KR100873992B1 - Soluble polyimide resin mixture composition for low temperature process and all organic thin film transistor device manufactured by using this as insulating film - Google Patents
Soluble polyimide resin mixture composition for low temperature process and all organic thin film transistor device manufactured by using this as insulating film Download PDFInfo
- Publication number
- KR100873992B1 KR100873992B1 KR1020070013494A KR20070013494A KR100873992B1 KR 100873992 B1 KR100873992 B1 KR 100873992B1 KR 1020070013494 A KR1020070013494 A KR 1020070013494A KR 20070013494 A KR20070013494 A KR 20070013494A KR 100873992 B1 KR100873992 B1 KR 100873992B1
- Authority
- KR
- South Korea
- Prior art keywords
- polyimide resin
- thin film
- organic
- soluble polyimide
- film transistor
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 126
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 67
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 239000010409 thin film Substances 0.000 title claims abstract description 51
- 239000010408 film Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- -1 polyphenylenevinylene Polymers 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 claims description 2
- 238000006358 imidation reaction Methods 0.000 claims 1
- 239000004642 Polyimide Substances 0.000 abstract description 59
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 abstract description 43
- 150000004984 aromatic diamines Chemical class 0.000 abstract description 17
- 239000002253 acid Substances 0.000 abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 abstract description 7
- 239000012212 insulator Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 47
- 239000000243 solution Substances 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 23
- 229910001873 dinitrogen Inorganic materials 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000000178 monomer Substances 0.000 description 13
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 9
- 150000004985 diamines Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 5
- 230000005669 field effect Effects 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920005575 poly(amic acid) Polymers 0.000 description 5
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 4
- IDXLMUPIWAJBRO-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-3-methylcyclohexane-1,2-dicarboxylic acid Chemical compound C1C(C(O)=O)C(C(O)=O)C(C)CC1C1C(=O)OC(=O)C1 IDXLMUPIWAJBRO-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 150000003949 imides Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WVOLTBSCXRRQFR-SJORKVTESA-N Cannabidiolic acid Natural products OC1=C(C(O)=O)C(CCCCC)=CC(O)=C1[C@@H]1[C@@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-SJORKVTESA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 3
- WVOLTBSCXRRQFR-DLBZAZTESA-M cannabidiolate Chemical compound OC1=C(C([O-])=O)C(CCCCC)=CC(O)=C1[C@H]1[C@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-DLBZAZTESA-M 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GYFUIPAIOWWVFV-UHFFFAOYSA-N 1-phenoxycyclohexa-3,5-diene-1,3-diamine Chemical compound C1C(N)=CC=CC1(N)OC1=CC=CC=C1 GYFUIPAIOWWVFV-UHFFFAOYSA-N 0.000 description 2
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 2
- NYQBRJSZBZNLAM-UHFFFAOYSA-N 4-phenoxycyclohexa-1,5-diene-1,4-diamine Chemical compound C1=CC(N)=CCC1(N)OC1=CC=CC=C1 NYQBRJSZBZNLAM-UHFFFAOYSA-N 0.000 description 2
- GGDKNFCCHJCIIO-UHFFFAOYSA-N 6-(1-phenylpropoxy)cyclohexa-2,4-diene-1,1-diamine Chemical compound C=1C=CC=CC=1C(CC)OC1C=CC=CC1(N)N GGDKNFCCHJCIIO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229940100630 metacresol Drugs 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- MPBZUKLDHPOCLS-UHFFFAOYSA-N 3,5-dinitroaniline Chemical compound NC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 MPBZUKLDHPOCLS-UHFFFAOYSA-N 0.000 description 1
- NZERLBCGTCROMD-UHFFFAOYSA-N 3-methyl-4,5-dioxo-1-(oxolan-2-yl)cyclohexane-1,2-dicarboxylic acid Chemical compound C1C(=O)C(=O)C(C)C(C(O)=O)C1(C(O)=O)C1OCCC1 NZERLBCGTCROMD-UHFFFAOYSA-N 0.000 description 1
- KAYAKFYASWYOEB-UHFFFAOYSA-N 3-octadec-1-enyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCCCC=CC1CC(=O)OC1=O KAYAKFYASWYOEB-UHFFFAOYSA-N 0.000 description 1
- BZWUYTRSEXHNEX-UHFFFAOYSA-N 6-(1,1,1,3,3,3-hexafluoropropan-2-yl)cyclohexa-2,4-diene-1,1-diamine Chemical compound NC1(C(C=CC=C1)C(C(F)(F)F)C(F)(F)F)N BZWUYTRSEXHNEX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OWDFFACCIGSTDA-UHFFFAOYSA-N Cc(cc1)ccc1N(C(c(c1c2)cc(C(N3C)=O)c2C3=O)=O)C1=O Chemical compound Cc(cc1)ccc1N(C(c(c1c2)cc(C(N3C)=O)c2C3=O)=O)C1=O OWDFFACCIGSTDA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 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
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 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
- 239000007790 solid phase Substances 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
- H10K10/471—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising only organic materials
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Thin Film Transistor (AREA)
Abstract
본 발명은 전유기 박막 트랜지스터 절연막용 가용성 폴리이미드 수지 혼합 조성물 및 이를 절연막으로 사용한 전유기 박막 트랜지스터 소자에 관한 것이다. 보다 상세하게는 지방족고리계 산이무수물을 적정비율 이상 포함하는 산이무수물과 저극성측쇄기를 갖는 방향족 디아민을 적정비율 이상 포함하는 방향족 디아민류를 용액중합함으로써, 용제에 우수한 용해성을 갖는 가용성 폴리이미드(SPI-1)를 제조하였으며, 이를 지방족 고리계산이무수물을 적정비율 이상 포함하는 산이무수물과 저극성측쇄기를 포함하지 않는 방향족 디아민으로부터 제조한 가용성 폴리이미드(SPI-2)와 용액상태에서 혼합하여 제조된 신규 가용성 폴리이미드 혼합 조성물에 관한 것이다. 상기 가용성 폴리이미드 혼합물은 뛰어난 내열성, 내용제성 및 낮은 표면 극성으로 인하여 전유기 박막 트랜지스터 절연체 소재로서 유용한 효과가 있으며, 특히 고온에서의 이미드화 공정이 요구되지 않는 특징을 가진다.The present invention relates to a soluble polyimide resin mixed composition for an all organic thin film transistor insulating film and an all organic thin film transistor device using the same as an insulating film. More specifically, a solution-soluble polyimide (SPI) having excellent solubility in a solvent by solution polymerization of an acid dianhydride containing an aliphatic ring-based acid dianhydride and an aromatic diamine containing an aromatic diamine having a low polar side chain group or more in an appropriate ratio or more. -1) was prepared by mixing it in a solution state with a soluble polyimide (SPI-2) prepared from an acid dianhydride containing an aliphatic ring-based dianhydride and an aromatic diamine without a low polar side chain group. A novel soluble polyimide mixed composition. The soluble polyimide mixture has a useful effect as an organic thin film transistor insulator material due to its excellent heat resistance, solvent resistance, and low surface polarity, and in particular, does not require an imidization process at a high temperature.
Description
도 1은 본 발명의 실시예 1에 따라 제조된 BPI-1을 게이트 유전체로 도입한 전유기 박막트랜지스터 소자의 I-V (output)곡선이다.1 is an I-V (output) curve of an all-organic thin film transistor device in which BPI-1 prepared according to Example 1 of the present invention is introduced as a gate dielectric.
도 2는 본 발명의 실시예 1에 따라 제조된 BPI-1을 게이트 유전체로 도입한 전유기 박막트랜지스터 소자의 I-V (transfer) 곡선이다.2 is an I-V (transfer) curve of an all-organic thin film transistor device in which BPI-1 prepared according to Example 1 of the present invention is introduced as a gate dielectric.
도 3은 본 발명의 실시예 3에 따라 제조된 BPI-3을 게이트 유전체로 도입한 전유기 박막트랜지스터 소자의 I-V (output)곡선이다.3 is an I-V (output) curve of an all-organic thin film transistor device in which BPI-3 prepared according to Example 3 of the present invention is introduced as a gate dielectric.
도 4는 본 발명의 실시예 3에 따라 제조된 BPI-3을 게이트 유전체로 도입한 전유기 박막트랜지스터 소자의 I-V (transfer) 곡선이다.4 is an I-V (transfer) curve of an all-organic thin film transistor device having BPI-3 prepared according to Example 3 of the present invention as a gate dielectric.
도 5는 본 발명의 실시예에서 제조된 상접촉(top-contact)소자의 구조를 나타내는 단면도이다.5 is a cross-sectional view showing the structure of a top-contact device manufactured in an embodiment of the present invention.
-도면 부호의 설명-Explanation of Drawing References
1 : 전극 2 : 기판1
3 : 유기절연막 4 : 소스전극3: organic insulating film 4: source electrode
5 : 드레인전극 6 : 유기반도체5
본 발명은 전유기 박막트랜지스터 절연체용 저온공정용 가용성 폴리이미드 수지 및 이를 절연막으로 사용하여 제조한 전유기 박막 트랜지스터(organic thin film transistor)에 관한 것으로서, 보다 상세하게는 지방족고리계 산이무수물을 적정비율 이상 포함하는 산이무수물과 저극성 측쇄기를 갖는 방향족 디아민을 적정비율 이상 포함하는 방향족 디아민류를 용액중합함으로써 용제에 우수한 용해성을 갖는 가용성 폴리이미드를 제조하고, 이를 지방족 고리계 산이무수물을 적정비율 이상 포함하는 산이무수물과 저극성측쇄기를 포함하지 않는 방향족 디아민으로부터 제조한 가용성 폴리이미드와 용액상태에서 혼합함으로써, 우수한 내열성, 표면경도 및 전기 절연성이 뛰어날 뿐만 아니라 표면의 극성이 제어되어 전유기 박막 트랜지스터의 절연체용 소재로서 유용한 효과가 있는 신규 가용성 폴리이미드 혼합 조성물 및 이로부터 제조된 폴리이미드 수지에 관한 것이다.The present invention relates to a soluble polyimide resin for low-temperature process for all organic thin film transistor insulator, and to an organic thin film transistor prepared using the same as an insulating film, and more particularly, to an aliphatic ring acid dianhydride. By solution-polymerizing aromatic diamines containing the acid dianhydrides and aromatic diamines having a low polar side chain group in an appropriate ratio or more, a soluble polyimide having excellent solubility in a solvent is prepared, and the alicyclic acid dianhydride is contained in an appropriate ratio or more. By mixing in solution with a soluble polyimide prepared from an acid dianhydride and an aromatic diamine that does not contain low polar side chain groups, it is excellent in heat resistance, surface hardness and electrical insulation, and the surface polarity is controlled to insulate the organic thin film transistor. Dragon As it relates to a polyimide resin prepared from novel soluble polyimide, and blend compositions therefrom with a useful effect.
일반적으로 폴리이미드 수지라 함은 방향족 테트라카르복실산 또는 그 유도체와 방향족 디아민 또는 방향족 디이소시아네이트를 축중합한 후, 이미드화하여 제조되는 고내열성 수지를 일컫는다. In general, the polyimide resin refers to a high heat resistant resin prepared by condensation polymerization of an aromatic tetracarboxylic acid or a derivative thereof with an aromatic diamine or an aromatic diisocyanate, followed by imidization.
폴리이미드 수지는 사용된 단량체의 종류에 따라 여러 가지의 분자구조를 가 질 수 있으며, 일반적으로 방향족 테트라카르복실산 성분으로서는 피로멜리트산이무수물(PMDA) 또는 비프탈산무수물(BPDA)을 사용하고 있고, 방향족 디아민 성분으로서는 파라-페닐렌디아민(p-PDA), 메타-페닐렌디아민(m-PDA), 4,4-옥시디아닐린(ODA), 4,4-메틸렌디아닐린(MDA), 2,2-비스아미노페닐헥사풀루오로프로판(HFDA), 메타비스아미노페녹시디페닐설폰(m-BAPS), 파라비스아미노페녹시디페닐설폰(p-BAPS), 1,4-비스아미노페녹시벤젠(TPE-Q), 1,3-비스아미노페녹시벤젠(TPE-R), 2,2-비스아미노페녹시페닐프로판(BAPP), 2,2-비스아미노페녹시페닐헥사풀루오로프로판(HFBAPP) 등의 방향족 디아민을 사용하여 중축합시켜 제조하고 있다. The polyimide resin may have various molecular structures depending on the type of monomer used. Generally, aromatic tetracarboxylic acid components use pyromellitic dianhydride (PMDA) or nonphthalic anhydride (BPDA). As the aromatic diamine component, para-phenylenediamine (p-PDA), meta-phenylenediamine (m-PDA), 4,4-oxydianiline (ODA), 4,4-methylenedianiline (MDA), 2 , 2-bisaminophenylhexafluoropropane (HFDA), metabisaminophenoxydiphenylsulfone (m-BAPS), parabisaminophenoxydiphenylsulfone (p-BAPS), 1,4-bisaminophenoxybenzene (TPE-Q), 1,3-bisaminophenoxybenzene (TPE-R), 2,2-bisaminophenoxyphenylpropane (BAPP), 2,2-bisaminophenoxyphenylhexafuluropropane ( And polycondensation using an aromatic diamine such as HFBAPP).
대부분의 폴리이미드 수지는 불용, 불융의 초고내열성 수지로서 (1) 뛰어난 내열산화성, (2) 높은 사용가능온도, (3) 약 260 ℃의 장기 사용 가능온도와 약 480 ℃의 단기 사용 가능온도를 나타내는 우수한 내열특성, (4) 내방사선성, (5) 우수한 저온 공정 특성, (6) 우수한 내약품성 등의 특성을 가지고 있다.Most polyimide resins are insoluble and insoluble ultra-high temperature resistant resins, which are characterized by (1) excellent thermal oxidation resistance, (2) high usable temperature, and (3) long-term temperature of about 260 ° C and short-term temperature of about 480 ° C. It has characteristics such as excellent heat resistance, (4) radiation resistance, (5) excellent low temperature process characteristics, and (6) excellent chemical resistance.
상기와 같은 방향족 폴리이미드 수지는 우수한 내열특성을 보유하는 장점이 있지만, 반면에 높은 극성기 밀도로 인해 표면장력이 높으며, 박막트랜지스터용 절연체로 적용하기에는 낮은 유전 상수 등을 가지고 있어 그 사용이 제한되어 용이하지 않은 단점을 가지고 있다. Aromatic polyimide resins as described above have the advantage of having excellent heat resistance characteristics, on the other hand, high surface tension due to high polar group density, and has a low dielectric constant to be applied as an insulator for thin film transistors. It does not have the disadvantage.
일반적으로 박막트랜지스터용 절연재로는 높은 유전상수를 갖는 무기박막, 예를 들면, 실리콘 질화물(silicon nitride), 바륨 스트론튬(barium strontium), 바륨 티타네이트(barium titanate) 등이 일반적으로 사용되고 있고, 대부분의 경우 박막 증착을 위해 고가의 진공 장비가 요구되는 단점이 있다. 이를 해결하기 위하 여 미국특허 제5,946,551호 등에는 비교적 저온에서 화학적 용액공정에 의해 무기박막의 전구체로부터 무기박막을 형성하는 방법을 제시하고 있으나, 이 경우에도 300 ~ 700 ℃ 정도의 높은 공정온도가 요구되어 공정온도가 200 ℃ 이하로 제한되어 있는 폴리카보네이트, 폴리설폰, 폴리에테르설폰과 같은 플라스틱 기판 위에서의 저온 박막화 공정이 어려운 단점을 안고 있다.In general, an inorganic thin film having a high dielectric constant, for example, silicon nitride, barium strontium, barium titanate, etc. is generally used as an insulating material for thin film transistors. In this case, expensive vacuum equipment is required for thin film deposition. In order to solve this problem, U.S. Patent No. 5,946,551, etc., proposes a method of forming an inorganic thin film from a precursor of an inorganic thin film by a chemical solution process at a relatively low temperature, but in this case, a high process temperature of about 300 to 700 ° C. is required. As a result, the low temperature thinning process on a plastic substrate such as polycarbonate, polysulfone, and polyethersulfone, in which the process temperature is limited to 200 ° C. or less, has a disadvantage.
박막트랜지스터의 고이동도 구현을 위한 절연체의 주요 요구 특성 중의 하나로서 펜타센(pentacene)과 같은 저극성 유기 반도체 물질과의 계면장력을 최소화함이 요구되고 있는 바, 이를 위해서는 유전체 표면의 표면장력을 제어된 신규 유기 소재의 개발이 크게 요구되고 있다.As one of the main required characteristics of the insulator for high mobility of thin film transistors, it is required to minimize the interfacial tension with low polar organic semiconductor materials such as pentacene. There is a great demand for the development of new controlled organic materials.
이에 본 발명의 발명자들은 상기와 같은 문제점을 해결하기 위하여, 이미드화 반응이 완전히 진행된 상태에서 유기 용제에 우수한 용해성을 갖는 특정의 가용성 폴리이미드(SPI, soluble polyimide) 수지들을 혼합한 조성물의 경우 상기의 문제점이 해결될 수 있는 사실을 알게 되어, 박막트랜지스터의 절연재로서 신규한 폴리이미드계 조성물을 제공하고 또한 이를 이용한 새로운 전유기박막 트랜지스터 소자를 제조할 수 있음을 알게 되어 본 발명을 완성하였다.Accordingly, the inventors of the present invention, in order to solve the above problems, in the case of a composition in which a specific soluble polyimide (SPI) resin mixture having excellent solubility in an organic solvent in the state that the imidization reaction is fully progressed The present invention has been completed by providing a novel polyimide composition as an insulating material of a thin film transistor and manufacturing a novel all organic thin film transistor device using the same.
구체적으로 살피면, 본 발명자들은 특정의 저극성측쇄기를 가지는 방향족 디아민과 함께 방향족 디아민 단량체를 포함하는 디아민 혼합물을 특정의 테트라카르복실산 이무수물과 중합 반응하여 가용성 폴리이미드 수지를 제조하였으며, 제조된 가용성 폴리이미드 수지는 용해 특성이 우수하여 N-메틸-2-피롤리돈과 같은 유기용제에 쉽게 용해되어 저온공정에서의 폴리이미드 박막형성이 가능할 뿐만 아니라 이로부터 제작된 전유기트랜지스터 소자는 전계효과 전하이동도가 뛰어남을 확인함으로써 본 발명을 완성하게 되었다. Specifically, the present inventors prepared a soluble polyimide resin by polymerizing a diamine mixture including an aromatic diamine monomer with an aromatic diamine having a specific low polar side chain group with a specific tetracarboxylic dianhydride. The polyimide resin has excellent dissolution characteristics, so it is easily dissolved in an organic solvent such as N-methyl-2-pyrrolidone to form a polyimide thin film in a low temperature process, and the organic organic transistor device manufactured therefrom has a field effect charge. The present invention was completed by confirming the excellent mobility.
또한 상기 가용성 폴리이미드 수지는 기존 폴리이미드 수지의 특성을 거의 그대로 유지하면서 N-메틸-2-피롤리돈과 같은 유기용제에 대한 우수한 용해 특성을 가지고 낮은 표면장력 및 높은 전계효과 전하이동도를 갖고 있어 130 ~ 180℃의 온도에서 박막형성이 가능하므로 저온공정이 요구되는 전유기 박막트랜지스터용 절연체로 유용하다. In addition, the soluble polyimide resin has excellent dissolution properties for organic solvents such as N-methyl-2-pyrrolidone while maintaining almost the same characteristics of the existing polyimide resin, and has low surface tension and high field effect charge mobility. Since it is possible to form a thin film at a temperature of 130 ~ 180 ℃, it is useful as an insulator for all organic thin film transistors that require low temperature process.
따라서 본 발명은 유기박막트랜지스터 등의 첨단 산업용 핵심 소재로서 우수한 물성을 갖으며, 저온 공정이 가능한 신규 구조의 가용성 폴리이미드 수지 혼합조성물 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a soluble polyimide resin mixture composition having a novel structure capable of low temperature process and having excellent physical properties as an advanced industrial core material such as an organic thin film transistor.
즉, 본 발명의 폴리이미드수지 조성물은, 가용성 폴리이미드 수지로서 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸시클로헥산-1,2-디카르복실산이무수물(DOCDA), 4-(2,5-디옥소테트라히드로퓨릴-3-일)-테트랄린-1,2-디카르복실산이무수물(DOTDA), 1,2,3,4-시클로부탄 테트라카르복실산이무수물(CBDA), 1,2,3,4-시클로펜탄 테트라카르복실산이무수물(CPDA), 바이시클로옥텐-2,3,5,6-테트라카르복실산이무수물(BODA)에서 선택되는 1종이상의 지방족 고리계 산이무수물과, 피로멜리트산이무수물, 벤조페논테트라카르복실산이무수물, 옥시디프탈산이무수물, 비프탈산이무수물 및 헥사플루오로이소프로필리덴디프탈산이무수물 등에서 선택되는 1종이 상의 방향족 테트라카르복실산 이무수물의 혼합물과 저극성알킬기가 치환된 숙시닉이미드 측쇄기를 갖는 방향족 디아민 및 방향족 디아민의 혼합물(A2)로부터 제조된 가용성 폴리이미드 수지와, That is, the polyimide resin composition of the present invention is 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride (DOCDA), 4 as a soluble polyimide resin. -(2,5-dioxotetrahydrofuryl-3-yl) -tetraline-1,2-dicarboxylic dianhydride (DOTDA), 1,2,3,4-cyclobutane tetracarboxylic dianhydride ( CBDA), 1,2,3,4-cyclopentane tetracarboxylic dianhydride (CPDA), at least one aliphatic ring selected from bicyclooctene-2,3,5,6-tetracarboxylic dianhydride (BODA) At least one aromatic tetracarboxyl selected from acid dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, oxydiphthalic dianhydride, nonphthalic dianhydride and hexafluoroisopropylidenediphthalic dianhydride. Aromatic diamines and aromatics having succinimide side chains substituted with mixtures of acid dianhydrides and low polar alkyl groups Soluble polyimide resins prepared from mixtures of group diamines (A2),
상기 가용성 폴리이미드 수지를, 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸시클로헥산-1,2-디카르복실산이무수물(DOCDA), 4-(2,5-디옥소테트라히드로퓨릴-3-일)-테트랄린-1,2-디카르복실산이무수물(DOTDA), 1,2,3,4-시클로부탄 테트라카르복실산이무수물(CBDA), 1,2,3,4-시클로펜탄 테트라카르복실산이무수물(CPDA), 바이시클로옥텐-2,3,5,6-테트라카르복실산이무수물(BODA)등에서 선택되는 1종이상의 지방족고리계 산이무수물과 피로멜리트산이무수물, 벤조페논테트라카르복실산이무수물, 옥시디프탈산이무수물, 비프탈산이무수물 및 헥사플루오로이소프로필리덴디프탈산이무수물 등에서 선택되는 1종 이상의 방향족 테트라카르복실산 이무수물의 혼합물을 방향족 디아민의 혼합물로부터 제조된 폴리이미드 수지와 용액 상태에서 혼합하여 제조함으로써 우수한 내열성, 용해성 및 뛰어난 전하이동도를 갖는 신규한 유기트랜지스터용 절연막에 적용 가능한 폴리이미드수지 조성물을 제조하였으며, 이를 절연막으로 이용한 신규한 유기트랜지스트 소자를 제조하였다.5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride (DOCDA), 4- (2,5-dioxotetra) Hydrofuryl-3-yl) -tetralin-1,2-dicarboxylic dianhydride (DOTDA), 1,2,3,4-cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,3, At least one aliphatic ring acid dianhydride and pyromellitic dianhydride selected from 4-cyclopentane tetracarboxylic dianhydride (CPDA), bicyclooctene-2,3,5,6-tetracarboxylic dianhydride (BODA) A mixture of one or more aromatic tetracarboxylic dianhydrides selected from benzophenone tetracarboxylic dianhydride, oxydiphthalic dianhydride, nonphthalic dianhydride, hexafluoroisopropylidenediphthalic dianhydride and the like from a mixture of aromatic diamines Excellent heat resistance by mixing the prepared polyimide resin and prepared in a solution state, A polyimide resin composition applicable to a novel insulating film for organic transistors having solubility and excellent charge mobility was prepared, and a novel organic transistor device using the same as an insulating film was prepared.
따라서 본 발명은, 우수한 내열성, 용해성 및 뛰어난 전하이동도를 갖는 저극성 알킬측쇄기를 갖는 가용성 폴리이미드 수지를 함유한 폴리이미드 혼합조성물을 제공하는 데 그 목적이 있다.Accordingly, an object of the present invention is to provide a polyimide mixed composition containing a soluble polyimide resin having a low polar alkyl side chain group having excellent heat resistance, solubility and excellent charge mobility.
본 발명의 구성을 더욱 상세히 설명하면 다음과 같다.Referring to the configuration of the present invention in more detail as follows.
본 발명은 다음 화학식 1로 표시되는 가용성 폴리이미드 수지와 다음 화학식 2 로 표시되는 폴리이미드 수지의 혼합 조성물 및 이를 이용하여 제조된 전유기 박막트랜지스터 절연막, 그리고 제조된 전유기박막트랜지스터 소자에 관한 것이다.The present invention relates to a mixed composition of a soluble polyimide resin represented by the following formula (1) and a polyimide resin represented by the following formula (2), an all-organic thin film transistor insulating film prepared using the same, and an all-organic thin film transistor device manufactured.
[화학식 1][Formula 1]
[화학식 2] [Formula 2]
상기 화학식 1 또는 2에서,In Chemical Formula 1 or 2,
상기 
상기 
상기 
(이때, R3은 탄소수가 1 내지 30 범위의 선형 또는 분지형의 알킬기) 중에서 선택된 1종 이상의 2가기로서, 반드시 상기 구조식 (f)의 알킬 측쇄기를 가지는 2가 방향족기를 포함하고, m은 1 내지 300 범위의 자연수를 나타낸다.Wherein R 3 is at least one divalent group selected from a linear or branched alkyl group having 1 to 30 carbon atoms, and must include a divalent aromatic group having an alkyl side chain group of the formula (f), and m is 1 Natural numbers in the range from -300.
본 발명에 따른 절연막용 조성물은 상기 화학식 1로 표시되는 가용성 폴리이미드수지와 상기 화학식 2로 표시되는 가용성 폴리이미드수지가 혼합된 조성물로서, 본 발명의 절연막용 조성물은 상기 화학식 1로 표시되는 가용성 폴리이미드수지가 1 ~ 99 중량%, 상기 화학식 2로 표시되는 가용성 폴리이미드수지가 1 ~ 99중량%의 범위 내에서 임의로 조절할 수 있다.The insulating film composition according to the present invention is a composition in which the soluble polyimide resin represented by Chemical Formula 1 and the soluble polyimide resin represented by Chemical Formula 2 are mixed, and the insulating film composition of the present invention is a soluble poly represented by Chemical Formula 1 The mid resin is 1 to 99% by weight, and the soluble polyimide resin represented by Formula 2 may be arbitrarily adjusted within the range of 1 to 99% by weight.
상기 수지의 혼합은 용액상태로 혼합하는 것이 성능면에서 가장 좋은데, 예를 들면 용액 블렌딩하여 혼합한다.Mixing of the resin is best in terms of performance mixing in a solution state, for example, by blending the solution mixed.
보다 바람직하게는 화학식 1로 표시되는 가용성 폴리이미드수지가 70~99 중량%, 상기 화학식 2로 표시되는 가용성 폴리이미드수지가 1~30 중량%의 범위 내에서 사용되는 것이 바람직하다. 이때 상기 화학식 2로 표시되는 가용성 폴리이미드수지의 함량이 1 중량% 미만으로 사용되는 경우 표면에너지 제어효과가 충분하지 않으며, 30중량%를 초과하는 경우 유기박막트랜지스터 소자의 누설전류가 증가하는 단점이 있다. More preferably, 70 to 99% by weight of the soluble polyimide resin represented by the general formula (1), and preferably 1 to 30% by weight of the soluble polyimide resin represented by the general formula (2). In this case, when the content of the soluble polyimide resin represented by Chemical Formula 2 is less than 1% by weight, the surface energy control effect is not sufficient, and when the content of the soluble polyimide resin exceeds 30% by weight, the leakage current of the organic thin film transistor element is increased. have.
또한, 본 발명은 상기 폴리이미드 혼합조성물을 코팅하여 제조한 유기트랜지스터용 절연막과 유기트랜지스터 소자를 제공하는 것을 본 발명의 또 다른 발명의 양태에 해당한다. In another aspect, the present invention is to provide an organic transistor insulating film and an organic transistor device prepared by coating the polyimide mixture composition.
즉, 본 발명은 도 5에 도시된 바와 같이, 유리 및 플라스틱 기판(2)위에 게이트 전극(1), 유기절연막(3), 유기반도체(6), 소스/드레인 전극(4,5) 및 그 보호층(별도 도시 않음)으로 이루어진 유기박막 트랜지스터에 있어서, 상기 화학식 1로 표시되는 가용성 폴리이미드수지와 화학식 2로 표시되는 가용성 폴리이미드수지의 혼합 조성물을 유기절연막으로 이용한 유기박막 트랜지스터도 본 발명의 한 양태이다.That is, the present invention, as shown in Figure 5, on the glass and
본 발명의 절연막의 형성방법은 이 기술분야에 통상적으로 사용하는 것이라면 제한되지 않으나, 예를 들면 폴리이미드 수지 혼합 조성물을 스핀코팅, 잉크젯 프린팅 또는 딥핑에서 선택되는 방법으로 형성하는 것이 가능하며, 상기 유기절연막의 두께 또한 필요에 의해 선택할 수 있는 것으로 크게 제한되지 않지만 통상적으로 30 nm 내지 500 nm인 것이 작업성이나 성능면에서 바람직하다.The method for forming the insulating film of the present invention is not limited as long as it is commonly used in the art, for example, it is possible to form the polyimide resin mixture composition by a method selected from spin coating, inkjet printing or dipping, and the organic Although the thickness of an insulating film can also be selected as needed, it is not restrict | limited normally, It is preferable from a workability and a performance point normally to be 30 nm-500 nm.
또한, 상기 유기절연막은 상기 폴리이미드 수지 혼합 조성물로 이루어진 박막위에 펜타센, 금속 페탈로시아닌, 폴리티오펜, 폴리페닐렌비닐렌 및 그 유도체로 이루어진 유기활성층을 더 구비하는 것도 가능하며, 상기 유기절연막과 유기활성층으로 이루어진 유기박막 트랜지스터의 전계이동도는 0.1 ~ 10㎠/Vs 정도로 측정되었다.In addition, the organic insulating film may further include an organic active layer made of pentacene, metal petalocyanine, polythiophene, polyphenylenevinylene and derivatives thereof on a thin film made of the polyimide resin mixture composition. The field mobility of the organic thin film transistor including the organic insulating layer and the organic active layer was measured in the range of 0.1 to 10
본 발명에서 화학식 1 및 화학식 2의 폴리이미드 수지를 제조함에 있어서, 테트라카르복실산이무수물 단량체로서 상기 (a)~(e)로 표시되는 지방족 테트라카르복실산이무수물을 필수 성분으로 채택되는데, 상기 지방족테트라카르복실산이무수물을 적절한 비율로 혼합 사용하여 기계적 특성과 내열성의 저하를 최소로 하면서도 용해성이 개선된 폴리이미드 수지를 제조할 수 있다. 본 발명에서는 상기 (a)~(e)로 표시되는 1종 이상의 지방족 테트라카르복실산의 함량은 전체 산이무수물 사용량에 대하여 1 내지 100 중량% 범위로 사용한다면, 본 발명에서 목적으로 하는 물성을 가지는 폴리이미드 조성물을 제조할 수 있다. In preparing the polyimide resin of Formula 1 and
또한 본 발명에서 화학식 2의 폴리이미드 수지성분은 그 단량체로서 (f)로 표시되는 방향족 디아민을 필수 성분으로 사용하게 되는데, 그 사용량은 전체 디아민 사용량에 대하여 1 내지 100 중량% 범위로 사용함으로써 본 발명에서 목적으로 하는 효과를 얻을 수 있다. 상기 (f)의 유닛을 제공하는 방향족 디아민을 사용함으로써 낮은 표면 극성을 갖는 가용성 폴리이미드 수지를 제공할 수가 있다.In addition, in the present invention, the polyimide resin component of Chemical Formula 2 uses the aromatic diamine represented by (f) as an essential component as its monomer, and the amount thereof is used in the range of 1 to 100% by weight based on the total amount of diamine. The desired effect can be obtained from. By using the aromatic diamine which provides the unit of said (f), the soluble polyimide resin which has low surface polarity can be provided.
또한 본 발명에 따른 상기 화학식 1 및 화학식 2로 표시되는 폴리이미드 수지는 테트라카르복실산이무수물 단량체와 디아민 단량체를 용액중합시켜 제조한다. In addition, the polyimide resin represented by
즉, 테트라카르복실산이무수물 단량체로서는 1,2,3,4-시클로부탄 테트라카르복실산이무수물[CBDA; (a)], 1,2,3,4-시클로펜탄 테트라카르복실산이무수물[CPDA; (b)], 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸시클로헥산-1,2-디카르복실산이무수물[DOCDA;(c)], 4-(2,5-디옥소테트라히드로퓨릴-3-일)-테트랄린-1,2-디카르복실산이무수물[DOTDA; (d)], 및 바이시클로옥텐-2,3,5,6-테트라카르복실산이무수물[BODA; (e)] 중에서 선택된 1종 또는 2종 이상의 지방족산이무수물이 필수성분으로 포함되고, 동시에 피로멜리트산이무수물, 벤조페논테트라카르복실산이무수물, 옥시디프탈산이무수물, 비프탈산이무수물 및 헥사플루오로이소프로필리덴디프탈산이무수물 등 중에서 선택된 1종 또는 2종 이상의 방향족 테트라카르복실산이무수물이 포함될 수 있다.That is, as the tetracarboxylic dianhydride monomer, 1,2,3,4-cyclobutane tetracarboxylic dianhydride [CBDA; (a)], 1,2,3,4-cyclopentane tetracarboxylic dianhydride [CPDA; (b)], 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride [DOCDA; (c)], 4- (2,5-di Oxotetrahydrofuryl-3-yl) -tetraline-1,2-dicarboxylic dianhydride [DOTDA; (d)], and bicyclooctene-2,3,5,6-tetracarboxylic dianhydride [BODA; One or two or more aliphatic dianhydrides selected from (e)] are included as essential ingredients, and at the same time, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, oxydiphthalic dianhydride, nonphthalic dianhydride and hexafluorine One or two or more aromatic tetracarboxylic dianhydrides selected from lysopropylidene diphthalic anhydride and the like may be included.
디아민 단량체로서는 파라-페닐렌디아민(p-PDA), 메타-페닐렌디아민(m-PDA), 4,4-옥시디아닐린(ODA), 4,4-메틸렌디아닐린(MDA), 2,2-비스아미노페닐헥사풀루오 로프로판(HFDA), 메타비스아미노페녹시디페닐설폰(m-BAPS), 파라비스아미노페녹시디페닐설폰(p-BAPS), 1,4-비스아미노페녹시벤젠(TPE-Q), 1,3-비스아미노페녹시벤젠(TPE-R), 2,2-비스아미노페녹시페닐프로판(BAPP) 및 2,2-비스아미노페녹시페닐헥사풀루오로프로판(HFBAPP) 등 중에서 선택된 1종 또는 2종 이상의 방향족 디아민을 사용할 수 있다. 화학식 2의 폴리이미드의 제조시에는 디아민 단량체로서 1-(3,5-디아미노펜닐)-3-알킬-숙시닉이미드를 필수성분으로 함유한다. As the diamine monomer, para-phenylenediamine (p-PDA), meta-phenylenediamine (m-PDA), 4,4-oxydianiline (ODA), 4,4-methylenedianiline (MDA), 2,2 -Bisaminophenylhexapulotropophane (HFDA), metabisaminophenoxydiphenylsulfone (m-BAPS), parabisaminophenoxydiphenylsulfone (p-BAPS), 1,4-bisaminophenoxybenzene ( TPE-Q), 1,3-bisaminophenoxybenzene (TPE-R), 2,2-bisaminophenoxyphenylpropane (BAPP) and 2,2-bisaminophenoxyphenylhexafuluropropane (HFBAPP One kind or two or more kinds of aromatic diamines selected from the like) may be used. In preparing the polyimide of
즉, 본 발명은 폴리아믹산 유도체를 제조함에 있어, 테트라카르복실산이무수물 단량체로서 상기 (a)~(e)로 표시되는 지방족 테트라카르복실산이무수물을 적절한 비율로 혼합 사용하여 기계적 특성과 내열성의 저하를 최소로 하면서도 용해성이 개선된 폴리이미드 수지를 제조할 수가 있다.That is, the present invention, in the preparation of a polyamic acid derivative, by using an aliphatic tetracarboxylic dianhydride represented by the above (a) to (e) as an appropriate ratio as a tetracarboxylic dianhydride monomer, mechanical properties and heat resistance deterioration It is possible to produce a polyimide resin with improved solubility while minimizing.
상기 (f)로 표시되는 방향족 디아민을 필수 단량체로 사용하여 제조된 본 발명에 따른 가용성 폴리이미드 수지 함유 폴리이미드 혼합조성물은 기존에 제조된 바 없는 신규한 물질로서, 저극성 알킬 측쇄기가 도입된 가용성 폴리이미드 수지와 폴리이미드의 혼합에 의하여 표면특성과 저온공정성 상기 물질의 적용에 의하여 제조된 전유기 박막트랜지스터 소자의 전기 절연특성이 특히 개선된 신규한 고분자 조성물이다. The soluble polyimide resin-containing polyimide mixed composition according to the present invention prepared by using the aromatic diamine represented by the above (f) as an essential monomer is a novel material that has not been prepared before, and has a low soluble alkyl side chain group introduced therein. Surface properties and low temperature processability by mixing polyimide resins and polyimide are novel polymer compositions in which the electrical insulation properties of all-organic thin film transistor devices manufactured by the application of the above materials are particularly improved.
이와 같은 본 발명의 화학식 1의 가용성 폴리이미드 수지는 중량평균 분자량(Mw) 5,000 내지 150,000 g/mol이고, 고유점도 범위 0.1 내지 3.0 dL/g, 유리전이온도 범위 150 내지 300 ℃의 특성을 가진다. 또한, 본 발명에 따른 가용성 폴리이미드 수지는 디메틸아세트아미드(DMAc), 디메틸포름아미드(DMF), N-메틸-2-피롤 리돈(NMP), 아세톤, 에틸아세테이트와 같은 비양성자성 극성용매를 비롯하여 메타-크레졸과 같은 유기용매에 대해 상온에서 쉽게 용해되는 특성을 가진다. 특히, 테트라히드로푸란(THF), 클로로포름과 같은 저비점 용매 및 감마-부티로락톤과 같은 저흡수성 용매에 대해서도 상온에서 10 중량% 이상의 높은 용해도를 나타낸다. 또한, 이들의 혼합용매에 대해서도 높은 용해도를 나타낸다. Such a soluble polyimide resin of
본 발명의 화학식 2의 폴리이미드수지는 중량평균 분자량(Mw) 10,000 내지 200,000 g/mol 정도, 고유점도 범위 0.1 내지 2.0 dL/g, 유리전이온도 범위 200 내지 400 ℃, 이미드화 온도범위 130 내지 250 ℃ 범위의 특성을 가진다. 또한, 본 발명에 따른 폴리이미드수지는 디메틸아세트아미드(DMAc), 디메틸포름아미드(DMF), N-메틸-2-피롤리돈(NMP), 아세톤, 에틸아세테이트와 같은 비양성자성 극성용매를 비롯하여 메타-크레졸과 같은 유기용매에 대해 상온에서 쉽게 용해되는 특성을 가진다. 특히, 테트라히드로푸란(THF), 클로로포름과 같은 저비점 용매 및 감마-부티로락톤과 같은 저흡수성 용매에 대해서도 상온에서 10 중량% 이상의 높은 용해도를 나타낸다. 또한, 이들의 혼합용매에 대해서도 높은 용해도를 나타낸다.The polyimide resin of the formula (2) of the present invention has a weight average molecular weight (Mw) of about 10,000 to 200,000 g / mol, intrinsic viscosity range of 0.1 to 2.0 dL / g, glass transition temperature range of 200 to 400 ℃, imidization temperature range of 130 to 250 It has a characteristic in the range of ℃. In addition, the polyimide resin according to the present invention includes aprotic polar solvents such as dimethylacetamide (DMAc), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), acetone and ethyl acetate. Easily dissolved at room temperature with respect to organic solvents such as meta-cresol. In particular, low solubility solvents such as tetrahydrofuran (THF), chloroform and low absorption solvents such as gamma-butyrolactone exhibit high solubility of 10% by weight or more at room temperature. Moreover, high solubility is shown also about these mixed solvents.
본 발명에 따른 상기 화학식 1로 표시되는 가용성 폴리이미드 수지는, 표면장력이 35 ~ 45 dyne/cm의 범위에 있으며, 유전상수가 3 ~ 5 범위에 있다. The soluble polyimide resin represented by
또한 본 발명의 상기 가용성 폴리이미드 수지가 혼합된 폴리이미드수지 혼합 조성물로부터 제조된 전유기 박막트랜지스터 소자의 전기 광학적 특성을 평가한 결과 절연파괴전압의 경우 3 ~ 7 MV/cm의 범위에 있으며, 10 KHz의 주파수에서 3 ~ 6의 유전상수를 보였으며, 표면장력은 35 ~ 45 dyne/cm의 범위에 있음을 알 수가 있 었다. 또한, 300 ~ 400 nm의 파장을 가지는 자외광을 조사함에 의해 10 ~ 50 ㎛의 미세패턴 형성이 가능하였다. In addition, as a result of evaluating the electro-optic properties of the organic thin film transistor device prepared from the polyimide resin mixture composition of the soluble polyimide resin of the present invention, the breakdown voltage is in the range of 3 ~ 7 MV / cm, 10 Dielectric constants of 3 to 6 were shown at the frequency of KHz, and surface tension was found to be in the range of 35 to 45 dyne / cm. In addition, by irradiating ultraviolet light having a wavelength of 300 ~ 400 nm it was possible to form a fine pattern of 10 ~ 50 ㎛.
본 발명에 따른 가용성 폴리이미드 수지가 혼합된 폴리이미드수지 혼합 조성물은 이상에서 설명한 바와 같이, 용해도가 우수하여 폴리카르보네이트(polycarbonate), 폴리설폰(polysulfone), 폴리에테르설폰(polyether sulfone) 등의 플라스틱 기판위에서 저온 공정이 가능할 뿐만 아니라 저극성 측쇄기의 도입에 의하여 표면 특성 및 전기절연특성이 특히 개선된 신규한 고분자 소재이다. As described above, the polyimide resin mixture composition in which the soluble polyimide resin is mixed is excellent in solubility, such as polycarbonate, polysulfone, polyether sulfone, and the like. It is a novel polymer material that enables low-temperature processing on plastic substrates, and especially improves surface and electrical insulation properties by introducing low polar side chain groups.
이와 같은 본 발명은 실시예에 의거하여 더욱 구체적으로 설명하는 바, 본 발명이 다음 실시예에 의하여 한정되는 것은 아니다.Such the present invention will be described in more detail based on Examples, but the present invention is not limited by the following Examples.
이와 같은 본 발명은 다음의 실시예에 의거하여 더욱 상세히 설명하겠는 바, 본 발명이 이에 한정되는 것은 아니다.Such a present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.
[합성예 1] Synthesis Example 1
1-(3,5-디니트로페닐)-3-(1-옥타데센)-숙시닉이미드(DN-IM-18)의 제조Preparation of 1- (3,5-dinitrophenyl) -3- (1-octadecene) -succinicimide (DN-IM-18)
교반기, 질소주입장치가 부착된 250 mL의 반응기에 질소가스를 서서히 통과시키면서 3,5-디니트로아닐린 9.2 g(0.05mole)을 반응용매인 아세틱산 50 mL에 용해시킨 후, 질소가스를 통과시키면서 2-옥타데센-1-일 숙신산 무수물 17.5 g(0.05mole)을 넣고, 24시간 동안 환류시켰다. 반응용액을 상온으로 냉각시킨 후, 석출된 고체를 얻었다. 수득된 고체를 메탄올에서 재결정하여, 16.2 g의 1-(3,5-디니트로펜닐)-3-(1-옥타데센)-숙시닉이미드(DN-IM-18)(융점 : 144 ℃, 1H NMR (CDCl3) δ= 9.06 (s, 1H, phenyl ring), 8.69 (d, 2H, phenyl ring), 1.25 (m, 30H, methylene), 0.85-0.90 (t, 3H, methyl) ppm IR (KBr) 1789 (C=O, asym, imide ring), 1713 (C=O, sym, imide ring) cm-1. 원소분석. C28H41N3O6 : 계산값 C 65.22, H 8.01, N 8.15 실험값 C 64.66, H 8.24, N, 7.84, 수율 63%)을 제조하였다.While slowly passing nitrogen gas through a 250 mL reactor equipped with a stirrer and a nitrogen injector, 9.2 g (0.05 mole) of 3,5-dinitroaniline was dissolved in 50 mL of acetic acid as a reaction solvent, and then passed through nitrogen gas. 17.5 g (0.05 mole) of 2-octadecen-1-yl succinic anhydride was added and refluxed for 24 hours. After the reaction solution was cooled to room temperature, a precipitated solid was obtained. The obtained solid was recrystallized in methanol to give 16.2 g of 1- (3,5-dinitrofenyl) -3- (1-octadecene) -succinicimide (DN-IM-18) (melting point: 144 DEG C, 1 H NMR (CDCl 3 ) δ = 9.06 (s, 1H, phenyl ring), 8.69 (d, 2H, phenyl ring), 1.25 (m, 30H, methylene), 0.85-0.90 (t, 3H, methyl) ppm IR (KBr) 1789 (C = O, asym, imide ring), 1713 (C = O, sym, imide ring) cm -1 .Elemental analysis C 28 H 41 N 3 O 6 : Calculated value C 65.22, H 8.01, N 8.15 experimental value C 64.66, H 8.24, N, 7.84, yield 63%) was prepared.
[합성예 2] Synthesis Example 2
1-(3,5-디아미노페닐)-3-옥타데실-숙시닉이미드(DA-IM-18)의 제조Preparation of 1- (3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM-18)
NMP와 에탄올(1/3 부피비) 100 mL에 DN-IM-18 10.3 g(0.02 mole)을 용해시킨 후, Pd/C(5%) 촉매(탄소입자의 표면에 금속 팔라듐을 5%의 양으로 도포한 촉매) 0.5 g과 함께 수소 반응기에 넣은 후, 60 ℃에서 2시간 동안 환원반응을 수행하였다. 반응혼합물을 여과한 후, 반응용매를 감압증류하였다. 1-(3,5-디아미노펜닐)-3-옥타데실-숙시닉이미드(DA-IM-18)를 수득하였다. 헥산/에틸아세테이트 공용매 중에서 재결정하여 6.87 g의 1-(3,5-디아미노펜닐)-3-옥타데실-숙시닉이미드(DA-IM-18)(융점 : 114 ℃, 1H NMR (CDCl3) δ=6.01 (s, 1H, phenyl ring), 5.97 (s, 2H, phenyl ring), 3.64 (s, 4H, amine protons), 1.25 (m, 30H, methylene), 0.85- 0.90 (t, 3H, methyl) ppm. IR (KBr) 3456 and 3370 (N=H), 1774 (C=O, asym, imide ring), 1701 (C=O, sym, imide ring) cm-1. 원소분석. C28H47N3O2 : 계산값. C 73.48, H 10.35, N 9.18 이론값 C 73.92, H 10.62, N, 9.03%,수율 75%)를 제조하였다.After dissolving 10.3 g (0.02 mole) of DN-IM-18 in 100 mL of NMP and ethanol (1/3 volume ratio), Pd / C (5%) catalyst (metal palladium on the surface of the carbon particles in an amount of 5%) After applying the catalyst) 0.5 g with a hydrogen reactor, a reduction reaction was carried out at 60 ℃ for 2 hours. After filtering the reaction mixture, the reaction solvent was distilled under reduced pressure. 1- (3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM-18) was obtained. 6.87 g of 1- (3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM-18) (melting point: 114 DEG C., 1 H NMR (Recrystallized from Hexane / Ethyl Acetate Cosolvent) CDCl 3 ) δ = 6.01 (s, 1H, phenyl ring), 5.97 (s, 2H, phenyl ring), 3.64 (s, 4H, amine protons), 1.25 (m, 30H, methylene), 0.85- 0.90 (t, 3H, methyl) ppm.IR (KBr) 3456 and 3370 (N = H), 1774 (C = O, asym, imide ring), 1701 (C = O, sym, imide ring) cm -1 .Elemental analysis. 28 H 47 N 3 O 2 : calculated value C 73.48, H 10.35, N 9.18 theoretical value C 73.92, H 10.62, N, 9.03%, yield 75%).
상기 합성예 2에서 제조한 저극성 알킬기가 치환된 숙시닉이미드 측쇄기를 가지고 있는 디아민 단량체로서 DA-IM-18는 재결정후의 수율이 50 % 이상으로 제조가 가능함을 확인할 수 있었으며, 공기 중에서 매우 우수한 저장안정성을 나타내었다.As a diamine monomer having a succinimide side chain substituted with a low polar alkyl group prepared in Synthesis Example 2, DA-IM-18 was able to be produced with a yield of 50% or more after recrystallization, and was excellent in air. Storage stability was shown.
[제조예 1][Production Example 1]
가용성폴리이미드 (SPI-1)의 제조Preparation of Soluble Polyimide (SPI-1)
교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 메틸렌 디아닐린(MDA) 3.57 g(0.018 mole)을 반응용매 m-크레졸에 용해시킨 후, 질소가스를 통과시키면서 고체상의 디옥소테트라히드로퓨릴-3-메틸시클로헥산-1,2-디카르복실산이무수물(DOCDA) 4.76 g(0.018 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 20 중량%로 고정하였으며, 반응온도를 상온에서 70℃까지 2시간, 70℃에서 180℃까지 2시간, 180℃에서 1시간동안 교반한 다음 메탄올에 여러번 세척하여 폴리이미드 (SPI-1)(고유점도, 0.7 dl/g)를 수득하였다.Dissolve methylene dianiline (MDA) 3.57 g (0.018 mole) in the reaction solvent m-cresol while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector, and then pass nitrogen gas through a solid di 4.76 g (0.018 mole) of oxotetrahydrofuryl-3-methylcyclohexane-1,2-dicarboxylic dianhydride (DOCDA) was added slowly. At this time, the solid content was fixed at 20% by weight, and the reaction temperature was stirred at 70 ° C. for 2 hours, 70 ° C. to 180 ° C. for 2 hours, and 180 ° C. for 1 hour, and then washed in methanol several times. Mid (SPI-1) (intrinsic viscosity, 0.7 dl / g) was obtained.
[제조예 2][Production Example 2]
가용성폴리이미드 (SPI-2)의 제조Preparation of Soluble Polyimide (SPI-2)
교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 메틸렌 디아닐린(MDA) 1.78 g(0.009 mole) 및 옥시디아닐린 1.8 g(0.009 mole) 을 반응용매 m-크레졸에 용해시킨 후, 질소가스를 통과시키면서 고체상의 디옥소테트라히드로퓨릴-3-메틸시클로헥산-1,2-디카르복실산이무수물 4.76 g(0.018 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 20 중량%로 고정하였으며, 반응온도를 상온에서 70℃까지 2시간, 70℃에서 180℃까지 2시간, 180℃에서 1시간 동안 교반한 다음 메탄올에 여러번 세척하여 폴리이미드 (SPI-2)(고유점도, 0.65 이/g)를 수득하였다.Methylene dianiline (MDA) 1.78 g (0.009 mole) and oxydianiline 1.8 g (0.009 mole) were dissolved in the reaction solvent m-cresol while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector. Thereafter, 4.76 g (0.018 mole) of dioxotetrahydrofuryl-3-methylcyclohexane-1,2-dicarboxylic dianhydride in solid phase was slowly added while passing through nitrogen gas. At this time, the solid content was fixed at 20% by weight, and the reaction temperature was stirred at 70 ° C. for 2 hours, 70 ° C. to 180 ° C. for 2 hours, and 180 ° C. for 1 hour, and then washed in methanol several times. Mid (SPI-2) (intrinsic viscosity, 0.65 2 g) was obtained.
[제조예 3][Production Example 3]
가용성 Availability 폴리이미드수지Polyimide resin ( ( SPISPI -3)의 제조-3) Preparation
교반기, 온도조절장치, 질소주입장치 및 냉각기를 부착한 250ml의 반응기에 질소가스를 서서히 통화시키면서 1-(3,5-디아미노펜닐)-3-옥타데실-숙시닉이미드(DA-IM-18) 9.15 g(0.02 mole)을 반응용매 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 고체상의 디옥소테트라히드로퓨릴-3-메틸시클로헥산-1,2-디카르복실산이무수물 5.28 g(0.02 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 20중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면 서 24시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 이 폴리아믹산 용액에 아세틱산 무수물 6.12 g(0.06 mole)과 피리딘 0.1 g(0.1 mole)을 넣고 상온에서 24시간동안 교반시킨 후 120 ℃에서 3시간동안 교반한 다음 메탄올에 여러번 세척하여 가용성 폴리이미드 (SPI-3)(고유점도, 0.12 dl/g)를 수득하였다.1- (3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM-) while slowly passing nitrogen gas into a 250 ml reactor equipped with a stirrer, a thermostat, a nitrogen injector and a cooler. 18) 9.15 g (0.02 mole) was dissolved in the reaction solvent N-methyl-2-pyrrolidone and then passed through nitrogen gas to solid dioxotetrahydrofuryl-3-methylcyclohexane-1,2-dicar 5.28 g (0.02 mole) diacid dianhydride was added slowly. At this time, the solid content (solid content) was fixed at 20% by weight, and stirred for 24 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. 6.12 g (0.06 mole) of acetic anhydride and 0.1 g (0.1 mole) of pyridine were added to the polyamic acid solution, stirred at room temperature for 24 hours, stirred at 120 ° C. for 3 hours, and washed with methanol several times to obtain soluble polyimide ( SPI-3) (intrinsic viscosity, 0.12 dl / g) was obtained.
[제조예 4][Production Example 4]
가용성 Availability 폴리이미드수지Polyimide resin ( ( SPISPI -4)의 제조-4) Preparation
교반기, 온도조절장치, 질소주입장치 및 냉각기를 부착한 250ml의 반응기에 질소가스를 서서히 통화시키면서 1-(3,5-디아미노펜닐)-3-옥타데실-숙시닉이미드(DA-IM-18) 4.6 g(0.01 mole)과 4,4-디아미노 디페닐메탄 1.98 g(0.01 mole)을 반응용매 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 고체상의 디옥소테트라히드로퓨릴-3-메틸시클로헥산-1,2-디카르복실산이무수물 5.28 g(0.02 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 20중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 24시간 동안 교반하여 폴리아믹산 용액(SPI)을 수득하였다. 이 폴리아믹산 용액에 아세틱산 무수물 6.12 g(0.06 mole)과 피리딘 0.1 g(0.1 mole)을 넣고 상온에서 24시간동안 교반시킨 후 120 ℃에서 3시간동안 교반한 다음 메탄올에 여러번 세척하여 가용성 폴리이미드 (SPI-4)(고유점도, 0.42 dl/g)를 수득하였다.1- (3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM-) while slowly passing nitrogen gas into a 250 ml reactor equipped with a stirrer, a thermostat, a nitrogen injector and a cooler. 18) Dissolve 4.6 g (0.01 mole) and 1.98 g (0.01 mole) of 4,4-diamino diphenylmethane in the reaction solvent N-methyl-2-pyrrolidone, and then pass the nitrogen gas through a solid dioxo 5.28 g (0.02 mole) of tetrahydrofuryl-3-methylcyclohexane-1,2-dicarboxylic dianhydride was added slowly. At this time, the solid content (solid content) was fixed to 20% by weight, and stirred for 24 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution (SPI). 6.12 g (0.06 mole) of acetic anhydride and 0.1 g (0.1 mole) of pyridine were added to the polyamic acid solution, stirred at room temperature for 24 hours, stirred at 120 ° C. for 3 hours, and washed with methanol several times to obtain soluble polyimide ( SPI-4) (intrinsic viscosity, 0.42 dl / g) was obtained.
[표 1]TABLE 1
MDA : 4,4'-메틸렌 디아닐린MDA: 4,4'-methylene dianiline
DOCDA : 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸시클로헥산-1,2-디카르복실산이무수물DOCDA: 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride
ODA : 옥시디아닐린ODA: Oxydianiline
[실시예 1] Example 1
교반기, 질소주입장치가 부착된 100 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 1의 SPI-1 1.96 g과 제조예 3의 가용성 폴리이미드(SPI-3) 0.04 g을 희석용매인 γ-부틸로락톤 8 g, 싸이클로헥사논 15 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하고 그 폴리이미드 혼합물을 BPI-1 이라고 하였다. Γ-butyl as a diluting solvent was added 1.96 g of SPI-1 of Preparation Example 1 and 0.04 g of soluble polyimide (SPI-3) of Preparation Example 3 while slowly passing nitrogen gas through a 100 ml reactor equipped with a stirrer and a nitrogen injection apparatus. 8 g of rockactone and 15 g of cyclohexanone were stirred for 24 hours to prepare a solution having a viscosity of 25 cps, and the polyimide mixture was referred to as BPI-1.
[실시예 2]Example 2
교반기, 질소주입장치가 부착된 100 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 1의 SPI-1 1.9 g과 제조예 3의 가용성 폴리이미드(SPI-3) 0.1 g을 희석용매인 γ-부틸로락톤 8 g, 싸이클로헥사논 15 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하고 그 폴리이미드 혼합물을 BPI-2 라고 하였다. Γ-butyl as a dilution solvent for 1.9 ml of SPI-1 of Preparation Example 1 and 0.1 g of soluble polyimide (SPI-3) of Preparation Example 3 while slowly passing nitrogen gas through a 100 ml reactor equipped with a stirrer and a nitrogen injection apparatus. 8 g of rockactone and 15 g of cyclohexanone were stirred for 24 hours to prepare a solution having a viscosity of 25 cps, and the polyimide mixture was referred to as BPI-2.
[실시예 3]Example 3
교반기, 질소주입장치가 부착된 100 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 1의 SPI-1 1.78 g과 제조예 3의 가용성 폴리이미드(SPI-3) 0.22 g을 희석용매인 γ-부틸로락톤 8 g, 싸이클로헥사논 15 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하고 그 폴리이미드 혼합물을 BPI-3 라고 하였다. While diluting nitrogen gas slowly through a 100 ml reactor equipped with a stirrer and a nitrogen injection device, 1.78 g of SPI-1 of Preparation Example 1 and 0.22 g of soluble polyimide (SPI-3) of Preparation Example 3 were diluted solvents of γ-butyl. 8 g of rockactone and 15 g of cyclohexanone were stirred for 24 hours to prepare a solution having a viscosity of 25 cps, and the polyimide mixture was referred to as BPI-3.
[실시예 4]Example 4
교반기, 질소주입장치가 부착된 100 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 1의 SPI-1 1.73 g과 제조예 3의 가용성 폴리이미드(SPI-3) 0.27 g을 희석용매인 γ-부틸로락톤 8 g, 싸이클로헥사논 15 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하고 그 폴리이미드 혼합물을 BPI-4 라고 하였다. Γ-butyl as a diluting solvent was added 1.73 g of SPI-1 of Preparation Example 1 and 0.27 g of soluble polyimide (SPI-3) of Preparation Example 3 while slowly passing nitrogen gas through a 100 ml reactor equipped with a stirrer and a nitrogen injection apparatus. 8 g of rockactone and 15 g of cyclohexanone were stirred for 24 hours to prepare a solution having a viscosity of 25 cps, and the polyimide mixture was referred to as BPI-4.
[실시예 5]Example 5
교반기, 질소주입장치가 부착된 100 ml의 반응기에 질소가스를 서서히 통과 시키면서 제조예 1의 SPI-1 1.65 g과 제조예 3의 가용성 폴리이미드(SPI-3) 0.35 g을 희석용매인 γ-부틸로락톤 8 g, 싸이클로헥사논 15 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하고 그 폴리이미드 혼합물을 BPI-5 라고 하였다. While slowly passing nitrogen gas through a 100 ml reactor equipped with a stirrer and a nitrogen injection device, 1.65 g of SPI-1 of Preparation Example 1 and 0.35 g of soluble polyimide (SPI-3) of Preparation Example 3 were diluted solvents of γ-butyl. 8 g of rockactone and 15 g of cyclohexanone were stirred for 24 hours to prepare a solution having a viscosity of 25 cps, and the polyimide mixture was referred to as BPI-5.
[실시예 6]Example 6
교반기, 질소주입장치가 부착된 100 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 1의 SPI-1 1.5 g과 제조예 3의 가용성 폴리이미드(SPI-3)0.5 g을 희석용매인 γ-부틸로락톤 8 g, 싸이클로헥사논 15 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하고 그 폴리이미드 혼합물을 BPI-6 라고 하였다. Γ-butyl as a dilution solvent for 1.5 ml of SPI-1 of Preparation Example 1 and 0.5 g of soluble polyimide (SPI-3) of Preparation Example 3 while slowly passing nitrogen gas through a 100 ml reactor equipped with a stirrer and a nitrogen injection apparatus. 8 g of rolactone and 15 g of cyclohexanone were stirred for 24 hours to prepare a solution having a viscosity of 25 cps, and the polyimide mixture was referred to as BPI-6.
[실시예 7]Example 7
교반기, 질소주입장치가 부착된 100 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 1의 SPI-1 1.44 g과 제조예 3의 가용성 폴리이미드(SPI-3) 0.56 g을 희석용매인 γ-부틸로락톤 8 g, 싸이클로헥사논 15 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하고 그 폴리이미드 혼합물을 BPI-7 라고 하였다. While slowly passing nitrogen gas through a 100 ml reactor equipped with a stirrer and a nitrogen injection device, 1.44 g of SPI-1 of Preparation Example 1 and 0.56 g of soluble polyimide (SPI-3) of Preparation Example 3 were diluted solvents of γ-butyl. 8 g of rockactone and 15 g of cyclohexanone were stirred for 24 hours to prepare a solution having a viscosity of 25 cps, and the polyimide mixture was referred to as BPI-7.
[비교예 1]Comparative Example 1
교반기, 질소주입장치가 부착된 100 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 1의 가용성 폴리이미드(SPI-1) 수지 2 g을 희석용매인 γ-부틸로락톤 25 g에 넣고 24 시간동안 교반하여 20 cps의 점도를 갖는 용액을 제조하고 그 폴리이미드 혼합물을 PI-1 이라고 하였다. While slowly passing nitrogen gas through a 100 ml reactor equipped with a stirrer and a nitrogen injector, 2 g of a soluble polyimide (SPI-1) resin of Preparation Example 1 was added to 25 g of γ-butylolactone, a diluting solvent, for 24 hours. The solution was stirred to prepare a solution having a viscosity of 20 cps and the polyimide mixture was referred to as PI-1.
[비교예 2]Comparative Example 2
교반기, 질소주입장치가 부착된 100 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 3의 가용성 폴리이미드(SPI-3) 수지 2g을 γ-부틸로락톤 25 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하고 그 폴리이미드 혼합물을 PI-2 라고 하였다. While slowly passing nitrogen gas through a 100 ml reactor equipped with a stirrer and a nitrogen injector, 2 g of a soluble polyimide (SPI-3) resin of Preparation Example 3 was added to 25 g of γ-butylolactone and stirred for 24 hours to 25 cps. A solution having a viscosity of was prepared and the polyimide mixture was called PI-2.
[표 2]TABLE 2
상기 표 2에 나타낸 바와 같이 실시예 1 ~ 7 및 비교예 1 ~ 2 에 따라 제조된 가용성 폴리이미드 및 가용성 폴리이미드 혼합 조성물 용액을 ITO 유리판 위에 0.05 ~ 1.0㎛의 두께의 범주에서 스핀 코팅한 후, 160 ℃의 온도에서 30 분 동안 열경화하여 얻은 폴리이미드 유도체 박막의 물성을 다음 표 3에 나타내었다.As shown in Table 2, the soluble polyimide and the soluble polyimide mixed composition solution prepared according to Examples 1 to 7 and Comparative Examples 1 to 2 were spin-coated on an ITO glass plate in a thickness of 0.05 to 1.0 μm, and then Physical properties of the polyimide derivative thin film obtained by thermal curing at a temperature of 160 ° C. for 30 minutes are shown in Table 3 below.
[표 3]TABLE 3
상기 표 3에서 나타난 바와 같이, 본 발명에 따른 가용성 폴리이미드 수지의 는 0.1~3.0 dL/g 범위의 고유점도를 가지는 것으로 확인되었다. 또한 상기 수지들은 용매주형에 의한 필름성형성 및 기계적 특성이 매우 우수한 것으로 나타났다. As shown in Table 3, the soluble polyimide resin according to the present invention was confirmed to have an intrinsic viscosity in the range of 0.1 ~ 3.0 dL / g. In addition, the resins were found to have excellent film forming and mechanical properties by solvent casting.
상기 표 3에서 나타난 바와 같이, 저극성 알킬기가 치환된 숙시닉이미드 측 쇄기가 도입된 가용성 폴리이미드를 함유하는 폴리이미드 혼합 조성물 용액으로부터 제조된 본 발명에 따른 폴리이미드 박막의 연필경도는 H~2H 정도로서, 이들이 도입되지 않은 비교예 1의 폴리이미드에 비해 표면경도가 현저히 개선되었다. 또한 저극성 알킬기가 치환된 숙시닉이미드 측쇄기가 도입된 가용성 폴리이미드 함유 폴리이미드 혼합 조성물 용액으로부터 제조된 박막의 표면에너지는 저극성 숙시닉이미드 측쇄기가 도입된 디아민의 함량이 증가함에 따라 감소하는 경향을 나타내었으며, 비교예 2의 가용성폴리이미드, PI-2 보다 약간 증가한 40~44 dyne/cm의 값을 보였다.As shown in Table 3, the pencil hardness of the polyimide thin film according to the present invention prepared from a polyimide mixed composition solution containing a soluble polyimide having a succinimide side chain group substituted with a low polar alkyl group is H ~ As about 2H, surface hardness was remarkably improved compared with the polyimide of Comparative Example 1 in which they were not introduced. In addition, the surface energy of the thin film prepared from the solution of the soluble polyimide-containing polyimide mixed composition in which the succinimide side chain group substituted with the low polar alkyl group was decreased was increased with increasing content of the diamine in which the low polar succinimide side chain group was introduced. The soluble polyimide of Comparative Example 2 showed a value of 40-44 dyne / cm slightly increased than that of PI-2.
[물성측정] [Property Measurement]
유기절연막의 제작 및 물성측정Fabrication and Properties Measurement of Organic Insulating Film
상기 실시예 1 ~ 7과 비교예 1 ~ 2에서 제조한 가용성 폴리이미드 용액을 절연막으로 코팅한 후 이를 이용하여 유기절연막의 물성을 측정하였다. 구체적인 측정방법은 다음과 같다. After coating the soluble polyimide solution prepared in Examples 1 to 7 and Comparative Examples 1 to 2 with an insulating film, the physical properties of the organic insulating film were measured using the same. The specific measuring method is as follows.
본 발명의 폴리이미드 절연체의 전기적 절연 특성을 평가하기 위하여 금 전극-폴리이미드 박막-금 전극(MIM) 구조를 가진 간단한 소자를 유리와 플라스틱 기판 위에 소자제작과 같은 조건으로 진공증착과 스핀코팅을 통하여 제작하였다. 즉, 실시예 1 ~ 7과 비교예 1 ~ 2로부터 제조된 폴리이미드 박막의 유전상수를 측정하기 위해서 본 발명에서는 유리기판 위에 40 nm 두께의 금을 약 10-6 torr의 진 공 하에서 열증착하였다. 여기에 폴리이미드(PI) 용액을 스핀 코팅하여 3000 ~ 5000 Å의 두께로 박막화 하고 90 ℃의 온도에서 10분간 열처리 후, 150 ℃의 온도에서 30 분 동안 건조하였다. 얻어진 폴리이미드 박막 위에 지름 2 cm의 금을 40 nm의 두께로 박막 증착한 후 임피던스 계전기(impedance analyzer)를 이용하여 1 MHz의 주파수에서 전기용량(capacitance)을 측정하여 유전상수를 계산하였다. 유전상수 및 표면장력 측정 결과를 다음 표 4에 나타내었다. In order to evaluate the electrical insulating properties of the polyimide insulator of the present invention, a simple device having a gold electrode-polyimide thin film-gold electrode (MIM) structure was subjected to vacuum deposition and spin coating under the same conditions as device fabrication on glass and plastic substrates. Produced. That is, in order to measure the dielectric constant of the polyimide thin films prepared from Examples 1 to 7 and Comparative Examples 1 to 2, 40 nm thick gold was thermally deposited on a glass substrate under a vacuum of about 10 −6 torr. . The polyimide (PI) solution was spin-coated thereto and thinned to a thickness of 3000 to 5000 kPa, heat treated at 90 ° C. for 10 minutes, and dried at 150 ° C. for 30 minutes. After depositing a thin film of gold with a diameter of 2 cm on the obtained polyimide thin film with a thickness of 40 nm, the dielectric constant was calculated by measuring a capacitance at a frequency of 1 MHz using an impedance analyzer. Dielectric constant and surface tension measurement results are shown in Table 4 below.
[표 4]TABLE 4
상기의 표 4에서 알 수 있듯이 본 발명의 실시예 1 ~ 7에 따라 제조된 폴리이미드계 수지들은 2.7 ~ 3.27범위의 유전상수와 40 ~ 44 dyne/cm 범위의 표면장력 을 가지고 있었으며 중합체 내에 옥타데실 측쇄기를 함유한 단량체인 DA-L-18IM의 함유량이 증가할수록 유전상수와 표면장력은 모두 감소하였다. As can be seen in Table 4, the polyimide resins prepared according to Examples 1 to 7 of the present invention had a dielectric constant in the range of 2.7 to 3.27 and surface tension in the range of 40 to 44 dyne / cm, and octadecyl in the polymer. As the content of DA-L-18IM, a monomer containing side chain groups, increased, both dielectric constant and surface tension decreased.
유기박막 트랜지스터의 제작 및 특성평가Fabrication and Characterization of Organic Thin Film Transistors
본 발명의 가용성 폴리이미드를 이용하여 유기 박막 트랜지스터를 제작하고 그 특성을 측정하였다. 유기반도체로는 유기 박막 트랜지스터에서 가장 널리 사용되고 상대적으로 좋은 성능을 가지는 펜타센을 사용하였다. 기판은 폴리에테르설폰과 같은 플라스틱 기판을 사용하였다. 탑접촉(top-contact)소자 제작방법은 다음과 같다. 기판 청결도는 전자 소자를 제작할 때 가장 중요한 요소 중의 하나이므로 세제, 증류수, 아세톤 그리고 아이소프로필알코올를 이용하여 초음파 세척을 한 후 오븐에서 충분히 건조시킨 것을 사용하였고, 플라스틱 기판은 시판되는 것을 별도의 세척공정 없이 보호막만 탈리시킨 후 그대로 사용하였다. An organic thin film transistor was fabricated using the soluble polyimide of the present invention and its properties were measured. As an organic semiconductor, pentacene, which is widely used in organic thin film transistors and has a relatively good performance, was used. The substrate used was a plastic substrate such as polyethersulfone. The method of manufacturing the top-contact device is as follows. Substrate cleanliness is one of the most important factors in the manufacture of electronic devices, so ultrasonic cleaning with detergent, distilled water, acetone, and isopropyl alcohol was used, followed by drying sufficiently in an oven. Only the protective film was detached and used as it is.
잘 세척된 기판 위에 먼저 금을 새도우마스크를 이용하여 1x10-6 torr의 진공에서 열 진공 증착하여 2 mm 너비의 게이트 전극을 40 nm 두께로 형성하였다. 그 위에 본 발명의 폴리이미드 혼합 조성액을 300 nm 두께로 스핀코팅하고, 90 ℃에서 10분 간 건조한 후, 150 ℃의 온도에서 가열함으로써 폴리이미드 절연막을 얻었다. 상기의 폴리이미드 절연막 위에 유기반도체인 펜타센을 1× 10-6 torr의 진공에서 열진공 증착을 이용하여 50 nm 두께로 증착하였다. 이때 펜타센의 결정화에 큰 영향을 미치는 기판의 온도는 90 ℃로 일정하게 유지하였다. 마지막으로 금을 게이트 증착과 같은 방법으로 40 nm의 두께로 증착하여 소오스와 드레인 전극을 형성하였다. 하접촉(bottom-contact) 소자는 펜타센과 소오스, 드레인 전극의 형성 순서를 서로 바꿈으로써 제작하였다. 위와 같이 제작된 소자의 특성은 에질런트 테크날리지사의 E5272장비를 이용하여 게이트 전압에 따른 드레인 전압-드레인 전류 및 드레인 전압에 따른 게이트 전압-드레인 전류 곡선들을 측정하여 포화영역(saturation) 영역에서 다음의 전류, 전압식을 이용하여 제반 특성들을 평가하였다. On the well cleaned substrate, gold was first thermally vacuum-deposited in a vacuum of 1 × 10 −6 torr using a shadow mask to form a 2 mm wide gate electrode having a thickness of 40 nm. The polyimide mixed composition of this invention was spin-coated at 300 nm thickness, dried at 90 degreeC for 10 minutes, and then heated at the temperature of 150 degreeC, and the polyimide insulating film was obtained. Pentacene, an organic semiconductor, was deposited on the polyimide insulating film to a thickness of 50 nm using thermal vacuum deposition in a vacuum of 1 × 10 −6 torr. At this time, the temperature of the substrate having a great influence on the crystallization of pentacene was kept constant at 90 ℃. Finally, gold was deposited to a thickness of 40 nm in the same manner as gate deposition to form a source and a drain electrode. Bottom-contact devices were fabricated by changing the order of formation of pentacene, source, and drain electrodes. The characteristics of the device fabricated as described above were measured in the saturation region by measuring the drain voltage-drain current according to the gate voltage and the gate voltage-drain current curve according to the drain voltage by using the E5272 device of Agilent Technology. Various characteristics were evaluated using the current and voltage equations.
VT 는 문턱전압, Vgs 는 인가된 게이트 전압, μ는 전계효과 전하이동도, W와 L은 채널의 너비와 길이, C는 절연막의 커패시턴스이다. 문턱전압은 
[표 5]TABLE 5
표 5에서 보듯이 DA-L-18IM가 포함되어있지 않은 절연막과 비교하여 DA-L-18IM가 포함된 절연막으로 제작된 유기박막 트랜지스터의 전계효과 전하 이동도, 누설전류, 문턱전압, 전류비 등 모든 성능이 월등히 향상되었음을 알 수 있다. As shown in Table 5, the field effect charge mobility, leakage current, threshold voltage, current ratio, etc. of organic thin film transistors made of an insulating film containing DA-L-18IM compared to the insulating film not containing DA-L-18IM. You can see that all the performance has improved significantly.
본 발명에 따른 폴리이미드 수지는 중량평균 분자량(Mw) 10,000 ~ 200,000 g/㏖ 범위, 고유점도 0.1 ~ 0.48 g/㎗ 범위, 열분해온도 380 ~ 450 ℃ 범위, 10 KHz의 주파수에서의 유전상수 2.7 ~ 3.27 범위, 표면장력 40 ~ 44 dyne/cm 범위에 있었다. 본 발명의 유기절연막을 이용하여 제작한 유기박막 트랜지스터의 제반 특성이 그게 향상되었으며 특히, 전계효과 전하이동도(field effect mobility)가 크게 향상되었고 그 전하이동도는 0.33 ~ 0.90 ㎠/Vs 범위에 있었다. Polyimide resin according to the present invention has a weight average molecular weight (Mw) 10,000 ~ 200,000 g / mol range, intrinsic viscosity 0.1 ~ 0.48 g / 0.1 range, pyrolysis temperature 380 ~ 450 ℃ range, dielectric constant at a frequency of 10 KHz 2.7 ~ It was in the range of 3.27 and surface tension of 40 to 44 dyne / cm. The overall characteristics of the organic thin film transistor fabricated using the organic insulating film of the present invention were improved, in particular, the field effect mobility was greatly improved and the charge mobility was in the range of 0.33 to 0.90
따라서, 본 발명의 폴리이미드 수지는 150 ℃ 범위의 저온공정특성, 우수한 전기적 특성, 내화학약품성 및 내열성을 보유함으로서 전유기 디스플레이 소자에 적용되는 트랜지스터용 절연체 재료로서의 응용이 가능할 뿐만 아니라 액정표시소자 제조의 복잡한 공정을 단축할 수 있는 효과가 있다.Accordingly, the polyimide resin of the present invention possesses low temperature process characteristics, excellent electrical characteristics, chemical resistance and heat resistance in the range of 150 ° C., thereby making it possible to be used as an insulator material for transistors applied to all organic display devices and to manufacture liquid crystal display devices. This can shorten the complicated process.
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| CN103189971B (en) | 2010-11-01 | 2016-02-17 | 巴斯夫欧洲公司 | As dielectric polyimides |
| US9187600B2 (en) | 2010-11-01 | 2015-11-17 | Basf Se | Polyimides as dielectric |
| KR20140139059A (en) * | 2012-03-28 | 2014-12-04 | 바스프 에스이 | Polyimides as dielectrics |
| KR101685035B1 (en) * | 2013-10-24 | 2016-12-12 | 한국화학연구원 | Polymer compound for forming organic gate insulator of thin-film transistor and thin-film transistor using the same |
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