KR100671116B1 - Hard mask composition having antireflection - Google Patents
Hard mask composition having antireflection Download PDFInfo
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- KR100671116B1 KR100671116B1 KR1020050068890A KR20050068890A KR100671116B1 KR 100671116 B1 KR100671116 B1 KR 100671116B1 KR 1020050068890 A KR1020050068890 A KR 1020050068890A KR 20050068890 A KR20050068890 A KR 20050068890A KR 100671116 B1 KR100671116 B1 KR 100671116B1
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- radiation
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- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 41
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 claims abstract description 23
- 230000005855 radiation Effects 0.000 claims abstract description 19
- 230000003667 anti-reflective effect Effects 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 238000005530 etching Methods 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 238000003384 imaging method Methods 0.000 claims description 22
- 239000003377 acid catalyst Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 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 claims description 8
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 6
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical group O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 5
- 229920003180 amino resin Polymers 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 claims description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- -1 glycoluril compound Chemical class 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 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 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 150000001454 anthracenes Chemical class 0.000 claims description 2
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 239000004640 Melamine resin Substances 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 238000000059 patterning Methods 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 24
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 20
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 239000003431 cross linking reagent Substances 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000005011 phenolic resin Substances 0.000 description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000012488 sample solution Substances 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000001312 dry etching Methods 0.000 description 4
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DAJPMKAQEUGECW-UHFFFAOYSA-N 1,4-bis(methoxymethyl)benzene Chemical compound COCC1=CC=C(COC)C=C1 DAJPMKAQEUGECW-UHFFFAOYSA-N 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000006117 anti-reflective coating Substances 0.000 description 3
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 3
- 229940008406 diethyl sulfate Drugs 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 229920003270 Cymel® Polymers 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- NJQJGRGGIUNVAB-UHFFFAOYSA-N 2,4,4,6-tetrabromocyclohexa-2,5-dien-1-one Chemical compound BrC1=CC(Br)(Br)C=C(Br)C1=O NJQJGRGGIUNVAB-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- NXKOSHBFVWYVIH-UHFFFAOYSA-N 2-n-(butoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical class CCCCOCNC1=NC(N)=NC(N)=N1 NXKOSHBFVWYVIH-UHFFFAOYSA-N 0.000 description 1
- KFVIYKFKUYBKTP-UHFFFAOYSA-N 2-n-(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCNC1=NC(N)=NC(N)=N1 KFVIYKFKUYBKTP-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- JCJNNHDZTLRSGN-UHFFFAOYSA-N anthracen-9-ylmethanol Chemical compound C1=CC=C2C(CO)=C(C=CC=C3)C3=CC2=C1 JCJNNHDZTLRSGN-UHFFFAOYSA-N 0.000 description 1
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical class N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- CNEKKZXYBHKSDC-UHFFFAOYSA-N ethyl acetate;propane-1,2-diol Chemical compound CC(O)CO.CCOC(C)=O CNEKKZXYBHKSDC-UHFFFAOYSA-N 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- IWQPFENGXVKSDO-UHFFFAOYSA-N phenol;2h-thiazine Chemical compound N1SC=CC=C1.OC1=CC=CC=C1 IWQPFENGXVKSDO-UHFFFAOYSA-N 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/094—Multilayer resist systems, e.g. planarising layers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
도 1은 실시예 2에서 제조된 중합체의 1H-NMR 스펙트럼이고, 및1 is the 1 H-NMR spectrum of the polymer prepared in Example 2, and
도 2는 실시예 2에서 제조된 중합체의 FT-IR 스펙트럼이다.2 is an FT-IR spectrum of the polymer prepared in Example 2. FIG.
본 발명은 리쏘그래픽 공정에 유용한 반사방지성을 갖는 하드마스크 조성물에 관한 것으로, 보다 상세하게는 짧은 파장 영역(예를 들어, 157, 193, 248nm)에서 강한 흡수를 갖는 방향족 고리(aromatic ring) 함유 중합체를 포함하는 것을 특징으로 하는 하드마스크 조성물에 관한 것이다.FIELD OF THE INVENTION The present invention relates to hardmask compositions having antireflective properties useful in lithographic processes, more particularly containing aromatic rings having strong absorption in short wavelength ranges (e.g., 157, 193, 248 nm). A hardmask composition comprising a polymer.
마이크로일렉트로닉스 산업에서 뿐만 아니라 마이크로스코픽 구조물(예를 들어, 마이크로머신, 마그네토레지스트 헤드 등)의 제작을 비롯한 다른 산업에서, 구조적 형상의 크기를 감소시키고자 하는 지속적인 요구가 존재한다. 마이크로일렉트로닉스 산업에서, 마이크로일렉트로닉 디바이스의 크기를 감소시켜, 주어진 칩 크기에 보다 많은 양의 회로를 제공하고자 하는 요구가 존재한다.In the microelectronics industry as well as in other industries, including the fabrication of microscopic structures (eg, micromachines, magnetoresist heads, etc.), there is a continuing need to reduce the size of structural features. In the microelectronics industry, there is a desire to reduce the size of microelectronic devices, thereby providing a larger amount of circuitry for a given chip size.
효과적인 리쏘그래픽 기법은 형상 크기의 감소를 달성시키는데 필수적이다. 리쏘그래픽은 소정의 기판 상에 패턴을 직접적으로 이미지화시킨다는 측면에서 뿐만 아니라 그러한 이미지화에 전형적으로 사용된 마스크를 제조한다는 측면에서 마이크로스코픽 구조물의 제조에 영향을 미친다.Effective lithographic techniques are essential to achieving a reduction in shape size. Lithographic influences the fabrication of microscopic structures not only in terms of directly imaging the pattern on a given substrate, but also in the manufacture of masks typically used for such imaging.
전형적인 리쏘그래픽 공정은 이미지화 방사선에 방사선-민감성 레지스트를 패턴 방식으로 노출시킴으로써 패턴화된 레지스트 층을 형성시키는 과정을 수반한다. 이어서, 이미지는 노출된 레지스트 층을 임의의 물질(전형적으로 수성 알칼리 현상액)과 접촉시킴으로써 현상시킨다. 이어서, 패턴은 패턴화된 레지스트 층의 개구부 내에 있는 그 물질을 에칭시킴으로써 이면 재료에 전사시킨다. 전사가 완료된 후, 잔류하는 레지스트 층은 제거한다.Typical lithographic processes involve forming a patterned resist layer by patterning exposing the radiation-sensitive resist to imaging radiation. The image is then developed by contacting the exposed resist layer with any material (typically an aqueous alkaline developer). The pattern is then transferred to the backing material by etching the material in the openings of the patterned resist layer. After the transfer is completed, the remaining resist layer is removed.
상기 리쏘그래픽 공정 중 대부분은 이미지화층, 예컨대 방사선 민감성 레지스트 재료층과 이면층 간의 반사성을 최소화시키는데 반사방지 코팅(ARC)을 사용하여 해상도를 증가시킨다. 그러나, 패터닝 후 ARC의 에칭 중에 많은 이미지화층도 소모되어, 후속 에칭 단계 중에 추가의 패터닝이 필요하게 될 수 있다.Most of the lithographic processes increase the resolution by using an antireflective coating (ARC) to minimize the reflectivity between the imaging layer, such as a layer of radiation sensitive resist material and backing layer. However, many imaging layers may also be consumed during the etching of the ARC after patterning, requiring further patterning during subsequent etching steps.
다시 말하면, 일부 리쏘그래픽 이미지화 공정의 경우, 사용된 레지스트는 레지스트 이면에 있는 층으로 소정의 패턴을 효과적으로 전사시킬 수 있을 정도로 후속적인 에칭 단계에 대한 충분한 내성을 제공하지 못한다. 많은 실제 예(예를 들면, 초박막 레지스트 층이 필요한 경우, 에칭 처리하고자 하는 이면 재료가 두꺼운 경우, 상당할 정도의 에칭 깊이가 필요한 경우 및/또는 소정의 이면 재료에 특정한 부식제(etchant)를 사용하는 것이 필요한 경우)에서, 일명 하드마스크 층이라는 것은 레지스트 층과 패턴화된 레지스트로부터 전사에 의해 패턴화될 수 있는 이면 재료 사이에 중간체로서 사용한다. 그 하드마스크 층은 패턴화된 레지스트 층으로부터 패턴을 수용하고, 이면 재료로 패턴을 전사시키는 데 필요한 에칭 공정을 견디어 낼 수 있어야 한다.In other words, for some lithographic imaging processes, the resist used does not provide sufficient resistance to subsequent etching steps to effectively transfer a desired pattern to the layer behind the resist. Many practical examples (e.g. when ultra thin resist layers are required, when the backing material to be etched is thick, when a significant amount of etching depth is required and / or by using an etchant specific to a given backing material) In what is needed, a so-called hardmask layer is used as an intermediate between the resist layer and the backing material which can be patterned by transfer from the patterned resist. The hardmask layer must be able to withstand the etching process required to receive the pattern from the patterned resist layer and transfer the pattern to the backing material.
종래 기술에서는 많은 하드마스크 재료가 존재하긴 하지만, 개선된 하드마스크 조성물에 대한 요구가 지속되고 있다. 그러한 많은 종래 기술상 재료는 기판에 도포하기 어려우므로, 예를 들면 화학적 또는 물리적 증착, 특수 용매, 및/또는 고온 소성의 이용이 필요할 수 있다. 고온 소성에 대한 필요성 없이도 스핀-코팅 기법에 의해 도포될 수 있는 하드마스크 조성물을 갖는 것이 바람직하다. 추가로, 이면 포토레지스트에 선택적으로 용이하게 에칭될 수 있으며, 동시에 특히 이면층이 금속 층인 경우 그 이면 층을 패턴화하는데 필요한 에칭 공정에 내성이 있는 하드마스크 조성물을 갖는 것이 바람직하다. 또한, 적당한 저장 수명을 제공하고, 이미지화 레지스트 층과의 저해한 상호작용(예를 들어, 하드마스크로부터 산 오염에 의한 것)을 피하는 것도 바람직하다. 추가로, 보다 짧은 파장(예, 157, 193, 248nm)의 이미지 방사선에 대한 소정의 광학 특성을 지닌 하드마스크 조성물을 갖는 것이 바람직하다.Although many hardmask materials exist in the prior art, there is a continuing need for improved hardmask compositions. Many such prior art materials are difficult to apply to substrates, and therefore may require the use of chemical or physical deposition, special solvents, and / or high temperature firing, for example. It is desirable to have a hardmask composition that can be applied by spin-coating techniques without the need for high temperature firing. In addition, it is desirable to have a hardmask composition that can easily be easily etched into the backside photoresist, while at the same time resisting the etching process required to pattern the backside layer, especially when the backside layer is a metal layer. It is also desirable to provide adequate shelf life and to avoid inhibited interactions with the imaging resist layer (eg, by acid contamination from the hardmask). In addition, it is desirable to have a hardmask composition having certain optical properties for image radiation of shorter wavelengths (eg, 157, 193, 248 nm).
결론적으로 에칭 선택성이 높고, 다중 에칭에 대한 내성이 충분하며, 레지스트와 이면층 간의 반사성을 최소화하는 반사방지 조성물을 사용하여 리쏘그래픽 기술을 수행하는 것이 요망된다. 이러한 리쏘그래픽 기술은 매우 세부적인 반도체 장치를 생산할 수 있게 할 것이다.In conclusion, it is desirable to perform lithographic techniques using antireflective compositions that have high etch selectivity, sufficient resistance to multiple etching, and minimize reflectivity between the resist and backing layer. This lithographic technology will enable the production of very detailed semiconductor devices.
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로, 리쏘그래픽 공정에서 유용하게 사용되는 신규한 하드마스크 조성물을 제공하는 것을 목적으로 한다.The present invention is to solve the problems of the prior art as described above, and an object of the present invention is to provide a novel hard mask composition usefully used in lithographic processes.
본 발명의 다른 목적은 본 발명의 하드마스크 조성물을 사용하여 기판 상의 이면 재료 층을 패턴화시키는 방법을 제공하는 것이다.Another object of the present invention is to provide a method of patterning a backing material layer on a substrate using the hardmask composition of the present invention.
즉, 본 발명의 한 측면은 스핀-온 반사방지 하드마스크 층의 형성에 적합한 조성물에 관한 것으로, 상기 조성물은That is, one aspect of the invention relates to a composition suitable for the formation of a spin-on antireflective hardmask layer, wherein the composition is
(a) 짧은 파장 영역에서 강한 흡수를 갖는 방향족 고리(aromatic ring) 함유 중합체;(a) an aromatic ring containing polymer having strong absorption in the short wavelength region;
(b) 가교 성분; 및(b) crosslinking components; And
(c) 산 촉매를 포함한다. (c) an acid catalyst.
본 발명의 다른 측면은 기판 상에 패턴화된 재료 형상을 형성시키는 방법에 관한 것으로, 상기 방법은Another aspect of the invention relates to a method of forming a patterned material shape on a substrate, the method of
(a) 기판 상에 재료 층을 제공하는 단계;(a) providing a layer of material on the substrate;
(b) 재료 층 위로 본 발명의 조성물을 이용한 반사방지 하드마스크 층을 형성시키는 단계;(b) forming an antireflective hardmask layer using the composition of the present invention over the material layer;
(c) 반사방지 층 위로 방사선-민감성 이미지화 층을 형성시키는 단계;(c) forming a radiation-sensitive imaging layer over the antireflective layer;
(d) 이미지화 층을 방사선에 패턴 방식으로 노출시킴으로써 이미지화 층 내에서 방사선-노출된 영역의 패턴을 생성시키는 단계;(d) generating a pattern of radiation-exposed areas within the imaging layer by exposing the imaging layer to the radiation in a pattern manner;
(e) 이미지화 층 및 반사방지 층의 부분을 선택적으로 제거하여 재료 층의 부분을 노출시키는 단계; 및(e) selectively removing portions of the imaging layer and antireflective layer to expose portions of the material layer; And
(f) 재료 층의 노출된 부분을 에칭함으로써 패턴화된 재료 형상을 형성시키는 단계를 포함한다.(f) forming the patterned material shape by etching the exposed portion of the material layer.
본 발명의 이러한 양태 및 다른 양태는 이하의 보다 상세한 설명에서 논의된다.These and other aspects of the invention are discussed in the detailed description below.
본 발명의 하드마스크 조성물은 짧은 파장 영역(예를 들어, 157, 193, 248nm)에서 강한 흡수를 갖는 방향족 고리(aromatic ring) 함유 중합체가 존재하는 것을 특징으로 한다.The hardmask composition of the present invention is characterized by the presence of an aromatic ring containing polymer having strong absorption in the short wavelength region (eg, 157, 193, 248 nm).
즉, 본 발명의 반사방지 하드마스크 조성물은That is, the antireflective hard mask composition of the present invention
(a) 짧은 파장 영역에서 강한 흡수를 갖는 방향족 고리(aromatic ring) 함유 중합체;(a) an aromatic ring containing polymer having strong absorption in the short wavelength region;
(b) 가교 성분; 및(b) crosslinking components; And
(c) 산 촉매를 포함한다.(c) an acid catalyst.
본 발명의 하드마스크 조성물에서, 상기 (a) 방향족 고리 함유 중합체의 방향족 고리는 중합체의 골격 부분 내에 존재하는 것이 바람직하다. 또한, 상기 방 향족 고리 함유 중합체는 가교 성분과 반응하는 중합체를 따라 분포된 다수의 반응성 부위를 함유하는 것이 바람직하며, 페놀, 크레졸, 나프톨을 그 단위 유니트에 포함하는 것이 바람직하다. 또한, 종래의 스핀-코팅에 의해 층을 형성시키는데 도움이 되는 용액 및 막 형성(film-forming) 특성을 가져야 한다.In the hardmask composition of the present invention, the aromatic ring of the (a) aromatic ring-containing polymer is preferably present in the skeleton portion of the polymer. In addition, the aromatic ring-containing polymer preferably contains a plurality of reactive sites distributed along the polymer reacting with the crosslinking component, and preferably includes phenol, cresol, and naphthol in its unit unit. In addition, they must have solution and film-forming properties to help form the layer by conventional spin-coating.
한편, 본 발명의 하드마스크 조성물에 사용되는 상기 (b) 가교 성분은 발생된 산에 의해 촉매 작용된 반응에서 가열에 의하여 중합체의 반복단위를 가교할 수 있는 것이 바람직하고, 상기 (c) 산 촉매는 열 활성화된 산 촉매인 것이 바람직하다.On the other hand, the crosslinking component (b) used in the hard mask composition of the present invention is preferably capable of crosslinking the repeating unit of the polymer by heating in a reaction catalyzed by the generated acid, and the (c) acid catalyst Is preferably a thermally activated acid catalyst.
구체적으로, 본 발명의 하드마스크 조성물에 사용되는 상기 (a) 방향족 고리 함유 중합체는 하기 화학식 1 내지 3으로 이루어진 군에서 선택된 1종 이상의 중합체를 포함하는 것이 바람직하다.Specifically, the (a) aromatic ring-containing polymer used in the hard mask composition of the present invention preferably comprises at least one polymer selected from the group consisting of the following Chemical Formulas 1 to 3.
*상기 식에서, n은 1≤n<190의 범위이고, In which n is in the range 1 ≦ n <190,
R1 및 R2는 각각 수소, 히드록시기(-OH), C1 -10의 알킬기, C6 -10의 아릴기, 알릴기 또는 할로겐 원자이며, 및R 1 and R 2 are each a hydrogen, a hydroxy group (-OH), C 1 -10 alkyl, C 6 -10 aryl group, an allyl group or a halogen atom of, and
R3 및 R4는 각각 수소이거나 가교 성분과 반응하는 반응성 부위 또는 발색단(chromophore) 부위를 포함한다. R 3 and R 4 each comprise a reactive site or a chromophore site which is hydrogen or reacts with a crosslinking component.
상기 식에서, Where
R5는 R 5 is
R6은 수소, C1 -10의 알킬기, C6 -10의 아릴기 또는 알릴기이며, 및R 6 is hydrogen, an alkyl group of C 1 -10, aryl group of C 6 -10 or an allyl group, and
n, R1, R2, R3 및 R4는 화학식 1에서 정의한 것과 같다. n, R 1 , R 2 , R 3 and R 4 are the same as defined in Chemical Formula 1.
상기 식에서, n, R1, R2, R3 및 R4는 화학식 1에서 정의한 것과 같다.Wherein n, R 1 , R 2 , R 3 and R 4 are the same as defined in Formula 1.
보다 구체적으로, 본 발명의 방향족 고리 함유 중합체의 반응성 부위 함유 기 R3 및 R4에서, 바람직한 반응성 부위로는 에폭시드기 또는 알콜 등이 가능하나, 이들로 한정되는 것은 아니다.More specifically, in the reactive site-containing groups R 3 and R 4 of the aromatic ring-containing polymer of the present invention, preferred reactive sites include, but are not limited to, epoxide groups or alcohols.
또한, 본 발명의 방향족 고리 함유 중합체의 발색단 함유 기 R3 및 R4에서, 바람직한 발색단 부위로는 193nm과 248nm 파장의 방사선의 경우 이미 중합체의 골격에 포함된 방향족 고리 자체가 적합한 발색단이지만, 여기에 추가로 R3, R4가 발색단 기능을 할 수 있는 구조인 페닐, 크리센(chrysene), 피렌, 플루오르안트렌, 안트론, 벤조페논, 티오크산톤, 안트라센 및 안트라센 유도체가 될 수 있다. 9-안트라센 메탄올은 바람직한 발색단이다. 발색단 부위는 페놀 티아진과 같은 가능한 탈활성화된 아미노 질소를 제외하고는 질소를 함유하지 않는 것이 바람직하다.In addition, in the chromophore-containing groups R 3 and R 4 of the aromatic ring-containing polymer of the present invention, preferred chromophore moieties are aromatic chromophores already included in the backbone of the polymer in the case of radiation of 193 nm and 248 nm wavelengths, In addition, R 3 and R 4 may be phenyl, chrysene, pyrene, fluoranthrene, anthrone, benzophenone, thioxanthone, anthracene and anthracene derivatives, which are structures capable of chromophore functions. 9-anthracene methanol is a preferred chromophore. The chromophore moiety preferably does not contain nitrogen except for possible deactivated amino nitrogen such as phenol thiazine.
본 발명의 하드마스크 조성물에서, 방향족 고리 함유 중합체는 상기 화학식 1 내지 3으로 이루어진 군에서 1종 선택된 단독 중합체 또는 2종 이상 선택된 공중합체가 포함되며, 이들 단독 중합체 및 공중합체의 블랜드 조합물 역시 포함한다.In the hard mask composition of the present invention, the aromatic ring-containing polymer includes a homopolymer or two or more copolymers selected from the group consisting of Chemical Formulas 1 to 3, and a blend combination of these homopolymers and copolymers is also included. do.
본 발명의 방향족 고리 함유 중합체는 중량 평균 분자량을 기준으로 1,000 ~ 30,000 인 것이 보다 바람직하다.As for the aromatic ring containing polymer of this invention, it is more preferable that it is 1,000-30,000 based on a weight average molecular weight.
한편, 본 발명의 하드마스크 조성물에 사용되는 상기 (b) 가교 성분은 생성된 산에 의해 촉매작용화될 수 있는 방식으로 방향족 고리 함유 중합체의 히드록시 와 반응될 수 있는 가교제인 것이 바람직하다. 일반적으로, 본 발명의 반사방지 하드마스크 조성물에 사용된 가교제로는 에테르화된 아미노 수지, 예를 들면 메틸화되거나 부틸화된 멜라민 수지(N-메톡시메틸-멜라민 수지 또는 N-부톡시메틸-멜라민 수지), 및 에테르화된 아미노 수지, 예를 들면 메틸화되거나 부틸화된 우레아 레진(Urea Resin) 수지(Cymel U-65 Resin 또는 UFR 80 Resin), 아래에 나타낸 구조와 같은 메틸화된/부틸화된 글리콜루릴(Powderlink 1174), 예를들면 캐나다 특허 제1 204 547호에 기재된 화합물, 2,6-비스(히드록시메틸)-p-크레졸 화합물을 비롯한 하기 구조를 갖는 화합물, 예를 들면 일본 특허 공개 제1-293339호에 기재된 화합물이 포함된다. 상기한 아미노수지 및 글리콜루릴은 사이텍 인더스트리(Cytec Industries)로부터 구입 가능하다. 또한 비스에폭시 계통의 화합물도 가교제로 사용할 수 있다.On the other hand, the crosslinking component (b) used in the hard mask composition of the present invention is preferably a crosslinking agent that can be reacted with the hydroxy of the aromatic ring-containing polymer in a manner that can be catalyzed by the generated acid. Generally, the crosslinking agents used in the antireflective hardmask compositions of the present invention include etherified amino resins, such as methylated or butylated melamine resins (N-methoxymethyl-melamine resins or N-butoxymethyl-melamines). Resins), and etherified amino resins, such as methylated or butylated Urea Resin resins (Cymel U-65 Resin or
본 발명의 하드마스크 조성물에 사용되는 상기 (c) 산 촉매는 p-톨루엔술폰산 모노 하이드레이트(p-toluenesulfonic acid mono hydrate) 등의 일반적인 유기산이 사용될 수 있고, 또한 보관안정성을 도모한 TAG(Thermal Acid Generater)계통의 화합물을 촉매로 사용할 수 있다. TAG는 열 처리시 산을 방출하도록 되어있는 산 생성제 화합물로서 예를 들어 피리딘 p-톨루엔술폰산(Pyridine p- toluenesulfonic acid), 2,4,4,6-테트라브로모시클로헥사디엔온, 벤조인 토실레이트, 2-니트로벤질 토실레이트, 및 유기 술폰산의 다른 알킬 에스테르 등을 사용하는 것이 바람직하다.As the acid catalyst (c) used in the hard mask composition of the present invention, a general organic acid such as p-toluenesulfonic acid mono hydrate (p-toluenesulfonic acid mono hydrate) may be used, and TAG (Thermal Acid Generater) having a storage stability. ) Can be used as a catalyst. TAG is an acid generator compound which is intended to release acid upon thermal treatment, for example pyridine p-toluenesulfonic acid, 2,4,4,6-tetrabromocyclohexadienone, benzoin Preference is given to using tosylate, 2-nitrobenzyl tosylate, other alkyl esters of organic sulfonic acids, and the like.
적합한 방사선-민감성 산 촉매의 예는 미국 특허 제5,886,102호 및 제5,939,236호에 기재되어 있다. 또한, 레지스트 기술 분야에서 공지된 다른 방사선-민감성 산 촉매도 이것이 반사방지 조성물의 다른 성분과 상용성이 있는 한 사용할 수 있다.Examples of suitable radiation-sensitive acid catalysts are described in US Pat. Nos. 5,886,102 and 5,939,236. In addition, other radiation-sensitive acid catalysts known in the resist art can be used as long as they are compatible with the other components of the antireflective composition.
본 발명의 하드마스크 조성물은 (a) 짧은 파장 영역에서 강한 흡수를 갖는 방향족 고리(aromatic ring) 함유 중합체 1~20 중량%, 보다 바람직하게는 3~10 중량%, (b) 가교 성분 0.1~5 중량%, 보다 바람직하게는 0.1~3 중량%, 및 (c) 산 촉매 0.001~0.05 중량%, 보다 바람직하게는 0.001~0.03 중량% 함유하는 것이 바람직하다.The hard mask composition of the present invention comprises (a) 1 to 20% by weight of an aromatic ring-containing polymer having strong absorption in a short wavelength region, more preferably 3 to 10% by weight, and (b) 0.1 to 5 crosslinking components. It is preferable to contain weight%, More preferably, 0.1 to 3 weight%, and (c) 0.001 to 0.05 weight% of an acid catalyst, More preferably, 0.001 to 0.03 weight%.
본 발명의 하드마스크 조성물은 추가적으로, 레지스트에 통상적으로 사용되는 프로필렌 글리콜 모노메틸 에테르 아세테이트와 같은 용매를 함유할 수 있으며, 이외에도 계면 활성제 등을 함유할 수 있다.The hardmask composition of the present invention may additionally contain a solvent such as propylene glycol monomethyl ether acetate commonly used in resists, and may also contain surfactants and the like.
한편, 본 발명은 상기 하드마스크 조성물을 사용하여 기판 상의 이면 재료 층을 패턴화시키는 방법을 포함한다.On the other hand, the present invention includes a method of patterning a backing material layer on a substrate using the hardmask composition.
구체적으로, 기판 상에 패턴화된 재료 형상을 형성시키는 방법은Specifically, the method of forming the patterned material shape on the substrate
(a) 기판 상에 재료 층을 제공하는 단계;(a) providing a layer of material on the substrate;
(b) 재료 층 위로 본 발명의 조성물을 이용한 반사방지 하드마스크 층을 형 성시키는 단계;(b) forming an antireflective hardmask layer using the composition of the present invention over the material layer;
(c) 반사방지 층 위로 방사선-민감성 이미지화 층을 형성시키는 단계;(c) forming a radiation-sensitive imaging layer over the antireflective layer;
(d) 이미지화 층을 방사선에 패턴 방식으로 노출시킴으로써 이미지화 층 내에서 방사선-노출된 영역의 패턴을 생성시키는 단계;(d) generating a pattern of radiation-exposed areas within the imaging layer by exposing the imaging layer to the radiation in a pattern manner;
(e) 이미지화 층 및 반사방지 층의 부분을 선택적으로 제거하여 재료 층의 부분을 노출시키는 단계; 및(e) selectively removing portions of the imaging layer and antireflective layer to expose portions of the material layer; And
(f) 재료 층의 노출된 부분을 에칭함으로써 패턴화된 재료 형상을 형성시키는 단계를 포함한다.(f) forming the patterned material shape by etching the exposed portion of the material layer.
본 발명에 따라 기판 상에 패턴화된 재료 형상을 형성시키는 방법은 구체적으로 하기와 같이 수행될 수 있다. 먼저, 알루미늄과 SiN(실리콘 나트라이드)등과 같은 패턴화하고자 하는 재료를 통상적인 방법에 따라 실리콘 기판 위에 형성시킨다. 본 발명의 하드마스크 조성물에 사용되는 패턴화하고자 하는 재료는 전도성, 반전도성, 자성 또는 절연성 재료인 것이 모두 가능하다. 이어서, 본 발명의 하드마스크 조성물을 사용하여 500Å ~ 4000Å 두께로 스핀-코팅에 의해 하드마스크층을 형성하고, 100℃ 내지 300℃에서 10초 내지 10분간 베이킹하여 하드마스크 층을 형성한다. 하드마스크층이 형성되면 방사선-민감성 이미지화층을 형성시키고, 상기 이미지화층을 통한 노광(exposure) 공정에 의해 패턴이 형성될 영역을 노출시키는 현상(develop)공정을 진행한다. 이어서, 이미지화층 및 반사방지층을 선택적으로 제거하여 재료층의 부분을 노출시키고, 일반적으로 CHF3/CF4 혼합가스 등을 이 용하여 드라이 에칭을 진행한다. 패턴화된 재료 형상이 형성된 후에는 통상의 포토레지스트 스트립퍼에 의해 잔류하는 임의의 레지스트를 제거할 수 있다.The method of forming the patterned material shape on the substrate according to the present invention may be specifically performed as follows. First, a material to be patterned, such as aluminum and SiN (silicon nitride), is formed on a silicon substrate according to a conventional method. The material to be patterned used in the hardmask composition of the present invention can be any conductive, semiconducting, magnetic or insulating material. Subsequently, a hard mask layer is formed by spin-coating with a hard mask composition of the present invention at a thickness of 500 kPa to 4000 kPa, and baked at 100 ° C to 300 ° C for 10 seconds to 10 minutes to form a hardmask layer. When the hard mask layer is formed, a radiation-sensitive imaging layer is formed, and a development process of exposing an area where a pattern is to be formed is performed by an exposure process through the imaging layer. Subsequently, the imaging layer and the anti-reflection layer are selectively removed to expose portions of the material layer, and in general, dry etching is performed using a CHF 3 / CF 4 mixed gas or the like. After the patterned material shape is formed, any remaining resist can be removed by conventional photoresist strippers.
따라서, 본 발명의 조성물 및 형성된 리쏘그래픽 구조물은 하기와 같은 반도체 제조공정에 따라 집적 회로 디바이스의 제조 및 설계에 사용될 수 있다. 예를 들면 금속 배선, 컨택트 또는 바이어스를 위한 홀, 절연 섹션(예, DT(Damascene Trench) 또는 STI(Shallow Trench Isolation)), 커패시터 구조물을 위한 트렌치 등과 같은 패턴화된 재료 층 구조물을 형성시키는 데 사용할 수 있다. 또한 본 발명은 임의의 특정 리쏘그래픽 기법 또는 디바이스 구조물에 국한되는 것이 아님을 이해해야 한다.Thus, the compositions of the present invention and formed lithographic structures can be used in the manufacture and design of integrated circuit devices in accordance with semiconductor manufacturing processes as follows. For example, it can be used to form patterned material layer structures, such as metal wiring, holes for contacts or bias, insulating sections (e.g., damascene trenches or shallow trench isolations), trenches for capacitor structures, and the like. Can be. It is also to be understood that the invention is not limited to any particular lithographic technique or device structure.
* 반도체 제조 공정* Semiconductor manufacturing process
이하에서 실시예를 통하여 본 발명을 보다 상세하게 설명하고자 하나, 하기의 실시예는 단지 설명의 목적을 위한 것으로 본 발명을 제한하기 위한 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are for illustrative purposes only and are not intended to limit the present invention.
실시예Example 1: 화합물 (1) 합성 1: Synthesis of Compound (1)
기계교반기, 냉각관, 300ml 적가 깔대기, 질소가스 도입관을 구비한 1ℓ의 4구 플라스크에 4,4'-(9-플루오레닐리덴)디페놀 28.03g (0.08몰)과 p-톨루엔술폰산 0.3g을 200g의 γ-부티로락톤에 녹인 용액을 담고 질소가스를 유입하면서 자기교반기로 교반하고 있는 오일조에서 플라스크를 가열하여 반응용액의 내부온도가 100℃에 도달한 시점에서, 적가 깔대기로 2-히드록시벤즈알데히드(2-hydroxybenzaldehyde) 7.94g을 1-메톡시-2-프로판올(1-methoxy-2-propanol) 100g에 녹인 용액을 30분간 천천히 적가하고 12시간 반응을 실시하였다. 반응종료 후 반응용기가 충분히 실온까지 냉각된 후, 반응용액을 메틸아민케톤(이하, MAK로 칭함)을 사용하여 20중량% 농도의 용액으로 조정하고, 3ℓ 분액깔대기로 3회 물세정하여 증발기로 농축하였다. 이어서 MAK와 메탄올을 사용하여 희석하고 15 중량% 농도의 MAK/메탄올=4/1(중량비)의 용액으로 조정하였다. 이 용액을 3ℓ 분액깔대기에 넣고, 이것에 n-헵탄을 첨가하여 모노머를 함유하는 저분자량체를 제거하여 목적하는 페놀수지(Mw=12,000, polydispersity=1.9, n=22)를 얻었다.28.03 g (0.08 mol) of 4,4 '-(9-fluorenylidene) diphenol and 0.3 p-toluenesulfonic acid in a 1 L four-necked flask equipped with a mechanical stirrer, a cooling tube, a 300 ml dropping funnel and a nitrogen gas introduction tube. g was dissolved in 200 g of γ-butyrolactone, the flask was heated in an oil bath stirred with a magnetic stirrer while introducing nitrogen gas, and when the internal temperature of the reaction solution reached 100 ° C, -A solution in which 7.94 g of 2-hydroxybenzaldehyde was dissolved in 100 g of 1-methoxy-2-propanol was slowly added dropwise for 30 minutes, and then reacted for 12 hours. After completion of the reaction, the reaction vessel was sufficiently cooled to room temperature, and then the reaction solution was adjusted to a solution of 20% by weight using methylamine ketone (hereinafter referred to as MAK), washed three times with a 3L separatory funnel, and concentrated on an evaporator. It was. It was then diluted with MAK and methanol and adjusted to a solution of 15 wt% MAK / methanol = 4/1 (weight ratio). The solution was placed in a 3 L separatory funnel, and n-heptane was added thereto to remove the low molecular weight containing the monomer to obtain the desired phenol resin (Mw = 12,000, polydispersity = 1.9, n = 22).
실시예Example 2: 화합물 (2) 합성 2: Synthesis of Compound (2)
기계교반기, 냉각관, 300ml 적가 깔대기, 질소가스 도입관을 구비한 1ℓ의 4구 플라스크에 질소가스를 유입하면서 1,4-비스(메톡시메틸)벤젠 8.31g(0.05몰)과 디에틸설페이트 0.154g(0.001몰)과 200g의 γ-부티로락톤을 담고 잘 저어주었다. 10분 후에 4,4'-(9-플루오레닐리덴)디페놀 28.02g(0.08몰)을 200g의 γ-부티로락톤에 녹인 용액을 30분간 천천히 적가한 다음, 12시간 동안 반응을 실시하였다. 반응종료 후 물을 사용하여 산을 제거한 후에 증발기로 농축하였다. 이어서 MAK와 메탄올을 사용하여 희석하고 15 중량% 농도의 MAK/메탄올=4/1(중량비)의 용액으로 조정하였다. 이 용액을 3ℓ 분액깔대기에 넣고, 이것에 n-헵탄을 첨가하여 모노머를 함유하는 저분자량체를 제거하여 목적하는 페놀수지(Mw=12,000, polydispersity=2.0, n=23)를 얻었다. 아울러, 합성된 페놀수지에 대한 1H-NMR 스펙트럼 및 FT-IR 스펙트럼을 측정하여 하기 도 1 및 도 2에 도시하였다.8.31 g (0.05 mol) of 1,4-bis (methoxymethyl) benzene and 0.154 diethyl sulfate were introduced into a 1 liter four-necked flask equipped with a mechanical stirrer, a cooling tube, a 300 ml dropping funnel, and a nitrogen gas introduction tube. Stir well with g (0.001 mol) and 200 g of γ-butyrolactone. After 10 minutes, a solution of 28.02 g (0.08 mol) of 4,4 '-(9-fluorenylidene) diphenol in 200 g of γ-butyrolactone was slowly added dropwise for 30 minutes, followed by reaction for 12 hours. . After completion of the reaction, the acid was removed using water, and then concentrated by an evaporator. It was then diluted with MAK and methanol and adjusted to a solution of 15 wt% MAK / methanol = 4/1 (weight ratio). The solution was placed in a 3 L separatory funnel, and n-heptane was added thereto to remove the low molecular weight containing the monomer to obtain the desired phenol resin (Mw = 12,000, polydispersity = 2.0, n = 23). In addition, 1 H-NMR spectrum and FT-IR spectrum of the synthesized phenol resin were measured and shown in FIGS. 1 and 2.
실시예Example 2-1: 화합물(3) 합성 2-1: Compound (3) Synthesis
기계교반기, 냉각관, 300ml 적가 깔대기, 질소가스 도입관을 구비한 1ℓ의 4구 플라스크에 질소가스를 유입하면서 1,4-비스(메톡시메틸)벤젠 8.31g(0.05몰)과 디에틸설페이트 0.154g(0.001몰)과 200g의 γ-부티로락톤을 담고 잘 저어주었다. 10분 후에 1-나프톨 11.54g(0.08몰)을 200g의 γ-부티로락톤에 녹인 용액을 30분간 천천히 적가한 다음, 12시간 동안 반응을 실시하였다. 반응종료 후 물을 사용하여 산을 제거한 후에 증발기로 농축하였다. 이어서 MAK와 메탄올을 사용하여 희석하고 15 중량% 농도의 MAK/메탄올=4/1(중량비)의 용액으로 조정하였다. 이 용액을 3ℓ 분액깔대기에 넣고, 이것에 n-헵탄을 첨가하여 모노머를 함유하는 저분자량체를 제거하여 목적하는 페놀수지(Mw=11,500, polydispersity=2.4, n=44)를 얻었다.8.31 g (0.05 mol) of 1,4-bis (methoxymethyl) benzene and 0.154 diethyl sulfate were introduced into a 1 liter four-necked flask equipped with a mechanical stirrer, a cooling tube, a 300 ml dropping funnel, and a nitrogen gas introduction tube. Stir well with g (0.001 mol) and 200 g of γ-butyrolactone. After 10 minutes, a solution of 11.54 g (0.08 mol) of 1-naphthol dissolved in 200 g of γ-butyrolactone was slowly added dropwise for 30 minutes, followed by reaction for 12 hours. After completion of the reaction, the acid was removed using water, and then concentrated by an evaporator. It was then diluted with MAK and methanol and adjusted to a solution of 15 wt% MAK / methanol = 4/1 (weight ratio). The solution was placed in a 3 L separatory funnel, and n-heptane was added thereto to remove the low molecular weight containing the monomer to obtain the desired phenol resin (Mw = 11,500, polydispersity = 2.4, n = 44).
실시예Example 2-2: 화합물 (4) 합성 2-2: Compound (4) Synthesis
기계교반기, 냉각관, 300ml 적가 깔대기, 질소가스 도입관을 구비한 1ℓ의 4구 플라스크에 질소가스를 유입하면서 1,4-비스(메톡시메틸)벤젠 8.31g(0.05몰)과 디에틸설페이트 0.154g(0.001몰)과 200g의 γ-부티로락톤을 담고 잘 저어주었다. 10분 후에 페놀 7.53g(0.08몰)을 200g의 γ-부티로락톤에 녹인 용액을 30분간 천천히 적가한 다음, 12시간 동안 반응을 실시하였다. 반응종료 후 물을 사용하여 산을 제거한 후에 증발기로 농축하였다. 이어서 MAK와 메탄올을 사용하여 희석하고 15 중량% 농도의 MAK/메탄올=4/1(중량비)의 용액으로 조정하였다. 이 용액을 3ℓ 분액깔대기에 넣고, 이것에 n-헵탄을 첨가하여 모노머를 함유하는 저분자량체를 제거하여 목적하는 페놀수지(Mw=10,300, polydispersity=2.3, n=48)를 얻었다.8.31 g (0.05 mol) of 1,4-bis (methoxymethyl) benzene and 0.154 diethyl sulfate were introduced into a 1 liter four-necked flask equipped with a mechanical stirrer, a cooling tube, a 300 ml dropping funnel, and a nitrogen gas introduction tube. Stir well with g (0.001 mol) and 200 g of γ-butyrolactone. After 10 minutes, a solution of 7.53 g (0.08 mol) of phenol in 200 g of γ-butyrolactone was slowly added dropwise for 30 minutes, followed by reaction for 12 hours. After completion of the reaction, the acid was removed using water, and then concentrated by an evaporator. It was then diluted with MAK and methanol and adjusted to a solution of 15 wt% MAK / methanol = 4/1 (weight ratio). The solution was placed in a 3 L separatory funnel, and n-heptane was added thereto to remove the low molecular weight containing the monomer to obtain the desired phenol resin (Mw = 10,300, polydispersity = 2.3, n = 48).
실시예Example 3: 화합물 (5) 합성 3: Synthesis of Compound (5)
기계교반기, 냉각관, 300ml 적가 깔대기, 질소가스 도입관을 구비한 1ℓ의 4구 플라스크에 질소가스를 유입하면서 4,4'-비스(클로로메틸)-1,1'-비페닐 12.56g(0.05몰)과 알루미늄 클로라이드 26.66g과 200g의 γ-부티로락톤을 담고 잘 저어주었다. 10분 뒤에 4,4'-(9-플루오레닐리덴)디페놀 35.03g (0.10몰)을 200g의 γ-부티로락톤에 녹인 용액을 30분간 천천히 적가한 다음, 12시간 동안 반응을 실시하였다. 반응종료 후 물을 사용하여 산을 제거한 후에 증발기로 농축하였다. 이 어서 MAK와 메탄올을 사용하여 희석하고 15 중량% 농도의 MAK/메탄올=4/1(중량비)의 용액으로 조정하였다. 이 용액을 3ℓ 분액깔대기에 넣고, 이것에 n-헵탄을 첨가하여 모노머를 함유하는 저분자량체를 제거하여 목적하는 페놀수지(Mw=4100, n=7~8)을 얻었다.12,56 g (0.05 g) of 4,4'-bis (chloromethyl) -1,1'-biphenyl while introducing nitrogen gas into a 1 liter four-necked flask equipped with a mechanical stirrer, a cooling tube, a 300 ml dropping funnel and a nitrogen gas introduction tube. Mole) and 26.66 g of aluminum chloride and 200 g of γ-butyrolactone were stirred well. After 10 minutes, a solution of 35.03 g (0.10 mol) of 4,4 '-(9-fluorenylidene) diphenol in 200 g of γ-butyrolactone was slowly added dropwise for 30 minutes, followed by reaction for 12 hours. . After completion of the reaction, the acid was removed using water, and then concentrated by an evaporator. This was followed by dilution with MAK and methanol and adjusted to a solution of 15 wt% MAK / methanol = 4/1 (weight ratio). The solution was placed in a 3 L separatory funnel, and n-heptane was added thereto to remove the low molecular weight containing the monomer to obtain a desired phenol resin (Mw = 4100, n = 7 to 8).
비교예Comparative example 1: 화합물 (6) 합성 1: Synthesis of Compound (6)
기계교반기, 냉각관, 300ml 적가 깔대기, 질소가스 도입관을 구비한 1ℓ의 4구 플라스크에 페놀 7.52g (0.08몰)과 p-톨루엔술폰산 0.3g을 200g의 γ-부티로락톤에 녹인 용액을 담고 질소가스를 유입하면서 자기교반기로 교반하고 있는 오일조에서 플라스크를 가열하여 반응용액의 내부온도가 100℃에 도달한 시점에서, 적가 깔대기로 37중량% 포름알데히드 수용액 5.27g(0.065몰)을 30분간 천천히 적가하고 12시간 반응을 실시하였다. 반응종료 후 반응용기가 충분히 실온까지 냉각된 후, 반응용액을 MAK을 사용하여 20중량% 농도의 용액으로 조정하고, 3ℓ 분액깔대기로 3회 물세정하여 증발기로 농축하였다. 이어서 MAK와 메탄올을 사용하여 희석하고 15 중량% 농도의 MAK/메탄올=4/1(중량비)의 용액으로 조정하였다. 이 용액을 3ℓ 분액깔대기에 넣고, 이것에 n-헵탄을 첨가하여 모노머를 함유하는 저분자량체를 제거하여 목적하는 페놀수지(Mw=6000, n=55~56)를 얻었다.In a 1 liter four-necked flask equipped with a mechanical stirrer, a cooling tube, a 300 ml dropping funnel and a nitrogen gas introduction tube, 7.52 g (0.08 mol) of phenol and 0.3 g of p-toluenesulfonic acid were dissolved in 200 g of γ-butyrolactone. When the flask was heated in an oil bath stirred with a magnetic stirrer while introducing nitrogen gas, and the reaction solution reached an internal temperature of 100 ° C, 5.27 g (0.065 mol) of 37% by weight aqueous formaldehyde solution was added to the dropping funnel for 30 minutes. The reaction mixture was slowly added dropwise and reacted for 12 hours. After completion of the reaction, the reaction vessel was sufficiently cooled to room temperature, the reaction solution was adjusted to a solution of 20% by weight concentration using MAK, washed three times with 3 L separatory funnel and concentrated by an evaporator. It was then diluted with MAK and methanol and adjusted to a solution of 15 wt% MAK / methanol = 4/1 (weight ratio). The solution was placed in a 3 L separatory funnel, and n-heptane was added thereto to remove the low molecular weight containing the monomer to obtain the desired phenol resin (Mw = 6000, n = 55 to 56).
실시예Example 4 4
실시예 1에서 만들어진 고분자 0.8g과 아래의 구조단위의 반복으로 이루어진 올리고머 상태인 가교제(Powderlink 1174) 0.2g과 피리디늄 P-톨루엔 술포네이트(Pyridinium P-toluene sulfonate) 2mg을 프로필렌글리콜모노에틸아세테이트(Propyleneglycolmonoethylacetate, 이하 PGMEA이라 칭함) 9g에 넣어서 녹인 후 여과하여 샘플용액을 만들었다.0.8 g of the polymer prepared in Example 1 and 0.2 g of a crosslinking agent (Powderlink 1174) which is an oligomeric state consisting of repeating the following structural units and 2 mg of pyridinium P-toluene sulfonate (propylene glycol monoethyl acetate) Propyleneglycolmonoethylacetate (hereinafter referred to as PGMEA) was added to 9g to dissolve and filtered to make a sample solution.
Powderlink 1174 구조Powderlink 1174 structure
실시예Example 5 5
실시예 2에서 만들어진 고분자 0.8g과 가교제(Powderlink 1174) 0.2g과 피리디늄 P-톨루엔 술포네이트 2mg을 PGMEA 9g에 넣어서 녹인 후 여과하여 샘플용액을 만들었다.0.8 g of the polymer prepared in Example 2, 0.2 g of a crosslinking agent (Powderlink 1174), and 2 mg of pyridinium P-toluene sulfonate were dissolved in PGMEA 9 g, and filtered to prepare a sample solution.
실시예Example 5-1 5-1
실시예 2-1에서 만들어진 고분자 0.8g과 가교제(Powderlink 1174) 0.2g과 피리디늄 P-톨루엔 술포네이트 2mg을 PGMEA 9g에 넣어서 녹인 후 여과하여 샘플용액을 만들었다. 0.8 g of the polymer prepared in Example 2-1, 0.2 g of a crosslinking agent (Powderlink 1174), and 2 mg of pyridinium P-toluene sulfonate were dissolved in PGMEA 9 g, followed by filtration to prepare a sample solution.
실시예Example 5-2 5-2
실시예 2-2에서 만들어진 고분자 0.8g과 가교제(Powderlink 1174) 0.2g과 피리디늄 P-톨루엔 술포네이트 2mg을 PGMEA 9g에 넣어서 녹인 후 여과하여 샘플용액을 만들었다. 0.8 g of the polymer prepared in Example 2-2, 0.2 g of a crosslinking agent (Powderlink 1174), and 2 mg of pyridinium P-toluene sulfonate were dissolved in PGMEA 9 g, followed by filtration to prepare a sample solution.
실시예Example 6 6
실시예 3에서 만들어진 고분자 0.8g과 가교제(Powderlink 1174) 0.2g과 피리디늄 P-톨루엔 술포네이트 2mg을 PGMEA 9g에 넣어서 녹인 후 여과하여 샘플용액을 만들었다.0.8 g of the polymer prepared in Example 3, 0.2 g of a crosslinking agent (Powderlink 1174), and 2 mg of pyridinium P-toluene sulfonate were dissolved in PGMEA 9 g, and then filtered to prepare a sample solution.
비교예Comparative example 2 2
비교예 1에서 만들어진 고분자 0.8g과 가교제(Cymel 303) 0.2g과 피리디늄 P-톨루엔 술포네이트 2mg을 PGMEA 9g에 넣어서 녹인 후 여과하여 샘플용액을 만들었다.0.8 g of the polymer prepared in Comparative Example 1, 0.2 g of a crosslinking agent (Cymel 303), and 2 mg of pyridinium P-toluene sulfonate were dissolved in PGMEA 9 g, and then filtered to prepare a sample solution.
실시예Example 7 7
실시예 4-6과 비교예 2에서 만들어진 샘플을 실리콘웨이퍼에 스핀-코팅법으로 코팅하여 60초간 200℃에서 구워서 두께 1500Å의 필름을 형성시켰다.The samples made in Example 4-6 and Comparative Example 2 were coated on a silicon wafer by spin-coating to bake at 200 ° C. for 60 seconds to form a film having a thickness of 1500 Å.
실시예Example 8 8
실시예 7에서 제조된 필름들에 대한 굴절률(refractive index) n과 흡광계수(extinction coefficient) k를 구하였다. 사용기기는 Ellipsometer(J. A. Woollam 사)이고 측정결과는 표 1과 같다.The refractive index n and extinction coefficient k of the films prepared in Example 7 were obtained. The instrument used was Ellipsometer (J. A. Woollam) and the measurement results are shown in Table 1.
표 1Table 1
실시예Example 9 9
실시예 4-6과 비교예 2에서 만들어진 샘플을 알루미늄이 입혀진 실리콘웨이퍼 위에 스핀-코팅법으로 코팅하여 60초간 200℃에서 구워서 두께 1500Å의 필름을 형성시켰다.Samples made in Examples 4-6 and Comparative Example 2 were coated on a silicon wafer coated with aluminum by spin-coating, and baked at 200 ° C. for 60 seconds to form a film having a thickness of 1500 Å.
실시예Example 10 10
실시예 9에서 제조된 필름위에 KrF용 포토레지스트를 코팅하고 110℃에서 60초간 굽고 ASML(XT:1400, NA 0.93)사의 노광장비를 사용해 노광을 한 다음 TMAH(2.38wt% 수용액)으로 현상하였다. 그리고 FE-SEM을 사용하여 90nm의 라인 앤 드 스페이스(line and space) 패턴을 고찰한 결과 하기 표 2와 같은 결과를 얻었다. 노광량의 변화에 따른 EL(expose latitude) 마진(margine)과 광원과의 거리변동에 따른 DoF(depth of focus) 마진(margine)을 고찰하여 표 2에 기록하였다.The photoresist for KrF was coated on the film prepared in Example 9, baked at 110 ° C. for 60 seconds, and exposed to light using an exposure equipment of ASML (XT: 1400, NA 0.93), followed by development with TMAH (2.38 wt% aqueous solution). And using a FE-SEM to examine the line and space (line and space) pattern of 90nm as shown in Table 2 below. The exposure latitude (EL) margin according to the change of the exposure dose and the depth of focus (DoF) margin according to the distance change with the light source are considered and recorded in Table 2.
표 2TABLE 2
실시예Example 11 11
실시예 10에서 패턴화된 시편을 CHF3/CF4 혼합가스를 사용하여 드라이 에칭을 진행하고 이어서 BCl3/Cl2 혼합가스를 사용하여 드라이 에칭을 다시 진행하였다. 마지막으로 O2가스를 사용하여 남아 있는 유기물을 모두 제거한 다음, FE SEM으로 단면을 고찰하여 표 3에 결과를 수록하였다.The patterned specimens in Example 10 were subjected to dry etching using a CHF 3 / CF 4 mixed gas, followed by dry etching again using a BCl 3 / Cl 2 mixed gas. Finally, after removing all remaining organics using O 2 gas, the cross section was examined by FE SEM and the results are listed in Table 3.
표 3TABLE 3
실시예Example 12 12
실시예 7에서 만들어진 시편을 CHF3/CF4 혼합가스를 사용하여 드라이 에칭을 진행하고 전후의 두께차를 표 4에 수록하였다.The specimen prepared in Example 7 was subjected to dry etching using a CHF 3 / CF 4 mixed gas, and the thickness differences before and after are listed in Table 4.
표 4Table 4
실시예Example 13 13
실시예 4-6과 비교예 2에서 만들어진 샘플을 SiN(실리콘나이트라이드)이 입혀진 실리콘웨이퍼 위에 스핀-코팅법으로 코팅하여 60초간 200℃에서 구워서 두께 1500Å의 필름을 형성시켰다.The samples made in Example 4-6 and Comparative Example 2 were coated by spin-coating on a silicon wafer coated with SiN (silicon nitride) and baked at 200 ° C. for 60 seconds to form a film having a thickness of 1500 Å.
실시예Example 14 14
실시예 13에서 제조된 필름위에 ArF용 포토레지스트를 코팅하고 110℃에서 60초간 굽고 ArF 노광장비인 ASML1250 (FN70 5.0 active, NA 0.82)를 사용해 노광을 한 다음 TMAH(2.38wt% 수용액)으로 현상하였다. 그리고 FE-SEM을 사용하여 80nm의 라인 앤드 스페이스(line and space) 패턴을 고찰한 결과 하기 표 5와 같은 결과를 얻었다. 노광량의 변화에 따른 EL(expose latitude) 마진(margine)과 광원과의 거리변동에 따른 DoF(depth of focus) 마진(margine)을 고찰하여 표 5에 기록하였다.The ArF photoresist was coated on the film prepared in Example 13, baked at 110 ° C. for 60 seconds, exposed to light using an ArF exposure equipment, ASML1250 (FN70 5.0 active, NA 0.82), and developed using TMAH (2.38 wt% aqueous solution). . And using a FE-SEM to examine the line and space (line and space) pattern of 80nm as shown in Table 5 below. The exposure latitude (EL) margin according to the change of the exposure dose and the depth of focus (DoF) margin according to the distance change with the light source were considered and recorded in Table 5.
표 5Table 5
실시예Example 15 15
실시예 14에서 패턴화된 시편을 CHF3/CF4 혼합가스를 사용하여 드라이 에칭을 진행하고 이어서 선택비를 달리한 CHF3/CF4 혼합가스를 사용하여 드라이 에칭을 다시 진행하였다. 마지막으로 O2가스를 사용하여 남아 있는 유기물을 모두 제거한 다음, FE SEM으로 단면을 고찰하여 표 6에 결과를 수록하였다.The patterned specimens in Example 14 were dry etched using CHF 3 / CF 4 mixed gas, and then dry etched again using CHF 3 / CF 4 mixed gas having different selectivity. Finally, all remaining organics were removed using O 2 gas, and then the cross-section was examined by FE SEM and the results are shown in Table 6.
표 6Table 6
본 발명에 따른 조성물은 매우 우수한 광학적 특성, 기계적 특성 및 에칭 선택비(etch selectivity) 특성을 제공하고, 동시에 스핀-온 도포 기법(spin-on application technique)을 이용하여 도포 가능한 특성을 제공한다. 또한, 상기 조성물은 우수한 저장 수명을 가지며, 최소이거나 전혀 없는 산 오염물질 함량을 갖는다.The compositions according to the invention provide very good optical, mechanical and etch selectivity properties, while at the same time providing applicability using a spin-on application technique. In addition, the compositions have good shelf life and have minimal or no acid pollutant content.
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