TWI453543B - Positive photosensitive resin composition and its application - Google Patents
Positive photosensitive resin composition and its application Download PDFInfo
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- TWI453543B TWI453543B TW101117459A TW101117459A TWI453543B TW I453543 B TWI453543 B TW I453543B TW 101117459 A TW101117459 A TW 101117459A TW 101117459 A TW101117459 A TW 101117459A TW I453543 B TWI453543 B TW I453543B
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- dye
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- unsubstituted
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- 239000011342 resin composition Substances 0.000 title claims description 34
- 239000000975 dye Substances 0.000 claims description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 66
- 229910052799 carbon Inorganic materials 0.000 claims description 66
- -1 cresol aromatic hydroxy compound Chemical class 0.000 claims description 66
- 229920003986 novolac Polymers 0.000 claims description 60
- 229920005989 resin Polymers 0.000 claims description 50
- 239000011347 resin Substances 0.000 claims description 50
- 239000000758 substrate Substances 0.000 claims description 50
- 125000004432 carbon atom Chemical group C* 0.000 claims description 43
- 239000002904 solvent Substances 0.000 claims description 34
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 20
- 229930003836 cresol Natural products 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- 239000010409 thin film Substances 0.000 claims description 17
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 239000004973 liquid crystal related substance Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 238000005227 gel permeation chromatography Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 9
- 239000001003 triarylmethane dye Substances 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 239000001007 phthalocyanine dye Substances 0.000 claims description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 238000005259 measurement Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 239000000987 azo dye Substances 0.000 claims description 6
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 6
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- 239000001000 anthraquinone dye Substances 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 3
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 3
- 230000001186 cumulative effect Effects 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 125000004442 acylamino group Chemical group 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000005415 substituted alkoxy group Chemical group 0.000 claims 1
- 229940124530 sulfonamide Drugs 0.000 claims 1
- 150000003456 sulfonamides Chemical class 0.000 claims 1
- 239000002966 varnish Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 238000005530 etching Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000002440 hydroxy compounds Chemical class 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- 229910052732 germanium Inorganic materials 0.000 description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 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 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 3
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical group OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 3
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical group C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical group NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- FJJYHTVHBVXEEQ-UHFFFAOYSA-N 2,2-dimethylpropanal Chemical compound CC(C)(C)C=O FJJYHTVHBVXEEQ-UHFFFAOYSA-N 0.000 description 2
- CPEXFJVZFNYXGU-UHFFFAOYSA-N 2,4,6-trihydroxybenzophenone Chemical compound OC1=CC(O)=CC(O)=C1C(=O)C1=CC=CC=C1 CPEXFJVZFNYXGU-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 2
- IHZXTIBMKNSJCJ-UHFFFAOYSA-N 3-{[(4-{[4-(dimethylamino)phenyl](4-{ethyl[(3-sulfophenyl)methyl]amino}phenyl)methylidene}cyclohexa-2,5-dien-1-ylidene)(ethyl)azaniumyl]methyl}benzene-1-sulfonate Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 IHZXTIBMKNSJCJ-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FFOPEPMHKILNIT-UHFFFAOYSA-N Isopropyl butyrate Chemical compound CCCC(=O)OC(C)C FFOPEPMHKILNIT-UHFFFAOYSA-N 0.000 description 2
- XNWPXDGRBWJIES-UHFFFAOYSA-N Maclurin Chemical compound OC1=CC(O)=CC(O)=C1C(=O)C1=CC=C(O)C(O)=C1 XNWPXDGRBWJIES-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- ZBNARPCCDMHDDV-UHFFFAOYSA-N chembl1206040 Chemical compound C1=C(S(O)(=O)=O)C=C2C=C(S(O)(=O)=O)C(N=NC3=CC=C(C=C3C)C=3C=C(C(=CC=3)N=NC=3C(=CC4=CC(=CC(N)=C4C=3O)S(O)(=O)=O)S(O)(=O)=O)C)=C(O)C2=C1N ZBNARPCCDMHDDV-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 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
- 238000011156 evaluation Methods 0.000 description 2
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- 229940011051 isopropyl acetate Drugs 0.000 description 1
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- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 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
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- YSGBMDFJWFIEDF-UHFFFAOYSA-N methyl 2-hydroxy-3-methylbutanoate Chemical compound COC(=O)C(O)C(C)C YSGBMDFJWFIEDF-UHFFFAOYSA-N 0.000 description 1
- HSDFKDZBJMDHFF-UHFFFAOYSA-N methyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OC HSDFKDZBJMDHFF-UHFFFAOYSA-N 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
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- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
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- QLTCALXWSNPPGR-UHFFFAOYSA-N phenol;2-phenylphenol Chemical class OC1=CC=CC=C1.OC1=CC=CC=C1C1=CC=CC=C1 QLTCALXWSNPPGR-UHFFFAOYSA-N 0.000 description 1
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- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- ILPVOWZUBFRIAX-UHFFFAOYSA-N propyl 2-oxopropanoate Chemical compound CCCOC(=O)C(C)=O ILPVOWZUBFRIAX-UHFFFAOYSA-N 0.000 description 1
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 229940030966 pyrrole Drugs 0.000 description 1
- TVRGPOFMYCMNRB-UHFFFAOYSA-N quinizarine green ss Chemical compound C1=CC(C)=CC=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=CC=C(C)C=C1 TVRGPOFMYCMNRB-UHFFFAOYSA-N 0.000 description 1
- JZWFDVDETGFGFC-UHFFFAOYSA-N salacetamide Chemical group CC(=O)NC(=O)C1=CC=CC=C1O JZWFDVDETGFGFC-UHFFFAOYSA-N 0.000 description 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 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
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- YXZRCLVVNRLPTP-UHFFFAOYSA-J turquoise blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Cu+2].NC1=NC(Cl)=NC(NC=2C=C(NS(=O)(=O)C3=CC=4C(=C5NC=4NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)NC=4NC(=C6C=C(C=CC6=4)S([O-])(=O)=O)NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)N5)C=C3)C(=CC=2)S([O-])(=O)=O)=N1 YXZRCLVVNRLPTP-UHFFFAOYSA-J 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- LLWJPGAKXJBKKA-UHFFFAOYSA-N victoria blue B Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)=C(C=C1)C2=CC=CC=C2C1=[NH+]C1=CC=CC=C1 LLWJPGAKXJBKKA-UHFFFAOYSA-N 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/008—Azides
- G03F7/0085—Azides characterised by the non-macromolecular additives
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
- G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1259—Multistep manufacturing methods
- H01L27/1288—Multistep manufacturing methods employing particular masking sequences or specially adapted masks, e.g. half-tone mask
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials For Photolithography (AREA)
Description
本發明係有關一種正型感光性樹脂組成物,詳言之,係有關一種蝕刻後顏色不脫落之正型感光性樹脂組成物及其應用。
隨著生活中各種電子產品走向輕、薄之趨勢,各種智慧型手機、薄型電視以及高效能微處理器已廣泛使用,而其中所應用之光微影製程越來越精密,且所形成之線寬亦越來越精細。
針對上述之目的,於日本公開特許平11-143067,公開一種正型感光性組成物,該組成物包含酚醛清漆樹脂、可吸收紫外光之染料、光酸發生劑與藉由酸催化之架橋劑。該專利使用氘取代之二甲基亞碸溶液,進行酚醛清漆樹脂的合成,可獲得感度與耐化性提升的效果。
然而前述之習知技術中,其金屬線路於蝕刻後,附著於金屬線路上之光阻圖案皆有光線遮蔽率不足或該圖案顏色易脫落之問題發生。且因光線遮蔽率不足或顏色之脫落之故,導致光阻無法遮蔽金屬線路之反射光線,特別是在半導體積體電路元件、薄膜電晶體之液晶顯示元件或觸控面板之製程中,使後續相關之黃光製程中之解析度降低。
有鑑於此,於本領域中有必要發展一種蝕刻後顏色不脫落之正型感光性樹脂組成物材料,以克服習知技術之問題。
本發明係有關於一種正型感光性樹脂組成物及其圖案形成方法,且特別是有關於一種使用在半導體積體電路元件、薄膜電晶體之液晶顯示元件或觸控面板之製造中,可於金屬線路上形成細小圖案,且該圖案能顯有顏色,並在蝕刻後顏色不脫落,利於遮蔽金屬線路的反射光線。
因此,本發明係有關一種正型感光性樹脂組成物,其包含:酚醛清漆樹脂(A);鄰萘醌二疊氮磺酸類之酯化物(B);染料(C);及溶劑(D);其中該酚醛清漆樹脂(A)係由甲酚類(cresol)芳香族羥基化合物與醛類化合物聚縮合而得,且基於凝膠滲透色層分析法所測得之酚醛清漆樹脂(A)分子量之積分面積100%,該酚醛清漆樹脂(A)中之甲酚二核體面積介於0.5%至6%;該染料(C)包含染料(C-1)及染料(C-2),且該染料(C-1)係選自由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成之群;及該染料(C-2)係為三芳甲烷系染料。
本發明亦提供一種薄膜電晶體陣列基板之製造方法,其中該薄膜電晶體陣列基板包含一基板及一圖案,該方法包含以前述之正型感光性樹脂組成物塗佈於該基板上以形成該圖案。
本發明再提供一種薄膜電晶體陣列基板,其係由前述之方法所製得。
本發明又提供一種液晶顯示元件,其包含前述之薄膜電晶體陣列基板。
本發明係有關一種正型感光性樹脂組成物,其包含:酚醛清漆樹脂(A);鄰萘醌二疊氮磺酸類之酯化物(B);染料(C);及溶劑(D);其中該酚醛清漆樹脂(A)係由甲酚類芳香族羥基化合物與醛類化合物聚縮合而得,且基於凝膠滲透色層分析法所測得之酚醛清漆樹脂(A)分子量之積分面積100%,該酚醛清漆樹脂(A)中之甲酚二核體面積介於0.5%至6%;該染料(C)包含染料(C-1)及染料(C-2),且該染料(C-1)係選自由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成之群;及該染料(C-2)係為三芳甲烷系染料。
本發明所言之酚醛清漆樹脂(A)係指由甲酚類芳香族羥基化合物及醛類聚縮合而得。
於本發明之具體例中,該甲酚類芳香族羥基化合物為:間-甲酚(m-cresol)、對-甲酚(p-cresol)、鄰-甲酚(o-cresol)等之甲酚類;2,3-二甲苯酚、2,5-二甲苯酚、3,5-二甲苯酚、3,4-二甲苯酚等之二甲酚(xylenol)類。上述化合物可單獨一種使用或混合複數種使用。
在不影響正型感光性樹脂組成物之物性下,本發明所言之酚醛清漆樹脂(A)亦可由其他類之芳香族羥基化合物及醛類聚縮合而得。
於本發明之具體例中,該其他類之芳香族羥基化合物為:苯酚(phenol);間-乙基苯酚、對-乙基苯酚、鄰-乙基苯酚、2,3,5-三甲基苯酚、2,3,5-三乙基苯酚、4-第三丁基苯酚、3-第三丁基苯酚、2-第三丁基苯酚、2-第三丁基-4-甲基苯酚、2-第三丁基-5-甲基苯酚、6-第三丁基-3-甲基苯酚等之烷基苯酚(alkyl phenol)類;對-甲氧基苯酚、間-甲氧基苯酚、對-乙氧基苯酚、間-乙氧基苯酚、對丙氧基苯酚、間-丙氧基苯酚等之烷氧基苯酚(alkoxy phenol)類;鄰-異丙烯基苯酚、對-異丙烯基苯酚、2-甲基-4-異丙烯基苯酚、2-乙基-4-異丙烯基苯酚等之異丙烯基苯酚(isopropenyl phenol)類;苯基苯酚(phenyl phenol)之芳基苯酚(aryl phenol)類;4,4'-二羥基聯苯、雙酚A、間-苯二酚(resorcinol)、對-苯二酚(hydroquinone)、1,2,3-苯三酚(pyrogallol)等之多羥基苯(polyhydroxyphenol)類等。
於本發明之具體例中,與甲酚類芳香族羥基化合物縮合之該醛類為:甲醛、多聚甲醛(paraformaldehyde)、三聚甲醛(trioxane)、乙醛、丙醛、丁醛、三甲基乙醛、丙烯醛(acrolein)、丁烯醛(crotonaldehyde)、環己醛(cyclo hexanealdehyde)、呋喃甲醛(furfural)、呋喃基丙烯醛(furylacrolein)、苯甲醛、對苯二甲醛(terephthal aldehyde)、苯乙醛、α-苯基丙醛、β-苯基丙醛、鄰-羥基苯
甲醛、間-羥基苯甲醛、對-羥基苯甲醛、鄰-甲基苯甲醛、間-甲基苯甲醛、對-甲基苯甲醛、鄰-氯苯甲醛、間-氯苯甲醛、對-氯苯甲醛、肉桂醛等。上述醛類可單獨一種使用或混合複數種使用。其中,該醛類較佳為甲醛。較佳地,該酚醛清漆樹脂(A)係在鹽酸、硫酸、甲酸、醋酸、草酸、對甲苯磺酸等習知的有機酸及/或無機酸之觸媒存在下,於常壓下進行縮合反應,並經脫水及除去未反應之單體類而得。本發明所言之「甲酚二核體」係指二個m
/p
/o
甲酚單體,透過亞甲基為鍵結,以m-m
、o-o
、p-p
等結合方式而形成之物。
於本發明之一具體實施例中,甲酚二核體之含量係以分餾技術或真空蒸餾法控制。分餾技術之一具體實施例係將合成之酚醛清漆樹脂在良溶媒中溶解,然後放入貧溶媒中,使酚醛清漆樹脂沈澱而成。此外,真空蒸餾法係在合成酚醛清漆樹脂時,以230℃以上,較佳大於250℃的溫度,配合1.3 kPa以下的壓力,進行減壓蒸餾而成。
根據本發明之酚醛清漆樹脂(A)基於凝膠滲透色層分析法所測得之酚醛清漆樹脂(A)分子量之積分面積100%,該酚醛清漆樹脂(A)中之甲酚二核體面積介於0.5%至6%,較佳介於0.5%至5.5%,更佳介於0.5%至5.0%。若甲酚二核體面積小於0.5%時,則處理過程成本過高;若甲酚二核體面積大於6%時,會有蝕刻後顏色脫落及解析度較差問題,雖不願受理論所限制,但咸信若樹脂中低分子量之甲酚二核體含量過高,則不易包覆染料,且甲酚二核體易溶
於鹼性的顯影液,會同時將顏料溶解帶走,造成顏色脫落的問題,並進一步造成解析度不佳的問題。
根據本發明該酚醛清漆樹脂(A)分子量之測定方法並無限制,於本發明之具體例中,該凝膠滲透色層分析法係將酚醛清漆樹脂(A)分子量介於200至150,000之訊號作積分,並以分子量及累積重量百分率獲得積分分子量分佈曲線;其中該凝膠滲透色層分析法係使用Waters®製之717 plus進樣儀;Agilent Technologies®製之79911GP-500、79911GP-502、79911GP-503或79911GP-504管柱及Waters®製之2414 RI Detector檢出器;移動相:四氫呋喃;流量:1.0 mL/min;注射量:100 μL;測定溫度:40℃;測定時間:60分鐘;分子量標準品為聚苯乙烯。
本發明所言之鄰萘醌二疊氮磺酸類之酯化物(B)可選用習知經常使用者,並無特別的限制。於本發明之較佳具體例中,該鄰萘醌二疊氮磺酸類之酯化物(B)為鄰萘醌二疊氮-4-磺酸、鄰萘醌二疊氮-5-磺酸、鄰萘醌二疊氮-6-磺酸等之鄰萘醌二疊氮磺酸與羥基化合物的酯化物,更佳為上述鄰萘醌二疊氮磺酸與多元羥基化合物的酯化物。上述化合物可完全酯化或部份酯化,前述羥基化合物之種類可例如:(一)羥基二苯甲酮類、(二)式(13)的羥基芳基化合物、(三)式(14)的(羥基苯基)烴類化合物以及(四)其他芳香族羥基化合物,茲分述如下:(一)羥基二苯甲酮類之具體例為2,3,4-三羥基二苯甲酮、2,4,4'-三羥基二苯甲酮、2,4,6-三羥基二苯甲酮、2,3,4,4'-
四羥基二苯甲酮、2,2',4,4'-四羥基二苯甲酮、2,3',4,4',6-五羥基二苯甲酮、2,2',3,4,4'-五羥基二苯甲酮、2,2',3,4,5'-五羥基二苯甲酮、2,3',4,5,5'-五羥基二苯甲酮或2,3,3',4,4',5'-六羥基二苯甲酮;(二)羥基芳基化合物之具體例為具有式(13)所示之結構式:
其中:R31
至R33
表示氫原子或低級之烷基(alkyl);R34
至R39
表示氫原子、鹵素原子、低級之烷基、低級之烷氧基(alkoxy)、低級之脂烯基(alkenyl)以及環烷基(cycloalkyl);R40
及R41
表示氫原子、鹵素原子及低級之烷基;x、y及z表示1至3的整數;及n表示0或1。
於本發明之較佳具體例中,具有式(13)所示之結構式之羥基芳基化合物為三(4-羥基苯基)甲烷、雙(4-羥基-3,5-二甲基苯基)-4-羥基苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-3-羥基苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-2-羥基苯基
甲烷、雙(4-羥基-2,5-二甲基苯基)-4-羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-3-羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-2-羥基苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-3,4-二羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-3,4-二羥基苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-2,4-二羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-2,4-二羥基苯基甲烷、雙(4-羥基苯基)-3-甲氧基-4-羥基苯基甲烷、雙(3-環己基-4-羥基苯基)-3-羥基苯基甲烷、雙(3-環己基-4-羥基苯基)-2-羥基苯基甲烷、雙(3-環己基-4-羥基苯基)-4-羥基苯基甲烷、雙(3-環己基-4-羥基-6-甲基芳基)-2-羥基苯基甲烷、雙(3-環己基-4-羥基-6-甲基苯基)-3-羥基苯基甲烷、雙(3-環己基-4-羥基-6-甲基苯基)-4-羥基苯基甲烷、雙(3-環己基-4-羥基-6-甲基苯基)-3,4-二羥基苯基甲烷、雙(3-環己基-6-羥基苯基)-3-羥基苯基甲烷、雙(3-環己基-6-羥基苯基)-4-羥基苯基甲烷、雙(3-環己基-6-羥基苯基)-2-羥基苯基甲烷、雙(3-環己基-6-羥基-4-甲基苯基)-2-羥基苯基甲烷、雙(3-環己基-6-羥基-4-甲基苯基)-4-羥基苯基甲烷、雙(3-環己基-6-羥基-4-甲基苯基)-3,4-二羥基苯基甲烷、1-[1-(4-羥基苯基)異丙基]-4-[1,1-雙(4-羥基苯基)乙基]苯或1-[1-(3-甲基-4-羥基苯基)異丙基]-4-[1,1-雙(3-甲基-4-羥基苯基)乙基]苯。
(三)(羥基苯基)烴類化合物之具體例為具有式(14)所示之結構式:
其中:R42
及R43
表示氫原子或低級烷基;及x'及y'表示1至3的整數。
於本發明之較佳具體例中,具有式(14)所示之結構式之(羥基苯基)烴類為2-(2,3,4-三羥基苯基)-2-(2',3',4'-三羥基苯基)丙烷、2-(2,4-二羥基苯基)-2-(2',4'-二羥基苯基)丙烷、2-(4-羥基苯基)-2-(4'-羥基苯基)丙烷、雙(2,3,4-三羥基苯基)甲烷或雙(2,4-二羥基苯基)甲烷。
(四)其他芳香族羥基化合物之具體例為苯酚、對-甲氧基苯酚、二甲基苯酚、對苯二酚、雙酚A、萘酚(naphthol)、鄰苯二酚(pyrocatechol)、1,2,3-苯三酚甲醚(pyrogallol monomethyl ether)、1,2,3-苯三酚-1,3-二甲基醚(pyrogallol-1,3-dimethyl ether)、3,4,5-三羥基苯甲酸(gallic acid)或部份酯化或部份醚化之3,4,5-三羥基苯甲酸。
前述羥基化合物較佳為2,3,4-三羥基二苯甲酮或2,3,4,4'-四羥氧基二苯甲酮。前述羥基化合物可單獨一種使用或混合數種使用。
根據本發明之正型感光性樹脂組成物中之鄰萘醌二疊氮磺酸類之酯化物(B),可使用含有醌二疊氮基的化合物,例如:鄰萘醌二疊氮-4(或5)-磺酸鹵鹽與上述(一)~(四)的
羥基化合物經縮合反應,可完全酯化或部份酯化而得之化合物。前述縮合反應通常在二氧雜環己烷(dioxane)、N-吡咯烷酮(N-pyrrolidone)、乙醯胺(acetamide)等有機溶媒中進行,較佳為在三乙醇胺(triethanolamine)、鹼金屬碳酸鹽或鹼金屬碳酸氫鹽等鹼性縮合劑存在下進行。
於本發明之較佳具體例中,基於羥基化合物中之羥基總量100莫耳%;更佳為50莫耳%以上;尤佳為60莫耳%以上的羥基與鄰萘醌二疊氮-4(或5)磺酸鹵鹽縮合而成酯化物,亦即酯化度在50%以上;更佳為60%以上。
於本發明之具體例中,基於酚醛清漆樹脂(A)之使用量為100重量份,本發明之鄰萘醌二疊氮磺酸類之酯化物(B)之使用量通常為5至50重量份;較佳為10至40重量份;更佳為20至30重量份。
本發明所言之染料(C)包含染料(C-1)及染料(C-2),且該染料(C-1)係選自由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成之群;及該染料(C-2)係為三芳甲烷系染料,當無使用染料(C-1)或染料(C-2)時,則有解析度差,殘膜率不足問題之問題。
雙偶氮系染料係為本發明所屬技術領域中具通常知識者可選用者,並有許多商用雙偶氮系染料可供選擇,例如:C.I.Acid Black 1、C.I.Acid Black 24、C.I.Reactive Black 5、C.I.Solvent Black 3(商品名Sudan Black 141;中央合成化學製、商品名Neptun Black X60;BASF製)及根本特殊化學製之商品名Oil Black DA-411等。
根據本發明之蒽醌系染料係為本發明所屬技術領域中具通常知識者可選用者,並有許多商用蒽醌系染料可供選擇,例如:C.I.Solvent Red 52、C.I.Solvent Red 111、C.I.Solvent Red 149、C.I.Solvent Red 150、C.I.Solvent Red 151、C.I.Solvent Red 168、C.I.Solvent Red 191、C.I.Solvent Red 207、C.I.Solvent Blue 35、C.I.Solvent Blue 36、C.I.Solvent Blue 63、C.I.Solvent Blue 78、C.I.Solvent Blue 83、C.I.Solvent Blue 87、C.I.Solvent Blue 94、C.I.Solvent Blue 97、C.I.Solvent Blue 101、C.I.Solvent Green 3、C.I.Solvent Green 20、C.I.Solvent Green 28、C.I.Solvent Violet 13、C.I.Solvent Violet 14、C.I.Solvent Violet 36、C.I.Disperse Red 22、C.I.Disperse Red 60、C.I.Disperse Violet 31、C.I.Disperse Violet 28、C.I.Vat Black 27及日本化藥製之商品名Kayaset Black A-N等。
根據本發明之三價鉻偶氮系染料係為本發明所屬技術領域中具通常知識者可選用者,並有許多商用三價鉻偶氮系染料可供選擇,例如:Solvent Black 27(商品名Neozapon Black X51;BASF製、商品名Van CHAKU Black Z1-1500;玄玄化學製)、Solvent Black 29(商品名VALIFAST BLACK 3808;ORIENT CHEMICALS製)、C.I.Solvent Black 34(商品名VALIFAST BLACK 3804;ORIENT CHEMICALS製)等。
根據本發明之染料(C-1)可單獨使用或混合多種使用。
根據本發明之三芳甲烷系染料(C-2)係為本發明所屬技術領域中具通常知識者可選用者,於本發明較佳之具體例中,該三芳甲烷系染料(C-2)具有下列通式(1)或式(2)所示之結構式或其鹽類:
式(1)中:R1
及R2
係獨立選自由氫原子、鹵素原子及具1至5個碳數之烷基所組成之群;R3
、R4
、R5
及R6
係獨立選自由氫原子、具1至5個碳數之烷基、苯基及芐基所組成之群;及R7
係選自由通式(3)、通式(4)及通式(5)所組成之群;
其中:R8
至R10
係選自由氫原子及-NR25
R26
所組成之群所組成之群;其中:R25
及R26
係獨立選自由氫原子、具1至5個碳數之烷基、芐基、苯基及p
位包含具1至3個碳數之烷基或具1至3個碳數之烷氧基取代之苯基所組成之群;及R11
至R16
係獨立選自由氫原子、羥基及-SO3-
所組成之群。
式(2)中:R21
及R22
係獨立選自由氫原子、鹵素原子及具1至5個碳數之烷基所組成之群;及R23
係選自由氫原子、-SO3-
、羧基、具1至3個碳數之烷基、具1至3個碳數之烷氧基及-NR25
R26
所組成之群;及R24
係選自由氫原子及-SO3-
所組成之群。
較佳地,根據本發明之R8
、R21
、R22
、R23
、R25
及R26
中
具1至3個碳數之烷基係為甲基、乙基或丙基;R8
及R23
中具1至3個碳數之烷氧基係為甲氧基、乙氧基或丙氧基;R25
及R26
中包含具1至3個碳數之烷氧基取代之苯基為p
-甲氧苯基、p
-乙氧苯基、p
-丙氧苯基;
根據本發明之三芳甲烷系染料可為通式(1)或通式(2)所示之結構式之鹽類,例如鈉、鉀等鹼金屬之鹽類或如三乙胺、2-乙基己基胺及1-胺基-3-苯基丁烷之胺鹽。此等鹽類亦可為與-SO3-
所形成之鹽類。
根據本發明之三芳甲烷系染料(C-2)有許多商用染料可供選擇,例如:C.I.Acid Green 3、C.I.Acid Green 9、C.I.Acid Green 16、C.I.Acid Green 50、C.I.Acid Blue 7、C.I.Acid Blue 83(商品名Brilliant Blue R;Trust Chem製)、C.I.Acid Blue 90、C.I.Acid Blue 108、C.I.Acid Violet 17(商品名Coomassie Violet R200;Sigma製)、C.I.Acid Violet 49、C.I.Solvent Green 15、C.I.Solvent Violet 8、C.I.Basic Blue 1、C.I.Basic Blue 5、C.I.Basic Blue 7(商品名Basonyl Blau 636;BASF製)、C.I.Basic Blue 8、C.I.Basic Blue 26、C.I.Solvent Blue 5、C.I.Solvent Blue 38、C.I.Basic Green 1、C.I.Basic Red 9、C.I.Basic Violet 3、C.I.Basic Violet 12、C.I.Basic Violet 14、Methyl Violet、Crystal Violet、Victoria Blue B、Oil Blue 613(ORIENT CHEMICALS製)、VALIFAST Blue 1621(ORIENT CHEMICALS製)、SBN Blue 701(保土谷化學公司製造)及其衍生物等。
根據本發明之三芳甲烷系染料(C-2)可單獨使用或混合多種使用。
較佳地,該染料(C)進一步包含染料(C-3),其中該染料(C-3)係為酞菁系染料。本發明所言之酞菁系染料較佳係具有為通式(6)所示之結構式:
其中:R27
表示取代基,較佳地,其係為下述通式(7)中之Ra1
至Ra8
與Rb1
至Rb8
所示之取代基;及n表示1至8範圍之整數;較佳為1至6;更佳為1至4。當n為2以上之整數時,多個存在的R27
可以相同或不同。
M係選自由金屬、金屬氯化物、金屬氧化物及金屬氫氧化物所組成之群。較佳地該金屬係選自由鋅、鎂、矽、錫、銠、鉑、鈀、鉬、錳、鉛、銅、鎳、鈷及鐵所組成之群;該金屬氯化物係選自由AlCl、InCl、FeCl、TiCl2
、SnCl2
、SiCl2
及GeCl2
所組成之群;該金屬氧化物係選自由TiO及VO所組成之群;該金屬氫氧化物為Si(OH)2
;更佳地,M係選自由鋅、鈀、銅、鎳、鈷及VO所組成之群;尤佳地,M係選自由鋅、銅、鈷及VO所組成之群;最佳地,
M係為銅。
於本發明之具體例中,該酞菁系染料較佳係具有為通式(7)所示之結構式:
其中:Ra1
至Ra8
與Rb1
至Rb8
係分別獨立選自由氫原子、鹵素原子、氰基、硝基、醛基(formyl)、羧基、磺基(sulfo)、具1至20個碳數之含取代或無取代之烷基、具6至14個碳數之含取代或無取代之芳基、具1至10個碳數之含取代或無取代之雜環基、具1至20個碳數之含取代或無取代之烷氧基、具6至14個碳數之含取代或無取代之芳氧基、具2至21個碳數之含取代或無取代之醯基、具1至20個碳數之含取代或無取代之烷基磺醯基(alkylsulfonyl)、具6至14個碳數之含取代或無取代之芳基磺醯基、具1至10個碳數之含取代或無取代之雜環系磺醯基(heterysulfonyl)、具1至25個碳數之含取代或無取代之胺基甲醯基(carbamoyl)、具0至32個碳數之含取代或無取代之胺磺醯基(sulfamoyl)、具2至20個碳數之含取代或無取代之烷氧羰基(alkoxycarbonyl)、
具7至15個碳數之含取代或無取代之芳氧羰基(aryloxycarbonyl)、具2至21個碳數之含取代或無取代之醯胺基(acylamino)、具1至20個碳數之含取代或無取代之磺醯基胺基(sulfonylamino)及具0至36個碳數之含取代或無取代之胺基所組成之群;其中,胺基中包括苯胺基。另外,為得較佳之溶劑相溶性,Ra1
至Ra8
與Rb1
至Rb8
中較佳至少8個為氫原子,Ra1
至Ra8
不全為氫原子。
Ra1
至Ra8
與Rb1
至Rb8
較佳係分別獨立選自由氫原子、鹵素原子、羧基、磺基、具1至16個碳數之含取代或無取代之烷基(例如:甲基、乙基、正丙基、異丙基)、具6至14個碳數之含取代或無取代之芳基(例如:苯基、p-甲氧基苯基、p-十八烷基苯基)、具1至16個碳數之含取代或無取代之烷氧基(例如:甲氧基、乙氧基、正辛氧基)、具6至10個碳數之含取代或無取代之芳氧基(例如:苯氧基、p-乙氧基苯氧基)、具1至20個碳數之含取代或無取代之烷基磺醯基(例如:甲烷磺醯基、正丙基磺醯基、正辛基磺醯基)、具6至14個碳數之含取代或無取代之芳基磺醯基(例如:甲苯磺醯基、苯磺醯基)、具0至20個碳數之含取代或無取代之胺磺醯基(例如:甲基胺磺醯基、正丁基胺磺醯基)、具1至17個碳數之烷氧羰基(例如:甲氧羰基、正丁氧羰基)、具7至15個碳數之含取代或無取代之芳氧羰基(例如:苯氧羰基)、具2至21個碳數之含取代或無取代之醯胺基(例如:乙醯胺基、三甲基乙醯胺基)及具1至18個碳數之磺醯基胺基(例如:甲烷磺醯基胺基、正丁烷磺醯基胺基)。
更佳地,Ra1
至Ra8
與Rb1
至Rb8
為係分別獨立選自由氫原子、鹵素原子、羧基、磺基、具1至16個碳數之含取代或無取代之烷基、具1至16個碳數之含取代或無取代之烷氧基、具1至20個碳數之含取代或無取代之烷基磺醯基、具6至14個碳數之含取代或無取代之芳基磺醯基、具2至20個碳數之含取代或無取代之胺磺醯基、具1至13個碳數之烷氧羰基、具2至21個碳數之含取代或無取代之醯胺基及具1至18個碳數之磺醯基胺基所組成之群。
尤佳地,Ra1
至Ra8
為係分別獨立選自由氫原子、鹵素原子、磺基、具1至16個碳數之含取代或無取代之烷氧基、具1至20個碳數之含取代或無取代之烷基磺醯基、具6至14個碳數之含取代或無取代之芳基磺醯基、具2至20個碳數之含取代或無取代之胺磺醯基、具2至21個碳數之含取代或無取代之醯胺基及具1至18個碳數之磺醯基胺基所組成之群;Rb1
至Rb8
為氫原子或鹵素原子。
最佳地,Ra1
至Ra8
為係分別獨立選自由氫原子、磺基、具1至20個碳數之無取代之烷基磺醯基、具6至14個碳數之無取代之芳基磺醯基及具7至20個碳數之無取代之胺磺醯基所組成之群;Rb1
至Rb8
為氫原子。
另外,為得較佳之溶劑相溶性,Ra1
和Ra2
中之任意一方、Ra3
和Ra4
中之任意一方、Ra5
和Ra6
中之任意一方以及Ra7
和Ra8
中之任意一方中,四個不同時為氫原子為較佳。
當Ra1
至Ra8
和Rb1
至Rb8
所示各基團具有取代基時,該取代基之具體例如下。
具1至20個碳數之鍊狀或環狀含取代或無取代之烷基(例如:甲基、乙基、異丙基、環己基、苄基、苯乙基)、具6至18個碳數之含取代或無取代之芳基(例如:苯基、氯苯基、2,4-二第三丁基苯基、1-萘基)、具2至20個碳數之含取代或無取代之烯基(例如:乙烯基、2-甲基乙烯基)、具2至20個碳數之含取代或無取代之炔基(例如:乙炔基、2-甲基乙炔基、2-苯基乙炔基)、鹵素原子(例如:氟、氯、溴、碘)、氰基、羥基、羧基、具2至20個碳數之含取代或無取代之醯基(例如:乙醯基、苯甲醯基、水楊醯基、三甲基乙醯基)、具1至20個碳數之含取代或無取代之烷氧基(例如:甲氧基、丁氧基、環己氧基)、具6至20個碳數之含取代或無取代之芳氧基(例如:苯氧基、1-萘氧基、p-甲氧基苯氧基)、具1至20個碳數之含取代或無取代之烷硫基(例如:甲硫基、丁硫基、苄硫基、3-甲氧基丙基硫基)、具6至20個碳數之含取代或無取代之芳硫基(例如:苯硫基、4-氯苯硫基)、具1至20個碳數之含取代或無取代之烷基磺醯基(例如:甲烷磺醯基、丁烷磺醯基)、具6至20個碳數之含取代或無取代之芳基磺醯基(例如:苯磺醯基、對甲苯磺醯基)、具1至17個碳數之含取代或無取代之胺基甲醯基(例如:無取代之胺基甲醯基、甲基胺基甲醯基、乙基胺基甲醯基、正丁基胺基甲醯基、二甲基胺基甲醯基)、具1至16個碳數之含取代或無取代醯胺基(例如:乙醯胺基、苯甲醯胺基)、具2至20個碳數之含取代或無取代醯氧基(例如:乙醯氧基、苯甲醯氧基)、具2至20個碳數之含取代或無取
代之烷氧羰基(例如:甲氧羰基、乙氧羰基)、5或6員之含取代或無取代之雜環基(例如:吡啶基、噻吩基、呋喃基、噻唑基、咪唑基、吡唑基等芳香族雜環基;吡咯烷環、哌啶環、嗎啉環、吡喃環、硫代吡喃環、二噁烷環、二硫戊環等非芳香族雜環基)。
Ra1
至Ra8
與Rb1
至Rb8
各基團中之取代基較佳係選自由具1至16個碳數之鏈狀或環狀含取代或無取代之烷基、具6至14個碳數之芳基、具1至16個碳數之烷氧基、具6至14個碳數之芳氧基、鹵素原子、具2至17個碳數之烷氧羰基、具1至10個碳數之胺基甲醯基及具1至10個碳數之醯胺基所組成之群。
更佳地;其係選自由具1至10個碳數之鏈狀或環狀之烷基、具6至10個碳數之芳基、具1至10個碳數之烷氧基、具6至10個碳數之芳氧基、氯原子、具2至11個碳數之烷氧羰基、具1至7個碳數之胺基甲醯基及具1至8個碳數之醯胺基所組成之群。
尤佳地;其係選自由具1至8個碳數之鏈狀或環狀無取代之烷基、具1至8個碳數之無取代之烷氧基、具3至9個碳數之無取代之烷氧羰基、苯基及氯原子所組成之群。最佳地,其係為具1至6個碳數之無取代之烷氧基。
根據本發明之通式(6)或(7)所示之化合物可在任意位置結合形成聚合物,此時各單元可相同或不同,亦可與聚苯乙烯、聚甲基丙烯酸酯、聚乙烯醇、纖維素等聚合物鏈相結合。
根據本發明之通式(6)或(7)所示之化合物可單獨使用特
定的化合物,也可以將多種結構不同的化合物混合使用。較佳地,其係使用取代基之取代位置不同的異構體的混合物。
於本發明之較佳具體例中,該酞菁系染料(C-3)具有式(8)、式(9)、式(10)、式(11)或式(12)所示之結構式。
根據本發明之酞菁系染料(C-3)有許多商用染料可供選擇,例如:C.I.Acid Blue 249、C.I.Solvent Blue 25、C.I.Solvent Blue 55、Solvent Blue 64(商品名Neptun Blue
698)、Solvent Blue 67、C.I.Solvent Blue 70(商品名Neozapon Blue 807;BASF製)、C.I.Direct Blue 199、C.I.Direct Blue 86(商品名Turquoise Blue;Italia Incorporation製)等。
若使用酞菁系染料(C-3)時,則可進一步提升解析度。
於本發明之較佳具體例中,該正型感光性樹脂組成物可依需要進一步包含紫環酮系(perinone)染料、苝系(perylene)染料、偶氮系(azo)染料、甲川系(methine)染料、喹啉系(quinoline)染料、吖嗪系(azine)染料、蔥醌系(anthraquinone)染料、靛藍系(indigo)染料、類菁系(oxonol)染料、噻嗪系(thiazine)染料、蒽吡啶酮系(anthrapyridone)染料、二苯駢派喃系(xanthene)染料或苯并吡喃系(benzopyran)染料等染料。
於本發明之較佳實施例中,基於酚醛清漆樹脂(A)之使用量為100重量份,該染料(C)之使用量為5至120重量份,較佳為10至100重量份,更佳為15至80重量份。
於本發明之較佳實施例中,基於酚醛清漆樹脂(A)之使用量為100重量份,該染料(C-1)之使用量為2至30重量份,較佳為3至15重量份,更佳為5至10重量份;該染料(C-2)之使用量為1至10重量份,較佳為2至9重量份,更佳為3至8重量份;該染料(C-3)之使用量為5至30重量份,較佳為7至28重量份,更佳為10至25重量份。
於本發明之具體例中,染料(C-1)之使用量與染料(C-2)之使用量之比值介於1至10之間,較佳為2至9之間,更佳
為3至7之間。當染料(C-1)之使用量與染料(C-2)之使用量之比值介於1至10之間時,則較不易產生蝕刻後顏色脫落。
本發明所言之溶劑(D)係指較易與其他有機成分互相溶解但又不與上述成分相互反應之有機溶劑。
於本發明之具體例中,該溶劑(D)為乙二醇單甲醚、乙二醇單乙醚、二乙二醇單乙醚、二乙二醇單正丙醚、二乙二醇單正丁醚、三乙二醇單甲醚、三乙二醇單乙醚、丙二醇單甲醚、丙二醇單乙醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單正丙醚、二丙二醇單正丁醚、三丙二醇單甲醚、三丙二醇單乙醚等之(聚)亞烷基二醇單烷醚類;乙二醇甲醚醋酸酯、乙二醇乙醚醋酸酯、丙二醇甲醚醋酸酯、丙二醇乙醚醋酸酯等之(聚)亞烷基二醇單烷醚醋酸酯類;二乙二醇二甲醚、二乙二醇甲基乙醚、二乙二醇二乙醚、四氫呋喃等之其他醚類;甲乙酮、環己酮、2-庚酮、3-庚酮等之酮類;2-羥基丙酸甲酯、2-羥基丙酸乙酯(乳酸乙酯)等乳酸烷酯類;2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基醋酸乙酯、羥基醋酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲基-3-甲氧基丁基醋酸酯、3-甲基-3-甲氧基丁基丙酸酯、醋酸乙酯、醋酸正丙酯、醋酸異丙酯、醋酸正丁酯、醋酸異丁酯、醋酸正戊酯、醋酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸甲酯、丙
酮酸乙酯、丙酮酸正丙酯、乙醯醋酸甲酯、乙醯醋酸乙酯、2-氧基丁酸乙酯等之其他酯類;甲苯、二甲苯等之芳香族烴類;N-甲基吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等之羧酸胺類。上述溶劑(D)可一種單獨使用或混合複數種使用。較佳地,該溶劑(D)為丙二醇單乙醚、丙二醇甲醚醋酸酯或乳酸乙酯。
於本發明之具體例中,基於酚醛清漆樹脂(A)之使用量為100重量份,上述溶劑(D)之使用量通常為500至2,000重量份;較佳為600至1,800重量份;更佳為700至1,500重量份。
根據本發明之正型感光性樹脂組成物較佳係進一步包含添加劑(E),該添加劑(E)較佳包括但不限於:密著助劑、表面平坦劑、稀釋劑以及增感劑等。
該密著助劑之具體例為三聚氰胺(melamine)化合物及矽烷系(silane)化合物,其作用在於增加正型感光性樹脂組成物與附著基板間的密著性,其中三聚氰胺之具體例為市售之Cymel-300、Cymel-303(CYTEC製造)、MW-30MH、MW-30、MS-11、MS-001、MX-750或MX-706(三和化學製)市售品。矽烷(silane)系化合物之具體例為乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基二甲
基甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-巰丙基三甲氧基矽烷或雙-1,2-(三甲氧基矽基)乙烷。
於本發明之具體例中,基於酚醛清漆樹脂(A)之使用量為100重量份,三聚氰胺化合物之密著助劑之使用量一般為0重量份至20重量份;較佳為0.5重量份至18重量份;更佳為1.0重量份至15重量份;矽烷系化合物之密著助劑之使用量一般為0重量份至2重量份;較佳為0.001重量份至1重量份;更佳為0.005重量份至0.8重量份。
該表面平坦劑之具體例為氟系界面活性劑或矽系界面活性劑。該氟系界面活性劑之具體例為Flourate FC-430、FC-431(3M製)或F top EF122A、122B、122C、126、BL20(Tochem product製)市售品。矽系界面活性劑之具體例為SF8427或SH29PA(Toray Dow Corning Silicone製)市售品。
於本發明之具體例中,基於酚醛清漆樹脂(A)之使用量為100重量份,上述界面活性劑之使用量一般為0重量份至1.2重量份;較佳為0.025重量份至1.0重量份;更佳為0.050重量份至0.8重量份。
該稀釋劑之具體例如為RE801或RE802(帝國Ink製)等市售品。
該增感劑之具體例為TPPA-1000P、TPPA-100-2C、TPPA-1100-3C、TPPA-1100-4C、TPPA-1200-24X、TPPA-1200-26X、TPPA-1300-235T、TPPA-1600-3M6C或TPPA-
MF市售品(日本本州化學工業製),其中較佳為TPPA-600-3M6C或TPPA-MF。上述之增感劑可單獨一種使用或者混合複數種使用。
於本發明之具體例中,基於酚醛清漆樹脂(A)之使用量為100重量份,該增感劑之使用量通常為0至20重量份;較佳為0.5至18重量份;更佳為1.0至15重量份。
此外,本發明亦可依需要再添加其他的添加劑,例如:可塑劑、安定劑等。
根據本發明之正型感光性樹脂組成物之製備係為本發明所屬技術領域中具通常知識者可實施者,具體言之,其係將上述酚醛清漆樹脂(A)、鄰萘醌二疊氮磺酸類之酯化物(B)、染料(C)以及溶劑(D)於攪拌器中攪拌,使其均勻混合成溶液狀態,並可視需要添加密著助劑、表面平坦劑、稀釋劑、可塑劑、安定劑、增感劑等添加劑(E)。
本發明亦提供一種薄膜電晶體陣列基板之製造方法,其中該薄膜電晶體陣列基板包含一基板及一圖案,該方法包含以前述之正型感光性樹脂組成物塗佈於該基板上以形成該圖案。
於本發明之具體例中,該正型感光性組成物可經由依序施予預烤(prebake)步驟、曝光步驟、顯影步驟及後烤(postbake)處理步驟後,而於基板形成圖案。
申言之,本發明使用前述正型感光性樹脂組成物形成圖案的方法,是藉由旋轉塗佈、流延塗佈或輥式塗佈等塗佈方法,將前述正型感光性樹脂組成物塗佈在基板上,並於
塗佈後,以預烤方式去除溶劑,而形成一預烤塗膜。其中,預烤之條件,依各成分之種類、配合比率而異,通常為溫度在70至110℃間,進行1至15分鐘。
預烤後,將該塗膜於指定之光罩下進行曝光,然後於23±2℃的溫度下浸漬於顯影液中,歷時15秒至5分鐘,藉此將不要之部分除去而形成特定的圖案。曝光所使用之光線,以g線、h線、i線等之紫外線為佳,而紫外線照射裝置可為(超)高壓水銀燈及金屬鹵素燈。
本發明所使用顯影液的具體例為氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、碳酸鉀、碳酸氫鉀、矽酸鈉、甲基矽酸鈉、氨水、乙胺、二乙胺、二甲基乙醇胺、氫氧化四甲胺、氫氧化四乙銨、膽鹼、吡咯、哌啶或1,8-二氮雜二環-[5,4,0]-7-十一烯之鹼性化合物。
較佳地,顯影液之濃度係0.001重量%至10重量%;更佳係0.005重量%至5重量%;尤佳係0.01重量%至1重量%。
使用前述鹼性化合物所構成之顯影液時,通常於顯影後以水洗淨,再以壓縮空氣或壓縮氮氣風乾前述塗膜。接著,使用熱板或烘箱等加熱裝置對前述塗膜進行後烤處理。後烤溫度通常為100至250℃,其中,使用熱板之加熱時間為1至60分鐘,使用烘箱之加熱時間為5至90分鐘。經過以上之處理步驟後,即可於基板形成圖案。
本發明再提供一種薄膜電晶體陣列基板,其係由前述之方法所製得。
於本發明之具體例中,其係將本發明之正型感光性樹脂
組成物以旋轉塗佈、流延塗佈或輥式塗佈等塗佈方式塗佈於一含有鋁、鉻、氮化矽或非結晶矽等之薄膜的玻璃基板或塑膠基板上而形成一正型光阻劑層,接著經過預烤、曝光、顯影及後烤處理形成感光性樹脂圖案之後,進行蝕刻及光阻剝離;重複上述步驟即可製得一含多數薄膜電晶體或電極之薄膜電晶體陣列基板。
請參閱第1圖,其係繪示根據本發明一實施例之LCD用TFT陣列基板的部分剖面示意圖。首先,於玻璃基板101上的鋁薄膜等處設置閘極102a及儲存電容Cs電極102b。其次,於閘極102a上覆蓋氧化矽膜(SiOx
)103或氮化矽膜(SiNx
)104等而形成絕緣膜,並於此絕緣膜上形成作為半導體活性層的非晶矽層(a-Si)105。接著,為了降低接面阻抗,可設置摻雜氮不純物的非晶矽層106於非晶矽層105上。之後,使用鋁等金屬,形成汲極107a及源極107b,其中汲極107a連接於資料訊號線(圖未繪示)上,而源極107b則連接於畫素電極(或子畫素電極)109上。而後,為保護作為半導體活性層的非晶矽層105、汲極107a或源極107b等,設置氮化矽膜等作為保護膜108。
本發明又提供一種液晶顯示元件,其包含前述之薄膜電晶體陣列基板。
根據本發明之液晶顯示元件,較佳可依需要包含有其他的部材。
上述液晶顯示元件的基本構成形態之具體例為(1)將TFT等之驅動元件與畫素電極(導電層)經排列所形成的上述本
發明之TFT陣列基板(驅動基板),與由彩色濾光片及對電極(導電層)所構成的彩色濾光片基板間介入間隔體並且對向配置,最後於間隙部份封入液晶材料而構成。或者,(2)將於上述本發明之TFT陣列基板上直接形成彩光濾光片之彩色濾光片一體型TFT陣列基板,與配置了對電極(導電層)之對向基板間介入間隔體並且對向配置,最後於間隙部份封入液晶材料而構成等,其中前述使用的液晶材料可為任何一種液晶化合物或液晶組成物,此處並未特別限定。
上述導電層之具體例為ITO膜;鋁、鋅、銅、鐵、鎳、鉻、鉬等之金屬膜;或二氧化矽等之金屬氧化膜。較佳地,其係為具透明性之膜層;更佳為ITO膜。
上述本發明之TFT陣列基板、彩色濾光片基板及對向基板等所使用之基材,其具體例為鈉鈣玻璃、低膨脹玻璃、無鹼玻璃或石英玻璃之習知玻璃,另外,也可採用由塑膠膜等構成的基板。
茲以下列實例予以詳細說明本發明,唯並不意謂本發明僅侷限於此等實例所揭示之內容。
依下表1及2所示之成分合成酚醛清漆樹脂(A)。
酚醛清漆樹脂(A-1)之合成
在一容積1000毫升之四頸錐瓶上設置氮氣入口、攪拌器、加熱器、冷凝管及溫度計,並導入氮氣且依表1所示用量加入進料組成物,上述進料組成物包括:間-甲酚0.7莫耳、對-甲酚0.3莫耳、甲醛0.65莫耳、草酸0.02莫耳。
攪拌四頸錐瓶之內容物,並將油浴溫度提升至100℃。聚縮合過程的反應溫度維持100℃,聚縮合時間6小時。聚縮合完成後,將溶劑脫揮,可得酚醛清漆樹脂(A-1)。
酚醛清漆樹脂(A-2)及(A-3)之合成
同酚醛清漆樹脂(A-1)之操作方法,不同之處係改變芳香族羥基化合物之種類及混合用量、醛類之用量、酸性觸媒之用量,以及反應溫度,其配方及反應條件載於表1。
酚醛清漆樹脂(A-4)之合成
將前述所得酚醛清漆樹脂(A-1)100重量份溶於溶劑丙二醇甲醚醋酸酯300重量份中,於室溫下持續攪拌至完全溶解。之後注入於乙苯(Ethylbenzene)2000重量份之中,同時持續攪拌30分鐘後,取出沉澱物,將溶劑脫揮後,可得酚醛清漆樹脂(A-4)。
酚醛清漆樹脂(A-5)之合成
將前述所得酚醛清漆樹脂(A-1)100重量份溶於溶劑丙二醇單甲醚醋酸酯300重量份中,於室溫下持續攪拌至完全溶解。之後注入於異丙苯3000重量份之中,同時持續攪拌30分鐘後,取出沉澱物,將溶劑脫揮後,可得酚醛清漆樹脂(A-5)。
酚醛清漆樹脂(A-6)之合成
將前述所得酚醛清漆樹脂(A-2)100重量份溶於溶劑丙二醇單甲醚醋酸酯300重量份中,於室溫下持續攪拌至完全溶解。之後注入於異丙苯2000重量份之中,同時持續攪拌30分鐘後,取出沉澱物,將溶劑脫揮後,重複上述溶解、沉澱、脫揮之步驟,可得酚醛清漆樹脂(A-6)。
酚醛清漆樹脂(A-7)之合成
將前述所得酚醛清漆樹脂(A-3)100重量份溶於溶劑丙二醇單甲醚醋酸酯300重量份中,於室溫下持續攪拌至完全溶解。之後注入於乙苯2000重量份及異丙苯1000重量份之中,同時持續攪拌30分鐘後,取出沉澱物,將溶劑脫揮後,重複上述溶解、沉澱、脫揮之步驟,可得酚醛清漆樹脂(A-7)。
酚醛清漆樹脂(A)中之甲酚二核體面積
以凝膠滲透色層分析法之操作方式係將酚醛清漆樹脂(A)之分子量介於200至150,000之訊號作積分,並以分子量及累積重量百分率獲得積分分子量分佈曲線;其中該凝膠滲透色層分析法係使用Waters®製之717 plus進樣儀;Agilent Technologies®製之79911GP-501、79911GP-502、79911GP-503或79911GP-504管柱及Waters®製之2414 RI Detector檢出器;移動相:四氫呋喃;流量:1.0 mL/min;注射量:100 μL;測定溫度:40℃;測定時間:60分鐘;分子量標準品為聚苯乙烯。
基於凝膠滲透色層分析法所測得之酚醛清漆樹脂(A)之
分子量之積分面積100%,測得該酚醛清漆樹脂(A)中之甲酚二核體面積占多少百分比。
其結果示於表1及2。
依下表3及4之比例配製正型感光性樹脂組成物。
實施例1
依表3所示之100重量份之酚醛清漆樹脂(A-4)、25重量份之2,3,4-三羥基二苯甲酮與1,2-萘醌二疊氮-5-磺酸之酯化物(平均酯化度為85%,以下簡稱B-1)、5重量份之2,3,4,4’-四羥基二苯甲酮與1,2-萘醌二疊氮-5-磺酸之酯化物(平均酯化度85%,以下簡稱B-2)、2重量份之C.I.Solvent Black 3(商品名Sudan Black 141;中央合成化學製,以下簡稱C-1-1)、1重量份之C.I.Acid Violet 17(商品名Coomassie Violet R200;Sigma製,以下簡稱C-2-1)溶解於丙二醇甲醚醋酸酯1000重量份溶劑中,即可製得正型感光性樹脂組成物。
實施例2至13及比較例1至6
實施例2至13及比較例1至6是以與實施例1相同的步驟來製備正型感光性樹脂組成物,不同的地方在於:改變原料的種類及其使用量,該原料的種類及其使用量如表3及4所示。
評價方式:蝕刻後脫色
將各實施例及比較例之正型感光性樹脂組成物於玻璃基板上以旋轉塗佈方式塗佈,在110℃下預烤160秒鐘,可得到約1.5 μm之預烤塗膜。將該預烤塗膜介於指定光阻底下,利用300 mJ/cm2
之紫外光(曝光機型號AG500-4N;M&R Nano Technology製)進行照射後,再以2.38%氫氧化四甲基銨溶液(tetramethylammonium hydroxide,簡稱TMAH)水溶液,於23℃下予以顯影1分鐘,將基板上曝光部份的塗膜除去,然後以純水洗淨得到圖案。以220℃溫度後烤40分鐘後,再於30℃以鋁酸蝕刻,製得一含圖案之玻璃基版,並以透光率測定儀(透光率測定儀型號NCPD-300;大塚科技股份有限公司製),測量含圖案之玻璃基版的透光頻譜(頻譜波長範圍為400nm至780nm),並以不含圖案之玻璃基版的透光頻譜作為基礎值,便可由透光率測定儀計算出透光率,比率範圍為0%~100%之間。
◎:透光率≦15%
○:15%<透光率≦40%
×:40%<透光率
解析度評價
將各實施例及比較例之正型感光性樹脂組成物,於玻璃基板上以旋轉塗佈方式塗佈,在110℃下預烤160秒鐘,可得到約1.5 μm之預烤塗膜。將該預烤塗膜介於線與間距(line and space)之光罩(日本Filcon製),利用300 mJ/cm2
之
紫外光(曝光機型號AG500-4N;M&R Nano Technology製)進行照射後,再以2.38%TMAH水溶液,於23℃下予以顯影1分鐘,將基板上曝光部份的塗膜除去,然後以純水洗淨,其形成的線條幅度的最小值定為解析度。
◎:線幅<2μm
○:2μm≦線幅<3μm
△:3μm≦線幅<5μm
×:線幅≧5μm
殘膜率
於前述檢測項目「解析度」中所得之預烤塗膜上任取一測定點測得一膜厚(δd1
),接著浸於23℃之顯影液(2.38%之TMAH水溶液)予以顯影1分鐘後,在相同的測定點測得另一膜厚(δd2
)。最後,經下式計算可得到殘膜率。
殘膜率(%)=[(δd2
)/δd1
)]×100
◎:殘膜率>95%
○:95%>殘膜率>90%
△:90%>殘膜率>85%
×:殘膜率≦85%
其結果示於表3及4。可知與比較例相較,根據本發明之實施例具有蝕刻後顏色不脫落之優點且解析度及殘膜率均佳。
上述實施例僅為說明本發明之原理及其功效,而非限制本發明。習於此技術之人士對上述實施例所做之修改及變化仍不違背本發明之精神。本發明之權利範圍應如後述之
申請專利範圍所列。
101‧‧‧玻璃基板
102a‧‧‧閘極
102b‧‧‧Cs電極
103‧‧‧氧化矽(SiOx
)膜
104‧‧‧氮化矽(SiNx
)膜
105‧‧‧非晶矽(a-Si)層
106‧‧‧摻雜氮不純物之非結晶矽層
107a‧‧‧集極
107b‧‧‧源極
108‧‧‧保護膜
109‧‧‧畫素電極
圖1為根據本發明一實施例之LCD用TFT陣列基板的部分剖面示意圖。
101‧‧‧玻璃基板
102a‧‧‧閘極
102b‧‧‧Cs電極
103‧‧‧氧化矽(SiOx
)膜
104‧‧‧氮化矽(SiNx
)膜
105‧‧‧非晶矽(a-Si)層
106‧‧‧摻雜氮不純物之非結晶矽層
107a‧‧‧集極
107b‧‧‧源極
108‧‧‧保護膜
109‧‧‧畫素電極
Claims (14)
- 一種正型感光性樹脂組成物,包含:酚醛清漆樹脂(A);鄰萘醌二疊氮磺酸類之酯化物(B);染料(C);及溶劑(D);其中該酚醛清漆樹脂(A)係由甲酚類芳香族羥基化合物與醛類化合物聚縮合而得,且基於凝膠滲透色層分析法所測得之酚醛清漆樹脂(A)分子量之積分面積100%,該酚醛清漆樹脂(A)中之甲酚二核體面積介於0.5%至6%;該染料(C)包含染料(C-1)及染料(C-2),且該染料(C-1)係選自由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成之群;及該染料(C-2)係為三芳甲烷系染料。
- 根據請求項1之正型感光性樹脂組成物,該凝膠滲透色層分析法係將酚醛清漆樹脂(A)分子量介於200至150,000之訊號作積分,並以分子量及累積重量百分率獲得積分分子量分佈曲線;其中該凝膠滲透色層分析法係使用Waters®製之717 plus進樣儀;Agilent Technologies®製之79911GP-501、79911GP-502、79911GP-503或79911GP-504管柱及Waters®製之2414 RI Detector檢出器;移動相:四氫呋喃;流量:1.0 mL/min;注射量:100 μL;測定溫度:40℃;測定時間:60分鐘;分子量標準品為聚苯乙烯。
- 根據請求項1之正型感光性樹脂組成物,其中基於酚醛 清漆樹脂(A)之使用量為100重量份,該鄰萘醌二疊氮磺酸類之酯化物(B)之使用量為5至50重量份。
- 根據請求項1之正型感光性樹脂組成物,其中染料(C-2)具有下列通式(1)或式(2)所示之結構式或其鹽類:
- 根據請求項1之正型感光性樹脂組成物,其中基於酚醛清漆樹脂(A)之使用量為100重量份,該染料(C)之使用量為5至120重量份。
- 根據請求項1之正型感光性樹脂組成物,其中基於酚醛清漆樹脂(A)之使用量為100重量份,該染料(C-1)之使用量為2至30重量份;及該染料(C-2)之使用量為1至10重量份。
- 根據請求項1之正型感光性樹脂組成物,其中染料(C-1)之使用量與染料(C-2)之使用量之比值介於1至10之間。
- 根據請求項1之正型感光性樹脂組成物,其中該染料(C)進一步包含染料(C-3),其中該染料(C-3)係為酞菁系染料。
- 根據請求項8之正型感光性樹脂組成物,其中該酞菁系染料(C-3)具有下列通式(6)所示之結構式或其鹽類:
- 根據請求項8之正型感光性樹脂組成物,其中基於酚醛清漆樹脂(A)之使用量為100重量份,該染料(C-3)之使用量為3至50重量份。
- 根據請求項1之正型感光性樹脂組成物,其中基於酚醛清漆樹脂(A)之使用量為100重量份,該溶劑(D)之使用量為500至2000重量份。
- 一種薄膜電晶體陣列基板之製造方法,其中該薄膜電晶體陣列基板包含一基板及一圖案,該方法包含以根據請求項1至11中任一項所述之正型感光性樹脂組成物塗佈於該基板上以形成該圖案。
- 一種薄膜電晶體陣列基板,其係由根據請求項12之方法所製得。
- 一種液晶顯示元件,其包含根據請求項13所述之薄膜電晶體陣列基板。
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CN105051597B (zh) * | 2014-03-04 | 2018-05-29 | Jsr株式会社 | 显示元件、感光性组合物以及电润湿显示器 |
TWI537683B (zh) * | 2014-09-16 | 2016-06-11 | 奇美實業股份有限公司 | 正型感光性樹脂組成物及其應用 |
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US5346799A (en) * | 1991-12-23 | 1994-09-13 | Ocg Microelectronic Materials, Inc. | Novolak resins and their use in radiation-sensitive compositions wherein the novolak resins are made by condensing 2,6-dimethylphenol, 2,3-dimethylphenol, a para-substituted phenol and an aldehyde |
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