used herein in the term "substituted or unsubstituted" means that at least one hydrogen atom in the functional group is via a hydroxyl group, a halogen atom, a sulfinyl group, a thiol group, a cyano group, an amine group, C 1 to C 30 alkyl, C 2 to C 30 alkenyl, C 2 to C 30 alkynyl, C 3 to C 30 cycloalkyl, C 3 to C 30 cycloalkenyl, C 6 to C 30 aryl, C 7 to C 30 arylalkyl, C 1 to C 20 heteroalkyl, C 2 to C 30 heterocycloalkyl, C 2 to C 30 heterocycloalkenyl, C 2 to C 30 heteroaryl, C 2 To C 30 heteroarylalkyl, C 1 to C 20 alkylamino, C 1 to C 30 alkoxy, C 6 to C 30 aryloxy, C 1 to C 20 aldehyde, C 1 to C 40 An alkyl ether group, a C 7 to C 20 aryl alkylene ether group, a C 1 to C 30 haloalkyl group, a P containing functional group, a B containing functional group, or a combination thereof.
在本文中，「含P官能基」可由式A表示，且「含B官能基」可由式B表示。 Herein, the "P-containing functional group" may be represented by Formula A, and the "B-containing functional group" may be represented by Formula B.
<式A>*-(O)n-(CH2)m-P(=O)(Ra)(Rb) <Formula A>*-(O) n -(CH 2 ) m -P(=O)(R a )(R b )
<式B>*-B(Rc)(Rd) <Formula B>*-B(R c )(R d )
(其中n為0或1；m為0至10的整數；以及 Ra、Rb、Rc以及Rd各自獨立地為氫、羥基、經取代或未經取代的C1至C20烷基、經取代或未經取代的C2至C20烯基、經取代或未經取代的C3至C20環烷基、經取代或未經取代的C1至C20鹵烷基、經取代或未經取代的C1至C20烷基磺酸酯基、經取代或未經取代的C1至C20烷基磺醯基、經取代或未經取代的C2至C20烷基醯胺基、經取代或未經取代的C3至C20烷基酯基、經取代或未經取代的C2至C20氰基烷基、經取代或未經取代的C1至C20烷氧基、經取代或未經取代的C6至C30芳基、經取代或未經取代的C6至C30芳基烷基或經取代或未經取代的C6至C30芳氧基，或 Ra及Rb或Rc及Rd彼此連接形成經取代或未經取代的C3至C20環烷基或經取代或未經取代的C3至C20雜環烷基。 (wherein n is 0 or 1; m is an integer from 0 to 10; and R a , R b , R c and R d are each independently hydrogen, hydroxy, substituted or unsubstituted C 1 to C 20 alkyl , substituted or unsubstituted C 2 to C 20 alkenyl, substituted or unsubstituted C 3 to C 20 cycloalkyl, substituted or unsubstituted C 1 to C 20 haloalkyl, substituted Or unsubstituted C 1 to C 20 alkyl sulfonate group, substituted or unsubstituted C 1 to C 20 alkylsulfonyl group, substituted or unsubstituted C 2 to C 20 alkyl hydrazine Amine, substituted or unsubstituted C 3 to C 20 alkyl ester group, substituted or unsubstituted C 2 to C 20 cyanoalkyl group, substituted or unsubstituted C 1 to C 20 alkane Oxy, substituted or unsubstituted C 6 to C 30 aryl, substituted or unsubstituted C 6 to C 30 arylalkyl or substituted or unsubstituted C 6 to C 30 aryloxy Or R a and R b or R c and R d are bonded to each other to form a substituted or unsubstituted C 3 to C 20 cycloalkyl group or a substituted or unsubstituted C 3 to C 20 heterocycloalkyl group.
較佳地，含P官能基為含P及O的官能基，例如-P(=O)(OH)2、-O-P(=O)(OH)2、-P(=O)(OCH2CH3)2以及-P(=O)(C2H4C6H5)(OCH2CH3)，且含B官能基為含B及O的官能基，例如-B(OH)2、-B(H)(CH3)以及-B(CH2CH3)2。 Preferably, the P-containing functional group is a functional group containing P and O, such as -P(=O)(OH) 2 , -OP(=O)(OH) 2 , -P(=O)(OCH 2 CH 3 ) 2 and -P(=O)(C 2 H 4 C 6 H 5 )(OCH 2 CH 3 ), and the B-containing functional group is a functional group containing B and O, such as -B(OH) 2 ,- B(H)(CH 3 ) and -B(CH 2 CH 3 ) 2 .
當無機膜沈積於圖案化晶圓(例如圖案化矽晶圓)上時，有機膜填充其中所形成的通孔。CMP漿料組成物需要在足夠 研磨速率下研磨有機膜以使沈積膜平坦化，需要改良經研磨表面上的平坦程度，以及需要在研磨之後使得無機膜上的殘餘物易於移除。無機膜可由二氧化矽及氮化矽中的至少一者形成，但不限於此。 When an inorganic film is deposited on a patterned wafer (eg, a patterned germanium wafer), the organic film fills the vias formed therein. The CMP slurry composition needs to be sufficient Grinding the organic film at the polishing rate to planarize the deposited film requires improvement in the flatness on the ground surface and the need to easily remove the residue on the inorganic film after grinding. The inorganic film may be formed of at least one of cerium oxide and cerium nitride, but is not limited thereto.
有機膜可具有顯著不同的研磨速率及在研磨之後的平坦性，視有機膜的材料而定。根據本發明的CMP漿料組成物為用於研磨具有高碳含量的有機膜的組成物。當使用CMP漿料組成物研磨有機膜時，CMP漿料組成物可改良研磨速率及有機膜的平坦性，且可有助於在研磨之後自無機膜移除殘餘物。 The organic film may have significantly different polishing rates and flatness after polishing, depending on the material of the organic film. The CMP slurry composition according to the present invention is a composition for grinding an organic film having a high carbon content. When the organic film is ground using the CMP slurry composition, the CMP slurry composition can improve the polishing rate and the flatness of the organic film, and can contribute to removing the residue from the inorganic film after the grinding.
作為研磨目標，根據本發明的有機膜具有比通常有機膜更高的碳含量、更高的膜密度以及更高的硬度，故所述有機膜不能使用含有聚合物粒子的用於有機膜的通常CMP漿料組成物研磨。另一方面，根據本發明的CMP漿料組成物能夠在高研磨速率下研磨有機膜而不因刮痕使表面條件劣化。特定言之，對有機膜的研磨速率可為約500埃/分鐘或大於500埃/分鐘，例如約1,000埃/分鐘或大於1,000埃/分鐘，且可介於例如約500埃/分鐘至約5,000埃/分鐘範圍內。在此範圍內，有機膜的研磨速率可確保達到所需水準。 As an abrasive target, the organic film according to the present invention has a higher carbon content, a higher film density, and a higher hardness than a usual organic film, so that the organic film cannot be generally used for an organic film containing a polymer particle. The CMP slurry composition is ground. On the other hand, the CMP slurry composition according to the present invention is capable of grinding an organic film at a high polishing rate without deteriorating surface conditions due to scratches. In particular, the rate of polishing the organic film can be about 500 angstroms per minute or greater than 500 angstroms per minute, such as about 1,000 angstroms per minute or greater than 1,000 angstroms per minute, and can range, for example, from about 500 angstroms per minute to about 5,000. Within a range of angstroms per minute. Within this range, the polishing rate of the organic film ensures that the desired level is achieved.
在一個實施例中，有機膜的碳含量可為約50原子%至約99原子%，例如約65原子%至約99原子%，例如約70原子%至約99原子%。舉例而言，有機膜的碳含量可為約65原子%、66原子%、67原子%、68原子%、69原子%、70原子%、71原子%、 72原子%、73原子%、74原子%、75原子%、76原子%、77原子%、78原子%、79原子%、80原子%、81原子%、82原子%、83原子%、84原子%、85原子%、86原子%、87原子%、88原子%、89原子%、90原子%、91原子%、92原子%、93原子%、94原子%或95原子%。在此範圍內，當使用金屬氧化物磨蝕劑研磨時，有機膜可具有高研磨速率，不受刮痕影響且可在經研磨表面上顯示出高平坦程度。 In one embodiment, the organic film may have a carbon content of from about 50 atomic percent to about 99 atomic percent, such as from about 65 atomic percent to about 99 atomic percent, such as from about 70 atomic percent to about 99 atomic percent. For example, the carbon content of the organic film may be about 65 atom%, 66 atom%, 67 atom%, 68 atom%, 69 atom%, 70 atom%, 71 atom%, 72 atom%, 73 atom%, 74 atom%, 75 atom%, 76 atom%, 77 atom%, 78 atom%, 79 atom%, 80 atom%, 81 atom%, 82 atom%, 83 atom%, 84 atom %, 85 atom%, 86 atom%, 87 atom%, 88 atom%, 89 atom%, 90 atom%, 91 atom%, 92 atom%, 93 atom%, 94 atom% or 95 atom%. Within this range, when ground using a metal oxide abrasive, the organic film can have a high polishing rate, is not affected by scratches, and can exhibit a high degree of flatness on the ground surface.
此外，有機膜的膜密度可為約0.5公克/立方公分至約2.5公克/立方公分，例如約1.0公克/立方公分至約2.0公克/立方公分，例如約1.2公克/立方公分至約1.6公克/立方公分。特定言之，有機膜的膜密度可為約0.5公克/立方公分、0.6公克/立方公分、0.7公克/立方公分、0.8公克/立方公分、0.9公克/立方公分、1.0公克/立方公分、1.1公克/立方公分、1.2公克/立方公分、1.3公克/立方公分、1.4公克/立方公分、1.5公克/立方公分、1.6公克/立方公分、1.7公克/立方公分、1.8公克/立方公分、1.9公克/立方公分、2.0公克/立方公分、2.1公克/立方公分、2.2公克/立方公分、2.3公克/立方公分、2.4公克/立方公分或2.5公克/立方公分。在此範圍內，當使用金屬氧化物磨蝕劑研磨時，有機膜可具有高研磨速率，不受刮痕影響且可在經研磨表面上顯示出高平坦程度。有機膜的硬度可為約0.4GPa或大於0.4GPa，例如約1.0GPa或大於1.0GPa，例如約1.3GPa或大於1.3GPa，例如約1.3GPa至1.5GPa。特定言之，有機膜的硬度可為約0.4GPa、0.5GPa、0.6GPa、 0.7GPa、0.8GPa、0.9GPa、1.0GPa、1.1GPa、1.2GPa、1.3GPa、1.4GPa或1.5GPa。在此範圍內，當使用金屬氧化物磨蝕劑研磨時，有機膜可具有高研磨速率，不受刮痕影響且可在經研磨表面上顯示出高平坦程度。 Further, the organic film may have a film density of from about 0.5 g/cm to about 2.5 g/cm, for example from about 1.0 g/cm to about 2.0 g/cm, for example from about 1.2 g/cm to about 1.6 g/ Cubic centimeters. Specifically, the organic film may have a film density of about 0.5 g/cm 3 , 0.6 g/cm 3 , 0.7 g/cm 2 , 0.8 g/cm 2 , 0.9 g/cm 2 , 1.0 g/cm 2 , 1.1 g. /cm ^ 3 , 1.2 g / cm ^ 3 , 1.3 g / cm ^ 3 , 1.4 g / cm ^ 3 , 1.5 g / cm ^ 3 , 1.6 g / cm ^ 3 , 1.7 g / cm ^ 3 , 1.8 g / cm ^ 3 , 1.9 g / cm Centimeters, 2.0 g/cm3, 2.1 g/cm3, 2.2 g/cm3, 2.3 g/cm3, 2.4 g/cm3 or 2.5 g/cm3. Within this range, when ground using a metal oxide abrasive, the organic film can have a high polishing rate, is not affected by scratches, and can exhibit a high degree of flatness on the ground surface. The hardness of the organic film may be about 0.4 GPa or greater than 0.4 GPa, such as about 1.0 GPa or greater than 1.0 GPa, such as about 1.3 GPa or greater than 1.3 GPa, such as from about 1.3 GPa to 1.5 GPa. Specifically, the hardness of the organic film may be about 0.4 GPa, 0.5 GPa, 0.6 GPa, 0.7 GPa, 0.8 GPa, 0.9 GPa, 1.0 GPa, 1.1 GPa, 1.2 GPa, 1.3 GPa, 1.4 GPa or 1.5 GPa. Within this range, when ground using a metal oxide abrasive, the organic film can have a high polishing rate, is not affected by scratches, and can exhibit a high degree of flatness on the ground surface.
另外，根據本發明的有機膜的酸值可實質上為0mg KOH/g。在使用包含聚合物磨蝕劑的用於有機膜的通常CMP漿料組成物研磨有機膜的情況下，存在研磨速率降低的問題。相反地，根據本發明的CMP漿料組成物可確保有機膜的研磨速率足以應用於CMP製程。術語「實質上」意指酸值不僅為0mg KOH/g而且在可接受的誤差界限下為0mg KOH/g。 Further, the acid value of the organic film according to the present invention may be substantially 0 mg KOH/g. In the case of grinding an organic film using a usual CMP slurry composition for an organic film containing a polymer abrasive, there is a problem that the polishing rate is lowered. In contrast, the CMP slurry composition according to the present invention can ensure that the polishing rate of the organic film is sufficient for the CMP process. The term "substantially" means that the acid value is not only 0 mg KOH/g but also 0 mg KOH/g at an acceptable margin of error.
特定言之，根據本發明的有機膜可藉由將包含含有經取代或未經取代的芳族基的化合物的有機膜組成物塗佈於無機膜上，接著在高溫下，例如在200℃至400℃下烘烤來製造。 Specifically, the organic film according to the present invention can be coated on an inorganic film by an organic film composition containing a compound containing a substituted or unsubstituted aromatic group, followed by high temperature, for example, at 200 ° C to It is made by baking at 400 °C.
本文所用術語「含有經取代或未經取代的芳族基的化合物」是指在烘烤之後不分解且使由包含所述化合物的組成物形成的有機膜具有高碳含量的化合物。未經取代的芳族基可為具有單環結構或其中二或更多個環稠合的多環結構的C6至C100、例如C6至C50未經取代的芳族基。舉例而言，未經取代的芳族基可包含由式2-1至式2-26表示的化合物。 The term "compound containing a substituted or unsubstituted aromatic group" as used herein means a compound which does not decompose after baking and which has an organic film formed of a composition containing the compound having a high carbon content. The unsubstituted aromatic group may be a C 6 to C 100 group having , for example, a C 6 to C 50 unsubstituted aromatic group having a single ring structure or a polycyclic structure in which two or more rings are fused. For example, the unsubstituted aromatic group may include a compound represented by Formula 2-1 to Formula 2-26.
<式2-8>
<式2-14>
<式2-20>
<式2-26>
(其中Z1至Z18各自獨立地為單鍵、經取代或未經取代的C1至C20伸烷基、經取代或未經取代的C2至C20伸烯基、經取代或未經取代的C2至C20伸炔基、經取代或未經取代的C3至C20伸環烷基、經取代或未經取代的C3至C20伸環烯基、經取代或未經取代的C6至C20伸芳基、經取代或未經取代的C2至C20伸雜芳基、-(C=O)-、-NRe-、-CRfRg-、氧(O)、硫(S)或其組合，且其中Re、Rf以及Rg各自獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、經取代或未經取代的C6至C20伸芳基、經取代或未經取代的C2至C20伸雜芳基或其組合)。 (wherein Z 1 to Z 18 are each independently a single bond, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 2 to C 20 alkyl group, substituted or not Substituted C 2 to C 20 alkynyl, substituted or unsubstituted C 3 to C 20 cycloalkyl, substituted or unsubstituted C 3 to C 20 cycloalkenyl, substituted or unsubstituted Substituted C 6 to C 20 extended aryl, substituted or unsubstituted C 2 to C 20 heteroaryl, -(C=O)-, -NR e -, -CR f R g -, oxygen (O), sulfur (S) or a combination thereof, and wherein R e , R f and R g are each independently hydrogen, substituted or unsubstituted C 1 to C 10 alkyl, halogen atom, substituted or not Substituted C 6 to C 20 extended aryl, substituted or unsubstituted C 2 to C 20 heteroaryl or combinations thereof.
在下文中，將更詳細地描述包含含有經取代或未經取代的芳族基的化合物的有機膜組成物的實施例。 Hereinafter, examples of organic film compositions containing a compound containing a substituted or unsubstituted aromatic group will be described in more detail.
在第一實施例中，有機膜組成物可包含具有由式3表示的單元的材料作為含有經取代或未經取代的芳族基的化合物。 In the first embodiment, the organic film composition may include a material having a unit represented by Formula 3 as a compound containing a substituted or unsubstituted aromatic group.
(其中滿足1a<190；R1為氫、羥基、鹵素原子、烯丙基、亞硫醯基、硫醇基、氰
基、經取代或未經取代的胺基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C1至C30雜烷基、經取代或未經取代的C2至C30烯基、經取代或未經取代的C2至C30炔基、經取代或未經取代的C3至C30環烷基、經取代或未經取代的C2至C30雜環烷基、經取代或未經取代的C3至C30環烯基、經取代或未經取代的C6至C30芳基、經取代或未經取代的C7至C30芳基烷基、經取代或未經取代的C1至C20雜烷基、經取代或未經取代的C2至C30雜環烷基、經取代或未經取代的C2至C30雜環烯基、經取代或未經取代的C2至C30雜芳基、經取代或未經取代的C2至C30雜芳基烷基、經取代或未經取代的C1至C20烷基胺基、經取代或未經取代的C1至C30烷氧基、經取代或未經取代的C1至C30雜烷氧基、經取代或未經取代的C6至C30芳氧基、經取代或未經取代的C1至C20醛基、經取代或未經取代的C1至C40烷基醚基、經取代或未經取代的C7至C20芳基伸烷基醚基、經取代或未經取代的C1至C30鹵烷基、含P官能基、含B官能基或其組合；R2為氫、經取代或未經取代的胺基、經取代或未經取代的C1至C20烷氧基、經取代或未經取代的C6至C30芳氧基、-NRhRi(Rh及Ri各自獨立地為經取代或未經取代的C1至C10烷基、或經取代或未經取代的C6至C10芳基)、羥基、鹵素原子、烯丙基、亞硫醯基、硫醇基、氰基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C1至C30雜烷基、經取代或未經取代的C2至C30烯基、經取代或未經取代的C2至C30炔基、經取代或未經取代的C3
至C30環烷基、經取代或未經取代的C2至C30雜環烷基、經取代或未經取代的C3至C30環烯基、經取代或未經取代的C6至C30芳基、經取代或未經取代的C7至C30芳基烷基、經取代或未經取代的C2至C30雜環烷基、經取代或未經取代的C2至C30雜環烯基、經取代或未經取代的C2至C30雜芳基、經取代或未經取代的C2至C30雜芳基烷基、經取代或未經取代的C1至C20烷基胺基、經取代或未經取代的C1至C30雜烷氧基、經取代或未經取代的C1至C20醛基、經取代或未經取代的C1至C40烷基醚基、經取代或未經取代的C7至C20芳基伸烷基醚基、經取代或未經取代的C1至C30鹵烷基、含P官能基、含B官能基或其組合；以及R3為選自由下式表示的經取代或未經取代的材料中的一者：
舉例而言，R2可為經取代或未經取代的C1至C10烷氧基。 For example, R 2 can be a substituted or unsubstituted C 1 to C 10 alkoxy group.
包含由式3表示的單元的材料可在烘烤有機膜組成物之後增加有機膜的碳含量、密度以及硬度。製備包含由式3表示的單元的材料的更詳細製程揭示於韓國專利第10-0866015號中。 The material containing the unit represented by Formula 3 can increase the carbon content, density, and hardness of the organic film after baking the organic film composition. A more detailed process for preparing a material comprising the unit represented by Formula 3 is disclosed in Korean Patent No. 10-0866015.
根據第一實施例的有機膜組成物可除包含由式3表示的單元的材料之外，更包含交聯組分、酸觸媒以及有機溶劑中的至少一者。特定言之，根據第一實施例的組成物可包含1重量%至20重量%的包含由式3表示的單元的材料、0.1重量%至5重量%的交聯組分、0.001重量%至0.05重量%的酸觸媒以及75重量%至98.8重量%的有機溶劑。 The organic film composition according to the first embodiment may further contain at least one of a crosslinking component, an acid catalyst, and an organic solvent in addition to the material including the unit represented by Formula 3. Specifically, the composition according to the first embodiment may contain 1% by weight to 20% by weight of the material comprising the unit represented by Formula 3, 0.1% by weight to 5% by weight of the crosslinking component, and 0.001% by weight to 0.05% % by weight of acid catalyst and from 75% to 98.8% by weight of organic solvent.
交聯組分可包含三聚氰胺樹脂(例如N-甲氧基甲基-三聚氰胺樹脂或N-丁氧基甲基-三聚氰胺樹脂)、甲基化脲樹脂或丁基化脲樹脂、胺基樹脂、由式4表示的甘脲衍生物、由式5表示的雙環氧化合物以及由式6表示的三聚氰胺衍生物中的至少一者。 The crosslinking component may comprise a melamine resin (for example, N-methoxymethyl-melamine resin or N-butoxymethyl-melamine resin), a methylated urea resin or a butylated urea resin, an amine resin, At least one of a glycoluril derivative represented by Formula 4, a diepoxide compound represented by Formula 5, and a melamine derivative represented by Formula 6 is used.
<式6>
酸觸媒可包含對甲苯磺酸單水合物、對甲苯磺酸吡啶、2,4,4,6-四溴環己二烯酮、安息香甲苯磺酸酯、2-硝基苄基甲苯磺酸酯(2-nitrobenzyl tosylate)以及有機磺酸的烷基酯中的至少一者。有機溶劑可為(但不限於)能夠充分溶解含有經取代或未經取代的芳族基的化合物的任何有機溶劑。舉例而言，有機溶劑可包含丙二醇單甲醚乙酸酯、環己酮、乳酸乙酯及其類似物。 The acid catalyst may comprise p-toluenesulfonic acid monohydrate, p-toluenesulfonic acid pyridine, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyltoluenesulfonic acid At least one of 2-nitrobenzyl tosylate and an alkyl ester of an organic sulfonic acid. The organic solvent may be, but not limited to, any organic solvent capable of sufficiently dissolving a compound containing a substituted or unsubstituted aromatic group. For example, the organic solvent may include propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, and the like.
有機膜可藉由將根據第一實施例的有機膜組成物塗佈至500埃至4000埃的厚度，接著在200℃至400℃下烘烤10秒至10分鐘來製造，但不限於此。 The organic film can be produced by coating the organic film composition according to the first embodiment to a thickness of 500 Å to 4000 Å, followed by baking at 200 ° C to 400 ° C for 10 seconds to 10 minutes, but is not limited thereto.
在第二實施例中，有機膜組成物可包含由式7表示的材料作為含有經取代或未經取代的芳族基的化合物。 In the second embodiment, the organic film composition may contain a material represented by Formula 7 as a compound containing a substituted or unsubstituted aromatic group.
(其中R4至R9及X1至X6各自獨立地為氫、羥基、鹵 素原子、烯丙基、亞硫醯基、硫醇基、氰基、經取代或未經取代的胺基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C1至C30雜烷基、經取代或未經取代的C2至C30烯基、經取代或未經取代的C2至C30炔基、經取代或未經取代的C3至C30環烷基、經取代或未經取代的C2至C30雜環烷基、經取代或未經取代的C3至C30環烯基、經取代或未經取代的C6至C30芳基、經取代或未經取代的C7至C30芳基烷基、經取代或未經取代的C2至C30雜環烯基、經取代或未經取代的C2至C30雜芳基、經取代或未經取代的C2至C30雜芳基烷基、經取代或未經取代的C1至C20烷基胺基、經取代或未經取代的C1至C30烷氧基、經取代或未經取代的C1至C30雜烷氧基、經取代或未經取代的C6至C30芳氧基、經取代或未經取代的C1至C20醛基、經取代或未經取代的C1至C40烷基醚基、經取代或未經取代的C7至C20芳基伸烷基醚基、經取代或未經取代的C1至C30鹵烷基、含P官能基、含B官能基或其組合；且n1至n6各自獨立地介於0至2的範圍且滿足2n1+n2+n3+n4+n5+n6 6)。 (wherein R 4 to R 9 and X 1 to X 6 are each independently hydrogen, hydroxy, halogen atom, allyl, sulfinyl, thiol, cyano, substituted or unsubstituted amino group, Substituted or unsubstituted C 1 to C 30 alkyl, substituted or unsubstituted C 1 to C 30 heteroalkyl, substituted or unsubstituted C 2 to C 30 alkenyl, substituted or unsubstituted Substituted C 2 to C 30 alkynyl, substituted or unsubstituted C 3 to C 30 cycloalkyl, substituted or unsubstituted C 2 to C 30 heterocycloalkyl, substituted or unsubstituted C 3 to C 30 cycloalkenyl, substituted or unsubstituted C 6 to C 30 aryl, substituted or unsubstituted C 7 to C 30 arylalkyl, substituted or unsubstituted C 2 to C 30 heterocycloalkenyl, substituted or unsubstituted C 2 to C 30 heteroaryl, substituted or unsubstituted C 2 to C 30 heteroarylalkyl, substituted or unsubstituted a C 1 to C 20 alkylamino group, a substituted or unsubstituted C 1 to C 30 alkoxy group, a substituted or unsubstituted C 1 to C 30 heteroalkoxy group, substituted or unsubstituted C 6 to C 30 aryloxy group, a substituted or non-substituted C 1 to C 20 aldehyde group, A substituted or non-substituted C 1 to C 40 alkyl ether group, a substituted or unsubstituted C 7 to C 20 alkylene aryl ether group, substituted or non-substituted C 1 to C 30 haloalkyl , containing a P functional group, a B containing functional group, or a combination thereof; and n1 to n6 are each independently in the range of 0 to 2 and satisfy 2 n 1 +n 2 +n 3 +n 4 +n 5 +n 6 6).
舉例而言，R4至R9可各自獨立地為經取代或未經取代的C1至C10烷基、經取代或未經取代的C6至C20芳基、經取代或未經取代的C3至C20環烷基、經取代或未經取代的C3至C20環烯基、含P官能基或含B官能基。 For example, R 4 to R 9 may each independently be a substituted or unsubstituted C 1 to C 10 alkyl group, a substituted or unsubstituted C 6 to C 20 aryl group, substituted or unsubstituted C 3 to C 20 cycloalkyl, substituted or unsubstituted C 3 to C 20 cycloalkenyl, P-containing or B-containing functional group.
舉例而言，X1至X6可各自獨立地為氫、羥基、經取代 或未經取代的C1至C20烷基胺基、胺基、含P官能基或含B官能基。 For example, X 1 to X 6 may each independently be hydrogen, hydroxy, substituted or unsubstituted C 1 to C 20 alkylamino, amine, P-containing or B-containing.
根據第二實施例的有機膜組成物實質上與根據第一實施例的有機膜組成物相同，除了根據第二實施例的有機膜組成物包含由式7表示的材料(代替包含由式3表示的單元的材料)作為含有經取代或未經取代的芳族基的化合物。因此，在下文中將僅詳細描述由式7表示的材料。 The organic film composition according to the second embodiment is substantially the same as the organic film composition according to the first embodiment except that the organic film composition according to the second embodiment contains the material represented by Formula 7 (instead of including the Formula 3) The material of the unit) is a compound containing a substituted or unsubstituted aromatic group. Therefore, only the material represented by Formula 7 will be described in detail below.
由式7表示的材料可為在不同位置處包含取代基的二或更多種化合物的混合物。因為由式7表示的材料包含在短波長(例如193nm或248nm)下顯示出強吸收的芳環且因此即使不使用特別的觸媒仍在高溫下交聯，故由式7表示的材料可防止因觸媒、特別是酸造成的污染。此外，由式7表示的芳族化合物的平均分子量可為500公克/莫耳至4000公克/莫耳。在此範圍內，有機膜組成物可形成具有適當厚度的有機膜或優良的薄膜。 The material represented by Formula 7 may be a mixture of two or more compounds containing a substituent at different positions. Since the material represented by Formula 7 contains an aromatic ring exhibiting strong absorption at a short wavelength (for example, 193 nm or 248 nm) and thus crosslinks at a high temperature even without using a special catalyst, the material represented by Formula 7 can be prevented. Contamination due to catalysts, especially acids. Further, the aromatic compound represented by Formula 7 may have an average molecular weight of from 500 g/m to 4000 g/m. Within this range, the organic film composition can form an organic film having an appropriate thickness or an excellent film.
由式7表示的材料可在烘烤有機膜組成物之後增加有機膜的碳含量、膜密度以及硬度。由式7表示的材料可藉由通常方法製備。舉例而言，由式7表示的材料可藉由使乙醯氯、苯甲醯氯、萘甲醯氯或環己烷羰基氯與蔻反應，接著還原所得材料來製備，但不限於此。製備由式7表示的材料的更詳細製程揭示於韓國專利第10-1311942號中。 The material represented by Formula 7 can increase the carbon content, film density, and hardness of the organic film after baking the organic film composition. The material represented by Formula 7 can be produced by a usual method. For example, the material represented by Formula 7 can be produced by reacting acetamidine chloride, benzamidine chloride, naphthoquinone chloride or cyclohexanecarbonyl chloride with hydrazine, followed by reduction of the resulting material, but is not limited thereto. A more detailed process for preparing the material represented by Formula 7 is disclosed in Korean Patent No. 10-1311942.
在第三實施例中，有機膜組成物可包含選自以下化合物(i)、(ii)以及(iii)的含有芳族基的聚合物作為含有經取代或未 經取代的芳族基的化合物。 In the third embodiment, the organic film composition may contain an aromatic group-containing polymer selected from the following compounds (i), (ii), and (iii) as containing substituted or unsubstituted Substituted aromatic group compound.
(i)包含由式8表示的單元的化合物。 (i) a compound comprising a unit represented by Formula 8.
(ii)包含由式8表示的單元的化合物及包含由式9表示的單元的化合物的混合物。 (ii) a mixture of a compound containing a unit represented by Formula 8 and a compound containing a unit represented by Formula 9.
(iii)包含由式10表示的單元的化合物。 (iii) a compound comprising a unit represented by Formula 10.
(其中c、d以及e各自獨立地為1至750；c及d滿足2c+d<1500；R10為選自由下式表示的經取代或未經取代的材料中的一者：
根據第三實施例的有機膜組成物實質上與根據第一實施例的有機膜組成物相同，除了根據第三實施例的有機膜組成物包含含有芳族基的聚合物(代替包含由式3表示的單元的材料) 作為含有經取代或未經取代的芳族基的化合物。因此，在下文中將僅詳細描述含有芳族基的聚合物。 The organic film composition according to the third embodiment is substantially the same as the organic film composition according to the first embodiment except that the organic film composition according to the third embodiment contains a polymer containing an aromatic group (instead of containing the formula 3) The material of the indicated unit) As a compound containing a substituted or unsubstituted aromatic group. Therefore, only the aromatic group-containing polymer will be described in detail hereinafter.
含有芳族基的聚合物在烘烤有機膜組成物之後可增加有機膜的碳含量、膜密度以及硬度，且可藉由通常方法製備。更多詳情揭示於韓國專利第10-0908601號中。 The aromatic group-containing polymer can increase the carbon content, film density, and hardness of the organic film after baking the organic film composition, and can be produced by a usual method. Further details are disclosed in Korean Patent No. 10-0908601.
在第四實施例中，有機膜組成物可包含選自以下材料的中的至少兩者作為含有經取代或未經取代的芳族基的化合物：包含由式3表示的單元的材料；由式7表示的材料；以及選自化合物(i)、(ii)以及(iii)的含有芳族基的聚合物。根據第四實施例的有機膜組成物實質上與根據第一實施例的有機膜組成物相同，除了根據第四實施例的有機膜組成物包含以上所述材料中的至少兩者。 In the fourth embodiment, the organic film composition may include at least two selected from the following materials as a compound containing a substituted or unsubstituted aromatic group: a material containing a unit represented by Formula 3; a material represented by 7; and an aromatic group-containing polymer selected from the group consisting of compounds (i), (ii), and (iii). The organic film composition according to the fourth embodiment is substantially the same as the organic film composition according to the first embodiment except that the organic film composition according to the fourth embodiment contains at least two of the above materials.
用於研磨有機膜的方法Method for grinding an organic film
根據本發明的一個實施例，用於研磨有機膜的方法可包含使用用於有機膜的CMP漿料組成物研磨具有高碳含量、高膜密度以及高硬度的有機膜，其中所述用於有機膜的CMP漿料組成物可包含根據本發明的實施例的用於有機膜的CMP漿料組成物。圖1(a)示出在研磨有機膜之前矽晶圓、無機膜以及有機碳膜堆疊的狀態。參照圖1(a)，對矽晶圓100進行圖案化以具有雕刻(engraved)部分。將無機膜110沈積於矽晶圓100上，且在無機膜上形成有機碳膜120，接著在200℃至400℃下烘烤。圖1(a)中的虛線T指示假想的研磨停止線。將用於有機膜的CMP漿料組成物塗佈於圖 1(a)中所示的有機膜上，接著將研磨墊安置在CMP漿料組成物上。接著，藉由旋轉矽晶圓100來研磨有機膜直至研磨停止線T，由此獲得如圖1(b)中所示的有機膜經研磨的矽晶圓。 According to an embodiment of the present invention, a method for polishing an organic film may include grinding an organic film having a high carbon content, a high film density, and a high hardness using a CMP slurry composition for an organic film, wherein the organic film is used for organic The CMP slurry composition of the film may comprise a CMP slurry composition for an organic film in accordance with an embodiment of the present invention. Fig. 1(a) shows a state in which a tantalum wafer, an inorganic film, and an organic carbon film are stacked before the organic film is polished. Referring to FIG. 1(a), the germanium wafer 100 is patterned to have an engraved portion. The inorganic film 110 is deposited on the tantalum wafer 100, and an organic carbon film 120 is formed on the inorganic film, followed by baking at 200 ° C to 400 ° C. The broken line T in Fig. 1(a) indicates an imaginary grinding stop line. Applying a CMP slurry composition for an organic film to the image On the organic film shown in 1 (a), the polishing pad is then placed on the CMP slurry composition. Next, the organic film is polished by rotating the germanium wafer 100 until the polishing stop line T, whereby the germanium wafer polished by the organic film as shown in FIG. 1(b) is obtained.
接著，將參照一些實例更詳細地描述本發明。應瞭解，這些實例僅出於說明目的而提供且不應以任何方式視為限制本發明。 Next, the present invention will be described in more detail with reference to some examples. It is to be understood that the examples are provided for illustration purposes only and are not to be considered as limiting the invention in any way.
製備實例1Preparation example 1
將包含溫度計、冷凝器、機械攪拌器以及滴液漏斗的2000毫升3頸燒瓶浸入140℃的油浴中。在加熱板上執行加熱且藉由磁鐵攪拌，並將冷凝器中的冷卻水溫度設定為40℃。將220公克(1.0莫耳)的1-甲氧基芘及138公克(1.0莫耳)的1,4-雙甲氧基甲基苯添加至反應器且隨後溶解於656公克丙二醇單甲醚乙酸酯中。此後，將4.6公克(0.03莫耳)的硫酸二乙酯添加至反應器。使反應器的溫度維持在130℃。藉由在聚合期間定期量測反應產物的分子量來確定反應完成點。此處，用於量測分子量的樣品是藉由淬滅(quench)1公克反應產物至室溫，接著用四氫呋喃作為溶劑稀釋0.02公克反應產物，使得溶液中的固體含量變成4重量%來製備。為在所確定的反應完成點完成反應，將4.48公克的0.03莫耳三乙醇胺作為中和劑添加至反應器，接著攪拌組分。接著，將反應產物緩慢冷卻至室溫。用500公克丙二醇單甲醚乙酸酯稀釋反應產物。接著，將溶劑添加至2000毫升分液漏斗。以90：10公克/公克的比率製備4公斤甲醇與乙二醇的混合物。在劇 烈攪拌下，將合成的聚合物溶液逐滴添加至醇混合物。自燒瓶底部表面收集所得聚合物且單獨儲存上清液。在上清液移除之後，藉由在減壓下旋轉蒸發60至10分鐘而自最終反應產物移除甲醇。 A 2000 ml 3-neck flask containing a thermometer, a condenser, a mechanical stirrer, and a dropping funnel was immersed in an oil bath at 140 °C. Heating was performed on a hot plate and stirred by a magnet, and the temperature of the cooling water in the condenser was set to 40 °C. 220 grams (1.0 moles) of 1-methoxyanthracene and 138 grams (1.0 moles) of 1,4-bismethoxymethylbenzene were added to the reactor and subsequently dissolved in 656 grams of propylene glycol monomethyl ether B. In the acid ester. Thereafter, 4.6 g (0.03 mol) of diethyl sulfate was added to the reactor. The temperature of the reactor was maintained at 130 °C. The reaction completion point is determined by periodically measuring the molecular weight of the reaction product during the polymerization. Here, the sample for measuring the molecular weight was prepared by quenching 1 g of the reaction product to room temperature, followed by diluting 0.02 g of the reaction product with tetrahydrofuran as a solvent so that the solid content in the solution became 4% by weight. To complete the reaction at the determined reaction completion point, 4.48 grams of 0.03 moles of triethanolamine was added to the reactor as a neutralizing agent, followed by stirring of the components. Next, the reaction product was slowly cooled to room temperature. The reaction product was diluted with 500 g of propylene glycol monomethyl ether acetate. Next, the solvent was added to a 2000 ml separatory funnel. A mixture of 4 kg of methanol and ethylene glycol was prepared at a ratio of 90:10 g/g. In the drama The resultant polymer solution was added dropwise to the alcohol mixture with vigorous stirring. The resulting polymer was collected from the bottom surface of the flask and the supernatant was separately stored. After the supernatant was removed, methanol was removed from the final reaction product by rotary evaporation under reduced pressure for 60 to 10 minutes.
在四氫呋喃下藉由GPC量測所獲得共聚物的分子量及分散度。結果，獲得包含由式11表示的單元、重量平均分子量為4000公克/莫耳且分散度為2.3的聚合物。 The molecular weight and dispersion of the copolymer were measured by GPC measurement under tetrahydrofuran. As a result, a polymer comprising a unit represented by Formula 11 and having a weight average molecular weight of 4000 g/mol and a degree of dispersion of 2.3 was obtained.
(其中a平均等於11，且Me為甲基)。 (where a is equal to 11 and Me is methyl).
將0.8公克所製備的聚合物、0.2公克由式4表示的交聯劑(寶德林(Powderlink)1174，氰特工業有限公司(Cytec Industries Inc.))以及2毫克對甲苯磺酸吡啶溶解於9公克丙二醇單甲醚乙酸酯中，接著過濾溶液，由此製備有機膜組成物。 0.8 g of the prepared polymer, 0.2 g of a crosslinking agent represented by Formula 4 (Powderlink 1174, Cytec Industries Inc.) and 2 mg of pyridine p-toluenesulfonate were dissolved in In 9 g of propylene glycol monomethyl ether acetate, the solution was filtered, whereby an organic film composition was prepared.
實例1Example 1
將5000埃厚的二氧化矽膜作為研磨停止膜沈積在包含表面上形成有雕刻圖案的圖案化晶圓上，接著形成2650埃厚的有機膜以填充二氧化矽膜表面上的雕刻圖案。有機膜是藉由將製備實例1的有機膜組成物塗佈於二氧化矽膜上，接著在400℃下烘烤來製造。 A 5000 angstrom thick ruthenium dioxide film was deposited as a polishing stop film on the patterned wafer including the engraved pattern on the surface, and then an organic film of 2650 angstroms thick was formed to fill the engraved pattern on the surface of the ruthenium dioxide film. The organic film was produced by coating the organic film composition of Preparation Example 1 on a ceria film, followed by baking at 400 °C.
施用製備實例1中所製備的有機膜組成物且在400℃下 烘烤120秒以獲得具有4700埃至4800埃厚度的樣本。使用奈米壓痕儀(海思創(Hysitron)TI750 Ubi)量測樣本的硬度。藉由將奈米壓痕儀的尖端加載於樣本上5秒，使尖端保持2秒且卸載尖端5秒來量測硬度。樣本的硬度為0.9GPa。使用元素分析儀(EA1112，賽默有限公司(Thermo Co.,Ltd.))量測同一樣本的碳含量。特定言之，藉由在O2存在下燃燒精確量的樣本來量測碳含量。樣本的碳含量為72原子%。使用X射線反射率(XRR)測試儀(X'Pert PRO，帕納科有限公司(PANalytical Co.,Ltd.))量測同一樣本的膜密度。特定言之，膜密度是藉由對經由樣本的X-射線輻射所獲得的繞射圖案與已知繞射圖案進行比較來量測。樣本的膜密度為1.4公克/立方公分。量測同一樣本的酸值。樣本的酸值為0mg KOH/g。 The organic film composition prepared in Preparation Example 1 was applied and baked at 400 ° C for 120 seconds to obtain a sample having a thickness of 4700 Å to 4800 Å. The hardness of the sample was measured using a nanoindenter (Hysitron TI750 Ubi). The hardness was measured by loading the tip of the nanoindenter on the sample for 5 seconds, holding the tip for 2 seconds and unloading the tip for 5 seconds. The hardness of the sample was 0.9 GPa. The carbon content of the same sample was measured using an elemental analyzer (EA1112, Thermo Co., Ltd.). In particular, the carbon content is measured by burning a precise amount of sample in the presence of O 2 . The carbon content of the sample was 72 atom%. The film density of the same sample was measured using an X-ray reflectance (XRR) tester (X'Pert PRO, PANalytical Co., Ltd.). In particular, the film density is measured by comparing a diffraction pattern obtained by X-ray irradiation of a sample with a known diffraction pattern. The film density of the sample was 1.4 g/cm 3 . Measure the acid value of the same sample. The acid value of the sample was 0 mg KOH/g.
製備包含超純水及如表1中所列出的組分的CMP漿料組成物，且在以下研磨條件下研磨。 A CMP slurry composition comprising ultrapure water and the components as listed in Table 1 was prepared and ground under the following grinding conditions.
實例2至實例3以及比較例1至比較例6Example 2 to Example 3 and Comparative Example 1 to Comparative Example 6
製備包含如表1中所列出的組分的CMP漿料組成物，且在以下研磨條件下研磨。 A CMP slurry composition containing the components as listed in Table 1 was prepared and ground under the following grinding conditions.
(1)CMP漿料組成物的組分的詳情(1) Details of the components of the CMP slurry composition
(A)金屬氧化物磨蝕劑：使用平均粒子直徑為60奈米的二氧化鈰(索爾維有限公司(SOLVAY Co.,Ltd.))。 (A) Metal oxide abrasive: Cerium oxide (SOLVAY Co., Ltd.) having an average particle diameter of 60 nm was used.
(B)氧化劑：使用硝酸鐵(三春化學有限公司(Samchun Chemical Co.,Ltd.))。 (B) Oxidizing agent: Iron nitrate (Samchun Chemical Co., Ltd.) was used.
(C)聚丙烯酸 (C) Polyacrylic acid
(c1)使用分子量為3,000公克/莫耳的PAA(奧德里奇有限公司(Aldrich Co.,Ltd.))。 (c1) PAA (Aldrich Co., Ltd.) having a molecular weight of 3,000 g/mole was used.
(c2)使用分子量為1,200公克/莫耳的PAA(奧德里奇有限公司)。 (c2) A PAA (Aldrich Co., Ltd.) having a molecular weight of 1,200 g/mole was used.
(c3)使用分子量為2,000公克/莫耳的PAA(奧德里奇有限公司)。 (c3) A PAA (Aldrich Co., Ltd.) having a molecular weight of 2,000 g/mole was used.
(c4)使用分子量為20,000公克/莫耳的PAA(奧德里奇有限公司)。 (c4) A PAA (Aldrich Co., Ltd.) having a molecular weight of 20,000 g/mole was used.
(c5)使用分子量為100,000公克/莫耳的PAA(奧德里奇有限公司)。 (c5) A PAA (Aldrich Co., Ltd.) having a molecular weight of 100,000 g/mole was used.
(c6)使用分子量為5,000公克/莫耳的PAA(奧德里奇有限公司)。 (c6) PAA (Aldrich Co., Ltd.) having a molecular weight of 5,000 g/mole was used.
(2)研磨條件，及研磨速率及選擇率的量測(2) Grinding conditions, and measurement of polishing rate and selectivity
使用H0800 CMP墊(富士紡有限公司(FUJIBO Co.,Ltd.))作為研磨墊。使用200毫米MIRRA研磨器(應用材料有限公司(Applied Materials(AMAT)Co.,Ltd.)，在0.8磅/平方吋(psi)壓縮壓力、200毫升/分鐘漿料流動速率、90轉/分(rpm)工作台速度以及90轉/分主軸速率(spindle speed)的條件下執行研磨1分鐘，接著量測研磨速率。結果顯示於表1中。經研磨表面上的平坦程度是藉由評估與無機膜相比CMP漿料組成物是否在有機膜上進行均一研磨來確定。使用薄膜厚度量測系統(ST4000， 科美儀器有限公司(K-MAC Co.,Ltd.))在經研磨膜的經研磨表面上量測在以上所述條件下進行研磨的經研磨膜的厚度(單位：埃)，接著由所量測的厚度計算研磨速率(單位：埃/分鐘)的標準差，由此獲得經研磨表面上的平坦性。基於所量測的研磨速率藉由方程式1計算選擇率。 A H0800 CMP pad (FUJIBO Co., Ltd.) was used as a polishing pad. A 200 mm MIRRA grinder (Applied Materials (AMAT) Co., Ltd.) was used at a compression pressure of 0.8 psi, a flow rate of 200 ml/min, and 90 rpm. Milling was performed for 1 minute under rpm) table speed and spindle speed of 90 rpm, and then the polishing rate was measured. The results are shown in Table 1. The degree of flatness on the ground surface was evaluated by inorganic The film is determined by whether the CMP slurry composition is uniformly ground on the organic film. Using a film thickness measurement system (ST4000, K-MAC Co., Ltd.) measured the thickness (unit: angstrom) of the ground film polished under the above conditions on the ground surface of the polished film, followed by The measured thickness calculates the standard deviation of the polishing rate (unit: angstrom/minute), thereby obtaining flatness on the ground surface. The selectivity is calculated by Equation 1 based on the measured polishing rate.
選擇率=α/β---方程式1，其中α為相對於有機膜的研磨速率且β為二氧化矽膜的研磨速率。 Selection rate = α / β - Equation 1, where α is the polishing rate with respect to the organic film and β is the polishing rate of the cerium oxide film.
如表1中所示，已證實與不包含聚丙烯酸的比較例1至比較例3的CPM漿料組成物及包含分子量大於3,500公克/莫耳的聚丙烯酸的比較例4至比較例6的CPM漿料組成物相比，包含分子量為3,500公克/莫耳或小於3,500公克/莫耳的聚丙烯酸的根據本發明的有機膜CPM漿料組成物相對於具有高碳含量、高膜密度以及高硬度的有機膜具有較高研磨速率以及對有機膜的較高選擇率。 As shown in Table 1, the CPM slurry compositions of Comparative Examples 1 to 3 which did not contain polyacrylic acid and the CPMs of Comparative Examples 4 to 6 including polyacrylic acids having a molecular weight of more than 3,500 g/mole were confirmed. The organic film CPM paste composition according to the present invention comprising a polyacrylic acid having a molecular weight of 3,500 g/mole or less than 3,500 g/mole has a high carbon content, a high film density and a high hardness compared to the slurry composition. The organic film has a higher polishing rate and a higher selectivity to the organic film.
應瞭解，可在不悖離本發明的精神及範疇的情況下由熟習此項技術者作出各種修改、變化、改變以及等效實施例。 It should be understood that various modifications, changes, and alterations and equivalents may be made by those skilled in the art without departing from the spirit and scope of the invention.
100‧‧‧矽晶圓 100‧‧‧矽 wafer
110‧‧‧無機膜 110‧‧‧Inorganic film
120‧‧‧有機碳膜 120‧‧‧Organic carbon film
T‧‧‧研磨停止線 T‧‧‧ grinding stop line
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020150068359A KR101861894B1 (en) | 2015-05-15 | 2015-05-15 | Cmp slurry composition for organic film and polishing method using the same |
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| TW201700663A TW201700663A (en) | 2017-01-01 |
| TWI595058B true TWI595058B (en) | 2017-08-11 |
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|---|---|
| KR (1) | KR101861894B1 (en) |
| CN (1) | CN107636110B (en) |
| TW (1) | TWI595058B (en) |
| WO (1) | WO2016186356A1 (en) |
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| KR102040310B1 (en) * | 2016-12-01 | 2019-11-04 | 삼성에스디아이 주식회사 | Cmp slurry composition and polishing method of organic film using the same |
| KR102544980B1 (en) | 2018-03-08 | 2023-06-20 | 삼성디스플레이 주식회사 | Thin film transistor substrate, display apparatus comprising the same, method for manufacturing thin film transistor substrate, and method for manufacturing display apparatus |
| KR102570805B1 (en) * | 2019-11-01 | 2023-08-24 | 삼성에스디아이 주식회사 | Cmp slurry composition for polishing tungsten pattern wafer and method for polishing tungsten pattern wafer using the same |
| KR20210079573A (en) * | 2019-12-20 | 2021-06-30 | 주식회사 케이씨텍 | Slurry composition for organic film |
| KR102465741B1 (en) * | 2020-06-09 | 2022-11-14 | 주식회사 케이씨텍 | Slurry composition for chemical mechanical polishing of organic film |
| KR102465745B1 (en) * | 2020-06-10 | 2022-11-14 | 주식회사 케이씨텍 | Slurry composition for organic film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080003829A1 (en) * | 2006-06-30 | 2008-01-03 | Dong Mok Shin | Chemical mechanical polishing slurry |
| TW201500531A (en) * | 2013-04-17 | 2015-01-01 | Cheil Ind Inc | CMP slurry composition for organic film and polishing method using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TW501197B (en) * | 1999-08-17 | 2002-09-01 | Hitachi Chemical Co Ltd | Polishing compound for chemical mechanical polishing and method for polishing substrate |
| CN1955239A (en) * | 2005-10-28 | 2007-05-02 | 安集微电子（上海）有限公司 | Chemical mechanical polishing material of copper |
| KR20090010169A (en) * | 2007-02-20 | 2009-01-29 | 스미토모덴키고교가부시키가이샤 | Polishing slurry, method for manufacturing the polishing slurry, nitride crystalline material and method for polishing surface of the nitride crystalline material |
| DE102008008184A1 (en) * | 2008-02-08 | 2009-08-13 | Evonik Degussa Gmbh | A method of polishing a silicon surface by means of a cerium oxide-containing dispersion |
| GB2477067B (en) * | 2008-11-06 | 2012-10-17 | Kao Corp | Polishing liquid composition for magnetic disk substrate |
| KR20100080067A (en) * | 2008-12-31 | 2010-07-08 | 제일모직주식회사 | Cmp slurry composition for polishing metal wiring |
| KR101340551B1 (en) * | 2010-12-31 | 2013-12-11 | 제일모직주식회사 | CMP slurry composition for selective polishing of silicon nitride |
| US8961807B2 (en) * | 2013-03-15 | 2015-02-24 | Cabot Microelectronics Corporation | CMP compositions with low solids content and methods related thereto |
| WO2014171766A1 (en) * | 2013-04-17 | 2014-10-23 | 제일모직 주식회사 | Organic film cmp slurry composition and polishing method using same |
| KR20150009914A (en) * | 2013-07-17 | 2015-01-27 | 삼성전자주식회사 | CMP composition for polishing an organic layer and method of forming a semiconductor device using the composition |
| US20150021513A1 (en) * | 2013-07-17 | 2015-01-22 | Yun-jeong Kim | Cmp slurry composition for polishing an organic layer and method of forming a semiconductor device using the same |
-
2015
- 2015-05-15 KR KR1020150068359A patent/KR101861894B1/en active IP Right Grant
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2016
- 2016-05-09 WO PCT/KR2016/004804 patent/WO2016186356A1/en active Application Filing
- 2016-05-09 CN CN201680027986.9A patent/CN107636110B/en active Active
- 2016-05-11 TW TW105114483A patent/TWI595058B/en active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080003829A1 (en) * | 2006-06-30 | 2008-01-03 | Dong Mok Shin | Chemical mechanical polishing slurry |
| TW201500531A (en) * | 2013-04-17 | 2015-01-01 | Cheil Ind Inc | CMP slurry composition for organic film and polishing method using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107636110A (en) | 2018-01-26 |
| TW201700663A (en) | 2017-01-01 |
| KR20160135081A (en) | 2016-11-24 |
| CN107636110B (en) | 2020-08-11 |
| WO2016186356A1 (en) | 2016-11-24 |
| KR101861894B1 (en) | 2018-05-29 |
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