CN1607685A - 用于制造有机绝缘体的组合物 - Google Patents
用于制造有机绝缘体的组合物 Download PDFInfo
- Publication number
- CN1607685A CN1607685A CNA2004100881621A CN200410088162A CN1607685A CN 1607685 A CN1607685 A CN 1607685A CN A2004100881621 A CNA2004100881621 A CN A2004100881621A CN 200410088162 A CN200410088162 A CN 200410088162A CN 1607685 A CN1607685 A CN 1607685A
- Authority
- CN
- China
- Prior art keywords
- titanium
- organic
- composition
- zirconium
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 239000012212 insulator Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 55
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 229920000620 organic polymer Polymers 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 14
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 9
- -1 silane compound Chemical class 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 239000004411 aluminium Substances 0.000 claims description 16
- 239000011368 organic material Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 11
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 10
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 238000004528 spin coating Methods 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- TZMFJUDUGYTVRY-UHFFFAOYSA-N ethyl methyl diketone Natural products CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 229920001195 polyisoprene Polymers 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 4
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 claims description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- SXEBSPSTEUQPJM-UHFFFAOYSA-N oxolane;titanium Chemical compound [Ti].C1CCOC1 SXEBSPSTEUQPJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 3
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims description 2
- BERXRDWPBSLJLU-UHFFFAOYSA-N 1,1,1,4,4,5-hexafluoropentane-2,3-dione Chemical compound FCC(F)(F)C(=O)C(=O)C(F)(F)F BERXRDWPBSLJLU-UHFFFAOYSA-N 0.000 claims description 2
- QUTGXAIWZAMYEM-UHFFFAOYSA-N 2-cyclopentyloxyethanamine Chemical compound NCCOC1CCCC1 QUTGXAIWZAMYEM-UHFFFAOYSA-N 0.000 claims description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 2
- BGGIUGXMWNKMCP-UHFFFAOYSA-N 2-methylpropan-2-olate;zirconium(4+) Chemical compound CC(C)(C)O[Zr](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C BGGIUGXMWNKMCP-UHFFFAOYSA-N 0.000 claims description 2
- KWSSKCHDFPPOQV-UHFFFAOYSA-N 2-oxopropanoic acid zirconium Chemical compound [Zr].C(C(=O)C)(=O)O KWSSKCHDFPPOQV-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 2
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 claims description 2
- PWVDYRRUAODGNC-UHFFFAOYSA-N CCN([Ti])CC Chemical compound CCN([Ti])CC PWVDYRRUAODGNC-UHFFFAOYSA-N 0.000 claims description 2
- DVOBFBBUJSCXOR-UHFFFAOYSA-N CCN([Zr])CC Chemical compound CCN([Zr])CC DVOBFBBUJSCXOR-UHFFFAOYSA-N 0.000 claims description 2
- YWATTXMDZQWERV-UHFFFAOYSA-N CN(C)[Hf] Chemical compound CN(C)[Hf] YWATTXMDZQWERV-UHFFFAOYSA-N 0.000 claims description 2
- ZLOKVAIRQVQRGC-UHFFFAOYSA-N CN(C)[Ti] Chemical compound CN(C)[Ti] ZLOKVAIRQVQRGC-UHFFFAOYSA-N 0.000 claims description 2
- PULVCHXDNLGASZ-UHFFFAOYSA-N CN(C)[Zr] Chemical compound CN(C)[Zr] PULVCHXDNLGASZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000004640 Melamine resin Substances 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- URQIVZBTTCUDJZ-UHFFFAOYSA-N [CH3-].[CH3-].[CH3-].[Ti+3].C[C]1[C](C)[C](C)[C](C)[C]1C Chemical compound [CH3-].[CH3-].[CH3-].[Ti+3].C[C]1[C](C)[C](C)[C](C)[C]1C URQIVZBTTCUDJZ-UHFFFAOYSA-N 0.000 claims description 2
- UEUMIMKGIUYUGH-UHFFFAOYSA-H [F-].[F-].[F-].[F-].[F-].[F-].[Zr+6] Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[Zr+6] UEUMIMKGIUYUGH-UHFFFAOYSA-H 0.000 claims description 2
- 229920000800 acrylic rubber Polymers 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 150000001399 aluminium compounds Chemical class 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 229940077746 antacid containing aluminium compound Drugs 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- PDRQZRNOXMTBLB-UHFFFAOYSA-N butan-1-ol;hafnium Chemical compound [Hf].CCCCO PDRQZRNOXMTBLB-UHFFFAOYSA-N 0.000 claims description 2
- 229920005549 butyl rubber Polymers 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- WOEQEDQNDRKHPV-UHFFFAOYSA-N ethanol;hafnium Chemical compound [Hf].CCO WOEQEDQNDRKHPV-UHFFFAOYSA-N 0.000 claims description 2
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002363 hafnium compounds Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- JDQLUYWHCUWSJE-UHFFFAOYSA-N methanolate;titanium(3+) Chemical compound [Ti+3].[O-]C.[O-]C.[O-]C JDQLUYWHCUWSJE-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920002480 polybenzimidazole Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001083 polybutene Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920000306 polymethylpentene Polymers 0.000 claims description 2
- 239000011116 polymethylpentene Substances 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 229920001955 polyphenylene ether Polymers 0.000 claims description 2
- 229920006375 polyphtalamide Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 claims description 2
- BIZGMTWBKDPTLH-UHFFFAOYSA-N propan-2-yl hypochlorite Chemical compound CC(C)OCl BIZGMTWBKDPTLH-UHFFFAOYSA-N 0.000 claims description 2
- 229940107700 pyruvic acid Drugs 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 150000004685 tetrahydrates Chemical class 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 2
- CMWCOKOTCLFJOP-UHFFFAOYSA-N titanium(3+) Chemical compound [Ti+3] CMWCOKOTCLFJOP-UHFFFAOYSA-N 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003755 zirconium compounds Chemical class 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- KKSAZXGYGLKVSV-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO KKSAZXGYGLKVSV-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000002800 charge carrier Substances 0.000 abstract description 29
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 36
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 9
- 238000001723 curing Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical group COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 4
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
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- 230000008901 benefit Effects 0.000 description 3
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- 238000009413 insulation Methods 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical group CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910020684 PbZr Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
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Abstract
本发明公开了一种用于制造有机绝缘体的组合物,该组合物包括:(i)至少1种有机-无机杂化材料;(ii)至少1种有机金属化合物及/或有机聚合物;(iii)至少1种用于溶解上述2种组分的溶剂,致使采用同样的组合物的有机绝缘体具有低的阈电压和驱动电压、高的电荷载体迁移率和Ion/Ioff比,从而增加了绝缘体特性。另外,可采用湿法进行有机绝缘膜的制造,因此,方法简便、成本降低。
Description
本发明的背景
本非临时申请要求的优先权按35U.S.C.§119(a)规定是在2003.10.15申请的韩国专利申请No.2003-71775,在这里一并列出供参考。
技术领域
本发明一般涉及用于制造有机绝缘体的组合物。更具体地说,本发明涉及用于制造有机绝缘体的组合物,以及采用该组合物制造的有机绝缘体。该组合物含有(i)有机-无机杂化材料;(ii)至少1种有机金属化合物和/或有机聚合物;以及(iii)一种用于溶解组分(i)和(ii)的溶剂。
相关技术的说明
薄膜晶体管(下面称作‘TFT’),已常在显示装置中使用,并由硅半导体膜、氧化的硅绝缘膜和金属电极构成。目前,用于半导体材料的有机TFT己经开发(美国专利No.5,347,114)。由于其具有良好的性质,该材料在世界各地己进行了研究。具体地说,有机TFT是挠性的,并便于制造,加速了它们在场显示器领域中的应用。
自从聚乙炔,一种具有半导体特性的共轭的有机聚合物的开发,对有机的聚合半导体材料的研究正在蓬勃开展。这种材料作为新型电子装置的基材,已在不同的领域得到广泛应用,例如,功能性电子装置和光学装置。这是由于在有机半导体中使用时,有机聚合物呈现很多优点:它们可采用各种不同的合成路线而低成本地进行合成;它们可容易地制成纤维或膜;以及它们呈现良好的挠性和优良的导电性。
作为使用有机导电性聚合物制造的很多装置中的一种,从1980年开始,对特征为含有有机聚合物的有机TFT作为活性膜已进行了研究。近几年来,对这种有机TFT在全世界进行了广泛研究。该有机TFT具有类似于常用的Si-TFT的结构,但其不同在于是一种代替硅的作为半导体材料使用的有机聚合物。在制造有机TFT的方法中,半导体层的薄膜是在大气压下通过印刷法进行制造。该法与使用等离子体法相反,其通过化学蒸汽沉积(CVD),该法烦琐但实质上是用于硅薄膜的形成。然而,对有机TFT来说,可使用一种采用塑料基材的连续辊压的辊压法,以致可低成本制造晶体管。
通常,在电荷载体迁移率中,有机TFT等于或优于非晶形硅TFT,但它们的驱动及阈电压非常高。采用非晶形硅和并五苯(pentacence),电荷载体迁移率呈0.6cm2/V-秒(N.Jackson,54th Annual Device Research Conference Digest1996),但存在一些问题,驱动电压大于100V,并且亚阈值电压是非晶形硅的50倍。
为了控制驱动电压和降低阈电压,针对采用高的k绝缘体进行非常少量的研究,不仅在硅TFT领域,而且在有机硅TFT领域(美国专利No.5,981,970,Science,Vol.283,p822~824,Organic Electronics 3,65~72)。例如,铁电绝缘材料,例如BaxSr1-xTiO3(BST)、Ta2O5、Y2O3或TiO2,以及具有介电比大于15的无机绝缘材料,例如PbZrxTi1-xO3(PZT)、Bi4Ti3O12、BaMgF4、SrBi2(Ta1-xNbx)2O9、Ba(Zr1-xTix)O3(BZT)、BaTiO3或SrTiO3已有报道(美国专利No.5,946,551)。采用这些材料的装置既可以采用沉积法(CVD,溅射法或ALD法)也可以采用溶胶-凝胶法进行涂布。已有报导装置的电荷载体迁移率小于0.6cm2/V-秒和驱动电压小于-5V。然而,就各种基体而论,因为大部分制造方法中要求高温(200~400℃),这限制了使用。还有,它难以采用印刷法制造装置。目前,含聚酰亚胺、BCB(苯并环丁烯)、光敏丙烯酰基等的有机绝缘膜,不能与无机绝缘体的性质相适应(美国专利No.6,232,157)。
目前,在各种驱动装置上使用有机TFT已作了很多研究。然而,为了实现有机TFT的实际使用,不仅液晶显示器(LCD)而且含有机电致发光装置的可挠性显示器,要求电荷载体迁移速率高于10cm2/V-秒。另外,为了简便和成本降低,要求在制造方法中,通过全印刷法或全旋涂法在塑料基材上涂布绝缘膜。针对具有简单的制造方法和改进的电荷载体迁移速率的有机绝缘体己进行了许多研究。焦点是提供一种形成有机活性层的有利条件,与无机绝缘膜相比,由此使有机活性层的颗粒大小增加。通常,这些有机绝缘膜显示的介电比为3~4,其要求30~50V的高驱动电压和15~20V的高阈值电压。
为了增加介电比,有人尝试在绝缘聚合物中分散纳米级大小的铁电陶瓷粒子(美国专利No.6,586,791)。但这方法也存在某些问题。陶瓷粒子影响有机活性层的形成,从而降低电荷载体迁移率或增加泄漏电流。这就需要使用具有良好介电性的另外绝缘膜。因此,在现有技术中,必须开发出具有高介电比和优良的绝缘性的并且增加半导体显示性的有机TFT。
本发明简述
鉴于上述问题进行本发明,本发明的目的是提供一种用于制造有机绝缘体的组合物,该有机绝缘体呈现低的阈值和驱动电压以及高的电荷载体迁移率。
本发明的另一目的是提供一种采用上述组合物制造有机绝缘体的方法。
本发明的又一目的是提供一种通过上述方法制造有机绝缘体。
本发明的再一目的是提供一种从上述组合物制造的有机TFT。
按照本发明的目的,提供一种用于制造有机绝缘体的组合物,该组合物含有(i)至少1种有机-无机杂化材料;(ii)至少1种有机金属化合物及/或有机聚合物;(iii)至少1种用于溶解组分(i)和(ii)的溶剂。
按照本发明的另一目的,提供一种用于制造有机绝缘体的方法,该法包括:用上述组合物涂布基材以形成绝缘膜;以及固化绝缘膜。
按照本发明的又一目的,提供一种用上述方法制造的有机绝缘体。
按照本发明的再一目的,提供一种有机薄膜晶体管,该晶体管含有:基体;门电极;绝缘膜;有机活性层;源-漏电极,其中,绝缘膜是上述有机绝缘体。
附图说明
本发明的上述及其他目的、特性和其他优点,通过结合附图的下列详细说明将更清楚地理解。其中:
图1是常用的薄膜晶体管的简略截面图;
图2是说明实施例5制造的有机TFT驱动特性图;
图3是说明实施例7制造的有机TFT驱动特性图。
本发明的详细说明
下面,对本发明进行更详细地的说明。
用于本发明有机绝缘体的组合物,包括:(i)至少1种有机-无机杂化材料;(ii)至少1种有机金属化合物及/或有机聚合物;(iii)至少1种用于溶解上述2种组分的溶剂。
在本发明中,有机-无机杂化材料可以是有机硅烷化合物或在有酸或碱催化剂存在下,通过有机硅烷化合物的水解和缩聚而形成的有机-无机杂化聚合物。优选的是,有机-无机杂化材料可以用式1、2或3表示的有机硅烷化合物,或在酸或碱催化剂和水存在下,在有机溶剂中,通过用式1、2或3表示的有机硅烷化合物的水解和缩聚而形成的有机-无机杂化聚合物:
式1
SiX1X2X3X4
式2
R1SiX1X2X3
式3
R1R2SiX1X2
在式1~3中,R1及R2各独立地表示氢原子、C1-10烷基、C3-10环烷基、C6-15芳基、C2-30丙烯酰基或含环氧基的烷基、环烷基或芳基;以及,
X1、X2、X3及X4各独立地表示卤原子或C1-5烷氧基。
作为用于制造有机-无机杂化聚合物的酸催化剂,可以举出盐酸、硝酸、苯磺酸、草酸、甲酸等。作为碱催化剂,可以举出氢氧化钾、氢氧化钠、三乙胺、碳酸氢钠、吡啶等。在水解和缩聚中使用的催化剂对单体总量的摩尔比,优选为0.000001∶1~10∶1。
在制造有机-无机杂化聚合物时使用的水对单体总量的摩尔比,优选为1∶1~1000∶1。
在制造有机-无机杂化聚合物时使用的有机溶剂的非限制实例,包括脂肪烃溶剂例如己烷;芳香烃溶剂例如苯甲醚、1,3,5-三甲基苯和二甲苯;酮类溶剂例如甲基异丁基酮、1-甲基-2-吡咯烷酮、环己酮和丙酮;醚类溶剂例如四氢呋喃和异丙醚;乙酸酯类溶剂例如乙酸乙酯、乙酸丁酯及丙二醇甲醚乙酸酯;醇类溶剂例如异丙醇和丁醇;酰胺类溶剂例如二甲基乙酰胺和二甲基甲酰胺;硅类溶剂;以及它们的混合物。
按照本发明,水解和缩聚优选是在温度0~200℃下进行0.1~100小时。
因此,制造的有机/无机杂化聚合物的Mw优选为3,000~300,000的范围。
按照本发明,有机金属化合物是指具有良好的绝缘性和高介电比的化合物,其包括具有介电比4或更大的金属氧化物。有机金属化合物的非限制实例,包括钛类化合物例如正丁醇钛(IV)、叔丁醇钛(IV)、乙醇钛(IV)、2-乙基己醇钛(IV)、异丙醇钛(IV)、(二-异丙氧基)双(乙酰基丙酮酸酯)钛(IV)、双(乙酰基丙酮酸酯)氧化钛(IV)、三氯三(四氢呋喃)钛(III)、三(2,2,6,6-四甲基-3,5-庚二酸酯基)钛(III)、(三甲基)五甲基环戊二烯基钛(IV)、五甲基环戊二烯基三氯化钛(IV)、五甲基环戊二烯基三甲氧基钛(IV)、四氯双(环已基巯基)钛(IV)、四氯双(四氢呋喃)钛(IV)、四氯二胺钛(IV)、四(二乙基氨基)钛(IV)、四(二甲基氨基)钛(IV)、双(叔丁基环戊二烯基)二氯化钛、双(环戊二烯基)二羰基钛(II)、双(环戊二烯基)二氯化钛、双(乙基环戊二烯基)二氯化钛、双(五甲基环戊二烯基)二氯化钛、双(异丙基环戊二烯基)二氯化钛、三(2,2,6,6-四甲基-3,5-庚二酸酯基)氧钛(IV)、三异丙氧基氯钛、环戊二烯基三氯化钛、二氯双(2,2,6,6-四甲基-3,5-庚二酸酯基)钛(IV)、二甲基双(叔丁基环戊二烯基)钛(IV)、和二(异丙氧基)双(2,2,6,6-四甲基-3,5-庚二酸酯基)钛(IV);锆类化合物例如正丁醇锆(IV)、叔丁醇锆(IV)、乙醇锆(IV)、异丙醇锆(IV)、正丙醇锆(IV)、乙酰基丙酮酸锆(IV)、六氟乙酰基丙酮酸锆(IV)、三氟乙酰基丙酮酸锆(IV)、四(二乙基氨基)锆、四(二甲基氨基)锆、四(2,2,6,6-四甲基-3,5-庚二酸酯基)锆(IV)、以及硫酸锆(IV)四水合物;铪类化合物例如正丁醇铪(IV)、叔丁醇铪(IV)、乙醇铪(IV)、异丙醇铪(IV)、异丙醇一异丙酸铪(IV)、乙酰基丙酮酸铪(IV)、四(二甲基氨基)铪;以及,铝类化合物例如正丁醇铝、叔丁醇铝(IV)、仲丁醇铝、乙醇铝、异丙醇铝、乙酰基丙酮酸铝、六氟乙酰基丙酮酸铝、三氟乙酰基丙酮酸铝、以及三(2,2,6,6-四甲基-3,5-庚二酸酯基)铝。
本发明组合物中使用的有机金属化合物的比例,基于100重量份的有机-无机杂化材料,优选为1~300重量份,更优选5~100重量份。当该比例大于300重量份时,产生过量的泄漏电流,致使Ion/Ioff比和电荷载体迁移率恶化。当该比例小于1重量份时,难以形成薄膜,并且电荷载体迁移率明显下降。
上述有机聚合物包括许多呈现绝缘性质的聚合物。绝缘性有机聚合物的非限制性实例包括聚酯、聚碳酸酯、聚乙烯醇、聚乙烯基缩丁醛、聚缩醛、聚芳化物、聚酰胺、聚酰胺酰亚胺、聚醚酰亚胺、聚亚苯基醚、聚亚苯基硫、聚醚砜、聚醚酮、聚邻苯二酰胺、聚醚腈、聚醚砜、聚苯并咪唑、聚碳化二酰亚胺、聚硅氧烷、聚甲基丙烯酸甲酯、聚甲基丙烯酰胺、腈橡胶、丙烯酸类橡胶、聚四氟乙烯、环氧树脂、酚树脂、蜜胺树脂、尿素树脂、聚丁烯、聚戊烯、聚(乙烯-共聚-丙烯)、聚(乙烯-共聚-丁二烯)、聚丁二烯、聚异戊二烯、聚(乙烯-共聚-丙烯二烯)、丁基橡胶、聚甲基戊烯、聚苯乙烯、聚(苯乙烯-共聚-丁二烯)、氢化聚(苯乙烯-共聚-丁二烯)、氢化聚异戊二烯以及氢化聚丁二烯。
本发明的组合物中使用的有机聚合物比例,基于100重量份的有机-无机杂化材料优选为0.01~50重量份,更优选0.1~25重量份。当该比例大于50时,装置的性质明显恶化。当该比例低于0.01重量份时,通过旋涂法难以形成薄膜。
在本发明中,有机绝缘体的电学性质,例如介电常数、泄漏电流等可通过改变有机-无机杂化材料的比例以及组合物中的有机金属化合物及/或有机聚合物加以控制。
本发明组合物中使用的有机溶剂的非限制性实例,包括脂肪烃溶剂例如己烷;芳香烃溶剂例如苯甲醚、1,3,5-三甲基苯和二甲苯;酮类溶剂例如甲基异丁基酮、1-甲基-2-吡咯烷酮、环己酮和丙酮;醚类溶剂例如四氢呋喃和异丙醚;乙酸酯类溶剂例如乙酸乙酯、乙酸丁酯及丙二醇甲醚乙酸酯;醇类溶剂例如异丙醇和丁醇;酰胺类溶剂例如二甲基乙酰胺和二甲基甲酰胺;硅类溶剂;以及它们的混合物。
有机溶剂的用量应足以使固体成分,包括有机-无机杂化材料和有机金属化合物,均匀地涂布在基材表面。在这方面,组合物中的有机溶剂含量为20~99.9重量%,优选70~95重量%。如果有机溶剂的浓度小于20重量%,固体成分部分不溶解。另一方面,如果有机溶剂的含量大于99.9重量%,最终的薄膜可以薄到1000或更低。
在本发明中,提供一种制造有机绝缘体的方法,该法包括:在基体上涂布上述组合物以及固化涂布的膜。本发明中涂布方法的非限制性实例包括:旋涂法、浸涂法、印刷法、喷涂法、和辊涂法,而旋涂法是最优选的。固化是在70~150℃温度下加热基体0.5~2小时而进行。
按照上述方法制造的有机绝缘体显示优良的绝缘性。当它用到TFF时,可以获得高的电荷载体迁移率、低的驱动和阈电压以及优良的Ion/Ioff比。尤其是,采用湿法例如印刷法或旋涂法可制得绝缘膜,因而所制造的有机TFT的性质方面可与使用CVD法制造的无机绝缘膜的TFT相匹敌。
此外,本发明提供一种含有上述有机绝缘体作为绝缘层的有机TFT。图1示出一般的有机薄膜晶体管(TFT)的简图。该TFT包括:基体1;绝缘膜2;有机活性膜3;门电极4;源电极5和漏电极6。但本发明可用于各神类型的TFT而不限于图1所示的TFT。
优选的是用塑料、玻璃、硅等制造基材。
在本发明的有机TFT中,有机活性层可用任何一种己知是有机半导体材料包括导电聚合物的任何材料进行制造。优选的是有机活性层由下列材料制造:并五苯、酞菁铜、聚噻吩、聚苯胺、聚乙炔、聚吡咯、聚亚苯基亚乙烯基或其衍生物,但又不限于此。
门电极和源电极/漏电极是由金(Au)、银(Ag)、铝(Al)、镍(Ni)和铟锡氧化物(ITO)制造,但又不限于此。
下面,参照下列实施例更详细地说明本发明。然而,这些实施例仅用于说明而不限制本发明的范围。
实施例1
采用甲基丙烯酰氧基丙基三甲氧基硅烷(下面称作MAPTMS)的聚合物作为有机-无机杂化材料。把80.531mmol(20g)的MAPTMS放入烧瓶中,然后,把去离子水中的盐酸溶液3.5ml(0.001021 mol盐酸/1ml水)导入烧瓶中。该混合物于室温下反应30分钟,然后,为了抑制反应,往混合物中添加四氢呋喃100ml和二乙醚100ml。把反应混合物转移至分液漏斗并用水洗涤3次。洗涤后,减压下使挥发性物质蒸发,产生无色的粘稠的液体MAPTMS聚合物。把该聚合物溶于15ml丙酮,并用0.2μm尺寸的过滤器过滤该溶液,以便脱除细小的粉末和杂质。然后,分离液相,在减压下脱除挥发性材料,得到13g无色液体聚合物。
把MAPTMS聚合物和四丁氧基钛(Ti(OC4H9)4)的混合物(70∶30重量比)溶于丁醇,浓度为10重量%。用旋涂法把该溶液涂布在玻璃基体上,以形成厚7000的膜,然后,把该膜于70℃热固化1小时,再于150℃固化30分钟,以产生绝缘膜。另外,通过OMBD(有机分子束沉积)沉积700的并五苯。这时,在2×10-6乇真空压力、基体温度80℃和沉积速率0.3A/秒的条件下进行沉积。然后,用具有通道长度100μm和通道宽度1μm的荫罩,在并五苯活性膜上形成源-漏电极,得到最终的有机TFT。所制造的有机TFT的电荷载体迁移率、阈值电压及Lon/Loff比按照下列说明进行测量,并示于表1。
(1)电荷载体迁移率、阈值电压
装置的电荷载体迁移率,通过下列公式(4)由(ISD)1/2和VG关系图的斜率进行计算,其中,按照下列饱和区域(1)和(2)的电流方程作图,并通过下列方程(3)计算钭率:
在上述方程(1)~(4)中,ISD:源-漏电流;μ或μFET:电荷载体迁移率;C0:绝缘层的电容;W:通道宽度;L:通道长度;VG:门电压;以及,VT:阈电压。
阈电压(VT)从VG轴横切表示(ISD)1/2和VG关系图的直线部分的延长线的交叉点得到。当阈电压的绝对值近似零时,电能消耗下降。
(2)Ion/Ioff比
Ion/Ioff比从启动时的最大电流和关闭时的最小电流比进行测定,并用下列方程(5)表示:
在上述方程(5)中,Ion:最大电流;Ioff:关闭状态的泄漏电流;μ:电荷载体迁移速率;σ:活性层导电率;q:电荷;NA:电荷密度;t:绝缘层厚度;C0:绝缘层的电容;VD:漏电压。
如由该方程所示,介电常数愈大以及介电膜的厚度愈小,所得到的Ion/Ioff比愈大。因此,介电膜的种类和厚度是决Ion/Ioff比的决定性因素。
表1
MAPTMS聚合物(g) | Ti(OC4H9)4(g) | Ion/Ioff比 | 电荷载体迁移率(cm2/V·s) | 阈电压(V) | |
实施例1 | 0.7 | 0.3 | 1000 | 15 | -4 |
如表1所示,有机TFT呈现大于10的电荷载体迁移率,其在已知的绝缘材料中是最大的值。另外,阈电压小于-5V,导致低电压驱动特性。
实施例2
制备7重量%的聚乙烯基丁醛(下面称作PVB)的丁醇溶液。以表2中所示的比例混合MAPTMS聚合物和PVB溶液,并用该混合物制造绝缘膜。形成绝缘膜的方法和制造有机TFT的方法都按照实施例1中同样的方法进行。另外,所得到的有机TFT的性质按照实施例1中同样的方法进行测量。
表2
PVB溶液(g) | MAPTMS聚合物(g) | Ion/Ioff比 | 电荷载体迁移率(cm2/V·s) | 阈电压(V) | |
实施例2-1 | 0.75 | 0.25 | 300,00 | 8 | -11.45 |
实施例2-2 | 0.5 | 0.5 | 200,00 | 8 | -8.7 |
如表2所示,有机TFT呈现大于105的Ion/Ioff比,大于8cm2/V·s的电荷载体迁移率,相应显示良好的晶体管特性。
实施例3
制备7重量%的PVB的丁醇溶液。按表3中所示的比例混合PVB溶液、MAPTMS聚合物和钛酸四丁酯,并把该混合物在铝基材上旋转涂布到2000厚的膜,然后,将该膜于70℃固化1小时和于150℃固化30分钟,以制成绝缘膜。在该绝缘膜上是沉积铝膜以形成M-I-M(金属-绝缘体-金属)的电容器结构。采用它,在100kHz测量单位面积的电容C0。从测得的介电比,按下式(6)测定介电常数:
C0=εε0(A/d) (6)
其中,C0是介电电容;ε和ε0分别为介电材料和真空的介电常数;A为装置的面积;以及d为介电材料的厚度。
表3
溶液(g) | Ti(OC4H9)4(g) | MAPTMS聚合物(g) | 介电常数κ | |
实施例3-1 | 0.1g | 0.25g | 0.25g | 5.82 |
实施例3-2 | 0.1g | 0.25g | 0.75g | 5.1 |
实施例3-3 | 0.1g | 0.75g | 0.25g | 7.1 |
实施例3-4 | 0.1g | 0.75g | 0.75g | 6.2 |
实施例4
制备7重量%的PVB的丁醇溶液。按表4中所示的比例混合PVB溶液、MAPTMS聚合物和钛酸四丁酯,并使用该混合物制造绝缘膜。形成绝缘膜的方法和制造有机TFT的方法按照实施例1中同样的方法来进行。另外,所得到的有机TFT的性质按照实施例1中同样的方法来进行测量。
表4
PVB溶液(g) | Ti(OC4H9)4(g) | MAPTMS聚合物(g) | Ion/Ioff比 | 电荷载体迁移率(cm2/V·s) | 阈电压(V) | |
实施例4-1 | 0.1 | 0.25 | 0.25 | 395 | 8.26 | -2.2 |
实施例4-2 | 0.1 | 0.25 | 0.75 | 67000 | 30 | -3.1 |
实施例4-3 | 0.1 | 0.75 | 0.25 | 12 | 0.65 | -0.3117 |
实施例4-4 | 0.1 | 0.75 | 0.75 | 1260 | 6.61 | -1 |
实施例4-5 | 0.3 | 0.5 | 0.5 | 1990 | 4.31 | -2.3 |
实施例4-6 | 0.5 | 0.25 | 0.25 | 2120 | 3.25 | -2.53 |
实施例4-7 | 0.5 | 0.25 | 0.75 | 70400 | 24.5 | -5.72 |
实施例4-8 | 0.5 | 0.75 | 0.25 | 16.2 | 1.48 | -1.37 |
实施例4-9 | 0.5 | 0.75 | 0.75 | 1180 | 3.77 | -0.485 |
在表4中可以看出,有机钛的增加导致电荷载体迁移率和Ion/Ioff比的降低,而阈电压也下降。此外,还看出MAPTMS聚合物的增加导致电荷载体迁移速率和Ion/Ioff比的增加,电荷载体迁移率增加到100倍、Ion/Ioff比增加到10000倍。
实施例5
往PVB溶液(7重量%)0.15g和钛酸四丁酯0.35g的混合物中分别混入0.1g、0.25g、0.5g及0.75g MAPTMS聚合物,并用这些混合物制造绝缘膜。形成绝缘膜的方法和制造有机TFT的方法按照实施例1中同样的方法进行。所得到的TFT的驱动特性示于图2。在图2中,随着有机-无机杂化材料量的增加,泄漏电流降低,通过的电流(on-current)及电荷载体迁移率增加。阈电压低于-5V,其比常用的有机绝缘体低。
实施例6
按表5中所示的比例,混合MAPTMS聚合物、环氧树脂及钛酸四丁酯,并往其中加入丁醇,制成溶液。按照实施例1同样的方式,用旋涂法把该溶液涂布在基材上,制成绝缘膜,然后,按照表5中所示的条件将其固化。按照实施例1的同样方式,制造有机TFT,有机TFT的性质按照实施例1的同样方式进行测量。
表5
环氧树脂(g) | Ti(OC4H9)4(g) | MAPTMS聚合物(g) | 固化条件 | κ | Ion/Ioff比 | 电荷载体迁移率(cm2/V·s) | 阈电压(V) | |
实施例6-1 | 0.05 | 0.45 | 0.25 | 加热固化(150℃) | 5.75 | 100 | 0.2 | -5 |
实施例6-2 | 0.05 | 0.45 | 0.5 | 加热固化(150℃) | 5.53 | 1000 | 6 | -3 |
实施例6-3 | 0.05 | 0.45 | 0.75 | 加热固化(150℃) | 5.76 | 9600 | 25 | -4.2 |
实施例6-4 | 0.05 | 0.45 | 0.25 | UV固化(600W,10min) | 5.9 | 31 | 0.1 | 0.1 |
实施例6-5 | 0.05 | 0.45 | 0.5 | UV固化(600W,10min) | 5.57 | 121000 | 30 | -6.5 |
实施例6-6 | 0.05 | 0.45 | 0.75 | UV固化(600W,10min) | 5.65 | 720000 | 47 | -9 |
在表5中,可以看到使用环氧树脂,导至和使用PVB时类似的驱动性质。还发现电学性质不仅随着所用的有机-无机杂化材料的量而且也随着固化方法而变化。在实施例6-6的情况下,该装置的电荷载体迁移率及Ion/Ioff比显示高值。
实施例7
往PVB溶液(7重量%)0.15g和钛酸四丁酯0.35g的混合物中加入0.75gMAPTMS,并把该混合物溶于丁醇以制造10重量%溶液。按照实施例1中同样的方法旋涂该溶液。按照实施例1中同样的方法进行有机TFT的制造,按照实施例中同样的方法测量得到的有机TFT的性质。从图3中,计算的Ion/Ioff比为约104以及电荷载体迁移速率为约3~5cm2/V·s。此时,Ion/Ioff比及电荷载体迁移速率降低至某种程度,但看到所制得的有机TFT,与现有的有机绝缘体相比,具有良好的性质。
为了说明的目的,尽管本发明公开了优选的实施方案,但在不偏离所附权利要求中所公开的本发明的范围和精神,可进行各种改进、添加和置换。
Claims (15)
1.一种用于制造有机绝缘体的组合物,其包括:(i)至少1种有机-无机杂化材料;(ii)至少1种有机金属化合物及/或有机聚合物;(iii)至少1种用于溶解上述组分(i)和(ii)的溶剂。
2.按照权利要求1的组合物,其中,有机-无机杂化材料是有机硅烷化合物或在有酸或碱催化剂存在下,通过有机硅烷化合物的水解和缩聚而形成的聚合物。
3.按照权利要求2的组合物,其中,有机硅烷化合物选自用下列式1~3表示的化合物:
式1
SiX1X2X3X4
式2
R1SiX1X2X3
式3
R1R2SiX1X2
其中,R1及R2各独立地表示氢原子、C1-10烷基、C3-10环烷基、C6-15芳基、C2-30丙烯酰基或含环氧基的烷基、环烷基或芳基;以及,
X1、X2、X3、X4各独立地表示卤原子或C1-5烷氧基。
4.按照权利要求1的组合物,其中,有机金属化合物是选自钛类化合物、锆类化合物、铪类化合物及铝类化合物。
5.按照权利要求4的组合物,其中,有机金属化合物选自正丁醇钛(IV)、叔丁醇钛(IV)、乙醇钛(IV)、2-乙基己醇钛(IV)、异丙醇钛(IV)、(二-异丙氧基)双(乙酰基丙酮酸酯)钛(IV)、双(乙酰基丙酮酸酯)氧化钛(IV)、三氯三(四氢呋喃)钛(III)、三(2,2,6,6-四甲基-3,5-庚二酸酯基)钛(III)、(三甲基)五甲基环戊二烯基钛(IV)、五甲基环戊二烯基三氯化钛(IV)、五甲基环戊二烯基三甲氧基钛(IV)、四氯双(环己基巯基)钛(IV)、四氯双(四氢呋喃)钛(IV)、四氯二胺钛(IV)、四(二乙基氨基)钛(IV)、四(二甲基氨基)钛(IV)、双(叔丁基环戊二烯基)二氯化钛、双(环戊二烯基)二羰基钛(II)、双(环戊二烯基)二氯化钛、双(乙基环戊二烯基)二氯化钛、双(五甲基环戊二烯基)二氯化钛、双(异丙基环戊二烯基)二氯化钛、三(2,2,6,6-四甲基-3,5-庚二酸酯基)氧钛(IV)、三异丙氧基氯钛、环戊二烯基三氯化钛、二氯双(2,2,6,6-四甲基-3,5-庚二酸酯基)钛(IV)、二甲基双(叔丁基环戊二烯基)钛(IV)、二(异丙氧基)双(2,2,6,6-四甲基-3,5-庚二酸酯基)钛(IV)、正丁醇锆(IV)、叔丁醇锆(IV)、乙醇锆(IV)、异丙醇锆(IV)、正丙醇锆(IV)、乙酰基丙酮酸锆(IV)、六氟乙酰基丙酮酸锆(IV)、三氟乙酰基丙酮酸锆(IV)、四(二乙基氨基)锆、四(二甲基氨基)锆、四(2,2,6,6-四甲基-3,5-庚二酸酯基)锆(IV)、硫酸锆(IV)四水合物、正丁醇铪(IV)、叔丁醇铪(IV)、乙醇铪(IV)、异丙醇铪(IV)、异丙醇一异丙酸铪(IV)、乙酰基丙酮酸铪(IV)、四(二甲基氨基)铪、正丁醇铝、叔丁醇铝(IV)、仲丁醇铝、乙醇铝、异丙醇铝、乙酰基丙酮酸铝、六氟乙酰基丙酮酸铝、三氟乙酰基丙酮酸铝、以及三(2,2,6,6-四甲基-3,5-庚二酸酯基)铝。
6.按照权利要求1的组合物,其中,有机金属化合物的比例,基于100重量份的有机-无机杂化材料为1~300重量份。
7.按照权利要求1的组合物,其中,有机聚合物选自聚酯、聚碳酸酯、聚乙烯醇、聚乙烯基缩丁醛、聚缩醛、聚芳化物、聚酰胺、聚酰胺酰亚胺、聚醚酰亚胺、聚亚苯基醚、聚亚苯基硫、聚醚砜、聚醚酮、聚邻苯二酰胺、聚醚腈、聚醚砜、聚苯并咪唑、聚碳化二酰亚胺、聚硅氧烷、聚甲基丙烯酸甲酯、聚甲基丙烯酰胺、腈橡胶、丙烯酸橡胶、聚四氟乙烯、环氧树脂、酚树脂、蜜胺树脂、尿素树脂、聚丁烯、聚戊烯、聚(乙烯-共聚-丙烯)、聚(乙烯-共聚-丁二烯)、聚丁二烯、聚异戊二烯、聚(乙烯-共聚-丙烯二烯)、丁基橡胶、聚甲基戊烯、聚苯乙烯、聚(苯乙烯-共聚-丁二烯)、氢化聚(苯乙烯-共聚-丁二烯)、氢化聚异戊二烯以及氢化聚丁二烯。
8.按照权利要求1的组合物,其中,有机聚合物的比例基于100重量份的有机-无机杂化材料为0.01~50重量份。
9.按照权利要求1的组合物,其中,溶剂选自脂肪烃溶剂;芳香烃溶剂;酮类溶剂;醚类溶剂;乙酸酯类溶剂;醇类溶剂;酰胺类溶剂;硅类溶剂;以及它们的混合物。
10.按照权利要求1的组合物,其中,组合物中的有机溶剂含量为20~99.9重量%。
11.一种制造有机绝缘体的方法,其中包括:
用权利要求1的组合物涂布基材以形成绝缘膜;以及
固化绝缘膜。
12.按照权利要求11的方法,其中,用旋涂法、浸涂法、印刷法、喷涂法或辊涂法涂布绝缘膜。
13.按照权利要求11的方法,其中,绝缘膜于70~150℃下固化0.5~2小时。
14.一种按照权利要求11的方法制造的有机绝缘体。
15.一种有机薄膜晶体管,其中包括:基材;门电极;绝缘膜;有机活性层和源-漏电极,其中绝缘膜是权利要求14的有机绝缘体。
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- 2004-10-06 EP EP20040256183 patent/EP1524299B1/en not_active Expired - Fee Related
- 2004-10-06 DE DE200460027980 patent/DE602004027980D1/de active Active
- 2004-10-07 JP JP2004294415A patent/JP4562027B2/ja not_active Expired - Fee Related
- 2004-10-14 CN CN2004100881621A patent/CN1607685B/zh not_active Expired - Fee Related
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2005
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CN101221981B (zh) * | 2007-01-09 | 2010-06-23 | 财团法人工业技术研究院 | 具有混合高介电材料层的电子元件及其制造方法 |
CN105190901A (zh) * | 2013-03-14 | 2015-12-23 | 东丽株式会社 | 场效应晶体管 |
CN105190901B (zh) * | 2013-03-14 | 2018-12-04 | 东丽株式会社 | 场效应晶体管 |
CN107112366A (zh) * | 2015-01-14 | 2017-08-29 | 日本曹达株式会社 | 有机薄膜晶体管 |
CN107112366B (zh) * | 2015-01-14 | 2020-07-10 | 日本曹达株式会社 | 有机薄膜晶体管 |
CN106478952A (zh) * | 2015-08-31 | 2017-03-08 | 三星电子株式会社 | 组合物、电子器件、薄膜晶体管、和电容器 |
CN106478952B (zh) * | 2015-08-31 | 2021-06-01 | 三星电子株式会社 | 组合物、电子器件、薄膜晶体管、和电容器 |
CN110072923A (zh) * | 2016-11-30 | 2019-07-30 | 瀚森有限责任公司 | 用于绝缘带的组合物 |
WO2018227788A1 (zh) * | 2017-06-15 | 2018-12-20 | 北京大学深圳研究生院 | 一种高介电常数的复合材料及其应用 |
US11322701B2 (en) | 2017-06-15 | 2022-05-03 | Peking University Shenzhen Graduate School | High dielectric constant composite material and application thereof |
Also Published As
Publication number | Publication date |
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US20050259212A1 (en) | 2005-11-24 |
KR101012950B1 (ko) | 2011-02-08 |
EP1524299A1 (en) | 2005-04-20 |
KR20050036171A (ko) | 2005-04-20 |
JP2005120371A (ja) | 2005-05-12 |
US8017245B2 (en) | 2011-09-13 |
US20060147715A1 (en) | 2006-07-06 |
JP4562027B2 (ja) | 2010-10-13 |
CN1607685B (zh) | 2012-02-29 |
DE602004027980D1 (de) | 2010-08-19 |
EP1524299B1 (en) | 2010-07-07 |
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