JP6186225B2 - ハードマスク - Google Patents
ハードマスク Download PDFInfo
- Publication number
- JP6186225B2 JP6186225B2 JP2013196367A JP2013196367A JP6186225B2 JP 6186225 B2 JP6186225 B2 JP 6186225B2 JP 2013196367 A JP2013196367 A JP 2013196367A JP 2013196367 A JP2013196367 A JP 2013196367A JP 6186225 B2 JP6186225 B2 JP 6186225B2
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- JP
- Japan
- Prior art keywords
- beta
- meth
- acrylate
- metal
- oligomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052751 metal Inorganic materials 0.000 claims description 73
- 239000002184 metal Substances 0.000 claims description 73
- 239000000178 monomer Substances 0.000 claims description 52
- 125000002524 organometallic group Chemical group 0.000 claims description 52
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 36
- 239000003446 ligand Substances 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 14
- 229910052735 hafnium Inorganic materials 0.000 claims description 13
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- -1 amine dinate Chemical class 0.000 claims description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000010937 tungsten Chemical group 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229910052715 tantalum Inorganic materials 0.000 claims description 11
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Chemical group 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Chemical group 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000001723 curing Methods 0.000 description 37
- 239000002904 solvent Substances 0.000 description 35
- 239000010410 layer Substances 0.000 description 28
- 229910044991 metal oxide Inorganic materials 0.000 description 20
- 150000004706 metal oxides Chemical class 0.000 description 20
- 235000012431 wafers Nutrition 0.000 description 20
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 13
- 229920002120 photoresistant polymer Polymers 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000005530 etching Methods 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000002902 organometallic compounds Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000004528 spin coating Methods 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000006117 anti-reflective coating Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 241001061127 Thione Species 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- QKFFSWPNFCXGIQ-UHFFFAOYSA-M 4-methylbenzenesulfonate;tetraethylazanium Chemical compound CC[N+](CC)(CC)CC.CC1=CC=C(S([O-])(=O)=O)C=C1 QKFFSWPNFCXGIQ-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 125000006528 (C2-C6) alkyl group Chemical group 0.000 description 1
- VNLSCKAQGGXPRI-UHFFFAOYSA-N 2,2,6,6-tetramethyl-3,5-dioxoheptanoic acid Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C(O)=O VNLSCKAQGGXPRI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- MQIFVWRGUHSEBB-UHFFFAOYSA-N CC(=O)CC(C)=O.CC(=O)CC(C)=O.CCCCO[Zr]OCCCC Chemical compound CC(=O)CC(C)=O.CC(=O)CC(C)=O.CCCCO[Zr]OCCCC MQIFVWRGUHSEBB-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- XYVQFUJDGOBPQI-UHFFFAOYSA-N Methyl-2-hydoxyisobutyric acid Chemical compound COC(=O)C(C)(C)O XYVQFUJDGOBPQI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 125000001539 acetonyl group Chemical group [H]C([H])([H])C(=O)C([H])([H])* 0.000 description 1
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HLOLVQSTCUVLJD-UHFFFAOYSA-N ethyl 3-oxobutanoate 3-oxohexanoic acid Chemical compound CCCC(=O)CC(O)=O.CCOC(=O)CC(C)=O HLOLVQSTCUVLJD-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000000671 immersion lithography Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000012257 stirred material Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
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Description
前記有機金属オリゴマーが、(i)金属含有ペンダント基を含むオリゴマー、(ii)式(2)のオリゴマー、
Zr(OBu)3メタクリレートモノマーの合成
Zr(OBu)3アクリレートモノマーの合成
他の金属−アルコキシド(メタ)アクリレートモノマーの合成
Zr(OBu)4を以下の金属アルコキシドで置き換えること以外は、実施例1および2の手法を繰り返す。
75/25 Zr(OBu)3メタクリレート/tert−ブチルアクリレートランダムコポリマーの調製
モノマー/開始剤の溶液は、以下をガラスバイアルに加えることにより調製された:トルエン中24%である実施例1からのZr(OBu)3メタクリレートを31.26g、および2.749gのtert−ブチルアクリレート。このバイアルを次いで穏やかに振とうしてモノマーを混合し、次いで氷浴中に置いて、温度を氷浴と平衡に至らせた。次に、0.302gのジメチル2,2’−アゾビス(2−メチルプロピオネート)開始剤(Wako Pure Chemical Industries,Ltd.から商品名V−106で入手可能)をバイアルに加え、その後に振とうすることにより開始剤を完全に溶解した。このバイアルを次いで氷浴中に再び戻し、必要になるまで置いた。
磁気撹拌子を含有し、熱電対、冷却水が循環しない凝縮器およびモノマー/開始剤供給ラインを備えた100mLの三つ口丸底フラスコを、加熱マントル内に設置した。トルエン(5.0g)をフラスコに加え、適当に撹拌しながら温度を99℃に上げた。モノマー/開始剤溶液は、撹拌しながらリアクタ温度を99℃に維持しつつ、Hamiltonデュアルシリンジポンプを用いて250μL/52秒の速度でフラスコに供給した。モノマー/開始剤溶液の添加が完了したら、フラスコを99℃でさらに2時間維持した。熱を次いで取り除き、反応混合物(ポリマー溶液)を室温まで冷却した。ポリマー溶液を次いで、さらなる精製を行わずにそのまま用いた。
Zr(OBu)3アクリレートホモポリマーの調製
磁気撹拌子を含有し、熱電対、冷却水が循環しない凝縮器およびモノマー/開始剤供給ラインを備えた100mLの三つ口丸底フラスコを、加熱マントル内に設置した。トルエン(10.0g)をフラスコに加え、適当に撹拌しながら温度を70℃に上げた。
Hf(OBu)3メタクリレート/tert−ブチルアクリレートランダムコポリマーの調製
実施例3からのHf(O−n−Bu)3メタクリレートを用いること以外は、実施例4の手法を繰り返す。
Ti(O−i−Pr)3アクリレートホモポリマーの調製
実施例3からのTi(O−i−Pr)3アクリレートを用いること以外は、実施例5の手法を繰り返す。
コポリマーの調製
以下のモノマーを表1中に示される相対量で用いること以外は、実施例4または実施例5の手法を繰り返す。表2中で用いられる略語は、以下の意味を持つ。TBA=tert−ブチルアクリレート、EHA=エチルヘキシルアクリレート、EHMA=エチルヘキシルメタクリレート、およびEA=エチルアクリレート。
Hf(OBu)アセチル−ジエチレングリコールコポリマーの調製
500mLの三つ口フラスコに還流凝縮器、機械的撹拌機および添加漏斗を装着させた。このリアクタに100g(0.21mol)のHf(OBu)4(Gelest Inc.から入手可能)を加えた。勢いよく撹拌したこの材料にペンタン−2,4−ジオン(42.5g、0.42mol)を非常にゆっくりと、6時間かけて加えた。反応混合物を一晩、室温で撹拌した。反応中に生成したn−ブタノールを真空下で除去し、次いで800mLの酢酸エチルを加えて、反応フラスコを室温で30分間、勢いよく撹拌した。この溶液を細フリットを通してろ過し、あらゆる不溶性産物を除去した。残った溶剤を真空下で除去し、青白色の固体を得た(100.4g、90%の収率)。この産物であるHf(OBu)2(acac)2を、さらなる精製を行わずに用いた。
Ti(OBu)アセチル−ジエチレングリコールコポリマーの調製
Dean−Starkトラップを備えたフラスコに、50gのTi(OR)2(acac)2(R=エチルまたはイソプロピル、TYZOR AA−105、DuPontから入手可能)および等モル量のジエチレングリコールを室温で加えた。この混合物を125℃に加熱し、1〜2日間撹拌して、蒸留物を回収した。この混合物を次いで冷却し、ヘプタン(500mL)中でクエンチした。結果として得られた沈殿を回収し、真空中で乾燥させて、以下の式(5)に示す構造を持つ35gの所望の産物が与えられた。
Zr(OBu)アセチル−ジエチレングリコールコポリマーの調製
トルエン/ブタノール中25重量%のジルコニウムビス(アセチルアセトン)−ビス(n−ブトキシド)(すなわちZr(acac)2(OBu)2)をGelest Inc.から得て、さらなる精製を行わずに用いた。200gのZr(acac)2(OBu)2から溶剤を除去し、残渣を250mLの酢酸エチルで希釈した。この混合物に等モル量のジエチレングリコールを室温で加え、次いでこの混合物を80℃で18時間還流した。次に反応混合物を冷却し、ろ過して白色沈殿を除去した。ロータリーエバポレーターを用いてろ液を少容量に濃縮し、この残渣をヘプタン中でクエンチした。沈殿を次いで回収し、真空中で乾燥させて、構造が式(6)により示される所望の産物が20.8g与えられた。
有機金属−アルキレンオキシドコポリマーの調製
以下の有機金属化合物およびアルキレンオキシドを用いること以外は、実施例9〜10の手法を繰り返す。
溶剤ストリップ試験
使用において、金属ハードマスク膜は、他のコーティング、例えばフォトレジストなどをハードマスク膜の上面に適用するのに一般に用いられる溶剤による除去に耐性であることが重要である。以下の溶剤ストリップ試験において、一般的なフォトレジスト溶剤であるプロピレングリコールメチルエーテルアセテート(PGMEA)を、ハードマスク膜を評価するのに用いた。
酸化Zr含有膜の調製
2つの試料を、下に示すように、実施例4からのZr(OBu)3メタクリレート/tert−ブチルアクリレート(Zr(OBu)3MA/TBA)ポリマーを、2−メチル−1−ブタノール(溶剤)および任意選択で熱酸発生剤としてp−トルエンスルホン酸テトラエチルアンモニウム塩(p−TSA−TEA)(Zr(OBu)3MA/TBAポリマーに対して2%)と一緒にすることにより調製した。
酸化Zr含有膜の熱安定性
実施例14からの試料1および2の各々から調製した所定の膜の熱安定性を評価した。ウェーハを試料1または2のいずれかでスピンコートし、次いで250または350℃のいずれかで60秒間硬化させ、膜厚を実施例13中に記載されたように測定した。ウェーハを次いで250℃で10分間ベークし、その後、膜厚を再度測定した。以下のデータから認められうるように、350℃で硬化させた膜は膜厚変化が5%未満であり、より良好な安定性を示した。
酸化Zr含有膜の調製
試料3は、PGMEA/MIBC中15.2%である実施例5からの10.53gのZr(OBu)3アクリレートホモポリマー(BuOZrAポリマー)を29.5gの2−メチル−1−ブタノールで希釈することにより調製した。
混合酸化Zr/Hf含有膜の調製
3つの試料を、下に示すように、実施例4からのZr(OBu)3MA/TBAポリマーをハフニウムアセトニルアセトネート(Hf(acac)4)およびトルエン(溶剤)と一緒にすることにより調製した。
混合酸化Zr/Hr含有膜の調製
Hf(acac)4をジブトキシビス(((Z)−4−オキソペンタ−2−エン−2−イル)オキシ)ハフニウム(Hf(BuO)アセチル)と置き換え、用いた溶剤がPGMEAであったこと以外は、実施例17の手法を繰り返した。試料の組成を下に示す。
酸化Hf含有膜の調製
試料9は、実施例9からの1.202gのHf(OBu)アセチル−ジエチレングリコールコポリマー(Hf(OBu)アセチル−DEG)を13.84gの2−メチル−1−ブタノール中に溶解することにより調製した。いくつかのウェーハを試料9でスピンコートし、次いで異なる温度で60秒間硬化させた。硬化後、各膜を実施例13の溶剤ストリップ試験に供した。膜厚の結果を表9中に(Å単位で)報告し、優れた溶剤耐性が示された。
酸化Zr含有膜の調製
試料10は、実施例11からの0.486gのZr(OBu)アセチル−ジエチレングリコールコポリマー(Zr(OBu)アセチル−DEG)を12.3gの2−メチル−1−ブタノール中に溶解することにより調製した。いくつかのウェーハを試料10でスピンコートし、次いで異なる温度で60秒間硬化させた。硬化後、各膜を実施例13の溶剤ストリップ試験に供した。膜厚の結果を表10中に(Å単位で)報告する。温度>150℃での膜硬化は、より良く優れた溶剤耐性をもたらした。
酸化Ti含有膜の調製
試料11は、実施例10からの0.505gのTi(OBu)アセチル−ジエチレングリコールコポリマー(Ti(OBu)アセチル−DEG)を12.78gの2−メチル−1−ブタノール中に溶解することにより調製した。いくつかのウェーハを試料10でスピンコートし、次いで異なる温度で60秒間硬化させた。硬化後、各膜を実施例13の溶剤ストリップ試験に供した。膜厚の結果を表11中に(Å単位で)報告する。温度>150℃での膜硬化は、より良く優れた溶剤耐性をもたらした。
表面接触角
実施例19、20および21からの膜からの表面接触角は、Kruss液滴形状分析機Model 100を用いて、DI水および0.25μLの液滴サイズを用いて、それらの表面接触角を決定するために評価した。結果を表12中に報告する。
酸化Zr含有膜の調製
2つの試料は、下に示すように、実施例4からのZr(OBu)3メタクリレート/tert−ブチルアクリレート(Zr(OBu)3MA/TBA、有機金属1)ポリマーおよび実施例11からのZr(BuO)アセチル−DEGポリマー(有機金属2)を、2−メチル−1−ブタノールおよびガンマ−ブチロラクトン(溶剤)と一緒にすることにより調製した。
エッチング速度の決定
酸化ハフニウム、酸化ジルコニウムおよび酸化チタンを含有する膜の試料は、2−メチル−1−ブタノール中3.8%の固形分で記載された組成を用いて実施例19、20および21をそれぞれ再現することにより調製した。これらの組成物の各々を1500rpmでいくつかのウェーハ上にスピンコートし、60秒間、200、250または350℃で硬化させた。
Claims (12)
- (a)電子デバイス基体を提供すること、(b)前記電子デバイス基体上に有機金属オリゴマーの層を配置すること、および(c)前記有機金属オリゴマーを硬化させて、前記電子デバイス基体上に金属酸化物層を形成することを含み、
前記有機金属オリゴマーが、
(i)金属含有ペンダント基を含むオリゴマーであって、重合単位として1種以上の式(1)
のモノマーを含むオリゴマー;
(ii)式(2)のオリゴマー、
電子デバイスを製造する方法。 - 各Lが(C1−C6)アルコキシから選択される、請求項1に記載の方法。
- 各L1がベータ−ジケトノン、ベータ−ヒドロキシケトン、ベータ−ジケチミネート、アミンジネート、グアニジネートおよびベータ−ヒドロキシイミンから選ばれる、請求項1に記載の方法。
- 各L1がアセトニルアセトネート、ヘキサフルオロアセトニルアセトネート、N,N’−ジメチル−メチルアミジナト、N,N’−ジエチル−メチルアミジナト、N,N’−ジエチル−エチルアミジナト、N,N’−ジ−イソ−プロピル−メチルアミジナト、N,N’−ジ−イソ−プロピル−イソ−プロピルアミジナト、N,N’−ジメチル−フェニルアミジナト、テトラメチルグアニジネートおよびテトラエチルグアニジネートから選択される、請求項3に記載の方法。
- m=2である、請求項1に記載の方法。
- p=2〜10である、請求項1に記載の方法。
- 工程(b)が有機金属オリゴマーおよび有機溶剤を含む組成物を用いて行われる、請求項1に記載の方法。
- 前記有機溶剤が<10,000ppmの水を含む、請求項7に記載の方法。
- 前記硬化工程の前に有機溶剤を除去する工程をさらに含む、請求項7に記載の方法。
- 前記金属含有ペンダント基を含むオリゴマーが、重合単位として、(メタ)アクリル酸、アルキル(メタ)アクリレート、ヒドロキシアルキル(メタ)アクリレート、アルケニル(メタ)アクリレート、および芳香族(メタ)アクリレートから選ばれる1種以上のモノマーをさらに含む、請求項1に記載の方法。
- 重合単位として、アルキル(メタ)アクリレートモノマー、アリール(メタ)アクリレートモノマー、ヒドロキシアルキル(メタ)アクリレートモノマー、アルケニル(メタ)アクリレート、(メタ)アクリル酸およびビニル芳香族モノマーから選ばれる1種以上のモノマーをさらに含む、請求項11に記載のポリマー。
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