CN105658742B - The composition for ink for including polythiophene for ink jet printing - Google Patents
The composition for ink for including polythiophene for ink jet printing Download PDFInfo
- Publication number
- CN105658742B CN105658742B CN201380080634.6A CN201380080634A CN105658742B CN 105658742 B CN105658742 B CN 105658742B CN 201380080634 A CN201380080634 A CN 201380080634A CN 105658742 B CN105658742 B CN 105658742B
- Authority
- CN
- China
- Prior art keywords
- ink
- composition
- organic solvent
- sulfolane
- polymethyl siloxane
- 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.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 150
- 238000007641 inkjet printing Methods 0.000 title claims abstract description 45
- 229920000123 polythiophene Polymers 0.000 title claims abstract description 23
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000002347 injection Methods 0.000 claims abstract description 11
- 239000007924 injection Substances 0.000 claims abstract description 11
- 239000000976 ink Substances 0.000 claims description 147
- 239000003960 organic solvent Substances 0.000 claims description 30
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 27
- 238000009835 boiling Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000010 aprotic solvent Substances 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims 4
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000009736 wetting Methods 0.000 abstract description 8
- 238000011161 development Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 45
- 239000007789 gas Substances 0.000 description 39
- 238000007639 printing Methods 0.000 description 39
- 210000004027 cell Anatomy 0.000 description 30
- 239000002904 solvent Substances 0.000 description 21
- -1 OLED pixel unit) Wet Substances 0.000 description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 150000002334 glycols Chemical class 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229920005573 silicon-containing polymer Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 230000033001 locomotion Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000003134 recirculating effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WGYZMNBUZFHYRX-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-ol Chemical compound COCC(C)OCC(C)O WGYZMNBUZFHYRX-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical class OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 210000003411 telomere Anatomy 0.000 description 2
- 102000055501 telomere Human genes 0.000 description 2
- 108091035539 telomere Proteins 0.000 description 2
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical class CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 1
- CDXFIRXEAJABAZ-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CDXFIRXEAJABAZ-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- DJNTZVRUYMHBTD-UHFFFAOYSA-N Octyl octanoate Chemical compound CCCCCCCCOC(=O)CCCCCCC DJNTZVRUYMHBTD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- PQAIAZSHCAFIQW-UHFFFAOYSA-N [Au].[Rb].[Ag] Chemical compound [Au].[Rb].[Ag] PQAIAZSHCAFIQW-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010866 blackwater Substances 0.000 description 1
- FFSAXUULYPJSKH-UHFFFAOYSA-N butyrophenone Chemical compound CCCC(=O)C1=CC=CC=C1 FFSAXUULYPJSKH-UHFFFAOYSA-N 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 239000012636 effector Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- IMKMFBIYHXBKRX-UHFFFAOYSA-M lithium;quinoline-2-carboxylate Chemical compound [Li+].C1=CC=CC2=NC(C(=O)[O-])=CC=C21 IMKMFBIYHXBKRX-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 1
- DCZNSJVFOQPSRV-UHFFFAOYSA-N n,n-diphenyl-4-[4-(n-phenylanilino)phenyl]aniline Chemical class C1=CC=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 DCZNSJVFOQPSRV-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- GJWGZSBNFSBUPX-UHFFFAOYSA-N pentyl octanoate Chemical compound CCCCCCCC(=O)OCCCCC GJWGZSBNFSBUPX-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 210000004722 stifle Anatomy 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/02—Polythioethers; Polythioether-ethers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electroluminescent Light Sources (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
The composition for ink comprising polythiophene and polymethyl siloxane is provided, it is formulated for ink jet printing Organic Light Emitting Diode (OLED) hole injection layer (HIL).Additionally provide the method using composition for ink ink jet printing HIL.The composition for ink of layer being used in ink jet printing Organic Light Emitting Diode (OLED) has been proposed.But, the problem of related to insufficient wetting characteristics of composition for ink, has restrained the development of printable ink, because unsuitable wetting causes uneven film to be formed, and therefore cause uneven luminous from the organic light-emitting diode pixel for being incorporated to print film.
Description
The cross reference of related application
This application claims the entitled ink group comprising polythiophene for ink jet printing submitted on October 31st, 2013
The priority of the U.S. Provisional Patent Application No. 61/898343 of compound, entire contents are incorporated herein by quoting.This Shen
It please be that September in 2012 is submitted on the 14th, and require the U.S. Provisional Patent Application No. 61/535 that September in 2011 is submitted on the 16th,
The part of the U.S. Patent Application No. 13/618,157 of the entitled film-forming agents for base material printing of 413 priority continues
Case, entire contents are incorporated herein by quoting.
Background
The composition for ink of ink jet printing layer being used in Organic Light Emitting Diode (OLED) has been proposed.However, with
The problem of insufficient wetting characteristics correlation of composition for ink, which has restrained, (stifle) development of printable ink, because
Cause uneven film to be formed for unsuitable wetting, and therefore cause from the Organic Light Emitting Diode picture for being incorporated to print film
The uneven of element lights.Hindered for OLED application ink-jet printable composition development another challenge be
While keeping sprayable ink formulations, it is impossible to which the living polymer of high concentration is incorporated into ink.
Summary
The composition for ink for including polythiophene is provided, it is formulated for ink jet printing OLED hole injection layer
(HIL).Some embodiments of composition for ink, which are characterised by being used as comprising polymethyl siloxane, pins down agent (pinning
agent).It is otherwise characterized in that comprising the aprotic solvent that can be incorporated to the polythiophene of high concentration in ink.Additionally provide
Use composition for ink ink jet printing HIL method.
An embodiment for forming the method for the HIL for Organic Light Emitting Diode comprises the following steps：In organic hair
The drop (i.e. an at least dropping liquid drips) of ink-jet printing inks composition, the picture on electrode layer in the pixel cell of optical diode
Plain unit is limited by pixel dike (bank)；With the volatile component evaporation for allowing composition for ink, injected so as to form hole
Layer.One embodiment of the composition for ink that can be used in the method includes：Conductive polythiophene；Water；It is at least one
Organic solvent；And polymethyl siloxane, wherein polymethyl siloxane are pind down with providing the contact line of the drop in pixel cell
Amount is present.
Some embodiments of composition for ink include：Poly- (3,4- ethyldioxythiophenes)；Water；It is at least one organic molten
Agent, it has the surface tension for being not more than 55 dynes/cm at 25 DEG C, the viscosity and at least at 25 DEG C no more than 15 cPs
200 DEG C of boiling point；And polymethyl siloxane.At least one organic solvent can be such as sulfolane.
When checking the following drawings, detailed description and appended claims, other principal characters of the invention and excellent
Point will become clear and definite for those skilled in the art.
Brief description
The exemplary of the present invention will hereinafter be described in reference to the drawings, wherein identical numeral represents identical
Element.
Fig. 1 is the block diagram for illustrating OLED ink-jet printing systems.
Fig. 2 is the schematic diagram for the gas confinement system that can accommodate the print system shown in Fig. 1.
Fig. 3 is included in the schematic diagram of the multiple OLED arranged in the matrix of pixel cell flat-panel monitor, each picture
Plain unit is limited by pixel dike.
Fig. 4 A are the composition for ink pind down in OLED pixel unit of the polymethyl siloxane comprising 0.08 wt.%
Microphoto image.
Fig. 4 B are the black and white line charts of the microphoto in Fig. 4 A.
Fig. 5 A are free from the microphoto image of the composition for ink of the spilling OLED pixel unit of polymethyl siloxane.
Fig. 5 B are the black and white line charts of the microphoto in Fig. 5 A.
Fig. 6 A are free from the microphoto image of the composition for ink of the dewetting OLED pixel unit of polymethyl siloxane.
Fig. 6 B are the black and white line charts of the microphoto in Fig. 6 A.
Fig. 7 A are by with by the use of the OLED pictures comprising polymethyl siloxane as the HIL for the ink compositions print for pining down agent
The luminous microphoto of element transmitting.
Fig. 7 B are the black and white line charts of the microphoto in Fig. 7 A.
Fig. 8 A are the luminous microphotos by OLED pixel emission, wherein HIL be by the use of comprising polymethyl siloxane as
Agent and sulfolane are pind down as the ink compositions print of organic solvent.
Fig. 8 B are the black and white line charts of the microphoto in Fig. 8 A.
Fig. 9 A are the luminous microphotos by OLED pixel emission, wherein HIL be by the use of comprising polymethyl siloxane as
Agent and 1,3- propane diols are pind down as the ink compositions print of organic solvent.
Fig. 9 B are the black and white line charts of the microphoto in Fig. 9 A.
Figure 10 be as described in example 2 above, before and after 30 minute free time of inkjet printing nozzle, combination of inks
The droplet size of thing relative to the time figure.
Figure 11 be as described in example 2 above, before and after 30 minute free time of inkjet printing nozzle, combination of inks
The liquid drop speed of thing relative to the time figure.
Figure 12 be as described in example 2 above, before and after 30 minute free time of inkjet printing nozzle, combination of inks
The drop angle of thing relative to the time figure.
It is described in detail
The composition for ink for including polythiophene is provided, it is formulated for ink jet printing OLED HIL.Additionally providing makes
With composition for ink ink jet printing HIL method.
Composition for ink is characterised by that the conductive polythiophene of high concentration is for example poly- (3,4- ethyldioxythiophenes)
(PEDOT), additionally providing makes them be very suitable for the profit being ink-jet printing on pixelation base material (such as OLED pixel unit)
Wet, injection and lag characteristic.In addition, the composition for ink provide thickness with high uniformity and homogeneity composition through printing
HIL.Therefore, for incorporating them into OLED therein, the HIL through printing contributes to the light emittance profile of high uniformity.By
The printability for the enhancing that the composition for ink provides can be at least partially attributed to, under appropriate concentration, poly- methyl silicon
The contact line that oxygen alkane can serve as the drop of pixel cell ink inside composition pins down the realization of agent.Led by providing contact line
System, polymethyl siloxane ensure to deposit to the trace (footprint) of the drop of the composition for ink in pixel cell in drying
Keep from its original form not changing during process.
One basic embodiment of composition for ink is comprising conductive polythiophene, polymethyl siloxane, at least one
The aqueous solution of organic solvent and water.A basic embodiment of OLED HIL method is formed using a kind of composition for ink
Including making conductive material (i.e. anode) of the droplet deposition of composition for ink in the pixel cell of organic LED array
Layer on, and allow the volatile component of composition for ink to evaporate, the step of leaving solid HIL.Permission volatile component (such as
Water and organic solvent) evaporation the step of can by make the composition for ink of printing be subjected to depressurize (being exposed to vacuum),
Promoted by making the composition for ink of printing exposed to the combination of high temperature or both.
Polymethyl siloxane is the silicone oil by siloxane polymerization.They are also referred to as methyl hydrogen siloxane or methyl silica
Alkane.Polymethyl siloxane is commercially available, and by Botanigenics (Northridge, CA) with trade name
Botanisil is sold as surfactant.These include Botanisil AD-13, AM-14, ATC-21, BPD-100,
CD-80、CD-90、CE-35、CM-12、CM-13、CM-70、CP-33、CPM-10、CS-50、CTS-45、DM-60M、DM-85、
DM-90、DM-91、DM-92、DM-93、DM-94、DM-95、DM-96、DM-97、DTS-13、DTS-35、GB-19、GB-20、GB-
23rd, GB-25, GB-35, L-23, ME-10, ME-12, PSS-150, PT-100, S-18, S-19, S-20, TSA-16 and TSS-1.
Polymethyl siloxane can with trade name SilSense be obtained from Lubrizol Corporation (Wickliffe,
Ohio).These include SilSense Copolyol-1 Silicone (PEG-33 (and) PEG-8 polydimethylsiloxanes
Alkane (and) PEG 14), SilSense DW-18 Silicone (dimethyl silicone polymer PEG-7 isostearates),
SilSense SW-12 Silicone (dimethyl silicone polymer PEG-7 cocounut oil acid esters), SilSense IWS (poly- two
Methylsiloxane alcohol ester dimethiconol stearate), SilSense A-21 Silicone (PEG-7 ammonia ends
Dimethyl silicone polymer), SilSense PE-100 Silicone (dimethyl silicone polymer PEG-8 phosphates) and
Ultrabee WD Silicone (dimethyl silicone polymer PEG-8 beeswaxs).
In the composition for ink of the present invention, the amount of polymethyl siloxane is carefully controlled so that polymethyl siloxane fills
When contact line pins down agent.This is important, because the composition for ink drop that it prevents from pining down is from the part dike of pixel cell
Depart from (pull away) (dewetting), it overflows with the other parts in pixel cell sometimes.It also prevents composition for ink
It is deposited in the side of pixel cell or sprawls beyond pixel cell, as will be occurred in the case of the more complete wetting.
The composition for ink can be used for forming HIL on a variety of OLED electrode materials.Most commonly, electrode base material will wrap
Containing transparent conductive material, such as transparent conductive oxide (TCO) or silicon.Polymethyl siloxane in composition for ink
Appropriate concentration range by the property depending on following base material.However, for given base material, polymethyl siloxane is provided and connect
The concentration range that tactile line pins down can by observe with different polymethyl siloxane concentration ink droplets wetting behavior come
Measure, the ink droplets are poured into a mould via drop（casting）Method is applied to surface.The side being illustrated with
Formula, some embodiments of composition for ink of the invention are included no more than 0.15 percentage by weight (wt.%), no more than 0.12
Wt.% or amount no more than 0.1 wt.% polymethyl siloxane, the gross weight meter based on composition for ink.This includes wherein poly-
Methylsiloxane further comprises wherein poly- first with the embodiment of composition for ink existing for 0.02 to 0.15 wt.% amount
Radical siloxane still further comprises wherein polymethyl siloxane with embodiment existing for 0.03 to 0.12 wt.% amount
With embodiment existing for 0.05 to 0.1 wt.% amount, the gross weight meter based on composition for ink.By HIL combination of inks
When thing is printed to the known anode material used in OLED, such scope is suitable.For example, pass through wherein
In the case of the OLED of anode transmitting light (being referred to as bottom-emission), transparent or semitransparent anode material is used.It is transparent
Or translucent anode material can include indium oxide, zinc oxide, tin indium oxide (ITO) and indium zinc oxide (IZO) etc..Wherein
In the case of OLED by cathode luminescence (being referred to as top to light), in transparent anode reflecting layer formed below.
Reflector material includes silver-colored (Ag), silver-palladium-copper (APC), silver-rubidium-gold (ARA), molybdenum-chromium (MoCr) etc..
Aqueous ink composition is further comprising one or more conductive polythiophenes.For example, in the composition for ink
PEDOT and PEDOT and poly- (styrene sulfonate) (poly (styrenesulfonate)) (PEDOT can be included:PSS) mixed
Compound.It is interesting to note that when being combined with appropriate solvent (discussing in greater detail below), what polythiophene can be very high is dense
Degree is comprised in composition for ink.For example, some embodiments of composition for ink include at least 30 wt.% polythiophene,
At least 40 wt.% polythiophene, at least 50 wt.% polythiophene, at least 55 wt.% polythiophene or at least 60 wt.%'s is poly-
Thiophene, the gross weight meter based on composition for ink.In such embodiments, the polythiophene can be PEDOT.
Aqueous ink composition includes at least one organic solvent.For example, composition, which can include, reduces said composition
The solvent of surface tension and/or viscosity, increase the solvent of the delay of the composition for ink of printing, or the group of the solvent of these types
Close.At least one organic solvent can be the solvent with relatively high boiling point, which increase the composition for ink of printing
Delay.This is favourable, because it helps to prevent composition for ink during printing in drying to print nozzles and blocked up
Fill in print nozzles.Such solvent desirably has at least 200 DEG C of boiling point.Even more desirably, they have at least 230 DEG C, extremely
Few 250 DEG C or even at least 280 DEG C boiling point.Glycol and glycols（glycols）As propane diols, pentanediol, diethylene glycol and
Triethylene glycol can be used for the example of the organic solvent of increase delay.Unfortunately, glycol and glycols tend to have phase
To high viscosity and surface tension, it can reduce the sprayable property of the composition for ink comprising them.Therefore, ink of the invention
Some embodiments of water composition are free of glycol and glycolic solvents.In these embodiments, can use has at least
The aprotic solvent of 240 DEG C of boiling point, the viscosity no more than 15 cPs and the surface tension no more than 55 dynes/cm replaces two
Alcohol or glycols.This includes the aprotic solvent with the viscosity no more than 12 cPs, and further comprises having and be not more than
Those of 10 cPs viscosity.For the purpose of present disclosure, the boiling point enumerated refers to boiling point at atmosheric pressure.
The viscosity and surface tension enumerated refer to viscosity and surface tension under printing temperature.For example, if printing occurs in room
Under temperature, then viscosity and surface tension will be those at about 25 DEG C.
Sulfolane, 2,3,4,5- thiophane -1,1- dioxide, also referred to as tetramethylene sulfone, it is relatively high boiling point,
One example of the aprotic solvent of relatively low viscosity, it provides good prolong in the case where not sacrificing sprayable property
Late.In addition, while good sprayable property is kept, the composition for ink comprising sulfolane as organic solvent can be incorporated to
Both solvent and polythiophene of high concentration.For example, the composition for ink can include at least 5 wt.%, at least 10 wt.% or extremely
The sulfolane of few 12 wt.% amount.The suitable concentration range of sulfolane in composition for ink includes about 3 wt.% to about 15
wt.%.Under these sulfolane concentration, composition for ink can be incorporated to the PEDOT (such as 35 to 70 wt.%) of high concentration.
In some composition for ink, sulfolane is main solvent, i.e., its account for the total organic solvent content of composition for ink be more than 50
wt.%.Other suitable solvents include propene carbonate and 1,3- dimethyl -3,4, (the 1H)-pyrimidone of 5,6- tetrahydrochysene -2, are also referred to as
For dimethylpropylene urea.
In order to strengthen the sprayable property of composition, composition for ink can further include and serve as surface tension reducer
Cosolvent.For example, the composition for ink comprising glycol, glycols, sulfolane or other high boiling solvents can be included than that
A little solvents have compared with low surface tension and typically more lower boiling additional solvent.Methyl proxitol or other similar ethers can
For the purpose.
Typically for the composition for ink applied available for ink jet printing, it should adjust（tailor）The composition for ink
Surface tension, viscosity, delay and wetting characteristics to allow composition in temperature (such as the room temperature for printing；~ 25 DEG C) under
It is allocated in no drying to nozzle or in the case of plug nozzle by inkjet printing nozzle.Therefore, optkmal characteristics are by root
Change according to such factor such as jet size, print speed printing speed and printing temperature.Generally, acceptable viscosity will include about 1 to
Those of about 20 cPs, and acceptable surface tension by include below about 50 dynes/cm those.In order to eliminate or minimum
Change spray nozzle clogging, the delay (at room temperature and not under a vacuum) of 20 minutes or longer (such as 30 minutes or longer)
It is desired, wherein delay refers to (such as significantly influenceing the drop speed of image quality the significantly reducing of performance being present
The reduction of degree) before, nozzle can be made to keep not covering and the idle time.
The ink-jet printer for being suitable for printing ink composition is commercially available, and the print head including drop on demand ink jet,
It is available from such as Fujifilm Dimatix (Lebanon, N.H.), Trident International
(Brookfield, Conn.)、Epson (Torrance, Calif.)、Hitachi Data systems Corporation
(Santa Clara, Calif.), Xaar PLC (Cambridge, United Kingdom), and Idanit
Technologies, Limited (Rishon Le Zion, Isreal) and Ricoh Printing Systems
America, Inc. (Simi Valley, CA).It is, for example, possible to use Dimatix Materials PrinterDMP-
3000。
As described in Fig. 1 block diagram, the various embodiments of OLED ink-jet printing systems 100 can be set by multiple
Standby, device and system etc. form, and it allows reliably to be placed into ink droplet on the ad-hoc location on base material.According to system and method
Various embodiments, print system can include, such as, but not limited to base material induction system 110, substrate support 120,
Kinematic system 130, print head set component 140, ink delivery system 150 and control system 160.
It can use base material induction system 110 that OLED base materials are inserted into print system 100 and removed from print system 100
Go.Depending on the various embodiments of print system 100, base material induction system 110 can be mechanical conveyor, have clamper
The base material floating of sub-assembly（floatation）Platform, the automation with end effector, and combinations thereof.In addition, printing
During process, can be able to be come supporting base material, the support meanss by support meanss 120, such as, but not limited to chuck
(chuck) or floating platform.Because printing needs relative motion between print head and base material, print system 100 it is various
Embodiment can have kinematic system 130, and it can be such as but not limited to portal frame (gantry) or split axle (split
Axis) XYZ system.
Print head set component 140 can include at least one printing head apparatus that can be attached to kinematic system 130.Printing
At least one printing head apparatus that brush header combination part 140 includes can have it is at least one can by least one hole with by
The ink jet printing head of the drop of the speed of control, speed and size jet ink composition.According to the print system 100 of this teaching
Various embodiments can have about 1 to about 60 printing head apparatus.In addition, the various embodiments of printing head apparatus can be
There is about 1 to about 30 ink jet printing head in each printing head apparatus, wherein each ink jet printing head can have about 16 to about
2048 nozzles.According to the various embodiments of print head set component 140, each nozzle of each ink jet printing head can discharge
About 0.1pL to about 200pL droplet size.Print head set component 140 with least one ink jet printing head can be with ink
Composition delivery system 150 is in fluid communication, and composition for ink can be supplied to printing by the composition for ink delivery system 150
One or more ink jet printing heads of head sub-assembly 140.
On the various embodiments of kinematic system 130, during printing process, print head set component 140 can be solid
Moved on fixed base material (portal frame type), or in the case where split axle configures, both print head set component 140 and base material may be used
With movement., can be by moving print head set component 140 relative to base material to carry for the various embodiments of split axle configuration
For the control of Z axis., can be with fixing printing head sub-assembly 140 in the further embodiment of kinematic system, and base material can be with
Moved relative to print head set component 140 on X and Y-axis, pass through the Z that the Z axis of print head set component 140 is mobile or passes through base material
Axle movement provides Z axis motion.During printing process, as print head set component 140 moves relative to base material, to be deposited on
The drop of jet ink composition when required position on base material is in orthochronous.
For the various embodiments of print system 100, control system 160 can be used for the function of controlling printing process.
The various embodiments of control system 160 can be by user interface by end-user access.Control system 180 can be used for controlling
Make, send data to base material induction system 110, substrate support 120, kinematic system 130, print head set component 140 and ink
Water delivery system 150, and receive from their data.Control system 160 can be computer system, microcontroller, specially
With integrated circuit (ASIC), field programmable gate array (FPGA), control and data message and can be sent and received
The electronic circuit of execute instruction, and combinations thereof.Control system 160 can include an electronic circuit or for example for offer component
Between communication purpose, in base material induction system 110, substrate support 120, kinematic system 130, print head set component
140 and composition for ink delivery system 150 in multiple electronic circuits for being distributed.
In addition, the various embodiments of the control system 160 of print system 100 can provide data processing, display and report
Accuse preparatory function.All such instrument controlling functions locally can be exclusively used in print system 100, or control system 160 can
To provide all or part of control, analysis and the remote control of function of reporting.Finally, the various embodiment party of printing equipment 100
Case can be contained in Fig. 2 closed system 200.
According to various embodiments, Fig. 2 is the signal of the gas confinement system 200 for the print system 100 that can accommodate Fig. 1
Figure.According to this teaching, the various embodiments of gas confinement system 200 can include gas confinement sub-assembly 250, be sealed with gas
Close the gas purification loop 230 and at least one heat regulating system 240 of the fluid communication of sub-assembly 250.In addition, gas confinement system
Various embodiments can have pressurized inert gas recirculating system 260, it can be supplied for operating various equipment, example
Base material such as OLED print systems floats the inert gas of platform.The various embodiments of pressurized inert gas recirculating system 260
The combination of compressor, air blower and both can be used as the various embodiments of inert gas recirculating system 260
Source.In addition, gas confinement system 200 can have filtering and the circulatory system (not to show in the inside of gas confinement system 200
Show), it can provide the printing environment of substantially low particle together with other components as floated platform.
As described in figure 2, for the various embodiments of the gas confinement sub-assembly 200 according to this teaching, gas
Purification circuit 230 can include outlet line 231, and it removes component 232 from gas confinement sub-assembly 250 to solvent, and so
Afterwards to gas purge system 234.Then purification is made to remove the lazy of solvent and other reactant gas material such as oxygen and vapor
Property gas is back to gas confinement sub-assembly 250 by suction line 233.Gas purification loop 230 can also include appropriate
Conduit and connector, and sensor, such as oxygen, vapor and solvent vapour sensor.Gas circulation can be provided separately
Unit such as fan, air blower or motor etc., or be integrated in such as gas purge system 234 to be returned by gas purification
The recyclegas of road 230.According to the various embodiments of gas confinement sub-assembly, although solvent removal system 232 and gas purification
Independent unit is shown as in the schematic diagram that system 234 is shown in fig. 2, but can be by solvent removal system 232 and gas
Cleaning system 234 accommodates together as single clean unit.Heat regulating system 240 can include, such as, but not limited at least
One cooler 241, it can have the fluid issuing pipeline 243 for being used for being recycled to cooling agent in gas confinement sub-assembly,
With for making cooling agent return to the fluid inlet line 245 of cooler.
For the various embodiments of gas confinement sub-assembly 200, gas source can be inert gas, such as nitrogen, appoint
What rare gas, and its any combination.For the various embodiments of gas confinement sub-assembly 200, gas source can be as clear
The gas source of clean dry air (CDA).For the various embodiments of gas confinement sub-assembly 200, gas source can be supply
Inert gas and such as source of the combination of CDA gas.
Gas confinement system 200 can keep every kind of material of various reactant gas materials it is horizontal in 100 ppm or
It is lower, such as 10 ppm or lower, 1.0 ppm or lower or 0.1 ppm or lower, the reactant gas material is including various
Reactive atmospheric gas such as vapor and oxygen, and organic solvent steam.In addition, the various embodiment party of gas confinement sub-assembly
Case can provide the low particle for the specification limit for meeting 1 grade of Atmospheric particulates to 5 grades of clean room standards according to ISO 14644
Environment.
Although what is be given above is exemplary OLED ink-jet printing systems and gas closed system, art technology
Personnel, which will be appreciated that, can use Fig. 1 and Fig. 2 one or more equipment and any combination and the extra equipment of device
Such system is built with device.
The product of final ink jet printing is the HIL of the thickness and composition with high uniformity.For example, across the whole of layer
It is possible that width, which has the layer of the thickness change no more than 10%,.Thickness across layer can use metering outfit such as contact pin type
Contact profile instrument (stylus contact profilometer) or interferometer microscope measure.For Through Optical Interference Spectra
Suitable interferometer is available commercially from Zygo instrumentation.
Composition for ink can be used for directly printing HIL in the OLED frameworks of multilayer.Typical OLED includes branch support group
Material, anode, negative electrode, the HIL configured on anode, and the luminescent layer (EML) configured between HIL and negative electrode.Can be in device
Present in other layers be included between HIL and luminescent layer and provide to assist to make hole transport to the hole transmission layer of luminescent layer,
And the electron transfer layer (ETL) configured between EML and negative electrode.Base material is typically transparent glass or plastic basis material.
In the framework of these multilayers, one or more layers in addition to HIL can be formed via ink jet printing, and can be with
Other layers are deposited using other film techniques.Typically, various layers will be formed in one or more pixel cells.Each pixel
Unit all includes bottom and limited by the dike for the circumference for limiting unit.It is optionally possible to use surface modification coatings such as surface
Surface in activating agent coating unit.However, in some embodiments, in the absence of such surfactant, because they
The luminous of luminescent layer can be quenched.
Fig. 3 is the schematic diagram of flat-panel monitor, and it includes multiple OLED arranged in the matrix of pixel cell.Fig. 3 is retouched
The enlarged drawing 320 in a region of panel 300 is stated, it shows the arrangement 330 of multiple pixel cells, including the picture to glow
Plain unit 332, the pixel cell 334 of green light and the pixel cell 336 of blue light-emitting.Furthermore, it is possible in flat panel display substrates
Upper formation integrated circuit 338 so that for the purpose for applying a voltage to each pixel in a controlled manner during use, electricity
Road is adjacent with each pixel cell.Size, shape and the aspect ratio of pixel cell can basis, such as, but not limited to required point
Resolution and change.For example, 100 ppi pixel cell density can be enough for the panel for computer display
, wherein for e.g., from about 300 ppi to about 450 ppi high-resolution, it can cause to obey on substrate surface effectively packaging
The various pixel cells design of higher picture element density.
Although disclosure above has been concentrated on the water-base ink for being formulated for HIL of the ink jet printing based on polythiophene
On composition, but the another aspect of this technology provides the HIL or HTL that are formulated for ink jet printing OLED non-aqueous, base
In the composition for ink of organic solvent.Organic HIL/HTL composition for ink includes the conventional component for being considered as wetting agent, still
Be incorporated into the amount carefully controlled in HTL inks so that it be actually prevented from possibly as wetting result generation not by
Sprawling for control is overflowed with pixel cell.In some embodiments, organic inks include：(1) hole-injecting material or hole pass
Defeated material；(2) one or more organic solvents, it makes, and hole is injected or hole mobile material dissolves；(3) fluorine-containing surfactants
Agent.Hole injection or hole mobile material typically with no more than about 5 wt.%, more typically no more than 2 wt.% and
Even more typically the amount no more than about 1 wt.% (e.g., from about 0.1 to about 1 wt.%) is present, the gross weight based on composition for ink
Meter.Organic solvent typically accounts for about 95 to about 99.8 wt.% of composition for ink.Fluorinated surfactant typically with no more than
About 0.15 wt.% amount is present.For example, in some embodiments of the composition for ink based on organic solvent, fluorinated surface
Activating agent exists with about 0.03 wt.% to about 0.1 wt.% amount.
As described above, the suitable hole-injecting material for the composition for ink based on organic solvent includes polythiophene.
Suitable hole mobile material includes polyvinylcarbazole or derivatives thereof, polysilane or derivatives thereof, had on side chain or main chain
Have the polyorganosiloxane ramification of aromatic amine, pyrazoline derivative, arylamine derivatives, stilbene derivative, triphenyl diamine derivative,
It is polyaniline or derivatives thereof, polythiophene or derivatives thereof, polyarylamine or derivatives thereof, polypyrrole or derivatives thereof, poly- (to Asia
Phenyl vinylene)（poly(p-phenylenevinylene)）Or derivatives thereof, or poly- (2,5- Asia thienyl ethenylidene)
（poly(2,5 thienylene vinylene)）Or derivatives thereof.
Suitable organic solvent for HIL/HTL composition for ink includes alkoxyl alcohol, alkylol, alkylbenzene, benzene first
Acid alkyl ester, alkylnaphthalene, amyl octylate, methyl phenyl ethers anisole, aryl alcohol, benzylalcohol, butyl benzene, butyrophenone, cis naphthalane, dipropyl two
Alcohol methyl ether, detergent alkylate, mesitylene, methoxypropanol, methyl benzoate, methyl naphthalene, methyl pyrrolidone, phenoxy group
Ethanol, 1,3- propane diols, pyrrolidones, trans naphthalane, benzene pentanone（valerophenon）, and its mixture.
Fluorine-containing surfactant is the surfactant for including fluorinated alkyl chain.E. I. du Pont de Nemours
The entitled Capstone and Zonyl of and Company (Wilmington, Delaware) merchandising fluorinated surfactant
Agent.Fluorine-containing surfactant can be for example fluorine-containing telomer (such as telomere (telomere) B monoethers and polyethylene glycol or 2- it is complete
Fluoroalkyl ethanol).Commercially available fluorine-containing surfactant includes Zonyl FS 1033D, Zonyl FS 1176, Zonyl
® FSG、Zonyl® FS-300、Zonyl® FSN、Zonyl® FSH、Zonyl® FSN、Zonyl® FSO、Zonyl®
FSN-100、Zonyl® FSO-100、Zonyl® FSH、Zonyl® FSN、Zonyl® FSO、Zonyl® FSH、Zonyl
® FSN、Zonyl® FSO、Zonyl® FS 500、Zonyl® FS 510、Zonyl® FSJ、Zonyl® FS-610、
Zonyl® 9361、Zonyl® FSA、FSP、FSE、FSJ、Zonyl® FSP、Zonyl® 9361、Zonyl® FSE、
Zonyl® FSA、Zonyl® UR、Zonyl® 8867L、Zonyl® FSG、Zonyl® 8857A、Foraperle®
225、Forafac® 1268、Forafac® 1157、Forafac® 1183、Zonyl® 8929B、Zonyl® 9155、
Zonyl® 9815、Zonyl® 9933LX、Zonyl® 9938、Zonyl® PFBI、Zonyl® PFBEI、Zonyl®
PFBE、Zonyl® PFHI、Zonyl® BA、-8- Zonyl® PFHEI、Zonyl® TM、Zonyl® 8932、Zonyl
® 7910、Zonyl® 7040、Foraperle® 321/325、Zonyl® 9464、Zonyl® NF、Zonyl® RP、
Zonyl® 321、Zonyl® 8740、Zonyl® 225、Zonyl® 227、Zonyl® 9977、Zonyl® 9027、
Zonyl 9671, Zonyl 9338 and Zonyl 9582, Capstone ST-500, Capstone ST-300,
Capstone® ST-200、Capstone® ST-110、Capstone® P-640、Capstone® P-623、
Capstone® P-620、Capstone® P-600、Capstone® FS-10、Capstone® FS-17、Capstone
® FS-22、Capstone® FS-30、Capstone® FS-31、Capstone® FS-3100、Capstone® FS-
34、Capstone® FS-35、Capstone® FS-50、Capstone® FS-51、Capstone® FS-60、
Capstone® FS-61、Capstone® FS-63、Capstone® FS-64、Capstone® FS-64、Capstone
® FS-65、Capstone® FS-66、Capstone® FS-81、Capstone® FS-83、Capstone® LPA、
Capstone® 1460、Capstone® 1157、Capstone® 1157D、Capstone® 1183、Capstone®
CPS、Capstone® E、Capstone® LMC、Capstone® CP、Capstone® PSB、Capstone® 4-I、
Capstone® 42-I、Capstone® 42-U、Capstone® 6-I、Capstone® 62-AL、Capstone®
62-I, Capstone 62-MA, Capstone TC, Capstone TR and Capstone TS.
Embodiment
Embodiment 1：Influence of the polymethyl siloxane to uniformity in pixel
The contact line provided by the polymethyl siloxane in HIL ink jet ink compositions is following examples merely illustrated to lead
Make of the improvement with caused uniformity of luminance.
Material and method.
The preparation of HIL composition for ink：
HIL composition for ink A and B are prepared with the component and concentration being displayed in Table 1.Both composition A and B include institute
Indicate the polymethyl siloxane of concentration.As a comparison case, prepare and be included in the composition listed in table 2 but lack polymethyl siloxane
Composition for ink (Comparative composition).
Table 1
。
Table 2
。
By the way that clean bottle is placed on balance and uses Pasteur pipettes by the desired amount of Botanisil
S-18 is transferred in bottle to prepare the composition for ink.Taring（tare）Balance, and successively by 1,3-PD, water and
DPGME is pipetted into bottle.Then bottle is removed from balance, is capped and rotates to mix the aqueous solution of gained.Then
Bottle is back to balance, and the desired amount of PEDOT dispersions (Haraeus Clevios TM PVP A1 4083) are moved
Liquid is into bottle.Then bottle is removed from balance, is capped and rotates so that other components of PEDOT and mixture are mixed
Close.Then the PEDOT composition for ink of (2.0 μm) filtering gained of polytetrafluoroethylene (PTFE) (PTFE) filter membrane are used, and will be filtered
Composition collect in amber bottle.Finally, before the use by this bottle of sonication 15 minutes.
In the case of no Botanisil S-18, contrast composition for ink is prepared using identical program.
Viscosity and stalagmometry：
Viscosity measurement is carried out using DV-I Prime Brookfield rheometers.Measured using SITA pressures in bubbles tension force
Measure surface tension.The composition for ink A and B comprising polymethyl siloxane and contrast composition for ink are provided in tables 1 and 2
The measured value of (Comparative composition).
HIL ink jet printings and OLED manufactures：
By on the ito anode in HIL ink compositions prints to OLED frameworks.OLED base material is with 0.5 mm
The glass of thickness, 60 nm ITO (tin indium oxide) anode pattern is made thereon（pattern）.Then make dike material (also by
Referred to as pixel confining layers) patterned on ITO, the unit of deposition ink jet printing layer formed therein.Dike material is to be designed for
The negative work photoresist of ink jet printing.The unit of gained has the dike that height is about 0.5 to 2 μm, and it is relative to unit
Bottom is in 45° angle so that the opening of each unit is more wider than its bottom.45° angle is the representative of typical dike angle, its model
It is trapped among about 5 ° to about 70 °.The width and length dimension of unit are 175 μm of about 60 x.Then the combination of inks of table 1 and 2 is used
HIL layer ink jet printings into unit, are dried under vacuum and toasted at high temperature to remove water and solvent from layer by thing.
The ink-jet printing system described in PCT application publication No. WO 2013/158310 is used to print HIL at room temperature
Composition for ink, the complete disclosure of the WO 2013/158310 is incorporated herein by quoting.By using HIL inks
Composition filling is overall（bulk）Ink housing tube carries out ink jet printing into pixel cell.The overall ink housing tube and master
The distribution holder wanted is in fluid communication, and provides HIL composition for ink without interruption to main point during printing
With holder.Then HIL composition for ink is fed in the print head including multiple nozzles, it is by the nozzle that HIL is black
Water composition is ejected into pixel cell.Typical droplet size is about 10 pl during printing, and will about 3 to 10 drop prints
Brush in each unit to form the drop of composition for ink in the cells.
Following manufacture is incorporated to the OLED of the HIL with composition for ink A printings.Htl layer is ink-jet printing on HIL layers, with
After be dried under vacuum and toast at high temperature to remove solvent and cause crosslinking in crosslinkable polymer.Then will
EML layers are ink-jet printing on htl layer, are then dried under vacuum and are toasted at high temperature to remove solvent.Using above-mentioned
Printing machine ink jet printing HTL and EML layer.The HTL composition for ink is by the dicyandiamide solution based on ester, (it is by 1:1 weight
The sad diethylester and octyl octanoate through distilling and deaerating of ratio mixture composition) in hole transport polymer material group
Into.The EML composition for ink is made up of the electroluminescent organic material in diethyl sebacate.
Then ETL layers are applied by vacuum thermal evaporation, with after-applied cathode layer.ETL materials include quinoline and close lithium
（lithium quinolate）(LiQ) emissive material is used as, and cathode layer is made up of 100 nm aluminium.
As a result.
The composition A and B that are printed onto in pixel cell drop are pind down to pixel dike, and both without experience overflow or
Disengaging is not undergone.Using being printed in pixel cell and pin down to the composition A of pixel cell (0.1 wt.% poly- first
Radical siloxane) image of HIL layers for preparing is shown in Fig. 4 A.On the contrary, it is printed onto the figure of the Comparative composition of pixel cell
As (Fig. 5 and 6) shows that in the case of in the absence of polymethyl siloxane composition for ink is uncontrollably sprawled and overflowed
The side 500 (Fig. 5 A) of pixel cell departs from (dewetting) with the dike of pixel cell, produces and overflows 600 with some pixel cells
The dewetting region 602 (Fig. 6 A) on the bottom of unit of combination.
For each microphoto that is being shown in above-mentioned Fig. 4 A-6A and being shown in following Fig. 7 A-9A, there is provided
Black and white line chart and it is marked as corresponding " B " figure.
It is investigated the electroluminescence characters of the HIL of the ink jet printing including being prepared with composition A OLED pixel.Once
OLED is manufactured, by applying electric current at diode both ends and light transmitting imaging is studied its electroluminescent uniformity.Institute
The luminescence display obtained is in Fig. 7 A microphoto.As in the figure, it can be seen that having with the composition for ink A HIL layers printed
Help the uniformly light-emitting of OLED pixel (being incorporated in the HIL layers).
Embodiment 2：Influence of the sulfolane to printing characteristic
Following examples merely illustrate the improved printing characteristic that HIL composition for ink is assigned by sulfolane.
Material and method.
The preparation of HIL composition for ink：
Prepare the HIL composition for ink for being included in polymethyl siloxane, sulfolane and the other compositions listed in table 3.
Table 3
| Composition | Wt.% |
| PEDOT | 59.9 |
| DPGME | 5 |
| Sulfolane | 10 |
| H2O | 25 |
| Surfactant (S18) | 0.1 |
| Viscosity [cP] | 5.9 |
| ST [dyne/cm] | 45.0 |
Composition for ink is prepared as described in example 1 above, except replacing 1,3-PD using sulfolane.
Viscosity and stalagmometry：
Viscosity and stalagmometry are carried out as described in Example 1.
HIL ink jet printings and OLED manufactures：
As described in example 1 above, print HIL composition for ink and form the OLED pixel for electroluminescent test.
Delay measurements：
The delay that ink is carried out using the ink-jet printing system described in PCT application publication No. WO 2013/158310 is surveyed
Amount.By projecting a nozzle（fire）And 300 data points of volume, speed and directionality are measured to measure.
Then make nozzle idle 30 minutes.Nozzle is restarted after 30 minutes, and records more than 300 individual data points.
Compared to the injection (end of the first data group, before 30 minute free time) of stable state, in the second data group
During beginning (after 30 minute free time), it (is typically that speed declines to draw and compare data group to find any Set-out slide effect
And stereomutation).
The delay measurements of ink are also carried out using Dimatix Fujifilm DMP-2831 printing machines.In observation drop
In setting, open all 16 nozzles and confirm that all nozzles are all projecting.Then injection is stopped 5 minutes.Restart
Spray and check and confirm that all nozzles are still working.Then, continuous injection 15 and 30 minutes is carried out.By delay time measurement
Sprayed for end and uncapped（uncapped）Ink in nozzle starts the time between drying, and the drying causes discomfort
When drop project.In order to determine when composition for ink is being dried, white light and the test under microscope of fluorescence mode they.
As a result.
Once OLED is manufactured, by applying electric current at each diode both ends and light transmitting imaging is studied theirs
Electroluminescent uniformity.OLED for the HIL with the ink compositions print with table 3 and with the ink group with table 1
The HIL of compound printing OLED measurement electroluminescent.The contrast of Fig. 8 and 9 microphoto is shown in HIL composition for ink
Sulfolane provide pixel light emission (Fig. 8 A) evenly than propane diols (Fig. 9 A).
In addition, maximum stable injection frequency (1000 Hz) ratio of the composition for ink comprising sulfolane includes glycol
The maximum stable injection frequency of composition for ink is higher.Finally, compared to only 15 minutes of the composition for ink comprising glycol,
The time delay of composition for ink comprising sulfolane is more than 30 minutes.Using in PCT application publication numbers WO 2013/
The result of the delayed test of ink-jet printing system measurement described in 158310 is shown in Figure 10 to 12.In these figures, will
Ink comprising sulfolane is named as P113.Figure 10 is that composition for ink is through 14 points with after 30 minute free time before the free time
The figure of the droplet size of clock.Figure 11 is that composition for ink is through the speed of the drop of 14 minutes with after 30 minute free time before the free time
The figure of degree.As in the figure, it can be seen that the liquid drop speed in restarting is only lower by 4% than the liquid drop speed before the free time.
Figure 12 be before the free time and 30 minute free time after, figure of the composition for ink through the drop angle of 14 minutes.Before the free time
Afterwards, the significant difference of drop angle is not observed.
Word " exemplary " is used herein to mean that as embodiment, example or illustration.Here depicted as " showing
Any aspect or design of example property " are not necessarily to be construed as preferably or more favourable than other side or design.In addition, with regard in the disclosure
For the purpose of appearance, unless specifically stated otherwise, " and " or the use of "or" be intended to include "and/or".
For the purpose for illustrating and describing, retouching above for exemplary of the invention has been showed
State.It is not intended to be exhaustive or limits the invention to exact form disclosed, and according to teaching above, modification and
Variant is possible, or can be obtained from the practice of the present invention.Select and describe embodiment to explain the original of the present invention
Reason and the practical application as the present invention, so that those skilled in the art can be in various embodiments and pre- using being suitable for
The various modifications of the special-purpose of phase use the present invention.It is intended to limit this hair by appended claims and their equivalent
Bright scope.
Claims (19)
1. forming the method for the hole injection layer for Organic Light Emitting Diode, methods described includes：
The drop of ink-jet printing inks composition on electrode layer in the pixel cell of Organic Light Emitting Diode, the pixel list
Member is limited by pixel dike, and the composition for ink includes：
Conductive polythiophene；
Water：
At least one organic solvent；With
Polymethyl siloxane, wherein polymethyl siloxane exist to provide the amount that the contact line of the drop in pixel cell pins down；
With
The volatile component of composition for ink is allowed to evaporate, so as to form hole injection layer.
2. the method for claim 1 wherein the conductive polythiophene is PEDOT.
3. the method for claim 2, wherein the PEDOT exists with least 50 wt% amount.
4. the method for claim 2, wherein the electrode layer includes transparent conductive material.
5. the method for claim 4, wherein the transparent conductive material is tin indium oxide, and polymethyl siloxane is with 0.03
Wt% to 0.12 wt% amount is present.
6. the method for claim 1 wherein at least one organic solvent is that have to be not more than 55 dynes/li at 25 DEG C
The aprotic solvent of the surface tension of rice and the viscosity no more than 15 cPs.
7. the method for claim 6, wherein at least one organic solvent has 240 DEG C or higher of boiling at atmosheric pressure
Point.
8. the method for claim 1 wherein at least one organic solvent is sulfolane.
9. the method for claim 8, wherein the sulfolane is main organic solvent in composition for ink.
10. the method for claim 8, wherein the sulfolane exists with least 5 wt% amount.
11. the method for claim 3, wherein the electrode layer includes tin indium oxide, polymethyl siloxane is with 0.05 wt% to 0.1
Wt% amount is present, and at least one organic solvent is sulfolane, and it exists with 5 to 12 wt% amount.
12. the method for claim 8, wherein the composition for ink further includes has lower surface tension than sulfolane
Second organic solvent of lower boiling point.
13. the method for claim 12, wherein second organic solvent is methyl proxitol.
14. the method for claim 1 wherein ink formulations have at 25 DEG C no more than 47 dynes per centimeters surface tension,
Viscosity at 25 DEG C no more than 15 cPs and time delay of at least 20 minutes at 25 DEG C.
15. composition for ink, it is included：
PEDOT：
Water：
At least one organic solvent, its have at 25 DEG C no more than 55 dynes per centimeters surface tension, at 25 DEG C less
In 15 cPs viscosity and at least 200 DEG C of boiling point；With
Polymethyl siloxane, wherein polymethyl siloxane exist to provide the amount that the contact line of the drop in pixel cell pins down.
16. the composition for ink of claim 15, wherein at least one organic solvent is sulfolane.
17. the composition for ink of claim 16, it is further included has lower surface tension and lower than sulfolane
Second organic solvent of boiling point.
18. the composition for ink of claim 17, wherein second organic solvent is methyl proxitol.
19. composition for ink, it is included：
50 to 70 wt% PEDOT；
3 wt% to 10 wt% sulfolane；With
0.03 to 0.12 wt% polymethyl siloxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810153650.8A CN108219588A (en) | 2013-10-31 | 2013-12-04 | For the composition for ink for including polythiophene of ink jet printing |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361898343P | 2013-10-31 | 2013-10-31 | |
| US61/898343 | 2013-10-31 | ||
| PCT/US2013/073175 WO2015065499A2 (en) | 2013-10-31 | 2013-12-04 | Polythiophene-containing ink compositions for inkjet printing |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810153650.8A Division CN108219588A (en) | 2013-10-31 | 2013-12-04 | For the composition for ink for including polythiophene of ink jet printing |
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| CN105658742A CN105658742A (en) | 2016-06-08 |
| CN105658742B true CN105658742B (en) | 2018-03-30 |
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| CN201810153650.8A Pending CN108219588A (en) | 2013-10-31 | 2013-12-04 | For the composition for ink for including polythiophene of ink jet printing |
| CN201380080634.6A Active CN105658742B (en) | 2013-10-31 | 2013-12-04 | The composition for ink for including polythiophene for ink jet printing |
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| EP (1) | EP3063800A4 (en) |
| JP (2) | JP6438041B2 (en) |
| KR (2) | KR20160078973A (en) |
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| WO (1) | WO2015065499A2 (en) |
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| US20180248122A1 (en) * | 2015-08-24 | 2018-08-30 | Dic Corporation | Ink composition for organic semiconductor device and organic semiconductor device including the same |
| CN108291105B (en) * | 2015-11-12 | 2021-09-10 | 广州华睿光电材料有限公司 | Composition for printing electronic devices and use thereof in electronic devices |
| CN105440802B (en) * | 2015-12-22 | 2017-12-12 | 江南大学 | It is a kind of can ultraviolet photodimerization PEDOT conductive inks and preparation method thereof |
| US20180323373A1 (en) * | 2017-05-05 | 2018-11-08 | Universal Display Corporation | Capacitive sensor for positioning in ovjp printing |
| US20200303648A1 (en) * | 2017-11-28 | 2020-09-24 | Sakai Display Products Corporation | Organic el light-emitting element and method for manufacturing same |
| KR102316066B1 (en) * | 2018-07-27 | 2021-10-21 | 주식회사 엘지화학 | Ink composition, organic light emitting device using the same and method of manufacturing the same |
| KR102156301B1 (en) * | 2018-09-06 | 2020-09-15 | (주)에스티아이 | Method of inkjet printing and inkjet printing apparatus |
| KR102170962B1 (en) * | 2018-12-10 | 2020-10-28 | (주)에스티아이 | Method of inkjet printing and inkjet printing apparatus |
| CN110137230B (en) * | 2019-05-21 | 2021-02-23 | 深圳市华星光电半导体显示技术有限公司 | OLED display panel and manufacturing method thereof |
| KR102243003B1 (en) * | 2020-12-22 | 2021-04-21 | 코오롱인더스트리 주식회사 | Composition for forming hole transport layer and semitransparent organic photovoltaics comprising the same |
| WO2023070618A1 (en) * | 2021-10-30 | 2023-05-04 | 华为技术有限公司 | Light-emitting element ink and application of polymer in same, and display apparatus and manufacturing method therefor |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US7833612B2 (en) * | 2003-09-12 | 2010-11-16 | Samsung Mobile Display Co., Ltd. | Substrate for inkjet printing and method of manufacturing the same |
| JP2005105070A (en) * | 2003-09-29 | 2005-04-21 | Seiko Epson Corp | Inkjet ink, method for film formation, method for producing electrooptical apparatus and electrooptical apparatus |
| JP2005105069A (en) * | 2003-09-29 | 2005-04-21 | Seiko Epson Corp | Inkjet ink, apparatus and method for liquid droplet discharge |
| JP4852818B2 (en) * | 2003-09-29 | 2012-01-11 | セイコーエプソン株式会社 | Manufacturing method of electro-optical device |
| JP2005144324A (en) * | 2003-11-14 | 2005-06-09 | Seiko Epson Corp | Film forming method, device manufacturing method and electro-optical device |
| GB0510382D0 (en) * | 2005-05-20 | 2005-06-29 | Cambridge Display Tech Ltd | Ink jet printing compositions in opto-electrical devices |
| WO2006123741A1 (en) * | 2005-05-20 | 2006-11-23 | Sumitomo Chemical Company, Limited | Polymer composition and polymer light-emitting device using same |
| JP5148843B2 (en) * | 2005-05-20 | 2013-02-20 | 住友化学株式会社 | High boiling point composition and polymer light emitting device using the same |
| WO2007106101A2 (en) * | 2006-03-02 | 2007-09-20 | E. I. Du Pont De Nemours And Company | Process for making contained layers and devices made with same |
| CN101563388B (en) * | 2006-07-21 | 2013-05-15 | 普莱克斯托尼克斯公司 | Sulfonation of conducting polymers and oled, photovoltaic, and ESD devices |
| JP2008081550A (en) * | 2006-09-26 | 2008-04-10 | Japan Aviation Electronics Industry Ltd | Ink for wiring material and method for producing the same |
| JP2008130790A (en) * | 2006-11-21 | 2008-06-05 | Seiko Epson Corp | Liquid body, organic el device, its manufacturing method, and electronic equipment |
| JP2008153159A (en) * | 2006-12-20 | 2008-07-03 | Dainippon Printing Co Ltd | Organic electroluminescent element and manufacturing method therefor |
| US7981323B2 (en) * | 2007-07-13 | 2011-07-19 | Konarka Technologies, Inc. | Selenium containing electrically conductive copolymers |
| CN101874084B (en) * | 2007-11-14 | 2013-05-22 | 柯尼卡美能达喷墨技术株式会社 | Nonaqueous ink-jet ink and method of ink-jet recording |
| JP2009238593A (en) * | 2008-03-27 | 2009-10-15 | Casio Comput Co Ltd | Light-emitting element and its manufacturing method |
| JP2009289474A (en) * | 2008-05-27 | 2009-12-10 | Casio Comput Co Ltd | Light-emitting device, and manufacturing method of light-emitting device |
| GB2466842B (en) * | 2009-01-12 | 2011-10-26 | Cambridge Display Tech Ltd | Interlayer formulation for flat films |
| JP5473705B2 (en) * | 2009-03-27 | 2014-04-16 | ユー・ディー・シー アイルランド リミテッド | Organic electroluminescent device and method for producing organic electroluminescent device |
| JP2011233480A (en) * | 2010-04-30 | 2011-11-17 | Ricoh Co Ltd | Forming method of laminate structure and manufacturing method of organic electroluminescent device |
| CA2808852A1 (en) * | 2010-08-20 | 2012-02-23 | Rhodia Operations | Films containing electrically conductive polymers |
| WO2013040468A1 (en) * | 2011-09-16 | 2013-03-21 | Kateeva, Inc | Film-forming formulations for substrate printing |
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2013
- 2013-12-04 WO PCT/US2013/073175 patent/WO2015065499A2/en active Application Filing
- 2013-12-04 CN CN201810153650.8A patent/CN108219588A/en active Pending
- 2013-12-04 KR KR1020167011210A patent/KR20160078973A/en active Application Filing
- 2013-12-04 JP JP2016552406A patent/JP6438041B2/en active Active
- 2013-12-04 KR KR1020187027819A patent/KR20180108917A/en not_active Application Discontinuation
- 2013-12-04 CN CN201380080634.6A patent/CN105658742B/en active Active
- 2013-12-04 EP EP13896242.8A patent/EP3063800A4/en not_active Withdrawn
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| Publication number | Publication date |
|---|---|
| WO2015065499A3 (en) | 2015-07-16 |
| EP3063800A2 (en) | 2016-09-07 |
| KR20180108917A (en) | 2018-10-04 |
| WO2015065499A2 (en) | 2015-05-07 |
| JP2017502485A (en) | 2017-01-19 |
| JP2018119164A (en) | 2018-08-02 |
| KR20160078973A (en) | 2016-07-05 |
| JP6438041B2 (en) | 2018-12-12 |
| CN105658742A (en) | 2016-06-08 |
| CN108219588A (en) | 2018-06-29 |
| EP3063800A4 (en) | 2017-06-21 |
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