TWI644958B - Resin composition, resist mask for dry etching, and pattern forming method - Google Patents
Resin composition, resist mask for dry etching, and pattern forming method Download PDFInfo
- Publication number
- TWI644958B TWI644958B TW103145324A TW103145324A TWI644958B TW I644958 B TWI644958 B TW I644958B TW 103145324 A TW103145324 A TW 103145324A TW 103145324 A TW103145324 A TW 103145324A TW I644958 B TWI644958 B TW I644958B
- Authority
- TW
- Taiwan
- Prior art keywords
- dry etching
- resin composition
- polymer
- pattern
- etching resist
- Prior art date
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- 238000001312 dry etching Methods 0.000 title claims abstract description 98
- 239000011342 resin composition Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 56
- 229920000642 polymer Polymers 0.000 claims abstract description 74
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 36
- 125000003118 aryl group Chemical group 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- 125000005647 linker group Chemical group 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 6
- 239000010408 film Substances 0.000 description 78
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 239000000243 solution Substances 0.000 description 35
- 239000000758 substrate Substances 0.000 description 33
- 150000002430 hydrocarbons Chemical group 0.000 description 23
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 22
- 239000002904 solvent Substances 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000576 coating method Methods 0.000 description 14
- -1 α-methylstyryl group Chemical group 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000007261 regionalization Effects 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 8
- 125000005842 heteroatom Chemical group 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 7
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001226 reprecipitation Methods 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004049 embossing Methods 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002601 GaN Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 150000008062 acetophenones Chemical class 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- XYRRJTMWSSGQGR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO.OCC(CO)(CO)CO XYRRJTMWSSGQGR-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-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
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YMUQRDRWZCHZGC-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO.CCC(CO)(CO)CO YMUQRDRWZCHZGC-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-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
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000534944 Thia Species 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
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- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
-
- 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
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F12/36—Divinylbenzene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/026—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing of layered or coated substantially flat surfaces
-
- 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
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
-
- 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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/16—Homopolymers or copolymers of alkyl-substituted styrenes
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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
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
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- G03F1/80—Etching
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- G—PHYSICS
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- 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
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
- G03F7/2055—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser for the production of printing plates; Exposure of liquid photohardening compositions
-
- 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
- G03F9/00—Registration or positioning of originals, masks, frames, photographic sheets or textured or patterned surfaces, e.g. automatically
- G03F9/70—Registration or positioning of originals, masks, frames, photographic sheets or textured or patterned surfaces, e.g. automatically for microlithography
- G03F9/7003—Alignment type or strategy, e.g. leveling, global alignment
- G03F9/7042—Alignment for lithographic apparatus using patterning methods other than those involving the exposure to radiation, e.g. by stamping or imprinting
-
- 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
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31144—Etching the insulating layers by chemical or physical means using masks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C2201/00—Manufacture or treatment of microstructural devices or systems
- B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
- B81C2201/0101—Shaping material; Structuring the bulk substrate or layers on the substrate; Film patterning
- B81C2201/0147—Film patterning
- B81C2201/015—Imprinting
- B81C2201/0153—Imprinting techniques not provided for in B81C2201/0152
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
本發明提供一種乾式蝕刻抗蝕劑用硬化性樹脂組合物,其特徵在於:其係含有具有特定結構之聚合物(A)者,且該聚合物(A)中之特定結構於聚合物(A)中為80~100重量%。
又,本發明提供一種特徵在於使該乾式蝕刻抗蝕劑用硬化性組合物硬化而成之乾式蝕刻用抗蝕遮罩、及作為具有藉由奈米壓印法之圖案者之乾式蝕刻用抗蝕遮罩。
Description
本發明提供一種乾式蝕刻性及精密圖案再現性優異之乾式蝕刻用抗蝕材料。
近年來,關於以半導體或LED(Lighting Emitting Diode,發光二極體)為代表之電子材料,伴隨高積體化之超小型化、高細密化不斷推進,尤其強烈要求製造較微米更細之奈米單位之圖案之技術。
作為細密圖案之製造方法,有各種各樣之方法,最常用為利用遮罩之蝕刻。其中,就高蝕刻精度而言,於形成高細密圖案之情形時大多使用乾式蝕刻。
為了提高所轉印之圖案之再現性或蝕刻速率,必需所使用之抗蝕劑之乾式蝕刻耐性較高。例如,非專利文獻1中,揭示出乾式蝕刻性根據被稱為大西參數之碳與其他原子之比率而不同,作為乾式蝕刻性較高之樹脂,可列舉聚苯乙烯。然而,聚苯乙烯之乾式蝕刻耐性雖較佳,但其不具有硬化性,故難以形成高細密之圖案。
另一方面,作為可形成高細密圖案之抗蝕劑,可較佳地使用包含具有(甲基)丙烯醯基之化合物之硬化性組合物。包含具有(甲基)丙烯醯基之化合物之硬化性組合物雖然圖案形成性優異,但由於分子中含有氧,故有乾式蝕刻性降低之問題。
[非專利文獻1]‧J. Electrochem Soc 143, 130 (1983) H. Gokan, S. Esho and Y. Ohnishi
本發明之課題在於提供一種作為乾式蝕刻性優異並且可形成高細密圖案,且轉印再現性優異之乾式蝕刻用抗蝕材料之樹脂組合物。
本發明者等人經過努力研究,結果發現,藉由使用具有特定結構之聚合物(A),可解決上述問題。
即,本發明提供一種乾式蝕刻抗蝕劑用硬化性樹脂組合物,其特徵在於:其係含有具有下述式(a-1)表示之結構之聚合物(A)者,且該聚合物(A)中之下述式(a-1)所表示之結構於聚合物(A)中為80~100重量%。
(上述式(a-1)中,X為X1或X2表示之結構單元,X1係以下述式(a-2)、X2係以下述式(a-3)表示,於將聚合物(A)中之X1之數設為m、X2之數設為n時,m為3以上之整數,n為0或1以上之整數,m/(m+n)為0.2~1之範圍,且p表示3~2000之整數。
[化2]
(式(a-2)中,Ar1表示具有1個以上芳香環之芳香族基,Y1為單鍵或包含碳數1~3之烴基之二價連結基,Z1為具有1個以上乙烯基之烴基,r1表示1~5之整數)
(式(a-3)中,Ar2表示具有1個以上芳香環之芳香族基,Y2為單鍵或包含碳數1~3之烴基之二價連結基))
又,本發明提供如技術方案1之乾式蝕刻抗蝕劑用硬化性樹脂組合物,其中上述式(a-1)中,X1為下述式(a-4)所表示者。
(Y3為單鍵或包含碳數1~3之烴基之二價連結基,Z2為具有1個以上乙烯基之烴基,r2表示1~5之整數)
又,本發明提供如技術方案1或2之乾式蝕刻抗蝕劑用硬化性樹
脂組合物,其中式(a-1)中,X2為下述式(a-5)所表示者。
(式(a-5)中,Y4表示單鍵或包含碳數1~3之烴基之二價連結基)
又,本發明提供上述乾式蝕刻抗蝕劑用硬化性樹脂組合物,其中聚合物(A)之分子量為300~100,000。
又,本發明提供上述乾式蝕刻抗蝕劑用硬化性樹脂組合物,其中聚合物(A)每1g之乙烯基之毫當量數為1.8~12.8meq/g。
又,本發明提供上述乾式蝕刻抗蝕劑用硬化性樹脂組合物,其中該組合物進而包含聚合性單體(B)。
又,本發明提供上述乾式蝕刻抗蝕劑用硬化性樹脂組合物,其中該樹脂組合物之大西參數為3.2以下。
(其中,此處所述之大西參數,係於將樹脂組合物中之固形物成分之總原子數設為N、總碳數設為NC、總氧數設為NO時,以N/(NC-NO)表示)
又,本發明提供一種乾式蝕刻用抗蝕遮罩,其係使上述乾式蝕刻抗蝕劑用硬化性樹脂組合物硬化而成。
又,本發明提供一種乾式蝕刻用抗蝕遮罩,其中上述乾式蝕刻用抗蝕遮罩為具有藉由奈米壓印法所形成之圖案者。
又,本發明提供一種圖案轉印方法,其特徵在於包括:對上述乾式蝕刻抗蝕劑用樹脂組合物按壓模具之步驟;使乾式蝕刻抗蝕劑用硬化性樹脂組合物硬化而形成圖案,獲得
具有圖案之硬化物之步驟;及將具有所獲得之圖案之硬化物作為抗蝕遮罩進行乾式蝕刻,而將圖案轉印至被加工體之步驟。
本發明之乾式蝕刻抗蝕劑用樹脂組合物提供一種乾式蝕刻性優異並且如奈米壓印般之高細密圖案之形成性及再現性亦優異之乾式蝕刻用抗蝕遮罩。
本發明之乾式蝕刻抗蝕劑用硬化性樹脂組合物為含有具有下述式(a-1)表示之結構之聚合物(A)者。
(上述式(a-1)中,X為X1或X2表示之結構單元,X1係以下述式(a-2)、X2係以下述式(a-3)表示,於將聚合物(A)中之X1之數設為m、X2之數設為n時,m為3以上之整數,n為0或1以上之整數,m/(m+n)為0.2~1之範圍,且p表示3~2000之整數。
[化7]
(式(a-2)中,Ar1表示具有1個以上芳香環之芳香族基,Y1為單鍵或包含碳數1~3之烴基之二價連結基,Z1為具有1個以上乙烯基之烴基,r1表示1~5之整數)
(式(a-3)中,Ar2表示具有1個以上芳香環之芳香族基,Y2為單鍵或包含碳數1~3之烴基之二價連結基)
上述聚合物(A)中,X1及X2分別為式(a-2)、(a-3)所表示之結構單元,關於各自之結構,只要為式(a-2)、(a-3)所表示之結構,則於聚合物(A)中可為單獨種類,亦可混合複數種。
式(a-2)、(a-3)中,Ar1及Ar2所表示之具有1個以上芳香環之芳香族基亦可含有雜原子,就乾式蝕刻性之觀點而言,較佳為不含雜原子之芳香環。具體而言,可列舉苯基、萘基、蒽基、菲基、芘基等下述式所表示之結構,亦可分別具有取代基,較佳為不具有取代基。
[化9]
於Ar1及Ar2所表示之具有1個以上芳香環之芳香族基具有取代基之情形時,取代基可列舉鹵素原子、碳數1~20之可進行取代之烷基、可進行取代之芳基、可進行取代之芳烷基等,較佳為苯基、苄基、環己基、金剛烷基等不使耐乾式蝕刻性降低之取代基。又,取代基彼此亦可鍵結而形成環狀結構。
式(a-2)所表示之結構單元X1含有Z1所表示之具有1個以上乙烯基之烴基。具有乙烯基之烴基可如亞乙烯基、伸乙烯基般乙烯基直接具有取代基,具體而言,可列舉:乙烯基、1-丙烯基、烯丙基、異丙烯基、1-丁烯基、2-丁烯基、甲基烯丙基、丁二烯基、苯乙烯基、α-甲基苯乙烯基、環己烯基、茚基、乙烯基萘基等,較佳為乙烯基。
式(a-2)所表示之結構單元X1具有Y1所表示之單鍵或包含碳數1~3之烴基之二價連結基。Y1亦可含有雜原子,就乾式蝕刻性之觀點而言,較佳為不含雜原子之烴基,較佳為碳數更少。具體而言,可列舉:亞甲基、伸乙基、伸丙基等,最佳為單鍵。
式(a-3)所表示之結構單元X2具有Y2所表示之單鍵或包含碳數1~3之烴基之二價連結基。Y1亦可含有雜原子,就乾式蝕刻性之觀點而言,較佳為不含雜原子之烴基,較佳為碳數更少。具體而言,可列舉:亞甲基、伸乙基、伸丙基等,最佳為單鍵。
X1及X2亦可具有取代基,例如亦可為式(a-2-2)作為X1或式(a-3-
2)作為X2般之結構。式中,R所表示之取代基可分別獨立,亦可相同,取代基之一部分亦可為氫原子。
(R可列舉氫原子、鹵素原子、碳數1~10之可進行取代之烷基、可進行取代之芳基,Ar1表示具有1個以上芳香環之芳香族基,Y1為單鍵或包含碳數1~3之烴基之二價連結基,Z1為具有1個以上乙烯基之烴基,r1表示1~5之整數)
(R可列舉氫原子、鹵素原子、碳數1~10之可進行取代之烷基、可進行取代之芳基,Ar2表示具有1個以上芳香環之芳香族基,Y2為單鍵或包含碳數1~3之烴基之二價連結基)
作為結構單元X1,例如可列舉如下述般之結構。
[化12]
作為結構單元X2,例如可列舉如下述般之結構。
作為聚合物(A)之較佳結構,可列舉X1以下述式(a-4)表示、X2以下述式(a-5)表示之下述結構。
[化14]
(式(a-4)中,Y3為單鍵或包含碳數1~3之烴基之二價連結基,Z2為具有1個以上乙烯基之烴基,r2表示1~5之整數)
(式(a-5)中,Y4表示單鍵或包含碳數1~3之烴基之二價連結基)
尤佳之聚合物(A)之結構為X僅由式(a-4)構成之二乙烯苯聚合物。
關於本發明之聚合物(A),其較佳分子量為300~100,000。若分子量為100,000以下,則圖案之形成性優異,故較佳。
關於本發明之聚合物(A),較佳為聚合物(A)每1g之乙烯基之毫當量數(meq/g)為1.8~12.8meq/g。其原因在於:若為1.8meq/g以上,則硬化性優異,若為12.8meq/g以下,則聚合物(A)之合成相對容易。
本發明中之聚合物(A)每1g之乙烯基之毫當量數(meq/g)可根據以下計算式算出。
(1/[聚合物(A)之分子量])×[聚合物(A)一分子中之乙烯基之個數]×1000
此處所述之聚合物(A)之分子量係表示聚合物(A)之理論計算值之分子量,聚合物(A)一分子中之乙烯基之個數係表示聚合物(A)一分子中之乙烯基之理論上之個數。
本發明之聚合物(A)之特徵在於:於該聚合物(A)中,式(a-1)表示之結構於聚合物(A)中為80~100重量%。若為80重量%以上,則成為乾式蝕刻性及細密圖案形成性優異之乾式蝕刻抗蝕劑。此時,於聚合物(A)中,式(a-1)所表示之結構以外之結構為任意,只要不損害本發明之效果,則例如可為鍵結有聚合起始劑之狀態,亦可鍵結有烴基或具有雜原子之官能基等。
本發明之乾式蝕刻抗蝕劑用硬化性樹脂組合物為含有上述聚合物(A)者。本發明之聚合物(A)為具有複數個芳香族之化合物,且乾式蝕刻耐性優異並且聚合性基為乙烯基,故相較於(甲基)丙烯醯基般之含有雜原子之聚合性基,乾式蝕刻耐性更優異。又,於如二乙烯苯般具有芳香族結構且具有乙烯基之單體或二聚物之情形時,由於乙烯基之反應性較低,故有硬化物之韌性不足,乾式蝕刻時發生圖案之破損等之可能性。由於本發明之聚合物(A)具有3個以上乙烯基,故反應性優異,因此圖案之再現性及轉印性優異。
本發明之樹脂組合物除含聚合物(A)以外,亦可含有聚合性單體(B)。作為聚合性單體(B),較佳為活性能量線硬化性單體,較佳為含有多官能(甲基)丙烯酸酯。多官能(甲基)丙烯酸酯並無特別限定,可使用公知者。例如可列舉:1,2-乙二醇二丙烯酸酯、1,2-丙二醇二丙
烯酸酯、1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、二丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、三丙二醇二丙烯酸酯、三羥甲基丙烷二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三(2-丙烯醯氧基)異氰尿酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二(三羥甲基丙烷)四丙烯酸酯、二(季戊四醇)五丙烯酸酯、二(季戊四醇)六丙烯酸酯等之於1分子中具有2個以上聚合性雙鍵之多官能(甲基)丙烯酸酯等。又,丙烯酸胺基甲酸酯、聚酯丙烯酸酯、環氧丙烯酸酯等亦可例示為多官能丙烯酸酯。該等可單獨使用,亦可併用2種以上。
關於本發明之樹脂組合物,為了調整樹脂組合物之固形物成分量或黏度,亦可使用分散介質。作為分散介質,只要為不損害本發明之效果之液狀介質即可,可列舉各種有機溶劑或液狀有機聚合物。
作為上述有機溶劑,例如可列舉:丙酮、甲基乙基酮(MEK)、甲基異丁基酮(MIBK)、環己酮等酮類,四氫呋喃(THF)、二氧戊環等環狀醚類,乙酸甲酯、乙酸乙酯、乙酸丁酯、丙二醇單甲醚乙酸酯等酯類,甲苯、二甲苯、苯甲醚等芳香族類,卡必醇、溶纖素、甲醇、異丙醇、丁醇、丙二醇單甲醚等醇類,可將該等單獨使用或併用而使用,其中,甲基異丁基酮就塗敷時之揮發性或溶劑回收之方面而言較佳。
所謂上述液狀有機聚合物,為對硬化反應無直接助益之液狀有機聚合物,例如可列舉:含羧基之聚合物改性物(Flowlen G-900、NC-500,共榮社)、丙烯酸系聚合物(Flowlen WK-20,共榮社)、特殊改性磷酸酯之胺鹽(HIPLAAD ED-251,楠本化成)、改性丙烯酸系嵌段共聚物(DISPERBYK 2000,BYK-Chemie)等。
又,關於本發明之樹脂組合物,只要為不損害本發明之效果之範圍,則亦可調配各種樹脂、反應性化合物、觸媒、聚合起始劑、有機填料、無機填料、有機溶劑、無機顏料、有機顏料、體質顏料、黏
土礦物、蠟、界面活性劑、穩定劑、流動調整劑、染料、調平劑、流變控制劑、紫外線吸收劑、抗氧化劑、塑化劑等。
本發明之乾式蝕刻抗蝕劑用硬化性樹脂組合物由於具有乙烯基,故可藉由照射活性能量線進行硬化,較佳為紫外線硬化。此時,較佳為調配光聚合起始劑。
作為光聚合起始劑,只要使用公知者即可,例如可較佳地使用選自由苯乙酮類、苄基縮酮類、二苯甲酮類所組成之群中之一種以上。作為上述苯乙酮類,可列舉:二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、4-(2-羥基乙氧基)苯基-(2-羥基-2-丙基)酮等。作為上述苄基縮酮類,例如可列舉:1-羥基環己基-苯基酮、苄基二甲基縮酮等。作為上述二苯甲酮類,例如可列舉:二苯甲酮、鄰苯甲醯苯甲酸甲酯等。作為上述安息香類等,例如可列舉:安息香、安息香甲醚、安息香異丙醚等。光聚合起始劑可單獨使用,亦可併用2種以上。
又,藉由與上述光聚合起始劑組合併用增感色素,可大幅提高感光性。作為增感色素之具體例,可列舉:硫系、系、酮系、噻喃鎓鹽系、基礎苯乙烯基系、部花青系、3-取代香豆素系、花青系、吖啶系、噻系等色素類。
關於進行紫外線硬化時所使用之光,例如可使用低壓水銀燈、高壓水銀燈、金屬鹵素燈、氙氣燈、氬雷射、氦-鎘雷射、紫外線發光二極體等。
藉由使本發明之乾式蝕刻抗蝕劑用硬化性樹脂組合物積層於基材,並進行硬化,從而可獲得抗蝕膜及具有抗蝕膜之積層體。
關於抗蝕膜之形成方法,只要使用公知慣用之方法即可,例如
可於基材表面塗佈作為液狀之乾式蝕刻抗蝕劑用硬化性樹脂組合物之抗蝕液後,進行硬化而獲得。於設為液狀乾式蝕刻抗蝕劑用硬化性樹脂組合物之情形時,關於乾式蝕刻抗蝕材料中之全部固形物成分之濃度,若考慮到塗佈性(例如,塗佈及溶劑去除後之膜厚收斂於所需範圍內之情況、該膜厚於整個被加工表面具有均勻性之情況、即便於被加工表面有若干凹凸亦追隨該凹凸形成厚度均勻之塗膜之情況等)等,則較佳為0.1質量%以上且20質量%以下,更佳為0.4質量%以上且5質量%以下,進而較佳為0.7質量%以上且2質量%以下。具體而言,只要以使塗膜之膜厚成為0.01~50μm之方式進行調整即可,更佳為0.02~35μm。
本發明之乾式蝕刻抗蝕劑用硬化性樹脂組合物由於可進行微細圖案加工,故膜厚亦可為1μm以下。
本發明之抗蝕膜亦可為如下者:利用擠出成形等公知之成形方法使本發明之乾式蝕刻抗蝕劑用硬化性樹脂組合物成膜為膜狀,或者將本發明之乾式蝕刻抗蝕劑用硬化性樹脂組合物塗佈於暫時支持膜上,進行乾燥,並對視需要經被覆膜覆蓋所形成之光硬化性組合物層表面的成為處理對象之表面進行加熱壓接從而積層。作為此時使用之暫時支持膜,例如可使用聚對苯二甲酸乙二酯膜、聚醯亞胺膜、聚醯胺醯亞胺膜、聚丙烯膜、聚苯乙烯膜等先前公知之膜。此時,於其等膜為具有抗蝕膜之製作時所需之耐溶劑性或耐熱性等者時,可於其等暫時支持膜上直接塗佈本發明之抗蝕材料並進行乾燥,從而製作本發明之抗蝕膜,又,即便其等膜為耐溶劑性或耐熱性等較低者,亦可例如於聚四氟乙烯膜或脫模膜等具有脫模性之膜上首先形成本發明之抗蝕材料後,於該層上積層耐溶劑性或耐熱性等較低之暫時支持膜,其後,剝離具有脫模性之膜,藉此製作本發明之抗蝕膜。
又,本發明之抗蝕膜亦可為藉由將本發明之乾式蝕刻抗蝕劑用
硬化性樹脂組合物塗佈於成為處理對象之表面上,使溶劑蒸發去除而形成塗佈膜,並利用該塗佈膜所製成者。作為塗佈方法,可列舉:噴霧法、旋轉塗佈法、浸漬法、輥塗法、刮刀塗佈法、刮刀輥法、刮刀法、淋幕式塗佈法、狹縫式塗佈法、絲網印刷法等。就生產性優異且容易控制膜厚之方面而言,較佳為使用旋轉塗佈法。
本發明之積層體為將本發明之抗蝕膜積層於基板而成之積層體。所使用之基板根據本發明之抗蝕膜之目的而不同,例如可列舉:石英、藍寶石、玻璃、光學膜、陶瓷材料、蒸鍍膜、磁性膜、反射膜、Al、Ni、Cu、Cr、Fe、不鏽鋼等金屬基材、絲網、紙、木材、矽等合成樹脂、SOG(Spin On Glass,旋塗式玻璃)、聚酯膜、聚碳酸酯膜、聚醯亞胺膜等聚合物基材、TFT(Thin-Film Transistor,薄膜電晶體)陣列基材、藍寶石或GaN等發光二極體(LED)基材、玻璃或透明塑膠基材、銦錫氧化物(ITO)或金屬等導電性基材、絕緣性基材、矽、氮化矽、聚矽酮、氧化矽、非晶矽等半導體製作基材等。該等者可為光透過性,亦可為非光透過性。
又,基材之形狀亦並無特別限定,可為平板、片狀、或於三維形狀之整個面或一部分具有曲率者等視目的之任意形狀。又,基材之硬度、厚度等亦並無特別限制。
又,關於基板,可已積層包含合成樹脂等之抗蝕劑下層膜,亦可用於複數層抗蝕劑。
本發明中之抗蝕膜可利用各種方法形成圖案。例如,可為光微影法、如雷射直接刻寫法般之光阻劑法,亦可以將已形成圖案之模具壓抵於硬化前之抗蝕膜之狀態進行硬化,而製成形成有圖案之抗蝕膜,其後,剝離模具,藉此形成圖案。
作為光微影法之例,例如於成為處理對象之基板上,利用上述方法進行成膜,將硬化前之抗蝕膜積層,其後通過遮罩膜藉由活性光進行圖像曝光。關於曝光時使用之光,例如可使用低壓水銀燈、高壓水銀燈、金屬鹵素燈、氙氣燈、氬雷射、氦-鎘雷射等。作為光照射量,根據所使用之光聚合起始劑之種類及量適當選擇。
另一方面,作為雷射直接刻寫法之例,利用上述方法進行成膜,將硬化前之抗蝕膜積層,其後藉由波長350~430nm之雷射光進行掃描曝光。作為其曝光光源,可列舉:碳弧燈、水銀燈、氙氣燈、金屬鹵素燈、螢光燈、鎢絲燈、鹵素燈及HeNe雷射、氬離子雷射、YAG雷射、HeCd雷射、半導體雷射、紅寶石雷射等雷射光源,尤佳為發出波長區域350~430nm之藍紫色區域之雷射光之光源,進而較佳為其中心波長為約405nm者。具體而言,可列舉在405nm處振盪之氮化銦鎵半導體雷射等。又,藉由雷射光源之掃描曝光方法並無特別限定,例如可列舉平面掃描曝光方式、外滾筒式掃描曝光方式、內滾筒式掃描曝光方式等,作為掃描曝光條件,將雷射之輸出光強度較佳為設為1~100mW,進而較佳為設為3~70mW,將振盪波長較佳為設為390~430nm,進而較佳為設為400~420nm,將光束點直徑較佳為設為2~30μm,進而較佳為設為4~20μm,將掃描速度較佳為設為50~500m/s,進而較佳為設為100~400m/s,將掃描密度較佳為設為2,000dpi以上,進而較佳為設為4,000dpi以上,從而進行掃描曝光。
其次,使用有機溶劑顯影液,將未曝光部之未硬化部分顯影去除。作為有機溶劑顯影液,只要為可使未曝光部溶解者即可,可自公知之有機溶劑中適當選擇。具體而言,可使用酮系溶劑、酯系溶劑、醇系溶劑、醯胺系溶劑、醚系溶劑等極性溶劑及烴系溶劑。
本發明之圖案形成方法為如下圖案轉印方法,該圖案轉印方法
之特徵在於包括:對上述含有聚合物(A)之乾式蝕刻抗蝕劑用樹脂組合物按壓模具之步驟;使乾式蝕刻抗蝕劑用硬化性樹脂組合物硬化而形成圖案,獲得具有圖案之硬化物之步驟;及將具有所獲得之圖案之硬化物作為抗蝕遮罩進行乾式蝕刻,而將圖案轉印至被加工體之步驟。
於使用模具形成圖案之情形時,以按壓形成有圖案之模具之方式接觸利用上述方法製作之膜,並加以保持,於該狀態下使乾式蝕刻抗蝕劑用硬化性樹脂組合物硬化,藉此,可於抗蝕膜形成圖案。本發明之乾式蝕刻抗蝕劑用硬化性樹脂組合物尤其亦可較佳地用於可形成100nm以下之圖案之奈米壓印。
所謂奈米壓印,為將事先藉由電子束微影法等製成特定之微細凹凸圖案之奈米壓印用模具壓抵於塗佈有抗蝕劑之基板,將奈米壓印用模具之凹凸轉印於基板之抗蝕膜之方法。一次處理所花費之時間有如下特徵:於例如1平方英吋以上之區域,與雷射直接刻寫法相比短時間內結束。
關於按壓具有凹凸結構之奈米壓印用模具之步驟,具體而言,一面按壓奈米壓印用模具,一面將包含上述乾式蝕刻抗蝕劑用硬化性樹脂組合物之抗蝕膜壓入至模具之微細形狀。此時,為了使上述乾式蝕刻抗蝕劑用硬化性樹脂組合物進一步追隨模具之微細形狀,亦可一面進行加熱而使黏度降低,一面進行按壓。其後,照射紫外線,使包含上述乾式蝕刻抗蝕劑用硬化性樹脂組合物之抗蝕膜硬化後,再將奈米壓印用模具分離,藉此可獲得於奈米壓印用模具所形成之微細形狀形成於包含上述乾式蝕刻抗蝕劑用硬化性樹脂組合物之抗蝕膜表面之圖案。
具體而言,以將奈米壓印用模具壓抵於設置於基材表面之包含
乾式蝕刻抗蝕劑用硬化性樹脂組合物之抗蝕膜上之方式使其接觸,進行夾持。作為奈米壓印用模具效率較佳地製造大面積之成形體之方法,亦較佳為如下方法:利用適合於輥製程之平面狀原版之升降方式、帶狀原版之貼合方式、輥狀原版之輥轉印方式、捲狀原版之輥轉印方式等方法而接觸。作為奈米壓印用模具之材質,作為使光透過之材質,可列舉:石英玻璃、紫外線透過玻璃、藍寶石、鑽石、聚二甲基矽氧烷等矽材料、氟樹脂、其他使光透過之樹脂材料等。又,只要所使用之基材為使光透過之材質,則奈米壓印用模具亦可為不使光透過之材質。作為不使光透過之材質,可列舉:金屬、矽、SiC、雲母等。
奈米壓印用模具如上所述,可選擇平面狀、帶狀、輥狀、捲狀等任意之形態。為了防止因懸浮污物等對原版造成污染等,較佳為對轉印面實施先前公知之脫模處理。
關於硬化之方法,可列舉:於模具為使光透過之材質之情形時自模具側照射光之方法、或於基材為使光透過之材質之情形時自基材側照射光之方法。作為用於光照射之光,只要為使光聚合起始劑發生反應之光即可,其中,就光聚合起始劑容易反應,可以更低溫度進行硬化之方面而言,較佳為450nm以下之波長之光(紫外線、X射線、γ射線等活性能量線)。就操作性之方面而言,尤佳為200至450nm之波長之光。具體而言,可使用上述紫外線硬化時所使用之光。
又,若所形成之圖案之追隨性有異常,則亦可於光照射時加熱至可獲得充分流動性之溫度。於加熱之情形時之溫度較佳為300℃以下,更佳為0℃至200℃,進而較佳為0℃至150℃,尤佳為25℃至80℃。於該溫度範圍內,於包含上述乾式蝕刻抗蝕劑用硬化性樹脂組合物之抗蝕膜所形成之微細圖案形狀之精度得以較高保持。
針對於上述任一方式,作為效率較佳地製造大面積之成形體之方法,均亦較佳為利用旨在適合於輥製程而於反應機內搬送之方法進行硬化之方法。
硬化步驟後,將成形體自模具剝離,藉此可獲得轉印有模具之凹凸圖案之凸凹圖案形成於包含上述乾式蝕刻抗蝕劑用硬化性樹脂組合物之抗蝕膜之硬化物之表面的抗蝕膜。就抑制基材之翹曲等變形,或提高凸凹圖案之精度之方面而言,較佳為如下方法:作為剝離步驟之溫度,抗蝕膜之溫度冷卻至常溫(25℃)附近後實施之方法,或即便於抗蝕膜於仍處於加熱狀態時進行剝離之情形時,以對抗蝕膜施加一定張力之狀態冷卻至常溫(25℃)附近之方法。
藉由對具有藉由上述方法形成圖案之抗蝕膜之積層體進行乾式蝕刻,可使圖案良好地形成於基板,可獲得藉由乾式蝕刻而轉印有圖案之圖案形成物。
包含本發明之乾式蝕刻抗蝕劑用硬化性樹脂組合物之抗蝕膜之乾式蝕刻耐性優異,故於該蝕刻時亦無圖案等變形之情況而可提供微細之蝕刻圖案。藉此,可將形成於抗蝕劑之圖案精度較佳地轉印於基板,故可獲得所獲得之圖案形成物之圖案再現性優異之圖案形成物。
作為用於乾式蝕刻之氣體,只要使用公知慣用者即可,例如可使用氧氣、一氧化碳、二氧化碳等含氧原子之氣體、氦氣、氮氣、氬氣等惰性氣體、氯氣、三氯化硼等氯系氣體、氟系氣體、氫氣、氨氣等,該等氣體可單獨使用,亦可適時混合使用。
藉由使用該等氣體之電漿進行乾式蝕刻,可於基材上形成所需之圖案。
其次,藉由實施例及比較例更具體地說明本發明。例中只要無特別說明,則「份」「%」為重量標準。
以下,列舉實施例及比較例進一步詳細地說明本發明,但本發明並不限定於該等實施例。
於氮氣環境下,使甲基三苯基溴化鏻(29.1g,81.1mmol)及第三丁醇鉀(9.88g,88.1mmol)於0℃下進行反應,製備亞甲三苯基磷烷,使之溶解於四氫呋喃(40mL)中。於其中滴加4-甲醯基苯乙烯(9.30g,70.5mmol)之四氫呋喃(60mL)溶液,於25℃下攪拌2小時而進行反應,其後添加水而使反應失活。使用二乙醚自反應溶液進行分液萃取,去除水層,對有機層添加硫酸鎂進行脫水後,將硫酸鎂過濾去除。藉由蒸發使有機層濃縮,向己烷中注入而使三苯基氧化膦析出,藉由過濾而去除後,藉由蒸發使溶劑濃縮,並藉由使用己烷溶劑之矽膠管柱層析法進行精製,藉由減壓分餾獲得1,4-二乙烯苯6.07g(產率66%)。藉由氣相層析法進行測定,結果1,4-二乙烯苯之純度為99%以上。
所獲得之聚合物之物性值如下所述。
1H-NMR(600MHz,CDCl3)δ(ppm):7.32(s,4H),6.66(dd,2H),5.70(d,2H),5.19(d,2H),
於氮氣環境下,將第二丁基鋰(0.0776mmol)之四氫呋喃溶液(6.60ml)添加至α-甲基苯乙烯(0.311mmol)中,於25℃下反應10秒後,進而於-78℃下反應30分鐘,於-78℃下添加第三丁醇鉀(0.932mmol)之四氫呋喃溶液(17.8mL),獲得起始劑溶液。
於氮氣環境下,將合成例1中獲得之1,4-二乙烯苯(1.56mmol)之四氫呋喃溶液(11.6mL)冷卻至-78℃,添加上述起始劑溶液並攪拌1分鐘。其後,添加脫氣過之甲醇而使其失活。將該溶液注入至甲醇200mL中,使其沈澱,回收其沈澱物,使用四氫呋喃及甲醇重複進行2次再沈澱精製,從而獲得大致白色之聚合物(A-1)0.23g(產率93%)。利用氣相層析法測定所獲得之聚合物(A-1),結果未殘存單體,又,1H-NMR測定之結果為於6.7ppm、5.6ppm、5.1ppm附近顯示出源自乙烯基之波峰,於7.3ppm附近顯示出源自芳香族結構之波峰,於0.80~0.00ppm顯示出源自主鏈-CH2-CH-之波峰,故其為於側鏈具有乙烯基之芳香族結構經單鍵而與主鏈連結之聚合物,因此對應於本發明之聚合物(A)。
所獲得之聚合物(A-1)之各物性值如下所述。
1H-NMR(600MHz,CDCl3)δ(ppm):7.3~6.0(m),5.61(br),5.13(br),3.0~0.80(m),0.80~0.00(m)
GPC(THF)聚苯乙烯換算:數量平均分子量3,080,Mw/Mn=1.04
於氮氣環境下,將第二丁基鋰(0.776mmol)之四氫呋喃溶液(13.2ml)及氯化鋰(18.63mmol)之四氫呋喃溶液(35.6mL)於-78℃下混合,獲得起始劑溶液。
於氮氣環境下,將合成例1中獲得之1,4-二乙烯苯(2.33mmol)之四氫呋喃溶液(23.2mL)冷卻至-78℃,添加上述起始劑溶液並攪拌1分鐘。其後,添加脫氣過之甲醇而使其失活。將該溶液注入至甲醇200mL中,使其沈澱,回收其沈澱物,使用四氫呋喃及甲醇重複進行2次再沈澱精製,從而獲得大致白色之聚合物(A-2)0.15g(產率42%)。利用氣相層析法測定所獲得之聚合物(A-2),結果未殘存單體,又,1H-
NMR測定之結果為於6.7ppm、5.6ppm、5.1ppm附近顯示出源自乙烯基之波峰,於7.3ppm附近顯示出源自芳香族結構之波峰,於0.80~0.00ppm顯示出源自主鏈-CH2-CH-之波峰,故其為於側鏈具有乙烯基之芳香族結構經單鍵而與主鏈連結之聚合物,因此對應於本發明之聚合物(A)。
所獲得之聚合物(A-2)之各物性值如下所述。
1H-NMR(600MHz,CDCl3)δ(ppm):7.3~6.0(m),5.7~5.5(m),5.3~5.1(m),3.0~0.80(m),0.80~0.00(m)
GPC(THF)聚苯乙烯換算:數量平均分子量400,Mw/Mn=2.04
於氮氣環境下,將第二丁基鋰(0.776mmol)之四氫呋喃溶液(13.2ml)添加至α-甲基苯乙烯(1.55mmol)中,於25℃下反應10秒後,進而於-78℃下反應30分鐘,於-78℃下添加第三丁醇鉀(9.32mmol)之四氫呋喃溶液(35.6mL),獲得起始劑溶液。
於氮氣環境下,將合成例1中獲得之1,4-二乙烯苯(1.56mmol)之四氫呋喃溶液(23.2mL)冷卻至-78℃,添加上述起始劑溶液並攪拌1分鐘。其後,添加脫氣過之甲醇而使其失活。將該溶液注入至甲醇200mL中,使其沈澱,回收其沈澱物,使用四氫呋喃及甲醇重複進行2次再沈澱精製,從而獲得大致白色之比較聚合物1 0.133g(產率31%)。利用氣相層析法測定所獲得之比較聚合物1,結果未殘存單體,又,1H-NMR測定之結果為於6.7ppm、5.6ppm、5.1ppm附近顯示出源自乙烯基之波峰,於7.3ppm附近顯示出源自芳香族結構之波峰,於0.80~0.00ppm顯示出源自主鏈-CH2-CH-之波峰,故其為於側鏈具有乙烯基之芳香族結構經單鍵而與主鏈連結之聚合物,但聚合物中僅有2個X1所表示之結構單元,而不對應於本發明之聚合物(A)。
所獲得之比較聚合物1之各物性值如下所述。
1H-NMR(600MHz,CDCl3)δ(ppm):7.3~6.0(m),55.7~5.5(m),5.3~5.1(m),3.0~0.80(m),0.80~0.00(m)
GPC(THF)聚苯乙烯換算:數量平均分子量500,Mw/Mn=1.05
於氮氣環境下,將苯乙烯(2.33mmol)之四氫呋喃溶液(11.6mL)冷卻至-78℃,添加第二丁基鋰(0.0776mmol)之四氫呋喃溶液(6.60ml)並攪拌1分鐘。其後,添加脫氣過之甲醇而使其失活。將該溶液注入至甲醇200mL中,使其沈澱,回收其沈澱物,使用四氫呋喃及甲醇重複進行2次再沈澱精製,從而獲得大致白色之比較聚合物20.23g(產率95%)。1H-NMR測定之結果為並無源自乙烯基之波峰,於7.3ppm附近顯示出源自芳香族結構之波峰,於0.80~0.00ppm顯示出源自主鏈-CH2-CH-之波峰,故其為於側鏈不具有乙烯基之聚苯乙烯,而不對應於本發明之聚合物(A)。
所獲得之比較聚合物2之各物性值如下所述。
1H-NMR(600MHz,CDCl3)δ(ppm):7.3~6.0(m),3.0~0.80(m),0.80~0.00(m)
GPC(THF)聚苯乙烯換算:數量平均分子量3,100,Mw/Mn=1.04
於具備攪拌機、冷卻管、溫度計、氯氣導入裝置之5L之四口燒瓶中添加聯苯709g、多聚甲醛276g、乙酸1381g、濃鹽酸958g,升溫至80℃。確認添加溶液為80℃後,使用木下式玻璃波爾濾器將氯化氫氣體以20g/hr之速度導入至添加溶液中。確認氯化氫氣體於添加溶
液中達到溶解飽和後,歷時1小時滴加磷酸1061g,進而反應30小時。反應結束後,立即自反應溶液去除下層,向有機層中添加甲苯2.3kg,利用400g之12.5%氫氧化鈉水溶液、飽和碳酸氫鈉水溶液、蒸餾水清洗有機層。將有機層蒸餾去除後,以白色固體之形式獲得900g氯中間物。
將上述中間物908g溶解於作為反應溶劑之二甲基甲醯胺(DMF)1603g,以相對於總量成為300ppm之方式添加碳酸鉀372g及對甲氧基苯酚。將中間物溶液升溫至40℃後,歷時1.5小時將丙烯酸323g滴加至中間物溶液中。滴加結束後,歷時2小時升溫至80℃,於80℃下加熱攪拌3小時。於所獲得之溶液中添加水3.4kg及甲苯1.8kg,進行萃取,其後清洗有機層直至成為中性。將有機層濃縮,獲得聚合性單體(B-1)995g。聚合性單體(B-1)於25℃下為液狀。
將上述獲得之聚合性單體(B-1)以如下條件進行氣相層析分析。
裝置:Agilent公司製造之「6850系列」
管柱:Agilent DB-1
載氣:He,流速1mL/min
注入溫度:300℃
檢測溫度:300℃
程式:50~325℃(升溫速度25℃/min)
利用氣相層析圖求出組成比,結果單官能丙烯酸酯為71.0%,二官能丙烯酸酯為20.2%,其他為8.8%。
基於下述表1所示之成分表進行調配,添加作為光聚合起始劑之2-苄基-2-二甲胺基-1-(4-啉基苯基)-1-丁酮(Irgacure-369:BASF公司製造)3重量份,獲得硬化性組合物。
使用甲基異丁基酮溶劑將實施例1~4及比較例1~4所示之組合物稀釋,以膜厚成為1.0μm之方式旋轉塗佈於矽晶圓基材上。藉由峰值波長375±5nm之LED光源(Ushio電機股份有限公司製造)於氮氣環境下自樹脂組合物側以1000mJ/cm2之光量對所獲得之積層體進行光照射而使其硬化,獲得硬化膜。
使用SAMCO股份有限公司製造之乾式蝕刻系統RIE-101iPH對所獲得之硬化膜供給氬氣/CF4=30/10(sccm)之混合氣體,於0.5Pa之真空下進行1分鐘電漿乾式蝕刻後,測定硬化膜之殘存膜厚,算出每分鐘之蝕刻速度。
使用SAMCO股份有限公司製造之乾式蝕刻系統RIE-101iPH對所獲得之硬化膜供給氬氣/Cl2/BCl3=20/15/20之混合氣體,於0.5Pa之真空下進行1分鐘電漿乾式蝕刻後,測定硬化膜之殘存膜厚,算出每分鐘之蝕刻速度。
將所獲得之蝕刻速度以甲酚酚醛清漆型光阻劑(AZ-5214 AZ Electronic Materials股份有限公司)之蝕刻速度之值成為1之方式進行標準化。標準值越小,表示乾式蝕刻耐性越優異,如下述般進行評價。
○:經標準化之蝕刻速度未達0.8
△:經標準化之蝕刻速度為0.8以上且未達1
×:經標準化之蝕刻速度為1以上
使用甲基異丁基酮溶劑將實施例1~4及比較例1~4中製成之硬化性組合物稀釋,以膜厚成為3.0μm之方式旋轉塗佈於玻璃基材上。藉由峰值波長375±5nm之LED光源(Ushio電機股份有限公司製造)於氮氣環境下自樹脂組合物側以1000mJ/cm2之光量對所獲得之積層體進行光照射而使其硬化,獲得硬化膜。利用棉棒中滲有異丙基醇溶劑而成者對所獲得之硬化膜表面擦拭10次,觀察硬化膜外觀之變化。硬化膜外觀之變化較少者表示進行由乙烯基之反應產生之交聯反應,於溶劑中之溶出較少,硬化性優異。
○:外觀無變化
×:被擦除而露出基板
使用甲基異丁基酮溶劑將實施例1~4及比較例1~4中製成之硬化性組合物稀釋,以膜厚成為300nm之方式旋轉塗佈於矽晶圓基材上。將所獲得之積層體設置於SCIVAX公司製造之奈米壓印裝置X300之下表面平台。將具有100nm之線/間隙圖案且以溝深為100nm之石英作為材質的圖案表面經氟系處理之模具設置於上述裝置之上表面平台。將裝置內設為真空後,於室溫或者塗膜之熔融溫度以上,以1.5氣壓之壓力使模具壓接於基板,使用峰值波長375±5nm之LED光源,以500mJ/cm2之條件自模具之背面對其曝光,將模具剝離,從而於基材上形成圖案。實施線圖案形狀剖面之掃描型電子顯微鏡觀察、及自圖案上表面之暗視野光學顯微鏡觀察,如下述般評價圖案形成性。
於藉由掃描型電子顯微鏡觀察之圖案剖面觀察中,
○:無圖案之缺損或崩塌。
×:圖案局部或整個面缺損及崩塌。
於自圖案上表面之100μm見方之視野內之暗視野光學顯微鏡觀察中,
○:以亮點之形式觀察到之圖案缺陷之面積未達5%
×:以亮點之形式觀察到之圖案缺陷之面積為5%以上
使用甲基異丁基酮溶劑及視需要使用收縮防止劑等表面改質劑,將實施例1~4及比較例1~4中製成之硬化性組合物稀釋,以膜厚成為500nm之方式旋轉塗佈於矽晶圓基材上。將所獲得之積層體設置於SCIVAX公司製造之奈米壓印裝置X300之下表面平台。將具有460nm間距之三角配列之孔圖案且以溝深為450nm之環烯烴聚合物(日本ZEON股份有限公司ZEONOR ZF-14)作為材質之模具設置於上述裝
置之上表面平台。將裝置內設為真空後,於室溫或者塗膜之熔融溫度以上,以1.5氣壓之壓力將模具壓接於基板,自模具之背面使用峰值波長375±5nm之LED光源,以500mJ/cm2之條件對其曝光,將模具剝離,從而於基材上形成圖案。實施支柱圖案形狀剖面之掃描型電子顯微鏡觀察、及自圖案上表面之暗視野光學顯微鏡觀察,以與上述相同之方式評價圖案形成性。
由表2可知,使用本發明之硬化性組合物形成之硬化物之乾式蝕刻耐性、硬化性、圖案形成性均良好。比較例1雖使用含有1,4-二乙烯苯單體之組合物,但於分子內僅具有2個乙烯基,故比較例1之組合物無法藉由光照射獲得硬化物。比較例2雖為含有於分子側鏈具有乙烯基之聚合物之組合物,但於聚合物中僅具有2個乙烯基,對比較例2之組合物光照射所得之硬化物之硬化性及圖案形成性較差,又,乾式蝕刻耐性亦不充分。比較例3為不含聚合物(A)而僅由含有氧原子之聚合性單體所構成之組合物,故乾式蝕刻耐性較差。比較例4為包含不具有乙烯基之聚合物之組合物,故未藉由光照射而硬化。
本發明之硬化性樹脂組合物由於乾式蝕刻性及精密圖案再現性
優異,故可較佳地用作乾式蝕刻用抗蝕材料。
Claims (10)
- 一種乾式蝕刻抗蝕劑用硬化性樹脂組合物,其特徵在於:其係含有具有下述式(a-1)所表示之結構之聚合物(A)者,且該聚合物(A)中之下述式(a-1)所表示之結構於聚合物(A)中為80~100重量%,
- 如請求項1之乾式蝕刻抗蝕劑用硬化性樹脂組合物,其中上述式(a-1)中,X1為下述式(a-4)所表示者,
- 如請求項1或2之乾式蝕刻抗蝕劑用硬化性樹脂組合物,其中上述式(a-1)中,X2為下述式(a-5)所表示者,
- 如請求項1或2之乾式蝕刻抗蝕用硬化性樹脂組合物,其中上述聚合物(A)之分子量為300~100,000。
- 如請求項1或2之乾式蝕刻抗蝕劑用硬化性樹脂組合物,其中聚合物(A)每1g之乙烯基之毫當量數(meq/g)為1.8~12.8meq/g。
- 如請求項1或2之乾式蝕刻抗蝕劑用硬化性樹脂組合物,其中該組合物進而含有聚合性單體(B)。
- 如請求項1或2之乾式蝕刻抗蝕劑用硬化性樹脂組合物,其中該樹脂組合物之大西參數為3.2以下,(其中,此處所述之大西參數,係於將乾式蝕刻抗蝕劑用硬化性樹脂組合物中之固形物成分之總原子數設為N、總碳數設為NC、總氧數設為NO時,以N/(NC-NO)表示)。
- 一種乾式蝕刻用抗蝕遮罩,其特徵在於:其係使如請求項1至7中任一項之乾式蝕刻抗蝕劑用硬化性樹脂組合物硬化而成。
- 如請求項8之乾式蝕刻用抗蝕遮罩,其中上述乾式蝕刻用抗蝕遮罩為具有藉由奈米壓印法所形成之圖案者。
- 一種圖案轉印方法,其特徵在於包括:對如請求項1至7中任一項之乾式蝕刻抗蝕劑用樹脂組合物按壓模具之步驟;使乾式蝕刻抗蝕劑用硬化性樹脂組合物硬化而形成圖案,獲得具有圖案之硬化物之步驟;及將具有所獲得之圖案之硬化物作為抗蝕遮罩進行乾式蝕刻,而將圖案轉印至被加工體之步驟。
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WO2019009143A1 (ja) * | 2017-07-04 | 2019-01-10 | 富士フイルム株式会社 | 赤外線受光素子の製造方法、光センサの製造方法、積層体、レジスト組成物およびキット |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005281551A (ja) * | 2004-03-30 | 2005-10-13 | Mitsubishi Paper Mills Ltd | 新規な重合性モノマー及びこれを含んでなる感光性組成物及び平版印刷版 |
JP2008233563A (ja) * | 2007-03-20 | 2008-10-02 | Jsr Corp | 放射線硬化性樹脂組成物 |
JP2010229262A (ja) * | 2009-03-26 | 2010-10-14 | Nippon Steel Chem Co Ltd | 末端変性多官能ビニル芳香族共重合体及びレジスト組成物 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4528332A (en) * | 1983-01-06 | 1985-07-09 | Asahi Kasei Kogyo Kabushiki Kaisha | Epoxy compounds, process for the preparation thereof and resist materials comprising thereof |
US4839261A (en) * | 1986-09-29 | 1989-06-13 | Asahi Kasei Kogyo Kabushiki Kaisha | Photocurable laminate |
WO1989003401A1 (en) * | 1987-10-08 | 1989-04-20 | Idemitsu Kosan Company Limited | Styrenic polymer and process for its production |
JPH01263646A (ja) * | 1988-04-15 | 1989-10-20 | Asahi Chem Ind Co Ltd | 新規無電解メツキ用光硬化性組成物 |
US8025831B2 (en) * | 2004-05-24 | 2011-09-27 | Agency For Science, Technology And Research | Imprinting of supported and free-standing 3-D micro- or nano-structures |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005281551A (ja) * | 2004-03-30 | 2005-10-13 | Mitsubishi Paper Mills Ltd | 新規な重合性モノマー及びこれを含んでなる感光性組成物及び平版印刷版 |
JP2008233563A (ja) * | 2007-03-20 | 2008-10-02 | Jsr Corp | 放射線硬化性樹脂組成物 |
JP2010229262A (ja) * | 2009-03-26 | 2010-10-14 | Nippon Steel Chem Co Ltd | 末端変性多官能ビニル芳香族共重合体及びレジスト組成物 |
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JP5831780B1 (ja) | 2015-12-09 |
US9777079B2 (en) | 2017-10-03 |
WO2015098662A1 (ja) | 2015-07-02 |
US20160272737A1 (en) | 2016-09-22 |
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