WO2012173721A1 - Epoxy formulations and processes for fabrication of opaque structures - Google Patents
Epoxy formulations and processes for fabrication of opaque structures Download PDFInfo
- Publication number
- WO2012173721A1 WO2012173721A1 PCT/US2012/037497 US2012037497W WO2012173721A1 WO 2012173721 A1 WO2012173721 A1 WO 2012173721A1 US 2012037497 W US2012037497 W US 2012037497W WO 2012173721 A1 WO2012173721 A1 WO 2012173721A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- epoxy
- dye
- group
- cation
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 239000004593 Epoxy Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title description 14
- 238000009472 formulation Methods 0.000 title description 12
- 230000008569 process Effects 0.000 title description 8
- 239000005007 epoxy-phenolic resin Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 18
- -1 aromatic sulfonium cation Chemical class 0.000 claims description 72
- 238000002835 absorbance Methods 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 229920003986 novolac Polymers 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 8
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910017048 AsF6 Inorganic materials 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 6
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 6
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims description 6
- 229940106691 bisphenol a Drugs 0.000 claims description 5
- 239000003504 photosensitizing agent Substances 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- ZIKLJUUTSQYGQI-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxypropoxy)propane Chemical compound CCOCC(C)OCC(C)OCC ZIKLJUUTSQYGQI-UHFFFAOYSA-N 0.000 claims description 3
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 claims description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 3
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 claims description 3
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000004001 thioalkyl group Chemical group 0.000 claims description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 238000005247 gettering Methods 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims 4
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 2
- 239000000945 filler Substances 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 9
- 150000001450 anions Chemical class 0.000 abstract description 7
- 239000000975 dye Substances 0.000 description 62
- 150000001875 compounds Chemical class 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 125000002091 cationic group Chemical group 0.000 description 15
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 14
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 11
- 125000000129 anionic group Chemical group 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000003930 superacid Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 238000000059 patterning Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 150000002118 epoxides Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000001712 DNA sequencing Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 108091028043 Nucleic acid sequence Proteins 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000006229 carbon black Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
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- 150000002921 oxetanes Chemical class 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
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- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- VQVGJEIVVJBMCV-UHFFFAOYSA-N (4-octoxyphenyl)-phenyliodanium Chemical compound C1=CC(OCCCCCCCC)=CC=C1[I+]C1=CC=CC=C1 VQVGJEIVVJBMCV-UHFFFAOYSA-N 0.000 description 1
- LKVSJOBCOXSNCF-UHFFFAOYSA-N 1,4,5,8,9-pentamethylcarbazole Chemical compound CN1C2=C(C)C=CC(C)=C2C2=C1C(C)=CC=C2C LKVSJOBCOXSNCF-UHFFFAOYSA-N 0.000 description 1
- HGERSUQOJQWENV-UHFFFAOYSA-N 1-pentan-2-yloxypropan-2-ol Chemical compound CCCC(C)OCC(C)O HGERSUQOJQWENV-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- HSDVRWZKEDRBAG-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COC(CCCCC)OCC1CO1 HSDVRWZKEDRBAG-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- FUWFDADDJOUNDL-UHFFFAOYSA-N 9,10-diethoxy-2-ethylanthracene Chemical compound CCC1=CC=C2C(OCC)=C(C=CC=C3)C3=C(OCC)C2=C1 FUWFDADDJOUNDL-UHFFFAOYSA-N 0.000 description 1
- GJNKQJAJXSUJBO-UHFFFAOYSA-N 9,10-diethoxyanthracene Chemical compound C1=CC=C2C(OCC)=C(C=CC=C3)C3=C(OCC)C2=C1 GJNKQJAJXSUJBO-UHFFFAOYSA-N 0.000 description 1
- JWJMBKSFTTXMLL-UHFFFAOYSA-N 9,10-dimethoxyanthracene Chemical compound C1=CC=C2C(OC)=C(C=CC=C3)C3=C(OC)C2=C1 JWJMBKSFTTXMLL-UHFFFAOYSA-N 0.000 description 1
- FAYVAXYICXQWOP-UHFFFAOYSA-N 9,10-dimethoxyanthracene-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2C(OC)=C(C=CC=C3)C3=C(OC)C2=C1 FAYVAXYICXQWOP-UHFFFAOYSA-N 0.000 description 1
- LBQJFQVDEJMUTF-UHFFFAOYSA-N 9,10-dipropoxyanthracene Chemical compound C1=CC=C2C(OCCC)=C(C=CC=C3)C3=C(OCCC)C2=C1 LBQJFQVDEJMUTF-UHFFFAOYSA-N 0.000 description 1
- FHYBJLCZRQQVAM-UHFFFAOYSA-N 9-ethyl-3-(9-ethylcarbazol-3-yl)carbazole Chemical compound C1=CC=C2C3=CC(C=4C=C5C6=CC=CC=C6N(C5=CC=4)CC)=CC=C3N(CC)C2=C1 FHYBJLCZRQQVAM-UHFFFAOYSA-N 0.000 description 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- QGJXVBICNCIWEL-UHFFFAOYSA-N 9-ethylcarbazole-3-carbaldehyde Chemical compound O=CC1=CC=C2N(CC)C3=CC=CC=C3C2=C1 QGJXVBICNCIWEL-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 108091005461 Nucleic proteins Proteins 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- YXGJZPSGJRTALL-UHFFFAOYSA-M [AlH2]OC1=CC=CC=C1 Chemical class [AlH2]OC1=CC=CC=C1 YXGJZPSGJRTALL-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 1
- NNOOIWZFFJUFBS-UHFFFAOYSA-M bis(2-tert-butylphenyl)iodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC(C)(C)C1=CC=CC=C1[I+]C1=CC=CC=C1C(C)(C)C NNOOIWZFFJUFBS-UHFFFAOYSA-M 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000001818 capillary gel electrophoresis Methods 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- SQZOLVDICGOBKT-UHFFFAOYSA-E di(octadecanoyloxy)alumanyl octadecanoate Chemical compound [Al+3].[Al+3].[Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SQZOLVDICGOBKT-UHFFFAOYSA-E 0.000 description 1
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- QPAQOQRHCLJMIL-UHFFFAOYSA-N diethoxy(propan-2-yloxy)alumane Chemical compound CCO[Al](OCC)OC(C)C QPAQOQRHCLJMIL-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- OWZDULOODZHVCQ-UHFFFAOYSA-N diphenyl-(4-phenylsulfanylphenyl)sulfanium Chemical compound C=1C=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1SC1=CC=CC=C1 OWZDULOODZHVCQ-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-O diphenylsulfanium Chemical compound C=1C=CC=CC=1[SH+]C1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-O 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940093858 ethyl acetoacetate Drugs 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000011331 genomic analysis Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002493 microarray Methods 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical class C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WJFFBNRZLBAVJH-UHFFFAOYSA-E trialuminum butanoate Chemical compound [Al+3].[Al+3].[Al+3].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O WJFFBNRZLBAVJH-UHFFFAOYSA-E 0.000 description 1
- VPXHMGPVTSICKP-UHFFFAOYSA-E trialuminum propanoate Chemical compound [Al+3].[Al+3].[Al+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O.CCC([O-])=O.CCC([O-])=O.CCC([O-])=O.CCC([O-])=O.CCC([O-])=O.CCC([O-])=O VPXHMGPVTSICKP-UHFFFAOYSA-E 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
- OPSWAWSNPREEFQ-UHFFFAOYSA-K triphenoxyalumane Chemical compound [Al+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 OPSWAWSNPREEFQ-UHFFFAOYSA-K 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
Definitions
- the present invention is directed to permanent epoxy film compositions and methods for fabrication of opaque structures, and more particularly to such permanent epoxy film compositions that utilize, among other things, a photoacid generator and a dye, wherein the anion component of the photoacid generator is structurally identical or of equivalent basicity to the anionic component of the dye.
- Cross-talk defined as the undesired migration of device-induced photonic signal from one or more pixels to adjacent pixels, is a particular problem with BioMEMS containing many microwells per square unit of measurement. As the density of such wells is increased, the chance for crosstalk and false positive signals also increases. In such devices, it would be advantageous to enhance the opacity of the wall in the selected detection wavelength, such as in the 500-600 nm range, to block emission from adjacent wells, thus reducing or, more desirably, eliminating cross-talk and boosting detection accuracy. Another example is seen in the field of advanced displays, where similar need for discrete pixels is required.
- the present invention is directed to a method of forming an opaque structure, comprising the steps of (a) providing the permanent epoxy film composition above; (b) applying the permanent epoxy film composition to a substrate to form a coated substrate; and (c) irradiating the coated substrate to form the opaque structure.
- any other anion-containing species in the formulation e.g., the anion of the dye
- any other anion-containing species in the formulation must also contain the hexafluoroantimonate species, or its basic equivalent, to prevent formation of weak protonic acid so that photo-hardening of the epoxy film will occur.
- the first component of the composition of the invention is an epoxy phenolic resin. While any class of epoxy phenolic resin may be used either as individual resin components, or as combined resin components in the compositions and methods of the present invention, epoxy-novolac resins are preferred for their lithographic properties, and can be obtained by known chemical methods. A particularly preferred example of an epoxy-novolac resin is that obtained from the reaction of bisphenol-A novolac and epichlorohydrin. Epoxy phenolic resins of weight average molecular weight ranging from 1000 to 11000 are preferred and resins with a weight average molecular weight ranging from 2000 to 7000 are particularly preferred.
- any common photoresist or permanent film solvent may be used.
- suitable solvents and solvent classes include, but are not limited to, ketones such as acetone, 2-butanone, 2-heptanone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, methyl t-butyl ketone, cyclopentanone, cyclohexanone; alkylene glycol ("glyme”) ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, diglyme, triglyme; ethers such as tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, dimethoxyethane; esters such as ethyl lactate, ethyl acetate, butyl acetate; long chain ether and alkylene glycol ether- esters including, but not limited to, those under the trade name "DO
- Examples of preferred photoacid generators having the A + B " ionic structure include aromatic sulfonium hexafluoroantimonate salts and aromatic sulfonium tris-(trifluoromethyl sulfonate) methide salts.
- aromatic iodonium complex salts and aromatic sulfonium complex salts include aromatic iodonium complex salts and aromatic sulfonium complex salts, di-(t- butylphenyl)iodonium triflate, diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4- nonylphenyl)iodonium hexafluorophosphate, [4-(octyloxy)phenyl]phenyliodonium
- photoacid generators listed above can be used alone or as mixtures of two or more compounds.
- Useful amounts of photoacid generators in the composition of the invention range from 0.25 to 10 wt%, based on the total weight of the epoxy-phenolic resin.
- the fourth component of the composition of the invention is an absorbing chemical species (e.g., a dye compound) that adds opacity (depending on detection wavelength used in a microwell or pixel application) to the final photocured structure made from the composition of the invention.
- the dye component used in the invention is also ionic and has the general structure C + D " , where C + is the cationic species and D " is the anionic species.
- Suitable cationic species for the dye include cyanine cation, aminoanthroquinone cation, azine cation, rhodamine cation, fushin cation, xanthene cation, and combinations thereof.
- the light- absorbing dyes are incorporated into the patterning formulations depending on technology application, from optical densities (O.D.) of 0.05/ micron up to 4/ micron, at either a preferred wavelength maximum, or over a broad wavelength maxima range, depending on the light blocking requirements of the film.
- optical densities O.D.
- cationic dye species include cationic cyanine dyes with the following structures (I) and (II):
- the anionic species D " of the dye component may be selected, for example, from SbF 6 ⁇ , BF 4 ⁇ , PF 6 " , AsF 6 " , (CF 3 S0 2 ) 3 C, (CF 3 CF 2 ) 3 PF 3 ⁇ , (C 6 F 5 ) 4 B ⁇ , as well as combinations thereof.
- combinations of two, three, four, or more dyes may also be used in the present invention.
- the anionic species of the dye component (D ) must be structurally identical to the anionic species of the PAG component (B ), or be of equivalent basicity, such that the acid produced during photolysis is not compromised by the stronger basic counterion of the dye.
- equivalent basicity means using a dye anion which does not slow lithographic film photospeed beyond that expected from increased film absorbance at 365nm.
- they dye component must also have hexafluoroantimonate as the anionic species, or its basic equivalent.
- the dye preferably has an absorbance range from 290 to 1500 nm and corresponds to the wavelengths of light that are to be absorbed.
- the dye is also transparent in a selected range of wavelengths corresponding to the demands of the application.
- transparent means >70% UV- Visible transmittance.
- Useful amounts of the ionic dye component in the composition of the invention preferably range from 0.25-50 wt%, and more preferably from 0.5-20 wt%, based on the total weight of the epoxy-phenolic resin.
- an additional epoxy resin in the composition may be used to adjust the lithographic contrast of the composition or to modify the optical absorbance of the film.
- the optional epoxy resin may have an epoxide equivalent weight ranging from 150 to 250 grams resin per equivalent of epoxide.
- optional epoxy resins suitable for use include EOCN 4400, an epoxy cresol-novolac with an epoxide equivalent weight of about 195 g/eq manufactured by Nippon Kayaku Co., Ltd., Tokyo, Japan; or cycloaliphatic epoxies as disclosed in U.S. Pat. Nos.
- a reactive monomer compound in the compositions according to the invention.
- Inclusion of reactive monomers in the composition helps to increase the flexibility of the uncured and cured film.
- Glycidyl ethers containing two or more glycidyl ether groups are examples of reactive monomers that can be used.
- Aliphatic and aromatic monofunctional and/or polyfunctional oxetane compounds are another group of optional reactive monomers that can be used in the present invention.
- Specific examples of the aliphatic or aromatic oxetane reactive monomers that can be used include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, xylylene dioxetane, bis(3-ethyl-3-oxetanylmethyl)ether, and the like.
- These monofunctional and/or polyfunctional oxetane compounds can be used alone or as mixtures of two or more.
- substitution position of these substituent groups is preferably at position 2 of the anthracene ring system.
- 9,10-Dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10- dipropoxyanthracene, 9,10-dimethoxy-2-ethylanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-dipropoxy-2-ethylanthracene, 9,10-dimethoxy-2-chloroanthracene, 9,10- dimethoxyanthracene-2- sulfonic acid, 9,1 O-dimethoxyanthracene-2-sulfonic acid methyl ester, 9,1 O-diethoxyanthracene-2- sulfonic acid methyl ester, 9,1 O-dimethoxyanthracene 2- carboxylic acid, 9,1 O-dimethoxyanthracene-2-carb- oxylic acid methyl ester, and the like
- optional adhesion promoting compounds that can be used in the invention include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- mercaptopropyltrimethoxysilane, vinyltrimethyoxysilane, [3-(methacryloyloxy)propyl]tri- methoxysilane, and the like.
- an organic aluminum compound can be used in the present invention as an ion-gettering agent.
- the organic aluminum compound is a compound that has the effect of adsorbing the ionic materials remaining in the cured product.
- the invention offers the advantage of choosing a particular dye (or combination of dyes) based on its specific absorbance and transparency wavelengths to fit a particular application.
- a dye component having a peak absorbance in the 500-600 nm wavelength range such as the cyanine dye clas
- 400-700nm wavelength range such as for photo-defining black matrix patterns for electronic displays.
- NIR near infrared
- Dye 1 733nm, 0.2-0.5 grams, depending on application details
- Dye 2, 808nm, 0.2-0.5 grams
- Dye 3, 855nm, 0.2-0.5 grams
- Dye 4 963nm, 0.2-0.5 grams
- Dye 5, 1027nm, 0.2-0.5 grams
- Dye 6, 1066nm, 0.2-0.5 grams.
- Example 9 we used the same procedure as in Example 9, but employed the corresponding sulfonium methide salt PAG in Example 8 and the corresponding [CF 3 S0 2 ] 3 C ⁇ counter-ion (methide) for the six (6) cationic cyanine dyes used in Example 8 for NIR applications.
- film transmission was in the 10-20% range over the 700-1200 nm wavelength range. Lithographic dose range was also comparable to Example 9.
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Abstract
The present invention is directed to a permanent epoxy film composition, comprising: an epoxy-phenolic resin; solvent; a photoacid generator having the structure A+B-, and a dye having the structure C+D-, wherein photoacid generator counterion B- and dye counterion D- are structurally identical or of equivalent basicity. In the composition of the invention, the dye anion is either structurally identical, or of equivalent basicity, to the anion of the photoacid generator, which favors completion of photoinitiated crosslinking that produces opaque films of excellent quality.
Description
EPOXY FORMULATIONS AND PROCESSES FOR
FABRICATION OF OPAQUE STRUCTURES
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is directed to permanent epoxy film compositions and methods for fabrication of opaque structures, and more particularly to such permanent epoxy film compositions that utilize, among other things, a photoacid generator and a dye, wherein the anion component of the photoacid generator is structurally identical or of equivalent basicity to the anionic component of the dye.
2. Brief Description of the Related Art
Photoimagable coatings are currently used in a wide variety of semiconductor and micromachining applications. In such applications, film imaging is accomplished by pattern- wise exposure of the coating to actinic radiation thereby inducing a solubility change in the coating such that the exposed or unexposed regions can be selectively removed by treatment with a suitable developer composition. Advanced electronic packaging applications requiring high density interconnects with a high aspect ratio (defined as the height to width ratio of the imaged feature), or applications involving the fabrication of micro-electromechanical devices (MEMS) often require photopatterning layers capable of producing uniform films and high aspect ratio patterns with vertical sidewall profiles at film thickness greater than one hundred microns.
Opaque materials have been disclosed, which are useful for controlling the amount of light that reaches a selective surface, especially in conjunction with the manufacture of semiconductors, integrated circuits, and MEMS devices and often using the above photoimagable films. For example, U.S. Patent No. 6,876,052 to Tai discloses use of an opaque material layer in the manufacture of a light-sensitive integrated circuit that prevents light from entering the semiconductor substrate and interfering with operation of the light- sensitive integrated circuit. U.S. Patent No. 7,358,535 to Shoji et al. discloses a photo- coupler semiconductor device that includes opaque elements which limit the amount of light reaching a certain light transmitting member in the device. U.S. Patent No. 7,642,175 to Patwardhan discloses a method of forming an optically opaque backcoat layer on back surfaces of a multiplicity of flip chip style integrated circuit devices formed on a wafer.
The ability to control opacity in permanent epoxy films and coatings employing chemically amplified photoacid generation, over a range of wavelengths, has application in a wide variety of manufacturing processes. As an example, bioMEMS manufacturers of optical DNA sequencing devices are now investigating epoxy permanent films, such as SU-8 permanent film resist, as materials for construction of 3-dimensional wall microarrays. These arrays require discrete detection capability within each well, without adjacent "cross-talk" due to light emission within a well resulting from the sequencing process. Cross-talk, defined as the undesired migration of device-induced photonic signal from one or more pixels to adjacent pixels, is a particular problem with BioMEMS containing many microwells per square unit of measurement. As the density of such wells is increased, the chance for crosstalk and false positive signals also increases. In such devices, it would be advantageous to enhance the opacity of the wall in the selected detection wavelength, such as in the 500-600 nm range, to block emission from adjacent wells, thus reducing or, more desirably, eliminating cross-talk and boosting detection accuracy. Another example is seen in the field of advanced displays, where similar need for discrete pixels is required.
The applications above are currently well suited to the advantages offered by epoxy cured materials. However, producing a photocured epoxy structures that provides a selected level of opacity is technically challenging. One challenge is that the curing of epoxy materials requires generation of so-called "superacids". Superacids span a range of ionic character, by pKa ranging from -1, the weakest of the superacids, to -25, among the strongest in class. Cationic photocuring of epoxy- novolac and other phenolic epoxy films requires photogeneration of superacids possessing ca. -25 pKa. Additionally, it is preferable that the photoacid generated result from 365nm, 405nm, or 436nm monochromatic or broadband film irradiance, in keeping with the mercury g, h and i-line wavelength outputs of standard photo- aligners and step-and-repeat printers.
Another challenge is the choice of organic molecule used for imparting the needed film opacity. Such a molecule must be chosen so that it absorbs light in one selected range of wavelengths but at the same time is transparent to light in another range of wavelengths. For example, the BioMEMS DNA sequencing process mentioned above uses a
chemiluminescence-generated light emission between 500 and 600 nm to confirm a positive DNA sequence match. Maintaining discrete microwell detection without light leakage into adjacent wells requires incorporation of an absorbing species (e.g., a dye) into the epoxy film to provide the required opacity to prevent crosstalk between adjacent wells. In addition to the
absorbance requirement, the dye structure must exhibit sufficient transparency in the 350 to 450nm UV window to allow effective printing of the epoxy wall structure.
There is thus a need for compositions and methods for fabricating opaque structures using photocurable epoxy formulations taking into account the above requirements. The present invention is believed to be an answer to that need.
SUMMARY OF THE INVENTION
In one aspect, the present invention is directed to a permanent epoxy film
composition, comprising 10-80 wt% of an epoxy-phenolic resin having a weight average molecular rate in the range of from 1000 to 11,000, wherein the wt% of the epoxy-phenolic resin in the composition is based on the total solid weight of the composition; 20-90 wt% of a solvent, based on the total weight of the composition; 0.25-10 wt% of a photoacid generator having the structure A+B" wherein the wt% of the photoacid generator in the composition is based on the total weight of the epoxy-phenolic resin; and 0.25-50 wt% of an ionic dye having the structure C+D" wherein B" and D" are structurally identical or of equivalent basicity, and wherein the wt% of the ionic dye in the composition is based on the total weight of the epoxy-phenolic resin.
In another aspect, the present invention is directed to a method of forming an opaque structure, comprising the steps of (a) providing the permanent epoxy film composition above; (b) applying the permanent epoxy film composition to a substrate to form a coated substrate; and (c) irradiating the coated substrate to form the opaque structure.
These and other aspects of the invention will become apparent from the following detailed description of the invention. DETAILED DESCRIPTION OF THE INVENTION
As indicated above, producing a photocured epoxy film that provides a selected level of opacity is technically challenging because the organic molecule that provides the opacity must satisfy several crucial criteria. First, the molecule must be compatible with the superacids required in the photocuring reaction. Second, the organic molecule must have an absorbance wavelength range in a selected range, yet be transparent in another range of wavelengths to allow effective photolithographic fabrication of the structure.
The present inventors have discovered that previous inability to harden permanent film epoxy using combinations of certain photoacid generators (PAGs) and cationic cyanine dyes was likely the result of conditions favoring the formation of weaker protonic acid from
the stronger base counter-ion associated with the dye structure. Without being bound by any particular theory, it was believed that the resulting weak acid does not initiate epoxy cross- linking and a solid structure could not be produced. The inventors have discovered that to counteract the formation of the weak acid, the dye counterion must be chosen to be structurally identical to the counterion of the PAG, or be of equivalent basicity, so that the acid produced during photolysis is not converted to the weaker acid. Thus, as explained in more detail in the Examples that follow, if hexafluoroantimonate acid is photogenerated from the photoacid generator, then any other anion-containing species in the formulation (e.g., the anion of the dye) must also contain the hexafluoroantimonate species, or its basic equivalent, to prevent formation of weak protonic acid so that photo-hardening of the epoxy film will occur.
Accordingly, the present invention is directed to a permanent epoxy film composition, comprising an epoxy-phenoic resin, solvent, a photoacid generator having the structure A+B", and a dye having the structure C+D", wherein B" and D" are structurally identical or of equivalent basicity. Each of these components is described in more detail below.
The first component of the composition of the invention is an epoxy phenolic resin. While any class of epoxy phenolic resin may be used either as individual resin components, or as combined resin components in the compositions and methods of the present invention, epoxy-novolac resins are preferred for their lithographic properties, and can be obtained by known chemical methods. A particularly preferred example of an epoxy-novolac resin is that obtained from the reaction of bisphenol-A novolac and epichlorohydrin. Epoxy phenolic resins of weight average molecular weight ranging from 1000 to 11000 are preferred and resins with a weight average molecular weight ranging from 2000 to 7000 are particularly preferred. EPPN Epoxy (EEW 160-175 g/eq); softening point 75-85°C); manufactured by Nippon Kayaku Co., Ltd., Tokyo, Japan; EOCN Epoxy (EEW 195-200); also manufactured by Nippon Kayaku Co., Ltd., and EPON SU-8 Resin (EEW of 195 to 230 g/eq and a softening point of 80 to 90°C) made by Resolution Performance Products, Houston, Tex., and the like are examples of epoxy-novolac epoxy resins suitable for use in the present invention. Total weight-percent quantities of epoxy-novolac used in preferred formulation
embodiments, either singly or in combinations of up to four epoxy resins, range from 10-80 wt%, based on the total solids weight of the composition.
The second component of the composition of the invention is a solvent or
combination of solvents. In practice, any common photoresist or permanent film solvent may be used. Examples of suitable solvents and solvent classes include, but are not limited to,
ketones such as acetone, 2-butanone, 2-heptanone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, methyl t-butyl ketone, cyclopentanone, cyclohexanone; alkylene glycol ("glyme") ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, diglyme, triglyme; ethers such as tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, dimethoxyethane; esters such as ethyl lactate, ethyl acetate, butyl acetate; long chain ether and alkylene glycol ether- esters including, but not limited to, those under the trade name "DOWANOL-P Series" such as propylene glycol monomethyl ether acetate, and propylene glycol monomethyl-n-butyl ether, "Dowanol E Series" such as Ethylene glycol n-butyl ether, Diethylene glycol n-butyl ether, cellosolve acetate, carbitol acetate; cyclic esters such as γ-butyrolactone; diluent aromatics such as toluene, xylene, tetramethylbenzene; low molecular weight alcohols such as isopropyl alcohol, n-butanol, isobutanol, n-pentanol, isopentyl alcohol, as well as combinations of two, three, four, or more of these solvents. Solvent amounts, either singly, or in combination, can range from 20-90 wt% of total formula weight.
The third component of the composition of the invention is a photoacid generator (PAG) which is a compound that generates an acidic species when irradiated with active rays, such as X-rays, UV radiation, light, and the like. The PAGs used in the invention are generally ionic, and have the general structure A+B", where A+ is the cationic species and B" is the anionic species. Suitable cationic species include aromatic sulfonium cation, aromatic iodonium cation, indolinium cation, as well as various combinations of these. Photoacid generators based on sulfonium or iodonium salts are well-known and have been extensively discussed in the literature (see for example. Crivello et al., "Photoinitiated Cationic
Polymerization with Triarylsulfonium Salts", Journal of Polymer Science: Polymer
Chemistry Edition, vol. 17, pp. 977-999 (1979)). Suitable anionic species for the PAG include SbF6 ", BF4 ~, PF6 ", AsF6 ", (CF3S02)3 , (CF3CF2)3PF3 ~, (C6F5)4B~, and the like, as long as they are capable of generating the required superacid to catalyze the curing reactions.
Examples of preferred photoacid generators having the A+B" ionic structure include aromatic sulfonium hexafluoroantimonate salts and aromatic sulfonium tris-(trifluoromethyl sulfonate) methide salts. Other useful photoacid generators having this general structure include aromatic iodonium complex salts and aromatic sulfonium complex salts, di-(t- butylphenyl)iodonium triflate, diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4- nonylphenyl)iodonium hexafluorophosphate, [4-(octyloxy)phenyl]phenyliodonium
hexafluoroantimonate, triphenylsulfonium triflate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium
tetrakis(pentafluorophenyl)borate, 4,4'-bis[diphenylsulfonium]diphenylsul- fide bis- hexafluorophosphate, 4,4'-bis[di(.beta.-hydroxyethoxy)phenylsulfo- nium]diphenylsulfide bis-hexafluoroantimonate, 4,4'-bis[di(.beta.-hydroxye- thoxy)(phenylsulfonium)diphenyl sulfide-bishexafluorophosphate 7-[di(p-tolyl)sulfonium]-2-isopropylthioxanthone
hexafluorophosphate, 7-[di(p-tolyl)sulfonium-2-isopropylthioxanthone
hexafluoroantimonate, 7-[di(p-tolyl)sulfonium]-2-isopropyl
tetrakis(pentafluorophenyl)borate, phenylcarbonyl-4'-diphenylsulfonium diphenylsulfide hexafluorophosphate, phenylcarbonyl-4'-diphenylsulfonium diphenylsulfide
hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4'-diphenylsulfonium diphenylsulfide hexafluorophosphate, 4-tert-butylphenylcarbonyl-4'-diphenylsulfonium diphenylsulfide hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4'-diphenylsulfonium diphenylsulfide tetrakis(pentafluorophenyl)borate, diphenyl [4-(phenylthio)phenyl] sulfonium
hexafluoroantimonate and the like can be cited as specific examples of the aromatic sulfonium complex salt that can be used. CYRACURE 6979 (aromatic sulfonium
hexafluroantimonate salt) available from Dow Chemicals is one example of a useful photoacid generator. The photoacid generators listed above can be used alone or as mixtures of two or more compounds. Useful amounts of photoacid generators in the composition of the invention range from 0.25 to 10 wt%, based on the total weight of the epoxy-phenolic resin.
The fourth component of the composition of the invention is an absorbing chemical species (e.g., a dye compound) that adds opacity (depending on detection wavelength used in a microwell or pixel application) to the final photocured structure made from the composition of the invention. The dye component used in the invention is also ionic and has the general structure C+D", where C+ is the cationic species and D" is the anionic species. Suitable cationic species for the dye include cyanine cation, aminoanthroquinone cation, azine cation, rhodamine cation, fushin cation, xanthene cation, and combinations thereof. The light- absorbing dyes are incorporated into the patterning formulations depending on technology application, from optical densities (O.D.) of 0.05/ micron up to 4/ micron, at either a preferred wavelength maximum, or over a broad wavelength maxima range, depending on the light blocking requirements of the film.
Examples of useful cationic dye species include cationic cyanine dyes with the following structures (I) and (II):
In the above structures (I) and (II), Ri and R2 may be independently H or any alkyl or isoalkyl group such as methyl, ethyl, propyl, isobutyl, sec-butyl, and the like. R3, R4, R5, R6 and R7 may be independently H or any Q to C18 alkyl or isoalkyl group, an aromatic (e.g., C6H5) group, or an aromatic group substituted with one or more Ci to C18 alkyl substituents and/or one or more halogen substituents.
The bridge structures between the two aromatic ring structures in Compounds (I) and (II) above can vary in length as shown in structures (III) - (V). The length of such bridge structure can be varied as a function of synthesis, and confers the required wavelength absorbance needed from the dye structure. The longer the bridge structure, the longer is the wavelength absorbance (Xmax) of the dye structure.
Additional useful cationic dye species include cationic cyanines of triphenylmethane VI), cationic cyanines of thiazine (VII), and cationic cyanines of oxazine (VIII).
In the above structures VI - VIII, each of Ri, R2, R3, R4, R5, R6 R7, Rs, R9, and Rio are independently selected from H, C1-C12 alkyl, alkaryl, haloalkyl, thioalkyl, thioalkaryl, haloalkaryl, hydroxyalkyl, hydroxyalkaryl, alkoxy, alkoxyaryl, branched C1-C12 polyalkoxy, and branched C1-C12 polyalkoxyaryl.
The anionic species D" of the dye component may be selected, for example, from SbF6 ~, BF4 ~, PF6 ", AsF6 ", (CF3S02)3C, (CF3CF2)3PF3 ~, (C6F5)4B~, as well as combinations
thereof. As will be appreciated by one of skill in the art, combinations of two, three, four, or more dyes may also be used in the present invention.
According to the invention, the anionic species of the dye component (D ) must be structurally identical to the anionic species of the PAG component (B ), or be of equivalent basicity, such that the acid produced during photolysis is not compromised by the stronger basic counterion of the dye. As defined herein, "equivalent basicity" means using a dye anion which does not slow lithographic film photospeed beyond that expected from increased film absorbance at 365nm. Thus, for example, if a hexafluoroantimonate anion is chosen as the anionic species for the photoacid generator, then they dye component must also have hexafluoroantimonate as the anionic species, or its basic equivalent. The dye preferably has an absorbance range from 290 to 1500 nm and corresponds to the wavelengths of light that are to be absorbed. The dye is also transparent in a selected range of wavelengths corresponding to the demands of the application. As defined herein, "transparent" means >70% UV- Visible transmittance. Useful amounts of the ionic dye component in the composition of the invention preferably range from 0.25-50 wt%, and more preferably from 0.5-20 wt%, based on the total weight of the epoxy-phenolic resin.
Additional optional ingredients may also be included in the compositions of the invention, as long as those optional ingredients do not interfere or interact with the dye species outlined above. The following describes potentially useful optional ingredients that may be added to the compositions of the invention.
Optionally, it may be beneficial in certain embodiments to use an additional epoxy resin in the composition. Depending on its chemical structure, this optional epoxy may be used to adjust the lithographic contrast of the composition or to modify the optical absorbance of the film. The optional epoxy resin may have an epoxide equivalent weight ranging from 150 to 250 grams resin per equivalent of epoxide. Examples of optional epoxy resins suitable for use include EOCN 4400, an epoxy cresol-novolac with an epoxide equivalent weight of about 195 g/eq manufactured by Nippon Kayaku Co., Ltd., Tokyo, Japan; or cycloaliphatic epoxies as disclosed in U.S. Pat. Nos. 4,565,859 and 4,481,017 wherein vinyl substituted alicyclic epoxide monomers are copolymerized with a compound containing at least one active hydrogen atom to produce a vinyl substituted polyether that is subsequently oxidized with a peracid to produce the alicyclic epoxy resin. A preferred commercial example is EHPE 3150 epoxy which has an epoxide equivalent weight of 170 to 190 g/eq and is manufactured by Daicel Chemical Industries, Ltd., Osaka, Japan. Preferred
amounts of optional epoxy range from 5-40 wt% of total solids, more preferably from 10-30 wt% of total solids, and most preferably from 15-30 wt% of total solids.
Optionally, it may be beneficial in certain embodiments to use a reactive monomer compound in the compositions according to the invention. Inclusion of reactive monomers in the composition helps to increase the flexibility of the uncured and cured film. Glycidyl ethers containing two or more glycidyl ether groups are examples of reactive monomers that can be used. Compounds with two or more functional groups are preferred and diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and the like are cited as examples. The glycidyl ethers can be used alone or as mixtures of two or more. Trimethylolpropane triglycidyl ether and polypropylene glycol diglycidyl ether are preferred examples of reactive monomers that can be used in the invention. Aliphatic and aromatic monofunctional and/or polyfunctional oxetane compounds are another group of optional reactive monomers that can be used in the present invention. Specific examples of the aliphatic or aromatic oxetane reactive monomers that can be used include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, xylylene dioxetane, bis(3-ethyl-3-oxetanylmethyl)ether, and the like. These monofunctional and/or polyfunctional oxetane compounds can be used alone or as mixtures of two or more.
Cycloaliphatic epoxy compounds can also be used as reactive monomer in this invention and 3,4-epoxycyclohexylmethyl methacrylate and 3,4-epoxycyclohexylmethyl-3',4'- epoxycyclohexane carboxylate may also be cited as examples. When an optional reactive monomer is used, the amount that may be used is 1-20 wt% of total solids in the composition, more preferably 2-15 wt% of total solids, and most preferably 4-10 wt% of total solids.
Optionally, it may be useful to include photosensitizer compounds in the composition in order to increase the efficiency of energy transfer from UV irradiation to the photoacid generator during actinic exposure. Consequently, the process time for exposure is decreased. Anthracene and N-alkyl carbazole compounds are examples of photosensitizers that can be used in the invention. Anthracene compounds with alkoxy groups at positions 9 and 10 (9,10-dialkoxyanthracenes) are preferred photosensitizers (G). Q to C4 alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups are cited as the preferred alkoxy groups. The 9,10-dialkoxyanthracenes can also have substituent groups. Halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, Ci to C4 alkyl groups such as methyl groups, ethyl groups, and propyl groups, sulfonic acid groups, sulfonate ester groups, carboxylic acid alkyl ester groups, and the like are cited as examples of substituent groups.
Ci to C4 alkyls, such as methyl, ethyl, and propyl, are given as examples of the alkyl moiety in the sulfonic acid alkyl ester groups and carboxylic acid alkyl ester groups. The
substitution position of these substituent groups is preferably at position 2 of the anthracene ring system. 9,10-Dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10- dipropoxyanthracene, 9,10-dimethoxy-2-ethylanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-dipropoxy-2-ethylanthracene, 9,10-dimethoxy-2-chloroanthracene, 9,10- dimethoxyanthracene-2- sulfonic acid, 9,1 O-dimethoxyanthracene-2-sulfonic acid methyl ester, 9,1 O-diethoxyanthracene-2- sulfonic acid methyl ester, 9,1 O-dimethoxyanthracene 2- carboxylic acid, 9,1 O-dimethoxyanthracene-2-carb- oxylic acid methyl ester, and the like can be cited as specific examples of the 9,10-dialkoxyanthracenes that can be used in the present invention. Examples of N-alkyl carbazole compounds useful in the invention include N-ethyl carbazole, N-ethyl-3-formyl-carbazole, 1,4,5,8,9-pentamethyl-carbazole, N-ethyl-3,6- dibenzoyl-9-ethylcarbazole and 9,9'-diethyl-3,3'-bicarbazole. The sensitizer compounds can be used alone or in mixtures of two or more. When used, optional photosensitizer component may be present in an amount that is 0.5 to 4.0 wt% relative to the total weight of the PAG in the composition, more preferred to use 0.5-3.0 wt% relative to the total weight of the PAG in the composition, and most preferred to use 1-2.5 wt% relative to the total weight of the PAG in the composition.
Examples of optional adhesion promoting compounds that can be used in the invention include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- mercaptopropyltrimethoxysilane, vinyltrimethyoxysilane, [3-(methacryloyloxy)propyl]tri- methoxysilane, and the like.
Optionally, it may be useful to include non-ionic compounds that absorb actinic rays and have an absorbance coefficient at 365 nm of 15 L/g.cm or higher. Such compounds can be used to provide a relief image cross section that has a reverse tapered shape such that the imaged material at the top of the image is wider than the imaged material at the bottom of the image. Benzophenone compounds such as 2,4-dihydroxybenzophenone and 2,2',4,4'- tetrahydroxybenzophenone, salicylic acid compounds such as phenyl salicylate and 4-t- butylphenyl salicylate, phenylacrylate compounds such as ethyl-2-cyano-3,3- diphenylacrylate, and 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, and the like are cited as specific examples of the compounds that can be used in the present invention either singly or as mixtures.
Optionally, an organic aluminum compound can be used in the present invention as an ion-gettering agent. There are no special restrictions on the organic aluminum compound as
long as it is a compound that has the effect of adsorbing the ionic materials remaining in the cured product. Alkoxyaluminum compounds such as tris-methoxyaluminum, tris- ethoxyaluminum, tris-isopropoxyaluminum, isopropoxydiethoxyaluminum, and tris- butoxyaluminum, phenoxyaluminum compounds such as tris-phenoxyaluminum and tris- para-methylphenoxyaluminum, tris-acetoxyaluminum, tris-aluminum stearate, tris-aluminum butyrate, tris-aluminum propionate, tris-aluminum acetylacetonate, tris-aluminum
tolylfluoroacetylacetate, tris-aluminum ethylacetoacetate, aluminum
diacetylacetonatodipivaloylmethanate, aluminum diisopropoxy(ethylacetoace- tate), and the like are given as specific examples. These components can be used alone or as a combination of two or more components.
Optional inorganic fillers such as barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, montmorillonite clays, and mica powder and various metal powders such as silver, aluminum, gold, iron, CuBiSr alloys, and the like can be used in the present invention. The content of inorganic filler may be 0.1 to 50 w% of the epoxy resin. Likewise, organic fillers such as polymethylmethacrylate, rubber, fluoropolymers, crosslinked epoxies, polyurethane powders and the like can be similarly incorporated.
When necessary, various materials such as crosslinking agents, thermoplastic resins, coloring agents, thickeners, and agents that promote or improve adhesion can be further used in the present invention. Crosslinking agents can include, for example, methoxylated melamine, butoxylated melamine, and alkoxylated glycouril compounds. CYMEL 303 from Cytec Industries, West Paterson, N.J., is a specific example of a suitable methoxylated melamine compound. Hardener 174 from Penninsula Polymers, North Kansas City, MO is a specific example of an alkoxylated glycouril compound. Polyether sulfone, polystyrene, polycarbonate, and the like are cited as examples of thermoplastic resins; titanium oxide, carbon black, naphthalene black, and the like are cited as examples of coloring agents;
asbestos, orben, bentonite, and montomorillonite are cited as examples of thickeners and silicone-containing, fluorine-containing, and polymeric defoaming agents are cited as examples of defoaming agents. When these additives and the like are used, their general content in the composition of the present invention is 0.05 to 10 wt% each, but this can be increased or decreased as needed in accordance with the application objective.
The composition of the present invention can be prepared by combining the four essential components and any of the above optional components, mixing uniformly, dissolving, dispersing, and the like with a roll mill, paddle mixer, or similar devices known in
the compounding art. It is particularly preferred that components are diluted with solvent and adjusted to a solution viscosity appropriate to the intended use of the composition. The materials are then applied to a substrate and manufactured and cured using known processes into the desired shapes or articles. Substrate materials that can be used include, but are not limited to, silicon, silicon dioxide, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium oxide, indium phosphide, copper, aluminum, nickel, iron, steel, copper- silicon alloys, indium-tin oxide coated glass, organic films such as polyimide and polyester, any substrate bearing patterned areas of metal, semiconductor, and insulating materials, and the like.
In terms of utility, the invention offers the advantage of choosing a particular dye (or combination of dyes) based on its specific absorbance and transparency wavelengths to fit a particular application. For example, as mentioned above, some automated DNA sequencing processes use chemicals that generate chemiluminescence emissions between 500 and 600nm to confirm a positive DNA sequence match. The choice of a dye component having a peak absorbance in the 500-600 nm wavelength range (such as the cyanine dye clas) would provide opacity to a BioMEMS structure that can prevent stray light in these wavelengths from interfering with optical detection in adjacent wells. In addition, the dye can also be chosen to have transparency in a selected range (e.g., 350 to 450nm) to allow proper and effective irradiation to produce the required photogenerated acid during the bioMEMS fabrication process. The invention is useful in the production of structures where specific wavelengths and quantities of light must be isolated within specific boundary volumes, such in micro wells or pixels. Examples of such applications include BioMEMS devices for analysis of nucleic acids, proteins, or other biological or chemical materials, displays, light absorbing films, and the like.
The cured products of the compositions according to the invention may also be used as permanent layers in articles of manufacture including MEMS and micromachine components. For example, it can be used for micromachine components as disclosed in Japanese Kokai Patent No. 2000-343,463; office components for ink jet heads as disclosed in Japanese Kokai Patent No. 2001-10,068; magnetic actuator (MEMS) components as disclosed in Japanese Kokai Patent No. 2001-71,299; microchips (μ-TAS) for capillary gel electrophoresis as disclosed in Japanese Kokai Patent No. 2001-157,855; as well as microfluidic channels and cell growth platforms for biological MEMs devices, microreactor components, dielectric layers, insulation layers, and resin substrates. As an additional
example from field of biological applications, the compositions according to the invention may be used to fabricate a plurality of microfluidic channels in devices for parallel, in- vitro screening of biomolecular activity as taught in U.S. Pat. Nos. 6,576,478 and 6,682,942. In the field of MEMS, the coated, imaged, and optionally cured products of the compositions according to the invention may be used in the fabrication of: micro-power switching devices as taught in U.S. Pat. No. 6,506,989; insulating layers in microrelay devices as taught in U.S. Pat. No. 6,624,730; drug delivery devices and sensors as taught in U.S. Pat. No. 6,663,615; multilayer relief structures as described in U.S. Pat. No. 6,582,890; and electromagnetic actuators as described in U.S. Pat. No. 6,674,350. Further and in the area of sensors, the compositions may be used, for example, in the fabrication of ultraminature fiber optic pressure transducers as taught in U.S. Pat. No. 6,506,313 and the fabrication of cantilever tips for application in atomic force microscopy (AFM) as taught in U.S. Pat. No. 6,219,140.
EXAMPLES
The present invention is further described in detail by means of the following
Examples and Comparisons. All parts and percentages are by weight and all temperatures are degrees Celsius unless explicitly stated otherwise.
Example 1.
For applications relating to BioMEMS devices, particularly in the area of genomic analysis and other applications requiring epoxy permanent film with non-actinic absorbance at or around 550nm wavelength, the following example permanent film formulation has application.
In a 500mL wide-mouth brown bottle, 100 grams of an epoxidized bisphenol-A novolac (EEW 195-205) was combined with 5 grams CyraCure 6976 PAG (aromatic sulfonium hexafluoroantimonate salt) and 45 grams of common photoresist or permanent film solvent (cyclopentanone or gamma butyrolactone, -70% solids). To this was added 0.3 weight percent of epoxy resin of Cy3 cationic cyanine dye (Structure I above), having
hexafluorantimonate anion (SbF6 ~) as the counterion (Fabricolor Holdings International Ltd, Paterson, NJ). This dye has an absorbance maximum of approximately 550 nm and optical transparency at 365nm. The mixture was roll-milled 24 hours under mild IR external heating conditions. The resulting viscous liquid was filtered through a 5 micron absolute
polypropylene cartridge and allowed to stand 24 hours. Thereafter, lOmL of the viscous liquid was spin-coated on a 150mm silicon wafer and subsequently baked at 95 C for 6
minutes on a soft-contact hotplate, resulting in a 30 micron thick film. The film was subsequently photopatterned using an EVG 620 Photoaligner equipped with broad-band i-line irradiation (i-line cutoff filter) and a multistep transmission mask. Following exposure, the wafer was post-exposure baked at 95 C for 6 minutes on a soft-contact hotplate and cooled to room temperature. Subsequent PGMEA solvent development for 5 minutes produced a well- resolved pattern with no adhesion loss. The photospeed required to produce a 30 micron line- space feature was ca. 500 mJ/cm .
Example 2.
Using the same procedure and materials as in Example 1 above, but substituting
CyraCure 6976 PAG with a methide-anion based photoacid generator (aromatic sulfonium tris-(trifluoromethyl sulfonate) methide salt), which absorbs actinic radiation between 193nm and 400nm. The resulting formulation was processed identically as in Example 1. The dose required to produce a 30 micron feature was ~ 400 mJ/cm . No adhesion loss was observed. The conjugate methide anion is of equal or lesser basicity (stronger acid) to that of hexafluoroantimonate. Thus, the use of trifluoromethyl sulfonate anion did not hinder crosslinking.
Example 3.
Using the same procedure and materials as in Example 2, but substituting the Cy3 cyanine hexafluoroantimonate dye (Structure 1) with the corresponding Cy3 cyanine iodide dye (e.g., using Γ in place of SbF6 ~). Identical processing, per Example 1, resulted in the exposed and post-exposure baked pattern washing off the wafer during development. No crosslinking was achieved. It is believed that the stronger conjugate iodide base of Cy3 cyanine interacted with the stronger photogenerated conjugate protonic acid of the exposed photoacid generator, thus reducing acid strength and preventing crosslinking.
Example 4.
Using the same procedure and materials as in Example 3, but substituting Cy3 cyanine hexafluoroantimonate dye with the corresponding Cy3 cyanine tris
(trifluoromethylsulfonate) methide dye, and processed in identical fashion per Example 1, resulted in crosslinking of the exposed film. The dose required to produce a 30 micron feature was < 400 mJ/cm ; no adhesion loss was observed. According to the invention, use of
identical counterions resulted in effective photoacid generation, which produced desired crosslinking upon post-exposure bake.
Comparative Example 5.
Using the same procedure in Example 4, but substituting the Cy3 cyanine methide anion dye with the corresponding Cy3 cyanine -based dye containing the borate anion, known to produce very strong super- acid on the order of antimonate and methide (BF4 ~ or (C6F5)4B~). Identical processing, per Example 1, produced a similar pattern. Here, it is believed that the similarly very weak base borate anion did not weaken the acidity of the methide acid. Hence, crosslinking occurred.
Comparative Example 6.
Using the same procedure in Example 5, but substituting the Cy3 cyanine methide dye with the corresponding Cy3 cyanine methane sulfonate dye. Identical processing, per Example 1, did not produce a pattern, as the film dissolved during development. The protonic acid of methane sulfonate conjugate base, (pKa = -2.6(H20)), is much weaker than the acids of antimonate, methide, and borate anions, respectively. Consequently, crosslinking did not occur during post-exposure bake. Example 7.
Described is an epoxy-novolac permanent film formulation requiring full visible light absorbance (400-700nm wavelength range), such as for photo-defining black matrix patterns for electronic displays. Using the same procedure as in Example 1, but with four (4) Cy3 to Cy5 cyanine hexafluoroantimonate salt dye combinations designed for visible absorbance in the 400-700nm range, from O.D. range >2/micron. 9.5 grams of a 65% solids bisphenol-A epoxy formulation, was used as the base material in the preparation of the "black film". To this was added 0.25 grams Dye 1.
= 446nm, 0.5 grams Dye 2. max = 550nm, 0.27 grams Dye 3.
= 645nm, and 0.15 grams Dye 4, = 690nm, as well as 6 grams of solvent to bring the final formulation to a spin-coated film thickness of ca. 3 microns on a 6 inch glass wafer. The resulting optical transmittance over 400-700nm range averaged <10%.
Photospeed was found < 2 J/cm dose range, which is relatively fast for a black film, owing to the 45% transmittance window of the black dye combination produced at 365nm. This feature represents an advantage over that of carbon black, for which no selective transmission
window exists over its broad absorbance range. As a result, no discemable adhesion loss was observed upon patterning and hardbake.
Example 8.
This example shows preparation of the corresponding "methide black" epoxy film, using the same procedure as in Example 7. As the cationic portion of the dye contributes exclusively to its UV- Visible spectral properties, the same weights of all four (4) dyes were used for this example. The corresponding triphenyl sulfonium methide salt PAG, using
[CF3S02]3C~ anion, and the four (4) corresponding cationic cyanine methide salts, each using [CF3S02]3C~ counter-ion, were specifically employed in this example. When processed as in Example 7, the resulting optical transmittance over the 400-750nm wavelength range was nearly identical to that in Example 7. Photospeed was, however, found slower, but doubling the amount of methide PAG as already in the base epoxy formulation solved the problem, with photospeed in the 1-2 J/cm range. No discemable adhesion loss was seen following patterning and hardbake.
Example 9.
For epoxy-novolac permanent film formulations requiring near infrared (NIR) blocking at wavelengths ranging from 700-1200nm, such as for remote controllers for display devices, heat blocks, etc., the following example is described. The same formulation and processing procedure was applied as in Example 2, using instead six (6) cationic cyanine hexafluoroantimonate salts. Dye 1, = 733nm, 0.2-0.5 grams, depending on application details, Dye 2,
= 808nm, 0.2-0.5 grams, Dye 3, = 855nm, 0.2-0.5 grams, Dye 4, = 963nm, 0.2-0.5 grams, Dye 5,
= 1027nm, 0.2-0.5 grams and Dye 6, = 1066nm, 0.2-0.5 grams. Resulting optical transmittance in the 700-1200nm wavelength range for a 5 micron film averaged <15%. A lithographic dose range from 200-700mJ/cm was found, depending on film thickness; the film transmittance at 365nm is very high; therefore the dyes have minimal impact of lithographic exposure, with full patterning retained following development.
Example 10.
In this example, we used the same procedure as in Example 9, but employed the corresponding sulfonium methide salt PAG in Example 8 and the corresponding [CF3S02]3C~ counter-ion (methide) for the six (6) cationic cyanine dyes used in Example 8 for NIR
applications. The same general results obtained, within the exposure and patterning ranges consistent with the NIR dyes in Example 9. Depending on film thickness (from (3-10 microns), film transmission was in the 10-20% range over the 700-1200 nm wavelength range. Lithographic dose range was also comparable to Example 9.
While the invention has been described above with reference to specific embodiments thereof, it is apparent that many changes, modifications, and variation can be made without departing from the inventive concept disclosed herein. Accordingly, it is intended to embrace all such changes, modifications, and variations that fall within the spirit and broad scope of the appended claims. All patent applications, patents, and other publications cited herein are incorporated by reference in their entirety.
Claims
1. A permanent epoxy film composition, comprising:
10-80 wt% of an epoxy-phenolic resin having a weight average molecular rate in the range of from 1000 to 11,000, wherein the wt% of said epoxy-phenolic resin in said composition is based on the total solid weight of the composition;
20-90 wt% of a solvent, based on the total weight of said composition;
0.25-10 wt% of a photoacid generator having the structure
A+B"
wherein said wt% of said photoacid generator in said composition is based on the total weight of said epoxy-phenolic resin; and
0.25-50 wt% of an ionic dye having the structure
C+D"
wherein B" and D" are structurally identical or of equivalent basicity, and wherein said wt% of said ionic dye in said composition is based on the total weight of said epoxy-phenolic resin.
2. The composition of claim 1, wherein said epoxy-phenolic resin comprises an epoxy- novolac resin.
3. The composition of claim 2, wherein said epoxy- novolac resin comprises an epoxidized bisphenol-A novolac resin.
4. The composition of claim 1, wherein said epoxy-phenolic resin has a weight average molecular weight ranging from 2,000 to 7,000.
5. The composition of claim 1, wherein said solvent is selected from the group consisting of acetone, 2-butanone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, methyl t-butyl ketone, cyclopentanone, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane,
dimethoxyethane, diglyme, triglyme, ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, gamma-butyrolactone, toluene, xylene, tetramethylbenzene, octane, decane, and combinations thereof.
6. The composition of claim 1, wherein the A+ component of said photoacid generator is selected from the group consisting of aromatic sulfonium cation, aromatic iodonium cation, indolinium cation, and combinations thereof.
7. The composition of claim 1, wherein the B" component of said photoacid generator is selected from the group consisting of SbF6 ~, BF4 ~, PF6 ", AsF6 ", (CF3S02)3C~, (CF3CF2)3PF3 ~, (C6F5)4B~, and combinations thereof.
8. The composition of claim 1, wherein the C+ component of said dye is selected from the group consisting of cyanine cation, aminoanthroquinone cation, azine cation, rhodamine cation, fushin cation, xanthene cation, and combinations thereof.
9. The composition of claim 1, wherein said dye has absorbance in the 500-600 nm range and transparency in the 350-450 nm range.
10. The composition of claim 1, wherein said C+ component of said dye is selected from the group consistin of
)
wherein Ri and R2 are independently selected from the group consisting of H, alkyl, and isoaklyl; and wherein R3, R4, R5, R6 and R7 are independently selected from the group consisting of H, one or more Q to C18 alkyl or isoalkyl groups, one or more aromatic groups, and an aromatic group substituted with one or more Q to C18 alkyl substituents and/or one or more halogen substituents.
11. The composition of claim 1, wherein said C+ component of said dye is selected from the group consisting of
wherein each of Rl5 R2, R3, R4, R5, R6 R7, R8, R9, and R10 are independently selected from H, CrC12 alkyl, alkaryl, haloalkyl, thioalkyl, thioalkaryl, haloalkaryl, hydroxyalkyl, hydroxyalkaryl, alkoxy, alkoxyaryl, branched CrC12 polyalkoxy, and branched CrC12 polyalkoxyaryl.
12. The composition of claim 1, wherein said D" component of said dye is selected from the group consisting of SbF6 ~, BF4 ~, PF6 ~, AsF6 ", (CF3S02)3C, (CF3CF2)3PF3 ~, (C6F5)4B~, and combinations thereof.
13. The composition of claim 1, further comprising from 0.1-40 wt% of additional additives selected from the group consisting of additional epoxy resins, reactive monomers photosensitizers, adhesion promotors, ion-gettering agents, fillers, crosslinking agents, and combinations thereof, based on the total solid weight of said composition.
14. A method of forming an opaque structure, comprising the steps of:
(a) providing a permanent epoxy film composition, comprising:
10-80 wt% of an epoxy-phenolic resin having a weight average molecular rate in the range of from 1000 to 11,000, wherein the wt% of said epoxy-phenolic resin in said composition is based on the total solid weight of the composition;
20-90 wt% of a solvent, based on the total weight of said composition;
0.25-10 wt% of a photoacid generator having the structure
A+B"
wherein said wt% of said photoacid generator in said composition is based on the total weight of said epoxy-phenolic resin; and
0.25-50 wt% of an ionic dye having the structure
C+D"
wherein B" and D" are structurally identical or of equivalent basicity, and wherein said wt% of said ionic dye in said composition is based on the total weight of said epoxy-phenolic resin;
(b) applying said permanent epoxy film composition to a substrate to form a coated substrate; and
(c) irradiating said coated substrate to form said opaque structure.
15. The method of claim 14, wherein said novolak resin is an epoxidized bisphenol-A novolac resin.
16. The method of claim 14, wherein said solvent is selected from the group consisting of acetone, 2-butanone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, methyl t-butyl ketone, cyclopentanone, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, dimethoxyethane, diglyme, triglyme, ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, gamma-butyrolactone, toluene, xylene, tetramethylbenzene, octane, decane, and combinations thereof.
17.. The method of claim 14, wherein the A+ component of said photoacid generator is selected from the group consisting of aromatic sulfonium cation, aromatic iodonium cation, indolinium cation, and combinations thereof.
18. The method of claim 14, wherein the B" component of said photoacid generator is selected from the group consisting of SbF6 ~, BF4 ~, PF6 ", AsF6 ", (CF3S02)3C~, (CF3CF2)3PF3 ~, (C6F5)4B~, and combinations thereof.
19. The method of claim 14, wherein the C+ component of said dye is selected from the group consisting of cyanine cation, aminoanthroquinone cation, azine cation, rhodamine cation, fushin cation, xanthene cation, and combinations thereof.
20. The method of claim 14, wherein said C+ component of said dye is selected from the group consistin of
wherein Ri and R2 are independently selected from the group consisting of H, alkyl, and isoaklyl; and wherein R3, R4, R5, R6 and R7 are independently selected from the group consisting of H, one or more Ci to C18 alkyl or isoalkyl groups, one or more aromatic groups, and an aromatic group substituted with one or more Ci to C18 alkyl substituents and/or one or more halogen substituents.
21. The method of claim 14, wherein said C+ component of said dye is selected from the group consisting of
wherein each of Rl5 R2, R3, R4, R5, R6 R7, R8, R9, and R10 are independently selected from H, C1-C12 alkyl, alkaryl, haloalkyl, thioalkyl, thioalkaryl, haloalkaryl, hydroxyalkyl, hydroxyalkaryl, alkoxy, alkoxyaryl, branched C1-C12 polyalkoxy, and branched C1-C12 polyalkoxyaryl.
22. The method of claim 14, wherein said D" component of said dye is selected from the group consisting of SbF6 ", BF4 ", PF6 ", AsF6 ", (CF3S02)3C, (CF3CF2)3PF3-, (C6F5)4B-, and combinations thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| US201161520651P | 2011-06-13 | 2011-06-13 | |
| US61/520,651 | 2011-06-13 |
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| Publication Number | Publication Date |
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| WO2012173721A1 true WO2012173721A1 (en) | 2012-12-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/US2012/037497 WO2012173721A1 (en) | 2011-06-13 | 2012-05-11 | Epoxy formulations and processes for fabrication of opaque structures |
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| US12189291B2 (en) | 2011-09-07 | 2025-01-07 | Kayaku Advanced Materials, Inc. | Epoxy formulations and processes for fabrication of relief patterns on low surface energy substrates |
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| US12189291B2 (en) | 2011-09-07 | 2025-01-07 | Kayaku Advanced Materials, Inc. | Epoxy formulations and processes for fabrication of relief patterns on low surface energy substrates |
| WO2013134104A3 (en) * | 2012-03-08 | 2015-06-18 | Microchem Corp. | Photoimageable compositions and processes for fabrication of relief patterns on low surface energy substrates |
| US11635688B2 (en) | 2012-03-08 | 2023-04-25 | Kayaku Advanced Materials, Inc. | Photoimageable compositions and processes for fabrication of relief patterns on low surface energy substrates |
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