TWI680354B - 使用含矽底層之方法以及用於形成含矽底層之組合物 - Google Patents
使用含矽底層之方法以及用於形成含矽底層之組合物 Download PDFInfo
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- TWI680354B TWI680354B TW106129052A TW106129052A TWI680354B TW I680354 B TWI680354 B TW I680354B TW 106129052 A TW106129052 A TW 106129052A TW 106129052 A TW106129052 A TW 106129052A TW I680354 B TWI680354 B TW I680354B
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- Prior art keywords
- silicon
- formula
- alkyl
- monomers
- hydrocarbyl moiety
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- 239000000203 mixture Substances 0.000 title claims abstract description 128
- 229910052710 silicon Inorganic materials 0.000 title claims description 63
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 58
- 239000010703 silicon Substances 0.000 title claims description 58
- 238000000034 method Methods 0.000 title claims description 39
- 229920005573 silicon-containing polymer Polymers 0.000 claims abstract description 82
- 229920000642 polymer Polymers 0.000 claims abstract description 74
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 229910018557 Si O Inorganic materials 0.000 claims abstract description 15
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims description 108
- 125000000217 alkyl group Chemical group 0.000 claims description 61
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 60
- 239000000758 substrate Substances 0.000 claims description 49
- 229910052799 carbon Inorganic materials 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 35
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 229920002120 photoresistant polymer Polymers 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 125000005843 halogen group Chemical group 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 150000002596 lactones Chemical group 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000008199 coating composition Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 3
- 238000004220 aggregation Methods 0.000 claims 1
- 230000002776 aggregation Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 81
- -1 biphenyl Methoxysilane Chemical compound 0.000 description 57
- 125000003118 aryl group Chemical group 0.000 description 28
- 239000000243 solution Substances 0.000 description 20
- 239000002253 acid Substances 0.000 description 19
- 235000012431 wafers Nutrition 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 239000004065 semiconductor Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 238000009472 formulation Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000005530 etching Methods 0.000 description 9
- 125000005842 heteroatom Chemical group 0.000 description 9
- 229920000620 organic polymer Polymers 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 8
- 239000003623 enhancer Substances 0.000 description 8
- 229910052736 halogen Chemical group 0.000 description 8
- 150000002367 halogens Chemical group 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 150000001241 acetals Chemical group 0.000 description 7
- 125000000304 alkynyl group Chemical group 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 229940116333 ethyl lactate Drugs 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000001335 aliphatic alkanes Chemical group 0.000 description 4
- 125000003282 alkyl amino group Chemical group 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000001020 plasma etching Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000012958 reprocessing Methods 0.000 description 3
- 125000003107 substituted aryl group Chemical group 0.000 description 3
- 125000003396 thiol group Chemical class [H]S* 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 description 2
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 description 2
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 description 2
- 125000004918 2-methyl-2-pentyl group Chemical group CC(C)(CCC)* 0.000 description 2
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 description 2
- NMUBRRLYMADSGF-UHFFFAOYSA-N 3-triethoxysilylpropan-1-ol Chemical compound CCO[Si](OCC)(OCC)CCCO NMUBRRLYMADSGF-UHFFFAOYSA-N 0.000 description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical group C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 2
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical group C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- OHBRHBQMHLEELN-UHFFFAOYSA-N acetic acid;1-butoxybutane Chemical compound CC(O)=O.CCCCOCCCC OHBRHBQMHLEELN-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical group 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
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- CSXPRVTYIFRYPR-UHFFFAOYSA-N bis(ethenyl)-diethoxysilane Chemical compound CCO[Si](C=C)(C=C)OCC CSXPRVTYIFRYPR-UHFFFAOYSA-N 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- MGGAITMRMJXXMT-UHFFFAOYSA-N cyclopentyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1CCCC1 MGGAITMRMJXXMT-UHFFFAOYSA-N 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical group C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
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- 239000005053 propyltrichlorosilane Substances 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 description 1
- YNJQKNVVBBIPBA-UHFFFAOYSA-M tetrabutylazanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+](CCCC)(CCCC)CCCC YNJQKNVVBBIPBA-UHFFFAOYSA-M 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 0.000 description 1
- WWIYWFVQZQOECA-UHFFFAOYSA-M tetramethylazanium;formate Chemical compound [O-]C=O.C[N+](C)(C)C WWIYWFVQZQOECA-UHFFFAOYSA-M 0.000 description 1
- MANNXDXMUHZSRP-UHFFFAOYSA-M tetramethylazanium;trifluoromethanesulfonate Chemical compound C[N+](C)(C)C.[O-]S(=O)(=O)C(F)(F)F MANNXDXMUHZSRP-UHFFFAOYSA-M 0.000 description 1
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical group C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- FCMZRNUHEXJWGB-UHFFFAOYSA-N trichloro(cyclopentyl)silane Chemical compound Cl[Si](Cl)(Cl)C1CCCC1 FCMZRNUHEXJWGB-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 1
- YFNYCSJNUJQGNF-UHFFFAOYSA-N triethoxy(1-triethoxysilylethenyl)silane Chemical group CCO[Si](OCC)(OCC)C(=C)[Si](OCC)(OCC)OCC YFNYCSJNUJQGNF-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
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- C08F230/08—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 containing silicon
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- C08F24/00—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 a heterocyclic ring containing oxygen
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- C08G73/12—Unsaturated polyimide precursors
- C08G73/128—Unsaturated polyimide precursors the unsaturated precursors containing heterocyclic moieties in the main chain
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- 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
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Abstract
本發明提供包含一或多種包含含Si-O鍵的主鏈的含矽聚合物、一或多種有機摻合物聚合物及固化催化劑的可濕剝離底層組合物。此等組合物適用於製造各種電子裝置。
Description
本發明大體上係關於底層及其使用方法,且尤其係關於可濕剝離含矽底層及其在製造電子裝置中的用途。
在習知光刻方法中,使用抗蝕圖案作為藉由適合蝕刻方法,諸如藉由反應性離子蝕刻(RIE)將圖案轉移至基板的遮罩。所用抗蝕劑的厚度持續減少使抗蝕圖案不適合作為藉由RIE方法轉移圖案的遮罩。因此,已使用三個、四個或更多個層作為圖案轉移的遮罩來開發替代方法。舉例而言,在三層方法中,將含矽抗反射層安置於底層/有機平坦化層與抗蝕劑層之間。由於此等層具有對氟及含氧RIE化學物質的交替選擇性,所以此三層流程提供由含Si層頂部上的抗蝕圖案至底層下的基板的高選擇性圖案轉移。
含矽底層對氧化物蝕刻化學物質的耐受性允許此層充當蝕刻遮罩。此類含矽底層由交聯矽氧烷網路組成。此等材料的抗蝕刻性由矽含量產生,其中較高矽含量提供較好抗蝕刻性。在當前193nm光刻方法中,此類含矽底層含有40%的矽。此等材料中的此類高矽含量及矽氧烷網路結構使得其移除具有挑戰性。含氟電漿與氫氟酸(HF)可用於移除(或剝離)此等含矽層。然而,F-電漿及HF將不僅移除此等含矽材料且亦移除需要保留的其他材料,諸如基板。使用較高濃度(諸如5重量%)的四甲基氫氧化銨(TMAH)進行濕式剝離可用於移除此等含矽層中的至少一些,但此等較高濃度的TMAH亦有損壞基板的風險。有時可使用「食人魚酸」(濃H2SO4+30% H2O2)移除具有相對較低量的矽(17%)的含矽層,但此類方法尚未證明在具有較高矽含量的含矽材料的情況下為成功的。
美國專利第7,955,782號揭示一種藉由在固化期間將二丙二醇(DPG)及四乙二醇(TEG)的混合物併入至矽氧烷層中改良含矽底層的可濕剝離性的方法。然而,併入含矽膜中的DPG及TEG的特定量係未知的,因為一部分DPG及TEG在含矽膜的固化期間揮發,其亦使膜中的矽的精確重量百分比未知。美國專利申請公開案第2014/0186774號揭示可藉由酸移除的含矽底層,其中含矽材料為具有多個在不存在Si-O-C及Si-OH鍵的情況下由羥基衍生的烴基的水性鹼不溶物。在此參考文獻中避免在含矽材料層的固化期間形成Si-O-Si鍵。儘管美國專利申請公開案第2014/0186774號中的含矽底層可為酸可剝離的,此類含矽底層可由於不具有Si-O-Si鍵而不在圖案轉移期間提供所需抗蝕刻性。因此,仍需要在圖案轉移期間提供所需蝕刻選擇性且易於可藉由濕式化學法移除的含矽底層。
其中R5選自藉由三級碳鍵結至氧的C4-20有機殘基或包含縮醛官能基的C4-20有機殘基;且R1選自H、C1-4烷基、C1-4鹵烷基、鹵基及CN;及一或多種固化催化劑。較佳地,組合物進一步包含一或多種有機溶劑。
本發明進一步提供由上文所述的組合物形成的用於多層抗蝕劑方法的含矽膜。
本發明亦提供一種包含以下的方法:(a)用包含一或多種包含含Si-O鍵的主鏈的可固化含矽聚合物、一或多種有機摻合物聚合物及一或多種有機溶劑的塗料組合物塗佈基板以在基板上形成可固化含矽聚合物層;(b)固化含矽聚合物層以形成矽氧烷底層;(c)在矽氧烷底層上安置光致抗蝕劑層;(d)逐圖案曝光光致抗蝕劑層以形成潛像;(e)對潛像顯影以形成在其中具有凸紋影像的圖案化光致抗蝕劑層;(f)將凸紋影像轉移至基板;及(g)藉由濕式剝離移除矽氧烷底層。
應瞭解,當一個元件被稱為「與」另一元件「相鄰」或「在」另一元件「上」時,其與另一元件直接相鄰或可直接位於另一元件上,或其間可存在插入元件。相比之下,當元件被稱為「與」另一元件「直接相鄰」或「直接位於」另一元件「上」時,不存在插入元件。應瞭解,儘管可使用術語第一、第二、第三等來描述各種元件、組件、區域、層 及/或區段,此等元件、組件、區域、層及/或區段不應受此等術語限制。此等術語僅用於區分一個元件、組件、區域、層或區段與另一元件、組件、區域、層或區段。因此,在不脫離本發明的教示的情況下,下文論述的第一元件、組件、區域、層或區段可稱為第二元件、組件、區域、層或區段。
除非上下文另外明確指示,否則如本說明書通篇所使用,以下縮寫應具有以下含義:℃=攝氏度;g=公克;mg=毫克;除非另外指出,否則ppm=按重量計的百萬分率;μm=微米(micron/micrometer);nm=奈米;Å=埃;L=公升;mL=毫升;sec.=秒;min.=分鐘;hr.=小時;且Da=道爾頓。除非另外指出,否則所有量均為重量百分比且所有比率均為莫耳比。所有數值範圍均為包括性的且可按任何順序組合,但顯然此類數值範圍限制於總計100%。除非另外指出,否則「重量%」係指以參考組合物的總重量計的重量百分比。冠詞「一(a)」、「一(an)」及「所述」係指單數及複數。如本文中所使用,術語「及/或」包含相關聯的所列項中的一或多個的任何以及所有組合。Mw係指重量平均分子量且藉由使用聚苯乙烯標準物的凝膠滲透層析法(GPC)測定。
如本說明書通篇所使用,術語「烷基」包括直鏈、分支鏈以及環狀烷基。術語「烷基」係指烷烴基,且包括烷烴單基、二基(伸烷基)及較高碳數基團。若任何烷基或雜烷基未指明碳數目,則預期1-12個碳。術語「雜烷基」係指用一或多個雜原子(例如氮、氧、硫、磷)置換基團內的一或多個碳原子的烷基,例如醚或硫醚。術語「烯基」係指烯烴基,且包括烯烴單基、二基(伸烯基)及較高碳數基團。 除非另外規定,否則「烯基」係指直鏈、分支鏈及環狀烯烴基團。術語「炔基」係指炔烴基,且包括炔烴單基、二基及較高碳數基團。「炔基」係指直鏈及分支鏈炔基。若任何烯基或炔基未指明碳數目,則預期2-12個碳。「有機殘基」係指任何有機部分的基團,除碳及氫以外,其亦可視情況含有一或多個雜原子,諸如氧、氮、矽、磷及鹵素。有機殘基可含有一或多個芳基或非芳基環或兩個芳基及非芳基環。術語「烴基」係指任何烴的基團,其可為脂族、環狀、芳族或其組合,且除碳及氫以外,其亦可視情況含有一或多個雜原子,諸如氧、氮、矽、磷及鹵素。烴基部分可含有芳基或非芳基環或兩個芳基及非芳基環,諸如一或多個脂環或芳環,或兩個脂環及芳環。當烴基部分含有兩個或更多個脂環時,此類脂環可經分離、稠合或為螺環。脂環烴基部分包括單一脂環,諸如環戊基及環己基,以及雙環,諸如二環戊二烯基、降冰片基及降冰片烯基。當烴基部分含有兩個或更多個芳環時,此類環可經分離或稠合。術語「固化」意指提高材料或組合物的分子量的任何方法,例如聚合或縮合。「可固化」係指能夠在某些條件下固化的任何材料。術語「低聚物」係指二聚物、三聚物、四聚物以及其他能夠進一步固化的相對低分子量材料。術語「聚合物」包括低聚物且係指均聚物、共聚物、三元共聚物、四元共聚物及其類似物。如本文所用,術語「(甲基)丙烯酸酯」係指丙烯酸酯及甲基丙烯酸酯。同樣,術語「(甲基)丙烯酸」、「(甲基)丙烯腈」及「(甲基)丙烯醯胺」分別係指丙烯酸及甲基丙烯酸、丙烯腈及甲基丙烯腈以及丙烯醯胺及甲基丙烯醯胺。
本發明的方法包含:(a)用包含一或多種包含含Si-O鍵的主鏈的可固化含矽聚合物、一或多種有機摻合物聚合物及一或多種有機溶劑的塗料組合物塗佈基板以在基板上形成可固化含矽聚合物層;(b)固化含矽聚合物層以形成矽氧烷底層;(c)在矽氧烷底層上安置光致抗蝕劑層;(d)逐圖案曝光光致抗蝕劑層以形成潛像;(e)對潛像顯影以形成在其中具有凸紋影像的圖案化光致抗蝕劑層;(f)將凸紋影像轉移至基板;及(g)藉由濕式剝離移除矽氧烷底層。較佳地,塗料組合物進一步包含一或多種固化催化劑。
任何包含含Si-O鍵的主鏈的可固化含矽聚合物可適當地用於本發明的組合物中。如本文所用,術語「主鏈」係指主聚合物鏈。較佳地,可固化含矽聚合物包含含(-Si-O-)重複單元,諸如(-SiL2-O-)z的主鏈,其中各L獨立地為單價或二價有機或無機基團且z為2至2000之整數。此類可固化含矽聚合物由一或多個矽單體的聚合單元形成。矽單體通常由鍵結至單體中矽的可水解部分的數量所指代。舉例而言,「M單體」係指具有一個可水解部分的矽單體,諸如式R3SiX的單體,「D單體」係指具有兩個可水解部分的矽單體,諸如式R2SiX2的單體,「T單體」係指具有三個可水解部分的矽單體,諸如式RSiX3的單體,且「Q單體」係指具有四個可水解部分的矽單體,諸如式SiX4的單體,其中各單體中的X為可水解部分且各單體中的R為不可水解部分。如本文所用,「可水解部分」係指在用以使矽烷單體縮合、固化或以其他方式聚合的條件下能夠水解的任何部分。矽單體中的例示性可水解部分包括(但不限於)鹵素、烷氧基、甲酸酯基、羥基、烯 氧基、羥亞胺基、胺基及其類似基團。
適用於本發明的含矽聚合物可包含M單體、D單體、T單體、Q單體,或前述中之任一者之二聚物或三聚物的任何組合作為聚合單元。較佳地,含矽聚合物包含一或多個D單體及/或一或多個T單體,且更佳一或多個T單體作為聚合單元。另外較佳的是含矽聚合物包含一或多個T單體及一或多個Q單體,且更佳兩個或更多個T單體及一個Q單體。較佳地,含矽聚合物包括一或多個選自式(3)、(4)、(5a)及(5b)的單體作為聚合單元:R3SiY3 (3)
SiY1 4 (4)
R5 2SiY2 2 (5a)
R5 3SiY2 (5b)
其中各Y、Y1及Y2獨立地為選自鹵基、C1-10烷氧基及-O-C(O)-R4的可水解部分;R3為C1-30烴基部分或經取代的C1-30烴基部分;各R4選自H、OH、C1-10烷基及C1-10烷氧基;且各R5獨立地為C1-30烴基部分或經取代的C1-30烴基部分。各Y、Y1及Y2較佳地選自溴、氯、C1-4烷氧基及-O-C(O)-C1-4烷基。更佳地,含矽聚合物包含一或多個上文所述的式(3)的單體及一或多個上文所述的式(4)的單體作為聚合單元。更佳的是本發明含矽聚合物包含兩個或更多個式(3)的單體及一個式(4)的單體作為聚合單元。在替代較佳實施例中,本發明含矽聚合物包含一或多個式(5a)的單體、一或多個式(5b)的單體,或一或多個式(5a)的單體及一或多個式(5b)的單體的混合物作為聚合單元。在另一較佳實施例中, 本發明含矽聚合物包含一或多個如上文所述的式(3)的單體、一或多個如上文所述的式(4)的單體及一或多個如上文所述的式(5a)及/或(5b)的單體作為聚合單元。另外較佳的是本發明含矽聚合物包含一或多個式(4)的單體,或一或多個式(5a)的單體,或一或多個式(5b)的單體,且更佳一或多個式(4)的單體及一或多個式(5a)及/或(5b)的單體作為聚合單元。
式(3)及(5a)及(5b)中的R3及R5的C1-30烴基部分可分別為任何具有1至30個碳原子的直鏈、分支鏈、脂環族或芳族烴基。R3或R5的適合的C1-30烴基部分包括(但不限於)C1-30烷基、C2-30烯基、C2-30炔基、C3-30環烷基及C6-30芳基,且較佳地為C1-20烷基、C2-20烯基、C2-20炔基、C3-20環烷基及C6-25芳基。式(3)及(5)中的R3及R5的經取代的C1-30烴基部分分別係指一或多個氫經一或多個選自以下的經取代部分置換的任何C1-30烴基部分:羥基、巰基、C1-20烷氧基、胺基、C1-20烷胺基、二-C1-20烷胺基、氰基、鹵素、環氧化物、-C(=O)O-R17、-C(=O)-N(R17)2及-C(=O)-O-C(=O)-R17,其中各R17選自H及C1-20烷基。
其中各R7獨立地選自C1-30烴基部分、經取代的C1-30烴基 部分及OR8;各R8選自H、Si(R9)xO(R10)y、C1-30烴基部分及經取代的C1-30烴基部分;各R9獨立地為C1-30烴基部分或經取代的C1-30烴基部分;各R10獨立地為H、C1-10烷基或-C(O)-C1-10烷基;各R11獨立地選自H、C1-10烷基及-C(O)-C1-10烷基;n係指聚合物中的式(6)的重複單元的數目且為1至100之整數;m係指聚合物中的式(7)的重複單元的數目且為0至50之整數;x=0至3;Y=0至3,且x+y=3。R6、R7、R8及R9的適合的C1-30烴基部分包括(但不限於)C1-30烷基、C2-30烯基、C2-30炔基、C3-30環烷基及C6-30芳基,且較佳地為C1-20烷基、C2-20烯基、C2-20炔基、C3-20環烷基及C6-25芳基。式(6)中的R6、R7、R8及R9的經取代的C1-30烴基部分係指一或多個氫經一或多個選自以下的經取代部分置換的任何C1-30烴基部分:羥基、巰基、C1-20烷氧基、胺基、C1-20烷胺基、二-C1-20烷胺基、氰基及鹵基。較佳地,R7為OR8。較佳地,各R10為C1-6烷氧基或-C(O)-C1-6烷基。較佳地,各R11獨立地選自H、C1-6烷基及-C(O)-C1-6烷基,且更佳選自H、C1-4烷基及-C(O)-C1-4烷基。較佳地,n為1至75且更佳2至50之整數。較佳地,m為1至75,且更佳2至50之整數。此類較佳的含矽聚合物較佳地具有一或多個選自H、-OH、Rt及ORt的端基,其中各Rt獨立地為C1-30烴基部分或經取代的C1-30烴基部分。
適用於形成含矽聚合物的較佳單體包括(但不限於)甲基三氯矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三乙醯氧基矽烷、乙基三氯矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、乙基三乙醯氧基矽烷、丙基三氯矽烷、 丙基三甲氧基矽烷、丙基三乙氧基矽烷、丙基三乙醯氧基矽烷、羥丙基三氯矽烷、羥丙基三甲氧基矽烷、羥丙基三乙氧基矽烷、羥丙基三乙醯氧基矽烷、巰基丙基三氯矽烷、巰基丙基三甲氧基矽烷、巰基丙基三乙氧基矽烷、巰基丙基三乙醯氧基矽烷、環戊基三氯矽烷、環戊基三甲氧基矽烷、環戊基三乙氧基矽烷、環戊基三乙醯氧基矽烷、乙烯基三氯矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三乙醯氧基矽烷、苯基三氯矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、苯基三乙醯氧基矽烷、聯苯基三氯矽烷、聯苯基三甲氧基矽烷、聯苯基三乙氧基矽烷、聯苯基三乙醯氧基矽烷、二甲基二氯矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二甲基二乙醯氧基矽烷、二乙基二氯矽烷、二乙基二甲氧基矽烷、二乙基二乙氧基矽烷、二乙基二乙醯氧基矽烷、二苯基二氯矽烷、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷、二苯基二乙醯氧基矽烷、甲基苯基二氯矽烷、甲基苯基二甲氧基矽烷、甲基苯基二乙氧基矽烷、甲基苯基二乙醯氧基矽烷、甲基乙烯基二氯矽烷、甲基乙烯基二甲氧基矽烷、甲基乙烯基二乙氧基矽烷、甲基乙烯基二乙醯氧基矽烷、二乙烯基二氯矽烷、二乙烯基二甲氧基矽烷、二乙烯基二乙氧基矽烷、二乙烯基二乙醯氧基矽烷、四氯矽烷、四甲氧基矽烷、四乙氧基矽烷及四乙醯氧基矽烷。
製備含矽聚合物的方法為此項技術中熟知的且任何適合方法可用於製備包含含Si-O鍵的主鏈的本發明可固化含矽聚合物。一般而言,用於形成本發明含矽聚合物的單體與水較佳地在可為酸性或鹼性的催化劑存在下,且視情況 在一或多種有機溶劑存在下反應。較佳地,使用酸催化劑。此類反應在適合的反應溫度下進行。單體可首先混合在一起,或可單獨地添加至反應容器中。所用的水量為熟習此項技術者熟知,且較佳地為相對於矽烷單體中所存在的各可水解部分0.5至1.5當量,且更佳0.75至1.25當量,但可使用更大或更小量的水。適合用於形成本發明含矽聚合物的反應溫度為0至130℃,且較佳地5至120℃。適合的酸催化劑包括礦物酸、羧酸以及磺酸,諸如烷磺酸及芳基磺酸。例示性酸催化劑包括(但不限於):氫氟酸、鹽酸、氫溴酸、硫酸、硝酸、過氯酸、磷酸、乙酸、丙酸、丁酸、草酸丙二酸、三氟乙酸、三氯乙酸、甲烷磺酸、三氟甲烷磺酸、乙烷磺酸、丙烷磺酸、苯磺酸、甲苯磺酸以及酚磺酸,且較佳地乙酸、丁酸、甲苯磺酸、三氟甲烷磺酸以及鹽酸。適合鹼性催化劑為熟習此項技術者所熟知。一般而言,此類酸催化劑的量在相對於矽烷單體0至1當量,較佳地0.05至0.9,且更佳0.05至0.75當量的範圍內。
多種視情況存在之有機溶劑可用於製備本發明含矽聚合物,諸如醇、酮、酯、醚、芳族烴、烷烴、內酯及其類似物。例示性有機溶劑包括(但不限於)甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、2-甲基-1-丙醇、4-甲基-2-戊醇、乙二醇、丙二醇、丙酮、乙腈、四氫呋喃、甲苯、己烷、乙酸乙酯、乳酸乙酯、環己烷、甲基-2-正戊基酮、丁二醇單甲醚、丙二醇單甲醚(PGME)、丙二醇單乙醚(PGEE)、乙二醇單甲醚、丁二醇單乙醚、丙二醇單乙醚、乙二醇單乙醚、丙二醇二甲醚、二乙二醇二甲醚、丙二醇單甲基醚乙酸 酯、丙二醇單乙醚乙酸酯、丙酮酸乙酯、乙酸丁酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸第三丁酯、丙酸第三丁酯、丙二醇單第三丁基醚乙酸酯、γ-丁內酯以及其混合物。相對於矽烷單體的總重量,此類視情況存在之有機溶劑的量為0至80%,且較佳地10至50%。
或者,一或多個式(3)、(4)、(5a)、或(5b)的矽單體或其二聚物或三聚物首先與水視情況在有機溶劑存在下,且視情況在催化劑,且較佳地酸催化劑存在下反應。在此類水解及/或縮合反應之後,所得含矽聚合物可視情況與一或多個額外單體反應。
適合的含矽聚合物具有1000至60000Da、較佳地2000至40000Da、且更佳3000至35000Da的Mw。必要時,含矽聚合物可藉由任何適合方式,諸如藉由沈澱、結晶、層析及其類似者自反應混合物分離。含矽聚合物可原樣使用或可另外藉由任何此項技術中已知的方式來純化。
任何有機聚合物可適用作本發明塗料組合物中的有機摻合物聚合物,其限制條件是此類有機聚合物不會使含矽聚合物不穩定,不會在組合物塗佈於基板,諸如半導體裝置基板上時與含矽聚合物分離,且相比於無有機聚合物的含矽聚合物的可濕剝離性增強含矽聚合物的可濕剝離性。較佳地,有機摻合物聚合物包含一或多個烯系不飽和單體作為聚合單元。較佳的烯系不飽和單體具有式(1):
其中Z選自C6-30芳基部分、經取代的C6-30芳基部分、CN 及C(=O)R23;R20選自H、C1-10烷基、C1-10鹵烷基、鹵基及C(=O)R24;R21及R22中之每一者獨立地選自H、C1-4烷基、C1-4鹵烷基、鹵基及CN;R23及R24中之每一者獨立地選自OR25及N(R26)2;R25選自H及C1-20烷基;且各R26獨立地選自H、C1-20烷基及C6-20芳基;其中Z及R20可結合在一起以形成5至7員不飽和環。如本文所用,術語「芳基」係指芳族碳環及芳族雜環。芳基部分較佳是芳族碳環。「經取代的芳基」係指一或多個氫經一或多個選自以下的取代基置換的任何芳基部分:鹵素、C1-6烷基、鹵基C1-6烷基、C1-6烷氧基、鹵基C1-6烷氧基、苯基以及苯氧基,較佳地選自鹵素、C1-6烷基、鹵基C1-4烷基、C1-6烷氧基、苯基及苯氧基,且更佳選自鹵素、C1-6烷基、C1-6烷氧基、苯基及苯氧基。較佳地,經取代的芳基具有1至3個取代基且更佳1或2個取代基。例示性烯系不飽和單體包括(但不限於):烯系不飽和酸酐單體,諸如順丁烯二酸酐、檸康酸酐及衣康酸酐,烯系不飽和醯亞胺單體,諸如順丁烯二醯亞胺;乙烯基芳族單體,諸如苯乙烯、羥基苯乙烯、α-甲基苯乙烯、β-甲基苯乙烯、芪、乙烯基伸萘基、羥基-乙烯基伸萘基、苊烯及乙烯基吡啶;烯系不飽和羧酸,諸如丁烯酸、檸康酸、衣康酸及(甲基)丙烯酸;烯系不飽和羧酸酯,諸如丁烯酸酯、衣康酸酯及(甲基)丙烯酸酯;(甲基)丙烯腈;(甲基)丙烯醯胺;及其類似物。適合的(甲基)丙烯酸酯單體包括(但不限於)(甲基)丙烯酸C7-10芳烷基酯、(甲基)丙烯酸羥基C1-10烷基酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸巰基C1-10烷基酯及(甲基)丙烯酸C1-10烷基酯。例示性(甲基)丙烯酸酯單體包括(但不限於)丙烯酸苯甲 酯、甲基丙烯酸苯甲酯、丙烯酸羥乙酯、甲基丙烯酸羥乙酯、丙烯酸羥丙酯、甲基丙烯酸羥丙酯、甲基丙烯酸巰基丙酯、甲基丙烯酸縮水甘油酯、丙烯酸甲酯及甲基丙烯酸甲酯。
其中ADG為酸可分解基團;且R1獨立地選自H、C1-4烷基、C1-4鹵烷基、鹵基及CN。R1較佳地獨立地選自H、C1-4烷基、C1-4氟烷基、氟及CN,更佳選自H、C1-4烷基、三氟甲基、氟及CN,甚至更佳選自H、甲基、三氟甲基、氟及CN,且最佳地,R1為H或甲基。在式(1a)中,ADG為具有2至30個碳原子的酸可分解基團。如本文所用,術語「酸可分解基團」係指能夠藉由酸分解以形成相比於酸可分解基團具有增加的水性鹼可溶性的不同官能基的任何官能基。適合的酸可分解基團包括(但不限於)-O-C4-30烴基部分,其中C4-30烴基部分經由二級碳原子或三級碳原子結合至氧原子,具有酸酐部分的C2-30烴基部分,具有醯亞胺部分的C2-30烴基部分及包含縮醛官能基的C4-30有機殘基。較佳的酸可分解基團為-O-C4-30烴基部分,其中C4-30烴基部分經由第三碳原子結合至氧原子,及包含縮醛官能基的C4-30有機殘基,且更佳-O-C4-30烴基部分,其中C4-20烴基部分經由三級碳原子結合至氧原子,及包含縮醛官能基的C4-20有機殘基。如本文所用,術語「縮醛」亦包含「縮酮」、「半縮醛」及「半縮酮」。例示 性酸可分解基團包括(但不限於)-NR3R4、-OR5及-O-C(=O)-R6,其中R3及R4各獨立地選自H、C1-20烷基及C6-10芳基;R5為經由二級碳或三級碳(亦即,分別結合至兩個或三個其他碳的碳)結合至氧的C4-30有機殘基或包含縮醛官能基的C4-30有機殘基;且R6選自H、C1-30烷基及C6-30芳基。較佳地,R5具有4至20個碳原子。另外較佳地,R5為分支鏈或環狀部分。當R5含有環狀部分時,此類環狀部分通常在環中具有4至8個原子,且較佳地在環中具有5或6個原子。R5可視情況含有一或多個雜原子,諸如氧。較佳地,R5為視情況含有一或多個雜原子的分支鏈脂族或環脂族部分。
其中R13、R14及R15中之每一者獨立地為具有1至6個碳原子的有機殘基;R13及R14可結合在一起以形成4至8員環;L為二價鍵聯基團或單一化學鍵;A表示縮醛官能基;且*指示與酯氧的連接點。較佳地,R13、R14及R15中之每一者獨立 地選自C1-6烷基。當R13及R14結合在一起以形成4至8員環時,此類環可為單環或可為雙環,且可視情況含有一或多個選自氧、硫及氮,較佳地氧及硫,且更佳氧的雜原子。較佳地,R13及R14可結合在一起以形成5至8員環。適合的4至8員環包括(但不限於)環戊基、環己基、環庚基、環辛基、降冰片基及氧雜雙環[2.2.1]庚基,較佳地環戊基、環己基、降冰片基及氧雜雙環[2.2.1]庚基,且更佳環戊基及環己基。適合的二價鍵聯基團包括C1-10伸烷基,且較佳地C1-5伸烷基。較佳地,縮醛官能基為5元或6員環環狀縮酮,且更佳由丙酮形成的環狀縮酮。R5的例示性部分包括(但不限於):第三丁基;2,3-二甲基-2-丁基;2,3,3-三甲基-2-丁基;2-甲基-2-丁基;2-甲基-2-戊基;3-甲基-3-戊基;2,3,4-三甲基-3-戊基;2,2,3,4,4-五甲基-3-戊基;1-甲基-1-環戊基;1-乙基-1-環戊基;1,2-二甲基-1-環戊基;1,2,5-三甲基-1-環戊基;1,2,2-三甲基-環戊基;1,2,2,5-四甲基-1-環戊基;1,2,2,5,5-五甲基-1-環戊基;1-甲基-1-環己基;1-乙基-1-環己基;1,2-二甲基-1-環己基;1,2,6-三甲基-1-環己基;1,2,2,6-四甲基-1-環己基;1,2,2,6,6-五甲基-1-環己基;2,4,6-三甲基-4-庚基;3-甲基-3-降冰片基;3-乙基-3-降冰片基;6-甲基-2-氧雜雙環[2.2.1]庚-6-基;及2-甲基-7-氧雜雙環[2.2.1]庚-2-基。較佳地,R5選自第三丁基;2,3-二甲基-2-丁基;2,3,3-三甲基-2-丁基;2-甲基-2-丁基;2-甲基-2-戊基;3-甲基-3-戊基;2,3,4-三甲基-3-戊基;2,2,3,4,4-五甲基-3-戊基;1-甲基-1-環戊基;1-乙基-1-環戊基;1,2-二甲基-1-環戊基;1,2,5-三甲基-1-環戊基;1,2,2-三甲基-環戊基;1,2,2,5-四甲基-1-環戊基;1,2,2,5,5-五甲基-1- 環戊基;1-甲基-1-環己基;1-乙基-1-環己基;1,2-二甲基-1-環己基;1,2,6-三甲基-1-環己基;1,2,2,6-四甲基-1-環己基;1,2,2,6,6-五甲基-1-環己基;及2,4,6-三甲基-4-庚基。適合的式(1)、(1a)及(1b)的單體可為市售的或由此項技術中已知的多種方法(如美國專利第6,136,501號;第6,379,861號;及第6,855,475號中所揭示)製得。
其中R1獨立地選自H、C1-4烷基、C1-4鹵烷基、鹵基及CN;且R2為具有內酯部分的單價有機殘基。在式(2)中,R2為包含內酯部分的C4-20單價有機殘基。R2可包括任何適合的內酯部分,且較佳地包含5至7元內酯,其可視情況經取代。內酯環上的適合的取代基為C1-10烷基部分。R2的適合的內酯部分為具有式(9)之彼等:
其中A為5至7員環內酯;各R16獨立地選自C1-10烷基;p為0至3之整數;Y為化學鍵或具有1至10個碳原子的二價鍵聯殘基;且*指示與酯的氧原子的連接點。較佳地,各R16獨立地選自C1-6烷基,且更佳C1-4烷基。R16的實例為甲基、乙基、正丙基、異丙基、正丁基、第二丁基及異丁基。 較佳地,p=0或1。Y的適合的二價鍵聯殘基包括(但不限於)具有1至20個碳原子的二價有機殘基。Y的適合的二價有機殘基包括(但不限於)C1-20烴基部分、C1-20含雜原子烴基部分及經取代的C1-20烴基部分。術語「C1-20含雜原子烴基部分」係指在烴基鏈內具有一或多個雜原子,諸如氮、氧、硫、磷的烴基部分。例示性雜原子包括(但不限於)-O-、-S-、-N(H)-、-N(C1-20烴基)-、-C(=O)-O-、-S(=O)-、-S(=O)2-、-C(=O)-NH-及其類似者。「經取代的C1-20烴基部分」係指一或多個氫經一或多個取代基,諸如鹵素、氰基、羥基、胺基、巰基及其類似基團置換的任何烴基部分。較佳地,R2選自γ-丁內酯(GBLO)、β-丁內酯、γ-戊內酯、δ-戊內酯及己內酯。更佳地,R2為GBLO。式(2)的單體一般為可商購的或可藉由此項技術中已知的方法製備。較佳地,本發明有機摻合物聚合物包含一或多個式(1)的單體及一或多個式(2)的單體,較佳地一或多個式(1a)的單體及一或多個式(2)的單體,且甚至更佳地一或多個式(1b)的單體及一或多個式(2)的單體作為聚合單元。
適用於製備本發明有機摻合物聚合物的烯系不飽和單體為此項技術中熟知的且一般可商購自多種來源或可藉由此項技術中熟知的方法製備。本發明的有機摻合物聚合物可藉由根據此項技術中熟知的方法,諸如用於製備(甲基)丙烯酸酯聚合物的方法的自由基聚合製備。製備摻合物聚合物的其他適合的聚合方法包括(但不限於)狄爾斯-阿爾德(Diels-Alder)、活性陰離子、縮合、交叉偶合、RAFT、ATRP及其類似方法。本發明摻合物聚合物通常具有1000至10000 Da、較佳地2000至8000Da、且更佳地2500至6000Da的Mw。熟習此項技術者應瞭解,可適當地使用有機摻合物聚合物的混合物。當本發明有機摻合物聚合物包含一或多個式(1)的單體及一或多個式(2)的單體作為聚合單元時,此類單體以式(1)的總單體:式(2)的總單體的1:99至99:1的莫耳比存在。較佳地,式(1)的總單體與式(2)的總單體的莫耳比為25:75至75:25,且更佳地為40:60至60:40。一或多個視情況存在之烯系不飽和第三單體可以0至式(1)及(2)的總單體的莫耳量的三倍的量使用。總的視情況存在之第三單體與式(1)及(2)的總單體的莫耳比為0:100至75:25,較佳地10:90至75:25,且更佳地25:70至75:25。
其中R5選自經由三級碳鍵結至氧的C4-20有機殘基或包含縮醛官能基的C4-20有機殘基;且R1選自H、C1-4烷基、C1-4鹵烷基、鹵基及CN;及一或多種固化催化劑。可適當地使用上文所述的含矽聚合物中之任一者。一或多種有機摻合物聚合物可用於本發明組合物。另外,一或多種有機溶劑可用於此等組合物。
本發明的組合物含有一或多種固化催化劑。適合 的固化催化劑包括(但不限於)熱酸產生劑、光酸產生劑及四級銨鹽,較佳地熱酸產生劑及四級銨鹽,且更佳地四級銨鹽。熱酸產生劑是在暴露於熱時釋放酸的任何化合物。熱酸產生劑在此項技術中為熟知的且一般為市售的,諸如來自King Industries,Norwalk,Connecticut。例示性熱酸產生劑包括(但不限於)胺封端強酸,諸如胺封端磺酸,如胺封端十二烷基苯磺酸。多種光酸產生劑在此項技術中為熟知的且亦一般為市售的,諸如來自Wako Pure Chemical Industries,Ltd.及BASF SE。適合的四級銨鹽為:四級銨鹵化物;四級銨羧酸鹽;四級銨磺酸鹽;四級銨硫酸氫鹽;及其類似物。較佳的四級銨鹽包括:苯甲基三烷基鹵化銨,諸如苯甲基三甲基氯化銨及苯甲基三乙基氯化銨;四烷基鹵化銨,諸如四甲基鹵化銨、四乙基鹵化銨及四丁基鹵化銨;四烷基銨羧酸鹽,諸如四甲基甲酸銨、四甲基乙酸銨、四甲基三氟甲磺酸銨、四丁基乙酸銨及四丁基三氟甲磺酸銨;四烷基銨磺酸鹽,諸如四甲基磺酸銨及四丁基磺酸銨;及其類似物。較佳的固化催化劑為四烷基鹵化銨,且更佳地四烷基氯化銨。此類四級銨鹽一般為可商購的,諸如獲自Sigma-Aldrich,或可藉由此項技術中已知的程序製備。此類視情況存在之固化催化劑在本發明組合物中的用量為總固體的0至10%,較佳地總固體的0.01至7%,且更佳地總固體的0.05至5%。
本發明組合物可包括一或多種視情況存在之組分,諸如有機溶劑、塗佈增強劑、一或多種用於含矽聚合物的穩定劑、一或多種二次聚合物及其類似物。用於本發明組合物的此類視情況存在之組分的量完全在熟習此項技術者的 能力內。
多種有機溶劑及水可視情況用於本發明組合物,其條件是此類溶劑溶解組合物的組分。較佳地,本發明組合物包含一或多種有機溶劑。可單獨使用有機溶劑或可使用有機溶劑的混合物。適合的有機溶劑包括(但不限於):酮,諸如環己酮及甲基-2-正戊酮;醇,諸如3-甲氧基丁醇、3-甲基-3-甲氧基丁醇、1-甲氧基-2-丙醇及1-乙氧基-2-丙醇;醚,諸如丙二醇甲醚(PGME)、丙二醇乙醚(PGEE)、乙二醇單甲醚、丙二醇單乙醚、乙二醇單乙醚、丙二醇二甲醚及二乙二醇二甲醚;酯,諸如丙二醇單甲醚乙酸酯(PGMEA)、丙二醇單乙醚乙酸酯、乳酸乙酯(EL)、羥基異丁酸甲酯(HBM)、丙酮酸乙酯、乙酸丁酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸第三丁酯、丙酸第三丁酯及丙二醇單-第三丁醚乙酸酯;內酯,諸如γ-丁內酯;及前述的任何組合。較佳的溶劑為PGME、PGEE、PGMEA、EL、HBM及其組合。
視情況將塗佈增強劑添加至本發明組合物中以改進塗佈於基板上的組合物膜或層的質量。此類塗佈增強劑可充當塑化劑、表面調平劑及其類似物。此類塗佈增強劑為熟習此項技術者所熟知且一般為市售的。例示性塗佈增強劑為:長鏈烷醇,諸如油烯醇、十六烷醇及其類似物;二醇,諸如三丙二醇、四乙二醇及其類似物;以及界面活性劑。儘管可使用任何適合的界面活性劑作為塗佈增強劑,此類界面活性劑通常為非離子型界面活性劑。例示性非離子型界面活性劑為含有伸烷氧基鍵,諸如伸乙基氧基、伸丙基氧基或伸乙基氧基與伸丙基氧基鍵的組合之彼等界面活性劑。較佳 地,在本發明組合物中使用一或多種塗佈增強劑。用於本發明組合物中的塗佈增強劑的量通常為總固體的0至10%,較佳地總固體的0.5至10%,且更佳地總固體的1至8%。
可視情況將一或多種含矽聚合物穩定劑添加至本發明組合物中。此類穩定劑適用於預防含矽聚合物在儲存期間的不合需要的水解或縮合。已知多種此類穩定劑,且較佳地,含矽聚合物穩定劑為酸。適用於矽氧烷聚合物的酸穩定劑包括(但不限於)羧酸、羧酸酐、無機酸及其類似物。例示性穩定劑包括草酸、丙二酸、丙二酸酐、蘋果酸、順丁烯二酸、順丁烯二酸酐、反丁烯二酸、檸康酸、戊二酸、戊二酸酐、己二酸、丁二酸、丁二酸酐以及硝酸。出人意料地發現包含一或多個式(1b)的單體作為聚合單元的有機摻合物聚合物在此類含矽聚合物酸穩定劑存在下在本發明塗料組合物中穩定。此類穩定劑以總固體的0至20%,較佳地總固體的0.1至15%,更佳地總固體的0.5至10%且更佳地總固體的1至10%的量使用。
視情況,一或多種二次聚合物可用於本發明組合物中,其限制條件為此類聚合物與組合物相容,亦即其不會使組合物或其任何組分不穩定且可溶於任何使用的有機溶劑中。此類二次聚合物為不同於本發明含矽聚合物及本發明有機摻合物聚合物的任何聚合物。適合的二次聚合物包括不具有含有Si-O鍵的主鏈的含矽聚合物,亦即,此類二次含矽聚合物具有不含Si-O鍵的主鏈。適合的二次聚合物亦包括任何不包含式(1)以及式(2)的單體作為聚合單元的有機聚合物。當使用時,此類二次聚合物通常以相比於含矽聚合物及 有機摻合物聚合物的相對較小量用於本發明組合物中。當使用時,本發明含矽及有機摻合物聚合物與二次聚合物的重量比為99:1至50:50,且較佳地為95:5至55:45。較佳地,無二次聚合物用於本發明組合物中。
本發明的組合物係藉由組合以下各者製備:一或多種包含含Si-O鍵的主鏈的可固化含矽聚合物;一或多種包含如上文所述的一或多個式(1)的單體及一或多個式(2)的單體作為聚合單元的有機摻合物聚合物;一或多種固化催化劑;及任何視情況存在之組分。較佳地,本發明組合物係藉由組合以下各者製備:一或多種包含含Si-O鍵的主鏈的可固化含矽聚合物;一或多種包含如上文所述的一或多個式(1)的單體及一或多個式(2)的單體作為聚合單元的有機摻合物聚合物;一或多種固化催化劑;一或多種有機溶劑;及任何視情況存在之組分。含矽聚合物與有機摻合物聚合物的重量比較佳地為95:5至50:50,且更佳地為80:20至60:40。
當本發明的組合物用作底層時,較佳地,組合物中的聚合物中的一或多種包含一或多個發色團部分。較佳地,本發明的含矽聚合物中的一或多種、視情況存在之摻合物聚合物中的一或多種、任何視情況存在之二次聚合物中的一或多種或此等的任何組合具有發色團部分,且更佳地本發明的含矽聚合物中的一或多種或本發明的有機摻合物聚合物中的一或多種具有發色團。更佳地,至少一種本發明的含矽聚合物具有一或多個發色團。適合的發色團為芳基部分、經取代的芳基部分、芳烷基部分或芳烯基部分,諸如C6-20芳基、經取代的C6-20芳基、C6-20芳烷基以及C8-30芳烯基。例示性 發色團部分包括(但不限於)苯基、萘基、蒽基、菲基、苯甲基、苯乙基、甲苯基、二甲苯基、苯乙烯基、乙烯基萘、乙烯基蒽、二苯并噻吩、噻噸酮、咔唑、吲哚、吖啶及其類似物,且較佳為苯基、萘基、蒽基、菲基、苯甲基等。此類發色團的選擇取決於所需的抗反射特性且在熟習此項技術者的能力內。
本發明組合物可藉由任何適合方式,諸如旋塗、狹縫塗佈、刀片刮抹、簾式塗佈、滾塗、噴塗、浸塗及其類似者安置於電子裝置基板上。旋塗為較佳的。在典型的旋塗法中,將本發明組合物塗覆至以500rpm至4000rpm速率旋轉15秒至90秒時段的基板上以在基板上獲得所需的含矽聚合物層。此類含矽聚合物層亦包含含矽聚合物以及有機摻合物聚合物,所述含矽聚合物包含含Si-O鍵的主鏈,所述有機摻合物聚合物包含如上文所述的一或多個式(1)的單體及一或多個式(2)的單體作為聚合單元。熟習此項技術者應瞭解,聚合物混合物層的厚度可藉由改變旋轉速度以及組合物的固體含量而調節。
各種各樣的電子裝置基板可用於本發明中,諸如:封裝基板,諸如多片模組;平板顯示器基板;積體電路基板;包括有機發光二級體(OLED)的發光二級體(LED)的基板;半導體晶圓;多晶矽基板;及其類似者。此類基板通常由矽、多晶矽、氧化矽、氮化矽、氮氧化矽、矽鍺、砷化鎵、鋁、藍寶石、鎢、鈦、鈦-鎢、鎳、銅以及金中的一或多者組成。適合的基板可呈晶圓形式,諸如用於製造積體電路、光學感測器、平板顯示器、積體光學電路以及LED之彼 等晶圓。如本文所用,術語「半導體晶圓」意圖涵蓋「電子裝置基板」、「半導體基板」、「半導體裝置」以及各種互連水平的各種封裝,包括單晶片晶圓、多晶片晶圓、各種水平的封裝或需要焊接連接的其他組合件。此類基板可為任何適合尺寸。較佳晶圓基板直徑為200毫米至300毫米,但具有較小及較大直徑的晶圓亦可適合地根據本發明採用。如本文所用,術語「半導體基板」包括具有包括半導體裝置的活性或可操作部分的一或多個半導體層或結構的任何基板。術語「半導體基板」定義為意指包含半導體材料的任何構造,包括(但不限於)整體半導體材料,例如單獨或在上面包含其他材料的組合件中的半導體晶圓,以及單獨或在包含其他材料的組合件中的半導體材料層。半導體裝置係指在上面已經或正在批量製造至少一個微電子裝置的半導體基板。
在塗佈於基板上之後,包含包含含Si-O鍵的主鏈的含矽聚合物;如上文所述的一或多種有機摻合物聚合物的含矽聚合物層視情況在相對較低溫度下軟烘烤以自底層移除任何溶劑及其他相對揮發性組分。通常,基板是在200℃、較佳地100℃至200℃且更佳地100℃至150℃的溫度下烘烤。烘烤時間通常為10秒至10分鐘,較佳地30秒至5分鐘,且更佳地60秒至90秒。當基板為晶圓時,此類烘烤步驟可藉由在熱板上加熱晶圓進行。此類軟焙烤步驟可作為固化含矽聚合物的一部分進行,或可一起省略。
接著將含矽聚合物層固化以形成矽氧烷底層。含矽聚合物經充分固化以使得膜不與隨後塗覆的有機層,諸如直接安置在矽氧烷底層上的光致抗蝕劑或其他有機層混合, 但仍維持矽氧烷底層膜的所需抗反射特性(n及k值)及蝕刻選擇性。含矽聚合物層可在含氧氛圍(諸如空氣)中或在惰性氛圍(諸如氮氣)中且在足以提供固化矽氧烷底層的條件(諸如加熱)下固化。此固化步驟較佳地在熱板式設備上進行,但烘箱固化可用於獲得等效結果。通常,此類固化藉由在350℃且較佳地200至250℃的固化溫度下加熱含矽聚合物層來進行。或者,可使用兩步固化過程或逐漸升溫固化過程。此類兩步及逐漸升溫固化條件為熟習此項技術者所熟知。所選固化溫度應對於用於釋放酸而幫助固化含矽聚合物膜的任何熱酸產生劑足夠。固化時間可為10秒至10分鐘,較佳地30秒至5分鐘,更佳地45秒至5分鐘,且仍更佳地45秒至90秒。最終固化溫度的選擇主要取決於所需固化速率,其中較高固化溫度需要較短固化時間。在這個固化步驟之後,矽氧烷底層表面可視情況藉由用鈍化劑,諸如二矽氮化合物,諸如六甲基二矽氮烷處理來鈍化,或藉由脫水烘烤步驟以移除任何吸附的水。藉由二矽氮化合物的此類鈍化處理通常在120℃下進行。
在固化含矽聚合物層以形成矽氧烷底層之後,一或多個處理層,諸如光致抗蝕劑、硬遮罩層、底部抗反射塗層(或BARC)及其類似者可安置於矽氧烷底層上。舉例而言,光致抗蝕劑層可諸如藉由旋塗直接安置於矽氧烷底層的表面上。或者,BARC層可直接塗佈於矽氧烷底層上,接著使BARC層固化且將光致抗蝕劑層直接塗佈於固化的BARC層上。在另一替代方案中,首先將有機底層塗佈於基板上且固化,接著將本發明的含矽聚合物層塗佈於固化的有機底層上,接著 使含矽聚合物層固化以形成矽氧烷底層,可將視情況存在之BARC層直接塗佈於矽氧烷底層上,接著使視情況存在之BARC層固化,且將光致抗蝕劑層直接塗佈於固化的BARC層上。可適合地使用各種各樣的光致抗蝕劑,諸如用於193nm光刻之彼等光致抗蝕劑,諸如以EPICTM品牌出售的購自Dow Electronic Materials(Marlborough,Massachusetts)之彼等光致抗蝕劑。適合的光阻劑可為正型顯影或負型顯影抗蝕劑,或可為習知負型抗蝕劑。接著使用圖案化光化輻射使光致抗蝕劑層成像(曝光),且接著使用適當顯影劑將曝光的光致抗蝕劑層顯影以提供圖案化光致抗蝕劑層。隨後使圖案由光致抗蝕劑層轉移至任何視情況存在之BARC層,且接著藉由適當蝕刻技術,諸如在適當電漿下的乾式蝕刻轉移至矽氧烷底層。通常,在此類蝕刻步驟期間亦移除光致抗蝕劑。隨後,使用適當技術,諸如在O2電漿下的乾式蝕刻將圖案轉移至存在的任何有機底層,且接著在適當時轉移至基板。在此等圖案轉移步驟之後,使用習知技術移除矽氧烷底層及任何視情況存在之有機底層。接著根據習知方式進一步處理電子裝置基板。
本發明組合物提供具有良好抗蝕刻性及高矽含量(45% Si,且較佳地20至30% Si)的矽氧烷底層。本文所述的含矽聚合物層及矽氧烷底層為可濕剝離的。「可濕剝離」的意思是本發明的含矽聚合物層及矽氧烷底層藉由使聚合物層或矽氧烷底層與習知濕式剝離組合物接觸基本上移除(95%的膜厚度),所述濕式剝離組合物為諸如:(1)鹼組合物水溶液,諸如鹼水溶液(通常約5%)或四甲基氫氧化銨水 溶液(通常5重量%),(2)氟離子剝離劑水溶液,諸如氟化銨/二氟化銨混合物,(3)硫酸及過氧化氫的混合物,或(4)氨及過氧化氫的混合物。本發明聚合物,且確切地說本發明矽氧烷底層的特定優勢為其在與氨及過氧化氫的混合物接觸時可濕剝離。適合的硫酸及過氧化氫的混合物為濃硫酸+30%過氧化氫。適合的氨及過氧化氫的混合物為1:1:5或1:1:10或1:5:40或1:1:40的重量比的氨+過氧化氫+水的混合物。較佳地,聚合物層或矽氧烷底層的膜厚度的97%,且更佳地99%係藉由使聚合物層或矽氧烷底層與以下各者接觸而移除:(i)硫酸及過氧化氫的混合物或(ii)氫氧化銨及過氧化氫的混合物。本發明聚合物層的另一優勢為其易於移除以允許基板,諸如晶圓的再操作。在此類再操作方法中,包含一或多種本發明的含矽聚合物及一或多種本發明的有機摻合物聚合物的上文所述的組合物塗佈於基板上。塗佈的聚合物層接著視情況經軟烘烤,且接著固化以形成矽氧烷底層。隨後,將光致抗蝕劑層塗佈於矽氧烷底層上,且使抗蝕劑層成像及顯影。接著可各自移除圖案化抗蝕劑層及矽氧烷底層以使晶圓進行再操作。使矽氧烷底層與上述可濕剝離組合物(諸如四甲基氫氧化銨組合物水溶液(通常5重量%))及氟離子剝離劑水溶液(諸如氟化銨/二氟化銨混合物)中之任一者在適合溫度下接觸以移除矽氧烷底層,以提供無或基本上無矽氧烷底層且必要時易於經歷額外再操作的基板。此類再操作包括將另一層本發明矽氧烷聚合物塗佈於基板上且如上文所述地處理矽氧烷聚合物塗層。
合成實例1:製備矽聚合物1.將含鹽酸(6.15g, 12.1N)的水(156g)經10min添加至甲基三甲氧基矽烷(99.80g)、苯基三甲氧基矽烷(50.41g)、乙烯基三甲氧基矽烷(62.75g)及原矽酸四乙酯(294g)及2-丙醇(467g)的混合物中。將反應混合物在室溫下攪拌1h,加熱至回流後維持24h且接著冷卻至室溫。溶液用PGEE(800g)稀釋且在減壓下移除低沸點反應混合物組分。所得溶液用PGEE稀釋以獲得矽聚合物1的最終10重量%溶液(Mw=9000Da)。
合成實例2:製備矽聚合物2.將含乙酸(35.5g)的水(160g)經10min添加至甲基三甲氧基矽烷(99.8g)、苯基三甲氧基矽烷(50.4g)、乙烯基三甲氧基矽烷(62.8g)及原矽酸四乙酯(294g)及PGMEA(467g)的混合物中。將反應混合物在室溫下攪拌1h,加熱至85℃後維持6h且接著冷卻至室溫。在減壓下移除低沸點反應混合物組分且用PGMEA稀釋所得溶液,獲得矽聚合物2的最終溶液(大約10-12重量%)(Mw=4000Da)。
合成實例3:製備矽聚合物3.將含鹽酸(0.265g,12.1N)的水(29.4g)經10min添加至乙烯基三甲氧基矽烷(4.75g)、苯基三甲氧基矽烷(12.7g)、雙(三乙氧基矽烷基)乙烯(83.5g)及2-丙醇(160g)的混合物中。將反應混合物在室溫下攪拌1h,加熱至回流後維持18h且接著冷卻至室溫。溶液用PGEE(300g)稀釋且在減壓下移除低沸點反應混合物組分。矽聚合物3的所得溶液用PGEE稀釋以獲得10重量%的最終濃度(Mw=28000Da)。
合成實例4:製備矽聚合物4.將含鹽酸(6.15g,12.1N)的水(225g)經10min添加至3-(3-(三乙氧基矽烷 基)丙基)二氫呋喃-2,5-二酮(223g)、苯基三甲氧基矽烷(50.41g)、乙烯基三甲氧基矽烷(62.75g)及原矽酸四乙酯(294g)及2-丙醇(467g)的混合物中。將反應混合物在室溫下攪拌1h,加熱至回流後維持24h且接著冷卻至室溫。溶液用PGEE(800g)稀釋且在減壓下移除低沸點反應混合物組分。所得溶液用PGEE稀釋以獲得矽聚合物4的最終10重量%溶液(Mw=3900Da)。
合成實例5:製備有機聚合物1.將甲基丙烯酸2-羥乙酯(HEMA)(3.34g)γ丁內酯甲基丙烯酸酯(GBLMA)(4.37g)及甲基丙烯酸第三丁酯(tBMA)(7.30g)溶解於1,3-二氧雜環戊烷(11.5g)中的溶液及V-65引發劑(2.55g)溶解於2:1 v/v四氫呋喃/乙腈(2.55g)中的溶液經2h逐滴添加至氮氣層下、75℃下的含有3-二氧雜環戊烷(26.7g)的反應容器中。在添加之後,反應溶液在75℃下再保持兩小時,冷卻至室溫,用15g THF稀釋且藉由逐滴添加至500mL攪拌的二異丙醚中而分離。沈澱的聚合物藉由真空過濾收集且經真空烘箱乾燥24h以獲得呈白色固體狀的聚合物1(9.40g,63%產率)。Mw測定為3800Da。
合成實例6-21.使用下表1中列出的單體根據以上合成實例5合成下表2中報導的有機聚合物2至17。聚合物2至17以50-99%產率分離且具有在3500-3800Da的範圍內的Mw。
比較調配物1.如下製備比較調配物1:組合2.38g來自合成實例1的矽聚合物1(矽聚合物溶液A);0.640g含四丁基氯化銨的PGEE於5.66g PGEE(催化劑1)中的0.1重量%溶液;及8.24g乳酸乙酯。
調配物實例1-19.根據比較調配物1的一般程序 製備下表4中描述的本發明的調配物1-19,除了使用表3中的組分。類似地製備表4中鑑別的比較調配物2及3。在表4中,表頭「有機聚合物/OPS」係指用於形成來自表3的特定有機聚合物溶液的來自實例5至21的本發明的有機聚合物。
可濕剝離性.測試的調配物樣品過濾通過0.2μm聚四氟乙烯注射器且在200mm裸矽晶圓上以1500rpm旋塗且使用ACT-8 Clean Track(Tokyo Electron Co.)在240℃下烘烤60秒。用來自Therma-wave Co的OptiProbeTM儀器量測各塗佈膜在烘烤之後的膜厚度。經塗佈的樣品接著使用1/1/5、1/1/10、1/5/40或1/1/40的w/w/w比率的30% NH4OH/30%H2O2/水的混合物評估SC-1可濕剝離性。SC-1混合物對於1/1/5、1/5/40及1/1/40剝離混合物加熱至70℃,且對於1/1/10w/w/w剝離溶液加熱至45℃。將各塗佈晶圓的試片浸入剝離溶液中5min。將試片自SC-1混合物移除且用去
離子水沖洗。各樣品的膜厚度損失計算為與SC-1剝離混合物接觸之前及之後的膜厚度的差異。視情況對於如上文所述地製備的獨立膜測試蝕刻之後的SC-1可剝離性。使用來自Plasma-Therm Co.的RIE790在氧氣、25sscm流量、180W功率及6毫托壓力下進行蝕刻60秒。
1/1/5 w/w/w比率的30% NH4OH/30% H2O2/水的剝離混合物的資料報導於表5中,對於1/5/40 w/w/w比率報導於表6中,對於1/1/10 w/w/w比率報導於表7中,對於1/1/40 w/w/w比率報導於表8中。標記為‘無蝕刻’的資料係藉由獲取塗佈晶圓之間的膜厚度與暴露於SC-1剝離混合物之後的膜厚度的差異計算為百分比。標記為「蝕刻之後」的資料係藉由獲取暴露於氧氣蝕刻之後的塗佈晶圓之間的膜厚度與相同晶圓在暴露於SC-1剝離混合物之後的膜厚度的差異而計算為百分比。
在表5至表8中,比較調配物1的剝離資料標準化為1.00,且以「◇」指示。勝過比較調配物1<2倍的本發明實例以「■」指示;勝過比較調配物1,2至10倍的本發明實例以「□」指示;勝過比較調配物1,10至30倍的本發明實例以「▽」指示;且勝過比較調配物1超過30倍的本發明實例以「◣」指示。
表5-8中的資料明顯地顯示本發明的調配物改進含矽材料的可濕剝離性。
Claims (16)
- 一種使用含矽底層之方法,其包含:(a)用包含一或多種包含含Si-O鍵的主鏈的可固化含矽聚合物、一或多種有機摻合物聚合物及一或多種有機溶劑的塗料組合物塗佈基板以在所述基板上形成可固化含矽聚合物層;(b)固化所述含矽聚合物層以形成矽氧烷底層;(c)在所述矽氧烷底層上安置光致抗蝕劑層;(d)逐圖案曝光所述光致抗蝕劑層以形成潛像;(e)對所述潛像顯影以形成在其中具有凸紋影像的圖案化光致抗蝕劑層;(f)將所述凸紋影像轉移至所述基板;及(g)藉由濕式剝離移除所述矽氧烷底層,其中所述有機摻合物聚合物包含一或多個式(1a)的單體和一或多個式(2)的單體作為聚合單體其中ADG為酸可分解基團;且R1獨立地選自H、C1-4烷基、C1-4鹵烷基、鹵基及CN;且R2為具有內酯部分的單價有機殘基。
- 如申請專利範圍第1項所述之方法,其中所述式(1a)的單體具有式(1b)的單體:其中R5選自經由三級碳結合至氧的C4-30有機殘基或包含縮醛官能基的C4-30有機殘基;且R1獨立地選自H、C1-4烷基、C1-4鹵烷基、鹵基及CN。
- 如申請專利範圍第1項所述之方法,其中R2的所述內酯部分為5至7員環或經取代的5至7員環。
- 如申請專利範圍第1項所述之方法,其中所述塗料組合物進一步包含一或多種固化催化劑。
- 如申請專利範圍第1項所述之方法,其中所述一或多種含矽聚合物包含一或多個選自式(3)、(4)、(5a)及(5b)的單體作為聚合單元:R3SiY3 (3) SiY1 4 (4) R5 2SiY2 2 (5a) R5 3SiY2 (5b)其中各Y、Y1及Y2獨立地為選自鹵基、C1-10烷氧基及-O-C(O)-R4的可水解部分;R3為C1-30烴基部分或經取代的C1-30烴基部分;各R4選自H、OH、C1-10烷基及C1-10烷氧基;且各R5獨立地為C1-30烴基部分或經取代的C1-30烴基部分。
- 如申請專利範圍第5項所述之方法,其中所述一或多種含矽聚合物包含一或多個式(6)的單元及視情況存在之一或多個式(7)的單元作為聚合單元:其中各R7獨立地選自C1-30烴基部分、經取代的C1-30烴基部分及OR8;各R8選自H、Si(R9)xO(R10)y、C1-30烴基部分及經取代的C1-30烴基部分;各R9獨立地為C1-30烴基部分或經取代的C1-30烴基部分;各R10獨立地為H、C1-10烷基或-C(O)-C1-10烷基;各R11獨立地選自H、C1-10烷基及-C(O)-C1-10烷基;n係指所述聚合物中的式(6)的重複單元的數目且為1至100之整數;m係指所述聚合物中的式(7)的重複單元的數目且為0至50之整數;x=0至3;Y=0至3,且x+y=3。
- 如申請專利範圍第1項所述之方法,其進一步包含在步驟(a)之前將一層高碳含量有機塗層塗佈於所述基板上。
- 如申請專利範圍第1項所述之方法,其中所述濕式剝離步驟包含使所述矽氧烷底層與硫酸及過氧化氫的混合物或氨及過氧化氫的混合物接觸。
- 一種用於形成含矽底層之組合物,其包含:一或多種包含含Si-O鍵的主鏈的可固化含矽聚合物;一或多種包含一或多個式(1b)的單體作為聚合單元的有機摻合物聚合物:其中R5選自經由三級碳鍵結至氧的C4-30有機殘基或包含縮醛官能基的C4-30有機殘基;且R1獨立地選自H、C1-4烷基、C1-4鹵烷基、鹵基及CN;及一或多種固化催化劑。
- 如申請專利範圍第9項所述之組合物,其進一步包含一或多種有機溶劑。
- 如申請專利範圍第9項所述之組合物,其中所述有機摻合物聚合物進一步包含一或多個式(2)的單體作為聚合單元:其中R1獨立地選自H、C1-4烷基、C1-4鹵烷基、鹵基及CN;且R2為具有內酯部分的單價有機殘基。
- 如申請專利範圍第11項所述之組合物,其中所述一或多個式(1b)單體及所述一或多個式(2)的單體是按1:99至99:1的莫耳比。
- 如申請專利範圍第11項所述之組合物,其中所述有機摻合物聚合物進一步包含一或多個烯系不飽和第三單體作為聚合單元。
- 如申請專利範圍第11項所述之組合物,其中R2的所述內酯部分為5至7員環或經取代的5至7員環。
- 如申請專利範圍第9項所述之組合物,其中所述一或多種含矽聚合物包含一或多個選自式(3)、(4)、(5a)及(5b)的單體作為聚合單元:R3SiY3 (3) SiY1 4 (4) R5 2SiY2 2 (5a) R5 3SiY2 (5b)其中各Y、Y1及Y2獨立地為選自鹵基、C1-10烷氧基及-O-C(O)-R4的可水解部分;R3為C1-30烴基部分或經取代的C1-30烴基部分;各R4選自H、OH、C1-10烷基及C1-10烷氧基;且各R5獨立地為C1-30烴基部分或經取代的C1-30烴基部分。
- 如申請專利範圍第15項所述之組合物,其中所述一或多種含矽聚合物包含一或多個式(6)的單元及視情況存在之一或多個式(7)的單元作為聚合單元:其中各R6獨立地選自C1-30烴基部分或經取代的C1-30烴基部分;各R7獨立地選自C1-30烴基部分、經取代的C1-30烴基部分及OR8;各R8選自H、Si(R9)xO(R10)y、C1-30烴基部分及經取代的C1-30烴基部分;各R9獨立地為C1-30烴基部分或經取代的C1-30烴基部分;各R10獨立地為H、C1-10烷基或-C(O)-C1-10烷基;各R11獨立地選自H、C1-10烷基及-C(O)-C1-10烷基;n係指所述聚合物中的式(6)的重複單元之數目且為1至100之整數;m係指所述聚合物中的式(7)的重複單元的數目且為0至50之整數;x=0至3;Y=0至3,且x+y=3。
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