WO2014171766A1 - Organic film cmp slurry composition and polishing method using same - Google Patents
Organic film cmp slurry composition and polishing method using same Download PDFInfo
- Publication number
- WO2014171766A1 WO2014171766A1 PCT/KR2014/003367 KR2014003367W WO2014171766A1 WO 2014171766 A1 WO2014171766 A1 WO 2014171766A1 KR 2014003367 W KR2014003367 W KR 2014003367W WO 2014171766 A1 WO2014171766 A1 WO 2014171766A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- substituted
- group
- unsubstituted
- organic film
- cmp slurry
- Prior art date
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 120
- 239000000203 mixture Substances 0.000 title claims abstract description 113
- 239000002002 slurry Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 19
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 7
- 239000002798 polar solvent Substances 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims description 36
- 125000000524 functional group Chemical group 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 21
- 125000003277 amino group Chemical group 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 19
- 239000007800 oxidant agent Substances 0.000 claims description 16
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000004104 aryloxy group Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 125000005011 alkyl ether group Chemical group 0.000 claims description 11
- 125000000304 alkynyl group Chemical group 0.000 claims description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 11
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 11
- 125000001033 ether group Chemical group 0.000 claims description 11
- 125000001188 haloalkyl group Chemical group 0.000 claims description 11
- 125000001072 heteroaryl group Chemical group 0.000 claims description 11
- 125000004366 heterocycloalkenyl group Chemical group 0.000 claims description 11
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 11
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- 125000004404 heteroalkyl group Chemical group 0.000 claims description 10
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- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 125000004446 heteroarylalkyl group Chemical group 0.000 claims description 9
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- 229910052723 transition metal Inorganic materials 0.000 claims description 9
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- 239000002184 metal Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- 125000004405 heteroalkoxy group Chemical group 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000013522 chelant Substances 0.000 claims description 3
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- 235000011090 malic acid Nutrition 0.000 claims description 3
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- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 description 180
- 238000006243 chemical reaction Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 5
- 238000001029 thermal curing Methods 0.000 description 5
- 0 *c1cccc2c1c(-c(ccc1c3cccc1)c3N)ccc2 Chemical compound *c1cccc2c1c(-c(ccc1c3cccc1)c3N)ccc2 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- -1 alcohol amines Chemical class 0.000 description 4
- 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 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 239000011572 manganese Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
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- 238000003756 stirring Methods 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
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- 238000000560 X-ray reflectometry Methods 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
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- 238000011049 filling Methods 0.000 description 2
- 238000005429 filling process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 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
- 229910052760 oxygen Inorganic materials 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
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 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
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- RVOJTCZRIKWHDX-UHFFFAOYSA-N cyclohexanecarbonyl chloride Chemical compound ClC(=O)C1CCCCC1 RVOJTCZRIKWHDX-UHFFFAOYSA-N 0.000 description 1
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- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 238000003475 lamination Methods 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- NSNPSJGHTQIXDO-UHFFFAOYSA-N naphthalene-1-carbonyl chloride Chemical compound C1=CC=C2C(C(=O)Cl)=CC=CC2=C1 NSNPSJGHTQIXDO-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical class OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 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
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride 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
- 150000003672 ureas Chemical class 0.000 description 1
Images
Classifications
-
- 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
- H01L21/3105—After-treatment
- H01L21/31058—After-treatment of organic layers
-
- 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
-
- 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
- C09K3/1472—Non-aqueous liquid suspensions
Definitions
- the present invention relates to an organic film CMP slurry composition and a polishing method using the same.
- the semiconductor manufacturing method includes forming an inorganic film such as a silicon oxide film and a silicon nitride film on a patterned silicon wafer, and gap-filling via-holes formed in the inorganic film. It includes a process to make.
- the gap-filling process is a process for filling the via-holes with the organic film material, and after the gap-filling process, a process of removing and planarizing the excessively formed organic film should be accompanied.
- the current spotlight is polishing by chemical mechanical polishing (CMP).
- the conventional organic film CMP slurry composition includes polymer abrasive particles because the organic film should be polished with a high polishing amount per unit time so as not to deteriorate surface conditions such as scratches.
- the organic film does not have the same material, depending on the organic film, when polishing with the conventional organic film CMP slurry composition, the flatness of the polished surface was also increased and the desired polishing amount could not be obtained.
- a metal oxide abrasive used for polishing a metal film such as silicon is used for polishing an organic film, a desired polishing amount may not be obtained depending on the organic film, and / or scratches may occur, resulting in low polishing surface flatness. .
- An object of the present invention is to provide an organic film CMP slurry composition having an excellent polishing effect on an organic film having high carbon content, film density and hardness.
- Another object of the present invention is that after polishing the surface of the organic film having high carbon content, film density and hardness, the polishing surface flatness is good, and the residue of the organic film material present in the polishing stop film layer can be easily removed. It is to provide an organic film CMP slurry composition capable of more uniform polishing.
- the organic film CMP slurry composition of the present invention comprises at least one of a polar solvent and a nonpolar solvent; And a metal oxide abrasive, which is acidic, and can polish an organic film having a carbon content of about 50 to 95 atom%.
- organic film polishing method of the present invention using the organic film CMP slurry composition, polishing an organic film having a carbon content of about 50 to 95 atm%, a film density of about 0.5 to 2.5 g / cm 3, and a hardness of about 0.4 GPa or more. It may include.
- the present invention provides an organic film CMP slurry composition having excellent polishing effect on an organic film having high carbon content, film density, and hardness.
- the present invention provides a more uniform surface after polishing for organic films having high carbon content, film density, and hardness, and can more easily remove residues of organic film materials present in the polishing stop film layer.
- An organic film CMP slurry composition capable of polishing was provided.
- 1 is a schematic diagram of an organic film polishing method of an embodiment of the present invention.
- substituted or unsubstituted means that a hydrogen atom in a functional group is a hydroxy group, a halogen atom, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted A substituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 Aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1
- the "functional group including P” may be represented by the following Chemical Formula A
- the “functional group including B” may be represented by the following Chemical Formula B:
- R, R ' are each independently hydrogen, hydroxyl, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C2 to C20 alkenyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or Unsubstituted C1 known C20 haloalkyl group, substituted or unsubstituted C1 to C20 alkylsulfonate group, substituted or unsubstituted C1 to C20 alkylsulfonyl group, substituted or unsubstituted C2 to C20 alkylamide group, Substituted or unsubstituted C3 to C20 alkyl ester group, substituted or unsubstituted C2 to C20 cyanoalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C6 to C30 aryl group, substituted Or an
- R, R ' are linked to each other to form a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C3 to C20 heterocycloalkyl group).
- “functional group comprising B” The functional group containing O may be, for example, -B (OH) 2 , -B (H) (CH 3 ), -B (CH 2 CH 3 ) 2 .
- the organic film fills the generated via-holes.
- the CMP slurry composition should be able to polish the organic film to a sufficient polishing rate and increase the flatness of the polished surface to remove the residues remaining in the inorganic film after polishing.
- the inorganic film may be a film formed of at least one of silicon oxide and silicon nitride, but is not limited thereto.
- the organic film may have a large difference in polishing amount per unit time and flatness after polishing depending on the material of the organic film.
- the organic film CMP slurry composition of the present invention is a composition for polishing an organic film having a high carbon content.
- the organic film CMP slurry composition can increase the amount and flatness of the organic film per unit time when the organic film is polished, and can easily remove residues remaining in the inorganic film after polishing. have.
- the organic film to be polished of the present invention has a relatively high carbon content, film density, and degree of cure compared to a conventional organic film, and thus cannot be polished with an organic film CMP slurry composition including conventional polymer particles.
- the CMP slurry composition of the present invention can polish the organic film with a high polishing amount per unit time without deteriorating the surface state due to scratching.
- the amount of polishing per unit time for the organic film may be about 500 kPa / min or more, for example, about 1,000 kPa / min or more, for example, about 500 to 5000 kPa / min, and may be applied to the process in the above range. Amount of polishing can be secured.
- the organic film has a carbon content of about 50 to 95 atom% such as about 65 to 95 atom% or about 70 to 92 atom%, such as about 65,66,67,68,69,70,71, 72,73,74,75,76,77,78,79,80,81,82,83,84,85,86,87,88,89,90,91,92,93,94 or 95 atom%
- the polishing amount is high, scratches do not occur, and the flatness of the polishing surface may be high.
- the organic film has a film density of about 0.5 to 2.5 g / cm 3 , for example about 1.0 to 2.0 g / cm 3 , for example about 1.2 to 1.6 g / cm 3 , for example about 0.5, 0.6, 0.7, 0.8, 0.9 , 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5 g / cm 3 , when polishing with a metal oxide abrasive in the above range
- the polishing amount is high, no scratch occurs, and the flatness of the polishing surface may be high.
- the organic film has a hardness of about 0.4 GPa or more, for example about 1.0 GPa or more, for example about 1.3 GPa or more, for example about 1.0 to 1.5 GPa, for example about 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, It may be 1.0, 1.1, 1.2, 1.3, 1.4, 1.5GPa, and in the above range when polishing with a metal oxide abrasive, the polishing amount is high, no scratches may occur and the flatness of the polishing surface may be high.
- the organic film to be polished of the present invention may have an acid value of about 0 mgKOH / g substantially.
- an organic film CMP slurry composition including a conventional polymer abrasive there is a problem that the polishing rate is lowered.
- the CMP slurry composition of the present invention can secure the amount of polishing per unit time of the organic film applicable to the CMP process.
- substantially includes not only the case where the acid value is 0 mgKOH / g but also a slight error at 0 mgKOH / g.
- the organic film to be polished of the present invention may be prepared by applying a composition containing a compound having a substituted or unsubstituted aromatic group on the inorganic film and then thermosetting (baking) at a high temperature, for example, about 200 to 400 ° C. .
- the "compound having a substituted or unsubstituted aromatic group” refers to a compound that does not decompose even after thermal curing so that the organic film formed of the composition can exhibit a high carbon content.
- the unsubstituted aromatic group means a single or fused polycyclic aromatic group having 6 to 100 carbon atoms, for example, 6 to 50 carbon atoms, and specifically, may include units of the following Chemical Formulas 1-1 to 1-26.
- the composition for forming an organic film may be a compound having a substituted or unsubstituted aromatic group may include a material including the following formula (2):
- n 1 ⁇ n ⁇ 190
- R 1 is hydrogen, a hydroxy group, a halogen atom, an allyl group, thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group , Substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalky
- R 2 is hydrogen, an amino group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryloxy group, a dialkylamino group (-NRR ', where R and R' are independently substituted with each other) Or unsubstituted C1 to C10 alkyl group or substituted or unsubstituted C6 to C10 aryl group), hydroxy group, halogen atom, allyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or Unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C
- R 3 is substituted or unsubstituted
- R 2 may be a substituted or unsubstituted C 1 to C 10 alkoxy group.
- the material including Chemical Formula 2 may increase carbon content, film density, and hardness after thermal curing of the organic film composition, and refer to Korean Patent No. 10-0866015 for a more detailed method of manufacturing the same.
- the composition of the first embodiment may further include at least one of a crosslinking component, an acid catalyst, and an organic solvent, in addition to the material including Chemical Formula 2. Specifically, about 1 to 20 wt% of the material represented by Formula 2, about 0.1 to 5 wt% of the crosslinking component, about 0.001 to 0.05 wt% of the acid catalyst, and about 75 to 98.8 wt% of the organic solvent.
- the crosslinking component may be a melamine resin (eg, N-methoxymethyl-melamine resin, N-butoxymethylmelamine resin), methylated or butylated urea resin, amino resin, glycoluril derivative of Formula 3, Bisepoxy compound, may include one or more of the melamine derivative of formula (5):
- Acid catalysts include p-toluenesulfonic acid monohydrate, pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, alkyl of euphonic acid It may include one or more of the esters.
- the organic solvent is not particularly limited as long as it is an organic solvent having sufficient solubility in a compound having a substituted or unsubstituted aromatic group, and examples thereof include propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate and the like.
- composition for forming an organic film of the first embodiment may be coated with a thickness of about 500 to 4000 kPa, and thermally cured at about 200 to 400 ° C. for about 10 seconds to 10 minutes to form an organic film, but is not limited thereto.
- the composition for forming an organic film may be a compound having a substituted or unsubstituted aromatic group and may include a material represented by the following formula (6):
- X 1 To X 6 are each independently hydrogen, hydroxy group, halogen atom, allyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted Or an unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 Cycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C
- n 1 to n 6 are each independently in a range of 0 to 2, and 2 ⁇ n 1 + n 2 + n 3 + n 4 + n 5 + n 6 ⁇ 6 ).
- R 4 to R 9 are each independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or It may be an unsubstituted C3 to C20 cycloalkenyl group, a functional group including P, or a functional group including B.
- X 1 to X 6 may be each independently hydrogen, a hydroxy group, a substituted or unsubstituted C 1 to C 20 alkylamine group, an amino group, a functional group including P, a functional group including B.
- the compound having a substituted or unsubstituted aromatic group is substantially the same as the organic film composition of the first embodiment except that the compound represented by Chemical Formula 6 is used instead of the material represented by Chemical Formula 2. Therefore, hereinafter, only the substance represented by Chemical Formula 6 will be described.
- the material represented by Chemical Formula 6 may be a mixture of two or more compounds having different positions of substituents, and may include an aromatic ring having strong absorption in a short wavelength region (for example, about 193 nm and 248 nm), and thus do not use a special catalyst. If not, the crosslinking reaction may be performed at a high temperature, thereby preventing contamination by a catalyst, particularly an acid, and the aromatic group compound of Formula 6 may have an average molecular weight of about 500 to 4000 g / mol, and the thickness of the organic film may be implemented or A good thin film can be formed.
- the material represented by Chemical Formula 6 may increase carbon content, film density, and hardness after thermal curing of the organic film composition.
- the material represented by Chemical Formula 6 may be prepared by a conventional method, for example, it may be prepared by reacting and reducing acetyl chloride, benzoyl chloride, naphthoyl chloride, cyclohexanecarbonyl chloride to coronene, but It is not limited.
- acetyl chloride benzoyl chloride, naphthoyl chloride, cyclohexanecarbonyl chloride to coronene, but It is not limited.
- Korea Patent Registration No. 10-1311942 For more detailed manufacturing method refer to Korea Patent Registration No. 10-1311942.
- the organic film composition may include an aromatic group-containing polymer selected from (i), (ii) and (iii) as a compound having a substituted or unsubstituted aromatic group:
- n and n are each 1 ⁇ n ⁇ 750, 1 ⁇ m ⁇ 750, and 2 ⁇ m + n ⁇ 1500,
- R 10 is substituted or unsubstituted
- R 11 is hydrogen, a hydroxy group, a halogen atom, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or Unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or
- R 12 is substituted or unsubstituted
- R 13 is substituted or unsubstituted
- R 14 is substituted or unsubstituted
- R 15 is substituted or unsubstituted
- R at R 10 , R 13 and R 15 are each independently hydrogen, hydroxy group, halogen atom, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or unsubstituted C1 to C30 alkyl group, substituted or Unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 Heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstitute
- the compound having a substituted or unsubstituted aromatic group is substantially the same as the organic film composition of the first embodiment except that the aromatic group-containing polymer is included in place of the material represented by Chemical Formula 2. Therefore, hereinafter, only the aromatic group-containing polymer will be described.
- the aromatic group-containing polymer may increase carbon content, film density and hardness after thermal curing of the organic film composition, and may be prepared by a conventional method, and refer to Korean Patent No. 10-0908601 for more details.
- the organic film composition is a compound having a substituted or unsubstituted aromatic group material comprising the formula (2); A substance represented by Chemical Formula 6; It may contain two or more of the aromatic group-containing polymers selected from the above (i), (ii) and (iii). It is substantially the same as the composition of the first embodiment except that it contains two or more kinds.
- the organic film CMP slurry composition of one embodiment of the present invention comprises at least one of a polar solvent and a nonpolar solvent; And a metal oxide abrasive, and may be acidic.
- the organic film to be polished of the present invention can be polished with a high polishing amount without scratching, and the flatness of the polishing surface can be increased.
- Polar and / or non-polar solvents reduce friction when polishing high-carbon organic films with metal oxide abrasives, and can be water, for example ultrapure water, organic amines, organic alcohols, organic alcohol amines, organic ethers, organic ketones, and the like.
- ultrapure water can be used.
- Polar and / or nonpolar solvents may be included in the balance in the CMP slurry composition.
- the metal oxide abrasive can polish the organic film having a high carbon content, film density and hardness with a high polishing amount.
- the polishing surface flatness could be increased by preventing scratches and the like from occurring during polishing of the organic film, which is the polishing target of the present invention.
- the metal oxide abrasive may include one or more of silica, alumina, ceria, titania, zirconia.
- silica may have a further effect of good dispersion stability
- ceria may have a further effect of no oxidizing agent or at least extremely high polishing rate.
- the metal oxide abrasive may be spherical particles having an average particle diameter of about 10 to 150 nm, for example, about 30 to 70 nm, for example, about 30, 35, 40, 45, 50, 55, 60, 65, 70 nm, Within this range, it is possible to achieve a sufficient polishing rate with respect to the organic film to be polished of the present invention, prevent scratches from occurring, and increase flatness.
- the metal oxide abrasive is about 0.1 to 20% by weight, for example about 0.1 to 15% by weight, for example about 0.1 to 5% by weight, for example about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6 in the CMP slurry composition.
- a sufficient polishing rate can be given to the organic film to be polished, a scratch can be prevented from occurring, and dispersion stability can be good.
- a sufficient polishing rate can be given to the organic film to be polished, a scratch can be prevented from occurring, and dispersion stability can be good.
- the present invention in the above range
- a sufficient polishing rate can be given to the organic film to be polished, a scratch can be prevented from occurring, and dispersion stability can be good.
- the CMP slurry composition is acidic, the CMP slurry composition has an effect of realizing a high polishing selectivity of the organic film with respect to the inorganic film, increasing the polishing amount per unit time with respect to the organic film, and increasing the flatness.
- the CMP slurry composition has a pH of about 6 or less, for example about 5 or less, for example about 1 to 5, for example about 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, Can be 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.
- the CMP slurry composition of one embodiment of the present invention can be adjusted to the pH in the above-described range.
- the pH adjusting agent may include one or more of inorganic acids such as nitric acid, phosphoric acid, hydrochloric acid, and sulfuric acid, and organic acids such as organic acids having a pKa value of about 6 or less, and may include, for example, one or more of acetic acid and citric acid. It is not limited.
- the CMP slurry composition may further comprise an additive.
- the CMP slurry composition may further include a polishing accelerator as an additive.
- the polishing rate for the inorganic film can be suppressed to increase the polishing selectivity for the inorganic film.
- the abrasive promoter may comprise one or more of organic acids such as malic acid, citric acid, formic acid, glutaric acid, oxalic acid, phthalic acid, succinic acid, tartaric acid, maleic acid, malonic acid.
- the polishing accelerator may be included in about 0.02 to 0.5% by weight of the CMP slurry composition, and may have no adverse effect on the polishing rate, the dispersion stability of the slurry, and the surface properties of the organic carbon film in the above range.
- the CMP slurry composition may further comprise the pH adjuster described above to make the pH acidic.
- the pH adjusting agent may be included to adjust the pH of the whole composition in the CMP slurry composition at an appropriate line to further increase the polishing selectivity for the inorganic film.
- the organic film CMP slurry composition of another embodiment of the present invention includes a polar and / or nonpolar solvent, a metal oxide abrasive, and an oxidizing agent, and may be acidic.
- the organic film CMP slurry composition of another embodiment of the present invention further includes an oxidizing agent as compared to the composition of the embodiment of the present invention, thereby increasing the polishing selectivity of the organic film to the inorganic film, increasing the polishing rate to the organic film, and There may be further effects of increasing the flatness.
- it further comprises an oxidizing agent is substantially the same as the organic film CMP slurry composition of one embodiment of the present invention. Therefore, hereinafter, only the oxidant will be described further.
- the oxidizing agent oxidizes the surface layer of the organic film to facilitate polishing of the organic carbon film having a high carbon content, film density, and curing degree, and facilitates polishing of the organic film, and evenly polishes the surface of the organic film when the inorganic film is exposed by polishing.
- the surface roughness can be made good.
- the residue of the organic film present in the inorganic film can be easily removed to allow a more uniform polishing.
- the oxidizing agent may include at least one of a metal salt having a multivalent oxidation state and a chelate compound of a transition metal.
- Multivalent means divalent or more, for example trivalent or more, for example tetravalent or more.
- Metal salts having a polyvalent oxidation state can increase the polishing rate for the organic film and lower the polishing rate for the inorganic film.
- the metal salt may include a metal such as a transition metal, a lanthanide element, and may further include halogen, ammonium, nitrate, or the like.
- the metal salt may include ceric ammonium salt, ferric halogen salt, ferric nitrate salt, and the like, and may include, for example, ceric ammonium nitrate, ferric nitrate, ferric chloride, and the like.
- the chelating compound of the transition metal can increase the polishing rate for the organic film and lower the polishing rate for the inorganic film.
- the transition metals include conventionally known transition metals of groups 3 to 12 of the periodic table, which may be iron, copper, manganese or chromium, for example.
- Chelates are oxalic acid, amino-substituted carboxylic acids (e.g., iminodiacetic acid, ethylenediaminedisuccinic acid, iminodisuccinic acid, aminopolycarboxylates such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, alpha-amino acids such as glycine, beta- Amino acids), hydroxyl-substituted carboxylic acids (eg, polycarboxylic acids including recipients such as glycolic acid, lactic acid, malic acid, citric acid, tartaric acid), phosphonocarboxylic acids, aminophosphonic acids; Combinations thereof.
- amino-substituted carboxylic acids e.g., iminodiacetic acid, ethylenediaminedisuccin
- the chelating compound of the transition metal may include, but is not limited to, one or more of Fe-containing compounds including propylenediaminetetraacetic acid-Fe and the like, Mn-containing compounds including propylenediaminetetraacetic acid-Mn and the like.
- the oxidant is about 0.001 to 15% by weight, for example about 0.01 to 5% by weight, for example about 0.05 to 3% by weight, for example about 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35 in the CMP slurry composition , 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.8, 0.85, 0.9, 0.95, 1, 1.5, 2, 2.5, 3 wt%, and the proper etching property for the organic film in the above range I can keep it.
- the stability of the oxidant may be increased to increase the polishing amount per unit time for the organic film, to improve the flatness of the polishing surface, and to increase the polishing selectivity for the inorganic film.
- the organic film polishing method of the present invention includes polishing an organic film having a high carbon content, a film density, and a high degree of curing by using an organic film CMP slurry composition, wherein the organic film CMP slurry composition comprises the organic film CMP slurry composition according to an embodiment of the present invention. It may include.
- FIG. 1A illustrates a lamination state of a silicon wafer, an inorganic film, and an organic carbon film before polishing an organic film, and the silicon wafer 100 is intaglio patterned locally.
- T represents an imaginary polishing stop line.
- a 2000 ml three-necked flask equipped with a thermometer, a condenser, a mechanical stirrer, and a dropping funnel was prepared, and then immersed in an oil bath at 140 ° C. Heating and stirring by magnets were performed on a hotplate and the cooling water temperature of the condenser was fixed at 40 ° C. 220 g of 1 mol of 1-methoxypyrene was added to the reactor, and 138 g of 1.0 mol of 1,4-bismethoxymethylbenzene was added and then dissolved in 656 g of propylene glycol monomethyl ether acetate. Then 4.6 g of 0.03 mol of diethylsulfate were added.
- the temperature of the reactor was maintained at 130 ° C.
- the molecular weight was measured at regular time intervals to determine the completion time of the reaction.
- the sample for measuring the molecular weight was prepared by diluting 1 g of the reactant, quenching to room temperature, 0.02 g of the sample was diluted to 4% by weight using tetrahydrofuran as a solvent.
- 0.03 mol of triethanolamine 4.48 g was added to the reactor as a neutralizing agent and terminated.
- the reaction was then slowly cooled to room temperature.
- the reaction was diluted with 500 g of propylene glycol monomethyl ether acetate.
- the solvent was then added to a 2000 ml separatory funnel.
- the molecular weight and the dispersity of the obtained copolymer were measured by GPC under tetrahydrofuran, and as a result, a polymer containing a unit represented by the following Chemical Formula 10 having a weight average molecular weight of 4000 dispersion of 2.3 was obtained.
- a mechanical stirrer, a cooling tube, a 2 L four-necked flask containing 30.1 g (0.1 mol) of coronene, 47.1 g (0.6 mol) of acetyl chloride, and 79.8 g (0.6 mol) of trichloroaluminum were dissolved in 1000 g of toluene.
- the reaction was terminated after stirring for 10 hours.
- 37.83 g (1.0 mol) of sodium borohydride was added to the obtained compound, and the reaction was carried out for 17 hours.
- a 5000 mm thick silica film was deposited on the pattern wafer having the negative pattern formed on the surface thereof, and an organic film of 2650 mm thick was formed to fill the negative pattern formed on the surface of the silica film.
- the organic film was prepared by applying the composition for forming an organic film of Preparation Example 1 onto a silica film and thermosetting at 400 ° C.
- the hardness was measured using a Nanoindentor (Hysitron TI750 Ubi) for the specimen of the thickness of 4700 ⁇ 4800 ⁇ prepared by coating the composition for forming an organic film of Preparation Example 1 and thermosetting at 400 °C for 120 seconds.
- the tip of the nanoindentor was measured by loading the specimen for 5 seconds, holding for 2 seconds and then unloading for 5 seconds, and the hardness was 0.9 GPa.
- the carbon content was measured using an elemental analyzer (EA1112, Thermo) on the same specimen. Specifically, the exact amount of the sample was burned in O 2 coexistence to measure the carbon content, the carbon content was 72atm%.
- Membrane density was measured on the same specimen using an X-RAY REFLECTIVITY (XRR) instrument (X'Pert PRO, PANalytical). Specifically, the diffraction pattern irradiated with X-rays was measured by comparing with a known diffraction pattern, and the film density was 1.4 g / cm 3 . The acid value was measured for the same specimen, and the acid value was 0 mg KOH / g.
- XRR X-RAY REFLECTIVITY
- a CMP slurry composition comprising ultrapure water and the components of Table 1 below was prepared and polished under the following polishing conditions.
- a 5000 mm thick silica film was deposited on the pattern wafer having the negative pattern formed on the surface thereof, and an organic film of 2650 mm thick was formed to fill the negative pattern formed on the surface of the silica film.
- the organic film was prepared by applying the composition for forming an organic film of Preparation Example 2 onto a silica film and thermosetting at 400 ° C.
- the composition for forming an organic film of Preparation Example 2 was applied and thermally cured at 400 ° C. for 120 seconds to prepare a specimen having a thickness of 4700 to 4800 mm 3.
- Hardness, carbon content, film density, and acid value were measured in the same manner as in Example 1. The hardness was 1.5 GPa, the carbon content was 80 atm%, the film density was 1.7 g / cm 3 , and the acid value was 0 mg KOH / g.
- a CMP slurry composition comprising ultrapure water and the components of Table 2 below was prepared and polished under the following polishing conditions.
- Example 1 the same procedure was followed except that the CMP slurry composition having the composition of Table 1 was used.
- Example 2 the same procedure was followed except that the CMP slurry composition having the composition of Table 2 was used.
- A Metal oxide abrasive: (a1) Ceria (SOLVAY company) with an average particle diameter of 60 nm, (a2) Colloidal silica (Evonic company) with an average particle diameter of 35 nm
- pH regulator potassium hydroxide (Samjeon Pure Chemical Co., Ltd.)
- polishing accelerator Formic acid (Daejunghwa Gold Co., Ltd.)
- polishing pad flatness is to evaluate whether the CMP slurry composition has balanced the polishing on the organic film compared to the inorganic film, and after performing the polishing as described above, a thin film thickness meter (ST4000, K-MAC) is applied to the polishing surface. It is a value obtained by measuring the thickness (unit: mm) of the polishing film, and calculating the standard deviation from the measured thickness.
- the organic film CMP slurry composition of the present invention has a high polishing amount per unit time and a high polishing surface flatness for the organic film having a high carbon content, film density, and hardness.
- Examples 2 to 18 further include a specific oxidizing agent as compared to Example 1, thereby confirming that the polishing rate is higher or the polishing surface flatness is higher for the organic film having a higher carbon content, film density, and hardness.
- the present invention provides an organic film CMP slurry composition having excellent polishing effect on an organic film having high carbon content, film density, and hardness.
- the present invention provides a more uniform surface after polishing for organic films having high carbon content, film density, and hardness, and can more easily remove residues of organic film materials present in the polishing stop film layer.
- An organic film CMP slurry composition capable of polishing was provided.
- the comparative example having a non-acidic pH even when the metal oxide abrasive was included it was confirmed that the polishing rate of the organic film having a high carbon content, film density and hardness is significantly lower than the embodiment, or the polishing surface flatness is lower .
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Abstract
The present invention relates to an organic film CMP slurry composition for polishing an organic film, which includes at least either of a polar solvent or a non-polar solvent and a metal oxide abrasive, is acidic, and has a carbon content of around 50 to 95 atm%, and a polishing method using the same.
Description
본 발명은 유기막 ＣＭＰ 슬러리 조성물 및 이를 이용한 연마방법에 관한 것이다.The present invention relates to an organic film CMP slurry composition and a polishing method using the same.
반도체 제조 방법은 패턴화된 실리콘 웨이퍼 위에 무기막 예를 들면 실리콘 산화물막, 실리콘 질화물막을 형성하는 공정을 포함하고, 무기막 내에 형성된 비어-홀(via-hole)을 갭-필링(gap-fill)하는 공정을 포함한다. 갭-필링 공정은 유기막 물질로 비어-홀을 채워주기 위한 공정이고, 갭-필 공정 후에는 과량으로 성막된 유기막을 제거하여 평탄화시키는 공정이 수반되어야 한다. 평탄화 기술로서 현재 각광받고 있는 것이 CMP(chemical mechanical polishing)에 의한 연마이다.The semiconductor manufacturing method includes forming an inorganic film such as a silicon oxide film and a silicon nitride film on a patterned silicon wafer, and gap-filling via-holes formed in the inorganic film. It includes a process to make. The gap-filling process is a process for filling the via-holes with the organic film material, and after the gap-filling process, a process of removing and planarizing the excessively formed organic film should be accompanied. As a planarization technique, the current spotlight is polishing by chemical mechanical polishing (CMP).
종래 유기막 CMP 슬러리 조성물은 유기막을 단위 시간당 높은 연마량으로 연마하되 스크래치와 같은 표면 상태의 악화가 없게 하여야 하므로 고분자 연마 입자를 포함하였다. 그러나, 유기막이 동일 재질을 갖는 것은 아니므로 유기막에 따라서는 종래 유기막 CMP 슬러리 조성물로 연마할 경우 연마면의 평탄도도 높이면서 동시에 원하는 연마량을 얻을 수 없었다. 그렇다고, 실리콘 등의 금속막 연마에 사용되는 금속산화물 연마제를 유기막 연마에 사용할 경우 유기막에 따라 원하는 연마량을 얻을 수 없거나 및/또는 스크래치등이 발생하여 연마면 평탄도가 낮아지는 문제점이 있었다. The conventional organic film CMP slurry composition includes polymer abrasive particles because the organic film should be polished with a high polishing amount per unit time so as not to deteriorate surface conditions such as scratches. However, since the organic film does not have the same material, depending on the organic film, when polishing with the conventional organic film CMP slurry composition, the flatness of the polished surface was also increased and the desired polishing amount could not be obtained. However, when a metal oxide abrasive used for polishing a metal film such as silicon is used for polishing an organic film, a desired polishing amount may not be obtained depending on the organic film, and / or scratches may occur, resulting in low polishing surface flatness. .
본 발명의 목적은 탄소 함량, 막 밀도 및 경도가 높은 유기막에 대해 연마 효과가 우수한 유기막 CMP 슬러리 조성물을 제공하는 것이다.An object of the present invention is to provide an organic film CMP slurry composition having an excellent polishing effect on an organic film having high carbon content, film density and hardness.
본 발명의 다른 목적은 탄소 함량, 막 밀도 및 경도가 높은 유기막에 대해 연마 후 연마면 평탄도가 좋고, 연마 정지막 층에 존재하는 유기막 물질의 잔류물(residue)을 쉽게 제거할 수 있으므로 보다 균일한 연마가 가능한 유기막 CMP 슬러리 조성물을 제공하는 것이다.Another object of the present invention is that after polishing the surface of the organic film having high carbon content, film density and hardness, the polishing surface flatness is good, and the residue of the organic film material present in the polishing stop film layer can be easily removed. It is to provide an organic film CMP slurry composition capable of more uniform polishing.
본 발명의 유기막 CMP 슬러리 조성물은 극성 용매, 비극성 용매 중 하나 이상; 및 금속산화물 연마제를 포함하고, 산성이고, 탄소 함량이 약 50 내지 95atom%인 유기막을 연마할 수 있다.The organic film CMP slurry composition of the present invention comprises at least one of a polar solvent and a nonpolar solvent; And a metal oxide abrasive, which is acidic, and can polish an organic film having a carbon content of about 50 to 95 atom%.
본 발명의 유기막 연마 방법은 상기 유기막 CMP 슬러리 조성물을 사용하여, 탄소 함량이 약 50 내지 95atm%이고 막 밀도가 약 0.5 내지 2.5g/cm3이고 경도가 약 0.4GPa 이상인 유기막을 연마하는 단계를 포함할 수 있다.In the organic film polishing method of the present invention, using the organic film CMP slurry composition, polishing an organic film having a carbon content of about 50 to 95 atm%, a film density of about 0.5 to 2.5 g / cm 3, and a hardness of about 0.4 GPa or more. It may include.
본 발명은 탄소 함량, 막 밀도 및 경도가 높은 유기막에 대해 연마 효과가 우수한 유기막 CMP 슬러리 조성물을 제공하였다. 본 발명은 탄소 함량, 막 밀도 및 경도가 높은 유기막에 대해 연마 후 연마면 평탄도가 좋고, 연마 정지막 층에 존재하는 유기막 물질의 잔류물(residue)을 쉽게 제거할 수 있으므로 보다 균일한 연마가 가능한 유기막 CMP 슬러리 조성물을 제공하였다.The present invention provides an organic film CMP slurry composition having excellent polishing effect on an organic film having high carbon content, film density, and hardness. The present invention provides a more uniform surface after polishing for organic films having high carbon content, film density, and hardness, and can more easily remove residues of organic film materials present in the polishing stop film layer. An organic film CMP slurry composition capable of polishing was provided.
도 1은 본 발명 일 실시예의 유기막 연마 방법의 모식도이다.1 is a schematic diagram of an organic film polishing method of an embodiment of the present invention.
첨부한 도면을 참고하여 실시예에 의해 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. 도면에서 본 발명을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 동일 또는 유사한 구성 요소에 대해서는 동일한 도면 부호를 붙였다.DETAILED DESCRIPTION Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. The drawings and description are to be regarded as illustrative in nature and not restrictive. Like reference numerals designate like elements throughout the specification.
본 명세서에서 "치환 또는 비치환된"은 작용기 중 수소 원자가 히드록시기, 할로겐 원자, 티오닐기, 티올기, 시아노기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C1 내지 C20 알데히드기, 치환 또는 비치환된 C1 내지 C40 알킬에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합을 포함할 수 있다.As used herein, "substituted or unsubstituted" means that a hydrogen atom in a functional group is a hydroxy group, a halogen atom, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted A substituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 Aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkenyl group, Substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C20 alkylamine group, Ring or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted C1 to C40 alkylether group, substituted or unsubstituted It may include a C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a functional group including P, a functional group including B or a combination thereof.
본 명세서에서 "P를 포함하는 작용기"는 하기 화학식 A로 표시될 수 있고, "B를 포함하는 작용기"는 하기 화학식 B로 표시될 수 있다:In the present specification, the "functional group including P" may be represented by the following Chemical Formula A, and the "functional group including B" may be represented by the following Chemical Formula B:
<화학식 A><Formula A>
*-(O)n-(CH2)m-P(=O)(R)(R') *-(O) n- (CH 2 ) mP (= O) (R) (R ')
<화학식 B><Formula B>
*-B(R)(R')* -B (R) (R ')
(상기 화학식 A, 화학식 B에서, *은 원소의 연결 부위이고, n은 0 또는 1이고, m은 0 내지 10의 정수이고,(In the above formula (A), (B), * is a linking site of the element, n is 0 or 1, m is an integer of 0 to 10,
R, R'은 각각 독립적으로, 수소, 수산기, 치환 또는 비치환된 C1 내지 C20의 알킬기, 치환 또는 비치환된 C2 내지 C20의 알케닐기, 치환 또는 비치환된 C3 내지 C20의 시클로알킬기, 치환 또는 비치환된 C1 기지 C20의 할로알킬기, 치환 또는 비치환된 C1 내지 C20의 알킬술포네이트기, 치환 또는 비치환된 C1 내지 C20의 알킬술포닐기, 치환 또는 비치환된 C2 내지 C20의 알킬아미드기, 치환 또는 비치환된 C3 내지 C20의 알킬에스테르기, 치환 또는 비치환된 C2 내지 C20의 시아노알킬기, 치환 또는 비치환된 C1 내지 C20의 알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C6 내지 C30 아릴알킬기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기이거나, 또는 R, R 'are each independently hydrogen, hydroxyl, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C2 to C20 alkenyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or Unsubstituted C1 known C20 haloalkyl group, substituted or unsubstituted C1 to C20 alkylsulfonate group, substituted or unsubstituted C1 to C20 alkylsulfonyl group, substituted or unsubstituted C2 to C20 alkylamide group, Substituted or unsubstituted C3 to C20 alkyl ester group, substituted or unsubstituted C2 to C20 cyanoalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C6 to C30 aryl group, substituted Or an unsubstituted C6 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 aryloxy group, or
R, R'은 서로 연결되어 치환 또는 비치환된 C3 내지 C20의 시클로알킬기 또는 치환 또는 비치환된 C3 내지 C20의 헤테로시클로알킬기를 형성한다).R, R 'are linked to each other to form a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C3 to C20 heterocycloalkyl group).
바람직하게는 "P를 포함하는 작용기"는 P와 O를 포함하는 작용기로, 예를 들면 -P(=O)(OH)2, -O-P(=O)(OH)2, -P(=O)(OCH2CH3)2, -P(=O)(C2H4C6H5)(OCH2CH3) 등이 될 수 있고, 예를 들면 "B를 포함하는 작용기"는 B와 O를 포함하는 작용기로 예를 들면 -B(OH)2, -B(H)(CH3), -B(CH2CH3)2가 될 수 있다.Preferably "functional group comprising P" is a functional group comprising P and O, for example -P (= 0) (OH) 2 , -OP (= 0) (OH) 2 , -P (= 0) ) (OCH 2 CH 3 ) 2 , -P (= O) (C 2 H 4 C 6 H 5 ) (OCH 2 CH 3 ), and the like. For example, "functional group comprising B" The functional group containing O may be, for example, -B (OH) 2 , -B (H) (CH 3 ), -B (CH 2 CH 3 ) 2 .
패턴화된 웨이퍼 예를 들면 실리콘 웨이퍼 위에 무기막을 증착하였을 때, 유기막은 생성된 비어-홀(via-hole)을 채워주게 된다. CMP 슬러리 조성물은 증착막의 평탄화를 위하여 유기막을 충분한 연마율로 연마할 수 있어야 하고 연마면의 평탄도도 높여주어야 하여 연마 후 무기막에 잔류하는 잔류물의 제거도 쉬어야 한다. 무기막은 실리콘 산화물, 실리콘 질화물 중 하나 이상으로 형성된 막일 수 있지만, 이에 제한되지 않는다.When an inorganic film is deposited on a patterned wafer, for example a silicon wafer, the organic film fills the generated via-holes. In order to planarize the deposited film, the CMP slurry composition should be able to polish the organic film to a sufficient polishing rate and increase the flatness of the polished surface to remove the residues remaining in the inorganic film after polishing. The inorganic film may be a film formed of at least one of silicon oxide and silicon nitride, but is not limited thereto.
유기막은 유기막의 재질에 따라 단위 시간당 연마량, 연마 후 평탄도가 크게 다를 수 있다. 본 발명의 유기막 CMP 슬러리 조성물은 탄소 함량이 높은 유기막을 연마하는 조성물로서, 유기막 연마시 유기막의 단위 시간당 연마량과 평탄도를 높이고, 연마 후 무기막에 잔류하는 잔류물의 제거도 쉽게 할 수 있다. The organic film may have a large difference in polishing amount per unit time and flatness after polishing depending on the material of the organic film. The organic film CMP slurry composition of the present invention is a composition for polishing an organic film having a high carbon content. The organic film CMP slurry composition can increase the amount and flatness of the organic film per unit time when the organic film is polished, and can easily remove residues remaining in the inorganic film after polishing. have.
본 발명의 연마 대상인 유기막은 탄소 함량, 막 밀도 및 경화도가 통상의 유기막 대비 상대적으로 높아서 종래의 고분자 입자를 포함하는 유기막 CMP 슬러리 조성물로 연마할 수 없었다. 반면에 본 발명의 CMP 슬러리 조성물은 유기막을 스크래치로 인한 표면 상태의 악화없이 단위 시간당 높은 연마량으로 연마할 수 있다. 구체적으로 유기막에 대한 단위 시간당 연마량은 약 500Å/min 이상, 예를 들면 약 1,000Å/min 이상, 예를 들면 약 500 내지 5000Å/min가 될 수 있고, 상기 범위에서 공정에 적용할 수 있을 정도의 연마량을 확보할 수 있다. The organic film to be polished of the present invention has a relatively high carbon content, film density, and degree of cure compared to a conventional organic film, and thus cannot be polished with an organic film CMP slurry composition including conventional polymer particles. On the other hand, the CMP slurry composition of the present invention can polish the organic film with a high polishing amount per unit time without deteriorating the surface state due to scratching. Specifically, the amount of polishing per unit time for the organic film may be about 500 kPa / min or more, for example, about 1,000 kPa / min or more, for example, about 500 to 5000 kPa / min, and may be applied to the process in the above range. Amount of polishing can be secured.
구체예에서, 유기막은 탄소 함량이 약 50 내지 95atom% 예를 들면 약 65 내지 95atom% 또는 예를 들면 약 70 내지 92atom%, 예를 들면 약 65,66,67,68,69,70,71,72,73,74,75,76,77,78,79,80,81,82,83,84,85,86,87,88,89,90,91,92,93,94 또는 95atom%가 될 수 있고, 상기 범위에서 금속산화물 연마제로 연마시 연마량이 높고 스크래치도 발생하지 않으며 연마면의 평탄도도 높을 수 있다. 유기막은 막 밀도가 약 0.5 내지 2.5g/cm3 예를 들면 약 1.0 내지 2.0g/cm3, 예를 들면 약 1.2 내지 1.6g/cm3, 예를 들면 약 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5g/cm3이 될 수 있고, 상기 범위에서 금속산화물 연마제로 연마시 연마량이 높고 스크래치도 발생하지 않으며 연마면의 평탄도도 높을 수 있다. 유기막은 경도가 약 0.4GPa 이상, 예를 들면 약 1.0GPa 이상, 예를 들면 약 1.3GPa 이상, 예를 들면 약 1.0 내지 1.5GPa, 예를 들면 약 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5GPa이 될 수 있고, 상기 범위에서 금속산화물 연마제로 연마시 연마량이 높고 스크래치도 발생하지 않으며 연마면의 평탄도도 높을 수 있다.In an embodiment, the organic film has a carbon content of about 50 to 95 atom% such as about 65 to 95 atom% or about 70 to 92 atom%, such as about 65,66,67,68,69,70,71, 72,73,74,75,76,77,78,79,80,81,82,83,84,85,86,87,88,89,90,91,92,93,94 or 95 atom% In the above range, when polishing with a metal oxide abrasive, the polishing amount is high, scratches do not occur, and the flatness of the polishing surface may be high. The organic film has a film density of about 0.5 to 2.5 g / cm 3 , for example about 1.0 to 2.0 g / cm 3 , for example about 1.2 to 1.6 g / cm 3 , for example about 0.5, 0.6, 0.7, 0.8, 0.9 , 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5 g / cm 3 , when polishing with a metal oxide abrasive in the above range The polishing amount is high, no scratch occurs, and the flatness of the polishing surface may be high. The organic film has a hardness of about 0.4 GPa or more, for example about 1.0 GPa or more, for example about 1.3 GPa or more, for example about 1.0 to 1.5 GPa, for example about 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, It may be 1.0, 1.1, 1.2, 1.3, 1.4, 1.5GPa, and in the above range when polishing with a metal oxide abrasive, the polishing amount is high, no scratches may occur and the flatness of the polishing surface may be high.
또한, 본 발명의 연마 대상인 유기막은 산가가 실질적으로 약 0mgKOH/g이 될 수 있다. 종래의 고분자 연마제를 포함하는 유기막 CMP 슬러리 조성물로 본 발명의 연마 대상인 유기막을 연마할 경우 연마 속도가 낮아진다는 문제점이 있었다. 반면, 본 발명의 CMP 슬러리 조성물은 CMP 공정에 적용할 만한 유기막의 단위 시간당 연마량을 확보할 수 있다. 상기 "실질적으로"는 산가가 0mgKOH/g인 경우뿐만 아니라 0mgKOH/g에서 약간의 오차가 가감되는 것도 포함한다. In addition, the organic film to be polished of the present invention may have an acid value of about 0 mgKOH / g substantially. When polishing an organic film, which is a polishing target of the present invention, with an organic film CMP slurry composition including a conventional polymer abrasive, there is a problem that the polishing rate is lowered. On the other hand, the CMP slurry composition of the present invention can secure the amount of polishing per unit time of the organic film applicable to the CMP process. The term "substantially" includes not only the case where the acid value is 0 mgKOH / g but also a slight error at 0 mgKOH / g.
구체적으로, 본 발명의 연마 대상인 유기막은 치환 또는 비치환된 방향족기를 갖는 화합물을 포함하는 조성물을 무기막 위에 도포한 후 고온 예를 들면 약 200 내지 400℃에서 열경화(baking)하여 제조될 수 있다. Specifically, the organic film to be polished of the present invention may be prepared by applying a composition containing a compound having a substituted or unsubstituted aromatic group on the inorganic film and then thermosetting (baking) at a high temperature, for example, about 200 to 400 ° C. .
상기 "치환 또는 비치환된 방향족기를 갖는 화합물"은 열경화 후에도 분해되지 않아서 조성물로 형성된 유기막이 높은 탄소 함량을 나타낼 수 있도록 하는 화합물을 의미한다. 상기 비치환된 방향족기는 탄소수 6 내지 100 예를 들면 탄소수 6 내지 50의 단일 또는 융합된(fused) 다환(polycyclic) 방향족기를 의미하는데, 구체적으로 하기 화학식 1-1 내지 1-26의 단위를 포함할 수 있다:The "compound having a substituted or unsubstituted aromatic group" refers to a compound that does not decompose even after thermal curing so that the organic film formed of the composition can exhibit a high carbon content. The unsubstituted aromatic group means a single or fused polycyclic aromatic group having 6 to 100 carbon atoms, for example, 6 to 50 carbon atoms, and specifically, may include units of the following Chemical Formulas 1-1 to 1-26. Can:
<화학식 1-1><Formula 1-1>
<화학식 1-2><Formula 1-2>
<화학식 1-3><Formula 1-3>
<화학식 1-4><Formula 1-4>
<화학식 1-5><Formula 1-5>
<화학식 1-6><Formula 1-6>
<화학식 1-7><Formula 1-7>
<화학식 1-8><Formula 1-8>
<화학식 1-9><Formula 1-9>
<화학식 1-10><Formula 1-10>
<화학식 1-11><Formula 1-11>
<화학식 1-12><Formula 1-12>
<화학식 1-13><Formula 1-13>
<화학식 1-14><Formula 1-14>
<화학식 1-15><Formula 1-15>
<화학식 1-16><Formula 1-16>
<화학식 1-17><Formula 1-17>
<화학식 1-18><Formula 1-18>
<화학식 1-19><Formula 1-19>
<화학식 1-20><Formula 1-20>
<화학식 1-21><Formula 1-21>
<화학식 1-22><Formula 1-22>
<화학식 1-23><Formula 1-23>
<화학식 1-24><Formula 1-24>
<화학식 1-25><Formula 1-25>
<화학식 1-26><Formula 1-26>
(상기 화학식 1-1 내지 1-26에서, Z1 내지 Z18은 각각 독립적으로 단일 결합, 치환 또는 비치환된 C1 내지 C20 알킬렌기, 치환 또는 비치환된 C2 내지 C20 알케닐렌기, 치환 또는 비치환된 C2 내지 C20 알키닐렌기, 치환 또는 비치환된 C3 내지 C20 사이클로알킬렌기, 치환 또는 비치환된 C3 내지 C20 사이클로알케닐렌기, 치환 또는 비치환된 C6 내지 C20 아릴렌기, 치환 또는 비치환된 C2 내지 C20 헤테로아릴렌기, -(C=O)-, -NRa-, -CRbRc-, 산소(O), 황(S) 또는 이들의 조합이고, 여기서 Ra 내지 Rc는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 할로겐 원자, 치환 또는 비치환된 C6 내지 C20 아릴렌기, 치환 또는 비치환된 C2 내지 C20 헤테로아릴렌기 또는 이들의 조합이다)(In the above Chemical Formulas 1-1 to 1-26, Z 1 to Z 18 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted A substituted C2 to C20 alkynylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C3 to C20 cycloalkenylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroaryl group, - (C = O) - , -NR a -, -CR b R c - , and oxygen (O), sulfur (S), or a combination thereof, wherein R a to R c are each Independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, or a combination thereof)
이하, 치환 또는 비치환된 방향족기를 갖는 화합물을 포함하는 유기막 형성용 조성물의 실시예를 보다 상세히 설명한다.Hereinafter, the Example of the composition for organic film formation containing the compound which has a substituted or unsubstituted aromatic group is demonstrated in detail.
제 1 구체예에서, 유기막 형성용 조성물은 치환 또는 비치환된 방향족기를 갖는 화합물로 하기 화학식 2를 포함하는 물질을 포함할 수 있다:In a first embodiment, the composition for forming an organic film may be a compound having a substituted or unsubstituted aromatic group may include a material including the following formula (2):
<화학식 2><Formula 2>
(상기 화학식 2에서, n은 1≤n<190이고, In Formula 2, n is 1 ≦ n <190,
R1은 수소, 히드록시기, 할로겐 원자, 알릴기, 티오닐기, 티올기, 시아노기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C1 내지 C30 헤테로알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C1 내지 C20 알데히드기, 치환 또는 비치환된 C1 내지 C40 알킬에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합이고,R 1 is hydrogen, a hydroxy group, a halogen atom, an allyl group, thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group , Substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 hetero Cycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkenyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 hetero Arylalkyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 heteroalkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, Substituted or unsubstituted C1 to C20 aldehyde groups, substituted or unsubstituted C1 to C40 alkylether groups, substituted or unsubstituted C7 to C20 arylalkylene ether groups, substituted or unsubstituted C1 to C30 haloalkyl groups, and P A functional group, a functional group including B, or a combination thereof,
R2는 수소, 아미노기, 치환 또는 비치환된 C1 내지 C20의 알콕시기, 치환 또는 비치환된 C6 내지 C20의 아릴옥시기, 디알킬아미노기(-NRR', 여기서 R, R'은 서로 독립적으로 치환 또는 비치환된 C1 내지 C10의 알킬기 또는 치환 또는 비치환된 C6 내지 C10의 아릴기), 히드록시기, 할로겐 원자, 알릴기, 티오닐기, 티올기, 시아노기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C1 내지 C30 헤테로알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C1 내지 C20 알데히드기, 치환 또는 비치환된 C1 내지 C40 알킬에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합이고,R 2 is hydrogen, an amino group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryloxy group, a dialkylamino group (-NRR ', where R and R' are independently substituted with each other) Or unsubstituted C1 to C10 alkyl group or substituted or unsubstituted C6 to C10 aryl group), hydroxy group, halogen atom, allyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or Unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycle An alkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, Substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkenyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or Unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 heteroalkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted C1 to C40 alkylether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to A C30 haloalkyl group, a functional group comprising P, a functional group comprising B, or a combination thereof,
R3은 치환 또는 비치환된,R 3 is substituted or unsubstituted,
중 어느 하나이다).Is either one).
예를 들면, R2는 치환 또는 비치환된 C1 내지 C10의 알콕시기가 될 수 있다.For example, R 2 may be a substituted or unsubstituted C 1 to C 10 alkoxy group.
상기 화학식 2를 포함하는 물질은 유기막 조성물의 열경화 후 탄소 함량, 막 밀도 및 경도를 높일 수 있고, 이의 보다 상세한 제조 방법은 한국등록특허 제10-0866015호를 참조한다. The material including Chemical Formula 2 may increase carbon content, film density, and hardness after thermal curing of the organic film composition, and refer to Korean Patent No. 10-0866015 for a more detailed method of manufacturing the same.
제1 구체예의 조성물은 상기 화학식 2를 포함하는 물질 이외에, 가교 성분, 산 촉매 및 유기용매 중 하나 이상을 더 포함할 수 있다. 구체적으로 상기 화학식 2로 표시되는 물질 약 1 내지 20중량%, 가교 성분 약 0.1 내지 5중량%, 산 촉매 약 0.001 내지 0.05중량%, 및 유기 용매 약 75 내지 98.8중량%를 포함할 수 있다.The composition of the first embodiment may further include at least one of a crosslinking component, an acid catalyst, and an organic solvent, in addition to the material including Chemical Formula 2. Specifically, about 1 to 20 wt% of the material represented by Formula 2, about 0.1 to 5 wt% of the crosslinking component, about 0.001 to 0.05 wt% of the acid catalyst, and about 75 to 98.8 wt% of the organic solvent.
가교 성분은 멜라민 수지(구체예로 N-메톡시메틸-멜라민수지, N-부톡시메틸멜라민수지), 메틸화되거나 부틸화된 우레아 수지, 아미노 수지, 하기 화학식 3의 글리콜루릴 유도체, 하기 화학식 4의 비스에폭시 화합물, 하기 화학식 5의 멜라민 유도체 중 하나 이상을 포함할 수 있다:The crosslinking component may be a melamine resin (eg, N-methoxymethyl-melamine resin, N-butoxymethylmelamine resin), methylated or butylated urea resin, amino resin, glycoluril derivative of Formula 3, Bisepoxy compound, may include one or more of the melamine derivative of formula (5):
<화학식 3><Formula 3>
<화학식 4><Formula 4>
<화학식 5><Formula 5>
산 촉매는 p-톨루엔술폰산 모노 하이드레이트, 피리디늄 p-톨루엔 술포네이트, 2,4,4,6-테트라브로모시클로헥사디엔온, 벤조인 토실레이트, 2-니트로벤질 토실레이트, 유기술폰산의 알킬에스테르 중 하나 이상을 포함할 수 있다. 유기용매는 치환 또는 비치환된 방향족기를 갖는 화합물에 대한 충분한 용해성을 갖는 유기용매라면 특별히 한정되지 않는데, 예를 들면 프로필렌글리콜모노메틸에테르아세테이트, 사이클로헥사논, 에틸락테이트 등을 들 수 있다.Acid catalysts include p-toluenesulfonic acid monohydrate, pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, alkyl of euphonic acid It may include one or more of the esters. The organic solvent is not particularly limited as long as it is an organic solvent having sufficient solubility in a compound having a substituted or unsubstituted aromatic group, and examples thereof include propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate and the like.
제1 구체예의 유기막 형성용 조성물은 약 500 내지 4000Å의 두께로 코팅하고, 약 200 내지 400℃에서 약 10초 내지 10분 동안 열경화시켜 유기막을 형성할 수 있지만, 이에 제한되지 않는다.The composition for forming an organic film of the first embodiment may be coated with a thickness of about 500 to 4000 kPa, and thermally cured at about 200 to 400 ° C. for about 10 seconds to 10 minutes to form an organic film, but is not limited thereto.
제 2 구체예에서, 유기막 형성용 조성물은 치환 또는 비치환된 방향족기를 갖는 화합물로 하기 화학식 6으로 표시되는 물질을 포함할 수 있다: In a second embodiment, the composition for forming an organic film may be a compound having a substituted or unsubstituted aromatic group and may include a material represented by the following formula (6):
<화학식 6><Formula 6>
(상기 화학식 6에서, R4 내지 R9, X1 내지 X6은 각각 독립적으로, 수소, 히드록시기, 할로겐 원자, 알릴기, 티오닐기, 티올기, 시아노기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C1 내지 C30 헤테로알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C1 내지 C20 알데히드기, 치환 또는 비치환된 C1 내지 C40 알킬에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합이고(In Formula 6, R 4 To R 9 , X 1 To X 6 are each independently hydrogen, hydroxy group, halogen atom, allyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted Or an unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 Cycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted Or an unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkenyl group, a substituted or unsubstituted C2 Or a C30 heteroaryl group, a substituted or unsubstituted C2 to C30 heteroarylalkyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 hetero Alkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted C1 to C40 alkylether group, substituted or unsubstituted C7 to C20 arylalkylene ether group , A substituted or unsubstituted C1 to C30 haloalkyl group, a functional group including P, a functional group including B, or a combination thereof
n1 내지 n6은 각각 독립적으로 0 내지 2의 범위에 있고, 2≤ n1+n2+n3+n4+n5+n6≤6이다).n 1 to n 6 are each independently in a range of 0 to 2, and 2 ≦ n 1 + n 2 + n 3 + n 4 + n 5 + n 6 ≦ 6 ).
예를 들면, R4 내지 R9은 각각 독립적으로 치환 또는 비치환된 C1 내지 C10의 알킬기, 치환 또는 비치환된 C6 내지 C20의 아릴기, 치환 또는 비치환된 C3 내지 C20의 사이클로알킬기, 치환 또는 비치환된 C3 내지 C20의 사이클로알케닐기, P를 포함하는 작용기 또는 B를 포함하는 작용기가 될 수 있다. For example, R 4 to R 9 are each independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or It may be an unsubstituted C3 to C20 cycloalkenyl group, a functional group including P, or a functional group including B.
예를 들면, X1 내지 X6은 각각 독립적으로 수소, 히드록시기, 치환 또는 비치환된 C1 내지 C20의 알킬아민기, 아미노기, P를 포함하는 작용기, B를 포함하는 작용기가 될 수 있다.For example, X 1 to X 6 may be each independently hydrogen, a hydroxy group, a substituted or unsubstituted C 1 to C 20 alkylamine group, an amino group, a functional group including P, a functional group including B.
치환 또는 비치환된 방향족기를 갖는 화합물로 상기 화학식 2로 표시되는 물질 대신에 상기 화학식 6으로 표시되는 물질을 포함하는 것을 제외하고는 제1 구체예의 유기막 조성물과 실질적으로 동일하다. 이에, 이하에서는 상기 화학식 6으로 표시되는 물질에 대해서만 설명한다.The compound having a substituted or unsubstituted aromatic group is substantially the same as the organic film composition of the first embodiment except that the compound represented by Chemical Formula 6 is used instead of the material represented by Chemical Formula 2. Therefore, hereinafter, only the substance represented by Chemical Formula 6 will be described.
상기 화학식 6으로 표시되는 물질은 치환기의 위치가 서로 상이한 2 이상의 화합물의 혼합물일 수 있고, 짧은 파장 영역(예:약 193nm, 248nm)에서 강한 흡수를 갖는 방향족 고리를 포함하여, 특별한 촉매를 사용하지 않더라도 높은 온도에서 가교 반응이 진행되므로 촉매 특히 산에 의한 오염을 방지할 수 있고, 화학식 6의 방향족기 화합물은 평균분자량이 약 500 내지 4000g/mol이 될 수 있고, 상기 범위에서 유기막의 두께 구현 또는 양호한 박막을 형성할 수 있다.The material represented by Chemical Formula 6 may be a mixture of two or more compounds having different positions of substituents, and may include an aromatic ring having strong absorption in a short wavelength region (for example, about 193 nm and 248 nm), and thus do not use a special catalyst. If not, the crosslinking reaction may be performed at a high temperature, thereby preventing contamination by a catalyst, particularly an acid, and the aromatic group compound of Formula 6 may have an average molecular weight of about 500 to 4000 g / mol, and the thickness of the organic film may be implemented or A good thin film can be formed.
상기 화학식 6으로 표시되는 물질은 유기막 조성물의 열경화 후 탄소 함량, 막 밀도 및 경도를 높일 수 있다. 상기 화학식 6으로 표시되는 물질은 통상의 방법으로 제조될 수 있으며, 예를 들면 코로넨에 아세틸클로라이드, 벤조일클로라이드, 나프토일클로라이드, 사이클로헥산카르보닐클로라이드를 반응시키고, 환원시켜 제조될 수 있지만, 이에 제한되지 않는다. 보다 상세한 제조 방법은 한국등록특허 제10-1311942호를 참고한다.The material represented by Chemical Formula 6 may increase carbon content, film density, and hardness after thermal curing of the organic film composition. The material represented by Chemical Formula 6 may be prepared by a conventional method, for example, it may be prepared by reacting and reducing acetyl chloride, benzoyl chloride, naphthoyl chloride, cyclohexanecarbonyl chloride to coronene, but It is not limited. For more detailed manufacturing method refer to Korea Patent Registration No. 10-1311942.
제3 구체예에서, 유기막 조성물은 치환 또는 비치환된 방향족기를 갖는 화합물로 하기 (i), (ii), (iii) 중에서 선택되는 방향족기 함유 중합체를 포함할 수 있다:In a third embodiment, the organic film composition may include an aromatic group-containing polymer selected from (i), (ii) and (iii) as a compound having a substituted or unsubstituted aromatic group:
(i) 하기 화학식 7로 표시되는 화합물,(i) a compound represented by the following formula (7),
(ii) 하기 화학식 7로 표시되는 화합물과 하기 화학식 8로 표시되는 화합물과의 혼합물,(ii) a mixture of a compound represented by the following formula (7) with a compound represented by the following formula (8),
(iii) 하기 화학식 9로 표시되는 화합물.(iii) The compound represented by following formula (9).
<화학식 7><Formula 7>
<화학식 8><Formula 8>
<화학식 9><Formula 9>
(상기 화학식 7 내지 9에서, m, n은 각각 1≤n<750, 1≤m<750, 2≤m+n<1500이고,In Formulas 7 to 9, m and n are each 1 ≦ n <750, 1 ≦ m <750, and 2 ≦ m + n <1500,
R10은 치환 또는 비치환된, R 10 is substituted or unsubstituted,
중 어느 하나이고,Any one of
R11은 수소, 히드록시기, 할로겐 원자, 티오닐기, 티올기, 시아노기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C1 내지 C20 알데히드기, 치환 또는 비치환된 C1 내지 C40 알킬에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합이고,R 11 is hydrogen, a hydroxy group, a halogen atom, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or Unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, Substituted or unsubstituted C2 to C30 heterocycloalkenyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylal Groups, substituted or unsubstituted C1 to C20 alkylamine groups, substituted or unsubstituted C1 to C30 alkoxy groups, substituted or unsubstituted C6 to C30 aryloxy groups, substituted or unsubstituted C1 to C20 aldehyde groups, substituted or unsubstituted A substituted C1 to C40 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a functional group comprising P, a functional group including B, or a combination thereof ,
R12는 치환 또는 비치환된, R 12 is substituted or unsubstituted,
중 어느 하나이고,Any one of
R13은 치환 또는 비치환된,R 13 is substituted or unsubstituted,
중 어느 하나이고,Any one of
R14은 치환 또는 비치환된, R 14 is substituted or unsubstituted,
중 어느 하나이고,Any one of
R15는 치환 또는 비치환된,R 15 is substituted or unsubstituted,
중 어느 하나이고,Any one of
R10, R13, R15에서 R은 각각 독립적으로 수소, 히드록시기, 할로겐 원자, 티오닐기, 티올기, 시아노기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C1 내지 C20 알데히드기, 치환 또는 비치환된 C1 내지 C40 알킬에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합이다)R at R 10 , R 13 and R 15 are each independently hydrogen, hydroxy group, halogen atom, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or unsubstituted C1 to C30 alkyl group, substituted or Unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 Heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted Or an unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkenyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or Substituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C1 To C20 aldehyde group, substituted or unsubstituted C1 to C40 alkylether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to C30 haloalkyl group, functional group comprising P, including B Is a functional group or a combination thereof)
치환 또는 비치환된 방향족기를 갖는 화합물로 상기 화학식 2로 표시되는 물질 대신에 상기 방향족기 함유 중합체를 포함하는 것을 제외하고는 제1 구체예의 유기막 조성물과 실질적으로 동일하다. 이에, 이하에서는 방향족기 함유 중합체에 대해서만 설명한다.The compound having a substituted or unsubstituted aromatic group is substantially the same as the organic film composition of the first embodiment except that the aromatic group-containing polymer is included in place of the material represented by Chemical Formula 2. Therefore, hereinafter, only the aromatic group-containing polymer will be described.
방향족기 함유 중합체는 유기막 조성물의 열경화 후 탄소 함량, 막 밀도 및 경도를 높일 수 있고, 통상의 방법으로 제조할 수 있고, 보다 상세한 내용은 한국등록특허 제10-0908601을 참조한다.The aromatic group-containing polymer may increase carbon content, film density and hardness after thermal curing of the organic film composition, and may be prepared by a conventional method, and refer to Korean Patent No. 10-0908601 for more details.
제4 구체예에서, 유기막 조성물은 치환 또는 비치환된 방향족기를 갖는 화합물로 상기 화학식 2를 포함하는 물질; 상기 화학식 6으로 표시되는 물질; 상기 (i), (ii), (iii) 중에서 선택되는 방향족기 함유 중합체 중 2종 이상을 포함할 수 있다. 2 종 이상을 포함하는 것을 제외하고는 제1 구체예의 조성물과 실질적으로 동일하다.In a fourth embodiment, the organic film composition is a compound having a substituted or unsubstituted aromatic group material comprising the formula (2); A substance represented by Chemical Formula 6; It may contain two or more of the aromatic group-containing polymers selected from the above (i), (ii) and (iii). It is substantially the same as the composition of the first embodiment except that it contains two or more kinds.
이하, 본 발명 일 실시예의 유기막 CMP 슬러리 조성물을 설명한다.Hereinafter, an organic film CMP slurry composition of an embodiment of the present invention will be described.
본 발명 일 실시예의 유기막 CMP 슬러리 조성물은 극성 용매, 비극성 용매 중 하나 이상; 및 금속산화물 연마제를 포함하고, 산성이 될 수 있다. 그 결과, 본 발명의 연마 대상인 유기막을 스크래치 없이 높은 연마량으로 연마할 수 있고, 연마면의 평탄도를 높일 수 있다.The organic film CMP slurry composition of one embodiment of the present invention comprises at least one of a polar solvent and a nonpolar solvent; And a metal oxide abrasive, and may be acidic. As a result, the organic film to be polished of the present invention can be polished with a high polishing amount without scratching, and the flatness of the polishing surface can be increased.
극성 및/또는 비극성 용매는 탄소 함량이 높은 유기막을 금속산화물 연마제로 연마시 마찰을 줄여주는 것으로, 물 예를 들면 초순수, 유기아민, 유기알코올, 유기알코올아민, 유기에테르, 유기케톤 등이 될 수 있고, 예를 들면 초순수를 사용할 수 있다. 극성 및/또는 비극성 용매는 CMP 슬러리 조성물 중 잔량으로 포함될 수 있다. Polar and / or non-polar solvents reduce friction when polishing high-carbon organic films with metal oxide abrasives, and can be water, for example ultrapure water, organic amines, organic alcohols, organic alcohol amines, organic ethers, organic ketones, and the like. For example, ultrapure water can be used. Polar and / or nonpolar solvents may be included in the balance in the CMP slurry composition.
금속산화물 연마제는 탄소 함량, 막 밀도 및 경도가 높은 유기막을 높은 연마량으로 연마할 수 있다. 특히 본 발명의 연마 대상인 유기막 연마시 스크래치 등이 발생하지 않게 하여 연마면 평탄도를 높일 수 있었다. 구체적으로, 금속산화물 연마제는 실리카, 알루미나, 세리아, 티타니아, 지르코니아 중 하나 이상을 포함할 수 있다. 특히, 실리카는 분산 안정성이 좋은 효과가 더 있을 수 있고, 세리아는 산화제가 없거나 극히 적어도 연마 속도가 높다는 효과가 더 있을 수 있다. The metal oxide abrasive can polish the organic film having a high carbon content, film density and hardness with a high polishing amount. In particular, the polishing surface flatness could be increased by preventing scratches and the like from occurring during polishing of the organic film, which is the polishing target of the present invention. Specifically, the metal oxide abrasive may include one or more of silica, alumina, ceria, titania, zirconia. In particular, silica may have a further effect of good dispersion stability, and ceria may have a further effect of no oxidizing agent or at least extremely high polishing rate.
금속산화물 연마제는 구형의 입자로 평균 입경이 약 10 내지 150nm, 예를 들면 약 30 내지 70nm, 예를 들면 약 30, 35, 40, 45, 50, 55, 60, 65, 70nm가 될 수 있고, 상기 범위에서 본 발명의 연마 대상인 유기막에 대해 충분한 연마 속도를 낼 수 있고, 스크래치가 발생하지 않게 할 수 있으며, 평탄도를 높일 수 있다.The metal oxide abrasive may be spherical particles having an average particle diameter of about 10 to 150 nm, for example, about 30 to 70 nm, for example, about 30, 35, 40, 45, 50, 55, 60, 65, 70 nm, Within this range, it is possible to achieve a sufficient polishing rate with respect to the organic film to be polished of the present invention, prevent scratches from occurring, and increase flatness.
금속산화물 연마제는 CMP 슬러리 조성물 중 약 0.1 내지 20중량%, 예를 들면 약 0.1 내지 15중량%, 예를 들면 약 0.1 내지 5중량%, 예를 들면 약 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5중량%로 포함될 수 있고, 상기 범위에서 본 발명의 연마 대상인 유기막에 대해 충분한 연마 속도를 낼 수 있고, 스크래치가 발생하지 않게 할 수 있고, 분산안정성이 좋을 수 있다. 바람직하게는, 금속산화물 연마제의 평균 입경은 높이되 슬러리 조성물 중 함량을 낮춤으로써 유기막에 대해 향상된 연마 속도, 무기막에 대해 낮은 연마 속도를 구현할 수 있었다.The metal oxide abrasive is about 0.1 to 20% by weight, for example about 0.1 to 15% by weight, for example about 0.1 to 5% by weight, for example about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6 in the CMP slurry composition. , 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1 , 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5% by weight, the present invention in the above range A sufficient polishing rate can be given to the organic film to be polished, a scratch can be prevented from occurring, and dispersion stability can be good. Preferably, by increasing the average particle diameter of the metal oxide abrasive, but lowering the content of the slurry composition, it was possible to achieve an improved polishing rate for the organic film, a low polishing rate for the inorganic film.
CMP 슬러리 조성물은 산성이 됨으로써, 무기막에 대한 유기막의 높은 연마 선택비를 구현하는 효과가 있고, 유기막에 대한 단위 시간당 연마량을 높이고, 평탄도를 높일 수 있다. 구체적으로, CMP 슬러리 조성물은 pH가 약 6 이하, 예를 들면 약 5 이하, 예를 들면 약 1 내지 5, 예를 들면 약 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5가 될 수 있다. 예를 들면 pH 조절제를 사용함으로써 본 발명 일 실시예의 CMP 슬러리 조성물을 상술한 범위의 pH로 조절할 수 있다. pH 조절제는 무기산 예를 들면 질산, 인산, 염산, 황산 중 하나 이상을 포함할 수 있고, 유기산 예를 들면 pKa 값이 약 6 이하인 유기산으로 예를 들면 초산, 시트르산 중 하나 이상을 포함할 수 있지만 이에 제한되지 않는다.Since the CMP slurry composition is acidic, the CMP slurry composition has an effect of realizing a high polishing selectivity of the organic film with respect to the inorganic film, increasing the polishing amount per unit time with respect to the organic film, and increasing the flatness. Specifically, the CMP slurry composition has a pH of about 6 or less, for example about 5 or less, for example about 1 to 5, for example about 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, Can be 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5. For example, by using a pH adjuster, the CMP slurry composition of one embodiment of the present invention can be adjusted to the pH in the above-described range. The pH adjusting agent may include one or more of inorganic acids such as nitric acid, phosphoric acid, hydrochloric acid, and sulfuric acid, and organic acids such as organic acids having a pKa value of about 6 or less, and may include, for example, one or more of acetic acid and citric acid. It is not limited.
CMP 슬러리 조성물은 첨가제를 더 포함할 수도 있다. 예를 들면, CMP 슬러리 조성물은 첨가제로 연마 촉진제를 더 포함할 수 있다. 연마촉진제를 더 포함함으로써, 무기막에 대한 연마 속도를 억제하여 무기막에 대한 연마선택비를 높일 수 있다. 연마촉진제는 유기산 예를 들면 말산, 시트르산, 포름산, 글루타르산, 옥살산, 프탈산, 숙신산, 타르타르산, 말레산, 말론산 중 하나 이상을 포함할 수 있다. 연마촉진제는 CMP 슬러리 조성물 중 약 0.02 내지 0.5중량%로 포함될 수 있고, 상기 범위에서 연마속도, 슬러리의 분산안정성, 유기계 탄소막의 표면특성에 악영향이 없을 수 있다.The CMP slurry composition may further comprise an additive. For example, the CMP slurry composition may further include a polishing accelerator as an additive. By further including the polishing promoter, the polishing rate for the inorganic film can be suppressed to increase the polishing selectivity for the inorganic film. The abrasive promoter may comprise one or more of organic acids such as malic acid, citric acid, formic acid, glutaric acid, oxalic acid, phthalic acid, succinic acid, tartaric acid, maleic acid, malonic acid. The polishing accelerator may be included in about 0.02 to 0.5% by weight of the CMP slurry composition, and may have no adverse effect on the polishing rate, the dispersion stability of the slurry, and the surface properties of the organic carbon film in the above range.
CMP 슬러리 조성물은 pH를 산성으로 만들기 위해 상술한 pH 조절제를 더 포함할 수 있다. pH 조절제는 CMP 슬러리 조성물 중 전체 조성물의 pH를 적절한 선에서 맞출 수 있도록 포함되어 무기막에 대한 연마 선택비를 더욱 높일 수 있다.The CMP slurry composition may further comprise the pH adjuster described above to make the pH acidic. The pH adjusting agent may be included to adjust the pH of the whole composition in the CMP slurry composition at an appropriate line to further increase the polishing selectivity for the inorganic film.
이하, 본 발명 다른 실시예의 유기막 CMP 슬러리 조성물을 설명한다.Hereinafter, the organic film CMP slurry composition of another embodiment of the present invention will be described.
본 발명 다른 실시예의 유기막 CMP 슬러리 조성물은 극성 및/또는 비극성 용매, 금속산화물 연마제, 및 산화제를 포함하고, 산성이 될 수 있다. 본 발명 다른 실시예의 유기막 CMP 슬러리 조성물은 본 발명 일 실시예의 조성물 대비 산화제를 더 포함함으로써, 무기막에 대한 유기막의 연마 선택비를 더 높이고, 유기막에 대한 연마속도를 더 높이고, 연마면의 평탄도를 높이는 효과가 더 있을 수 있다. 산화제를 더 포함하는 점을 제외하고는 본 발명 일 실시예의 유기막 CMP 슬러리 조성물과 실질적으로 동일하다. 이에, 이하에서는 산화제에서만 더 설명한다.The organic film CMP slurry composition of another embodiment of the present invention includes a polar and / or nonpolar solvent, a metal oxide abrasive, and an oxidizing agent, and may be acidic. The organic film CMP slurry composition of another embodiment of the present invention further includes an oxidizing agent as compared to the composition of the embodiment of the present invention, thereby increasing the polishing selectivity of the organic film to the inorganic film, increasing the polishing rate to the organic film, and There may be further effects of increasing the flatness. Except that it further comprises an oxidizing agent is substantially the same as the organic film CMP slurry composition of one embodiment of the present invention. Therefore, hereinafter, only the oxidant will be described further.
산화제는 탄소 함량, 막 밀도 및 경화도가 높은 유기계 탄소막이 연마가 잘 되도록 하기 위해 유기막의 표면층을 산화시켜 유기막의 연마가 용이하도록 하고, 연마에 의해 무기막이 노출될 때 유기막의 표면을 고르게 하여 연마 이후에도 표면 거칠기(roughness)가 좋도록 할 수 있다. 또한, 무기막에 존재하는 유기막의 잔류물이 쉽게 제거되도록 하여 보다 균일한 연마가 되도록 할 수 있다.The oxidizing agent oxidizes the surface layer of the organic film to facilitate polishing of the organic carbon film having a high carbon content, film density, and curing degree, and facilitates polishing of the organic film, and evenly polishes the surface of the organic film when the inorganic film is exposed by polishing. The surface roughness can be made good. In addition, the residue of the organic film present in the inorganic film can be easily removed to allow a more uniform polishing.
구체적으로, 산화제는 다가의 산화상태를 갖는 금속염, 전이금속의 킬레이트 화합물 중 하나 이상을 포함할 수 있다. 상기 "다가"는 2가 이상, 예를 들면 3가 이상, 예를 들면 4가 이상을 의미한다.Specifically, the oxidizing agent may include at least one of a metal salt having a multivalent oxidation state and a chelate compound of a transition metal. "Multivalent" means divalent or more, for example trivalent or more, for example tetravalent or more.
다가의 산화상태를 갖는 금속염은 유기막에 대한 연마 속도를 높이고, 무기막에 대한 연마 속도를 낮출 수 있다. 금속염은 전이금속, 란탄족 원소 등의 금속을 포함할 수 있고, 추가로 할로겐, 암모늄, 니트레이트 등을 포함할 수 있다. 구체적으로, 금속염은 세릭 암모늄염, 페릭 할로겐염, 페릭 니트레이트염 등을 포함할 수 있고, 예를 들면 세릭암모늄니트레이트, 페릭 니트레이트, 페릭 클로라이드 등을 포함할 수 있다.Metal salts having a polyvalent oxidation state can increase the polishing rate for the organic film and lower the polishing rate for the inorganic film. The metal salt may include a metal such as a transition metal, a lanthanide element, and may further include halogen, ammonium, nitrate, or the like. Specifically, the metal salt may include ceric ammonium salt, ferric halogen salt, ferric nitrate salt, and the like, and may include, for example, ceric ammonium nitrate, ferric nitrate, ferric chloride, and the like.
전이금속의 킬레이트 화합물은 유기막에 대한 연마 속도를 높이고, 무기막에 대한 연마 속도를 낮출 수 있다. The chelating compound of the transition metal can increase the polishing rate for the organic film and lower the polishing rate for the inorganic film.
전이금속의 킬레이트 화합물에서, 전이금속은 주기율표 3족 내지 12족의 통상의 알려진 전이금속을 포함하는데, 예를 들면 철, 구리, 망간 또는 크롬이 될 수 있다. 킬레이트는 옥살산, 아미노-치환된 카르복시산(예: 이미노디아세트산, 에틸렌디아민디숙신산, 이미노디숙신산, 에틸렌디아민테트라아세트산, 니트릴로트리아세트산과 같은 아미노폴리카르복실레이트, 글리신과 같은 알파-아미노산, 베타-아미노산), 수산기 치환된 카르복시산(예:글리콜산, 락트산, 또한, 말산, 시트르산, 타르타르산과 같은 수신가 포함 폴리카르복시산), 포스포노카르복시산, 아미노포스폰산; 이들의 조합을 포함할 수 있다. 예를 들면, 전이금속의 킬레이트 화합물은 프로필렌디아민테트라아세트산-Fe 등을 포함하는 Fe 포함 화합물, 프로필렌디아민테트라아세트산-Mn 등을 포함하는 Mn 포함 화합물 중 하나 이상을 포함할 수 있지만 이에 제한되지 않는다.In chelating compounds of transition metals, the transition metals include conventionally known transition metals of groups 3 to 12 of the periodic table, which may be iron, copper, manganese or chromium, for example. Chelates are oxalic acid, amino-substituted carboxylic acids (e.g., iminodiacetic acid, ethylenediaminedisuccinic acid, iminodisuccinic acid, aminopolycarboxylates such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, alpha-amino acids such as glycine, beta- Amino acids), hydroxyl-substituted carboxylic acids (eg, polycarboxylic acids including recipients such as glycolic acid, lactic acid, malic acid, citric acid, tartaric acid), phosphonocarboxylic acids, aminophosphonic acids; Combinations thereof. For example, the chelating compound of the transition metal may include, but is not limited to, one or more of Fe-containing compounds including propylenediaminetetraacetic acid-Fe and the like, Mn-containing compounds including propylenediaminetetraacetic acid-Mn and the like.
산화제는 CMP 슬러리 조성물 중 약 0.001 내지 15중량%, 예를 들면 약 0.01 내지 5중량%, 예를 들면 약 0.05 내지 3중량%, 예를 들면 약 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.8, 0.85, 0.9, 0.95, 1, 1.5, 2, 2.5, 3중량%로 포함될 수 있고, 상기 범위에서 유기막에 대한 적절한 에칭성을 유지할 수 있다. CMP 슬러리 조성물은 산성이 됨으로써 산화제의 안정성을 높여 유기막에 대한 단위시간당 연마량을 높이고, 연마면의 평탄도를 좋게 하고, 무기막에 대한 연마 선택비를 높일 수 있다. The oxidant is about 0.001 to 15% by weight, for example about 0.01 to 5% by weight, for example about 0.05 to 3% by weight, for example about 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35 in the CMP slurry composition , 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.8, 0.85, 0.9, 0.95, 1, 1.5, 2, 2.5, 3 wt%, and the proper etching property for the organic film in the above range I can keep it. As the CMP slurry composition becomes acidic, the stability of the oxidant may be increased to increase the polishing amount per unit time for the organic film, to improve the flatness of the polishing surface, and to increase the polishing selectivity for the inorganic film.
이하, 본 발명의 유기막 연마 방법을 설명한다. Hereinafter, the organic film polishing method of the present invention will be described.
본 발명의 유기막 연마 방법은 유기막 CMP 슬러리 조성물을 사용하여 탄소함량, 막밀도 및 경화도가 높은 유기막을 연마하는 단계를 포함하고, 유기막 CMP 슬러리 조성물은 본 발명 실시예의 유기막 CMP 슬러리 조성물을 포함할 수 있다. 이하, 도 1의 (a)를 참조하면, 도 1의 (a)는 유기막 연마 전 실리콘 웨이퍼, 무기막, 유기계 탄소막의 적층 상태를 나타낸 것으로, 실리콘 웨이퍼(100)가 음각으로 패턴화되어 국부적으로 오목부가 형성되고, 실리콘 웨이퍼(100) 위에 무기막(110)을 증착하고, 무기막 위에 유기계 탄소막(120)을 도포하고 200 내지 400℃에서 열경화시켜 제조한다. 도 1의 (a)에서 T는 가상의 연마 정지선을 나타낸다. 도 1의 (a)의 유기막 위에 유기막 CMP 슬러리 조성물을 도포하고 연마패드를 설치한 후 실리콘 웨이퍼(100)을 회전시킴으로써 연마하게 되고, 연마 정지선(T)에 도달할 때까지 연마하여 도 1의 (b)의 연마 정지선(T)까지 연마한다.The organic film polishing method of the present invention includes polishing an organic film having a high carbon content, a film density, and a high degree of curing by using an organic film CMP slurry composition, wherein the organic film CMP slurry composition comprises the organic film CMP slurry composition according to an embodiment of the present invention. It may include. Hereinafter, referring to FIG. 1A, FIG. 1A illustrates a lamination state of a silicon wafer, an inorganic film, and an organic carbon film before polishing an organic film, and the silicon wafer 100 is intaglio patterned locally. The concave portion is formed, and the inorganic film 110 is deposited on the silicon wafer 100, the organic carbon film 120 is coated on the inorganic film, and manufactured by thermal curing at 200 to 400 ° C. In FIG. 1A, T represents an imaginary polishing stop line. After coating the organic film CMP slurry composition on the organic film of FIG. 1A and installing the polishing pad, the silicon wafer 100 is rotated and polished, and polished until the polishing stop line T is reached. Polish to the polishing stop line T of (b).
이하 실시예를 들어 본 발명을 보다 구체적으로 설명하나 하기 실시예들은 단지 설명을 위한 것으로서 본 발명의 보호 범위를 제한하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are merely illustrative and are not intended to limit the protection scope of the present invention.
제조예 1Preparation Example 1
온도계, 콘덴서, 기계교반기, 적가 깔때기를 구비한 2000ml 3구 플라스크를 준비한 후 140℃의 오일욕조속에 담궜다. 가열과 자석에 의한 교반을 핫플레이트 위에서 행하였으며 콘덴서의 냉각수 온도는 40℃로 고정하였다. 1mol의 1-메톡시피렌 220g을 반응기에 가하고, 1.0mol의 1,4-비스메톡시메틸벤젠 138g을 가한 후 656g의 프로필렌글리콜모노메틸에테르아세테이트에 녹였다. 그후 0.03mol의 디에틸설페이트 4.6g을 첨가하였다. 반응기의 온도를 130℃로 유지하였다. 중합이 진행되는 동안 일정 시간 간격으로 분자량을 측정하여 반응완료시점을 결정하였다. 이때 분자량을 측정하기 위한 샘플은 1g의 반응물을 채취하여 상온으로 급랭시킨 후 그 중 0.02g을 취하여 용매인 테트라히드로푸란을 사용하여 고형분이 4중량%가 되도록 희석시켜 준비하였다. 결정된 반응완료시점에서 반응 종결을 위해 중화제로 0.03mol의 트리에탄올아민 4.48g을 반응기에 첨가하고 교반하였다. 그 후 반응물을 상온으로 서서히 냉각하였다. 상기 반응물을 500g의 프로필렌글리콜모노메틸에테르아세테이트를 이용하여 희석하였다. 그 후 용매를 2000ml의 분리깔때기에 가하였다. 90:10 g/g 비의 메탄올:에틸렌글리콜 혼합물을 4kg 준비하였다. 상기 합성된 고분자 용액을 격렬한 교반 하에서 상기 알콜 혼합물에 적하하였다. 결과물인 고분자는 플라스크 바닥면에 수집되었고, 상등액은 별도로 보관하였다. 상등액을 제거한 후 60℃에서 10분 동안 감압하 회전 증발에 의해 최종 반응물의 메탄올을 제거하였다.A 2000 ml three-necked flask equipped with a thermometer, a condenser, a mechanical stirrer, and a dropping funnel was prepared, and then immersed in an oil bath at 140 ° C. Heating and stirring by magnets were performed on a hotplate and the cooling water temperature of the condenser was fixed at 40 ° C. 220 g of 1 mol of 1-methoxypyrene was added to the reactor, and 138 g of 1.0 mol of 1,4-bismethoxymethylbenzene was added and then dissolved in 656 g of propylene glycol monomethyl ether acetate. Then 4.6 g of 0.03 mol of diethylsulfate were added. The temperature of the reactor was maintained at 130 ° C. During the polymerization, the molecular weight was measured at regular time intervals to determine the completion time of the reaction. At this time, the sample for measuring the molecular weight was prepared by diluting 1 g of the reactant, quenching to room temperature, 0.02 g of the sample was diluted to 4% by weight using tetrahydrofuran as a solvent. At the completion of the reaction, 0.03 mol of triethanolamine 4.48 g was added to the reactor as a neutralizing agent and terminated. The reaction was then slowly cooled to room temperature. The reaction was diluted with 500 g of propylene glycol monomethyl ether acetate. The solvent was then added to a 2000 ml separatory funnel. 4 kg of a methanol: ethylene glycol mixture in a 90:10 g / g ratio were prepared. The synthesized polymer solution was added dropwise to the alcohol mixture under vigorous stirring. The resulting polymer was collected at the bottom of the flask and the supernatant was stored separately. After removing the supernatant, methanol of the final reaction product was removed by rotary evaporation at 60 ° C. under reduced pressure for 10 minutes.
얻어진 공중합체의 분자량 및 분산도를 테트라하이드로푸란 하에서 GPC에 의해 측정한 결과 중량평균분자량 4000 분산도 2.3의 하기 화학식 10의 단위를 포함하는 고분자를 얻었다.The molecular weight and the dispersity of the obtained copolymer were measured by GPC under tetrahydrofuran, and as a result, a polymer containing a unit represented by the following Chemical Formula 10 having a weight average molecular weight of 4000 dispersion of 2.3 was obtained.
<화학식 10><Formula 10>
(평균 n=11, Me는 메틸기)(Average n = 11, Me is methyl group)
상기에서 제조한 고분자 0.8g, 상기 화학식 3의 가교제 0.2g(Powderlink 1174, Cytec Industries Inc)과 피리디늄 p-톨루엔술포네이트 2mg을 프로필렌글리콜모노메틸에테르아세테이트 9g에 넣어서 녹인 후 여과하여 유기막 형성용 조성물을 제조하였다.0.8 g of the polymer prepared above, 0.2 g of a crosslinking agent of Formula 3 (Powderlink 1174, Cytec Industries Inc) and 2 mg of pyridinium p-toluenesulfonate were dissolved in 9 g of propylene glycol monomethyl ether acetate, and then filtered to form an organic film. The composition was prepared.
제조예 2Preparation Example 2
기계교반기, 냉각관, 2L의 4구 플라스크에 코로넨 30.1g(0.1mol), 아세틸클로라이드 47.1g(0.6mol), 트리클로로알루미늄 79.8g(0.6mol)을 1000g의 톨루엔에 녹인 용액을 담고 교반기로 교반하여 10시간 반응을 실시한 후 반응을 종료하였다. 반응종료 후 물을 사용하여 트리클로로알루미늄을 제거한 후 얻어진 화합물에 수소화붕소나트륨 37.83g(1.0mol)을 넣어준 후 17시간 반응을 실시하였다. 반응 종료 후 물/메탄올 혼합물을 사용하여 반응 부수물을 제거하였고, 하기 화학식 11로 표시되는 화합물(평균분자량:530g/mol, 1≤n1+n2+n3+n4+n5+n6≤6)을 얻었다.A mechanical stirrer, a cooling tube, a 2 L four-necked flask containing 30.1 g (0.1 mol) of coronene, 47.1 g (0.6 mol) of acetyl chloride, and 79.8 g (0.6 mol) of trichloroaluminum were dissolved in 1000 g of toluene. The reaction was terminated after stirring for 10 hours. After completion of the reaction, after removing trichloroaluminum with water, 37.83 g (1.0 mol) of sodium borohydride was added to the obtained compound, and the reaction was carried out for 17 hours. After the reaction was completed, the reaction by-products were removed using a water / methanol mixture to obtain a compound represented by the following formula (11) (average molecular weight: 530 g / mol, 1 ≦ n1 + n2 + n3 + n4 + n5 + n6 ≦ 6). .
<화학식 11><Formula 11>
얻은 화학식 11로 표시되는 화합물 0.8g을 프로필렌글리콜모노메틸에테르아세테이트 9g에 넣어서 녹인 후 여과하여 유기막 형성용 조성물을 제조하였다.0.8 g of the compound represented by Formula 11 was dissolved in 9 g of propylene glycol monomethyl ether acetate, and then filtered to prepare a composition for forming an organic film.
실시예 1 내지 9Examples 1-9
표면에 음각 패턴이 형성된 패턴 웨이퍼 상에 연마 정지막으로 5000Å 두께의 실리카막을 증착하고, 실리카막 표면에 형성된 음각 패턴을 충진하기 위하여 2650Å 두께의 유기막을 형성하였다. 유기막은 제조예 1의 유기막 형성용 조성물을 실리카막 위에 도포하고, 400℃에서 열경화시켜 제조하였다.A 5000 mm thick silica film was deposited on the pattern wafer having the negative pattern formed on the surface thereof, and an organic film of 2650 mm thick was formed to fill the negative pattern formed on the surface of the silica film. The organic film was prepared by applying the composition for forming an organic film of Preparation Example 1 onto a silica film and thermosetting at 400 ° C.
제조예 1의 유기막 형성용 조성물을 도포하고 400℃에서 120초동안 열경화시켜 제조된 두께 4700 내지 4800Å의 시편에 대해 Nanoindentor(Hysitron TI750 Ubi)를 사용하여 경도를 측정하였다. Nanoindentor의 팁이 시편에 5초 동안 들어가고(loading), 2초 동안 머무른 후(holding) 5초 동안 빠져나오는(unloading) 방법으로 측정하였고, 경도는 0.9GPa이 되었다. 동일 시편에 대해 원소분석기 (EA1112, Thermo)를 사용하여 탄소 함량을 측정하였다. 구체적으로 정확한 양의 시료를 O2 공존하에서 연소시켜 탄소 함량을 측정하였고, 탄소 함량은 72atm%이었다. 동일 시편에 대해 XRR(X-RAY REFLECTIVITY) 장치(X'Pert PRO, PANalytical)를 사용하여 막 밀도를 측정하였다. 구체적으로 X선을 조사시켜 나온 회절 패턴을 기존에 알고 있는 회절 패턴과 비교하여 측정하였고, 막밀도는 1.4g/cm3이었다. 동일 시편에 대해 산가를 측정하였고, 산가는 0mgKOH/g이었다. The hardness was measured using a Nanoindentor (Hysitron TI750 Ubi) for the specimen of the thickness of 4700 ~ 4800 Å prepared by coating the composition for forming an organic film of Preparation Example 1 and thermosetting at 400 ℃ for 120 seconds. The tip of the nanoindentor was measured by loading the specimen for 5 seconds, holding for 2 seconds and then unloading for 5 seconds, and the hardness was 0.9 GPa. The carbon content was measured using an elemental analyzer (EA1112, Thermo) on the same specimen. Specifically, the exact amount of the sample was burned in O 2 coexistence to measure the carbon content, the carbon content was 72atm%. Membrane density was measured on the same specimen using an X-RAY REFLECTIVITY (XRR) instrument (X'Pert PRO, PANalytical). Specifically, the diffraction pattern irradiated with X-rays was measured by comparing with a known diffraction pattern, and the film density was 1.4 g / cm 3 . The acid value was measured for the same specimen, and the acid value was 0 mg KOH / g.
초순수 및 하기 표 1의 성분을 포함하는 CMP 슬러리 조성물을 제조하고, 하기의 연마 조건으로 연마하였다.A CMP slurry composition comprising ultrapure water and the components of Table 1 below was prepared and polished under the following polishing conditions.
실시예 10 내지 18Examples 10 to 18
표면에 음각 패턴이 형성된 패턴 웨이퍼 상에 연마 정지막으로 5000Å 두께의 실리카막을 증착하고, 실리카막 표면에 형성된 음각 패턴을 충진하기 위하여 2650Å 두께의 유기막을 형성하였다. 유기막은 제조예 2의 유기막 형성용 조성물을 실리카막 위에 도포하고, 400℃에서 열경화시켜 제조하였다.A 5000 mm thick silica film was deposited on the pattern wafer having the negative pattern formed on the surface thereof, and an organic film of 2650 mm thick was formed to fill the negative pattern formed on the surface of the silica film. The organic film was prepared by applying the composition for forming an organic film of Preparation Example 2 onto a silica film and thermosetting at 400 ° C.
제조예 2의 유기막 형성용 조성물을 도포하고 400℃에서 120초동안 열경화시켜 제조된 두께 4700 내지 4800Å의 시편을 제조하였다. 실시예 1과 동일 방법으로 경도, 탄소 함량, 막밀도, 산가를 측정하였다. 경도는 1.5GPa, 탄소 함량은 80atm%, 막 밀도는 1.7g/cm3, 산가는 0mgKOH/g이었다. The composition for forming an organic film of Preparation Example 2 was applied and thermally cured at 400 ° C. for 120 seconds to prepare a specimen having a thickness of 4700 to 4800 mm 3. Hardness, carbon content, film density, and acid value were measured in the same manner as in Example 1. The hardness was 1.5 GPa, the carbon content was 80 atm%, the film density was 1.7 g / cm 3 , and the acid value was 0 mg KOH / g.
초순수 및 하기 표 2의 성분을 포함하는 CMP 슬러리 조성물을 제조하고, 하기의 연마 조건으로 연마하였다.A CMP slurry composition comprising ultrapure water and the components of Table 2 below was prepared and polished under the following polishing conditions.
비교예 1 내지 3Comparative Examples 1 to 3
실시예 1에서, 하기 표 1의 조성을 갖는 CMP 슬러리 조성물을 사용한 것을 제외하고는 동일한 방법으로 실시하였다.In Example 1, the same procedure was followed except that the CMP slurry composition having the composition of Table 1 was used.
비교예 4 내지 6Comparative Examples 4 to 6
실시예 2에서, 하기 표 2의 조성을 갖는 CMP 슬러리 조성물을 사용한 것을 제외하고는 동일한 방법으로 실시하였다.In Example 2, the same procedure was followed except that the CMP slurry composition having the composition of Table 2 was used.
(1)CMP 슬러리 조성물 각 성분의 사양(1) Specification of each component of CMP slurry composition
(A)금속산화물 연마제 : (a1) 평균입경이 60㎚의 세리아(SOLVAY社), (a2) 평균입경이 35㎚의 콜로이달 실리카(Evonic社)(A) Metal oxide abrasive: (a1) Ceria (SOLVAY company) with an average particle diameter of 60 nm, (a2) Colloidal silica (Evonic company) with an average particle diameter of 35 nm
(B)산화제:(b1)세릭암모늄니트레이트(삼전순약社), (b2)페릭니트레이트(JUNSEI社), (b3)과산화수소(동우화인켐社), (b4)암모늄 퍼설페이트(대정화금社)(B) Oxidizing agent: (b1) Ceric ammonium nitrate (Samjeon Pure Chemical Co., Ltd.), (b2) Ferric nitrate (JUNSEI Co.), (b3) Hydrogen peroxide (Dongwoo Fine Chem Co.), (b4) Ammonium persulfate社)
(C)pH 조절제:수산화칼륨(삼전순약社)(C) pH regulator: potassium hydroxide (Samjeon Pure Chemical Co., Ltd.)
(D)연마촉진제:포름산(대정화금社)(D) Polishing accelerator: Formic acid (Daejunghwa Gold Co., Ltd.)
*표 1과 표 2 중 성분의 단위는 중량%이다.* The unit of component in Table 1 and Table 2 is weight%.
(2)연마 조건, 연마량 및 연마 평탄도(2) polishing conditions, polishing amount and polishing flatness
연마 패드로는 FUJIBO社의 H0800 CMP 패드를 사용하였다. 어플라이드머티리얼(Applied Materials; AMAT)社의 200mm MIRRA 장비를 사용하여 하강압력 1.0psi, 슬러리 유속 200mL/분, 정반(table)과 스핀들(spindle) 속도를 모두 90rpm으로 하여 1분간 연마를 수행한 후 연마량을 측정하여 하기 표 1과 2에 나타내었다. 연마면 평탄도는 CMP 슬러리 조성물이 무기막 대비 유기막에 대한 연마를 균형있게 하였는지 여부를 평가하는 것으로서, 상기와 같이 연마를 수행한 후 연마면에 대해 박막 두께 측정기(ST4000, K-MAC)을 사용하여 연마막의 두께(단위:Å)를 측정하고, 측정된 두께로부터 표준편차를 구한 값이다.FUJIBO's H0800 CMP pad was used as the polishing pad. Using Applied Materials (AMAT) 200mm MIRRA equipment, polishing was performed for 1 minute at a lower pressure of 1.0 psi, a slurry flow rate of 200 mL / minute, and a table and spindle speed of 90 rpm. The amount was measured and shown in Tables 1 and 2 below. Polishing surface flatness is to evaluate whether the CMP slurry composition has balanced the polishing on the organic film compared to the inorganic film, and after performing the polishing as described above, a thin film thickness meter (ST4000, K-MAC) is applied to the polishing surface. It is a value obtained by measuring the thickness (unit: mm) of the polishing film, and calculating the standard deviation from the measured thickness.
표 1
Table 1
| 실시예 | 비교예 | ||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 1 | 2 | 3 | ||
| (A)연마제 | (a1) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| (B)산화제 | (b1) | - | 0.4 | 0.4 | 2.5 | 0.05 | 2.5 | - | - | - | - | - | 0.4 |
| (b2) | - | - | - | - | - | - | 0.4 | 2.5 | 0.05 | - | - | - | |
| (b3) | - | - | - | - | - | - | - | - | - | 3 | - | - | |
| (b4) | - | - | - | - | - | - | - | - | - | - | 0.5 | - | |
| (C)pH 조절제 | - | - | - | - | - | - | - | - | - | - | - | 0.3 | |
| 슬러리 pH값 | 4.5 | 1.8 | 1.9 | 1.3 | 1.9 | 1.4 | 2.1 | 1.4 | 2.6 | 8.2 | 10.3 | 7 | |
| 유기막 연마량(Å/min) | 1000 | 1600 | 2000 | 1400 | 1500 | 1100 | 1900 | 1300 | 1400 | 42 | 100 | 30 | |
| 연마면 평탄도 | 23 | 12 | 11 | 10 | 15 | 12 | 16 | 12 | 14 | 90 | 140 | 80 | |
| Example | Comparative example | ||||||||||||
| One | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | One | 2 | 3 | ||
| (A) Polishing agent | (a1) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| (B) oxidizing agent | (b1) | - | 0.4 | 0.4 | 2.5 | 0.05 | 2.5 | - | - | - | - | - | 0.4 |
| (b2) | - | - | - | - | - | - | 0.4 | 2.5 | 0.05 | - | - | - | |
| (b3) | - | - | - | - | - | - | - | - | - | 3 | - | - | |
| (b4) | - | - | - | - | - | - | - | - | - | - | 0.5 | - | |
| (C) pH regulator | - | - | - | - | - | - | - | - | - | - | - | 0.3 | |
| Slurry pH value | 4.5 | 1.8 | 1.9 | 1.3 | 1.9 | 1.4 | 2.1 | 1.4 | 2.6 | 8.2 | 10.3 | 7 | |
| Organic film polishing amount (연마 / min) | 1000 | 1600 | 2000 | 1400 | 1500 | 1100 | 1900 | 1300 | 1400 | 42 | 100 | 30 | |
| Polished Surface Flatness | 23 | 12 | 11 | 10 | 15 | 12 | 16 | 12 | 14 | 90 | 140 | 80 | |
표 2
TABLE 2
| 실시예 | 비교예 | ||||||||||||
| 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 4 | 5 | 6 | ||
| (A)연마제 | (a2) | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| (B)산화제 | (b1) | 0.4 | 0.4 | 2.5 | 0.05 | 2.5 | - | - | - | 0.4 | - | - | 0.4 |
| (b2) | - | - | - | - | - | 0.4 | 2.5 | 0.05 | - | - | - | - | |
| (b3) | - | - | - | - | - | - | - | - | - | 3 | - | - | |
| (b4) | - | - | - | - | - | - | - | - | - | - | 0.5 | - | |
| (C)pH 조절제 | - | - | - | - | - | - | - | - | - | - | - | 0.3 | |
| (D)연마 촉진제 | - | - | - | - | - | - | - | - | 0.4 | - | - | - | |
| 슬러리 pH값 | 1.7 | 1.7 | 1.2 | 2.0 | 1.2 | 2.2 | 1.3 | 2.5 | 1.8 | 8 | 10 | 8 | |
| 유기막 연마량(Å/min) | 1500 | 1900 | 1300 | 1200 | 1000 | 1800 | 1100 | 1200 | 2500 | 10 | 10 | 5 | |
| 연마면 평탄도 | 10 | 7 | 6 | 2 | 8 | 5 | 3 | 2 | 1 | 70 | 90 | 60 | |
| Example | Comparative example | ||||||||||||
| 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 4 | 5 | 6 | ||
| (A) Polishing agent | (a2) | One | One | One | One | One | One | One | One | One | One | One | One |
| (B) oxidizing agent | (b1) | 0.4 | 0.4 | 2.5 | 0.05 | 2.5 | - | - | - | 0.4 | - | - | 0.4 |
| (b2) | - | - | - | - | - | 0.4 | 2.5 | 0.05 | - | - | - | - | |
| (b3) | - | - | - | - | - | - | - | - | - | 3 | - | - | |
| (b4) | - | - | - | - | - | - | - | - | - | - | 0.5 | - | |
| (C) pH regulator | - | - | - | - | - | - | - | - | - | - | - | 0.3 | |
| (D) Polishing accelerator | - | - | - | - | - | - | - | - | 0.4 | - | - | - | |
| Slurry pH value | 1.7 | 1.7 | 1.2 | 2.0 | 1.2 | 2.2 | 1.3 | 2.5 | 1.8 | 8 | 10 | 8 | |
| Organic film polishing amount (연마 / min) | 1500 | 1900 | 1300 | 1200 | 1000 | 1800 | 1100 | 1200 | 2500 | 10 | 10 | 5 | |
| Polished Surface Flatness | 10 | 7 | 6 | 2 | 8 | 5 | 3 | 2 | One | 70 | 90 | 60 | |
*연마면 평탄도(uniformity) : 낮을수록 우수* Uniformity if polished: the lower the better
상기 표 1 내지 2에서 나타난 바와 같이, 본 발명의 유기막 CMP 슬러리 조성물은 탄소 함량, 막 밀도 및 경도가 높은 유기막에 대해 단위 시간당 연마량이 높고, 연마면 평탄도가 높음을 확인하였다. 또한, 실시예 2 내지 18은 실시예 1 대비 특정 산화제를 더 포함함으로써 탄소 함량, 막밀도 및 경도가 높은 유기막에 대해 연마 속도도 더 높이거나, 연마면 평탄도를 더 높임을 확인하였다.As shown in Tables 1 to 2, it was confirmed that the organic film CMP slurry composition of the present invention has a high polishing amount per unit time and a high polishing surface flatness for the organic film having a high carbon content, film density, and hardness. In addition, Examples 2 to 18 further include a specific oxidizing agent as compared to Example 1, thereby confirming that the polishing rate is higher or the polishing surface flatness is higher for the organic film having a higher carbon content, film density, and hardness.
따라서, 본 발명은 탄소 함량, 막 밀도 및 경도가 높은 유기막에 대해 연마 효과가 우수한 유기막 CMP 슬러리 조성물을 제공하였다. 본 발명은 탄소 함량, 막 밀도 및 경도가 높은 유기막에 대해 연마 후 연마면 평탄도가 좋고, 연마 정지막 층에 존재하는 유기막 물질의 잔류물(residue)을 쉽게 제거할 수 있으므로 보다 균일한 연마가 가능한 유기막 CMP 슬러리 조성물을 제공하였다.Accordingly, the present invention provides an organic film CMP slurry composition having excellent polishing effect on an organic film having high carbon content, film density, and hardness. The present invention provides a more uniform surface after polishing for organic films having high carbon content, film density, and hardness, and can more easily remove residues of organic film materials present in the polishing stop film layer. An organic film CMP slurry composition capable of polishing was provided.
반면에, 금속산화물 연마제를 포함하더라도 산성이 아닌 pH를 갖는 비교예는 탄소 함량, 막밀도 및 경도가 높은 유기막의 연마 속도가 실시예 대비 현저하게 낮거나, 연마면 평탄도가 더 낮음을 확인하였다.On the other hand, the comparative example having a non-acidic pH even when the metal oxide abrasive was included, it was confirmed that the polishing rate of the organic film having a high carbon content, film density and hardness is significantly lower than the embodiment, or the polishing surface flatness is lower .
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
Claims (21)
- 극성 용매, 비극성 용매 중 하나 이상; 및 금속산화물 연마제를 포함하고, 산성이고, 탄소 함량이 약 50 내지 95atom%인 유기막을 연마하기 위한 유기막 CMP 슬러리 조성물.At least one of a polar solvent and a nonpolar solvent; And a metal oxide abrasive, wherein the organic film CMP slurry composition is for polishing an organic film that is acidic and has a carbon content of about 50-95 atom%.
- 제1항에 있어서, 상기 유기막은 막 밀도가 약 0.5 내지 2.5g/cm3이고 경도(hardness)가 약 0.4GPa 이상인 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 1, wherein the organic film has a film density of about 0.5 to 2.5 g / cm 3 and a hardness of about 0.4 GPa or more.
- 제1항에 있어서, 상기 유기막은 막 밀도가 약 1.0 내지 2.0g/cm3이고 경도가 약 1.0GPa 이상인 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 1, wherein the organic film has a film density of about 1.0 to 2.0 g / cm 3 and a hardness of about 1.0 GPa or more.
- 제1항에 있어서, 상기 금속산화물 연마제는 실리카, 알루미나, 세리아, 티타니아, 지르코니아 중 하나 이상을 포함하는 유기막 CMP 슬러리 조성물. The organic film CMP slurry composition of claim 1, wherein the metal oxide abrasive includes at least one of silica, alumina, ceria, titania, and zirconia.
- 제1항에 있어서, 상기 금속산화물 연마제는 상기 조성물 중 약 0.1 내지 20중량%로 포함되는 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 1, wherein the metal oxide abrasive is included in about 0.1 to 20% by weight of the composition.
- 제1항에 있어서, 상기 산성은 pH 약 6 이하인 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 1, wherein the acidity is pH of about 6 or less.
- 제1항에 있어서, 상기 산성은 pH 약 5 이하인 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 1, wherein the acidity is pH of about 5 or less.
- 제1항에 있어서, 다가의 산화상태를 갖는 금속염, 전이금속의 킬레이트 중 하나 이상의 산화제를 더 포함하는 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 1, further comprising at least one oxidizing agent of a metal salt having a polyvalent oxidation state and a chelate of a transition metal.
- 제8항에 있어서, 상기 산화제는 상기 조성물 중 약 0.001 내지 15중량%로 포함되는 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 8, wherein the oxidant comprises about 0.001 to 15 weight percent of the composition.
- 제8항에 있어서, 상기 산화제는 상기 조성물 중 약 0.01 내지 5중량%로 포함되는 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 8, wherein the oxidant comprises about 0.01 to 5 weight percent of the composition.
- 제8항에 있어서, 상기 다가의 산화상태를 갖는 금속염은 세릭 암모늄염, 페릭 니트레이트, 페릭 클로라이드 중 하나 이상을 포함하는 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 8, wherein the metal salt having a polyvalent oxidation state comprises at least one of ceric ammonium salt, ferric nitrate, and ferric chloride.
- 제8항에 있어서, 상기 전이금속의 킬레이트는 프로필렌디아민테트라아세트산-Fe 등의 Fe화합물 또는 프로필렌디아민테트라아세트산-Mn 등 Mn 화합물 중 하나 이상을 포함하는 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 8, wherein the chelate of the transition metal comprises at least one of a Fe compound such as propylenediaminetetraacetic acid-Fe or a Mn compound such as propylenediaminetetraacetic acid-Mn.
- 제1항에 있어서, 상기 조성물은 pH 조절제를 더 포함하는 유기막 CMP 슬러리 조성물. The organic film CMP slurry composition of claim 1, wherein the composition further comprises a pH adjuster.
- 제1항에 있어서, 상기 조성물은 말산, 시트르산, 포름산, 글루타르산, 옥살산, 프탈산, 숙신산, 타르타르산, 말레산, 말론산 중 하나 이상의 연마촉진제를 더 포함하는 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 1, wherein the composition further comprises at least one polishing accelerator of malic acid, citric acid, formic acid, glutaric acid, oxalic acid, phthalic acid, succinic acid, tartaric acid, maleic acid, malonic acid.
- 제1항에 있어서, 상기 유기막은 치환 또는 비치환된 방향족기를 갖는 화합물을 포함하는 유기막 형성용 조성물로 형성된 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 1, wherein the organic film is formed of an organic film-forming composition containing a compound having a substituted or unsubstituted aromatic group.
- 제15항에 있어서, 상기 치환된 방향족기를 갖는 화합물은 하기 화학식 A로 표시되는 작용기, 하기 화학식 B로 표시되는 작용기 중 하나 이상으로 치환된 것인 유기막 CMP 슬러리 조성물:The organic film CMP slurry composition of claim 15, wherein the compound having a substituted aromatic group is substituted with at least one of a functional group represented by Formula A and a functional group represented by Formula B:<화학식 A><Formula A>*-(O)n-(CH2)m-P(=O)(R)(R') *-(O) n- (CH 2 ) mP (= O) (R) (R ')<화학식 B><Formula B>*-B(R)(R')* -B (R) (R ')(상기 화학식 A, 화학식 B에서, n은 0 또는 1이고, m은 0 내지 10의 정수이고,(In Formula A, Formula B, n is 0 or 1, m is an integer of 0 to 10,R, R'은 각각 독립적으로, 수소, 수산기, 치환 또는 비치환된 C1 내지 C20의 알킬기, 치환 또는 비치환된 C2 내지 C20의 알케닐기, 치환 또는 비치환된 C3 내지 C20의 시클로알킬기, 치환 또는 비치환된 C1 기지 C20의 할로알킬기, 치환 또는 비치환된 C1 내지 C20의 알킬술포네이트기, 치환 또는 비치환된 C1 내지 C20의 알킬술포닐기, 치환 또는 비치환된 C2 내지 C20의 알킬아미드기, 치환 또는 비치환된 C3 내지 C20의 알킬에스테르기, 치환 또는 비치환된 C2 내지 C20의 시아노알킬기, 치환 또는 비치환된 C1 내지 C20의 알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C6 내지 C30 아릴알킬기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기이거나, 또는 R, R 'are each independently hydrogen, hydroxyl, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C2 to C20 alkenyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or Unsubstituted C1 known C20 haloalkyl group, substituted or unsubstituted C1 to C20 alkylsulfonate group, substituted or unsubstituted C1 to C20 alkylsulfonyl group, substituted or unsubstituted C2 to C20 alkylamide group, Substituted or unsubstituted C3 to C20 alkyl ester group, substituted or unsubstituted C2 to C20 cyanoalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C6 to C30 aryl group, substituted Or an unsubstituted C6 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 aryloxy group, orR, R'은 서로 연결되어 치환 또는 비치환된 C3 내지 C20의 시클로알킬기 또는 치환 또는 비치환된 C3 내지 C20의 헤테로시클로알킬기를 형성한다). R, R 'are linked to each other to form a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C3 to C20 heterocycloalkyl group).
- 제1항에 있어서, 상기 유기막은 하기 화학식 2를 포함하는 물질을 포함하는 유기막 형성용 조성물로 형성되는 유기막 CMP 슬러리 조성물:The organic film CMP slurry composition of claim 1, wherein the organic film is formed of an organic film-forming composition comprising a material including the following Chemical Formula 2.<화학식 2><Formula 2>
(상기 화학식 2에서, n은 1≤n<190이고, In Formula 2, n is 1 ≦ n <190,R1은 수소, 히드록시기, 할로겐 원자, 알릴기, 티오닐기, 티올기, 시아노기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C1 내지 C30 헤테로알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C1 내지 C20 알데히드기, 치환 또는 비치환된 C1 내지 C40 알킬에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합이고,R 1 is hydrogen, a hydroxy group, a halogen atom, an allyl group, thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group , Substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 hetero Cycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkenyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 hetero Arylalkyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 heteroalkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, Substituted or unsubstituted C1 to C20 aldehyde groups, substituted or unsubstituted C1 to C40 alkylether groups, substituted or unsubstituted C7 to C20 arylalkylene ether groups, substituted or unsubstituted C1 to C30 haloalkyl groups, and P A functional group, a functional group including B, or a combination thereof,R2는 수소, 아미노기, 치환 또는 비치환된 C1 내지 C10의 알콕시기, 치환 또는 비치환된 C6 내지 C10의 아릴옥시기, 디알킬아미노기(-NRR', 여기서 R, R'은 서로 독립적으로 치환 또는 비치환된 C1 내지 C10의 알킬기 또는 치환 또는 비치환된 C6 내지 C10의 아릴기), 히드록시기, 할로겐 원자, 알릴기, 티오닐기, 티올기, 시아노기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C1 내지 C30 헤테로알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C1 내지 C20 알데히드기, 치환 또는 비치환된 C1 내지 C40 알킬에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합이고,R 2 is hydrogen, an amino group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C6 to C10 aryloxy group, a dialkylamino group (-NRR ', where R and R' are independently substituted with each other) Or unsubstituted C1 to C10 alkyl group or substituted or unsubstituted C6 to C10 aryl group), hydroxy group, halogen atom, allyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or Unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycle An alkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, Substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkenyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or Unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 heteroalkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted C1 to C40 alkylether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to A C30 haloalkyl group, a functional group comprising P, a functional group comprising B, or a combination thereof,R3은 치환 또는 비치환된,R 3 is substituted or unsubstituted,
중 어느 하나이다).Is either one). - 제1항에 있어서, 상기 유기막은 하기 화학식 6으로 표시되는 물질을 포함하는 유기막 형성용 조성물로 형성되는 유기막 CMP 슬러리 조성물:According to claim 1, wherein the organic film is an organic film CMP slurry composition formed of a composition for forming an organic film containing a material represented by the formula (6):<화학식 6><Formula 6>
(상기 화학식 6에서, R4 내지 R9, X1 내지 X6은 각각 독립적으로, 수소, 히드록시기, 할로겐 원자, 알릴기, 티오닐기, 티올기, 시아노기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C1 내지 C30 헤테로알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C1 내지 C20 알데히드기, 치환 또는 비치환된 C1 내지 C40 알킬에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합이고,(In Formula 6, R 4 To R 9 , X 1 To X 6 are each independently hydrogen, hydroxy group, halogen atom, allyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted Or an unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 Cycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted Or an unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkenyl group, a substituted or unsubstituted C2 Or a C30 heteroaryl group, a substituted or unsubstituted C2 to C30 heteroarylalkyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 hetero Alkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted C1 to C40 alkylether group, substituted or unsubstituted C7 to C20 arylalkylene ether group , A substituted or unsubstituted C1 to C30 haloalkyl group, a functional group including P, a functional group including B, or a combination thereof,n1 내지 n6은 각각 독립적으로 0 내지 2의 범위에 있고, 2≤ n1+n2+n3+n4+n5+n6≤6이다).n 1 to n 6 are each independently in a range of 0 to 2, and 2 ≦ n 1 + n 2 + n 3 + n 4 + n 5 + n 6 ≦ 6 ). - 제1항에 있어서, 상기 유기막은 하기 (i), (ii), (iii) 중에서 선택되는 방향족기 함유 중합체를 포함하는 유기막 형성용 조성물로 형성되는 유기막 CMP 슬러리 조성물:The organic film CMP slurry composition according to claim 1, wherein the organic film is formed of a composition for forming an organic film containing an aromatic group-containing polymer selected from (i), (ii) and (iii):(i) 하기 화학식 7로 표시되는 화합물,(i) a compound represented by the following formula (7),(ii) 하기 화학식 7로 표시되는 화합물과 하기 화학식 8로 표시되는 화합물과의 혼합물,(ii) a mixture of a compound represented by the following formula (7) with a compound represented by the following formula (8),(iii) 하기 화학식 9로 표시되는 화합물(iii) a compound represented by the following formula (9)<화학식 7><Formula 7>
<화학식 8><Formula 8>
<화학식 9><Formula 9>
(상기 화학식 7 내지 9에서, m, n은 각각 1≤n<750, 1≤m<750, 2≤m+n<1500이고,In Formulas 7 to 9, m and n are each 1 ≦ n <750, 1 ≦ m <750, and 2 ≦ m + n <1500,R10은 치환 또는 비치환된,R 10 is substituted or unsubstituted,
중 어느 하나이고Is eitherR11은 수소, 히드록시기, 할로겐 원자, 티오닐기, 티올기, 시아노기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C1 내지 C20 알데히드기, 치환 또는 비치환된 C1 내지 C40 알킬에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합이고,R 11 is hydrogen, a hydroxy group, a halogen atom, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or Unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, Substituted or unsubstituted C2 to C30 heterocycloalkenyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylal Groups, substituted or unsubstituted C1 to C20 alkylamine groups, substituted or unsubstituted C1 to C30 alkoxy groups, substituted or unsubstituted C6 to C30 aryloxy groups, substituted or unsubstituted C1 to C20 aldehyde groups, substituted or unsubstituted A substituted C1 to C40 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a functional group comprising P, a functional group including B, or a combination thereof ,R12는 치환 또는 비치환된, R 12 is substituted or unsubstituted,
중 어느 하나이고,Any one ofR13은 치환 또는 비치환된,R 13 is substituted or unsubstituted,
중 어느 하나이고,Any one ofR14은 치환 또는 비치환된, R 14 is substituted or unsubstituted,
중 어느 하나이고,Any one ofR15는 치환 또는 비치환된, R 15 is substituted or unsubstituted,
중 어느 하나이고,Any one ofR10, R13, R15에서 R은 각각 독립적으로 수소, 히드록시기, 할로겐 원자, 티오닐기, 티올기, 시아노기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C1 내지 C20 알데히드기, 치환 또는 비치환된 C1 내지 C40 알킬에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합이다.R at R 10 , R 13 and R 15 are each independently hydrogen, hydroxy group, halogen atom, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or unsubstituted C1 to C30 alkyl group, substituted or Unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 Heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted Or an unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkenyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or Substituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C1 To C20 aldehyde group, substituted or unsubstituted C1 to C40 alkylether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to C30 haloalkyl group, functional group comprising P, including B Is a functional group or a combination thereof. - 제1항에 있어서, 상기 유기막은 산가가 약 0mgKOH/g인 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 1, wherein the organic film has an acid value of about 0 mgKOH / g.
- 제1항 내지 제20항 중 어느 한 항의 유기막 CMP 슬러리 조성물을 사용하여, 탄소 함량이 약 50 내지 95atm%이고 막 밀도가 약 0.5 내지 2.5g/cm3이고 경도가 약 0.4GPa 이상인 유기막을 연마하는 단계를 포함하는 유기막 연마방법.The organic film CMP slurry composition of any one of claims 1 to 20 is used to polish an organic film having a carbon content of about 50 to 95 atm%, a film density of about 0.5 to 2.5 g / cm 3, and a hardness of about 0.4 GPa or more. Organic film polishing method comprising the step of.
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| CN107636110A (en) * | 2015-05-15 | 2018-01-26 | 三星Sdi株式会社 | For organic film slurry composition for CMP and use its Ginding process |
| CN107922819A (en) * | 2015-08-21 | 2018-04-17 | 三星Sdi株式会社 | For the CMP slurry constituent of organic film, its preparation method and the method for grinding organic film using it |
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