JP2000323276A - Manufacture of organic el element, organic el element, and ink composition - Google Patents
Manufacture of organic el element, organic el element, and ink compositionInfo
- Publication number
- JP2000323276A JP2000323276A JP11134320A JP13432099A JP2000323276A JP 2000323276 A JP2000323276 A JP 2000323276A JP 11134320 A JP11134320 A JP 11134320A JP 13432099 A JP13432099 A JP 13432099A JP 2000323276 A JP2000323276 A JP 2000323276A
- Authority
- JP
- Japan
- Prior art keywords
- ink composition
- organic
- ink
- light emitting
- hole injection
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 157
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 95
- 239000000463 material Substances 0.000 claims abstract description 89
- 238000002347 injection Methods 0.000 claims abstract description 54
- 239000007924 injection Substances 0.000 claims abstract description 54
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims description 28
- 229920000553 poly(phenylenevinylene) Polymers 0.000 claims description 18
- 238000005192 partition Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- -1 poly (paraphenylene vinylene) Polymers 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 5
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 5
- 229920000123 polythiophene Polymers 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 230000001268 conjugating effect Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 120
- 239000010408 film Substances 0.000 description 38
- 238000000059 patterning Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000005525 hole transport Effects 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 239000007850 fluorescent dye Substances 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 239000005871 repellent Substances 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 229920000547 conjugated polymer Polymers 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005499 meniscus Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- MUSLHCJRTRQOSP-UHFFFAOYSA-N rhodamine 101 Chemical compound [O-]C(=O)C1=CC=CC=C1C(C1=CC=2CCCN3CCCC(C=23)=C1O1)=C2C1=C(CCC1)C3=[N+]1CCCC3=C2 MUSLHCJRTRQOSP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- DTZWGKCFKSJGPK-VOTSOKGWSA-N (e)-2-(2-methyl-6-(2-(1,1,7,7-tetramethyl-1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinolin-9-yl)vinyl)-4h-pyran-4-ylidene)malononitrile Chemical compound O1C(C)=CC(=C(C#N)C#N)C=C1\C=C\C1=CC(C(CCN2CCC3(C)C)(C)C)=C2C3=C1 DTZWGKCFKSJGPK-VOTSOKGWSA-N 0.000 description 1
- DZNJMLVCIZGWSC-UHFFFAOYSA-N 3',6'-bis(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 DZNJMLVCIZGWSC-UHFFFAOYSA-N 0.000 description 1
- KQFZOWUXULRDDS-UHFFFAOYSA-N 4h-quinolizine-1-carboxylic acid Chemical compound C1=CC=CN2CC=CC(C(=O)O)=C21 KQFZOWUXULRDDS-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920000285 Polydioctylfluorene Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 101710100266 Serine/threonine-protein phosphatase 6 catalytic subunit Proteins 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 1
- CHZWRIFDYXSVOD-UHFFFAOYSA-M chromenylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.[O+]1=CC=CC2=CC=CC=C21 CHZWRIFDYXSVOD-UHFFFAOYSA-M 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 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
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000503 poly(2,5-furylene vinylene) polymer Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- DJWWHVKRLDNDJK-UHFFFAOYSA-N rhodamine 640 perchlorate Chemical compound [O-]Cl(=O)(=O)=O.OC(=O)C1=CC=CC=C1C(C1=CC=2CCCN3CCCC(C=23)=C1O1)=C2C1=C(CCC1)C3=[N+]1CCCC3=C2 DJWWHVKRLDNDJK-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000035922 thirst Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】ディスプレイ、表示光源など
に用いられる電気的発光素子である有機ＥＬ素子の製造
方法、有機ＥＬ素子、その正孔注入層や発光層の形成に
用いられるインク組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an organic EL device which is an electric light emitting device used for a display, a display light source and the like, an organic EL device, and an ink composition used for forming a hole injection layer and a light emitting layer thereof.
【０００２】[0002]
【従来の技術】近年液晶ディスプレイに替わる自発発光
型ディスプレイとして発光層に有機物を用いた発光素子
の開発が加速している。有機ＥＬ（エレクトロルミネセ
ンス）素子における有機物からなる発光層の形成プロセ
スとして、Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．５１（１
２）、２１ Ｓｅｐｔｅｍｂｅｒ １９８７の９１３ペ
ージに示されているように低分子材料を蒸着法で成膜す
る方法と、 Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．７１
（１）、７ Ｊｕｌｙ １９９７の３４ページから示さ
れているように高分子材料を塗布する方法が主に開発さ
れている。2. Description of the Related Art In recent years, the development of a light emitting element using an organic material in a light emitting layer has been accelerated as a spontaneous light emitting display replacing a liquid crystal display. As a process for forming a light emitting layer made of an organic material in an organic EL (electroluminescence) element, Appl. Phys. Lett. 51 (1
2), a method of depositing a low molecular material by a vapor deposition method as shown on page 913 of 21 September 1987, Appl. Phys. Lett. 71
(1), 7 A method of applying a polymer material as mainly shown on page 34 of July 1997 has been developed.
【０００３】カラー化の手段としては低分子系材料を用
いる場合、所定パターンのマスク越しに異なる発光色の
発光材料を所望の画素対応部分に蒸着し形成する方法が
行われている。一方、高分子系材料を用いる場合、微細
かつ容易にパターニングができることからインクジェッ
ト法を用いたカラー化が注目されている。インクジェッ
ト法による有機ＥＬ素子の作製については、例えば、特
開平７−２３５３７８、特開平１０−１２３７７、特開
平１０−１５３９８７、特開平１１−４０３５８、特開
平１１−５４２７０に開示されている。As a means of colorization, when a low molecular material is used, a method has been used in which a luminescent material of a different luminescent color is vapor-deposited on a portion corresponding to a desired pixel through a mask of a predetermined pattern. On the other hand, when a polymer-based material is used, colorization using an inkjet method has attracted attention because it can be finely and easily patterned. The production of the organic EL element by the ink jet method is disclosed in, for example, JP-A-7-235378, JP-A-10-12377, JP-A-10-153987, JP-A-11-40358, and JP-A-11-54270.
【０００４】さらに有機ＥＬ素子では、発光効率、耐久
性を向上させるために、正孔注入層または正孔輸送層を
陽極と発光層の間に形成することが提示されている（Ａ
ｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．５１、２１ Ｓｅｐｔｅ
ｍｂｅｒ １９８７の９１３ページ）。従来、バッファ
層や正孔注入層としては導電性高分子、例えばポリチオ
フェン誘導体やポリアニリン誘導体（Ｎａｔｕｒｅ，３
５７，４７７、１９９２）を用い、スピンコート等の塗
布法により膜を形成する。低分子系材料の正孔注入層ま
たは正孔輸送層として、フェニルアミン誘導体を蒸着で
形成して用いることが多かった。Further, in the organic EL device, it has been proposed that a hole injection layer or a hole transport layer is formed between an anode and a light emitting layer in order to improve luminous efficiency and durability (A).
ppl. Phys. Lett. 51, 21 Septe
mber 1987, page 913). Conventionally, a conductive polymer such as a polythiophene derivative or a polyaniline derivative (Nature, 3
57, 477, 1992) to form a film by a coating method such as spin coating. A phenylamine derivative is often formed by vapor deposition and used as a hole injection layer or a hole transport layer of a low molecular material.
【０００５】[0005]
【発明が解決しようとする課題】有機ＥＬ素子におい
て、正孔注入層及び発光層の積層構造を形成する際に、
正孔注入層及び発光層を構成する有機薄膜を材料を無駄
にせず、簡便にかつ微細にパターニングして成膜する手
段が要求されている。SUMMARY OF THE INVENTION In an organic EL device, when forming a laminated structure of a hole injection layer and a light emitting layer,
There is a demand for a means for easily and finely patterning the organic thin film constituting the hole injection layer and the light emitting layer without wasting the material.
【０００６】インクジェット方式は大変有効である。し
かし、インクジェット法による安定な吐出性を満たし、
かつ材料の特性を損なわずに機能膜として成膜できるイ
ンク組成物の調製は大変難しい課題である。有機ＥＬ素
子の製造において、インク組成物については特開平１１
−４０３５８、特開平１１−５４２７０に記載されてい
る。これら刊行物では吐出性の点からＤＭＦ（ジメチル
ホルムアミド）や湿潤剤としてグリセリンやジエチレン
グリコール等の高沸点溶媒を使用した組成物が記載され
ている。ＤＭＦは熱、酸、アルカリに対する安定性に問
題があり、グリセリンやジエチレングリコールといった
高級アルコールは緑色発光材料としてポリパラフェニレ
ンビニレン（ＰＰＶ）を用いる場合、ＰＰＶ前駆体と共
役化の過程で反応し特性を阻害してしまう問題がある。
また、特にグリセリンは除去するのが困難である。[0006] The ink jet system is very effective. However, satisfying the stable ejection property by the inkjet method,
In addition, it is very difficult to prepare an ink composition that can be formed into a functional film without deteriorating the properties of the material. In the production of an organic EL device, an ink composition is disclosed in
-40358 and JP-A-11-54270. These publications describe compositions using DMF (dimethylformamide) and a high-boiling solvent such as glycerin or diethylene glycol as a wetting agent from the viewpoint of dischargeability. DMF has a problem in stability against heat, acid, and alkali. Higher alcohols such as glycerin and diethylene glycol react with polyparaphenylene vinylene (PPV) in a conjugation process when polyparaphenylene vinylene (PPV) is used as a green light-emitting material. There is a problem that hinders.
Also, glycerin is particularly difficult to remove.
【０００７】また、パターニングの分解能を上げるた
め、ノズル径を小さくし、より小さなインクジェット液
滴を形成しようとすると、液滴が小さくなればなるほど
インクは乾きやすくなるといった問題も生じている。Further, in order to increase the resolution of patterning, when the nozzle diameter is reduced to form a smaller inkjet droplet, there is a problem that the smaller the droplet, the easier the ink dries.
【０００８】さらに、インクジェット法のみならず塗布
法で有機層を積層する場合、組成物の溶媒が下地層の有
機膜を溶解する、いわゆる相溶性が問題となる。具体的
には正孔注入層（または正孔輸送層）の上に発光層を形
成する場合である。Further, when an organic layer is laminated not only by the ink-jet method but also by a coating method, so-called compatibility in which the solvent of the composition dissolves the organic film of the underlayer becomes a problem. Specifically, this is a case where a light emitting layer is formed on a hole injection layer (or a hole transport layer).
【０００９】そこで本発明の課題とするところは、簡
便、短時間、低コストで特性の優れた有機積層膜からな
る有機ＥＬ素子を製造する方法ならびにそれを可能にす
るインク組成物を提供するところにある。Accordingly, an object of the present invention is to provide a method for producing an organic EL device comprising an organic laminated film having excellent properties in a simple, short-time, low-cost manner and an ink composition enabling the method. It is in.
【００１０】[0010]
【課題を解決するための手段】本発明によれば、下記
（１）〜（５）の有機ＥＬ素子の製造方法が提供され
る。According to the present invention, there are provided the following methods (1) to (5) for manufacturing an organic EL device.
【００１１】（１）正孔注入層と発光層を、陽極および
陰極で狭持した構造の有機ＥＬ素子の製造方法であっ
て、基板上の所定の領域に有機化合物からなる正孔注入
材料を含むインク組成物をインクジェット方式により塗
布し正孔注入層を形成する工程と、有機化合物からなる
発光材料を含むインク組成物をインクジェット方式によ
り塗布し発光層を形成する工程とを具備することを特徴
とする有機ＥＬ素子の製造方法。(1) A method for manufacturing an organic EL device having a structure in which a hole injection layer and a light emitting layer are sandwiched between an anode and a cathode, wherein a hole injection material made of an organic compound is provided in a predetermined region on a substrate. A hole-injecting layer by applying an ink composition containing the compound by an ink-jet method, and a step of forming a light-emitting layer by applying an ink composition containing a light-emitting material composed of an organic compound by an ink-jet method. A method for manufacturing an organic EL device.
【００１２】当該方法は有機化合物からなる正孔注入層
及び発光層の両方をインクジェット方式で形成したもの
である、かかる方法により、簡便な方法で全ての有機層
を形成することができ、またいずれの層も高い性能とす
ることができる。In this method, both a hole injection layer and a light emitting layer made of an organic compound are formed by an ink jet method. With this method, all the organic layers can be formed by a simple method. Layers can also have high performance.
【００１３】尚、本発明において、正孔注入層とは、陽
極側から発光層に有効に正孔を注入させ得る層であり、
正孔輸送機能をも有する。また、正孔注入層と共に、正
孔輸送機能を有する正孔輸送層を別層で設けてもよい。In the present invention, the hole injection layer is a layer capable of effectively injecting holes from the anode side into the light emitting layer.
It also has a hole transport function. Further, a hole transport layer having a hole transport function may be provided as a separate layer together with the hole injection layer.
【００１４】（２）有機ＥＬ素子が基板上に複数の画素
を有する素子であり、基板上に該画素毎を隔てる隔壁を
設け、該隔壁間の領域に前記正孔注入層及び前記発光層
を形成することを特徴とする（１）の有機ＥＬ素子の製
造方法。(2) The organic EL element is an element having a plurality of pixels on a substrate, a partition is provided on the substrate to separate the pixels, and the hole injection layer and the light emitting layer are provided in a region between the partitions. (1) The method for manufacturing an organic EL device according to (1).
【００１５】当該（２）の方法により、異なる発光層が
混合することなく、多色で且つ高精細の有機ＥＬ素子を
容易に得ることができる。According to the method (2), a multicolor and high-definition organic EL device can be easily obtained without mixing different light emitting layers.
【００１６】（３）有機ＥＬ素子が基板上に複数の画素
を有する素子であり、基板上に該画素毎を隔てる隔壁を
設け、酸素ガスプラズマとフロロカーボンガスプラズマ
の連続処理工程を経て、前記正孔注入層と前記発光層を
形成することを特徴とする（１）の有機ＥＬ素子の製造
方法。(3) The organic EL device is a device having a plurality of pixels on a substrate, a partition is provided on the substrate to separate the pixels, and the organic EL device is subjected to a continuous processing step of oxygen gas plasma and fluorocarbon gas plasma. The method for producing an organic EL device according to (1), wherein a hole injection layer and the light emitting layer are formed.
【００１７】当該（３）の方法により、基板上に液滴の
濡れ性の違いを付与することができ、インクジェット液
滴の微細パターニングが可能となる。According to the method (3), a difference in wettability of droplets can be provided on the substrate, and fine patterning of ink-jet droplets can be performed.
【００１８】（４）前記有機化合物からなる正孔注入材
料を含むインク組成物をインクジェット方式により塗布
した後、該インク組成物の溶媒を除去して、正孔注入層
を得ること、及び前記有機化合物からなる発光材料を含
むインク組成物をインクジェット方式により塗布した
後、該インク組成物の溶媒を除去し、発光層を得ること
を特徴とする（１）の有機ＥＬ素子の製造方法。(4) After applying an ink composition containing a hole injecting material comprising the organic compound by an ink jet method, a solvent of the ink composition is removed to obtain a hole injecting layer; (1) The method for producing an organic EL device according to (1), wherein an ink composition containing a light emitting material made of a compound is applied by an inkjet method, and then the solvent of the ink composition is removed to obtain a light emitting layer.
【００１９】当該（４）の方法により所望の特性の正孔
注入層及び発光層としての有機固体薄膜を形成すること
ができる。By the method (4), an organic solid thin film as a hole injection layer and a light emitting layer having desired characteristics can be formed.
【００２０】（５）前記有機化合物からなる正孔注入材
料を含むインク組成物をインクジェット法により塗布し
た後、さらに熱処理により該インク組成物の材料を硬化
あるいは共役化させて正孔注入層を得ること、及び前記
有機化合物からなる発光材料を含むインク組成物をイン
クジェット方式により塗布した後、さらに熱処理により
該インク組成物の材料を硬化あるいは共役化させて発光
層を得ることを特徴とする（１）の有機ＥＬ素子の製造
方法。(5) After the ink composition containing the hole injection material comprising the organic compound is applied by an ink jet method, the material of the ink composition is cured or conjugated by heat treatment to obtain a hole injection layer. And applying an ink composition containing a luminescent material comprising the organic compound by an ink jet method, and then curing or conjugating the material of the ink composition by heat treatment to obtain a luminescent layer (1). A) a method for manufacturing an organic EL element.
【００２１】当該（５）の方法により、優れた機能を有
する正孔注入層および発光層を形成できる。According to the method (5), a hole injection layer and a light emitting layer having excellent functions can be formed.
【００２２】また、本発明によれば、下記（６）乃至
（１５）のインク組成物が提供される。（６）有機ＥＬ
素子の製造においてインクジェット法により塗布される
正孔注入材料又は発光材料を含むインク組成物であっ
て、粘度が１〜２０ｍＰａ・ｓ、表面張力が２０〜７０
ｍＮ／ｍ 、インクジェットヘッドのノズル面を構成す
る材料に対する接触角が３０〜１７０°であることを特
徴とするインク組成物。Further, according to the present invention, the following ink compositions (6) to (15) are provided. (6) Organic EL
An ink composition containing a hole injection material or a luminescent material applied by an ink-jet method in the production of an element, having a viscosity of 1 to 20 mPa · s and a surface tension of 20 to 70.
An ink composition having a mN / m 2 and a contact angle with a material constituting a nozzle surface of an inkjet head of 30 to 170 °.
【００２３】当該（６）のインク組成物によれば、特に
インクジェット法により塗布する場合に、ノズル孔の目
詰まり、インク液滴の飛行曲がりを押さえるとともに吐
出を円滑にし、吐出量および吐出タイミングの制御が可
能となり、インクジェット方式による安定な吐出が可能
となる。According to the ink composition (6), particularly when the ink composition is applied by an ink-jet method, the clogging of the nozzle holes and the bending of the ink droplets can be suppressed and the discharge can be smoothly performed. Control becomes possible, and stable ejection by the inkjet method becomes possible.
【００２４】（７）固型分濃度が０．０１〜１０．０ｗ
ｔ％であことを特徴とする（６）のインク組成物。(7) The solid component concentration is 0.01 to 10.0 w
The ink composition according to (6), wherein the content is t%.
【００２５】当該（７）のインク組成物によれば、イン
クジェット法により塗布する場合に、吐出性を損なうこ
となく所望の膜厚を得ることが可能となる。According to the ink composition (7), a desired film thickness can be obtained without impairing the dischargeability when the composition is applied by an ink-jet method.
【００２６】（８）蒸気圧が０．００１〜５０ｍｍＨｇ
（室温）の少なくとも一種の溶媒を含むことを特徴とす
る（６）又は（７）のインク組成物。(8) A vapor pressure of 0.001 to 50 mmHg
The ink composition according to (6) or (7), comprising at least one solvent (at room temperature).
【００２７】当該（８）のインク組成物によれば、イン
クジェットにより塗布する際に、インクの乾きを抑える
ことができ、ノズル孔での目詰まりをなくすことができ
る。 （９）前記インク組成物の溶媒が非プロトン性環状極性
溶媒であることを特徴と（８）のいずれかのインク組成
物。According to the ink composition (8), it is possible to suppress drying of the ink when the ink composition is applied by ink jet, and to eliminate clogging in the nozzle hole. (9) The ink composition according to any of (8), wherein the solvent of the ink composition is an aprotic cyclic polar solvent.
【００２８】当該（９）のインク組成物は、正孔注入材
料あるいは発光材料の特性を損ねることなく、安定に分
散または溶解し、インクジェット法により塗布する際に
安定な吐出が可能となる。The ink composition (9) is stably dispersed or dissolved without impairing the properties of the hole injecting material or the luminescent material, and enables stable ejection when applied by an inkjet method.
【００２９】（１０）グリコールエーテル系酢酸を含む
ことを特徴とする（６）乃至（９）のいずれかのインク
組成物。(10) The ink composition according to any one of (6) to (9), further comprising a glycol ether acetic acid.
【００３０】当該（１０）のインク組成物によれば、イ
ンクの乾きを抑えることができるだけでなく、成膜性を
向上することができる。According to the ink composition (10), not only the drying of the ink can be suppressed, but also the film formability can be improved.
【００３１】（１１）低級アルコールを２０ｗｔ％以下
含むことを特徴とする（６）乃至（１０）のいずれかの
インク組成物。(11) The ink composition according to any one of (6) to (10), wherein the ink composition contains 20% by weight or less of a lower alcohol.
【００３２】当該（１１）のインク組成物によれば、特
にインクジェット法により塗布する際に、インクの吐出
性を損ねることなく表面張力および粘度を所望の値に調
整することが可能となる。According to the ink composition (11), it is possible to adjust the surface tension and the viscosity to desired values without impairing the ejection property of the ink, particularly when the ink composition is applied by an ink jet method.
【００３３】（１２）前記インク組成物が正孔注入材料
を含むものであり、該正孔注入材料としてポリチオフェ
ン誘導体とポリスチレンスルフォン酸の混合物を含むこ
とを特徴とする（６）のインク組成物。(12) The ink composition according to (6), wherein the ink composition contains a hole injecting material, and the hole injecting material contains a mixture of a polythiophene derivative and polystyrenesulfonic acid.
【００３４】当該（１２）のインク組成物によれば、特
にインクジェット法により塗布する際に、吐出性、成膜
性ともに優れ、有機ＥＬ素子において高性能の正孔注入
層を得ることが可能となる。According to the ink composition (12), it is possible to obtain a high-performance hole injection layer in an organic EL device, which is excellent in both ejection property and film-forming property, particularly when the composition is applied by an inkjet method. Become.
【００３５】（１３）更に熱硬化剤としてシランカップ
リング剤を含有することを特徴とする（１２）のインク
組成物。(13) The ink composition according to (12), further comprising a silane coupling agent as a thermosetting agent.
【００３６】当該（１３）のインク組成物を用いれば、
特にインクジェット法により塗布することで、有機ＥＬ
素子において発光層との相溶を起こさない正孔注入層を
形成することができる。When the ink composition of (13) is used,
In particular, by applying by an inkjet method, organic EL
In the device, a hole injection layer that does not cause compatibility with the light emitting layer can be formed.
【００３７】（１４）前記インク組成物が発光材料を含
むものであり、該発光材料として、ポリ（パラフェニレ
ンビニレン）およびその誘導体の前駆体を含むことを特
徴とする（６）のインク組成物。(14) The ink composition according to (6), wherein the ink composition contains a light emitting material, and the light emitting material contains a precursor of poly (paraphenylene vinylene) and a derivative thereof. .
【００３８】当該（１４）のインク組成物によれば、特
にインクジェット法に塗布する際の吐出性、成膜性が優
れ、有機ＥＬ素子において発光特性の優れた緑色または
赤色発光層用インク組成物とすることができる。According to the ink composition of (14), the ink composition for a green or red light emitting layer has excellent discharge properties and film forming properties particularly when applied by an ink jet method, and has excellent light emission characteristics in an organic EL device. It can be.
【００３９】（１５）前記発光材料として低分子色素を
ドープしたものを使用することを特徴とする（１４）の
インク組成物。(15) The ink composition according to (14), wherein a light-emitting material doped with a low-molecular dye is used.
【００４０】当該（１５）のインク組成物によれば、特
にインクジェット法に塗布する際の吐出性、成膜性およ
び発光特性の優れた緑色または赤色発光層用インク組成
物とすることができる。According to the ink composition (15), an ink composition for a green or red light emitting layer having excellent dischargeability, film formability, and light emission characteristics when applied by an ink jet method can be obtained.
【００４１】上記（６）乃至（１５）のインク組成物
は、夫々、（１）乃至（５）の有機ＥＬ素子の製造方法
における正孔注入層や発光層の形成工程において好適に
用いることができる。The above ink compositions (6) to (15) can be suitably used in the step of forming a hole injection layer and a light emitting layer in the method for producing an organic EL device of (1) to (5), respectively. it can.
【００４２】また、本発明によれば、上記方法により得
られた、高性能の有機ＥＬ素子が提供される。Further, according to the present invention, there is provided a high-performance organic EL device obtained by the above method.
【００４３】[0043]
【発明の実施の形態】以下、本発明の実施形態について
詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail.
【００４４】本発明のインクジェット方式による有機Ｅ
Ｌ素子の製造方法とは、素子を形成する有機物からなる
正孔注入材料、ならびに有機物からなる発光材料を溶媒
に溶解または分散させたインク組成物を、インクジェッ
トヘッドから吐出させて例えば透明電極が形成され画素
を構成する基板上に塗布し、正孔注入層ならびに発光層
を形成する方法である。かかるインクジェット方式によ
れば、微細なパターニングを簡便にかつ短時間で行うこ
とができ、多色化が可能である。また、必要な場所に必
要量の材料を塗布すればいいので大面積の基板になって
も材料を無駄にすることは無い。Organic E by the inkjet method of the present invention
The method for manufacturing an L element is a method in which a hole injection material composed of an organic substance forming the element and an ink composition in which a luminescent material composed of an organic substance is dissolved or dispersed in a solvent are ejected from an inkjet head to form, for example, a transparent electrode This is a method in which a hole injection layer and a light emitting layer are formed by coating on a substrate constituting a pixel. According to such an ink jet system, fine patterning can be performed easily and in a short time, and multi-coloring can be achieved. In addition, since a necessary amount of material may be applied to a necessary place, the material is not wasted even if the substrate has a large area.
【００４５】本発明の有機ＥＬ素子に製造方法において
使用されるインクジェット用ヘッドの構造を図１および
図２に示す。当該インクジェット用ヘッド１０は、例え
ばステンレス製のノズルプレート１１と振動板１３とを
備え、両者は仕切部材（リザーバープレート）１５を介
して接合されている。ノズルプレート１１と振動板１３
との間には、仕切部材１５によって複数のインク室１９
と液溜り２１とが形成されている。インク室１９および
液溜り２１の内部は本発明のインク組成物で満たされて
おり、インク室１９と液溜り２１とは供給口２３を介し
て連通している。さらに、ノズルプレート１１には、イ
ンク室１９からインク組成物をジェト状に噴射するため
のノズル孔２５が設けられている。一方、インクジェッ
ト用ヘッド１０には、液溜り２１にインク組成物を供給
するためのインク導入孔２７が形成されている。また、
振動板１３のインク室１９に対向する面と反対側の面上
には、前記空間１９の位置に対応させて圧電素子２９が
接合されている。FIGS. 1 and 2 show the structure of an ink jet head used in the method of manufacturing the organic EL device of the present invention. The inkjet head 10 includes, for example, a stainless steel nozzle plate 11 and a vibration plate 13, and both are joined via a partition member (reservoir plate) 15. Nozzle plate 11 and diaphragm 13
Between the ink chambers 19 by the partition member 15.
And a liquid reservoir 21 are formed. The insides of the ink chamber 19 and the liquid reservoir 21 are filled with the ink composition of the present invention, and the ink chamber 19 and the liquid reservoir 21 communicate with each other through a supply port 23. Further, the nozzle plate 11 is provided with a nozzle hole 25 for jetting the ink composition from the ink chamber 19 in a jet shape. On the other hand, the ink-jet head 10 is provided with an ink introduction hole 27 for supplying the ink composition to the liquid reservoir 21. Also,
On the surface of the vibration plate 13 opposite to the surface facing the ink chamber 19, a piezoelectric element 29 is joined so as to correspond to the position of the space 19.
【００４６】この圧電素子２９は一対の電極３１の間に
位置し、通電すると圧電素子２９が外側に突出するよう
に撓曲する。これによってインク室１９の容積が増大す
る。したがって、インク室１９内に増大した容積分に相
当するインク組成物が液溜り２１から供給口２３を介し
て流入する。次に、圧電素子２９への通電を解除する
と、該圧電素子２９と振動板１３はともに元の形状に戻
る。これにより空間１９も元の容積に戻るためインク室
１９内部のインク組成物の圧力が上昇し、ノズル孔２５
から基板に向けてインク組成物が噴出する。The piezoelectric element 29 is located between the pair of electrodes 31 and, when energized, bends so that the piezoelectric element 29 protrudes outward. Thereby, the volume of the ink chamber 19 increases. Therefore, the ink composition corresponding to the increased volume flows into the ink chamber 19 from the liquid reservoir 21 through the supply port 23. Next, when the energization of the piezoelectric element 29 is released, both the piezoelectric element 29 and the diaphragm 13 return to their original shapes. As a result, the space 19 also returns to the original volume, so that the pressure of the ink composition inside the ink chamber 19 increases, and the nozzle hole 25
, The ink composition is ejected toward the substrate.
【００４７】なお、ノズル孔２５の周辺部には、インク
組成物の飛行曲がり・孔詰まりを防止するために撥イン
ク層２６が設けられている。すなわち、ノズル孔２５の
周辺部は、図２に示すように例えばＮｉ−テトラフルオ
ロエチレン共析メッキ層からなる撥インク層２６が設け
られている。An ink repellent layer 26 is provided around the nozzle hole 25 to prevent the ink composition from bending and clogging. That is, as shown in FIG. 2, an ink-repellent layer 26 made of, for example, a Ni-tetrafluoroethylene eutectoid plating layer is provided around the nozzle hole 25.
【００４８】本発明の有機ＥＬ素子の製造方法におい
て、前記インクジェット用ヘッドから吐出させて用いる
正孔注入材料、あるいは発光材料を含むインク組成物は
以下のような特性を有するものである。In the method for manufacturing an organic EL device of the present invention, the ink composition containing a hole injection material or a luminescent material used by discharging from the ink jet head has the following characteristics.
【００４９】インク組成物の粘度は好ましくは１〜２０
ｍＰａ・ｓであって、特に好ましくは２〜８ｍＰａ・ｓ
である。インク組成物の粘度が１ｍＰａ・ｓ未満である
場合、吐出量の制御が困難になるばかりでなく、固型分
濃度が過少となり十分な膜を形成できないことがある。
２０ｍＰａ・ｓを超える場合、ノズル孔からインク組成
物を円滑に吐出させることができない恐れがあり、ノズ
ル孔を大きくする等の装置の仕様を変更する必要が生じ
ることがある。更に粘度が大きい場合、インク組成物中
の固型分が析出し易く、ノズル孔の目詰まり頻度が高く
なる。The viscosity of the ink composition is preferably from 1 to 20.
mPa · s, particularly preferably 2 to 8 mPa · s
It is. When the viscosity of the ink composition is less than 1 mPa · s, not only is it difficult to control the ejection amount, but also the concentration of the solid component is too low to form a sufficient film in some cases.
If it exceeds 20 mPa · s, the ink composition may not be able to be smoothly discharged from the nozzle holes, and it may be necessary to change the specifications of the apparatus such as enlarging the nozzle holes. When the viscosity is further large, solid components in the ink composition tend to precipitate, and the frequency of clogging of the nozzle holes increases.
【００５０】また、インク組成物の表面張力は好ましく
は２０〜７０ｍＮ／ｍであって、特に好ましくは２５〜
４５ｍＮ／ｍである。この範囲の表面張力にすることに
より、インク吐出の際の飛行曲がりを抑えることができ
る。表面張力が２０ｍＮ／ｍ未満であると、インク組成
物のノズル面上での濡れ性が増大するため、インク組成
物を吐出する際、インク組成物がノズル孔の周囲に非対
称に付着することがある。この場合、ノズル孔に付着し
た組成物と吐出しようとする付着物との相互間に引力が
働くため、インク組成物は不均一な力により吐出される
ことになり目標位置に到達できない所謂飛行曲がりが生
じ、もちろんその頻度も高くなる。また、７０ｍＮ／ｍ
を超えるとノズル先端でのメニスカスの形状が安定しな
いためインク組成物の吐出量、吐出タイミングの制御が
困難になる。The surface tension of the ink composition is preferably from 20 to 70 mN / m, particularly preferably from 25 to 70 mN / m.
45 mN / m. By setting the surface tension in this range, it is possible to suppress flight bending at the time of ink ejection. When the surface tension is less than 20 mN / m, the wettability of the ink composition on the nozzle surface increases, so that when the ink composition is ejected, the ink composition may adhere asymmetrically around the nozzle hole. is there. In this case, an attractive force acts between the composition adhering to the nozzle hole and the adhering matter to be ejected, so that the ink composition is ejected by a non-uniform force, so-called flight bending that cannot reach the target position. And, of course, the frequency increases. Also, 70mN / m
If it exceeds, the shape of the meniscus at the nozzle tip is not stable, so that it becomes difficult to control the discharge amount and the discharge timing of the ink composition.
【００５１】インクジェット用ヘッドに設けられたイン
ク組成物を吐出するノズル面を構成する材料に対する接
触角は好ましくは３０°〜１７０°であり、特に好まし
くは３５°〜６５°である。インク組成物がこの範囲の
接触角を持つことによって、インク組成物の飛行曲がり
を制御することができ、精密なパターンニングが可能と
なる。この接触角が３０°未満である場合、インク組成
物のノズル面を構成する材料に対する濡れ性が増大する
ため、表面張力の場合と同様、飛行曲がりが生じる。ま
た。１７０°を超えると、インク組成物とノズル孔の相
互作用が極小となり、ノズル先端でのメニスカスの形状
が安定しないためインク組成物の吐出量、吐出タイミン
グの制御が困難になる。The contact angle with respect to the material constituting the nozzle surface for discharging the ink composition provided in the ink jet head is preferably 30 ° to 170 °, particularly preferably 35 ° to 65 °. When the ink composition has a contact angle in this range, the flight deflection of the ink composition can be controlled, and precise patterning can be performed. When the contact angle is less than 30 °, the wettability of the ink composition with respect to the material constituting the nozzle surface increases, so that a flight bend occurs as in the case of the surface tension. Also. If it exceeds 170 °, the interaction between the ink composition and the nozzle hole becomes extremely small, and the shape of the meniscus at the nozzle tip becomes unstable, so that it becomes difficult to control the discharge amount and the discharge timing of the ink composition.
【００５２】ここで飛行曲がりとは、インク組成物を前
記ノズルから吐出させたとき、ドットの着弾した位置
が、目標位置に対して５０μｍ以上のずれを生じること
をいう。主にノズル孔の濡れ性が不均一である場合やイ
ンク組成物の固型成分の付着による目詰まり等によって
発生する。Here, the flight deflection means that when the ink composition is ejected from the nozzle, the position where the dot lands is shifted by 50 μm or more from the target position. This is mainly caused by non-uniform wettability of the nozzle holes or clogging due to adhesion of solid components of the ink composition.
【００５３】インク組成物の固型分濃度は、組成物全体
に対して０．０１〜１０．０ｗｔ％が好ましく、０．１
〜５．０ｗｔ％が更に好ましい。固型分濃度が低すぎる
と必要な膜厚を得るために吐出回数が多くなってしまい
量産効率が悪くなってしまう。また高すぎても粘度が高
くなってしまい吐出性に影響を与える。The solid concentration of the ink composition is preferably 0.01 to 10.0% by weight, and
-5.0 wt% is more preferable. If the solid component concentration is too low, the number of ejections increases to obtain a required film thickness, and mass production efficiency deteriorates. Also, if it is too high, the viscosity becomes high, which affects the dischargeability.
【００５４】上記固型分は室温での蒸気圧が０．００５
〜５０ｍｍＨｇの少なくとも一つ以上の溶媒に溶解また
は分散していることが望ましい。渇きにくい溶媒を用い
ることによりインク組成物がノズル孔で乾燥し、増粘、
凝集、固型分の付着が起こることを防ぐことができる。
しかし、蒸気圧が０．００５ｍｍＨｇを下回るような溶
媒は、成膜過程で溶媒の除去が困難であるため適さな
い。The solid component has a vapor pressure of 0.005 at room temperature.
Desirably, it is dissolved or dispersed in at least one solvent of 50 mmHg or more. The ink composition is dried at the nozzle holes by using a solvent which is not thirst-dry, and the ink composition is thickened.
Aggregation and adhesion of solid components can be prevented.
However, a solvent having a vapor pressure lower than 0.005 mmHg is not suitable because it is difficult to remove the solvent during the film formation process.
【００５５】このような溶媒としては、γ−ブチロラク
トン、Ｎ−メチルピロリドン（ＮＭＰ）、１、３−ジメ
チル−２−イミダゾリジノン（ＤＭＩ）およびその誘導
体などの非プロトン性環状極性溶媒、またはカルビトー
ルアセテート（ＣＡ）、ブチルカルビトールアセテート
（ＢＣＡ）などのグリコールエーテル系酢酸が挙げられ
る。ＣＡ，ＢＣＡ等の溶媒は成膜性をあげる点でも有効
である。Examples of such a solvent include aprotic cyclic polar solvents such as γ-butyrolactone, N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI) and derivatives thereof, and carboxy. Glycol ether acetic acid such as tall acetate (CA) and butyl carbitol acetate (BCA) can be mentioned. Solvents such as CA and BCA are also effective in increasing the film forming property.
【００５６】一方、メタノール（ＭｅＯＨ）、エタノー
ル（ＥｔＯＨ）、プロピルアルコール等の低級アルコー
ルは表面張力、粘度の調製に有効であるが、揮発性が高
いため、２０ｗｔ％以下であることが望ましい。On the other hand, lower alcohols such as methanol (MeOH), ethanol (EtOH) and propyl alcohol are effective in adjusting the surface tension and viscosity, but are preferably 20 wt% or less because of their high volatility.
【００５７】尚、上述の特性は、有機ＥＬ素子において
正孔輸送層を形成する場合の同層を構成する正孔輸送材
料の特性としても好適である。The above characteristics are also suitable as the characteristics of the hole transport material constituting the hole transport layer when the hole transport layer is formed in the organic EL device.
【００５８】以下、本発明を実施例に沿って更に詳細に
説明する。Hereinafter, the present invention will be described in more detail with reference to examples.
【００５９】（実施例１）実施例１は有機ＥＬ素子の製
造においてインクジェット法により塗布する正孔注入層
形成用インク組成物に関する。Example 1 Example 1 relates to an ink composition for forming a hole injection layer applied by an ink-jet method in the production of an organic EL device.
【００６０】本発明では、正孔注入材料として、ポリチ
オフェン誘導体であるＰＥＤＴ（ポリエチレンジオキシ
チオフェン）In the present invention, a polythiophene derivative, PEDT (polyethylenedioxythiophene), is used as the hole injection material.
【００６１】[0061]
【化１】 Embedded image
【００６２】とＰＳＳ（ポリスチレンスルフォン酸）And PSS (polystyrene sulfonic acid)
【００６３】[0063]
【化２】 Embedded image
【００６４】の混合物を用いた。これらはバイトロンＰ
としてバイエル社から購入することができる。正孔注入
材料（又は正孔輸送層の材料となる正孔輸送材料）とし
ては、ポリアニリン、ポルフィリン化合物、ピリジン誘
導体などが挙げられるが、熱的に耐久性のある高分子
で、水などの極性溶媒に分散できるバイトロンＰがイン
クジェット方式には適している。バイトロンＰを用いて
表１に示すインク組成物を調製した。The mixture was used. These are Baytron P
Can be purchased from Bayer. Examples of the hole injecting material (or the hole transporting material serving as the material of the hole transporting layer) include polyaniline, a porphyrin compound, a pyridine derivative, and the like. Baytron P, which can be dispersed in a solvent, is suitable for the ink jet system. Ink compositions shown in Table 1 were prepared using Baytron P.
【００６５】[0065]
【表１】 [Table 1]
【００６６】発光層との相溶を防ぐため、加熱処理によ
り架橋するシランカップリング剤としてγ−グリシジル
オキシプロピルトリメトキシシランを用い、導電性高分
子と同重量添加した。最終的なインク組成物の固型分濃
度は０．１６ｗｔ％であった。In order to prevent compatibility with the light emitting layer, γ-glycidyloxypropyltrimethoxysilane was used as a silane coupling agent for crosslinking by heat treatment, and was added in the same weight as the conductive polymer. The final solid concentration of the ink composition was 0.16 wt%.
【００６７】表２に上記組成物の粘度、表面張力、イン
クジェット用ヘッドのインク吐出ノズル面を構成する材
料に対する接触角、吐出性、パターニング性および成膜
性を評価した結果を示す。インク組成物の物理的性質お
よび吐出特性については以下の方法で評価した。Table 2 shows the results of evaluation of the viscosity, surface tension, contact angle with respect to the material constituting the ink ejection nozzle surface of the ink jet head, ejection properties, patterning properties, and film forming properties of the composition. The physical properties and ejection characteristics of the ink composition were evaluated by the following methods.
【００６８】粘度：Ｅ型粘度計により２０℃における値
を測定した。Viscosity: The value at 20 ° C. was measured with an E-type viscometer.
【００６９】表面張力：プレート法により同じく２０℃
における値を測定した。Surface tension: 20 ° C. by the plate method
Was measured.
【００７０】接触角：インクジェット用ヘッドのインク
吐出ノズル面を構成する材料（ Ｎｉ−テトラフルオロ
エチレン共析メッキ撥水層）上での静的接触角として測
定した。Contact angle: The contact angle was measured as a static contact angle on the material (Ni-tetrafluoroethylene eutectoid plating water-repellent layer) constituting the ink discharge nozzle surface of the ink jet head.
【００７１】吐出特性：インクジェットプリンター用ヘ
ッド（エプソン社製ＭＪ−９３０Ｃ）を用いた。飛行曲
がりはヘッドと基板の距離を０．６ｍｍにした時の基板
上でのインク液滴の着弾ばらつきを測定した。ノズル孔
の目詰まり頻度として、インク組成物を連続吐出（周波
数７２００Ｈｚ）し、析出したインク組成物の固型分等
によりノズル孔が目詰まりし、吐出不能になった状態に
至るまでに要する時間を測定した。Ejection characteristics: An ink jet printer head (MJ-930C manufactured by Epson Corporation) was used. The flight deflection measured the landing variation of ink droplets on the substrate when the distance between the head and the substrate was 0.6 mm. The nozzle hole clogging frequency is the time required for the ink composition to be continuously ejected (frequency 7200 Hz) and for the nozzle hole to be clogged by the solid component of the deposited ink composition and to be in a state where ejection becomes impossible. Was measured.
【００７２】パターニング性、成膜性：図３（ａ）及び
（ｂ）に示したテストセルに吐出し、室温、真空中で溶
媒を除去した後、大気中２００℃、１０分熱処理して形
成された膜の膜質（凝集、平坦性等）を顕微鏡で観察し
た。テストセルはＩＴＯ基板４１上に形成した２μｍ厚
ポリイミド４０を３０μｍ径で開口した画素（４０μｍ
ピッチ）を有するものである。吐出前に、酸素ガスプラ
ズマとフロロカーボンガスプラズマの連続処理を行い、
ポリイミド表面は撥水化、ＩＴＯ表面は親水化したもの
を用いた。尚、前記プラズマ処理は真空中、大気中のい
ずれの雰囲気であってもよい。そして、インクジェット
装置４２のインクジェットヘッド４３からインク組成物
４４を開口部に吐出し膜を得て評価した。結果を下記表
２に示す。Patterning property, film forming property: formed by discharging into the test cell shown in FIGS. 3A and 3B, removing the solvent in a vacuum at room temperature, and then heat-treating at 200 ° C. in the air for 10 minutes. The film quality (aggregation, flatness, etc.) of the film thus obtained was observed with a microscope. The test cell is a pixel (40 μm) in which a 2 μm thick polyimide 40 formed on an ITO substrate 41 is opened with a diameter of 30 μm.
Pitch). Before discharge, perform continuous processing of oxygen gas plasma and fluorocarbon gas plasma,
The polyimide surface was made water-repellent and the ITO surface was made hydrophilic. The plasma treatment may be performed in either a vacuum or air atmosphere. Then, the ink composition 44 was discharged from the ink jet head 43 of the ink jet device 42 to the opening to obtain a film, which was evaluated. The results are shown in Table 2 below.
【００７３】[0073]
【表２】 [Table 2]
【００７４】表２に示すように、吐出性、パターニング
性、成膜性とも十分、実用レベルに達するものであっ
た。尚、表１の組成中例えば、メタノール（ＭｅＯ
Ｈ）、イソプロピルアルコール（ＩＰＡ）の添加量が２
０％を超える組成物を調製して上記同様に成膜し、評価
したところ、または、１，３−ジメチル−２−イミダゾ
リジン（ＤＭＩ）を添加せず水で置き換えた組成物を調
製して上記同様に成膜して評価したところ、上記物理的
な値を満たしても、インク組成物の渇きにより吐出中、
目詰まりを起こしてしまった。As shown in Table 2, the ejection properties, patterning properties, and film-forming properties were sufficient and reached practical levels. In the composition shown in Table 1, for example, methanol (MeO
H), the addition amount of isopropyl alcohol (IPA) is 2
When a composition exceeding 0% was prepared and a film was formed and evaluated in the same manner as described above, or a composition in which 1,3-dimethyl-2-imidazolidin (DMI) was added and replaced with water without addition was prepared. When the film was formed and evaluated in the same manner as above, even if the above physical values were satisfied, during ejection due to thirst of the ink composition,
I have clogged.
【００７５】（実施例２）実施例２は発光層用インク組
成物に関する。Example 2 Example 2 relates to an ink composition for a light emitting layer.
【００７６】本発明では、緑色発光材料としてポリ（パ
ラフェニレンビニレン）（ＰＰＶ）を用いた。In the present invention, poly (paraphenylene vinylene) (PPV) was used as the green light emitting material.
【００７７】発光層を形成し得る有機化合物としては、
ＰＰＶの他に、ＰＴＶ（ポリ（２、５−チエニレンビニ
レン））等のポリアルキルチオフェン、ＰＦＶ（ポリ
（２、５−フリレンビニレン））、ポリパラフェニレ
ン、ポリアルキルフルオレン等のポリアリレンビニレ
ン、ピラゾリンダイマー、キノリジンカルボン酸、ベン
ゾピリリウムパークロレート、ベンゾピラノキノリジ
ン、フェナントロリンユウロピウム錯体等が挙げられ、
これらを1種または2種以上混合して用いることができ
る。 これらのなかでも高分子有機化合物からなるもの
が好ましい。高分子有機化合物は成膜性に優れ、発光層
の耐久性は極めて良好である。高分子系材料は分子設計
上幅広い自由度を持ち、ＥＬ発光素子の合理的設計が可
能である。また、可視領域の禁止帯幅と比較的高い導電
性を有しており、なかでも共役系高分子はこのような傾
向が顕著である。発光層材料としては、共役系高分子そ
のもの、あるいは加熱等により共役化（成膜）する共役
系高分子の前駆体が用いられる。これらのなかでもＰＰ
Ｖまたはその誘導体が特に好ましい。 ＰＰＶ誘導体の
前駆体として、ＭＯ−ＰＰＶ（ポリ（２、５−ジメトキ
シ−１、４−フェニレンビニレン））前駆体、ＣＮ−Ｐ
ＰＶ（ポリ（２、５−ビスヘキシルオキシ−１、４−フ
ェニレン−（１−シアノビニレン）））前駆体等が挙げ
られる。ＰＰＶまたはその誘導体の共役化（成膜）前の
前駆体は、水あるいは極性溶媒に可溶であり、インクジ
ェット方式によるパターン形成に適している。さらに、
ＰＰＶまたはその誘導体は強い蛍光を持ち、二重結合の
π電子がポリマー鎖上で非局在化している導電性高分子
でもあるためＰＰＶの薄膜は正孔注入輸送層としても機
能し、高性能の有機ＥＬ素子を得ることができる。The organic compound capable of forming the light emitting layer includes:
In addition to PPV, polyalkylthiophenes such as PTV (poly (2,5-thienylenevinylene)), polyarylenes such as PFV (poly (2,5-furylenevinylene)), polyparaphenylene and polyalkylfluorene Vinylene, pyrazoline dimer, quinolizine carboxylic acid, benzopyrylium perchlorate, benzopyranoquinolidine, phenanthroline europium complex and the like,
These can be used alone or in combination of two or more. Among these, those composed of high molecular organic compounds are preferred. The high molecular weight organic compound has excellent film-forming properties and the durability of the light-emitting layer is extremely good. A polymer material has a wide degree of freedom in molecular design, and enables rational design of an EL light emitting device. Further, it has a forbidden band width in the visible region and relatively high conductivity, and the conjugated polymer is particularly prone to this tendency. As the light emitting layer material, a conjugated polymer itself or a precursor of a conjugated polymer that is conjugated (formed into a film) by heating or the like is used. Among these, PP
V or a derivative thereof is particularly preferred. As precursors of PPV derivatives, MO-PPV (poly (2,5-dimethoxy-1,4-phenylenevinylene)) precursor, CN-P
PV (poly (2,5-bishexyloxy-1,4-phenylene- (1-cyanovinylene))) precursor and the like. The precursor of PPV or its derivative before conjugation (film formation) is soluble in water or a polar solvent, and is suitable for pattern formation by an inkjet method. further,
PPV or its derivative has strong fluorescence and is a conductive polymer in which the π electron of the double bond is delocalized on the polymer chain. Therefore, the PPV thin film also functions as a hole injection transport layer, and has high performance. Can be obtained.
【００７８】[0078]
【化３】 Embedded image
【００７９】ポリ（パラフェニレンビニレン）前駆体
（水／ＭｅＯＨ＝５／９５混合溶液）を用いて表３に示
すインク組成物を調製した。固型分濃度は０．３ｗｔ％
であった。An ink composition shown in Table 3 was prepared using a poly (paraphenylene vinylene) precursor (a mixed solution of water / MeOH = 5/95). Solid content concentration is 0.3wt%
Met.
【００８０】[0080]
【表３】 [Table 3]
【００８１】表４に上記組成物の粘度、表面張力、イン
クジェット用ヘッドのインク吐出ノズル面を構成する材
料に対する接触角、吐出性、パターニング性および成膜
性を評価した結果を示す。インク組成物の物理的性質お
よび吐出特性については実施例１と同様の方法で評価し
た。成膜性は吐出後、室温、真空中で溶媒を除去し、窒
素雰囲気中、１５０℃、4時間処理したもので評価し
た。Table 4 shows the results of evaluation of the viscosity, surface tension, contact angle with respect to the material constituting the ink discharge nozzle surface of the ink jet head, dischargeability, patterning property and film formability of the composition. The physical properties and ejection characteristics of the ink composition were evaluated in the same manner as in Example 1. The film forming property was evaluated by removing the solvent in a vacuum at room temperature after discharge, and treating in a nitrogen atmosphere at 150 ° C. for 4 hours.
【００８２】[0082]
【表４】 [Table 4]
【００８３】表４に示すように、吐出性、パターニング
性、成膜性とも十分、実用レベルに達するものであっ
た。これに対し、例えば、 ＤＭＩをジメチルホルムア
ミド（ＤＭＦ）で置き換えたあるいは、ブチルカルビト
ールアセテート（ＢＣＡ）をグリセリンで置き換えたイ
ンク組成物を調製し上記同様の成膜及び評価を行ったと
ころ、吐出性に問題はなかったが、発光効率が低く、発
光色も短波長側にシフトしたものであった。固型分濃度
を０．３ｗｔ％より濃くしたい場合は、前駆体溶液を２
０ｗｔ％以上添加するとＭｅＯＨ含有量が増え、インク
が渇きやすくなり、飛行曲がりや目詰まりを生じるた
め、前駆体溶液を溜去して濃縮したものを用いた。As shown in Table 4, the ejection property, the patterning property, and the film-forming property were sufficient and reached the practical level. On the other hand, for example, an ink composition in which DMI was replaced with dimethylformamide (DMF) or butyl carbitol acetate (BCA) was replaced with glycerin was prepared and subjected to the same film formation and evaluation as described above. Although there was no problem, the luminous efficiency was low and the luminescent color was shifted to the short wavelength side. When it is desired to make the solid content concentration higher than 0.3 wt%,
When 0 wt% or more is added, the MeOH content increases, the ink becomes liable to dry, and flight bending and clogging occur. Therefore, the precursor solution was distilled off and concentrated.
【００８４】（実施例３）実施例３は発光層用インク組
成物に関する。Example 3 Example 3 relates to an ink composition for a light emitting layer.
【００８５】本実施例では、実施例２で用いたＰＰＶ前
駆体インク組成物に赤色発光材料として低分子蛍光色素
であるローダミン１０１を添加したものを用いた。In the present embodiment, the PPV precursor ink composition used in Example 2 was added with rhodamine 101, which is a low molecular weight fluorescent dye, as a red light emitting material.
【００８６】低分子系の蛍光色素をドープする方法は、
発光層の発光特性を変化させることができ、例えば、発
光効率の向上、または発光波長をかえる手段として大変
有効である。蛍光色素のドープにより色純度の高い赤
色、緑色発光を得ることができる。A method of doping a low molecular fluorescent dye is as follows.
It is possible to change the light emission characteristics of the light emitting layer, and is very effective as, for example, a means for improving the light emission efficiency or changing the light emission wavelength. Red and green luminescence with high color purity can be obtained by doping with a fluorescent dye.
【００８７】赤色発光層に用いられる蛍光色素として
は、レーザー色素のＤＣＭあるいはローダミンまたはロ
ーダミン誘導体、ペリレン等を用いることができる。こ
れらの蛍光色素は、低分子であるため溶媒に可溶であ
り、ＰＰＶ等と相溶性がよく、均一で安定した発光層の
形成が容易である。ローダミン誘導体蛍光色素として
は、例えばローダミンＢ，ローダミンＢベース、ローダ
ミン６Ｇ，ローダミン１０１過塩素酸塩等が挙げられこ
れらを2種以上混合したものであってもよい。As the fluorescent dye used for the red light emitting layer, DCM of laser dye, rhodamine or rhodamine derivative, perylene or the like can be used. These fluorescent dyes are low in molecular weight and are soluble in solvents, have good compatibility with PPV and the like, and facilitate formation of a uniform and stable light emitting layer. Examples of the rhodamine derivative fluorescent dye include rhodamine B, rhodamine B base, rhodamine 6G, and rhodamine 101 perchlorate, and a mixture of two or more of these may be used.
【００８８】また、緑色発光層に用いられる蛍光色素と
しては、キナクリドン、ルブレン、ＤＣＪＴおよびそれ
らの誘導体が挙げられる。これらの蛍光色素は、上記赤
色蛍光色素と同様、低分子であるため溶媒に可溶であ
り、またＰＰＶ等と相溶性がよく発光層の形成が容易で
ある。The fluorescent dyes used in the green light emitting layer include quinacridone, rubrene, DCJT and derivatives thereof. These fluorescent dyes, like the red fluorescent dyes described above, have low molecular weight and are soluble in solvents, and have good compatibility with PPV and the like, and facilitate formation of a light emitting layer.
【００８９】本実施例では、下記表５に示す赤色発光層
用インク組成物を調製した。In this example, ink compositions for a red light emitting layer shown in Table 5 below were prepared.
【００９０】[0090]
【表５】 [Table 5]
【００９１】表６に上記組成物の粘度、表面張力、イン
クジェット用ヘッドのインク吐出ノズル面を構成する材
料に対する接触角、吐出性、パターニング性および成膜
性を評価した結果を示す。インク組成物の物理的性質お
よび吐出特性、成膜性については実施例２と同様の方法
で評価した。Table 6 shows the results of evaluation of the viscosity, surface tension, contact angle with respect to the material constituting the ink ejection nozzle surface of the ink jet head, ejection property, patterning property and film forming property of the composition. The physical properties, ejection characteristics, and film formability of the ink composition were evaluated in the same manner as in Example 2.
【００９２】[0092]
【表６】 [Table 6]
【００９３】表６に示すように、吐出性、パターニング
性、成膜性とも十分、実用レベルに達するものであっ
た。ローダミン１０１のドープ量はＰＰＶ前駆体に対し
１．５ｗｔ％添加した場合、もっとも効率よく、赤色発
光を示した。As shown in Table 6, the ejection properties, patterning properties, and film-forming properties were sufficient and reached practical levels. When the doping amount of rhodamine 101 was 1.5 wt% relative to the PPV precursor, red light emission was most efficiently exhibited.
【００９４】（実施例４）実施例４はインクジェット方
式による有機ＥＬ素子の製造方法に関する。図４は3色
のフルカラー有機ＥＬ素子の製造工程を示したものであ
る。Example 4 Example 4 relates to a method for manufacturing an organic EL device by an ink-jet method. FIG. 4 shows a manufacturing process of three full-color organic EL elements.
【００９５】透明基板１０４は、支持体であると同時に
光を取り出す面として機能する。従って、透明基板１０
４は、光の透過特性や熱的安定性を考慮して選択され
る。透明基板材料としては、例えばガラス基板、透明プ
ラスチック等が挙げられるが、耐熱性に優れることから
ガラス基板が好ましい。The transparent substrate 104 functions not only as a support but also as a surface from which light is extracted. Therefore, the transparent substrate 10
4 is selected in consideration of light transmission characteristics and thermal stability. Examples of the transparent substrate material include a glass substrate and a transparent plastic, and a glass substrate is preferable because of its excellent heat resistance.
【００９６】まず、透明基板１０４上に、画素電極１０
１、１０２、１０３を形成した。形成方法としては、例
えばフォトリソグラフィー、真空蒸着、スパッタリング
法、パイロゾル法等が挙げられるが、フォトリソグラフ
ィーによることが好ましい。画素電極としては透明画素
電極が好ましく、透明画素電極を構成する材料として
は、酸化スズ膜、ＩＴＯ膜、酸化インジウムと酸化亜鉛
との複合酸化物膜等が挙げられる。First, the pixel electrode 10 is placed on the transparent substrate 104.
1, 102 and 103 were formed. Examples of the formation method include photolithography, vacuum deposition, sputtering, and a pyrosol method, but photolithography is preferred. A transparent pixel electrode is preferable as the pixel electrode, and examples of a material forming the transparent pixel electrode include a tin oxide film, an ITO film, and a composite oxide film of indium oxide and zinc oxide.
【００９７】次に隔壁（バンク）１０５を感光性ポリイ
ミドで形成し、上記の各透明画素電極間を埋めた。これ
によりコントラストの向上、発光材料の混色の防止、画
素と画素との間からの光洩れ等を防止することができ
る。Next, the partition (bank) 105 was formed of photosensitive polyimide, and the space between the transparent pixel electrodes was filled. As a result, it is possible to improve contrast, prevent color mixing of light emitting materials, and prevent light leakage between pixels.
【００９８】隔壁１０５を構成する材料としては、ＥＬ
材料の溶媒に対し耐久性を有するものえあれば特に限定
されないが、フロロカーボンガスプラズマ処理によりテ
フロン化できることから、例えばアクリル樹脂、エポキ
シ樹脂、感光性ポリイミド等お有機材料が好ましい。液
状ガラス等の無機材料を下層にした積層隔壁であっても
よい。また、隔壁１０５は上記材料にカーボンブラック
等を混入してブラックレジストとしてもよい。この隔壁
１０５の形成方法としては、例えばフォトリソグラフィ
ー等が挙げられる。The material constituting the partition 105 is EL
The material is not particularly limited as long as it has durability with respect to the solvent of the material. However, organic materials such as acrylic resin, epoxy resin, and photosensitive polyimide are preferable because Teflon can be formed by fluorocarbon gas plasma treatment. It may be a laminated partition in which an inorganic material such as liquid glass is used as a lower layer. Further, the partition 105 may be formed as a black resist by mixing carbon black or the like into the above material. Examples of a method for forming the partition 105 include photolithography.
【００９９】正孔注入層（更に正孔輸送層）用インク組
成物を塗布する直前に、上記基板の酸素ガスとフロロカ
ーボンガスプラズマの連続プラズマ処理を行った。これ
によりポリイミド表面は撥水化、ＩＴＯ表面は親水化さ
れ、インクジェット液滴を微細にパターニングするため
の基板側の濡れ性の制御ができる。プラズマを発生する
装置としては、真空中でプラズマを発生する装置でも、
大気中でプラズマを発生する装置でも同様に用いること
ができる。Immediately before applying the ink composition for the hole injection layer (and the hole transport layer), the substrate was subjected to continuous plasma treatment with oxygen gas and fluorocarbon gas plasma. Thereby, the polyimide surface is made water-repellent and the ITO surface is made hydrophilic, so that the wettability on the substrate side for finely patterning the inkjet droplets can be controlled. As a device that generates plasma, even a device that generates plasma in a vacuum,
An apparatus that generates plasma in the atmosphere can be used similarly.
【０１００】次に、実施例１で挙げた正孔注入層用イン
ク組成物をインクジェットプリント装置１０９のヘッド
１１０（エプソン社製ＭＪ−９３０Ｃ）から吐出し、各
画素電極１０１、１０２、１０３上にパターニング塗布
を行った。塗布後、真空中（１ｔｏｒｒ）、室温、２０
分という条件で溶媒を除去し、その後、大気中、２００
℃（ホットプレート上）、１０分の熱処理により、実施
例２、３で挙げた発光層用インク組成物と相溶しない正
孔注入層１２０を形成した。膜厚は４０ｎｍであった。
本実施例では各画素とも共通の正孔注入層を形成した
が、場合によっては各発光層毎で発光層に適した正孔注
入材料（または正孔輸送材料）を用いて形成しても良
い。Next, the ink composition for a hole injection layer described in Example 1 was ejected from the head 110 (MJ-930C manufactured by Epson Corporation) of the ink jet printing apparatus 109, and was discharged onto each of the pixel electrodes 101, 102 and 103. Patterning coating was performed. After application, in vacuum (1 torr), room temperature, 20
Minutes, the solvent is removed.
C. (on a hot plate) by heat treatment for 10 minutes to form a hole injection layer 120 incompatible with the light emitting layer ink composition described in Examples 2 and 3. The film thickness was 40 nm.
In this embodiment, a common hole injection layer is formed for each pixel. However, in some cases, a hole injection material (or a hole transport material) suitable for the light emitting layer may be formed for each light emitting layer. .
【０１０１】さらに実施例３で挙げた赤色発光層用イン
ク組成物、ならびに実施例２で挙げた緑色発光層用イン
ク組成物をインクジェット方式により正孔注入層１２０
上を介して画素電極１０１ならびに１０２上にパターニ
ン状に塗布した。塗布後、真空中（１ｔｏｒｒ）、室
温、２０分という条件で溶媒を除去し、続けて窒素雰囲
気中、１５０℃、4時間の熱処理により共役化させ赤色
発光層１０６、緑色発光層１０７を形成した。膜厚は５
０ｎｍであった。熱処理により共役した発光層は溶媒に
不溶である。Further, the ink composition for a red light-emitting layer described in Example 3 and the ink composition for a green light-emitting layer described in Example 2 were applied to the hole injection layer 120 by an ink jet method.
It was applied in a pattern on the pixel electrodes 101 and 102 via the upper portion. After the application, the solvent was removed under vacuum (1 torr) at room temperature for 20 minutes, and then conjugated by heat treatment at 150 ° C. for 4 hours in a nitrogen atmosphere to form a red light emitting layer 106 and a green light emitting layer 107. . The film thickness is 5
It was 0 nm. The light emitting layer conjugated by the heat treatment is insoluble in the solvent.
【０１０２】かかるインクジェット方式によれば、微細
なパターニングを簡便にかつ短時間で行うことができ
る。また、インク組成物の固型分濃度および吐出量を変
えることにより膜厚を変えることが可能である。According to such an ink jet system, fine patterning can be performed easily and in a short time. Further, the film thickness can be changed by changing the solid component concentration and the ejection amount of the ink composition.
【０１０３】また、発光層を形成する前に正孔注入層１
２０に酸素ガスとフロロカーボンガスプラズマの連続プ
ラズマ処理を行ってもよい。これにより正孔注入または
正孔輸送層１２０上にフッ素化物層が形成され、イオン
化ポテンシャルが高くなることにより正孔注入効率が増
し、発光効率の高い有機ＥＬ素子を提供できる。Before forming the light emitting layer, the hole injection layer 1
20 may be subjected to continuous plasma treatment of oxygen gas and fluorocarbon gas plasma. As a result, a fluorinated layer is formed on the hole injection or hole transport layer 120, and the ionization potential is increased, thereby increasing the hole injection efficiency and providing an organic EL device with high luminous efficiency.
【０１０４】次いで、青色発光層１０８を赤色発光層１
０６、緑色発光層１０７および正孔注入層１２０上を介
して画素電極１０３上に形成した。これにより、赤、
緑、青の3原色を形成するのみならず、赤色発光層およ
び１０６緑色発光層１０７と隔壁１０５との段差を埋め
て平坦化することができる。これにより、上下電極間の
ショートを確実に防ぐことができる。青色発光層の膜厚
を調整することで、青色発光層は赤色発光層および緑色
発光層との積層構造において、電子注入輸送層として作
用し、青色には発光しない。Next, the blue light emitting layer 108 is replaced with the red light emitting layer 1.
06, on the pixel electrode 103 via the green light emitting layer 107 and the hole injection layer 120. This allows red,
In addition to forming the three primary colors of green and blue, it is possible to fill the steps between the red light-emitting layer and the green light-emitting layer 106 and the partition wall 105 and to planarize them. As a result, a short circuit between the upper and lower electrodes can be reliably prevented. By adjusting the thickness of the blue light emitting layer, the blue light emitting layer acts as an electron injection / transport layer in the stacked structure of the red light emitting layer and the green light emitting layer, and does not emit blue light.
【０１０５】かかる青色発光層１０８の形成方法として
は特に限定されず、湿式法として一般的なスピンコート
法またはインクジェット法でも成膜可能である。本実施
例では、ポリジオクチルフルオレンのキシレン溶液をス
ピンコートして、膜厚４５ｎｍの青色発光層１０８を形
成した。The method for forming the blue light emitting layer 108 is not particularly limited, and a film can be formed by a general spin coating method or an ink jet method as a wet method. In this example, a blue light-emitting layer 108 having a thickness of 45 nm was formed by spin coating a xylene solution of polydioctylfluorene.
【０１０６】青色発光層としては他にポリフルオレン誘
導体であるポリジヘキシルフルオレンや、その他の重合
基との共重合体が挙げられ、青色蛍光色素や電子注入輸
送能をもつ有機化合物を添加してもよい。Examples of the blue light-emitting layer include polydihexylfluorene, which is a polyfluorene derivative, and copolymers with other polymer groups. A blue fluorescent dye or an organic compound having an electron injecting / transporting ability may be added. Good.
【０１０７】電子注入輸送層を形成し得る有機化合物と
しては、ＰＢＤ，ＯＸＤ−８等のオキサジアゾール誘導
体、ＤＳＡ、アルミキノール錯体、Ｂｅｂｑ、トリアゾ
ール誘導体、アゾメチン錯体、ポルフィン錯体等が挙げ
られる。Examples of the organic compound capable of forming the electron injecting and transporting layer include oxadiazole derivatives such as PBD and OXD-8, DSA, aluminum quinol complex, Bebq, triazole derivative, azomethine complex, and porphine complex.
【０１０８】本実施例のように、有機発光層のうち２色
をインクジェット方式により形成し、他の一色を従来の
塗布方法で形成することにより、インクジェット方式に
あまり適さない発光材料であっても、インクジェット方
式に用いられる他の有機発光材料と組み合わせることに
よりフルカラー有機ＥＬ素子を形成することができるた
め、素子設計の自由度が増す。インクジェット方式以外
の従来の塗布方法としては、印刷法、転写法、ディッピ
ング法、スピンコート法、キャスト法、キャピラリー
法、ロールコート法、バーコート法等が挙げられる。As in this embodiment, by forming two colors of the organic light emitting layer by the ink jet method and forming the other color by the conventional coating method, even if the light emitting material is not very suitable for the ink jet method. Since a full-color organic EL element can be formed by combining with another organic light emitting material used in an ink jet system, the degree of freedom in element design is increased. Conventional coating methods other than the inkjet method include a printing method, a transfer method, a dipping method, a spin coating method, a casting method, a capillary method, a roll coating method, a bar coating method, and the like.
【０１０９】最後に、陰極（対向電極）１１３を形成し
た。陰極１１３としては金属薄膜電極が好ましく、陰極
を構成する金属としては、例えばＭｇ、Ａｇ、Ａｌ、Ｌ
ｉ等が挙げられる。また、これらの他に仕事関数の小さ
い材料を用いることができ、例えばアルカリ金属や、Ｃ
ａ等のアルカリ土類金属およびこれらを含む合金を用い
ることができる。また金属のフッ素化物も適応できる。
このような陰極１１３は蒸着法およびスパッタ法等によ
り形成することができる。本実施例では、Ｃａを真空加
熱蒸着法で１００ｎｍ、さらにＡｌをスパッタ法で１２
００ｎｍ積層して陰極とした。Finally, a cathode (opposite electrode) 113 was formed. As the cathode 113, a metal thin film electrode is preferable, and as a metal constituting the cathode, for example, Mg, Ag, Al, L
i and the like. In addition, a material having a small work function can be used in addition to the above materials.
Alkaline earth metals such as a and alloys containing these can be used. Fluoride of metal is also applicable.
Such a cathode 113 can be formed by an evaporation method, a sputtering method, or the like. In this embodiment, Ca is 100 nm by the vacuum heating evaporation method, and Al is 12 nm by the sputtering method.
A cathode was formed by laminating 00 nm.
【０１１０】さらに陰極１１３の上に保護膜を形成して
もよい。保護膜を形成することにより、陰極１１３およ
び各発光層１０６、１０７、１０８の劣化、損傷および
剥離等を防止しすることができた。A protective film may be formed on the cathode 113. By forming the protective film, it was possible to prevent the cathode 113 and each of the light emitting layers 106, 107, and 108 from being deteriorated, damaged, and peeled off.
【０１１１】このような保護膜の構成材料としては、エ
ポキシ樹脂、アクリル樹脂、液状ガラス等が挙げられ
る。また、保護膜の形成方法としては、例えばスピンコ
ート法、キャスティング法、ディッピング法、バーコー
ト法、ロールコート法、キャピラリー法等が挙げられ
る。As a constituent material of such a protective film, an epoxy resin, an acrylic resin, a liquid glass or the like can be used. Examples of the method for forming the protective film include a spin coating method, a casting method, a dipping method, a bar coating method, a roll coating method, and a capillary method.
【０１１２】本実施例で得られた有機ＥＬ素子では、各
色の画素とも５Ｖ以下の低電圧でも１００ｃｄ／ｍ２以
上の輝度が得られた。また、インクジェット方式により
形成した赤色画素、緑色画素においては、発光効率がそ
れぞれ０．１５ｌｍ／Ｗ、０．２５ｌｍ／Ｗであり、発
光寿命（一定電流を印加し、連続発光させた場合、初期
輝度に対し５０％低下するまでの時間）も２０００時間
以上であった。In the organic EL device obtained in this example, luminance of 100 cd / m 2 or more was obtained for each color pixel even at a low voltage of 5 V or less. The red pixel and the green pixel formed by the inkjet method have luminous efficiencies of 0.15 lm / W and 0.25 lm / W, respectively. (Time to decrease by 50%) was also 2000 hours or more.
【０１１３】上記同様の材料を用い、スピンコートで正
孔注入層および発光層を同じ積層構造で形成した赤色発
光素子、緑色発光素子のものと同程度であった。このよ
うに、インクジェット方式においても優れた特性を示
し、スピンコート品に劣らない素子を形成することがで
きた。Using the same material as described above, it was comparable to that of the red light emitting element and the green light emitting element in which the hole injection layer and the light emitting layer were formed in the same laminated structure by spin coating. As described above, excellent characteristics were exhibited in the ink jet system, and an element not inferior to the spin-coated product could be formed.
【０１１４】[0114]
【発明の効果】以上本発明によれば、正孔注入層及び発
光層の両方をインクジェット法で形成し、低コストで簡
易迅速に有機ＥＬ素子を得ることができる。また、吐出
性、パターニング性および成膜性に優れた正孔注入用イ
ンク組成物および発光材層用インク組成物を提供するこ
とができた。また、該インク組成物を用い、インクジェ
ット方式により正孔注入または正孔輸送層および発光層
を簡便かつ容易にパターン形成でき、積層構造からなる
特性の優れた高精細フルカラー有機ＥＬ素子を製造する
ことができる。As described above, according to the present invention, both the hole injection layer and the light emitting layer are formed by the ink jet method, and the organic EL device can be obtained easily at low cost and quickly. Further, it was possible to provide an ink composition for hole injection and an ink composition for a luminescent material layer having excellent ejection properties, patterning properties and film-forming properties. Further, using the ink composition, a hole injection or hole transport layer and a light emitting layer can be easily and easily patterned by an ink-jet method, and a high-definition full-color organic EL device having a layered structure and excellent characteristics is manufactured. Can be.
【図１】本発明の有機薄膜ＥＬ素子の製造に用いられる
インクジェット用プリンターヘッドの構造の一例を示す
平面斜視図である。FIG. 1 is a plan perspective view showing an example of the structure of an ink jet printer head used for manufacturing an organic thin film EL device of the present invention.
【図２】本発明の有機薄膜ＥＬ素子の製造に用いられる
インクジェット用プリンターヘッドのノズル部分の構造
の一例を示す断面図である。FIG. 2 is a cross-sectional view showing an example of a structure of a nozzle portion of an ink jet printer head used for manufacturing an organic thin film EL device of the present invention.
【図３】本発明の実施例において、インク組成物のパタ
ーニング性、成膜性評価に用いるテストセルを示す図で
ある。FIG. 3 is a view showing a test cell used for evaluation of patterning property and film forming property of an ink composition in Examples of the present invention.
【図４】本発明の有機ＥＬ素子の製造方法の一例を示す
断面図である。FIG. 4 is a cross-sectional view illustrating an example of the method for manufacturing an organic EL device of the present invention.
１０ インクジェット用ヘッド １１ ノズルプレート １３ 振動板 １５ 仕切部材 １９ インク室 ２１ 液溜り ２３ 供給口 ２５ ノズル孔 ２６ 撥インク層 ２７ インク導入孔 ２９ 圧電素子 ３１ 電極 ３３ ノズル面 ４０ ポリイミド隔壁 ４１ ＩＴＯ ４２ インクジェットプリント装置 ４３ インクジェットヘッド ４４ インク組成物 １０１ 画素電極（赤） １０２ 画素電極（緑） １０３ 画素電極（青） １０４ 透明基板 １０５ 隔壁 １０６ 発光層（赤） １０７ 発光層（緑） １０８ 発光層（青） １０９ インクジェットプリント装置 １１０ インクジェトヘッド １１３ 陰極 １２０ 正孔注入層 REFERENCE SIGNS LIST 10 inkjet head 11 nozzle plate 13 diaphragm 15 partition member 19 ink chamber 21 liquid reservoir 23 supply port 25 nozzle hole 26 ink repellent layer 27 ink introduction hole 29 piezoelectric element 31 electrode 33 nozzle surface 40 polyimide partition 41 ITO 42 inkjet printing device 43 Ink Composition 44 Ink Composition 101 Pixel Electrode (Red) 102 Pixel Electrode (Green) 103 Pixel Electrode (Blue) 104 Transparent Substrate 105 Partition 106 Light Emitting Layer (Red) 107 Light Emitting Layer (Green) 108 Light Emitting Layer (Blue) 109 Inkjet Printing device 110 Inkjet head 113 Cathode 120 Hole injection layer
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 3K007 AB03 AB04 AB18 CA01 CA05 CB01 DA00 DB03 EB00 FA00 FA01 FA03 5C094 AA05 AA08 AA24 AA43 BA27 CA23 EA05 EB02 GB10 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 3K007 AB03 AB04 AB18 CA01 CA05 CB01 DA00 DB03 EB00 FA00 FA01 FA03 5C094 AA05 AA08 AA24 AA43 BA27 CA23 EA05 EB02 GB10
Claims (26)
で狭持した構造の有機ＥＬ素子の製造方法であって、基
板上の所定の領域に有機化合物からなる正孔注入材料を
含むインク組成物をインクジェット方式により塗布し正
孔注入層を形成する工程と、有機化合物からなる発光材
料を含むインク組成物をインクジェット方式により塗布
し発光層を形成する工程とを具備することを特徴とする
有機ＥＬ素子の製造方法。1. A method of manufacturing an organic EL device having a structure in which a hole injection layer and a light emitting layer are sandwiched between an anode and a cathode, wherein a predetermined region on a substrate includes a hole injection material made of an organic compound. A step of forming a hole injection layer by applying an ink composition by an ink-jet method, and a step of forming a light-emitting layer by applying an ink composition containing a light-emitting material composed of an organic compound by an ink-jet method. Of manufacturing an organic EL device.
を有する素子であり、基板上に該画素毎を隔てる隔壁を
設け、該隔壁間の領域に前記正孔注入層及び前記発光層
を形成することを特徴とする請求項１記載の有機ＥＬ素
子の製造方法。2. The organic EL element is an element having a plurality of pixels on a substrate, a partition separating the pixels is provided on the substrate, and the hole injection layer and the light emitting layer are provided in a region between the partitions. 2. The method according to claim 1, wherein the organic EL device is formed.
を有する素子であり、基板上に該画素毎を隔てる隔壁を
設け、酸素ガスプラズマとフロロカーボンガスプラズマ
の連続処理工程を経て、前記正孔注入層と、前記発光層
を形成することを特徴とする請求項１記載の有機ＥＬ素
子の製造方法。3. The organic EL element is an element having a plurality of pixels on a substrate, a partition is provided on the substrate to separate the pixels, and the organic EL element is subjected to a continuous processing step of oxygen gas plasma and fluorocarbon gas plasma. 2. The method according to claim 1, wherein a hole injection layer and the light emitting layer are formed.
含むインク組成物をインクジェット方式により塗布した
後、該インク組成物の溶媒を除去して、正孔注入層を得
ること、及び前記有機化合物からなる発光材料を含むイ
ンク組成物をインクジェット方式により塗布した後、該
インク組成物の溶媒を除去し、発光層を得ることを特徴
とする請求項１記載の有機ＥＬ素子の製造方法。4. An ink composition containing a hole injecting material comprising the organic compound is applied by an ink jet method, and then a solvent of the ink composition is removed to obtain a hole injecting layer. 2. The method for producing an organic EL device according to claim 1, wherein an ink composition containing a luminescent material is applied by an ink-jet method, and then the solvent of the ink composition is removed to obtain a luminescent layer.
含むインク組成物をインクジェット法により塗布した
後、さらに熱処理により該インク組成物の材料を硬化あ
るいは共役化させて正孔注入層を得ること、及び前記有
機化合物からなる発光材料を含むインク組成物をインク
ジェット方式により塗布した後、さらに熱処理により該
インク組成物の材料を硬化あるいは共役化させて発光層
を得ることを特徴とする請求項１記載の有機ＥＬ素子の
製造方法。5. An ink composition containing a hole injection material comprising the organic compound is applied by an inkjet method, and then the material of the ink composition is cured or conjugated by heat treatment to obtain a hole injection layer. And applying an ink composition containing a luminescent material comprising the organic compound by an ink-jet method, and further curing or conjugating the material of the ink composition by heat treatment to obtain a luminescent layer. The method for producing the organic EL device according to the above.
むインク組成物の粘度が１〜２０ｍＰａ・ｓ、表面張力
が２０〜７０ｍＮ／ｍ 、インクジェットヘッドのノズ
ル面を構成する材料に対する接触角が３０〜１７０°で
あることを特徴とする請求項１乃至５記載のいずれかに
記載の有機ＥＬ素子の製造方法。6. The ink composition containing the hole injection material or the luminescent material has a viscosity of 1 to 20 mPa · s, a surface tension of 20 to 70 mN / m, and a contact angle with a material constituting a nozzle surface of an inkjet head. The method for producing an organic EL device according to claim 1, wherein the angle is 30 to 170 °.
１〜１０．０ｗｔ％であることを特徴とする請求項６記
載の有機ＥＬ素子の製造方法。7. The ink composition having a solid content concentration of 0.0
The method for producing an organic EL device according to claim 6, wherein the content is 1 to 10.0 wt%.
〜５０ｍｍＨｇ（室温）の少なくとも一種の溶媒を含む
ことを特徴とする請求項６又は７記載の有機ＥＬ素子。8. The ink composition having a vapor pressure of 0.001.
8. The organic EL device according to claim 6, wherein the organic EL device contains at least one solvent having a temperature of from about 50 mmHg (room temperature).
環状極性溶媒であることを特徴とする請求項８記載の有
機ＥＬ素子の製造方法。9. The method according to claim 8, wherein the solvent of the ink composition is an aprotic cyclic polar solvent.
ル系酢酸を含むことを特徴とする請求項６乃至９のいず
れかに記載の有機ＥＬ素子の製造方法。10. The method for producing an organic EL device according to claim 6, wherein the ink composition contains a glycol ether-based acetic acid.
２０ｗｔ％以下含むことを特徴とする請求項６乃至１０
のいずれかに記載の有機ＥＬ素子の製造方法。11. The ink composition according to claim 6, wherein the ink composition contains 20% by weight or less of a lower alcohol.
The method for producing an organic EL device according to any one of the above.
むものであり、該正孔注入材料としてポリチオフェン誘
導体とポリスチレンスルフォン酸の混合物を含むことを
特徴とする請求項６記載の有機ＥＬ素子の製造方法。12. The organic EL device according to claim 6, wherein the ink composition contains a hole injecting material, and the hole injecting material contains a mixture of a polythiophene derivative and polystyrenesulfonic acid. Production method.
グ剤を含有することを特徴とする請求項１２記載の有機
ＥＬ素子の製造方法。13. The method for producing an organic EL device according to claim 12, further comprising a silane coupling agent as a thermosetting agent.
のであり、該発光材料として、ポリ（パラフェニレンビ
ニレン）およびその誘導体の前駆体を含むことを特徴と
する請求項６記載の有機ＥＬ素子の製造方法。14. The organic EL device according to claim 6, wherein the ink composition contains a light emitting material, and the light emitting material contains a precursor of poly (paraphenylene vinylene) and a derivative thereof. Manufacturing method.
プしたものを使用することを特徴とする請求項１４記載
の有機ＥＬ素子の製造方法。15. The method according to claim 14, wherein a light-emitting material doped with a low-molecular dye is used.
方法により製造される有機ＥＬ素子。16. An organic EL device manufactured by the method according to claim 1.
ェット法により塗布される、正孔注入材料又は発光材料
を含むインク組成物であって、粘度が１〜２０ｍＰａ・
ｓ、表面張力が２０〜７０ｍＮ／ｍ 、インクジェット
ヘッドのノズル面を構成する材料に対する接触角が３０
〜１７０°であることを特徴とするインク組成物。17. An ink composition containing a hole injecting material or a luminescent material, which is applied by an inkjet method in the production of an organic EL device, and has a viscosity of 1 to 20 mPa · s.
s, the surface tension is 20 to 70 mN / m 2, and the contact angle with the material constituting the nozzle surface of the inkjet head is 30
An ink composition characterized by being at an angle of -170 °.
％であことを特徴とする請求項１７記載のインク組成
物。18. The solid content concentration is 0.01 to 10.0 wt.
The ink composition according to claim 17, wherein
（室温）の少なくとも一種の溶媒を含むことを特徴とす
る請求項１７又は１８記載のインク組成物。19. A vapor pressure of 0.001 to 50 mmHg
19. The ink composition according to claim 17, further comprising at least one solvent of (room temperature).
性環状極性溶媒であることを特徴と請求項１９記載のイ
ンク組成物。20. The ink composition according to claim 19, wherein the solvent of the ink composition is an aprotic cyclic polar solvent.
ことを特徴とする請求項１７乃至２０のいずれかにイン
ク組成物。21. The ink composition according to claim 17, comprising the glycol ether acetic acid.
ことを特徴とする請求項１７乃至２１記載のインク組成
物。22. The ink composition according to claim 17, further comprising 20% by weight or less of a lower alcohol.
むものであり、該正孔注入材料としてポリチオフェン誘
導体とポリスチレンスルフォン酸の混合物を含むことを
特徴とする請求項１７記載のインク組成物。23. The ink composition according to claim 17, wherein the ink composition contains a hole injecting material, and the hole injecting material contains a mixture of a polythiophene derivative and polystyrenesulfonic acid.
グ剤を含有することを特徴とする請求項１７記載のイン
ク組成物。24. The ink composition according to claim 17, further comprising a silane coupling agent as a thermosetting agent.
のであり、該発光材料として、ポリ（パラフェニレンビ
ニレン）およびその誘導体の前駆体を含むことを特徴と
する請求項１７記載のインク組成物。25. The ink composition according to claim 17, wherein the ink composition contains a light emitting material, and the light emitting material contains a precursor of poly (paraphenylene vinylene) and a derivative thereof. .
プしたものを使用することを特徴とする請求項２５記載
のインク組成物。26. The ink composition according to claim 25, wherein a material doped with a low molecular dye is used as the light emitting material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11134320A JP2000323276A (en) | 1999-05-14 | 1999-05-14 | Manufacture of organic el element, organic el element, and ink composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11134320A JP2000323276A (en) | 1999-05-14 | 1999-05-14 | Manufacture of organic el element, organic el element, and ink composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006331375A Division JP4513800B2 (en) | 2006-12-08 | 2006-12-08 | Manufacturing method of organic EL element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000323276A true JP2000323276A (en) | 2000-11-24 |
Family
ID=15125563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11134320A Withdrawn JP2000323276A (en) | 1999-05-14 | 1999-05-14 | Manufacture of organic el element, organic el element, and ink composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000323276A (en) |
Cited By (60)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1219980A2 (en) * | 2000-12-21 | 2002-07-03 | Seiko Epson Corporation | Method and apparatus for producing color filter, method and apparatus for manufacturing liquid crystal device, method and apparatus for manufacturing EL device, method of discharging material, apparatus for controlling head and electronic apparatus |
| WO2003022010A1 (en) * | 2001-08-30 | 2003-03-13 | Fujitsu Limited | Method for manufacturing organic el device and organic el device |
| JP2003077652A (en) * | 2001-08-31 | 2003-03-14 | Dainippon Printing Co Ltd | Manufacturing method for electroluminescent element |
| WO2003026359A1 (en) * | 2001-09-12 | 2003-03-27 | Seiko Epson Corporation | Patterning method, film forming method, patterning device, film forming device, electro-optic device and production method therefor, electronic apparatus, and electronic device and production method therefor |
| WO2003045115A1 (en) * | 2001-11-22 | 2003-05-30 | Nippon Soda Co.,Ltd. | El device |
| JP2003168569A (en) * | 2001-11-26 | 2003-06-13 | Samsung Sdi Co Ltd | Full color organic electroluminescent display element and manufacturing method of the same |
| EP1225472A3 (en) * | 2001-01-15 | 2003-09-17 | Seiko Epson Corporation | Material discharging apparatus and method for producing color filters, liquid crystal and electroluminescent devices |
| EP1366920A1 (en) | 2002-05-31 | 2003-12-03 | Seiko Epson Corporation | Optical head and image forming apparatus employing the same |
| EP1371101A1 (en) * | 2001-03-22 | 2003-12-17 | Microemissive Displays Limited | Method of creating an electroluminescent device |
| JP2004330136A (en) * | 2003-05-09 | 2004-11-25 | Seiko Epson Corp | Method for drying liquid film and method for manufacturing organic el panel, electrooptic panel and electronic equipment, and apparatus for drying liquid film, electrooptic panel, electrooptic apparatus and electronic equipment |
| US6825867B2 (en) | 2001-07-09 | 2004-11-30 | Seiko Epson Corporation | Organic electroluminescent array exposure head, method of fabricating the same, and image forming apparatus using the same |
| US6879099B2 (en) | 2002-07-10 | 2005-04-12 | Kabushiki Kaisha Toshiba | Organic EL element and organic EL display |
| JP2005514726A (en) * | 2001-07-21 | 2005-05-19 | コビオン オーガニック セミコンダクターズ ゲーエムベーハー | Organic semiconductor solution |
| US6918666B2 (en) | 2002-03-13 | 2005-07-19 | Ricoh Company, Ltd. | Fabrication of functional device mounting board making use of inkjet technique |
| JP2005197155A (en) * | 2004-01-09 | 2005-07-21 | Dainippon Printing Co Ltd | Light emitting element and its manufacturing method |
| JP2006059796A (en) * | 2004-07-22 | 2006-03-02 | Sharp Corp | Organic light-emitting element, display device equipped with the same, and manufacturing method of organic lightemitting element |
| JP2006100765A (en) * | 2004-09-01 | 2006-04-13 | Fuji Xerox Co Ltd | Organic electroluminescent element |
| WO2006041207A1 (en) * | 2004-10-15 | 2006-04-20 | Sumitomo Chemical Company, Limited | Solution composition and polymer light-emitting device |
| US7081912B2 (en) | 2002-03-11 | 2006-07-25 | Seiko Epson Corporation | Optical writing head such as organic EL array exposure head, method of manufacturing the same, and image forming apparatus using the same |
| US7119826B2 (en) | 2002-12-16 | 2006-10-10 | Seiko Epson Corporation | Oranic EL array exposure head, imaging system incorporating the same, and array-form exposure head fabrication process |
| JP2006278126A (en) * | 2005-03-29 | 2006-10-12 | Seiko Epson Corp | Manufacturing method of device, manufacturing method of el device, el device and electronic apparatus |
| WO2006115283A1 (en) * | 2005-04-25 | 2006-11-02 | Showa Denko K. K. | Method of producing a display device |
| US7166242B2 (en) | 2002-08-02 | 2007-01-23 | Seiko Epson Corporation | Composition, organic conductive layer including composition, method for manufacturing organic conductive layers, organic EL element including organic conductive layer, method for manufacturing organic EL elements semiconductor element including organic conductive layer, method for manufacturing semiconductor elements, electronic device, and electronic apparatus |
| US7201859B2 (en) | 2001-06-25 | 2007-04-10 | Samsung Sdi Co., Ltd. | Hole transport layer and method for manufacturing the organic EL device by using the same |
| JP2007242272A (en) * | 2006-03-06 | 2007-09-20 | Dainippon Printing Co Ltd | Manufacturing method of electroluminescent element |
| US7285904B2 (en) | 2001-08-01 | 2007-10-23 | Samsung Sdi Co., Ltd. | Organic EL display with an organic compound derivative layer |
| WO2007125768A1 (en) * | 2006-04-26 | 2007-11-08 | Sharp Kabushiki Kaisha | Organic electroluminescent display and method for fabricating the same |
| US7294960B2 (en) | 2003-08-08 | 2007-11-13 | Seiko Epson Corporation | Organic electroluminescent device with HIL/HTL specific to each RGB pixel |
| US7301273B2 (en) | 2003-02-20 | 2007-11-27 | Barco Nv | Display element array for emissive, fixed format display |
| US7307381B2 (en) | 2002-07-31 | 2007-12-11 | Dai Nippon Printing Co., Ltd. | Electroluminescent display and process for producing the same |
| JP2008506241A (en) * | 2004-07-12 | 2008-02-28 | シャンハイ ジングフェング エレクトロニクス コーポレーション | Method for improving charge injection into organic films in organic thin film devices |
| US7345141B2 (en) | 2001-11-22 | 2008-03-18 | Sharp Kabushiki Kaisha | Polymer material having carrier transport property, and organic thin film element, electronic device, and conductor line which use same |
| JP2008098583A (en) * | 2006-10-16 | 2008-04-24 | Dainippon Printing Co Ltd | Organic electroluminescent device and its manufacturing method |
| WO2008056722A1 (en) * | 2006-11-09 | 2008-05-15 | Idemitsu Kosan Co., Ltd. | Organic el material-containing solution, method for forming thin film of organic el material, thin film of organic el material, and organic el device |
| WO2008056723A1 (en) * | 2006-11-09 | 2008-05-15 | Idemitsu Kosan Co., Ltd. | Organic el material-containing solution, method for forming thin film of organic el material, thin film of organic el material, and organic el device |
| US7378790B2 (en) | 2001-05-02 | 2008-05-27 | Seiko Epson Corporation | Color display substrate, color filter substrate, color luminescent substrate, manufacturing method of color display substrate, electro-optical apparatus, electronic device, film-forming method, film-forming apparatus, and display motherboard |
| WO2008081823A1 (en) * | 2006-12-29 | 2008-07-10 | Idemitsu Kosan Co., Ltd. | Solution containing organic el material, method for synthesis of organic el material, compound synthesized by the synthesis method, method for formation of thin film of organic el material, thin film of organic el material, organic el element |
| US7470976B2 (en) | 2000-11-27 | 2008-12-30 | Seiko Epson Corporation | Organic electroluminescent device, manufacturing method therefor, and electronic devices therewith |
| US7499143B2 (en) | 2003-03-12 | 2009-03-03 | Seiko Epson Corporation | Liquid crystal discharging method, and liquid crystal discharging device |
| US7517549B2 (en) | 2002-01-23 | 2009-04-14 | Seiko Epson Corporation | Method of, and apparatus for, manufacturing organic EL device; organic EL device; electronic device; and liquid droplet ejection apparatus |
| JP2009170946A (en) * | 2001-12-18 | 2009-07-30 | Seiko Epson Corp | Light-emitting device, electro-optical device, and electronic device |
| US7727641B2 (en) | 2006-03-27 | 2010-06-01 | Seiko Epson Corporation | Compound for organic electroluminescence and organic electroluminescent device |
| US7727642B2 (en) | 2006-04-13 | 2010-06-01 | Seiko Epson Corporation | Compound for organic electroluminescence and organic electroluminescent device |
| JP2010212256A (en) * | 2002-11-15 | 2010-09-24 | Universal Display Corp | Structure and method of fabricating organic devices |
| US7833612B2 (en) | 2003-09-12 | 2010-11-16 | Samsung Mobile Display Co., Ltd. | Substrate for inkjet printing and method of manufacturing the same |
| WO2011118654A1 (en) * | 2010-03-26 | 2011-09-29 | 住友化学株式会社 | Method for manufacturing light-emitting device |
| JP2011243583A (en) * | 2011-08-05 | 2011-12-01 | Semiconductor Energy Lab Co Ltd | Light-emitting device and manufacturing method thereof |
| JP4858682B2 (en) * | 2003-06-04 | 2012-01-18 | 日本ゼオン株式会社 | Substrate manufacturing method |
| US8153184B2 (en) | 2001-11-26 | 2012-04-10 | Samsung Mobile Display Co., Ltd. | Organic EL display device and method of manufacturing the same |
| US8181595B2 (en) | 2002-12-24 | 2012-05-22 | Seiko Epson Corporation | Liquid droplet ejecting apparatus, electro-optical device, method of manufacturing the electro-optical device, and electronic apparatus |
| US8277955B2 (en) | 2006-10-17 | 2012-10-02 | Seiko Epson Corporation | Compound for organic EL device and organic EL device |
| US8410476B2 (en) | 2007-09-28 | 2013-04-02 | Sharp Kabushiki Kaisha | Organic electroluminescent display device and production method thereof |
| US8415660B2 (en) | 2001-06-20 | 2013-04-09 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting device |
| JP2013516053A (en) * | 2009-12-23 | 2013-05-09 | メルク パテント ゲーエムベーハー | Composition comprising a polymeric binder |
| US8790792B2 (en) | 2007-03-27 | 2014-07-29 | Seiko Epson Corporation | Organic electroluminescent device |
| US8822982B2 (en) | 2001-06-20 | 2014-09-02 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting device and electronic apparatus |
| JP2015173113A (en) * | 2015-03-27 | 2015-10-01 | 株式会社半導体エネルギー研究所 | Method of manufacturing light-emitting device |
| WO2019078085A1 (en) | 2017-10-19 | 2019-04-25 | 住友化学株式会社 | Organic electronic device manufacturing method |
| JP2020516034A (en) * | 2017-03-31 | 2020-05-28 | メルク パテント ゲーエムベーハー | Printing method for organic light emitting diode (OLED) |
| JP2020111647A (en) * | 2019-01-09 | 2020-07-27 | 信越ポリマー株式会社 | Conductive polymer aqueous dispersion, method for producing conductive polymer composite, method for producing conductive polymer-containing solution and method for producing conductive film |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0384892A (en) * | 1989-08-25 | 1991-04-10 | Seiko Epson Corp | Luminous element |
| JPH0633048A (en) * | 1992-07-15 | 1994-02-08 | Showa Denko Kk | Organic thin film electroluminescent element |
| JPH07509339A (en) * | 1992-07-27 | 1995-10-12 | ケンブリッジ ディスプレイ テクノロジー リミテッド | electroluminescence device |
| JPH0848858A (en) * | 1994-05-06 | 1996-02-20 | Bayer Ag | Conductive coating |
| JPH09504137A (en) * | 1994-08-08 | 1997-04-22 | フィリップス エレクトロニクス ネムローゼ フェンノートシャップ | Cathode ray tube with display screen having conductive coating |
| JPH09279135A (en) * | 1996-04-17 | 1997-10-28 | Toyota Central Res & Dev Lab Inc | Electroluminescent element |
| JPH1012377A (en) * | 1996-06-19 | 1998-01-16 | Seiko Epson Corp | Manufacture of active matrix type organic el display body |
| WO1998012689A1 (en) * | 1996-09-19 | 1998-03-26 | Seiko Epson Corporation | Matrix type display device and method of production thereof |
| JPH1088030A (en) * | 1996-08-19 | 1998-04-07 | Bayer Ag | Scratch-resistant, conductive coating |
| JPH1095787A (en) * | 1996-07-17 | 1998-04-14 | Fuji Xerox Co Ltd | Silane compound and its production |
| JPH10153967A (en) * | 1996-11-25 | 1998-06-09 | Seiko Epson Corp | Full-color organic el display device and its production |
| WO1998036406A1 (en) * | 1997-02-17 | 1998-08-20 | Seiko Epson Corporation | Current-driven emissive display device and method for manufacturing the same |
| JPH1187063A (en) * | 1997-09-01 | 1999-03-30 | Seiko Epson Corp | Electroluminescent element |
| JP2000306669A (en) * | 1999-04-20 | 2000-11-02 | Canon Inc | Organic luminescent element |
-
1999
- 1999-05-14 JP JP11134320A patent/JP2000323276A/en not_active Withdrawn
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0384892A (en) * | 1989-08-25 | 1991-04-10 | Seiko Epson Corp | Luminous element |
| JPH0633048A (en) * | 1992-07-15 | 1994-02-08 | Showa Denko Kk | Organic thin film electroluminescent element |
| JPH07509339A (en) * | 1992-07-27 | 1995-10-12 | ケンブリッジ ディスプレイ テクノロジー リミテッド | electroluminescence device |
| JPH0848858A (en) * | 1994-05-06 | 1996-02-20 | Bayer Ag | Conductive coating |
| JPH09504137A (en) * | 1994-08-08 | 1997-04-22 | フィリップス エレクトロニクス ネムローゼ フェンノートシャップ | Cathode ray tube with display screen having conductive coating |
| JPH09279135A (en) * | 1996-04-17 | 1997-10-28 | Toyota Central Res & Dev Lab Inc | Electroluminescent element |
| JPH1012377A (en) * | 1996-06-19 | 1998-01-16 | Seiko Epson Corp | Manufacture of active matrix type organic el display body |
| JPH1095787A (en) * | 1996-07-17 | 1998-04-14 | Fuji Xerox Co Ltd | Silane compound and its production |
| JPH1088030A (en) * | 1996-08-19 | 1998-04-07 | Bayer Ag | Scratch-resistant, conductive coating |
| WO1998012689A1 (en) * | 1996-09-19 | 1998-03-26 | Seiko Epson Corporation | Matrix type display device and method of production thereof |
| JPH10153967A (en) * | 1996-11-25 | 1998-06-09 | Seiko Epson Corp | Full-color organic el display device and its production |
| WO1998036406A1 (en) * | 1997-02-17 | 1998-08-20 | Seiko Epson Corporation | Current-driven emissive display device and method for manufacturing the same |
| JPH1187063A (en) * | 1997-09-01 | 1999-03-30 | Seiko Epson Corp | Electroluminescent element |
| JP2000306669A (en) * | 1999-04-20 | 2000-11-02 | Canon Inc | Organic luminescent element |
Cited By (109)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8698136B2 (en) | 2000-11-27 | 2014-04-15 | Seiko Epson Corporation | Methods of manufacturing an organic electroluminescent device |
| US7521709B2 (en) | 2000-11-27 | 2009-04-21 | Seiko Epson Corporation | Organic electroluminescent device, manufacturing method therefor, and electronic devices therewith |
| US7470976B2 (en) | 2000-11-27 | 2008-12-30 | Seiko Epson Corporation | Organic electroluminescent device, manufacturing method therefor, and electronic devices therewith |
| US7755277B2 (en) | 2000-11-27 | 2010-07-13 | Seiko Epson Corporation | Organic electroluminescent device, manufacturing method therefor, and electronic devices therewith |
| US8128448B2 (en) | 2000-11-27 | 2012-03-06 | Seiko Epson Corporation | Methods of manufacturing an organic electroluminescent device |
| US7990052B2 (en) | 2000-11-27 | 2011-08-02 | Seiko Epson Corporation | Organic electroluminescent device |
| US8454403B2 (en) | 2000-11-27 | 2013-06-04 | Seiko Epson Corporation | Methods of manufacturing an organic electroluminescent device |
| EP1219980A2 (en) * | 2000-12-21 | 2002-07-03 | Seiko Epson Corporation | Method and apparatus for producing color filter, method and apparatus for manufacturing liquid crystal device, method and apparatus for manufacturing EL device, method of discharging material, apparatus for controlling head and electronic apparatus |
| US7481515B2 (en) | 2000-12-21 | 2009-01-27 | Seiko Epson Corporation | Method and apparatus for producing color filter, method and apparatus for manufacturing liquid crystal device, method and apparatus for manufacturing EL device, method of discharging material, apparatus for controlling head and electronic apparatus |
| KR100538864B1 (en) * | 2000-12-21 | 2005-12-23 | 세이코 엡슨 가부시키가이샤 | Method and apparatus for producing color filter, method and apparatus for manufacturing liquid crystal device, method and apparatus for manufacturing el device, method of discharging material, apparatus for controlling head and electronic apparatus |
| EP1219980A3 (en) * | 2000-12-21 | 2004-04-14 | Seiko Epson Corporation | Method and apparatus for producing color filter, method and apparatus for manufacturing liquid crystal device, method and apparatus for manufacturing EL device, method of discharging material, apparatus for controlling head and electronic apparatus |
| US7901741B2 (en) | 2001-01-15 | 2011-03-08 | Seiko Epson Corporation | Apparatus and method for producing color filters by discharging material |
| EP1852733A1 (en) * | 2001-01-15 | 2007-11-07 | Seiko Epson Corporation | Material discharging apparatus and method for producing color filters, liquid crystal and electroluminescent devices |
| US7182815B2 (en) | 2001-01-15 | 2007-02-27 | Seiko Epson Corporation | Apparatus and method for producing color filters by discharging material |
| EP1225472A3 (en) * | 2001-01-15 | 2003-09-17 | Seiko Epson Corporation | Material discharging apparatus and method for producing color filters, liquid crystal and electroluminescent devices |
| EP1371101A1 (en) * | 2001-03-22 | 2003-12-17 | Microemissive Displays Limited | Method of creating an electroluminescent device |
| US7595588B2 (en) | 2001-03-22 | 2009-09-29 | Microemissive Displays Limited | Electroluminescent device and method of making same |
| US7378790B2 (en) | 2001-05-02 | 2008-05-27 | Seiko Epson Corporation | Color display substrate, color filter substrate, color luminescent substrate, manufacturing method of color display substrate, electro-optical apparatus, electronic device, film-forming method, film-forming apparatus, and display motherboard |
| US8822982B2 (en) | 2001-06-20 | 2014-09-02 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting device and electronic apparatus |
| US9178168B2 (en) | 2001-06-20 | 2015-11-03 | Semiconductor Energy Laboratory Co., Ltd. | White light emitting device |
| US9166180B2 (en) | 2001-06-20 | 2015-10-20 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting device having an organic light emitting diode that emits white light |
| US9276224B2 (en) | 2001-06-20 | 2016-03-01 | Semiconductor Energy Laboratory Co., Ltd. | Organic light emitting device having dual flexible substrates |
| US8415660B2 (en) | 2001-06-20 | 2013-04-09 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting device |
| JP2007103384A (en) * | 2001-06-25 | 2007-04-19 | Samsung Sdi Co Ltd | Method for manufacturing organic electroluminescent device using hole transport layer for organic electroluminescent device |
| US7201859B2 (en) | 2001-06-25 | 2007-04-10 | Samsung Sdi Co., Ltd. | Hole transport layer and method for manufacturing the organic EL device by using the same |
| US6825867B2 (en) | 2001-07-09 | 2004-11-30 | Seiko Epson Corporation | Organic electroluminescent array exposure head, method of fabricating the same, and image forming apparatus using the same |
| JP2005514726A (en) * | 2001-07-21 | 2005-05-19 | コビオン オーガニック セミコンダクターズ ゲーエムベーハー | Organic semiconductor solution |
| KR100915570B1 (en) * | 2001-07-21 | 2009-09-03 | 메르크 파텐트 게엠베하 | Solutions of organic semiconductors |
| US7285904B2 (en) | 2001-08-01 | 2007-10-23 | Samsung Sdi Co., Ltd. | Organic EL display with an organic compound derivative layer |
| US8039039B2 (en) | 2001-08-30 | 2011-10-18 | Sharp Kabushiki Kaisha | Method of manufacturing organic EL device, and organic EL device |
| JPWO2003022010A1 (en) * | 2001-08-30 | 2004-12-24 | 富士通株式会社 | Method of manufacturing organic EL device and organic EL device |
| WO2003022010A1 (en) * | 2001-08-30 | 2003-03-13 | Fujitsu Limited | Method for manufacturing organic el device and organic el device |
| US7131881B2 (en) | 2001-08-30 | 2006-11-07 | Sharp Kabushiki Kaisha | Method of manufacturing organic EL device, and organic EL device |
| JP4522698B2 (en) * | 2001-08-30 | 2010-08-11 | シャープ株式会社 | Manufacturing method of organic EL device |
| JP2003077652A (en) * | 2001-08-31 | 2003-03-14 | Dainippon Printing Co Ltd | Manufacturing method for electroluminescent element |
| WO2003026359A1 (en) * | 2001-09-12 | 2003-03-27 | Seiko Epson Corporation | Patterning method, film forming method, patterning device, film forming device, electro-optic device and production method therefor, electronic apparatus, and electronic device and production method therefor |
| WO2003045115A1 (en) * | 2001-11-22 | 2003-05-30 | Nippon Soda Co.,Ltd. | El device |
| US7345141B2 (en) | 2001-11-22 | 2008-03-18 | Sharp Kabushiki Kaisha | Polymer material having carrier transport property, and organic thin film element, electronic device, and conductor line which use same |
| JP2003168569A (en) * | 2001-11-26 | 2003-06-13 | Samsung Sdi Co Ltd | Full color organic electroluminescent display element and manufacturing method of the same |
| US8153184B2 (en) | 2001-11-26 | 2012-04-10 | Samsung Mobile Display Co., Ltd. | Organic EL display device and method of manufacturing the same |
| US8142839B2 (en) | 2001-11-26 | 2012-03-27 | Samsung Mobile Display Co., Ltd. | Method for fabricating a display device |
| US7696689B2 (en) | 2001-11-26 | 2010-04-13 | Samsung Mobile Display Co., Ltd. | Organic EL display device having an organic EL layer formed on an exposed underlying layer |
| US7705534B2 (en) | 2001-11-26 | 2010-04-27 | Samsung Mobile Display Co., Ltd. | Organic EL display device |
| JP2007280963A (en) * | 2001-11-26 | 2007-10-25 | Samsung Sdi Co Ltd | Full color organic electroluminescence display element |
| JP2009170946A (en) * | 2001-12-18 | 2009-07-30 | Seiko Epson Corp | Light-emitting device, electro-optical device, and electronic device |
| US8101946B2 (en) | 2001-12-18 | 2012-01-24 | Seiko Epson Corporation | Light-emission device, method of manufacturing same, electro-optical device and electronic device |
| US7517549B2 (en) | 2002-01-23 | 2009-04-14 | Seiko Epson Corporation | Method of, and apparatus for, manufacturing organic EL device; organic EL device; electronic device; and liquid droplet ejection apparatus |
| US7081912B2 (en) | 2002-03-11 | 2006-07-25 | Seiko Epson Corporation | Optical writing head such as organic EL array exposure head, method of manufacturing the same, and image forming apparatus using the same |
| US8517530B2 (en) | 2002-03-13 | 2013-08-27 | Ricoh Company, Ltd. | Fabrication of functional device mounting board making use of inkjet technique |
| US7553375B2 (en) | 2002-03-13 | 2009-06-30 | Ricoh Company, Ltd. | Fabrication of functional device mounting board making use of inkjet technique |
| US6918666B2 (en) | 2002-03-13 | 2005-07-19 | Ricoh Company, Ltd. | Fabrication of functional device mounting board making use of inkjet technique |
| EP1564007A1 (en) | 2002-05-31 | 2005-08-17 | Seiko Epson Corporation | Optical head and image forming apparatus employing the same |
| EP1564008A1 (en) | 2002-05-31 | 2005-08-17 | Seiko Epson Corporation | Optical head and image forming apparatus employing the same |
| EP1366920A1 (en) | 2002-05-31 | 2003-12-03 | Seiko Epson Corporation | Optical head and image forming apparatus employing the same |
| US6879099B2 (en) | 2002-07-10 | 2005-04-12 | Kabushiki Kaisha Toshiba | Organic EL element and organic EL display |
| US7307381B2 (en) | 2002-07-31 | 2007-12-11 | Dai Nippon Printing Co., Ltd. | Electroluminescent display and process for producing the same |
| US8267735B2 (en) | 2002-07-31 | 2012-09-18 | Dai Nippon Printing Co., Ltd. | Pattern formation method for electroluminescent element |
| US7166242B2 (en) | 2002-08-02 | 2007-01-23 | Seiko Epson Corporation | Composition, organic conductive layer including composition, method for manufacturing organic conductive layers, organic EL element including organic conductive layer, method for manufacturing organic EL elements semiconductor element including organic conductive layer, method for manufacturing semiconductor elements, electronic device, and electronic apparatus |
| EP1561248B1 (en) * | 2002-11-15 | 2020-01-22 | Universal Display Corporation | Method of fabricating organic devices |
| KR101199604B1 (en) | 2002-11-15 | 2012-11-08 | 유니버셜 디스플레이 코포레이션 | Structure and method of fabricating organic devices |
| JP2010212256A (en) * | 2002-11-15 | 2010-09-24 | Universal Display Corp | Structure and method of fabricating organic devices |
| US7119826B2 (en) | 2002-12-16 | 2006-10-10 | Seiko Epson Corporation | Oranic EL array exposure head, imaging system incorporating the same, and array-form exposure head fabrication process |
| US8181595B2 (en) | 2002-12-24 | 2012-05-22 | Seiko Epson Corporation | Liquid droplet ejecting apparatus, electro-optical device, method of manufacturing the electro-optical device, and electronic apparatus |
| US7301273B2 (en) | 2003-02-20 | 2007-11-27 | Barco Nv | Display element array for emissive, fixed format display |
| US7499143B2 (en) | 2003-03-12 | 2009-03-03 | Seiko Epson Corporation | Liquid crystal discharging method, and liquid crystal discharging device |
| US8780317B2 (en) | 2003-03-12 | 2014-07-15 | Seiko Epson Corporation | Film forming method, film forming device, liquid crystal arrangement method, liquid crystal arrangement device, liquid crystal device, liquid crystal device production method and electronic equipment |
| JP2004330136A (en) * | 2003-05-09 | 2004-11-25 | Seiko Epson Corp | Method for drying liquid film and method for manufacturing organic el panel, electrooptic panel and electronic equipment, and apparatus for drying liquid film, electrooptic panel, electrooptic apparatus and electronic equipment |
| JP4858682B2 (en) * | 2003-06-04 | 2012-01-18 | 日本ゼオン株式会社 | Substrate manufacturing method |
| US7294960B2 (en) | 2003-08-08 | 2007-11-13 | Seiko Epson Corporation | Organic electroluminescent device with HIL/HTL specific to each RGB pixel |
| US7833612B2 (en) | 2003-09-12 | 2010-11-16 | Samsung Mobile Display Co., Ltd. | Substrate for inkjet printing and method of manufacturing the same |
| JP2005197155A (en) * | 2004-01-09 | 2005-07-21 | Dainippon Printing Co Ltd | Light emitting element and its manufacturing method |
| JP2008506241A (en) * | 2004-07-12 | 2008-02-28 | シャンハイ ジングフェング エレクトロニクス コーポレーション | Method for improving charge injection into organic films in organic thin film devices |
| US7495389B2 (en) | 2004-07-22 | 2009-02-24 | Sharp Kabushiki Kaisha | Organic light emitting element including auxiliary electrode, display device including the same and method for manufacturing the organic light emitting element |
| JP2006059796A (en) * | 2004-07-22 | 2006-03-02 | Sharp Corp | Organic light-emitting element, display device equipped with the same, and manufacturing method of organic lightemitting element |
| JP2006100765A (en) * | 2004-09-01 | 2006-04-13 | Fuji Xerox Co Ltd | Organic electroluminescent element |
| GB2434584B (en) * | 2004-10-15 | 2009-09-09 | Sumitomo Chemical Co | Solution composition and polymer light-emitting device |
| GB2434584A (en) * | 2004-10-15 | 2007-08-01 | Sumitomo Chemical Co | Solution composition and polymer light-emitting device |
| US7910025B2 (en) | 2004-10-15 | 2011-03-22 | Sumitomo Chemical Co., Ltd. | Solution composition and polymer light-emitting device |
| WO2006041207A1 (en) * | 2004-10-15 | 2006-04-20 | Sumitomo Chemical Company, Limited | Solution composition and polymer light-emitting device |
| JP2006278126A (en) * | 2005-03-29 | 2006-10-12 | Seiko Epson Corp | Manufacturing method of device, manufacturing method of el device, el device and electronic apparatus |
| US8016629B2 (en) | 2005-04-25 | 2011-09-13 | Showa Denko K.K. | Method of producing a display device |
| WO2006115283A1 (en) * | 2005-04-25 | 2006-11-02 | Showa Denko K. K. | Method of producing a display device |
| JP2007242272A (en) * | 2006-03-06 | 2007-09-20 | Dainippon Printing Co Ltd | Manufacturing method of electroluminescent element |
| US7727641B2 (en) | 2006-03-27 | 2010-06-01 | Seiko Epson Corporation | Compound for organic electroluminescence and organic electroluminescent device |
| US7727642B2 (en) | 2006-04-13 | 2010-06-01 | Seiko Epson Corporation | Compound for organic electroluminescence and organic electroluminescent device |
| KR101387667B1 (en) * | 2006-04-13 | 2014-04-21 | 세이코 엡슨 가부시키가이샤 | Compound for organic electroluminescence and organic electroluminescent device |
| WO2007125768A1 (en) * | 2006-04-26 | 2007-11-08 | Sharp Kabushiki Kaisha | Organic electroluminescent display and method for fabricating the same |
| US8232940B2 (en) | 2006-04-26 | 2012-07-31 | Sharp Kabushiki Kaisha | Organic electroluminescent display device and production method thereof |
| JP2008098583A (en) * | 2006-10-16 | 2008-04-24 | Dainippon Printing Co Ltd | Organic electroluminescent device and its manufacturing method |
| US8277955B2 (en) | 2006-10-17 | 2012-10-02 | Seiko Epson Corporation | Compound for organic EL device and organic EL device |
| WO2008056722A1 (en) * | 2006-11-09 | 2008-05-15 | Idemitsu Kosan Co., Ltd. | Organic el material-containing solution, method for forming thin film of organic el material, thin film of organic el material, and organic el device |
| WO2008056723A1 (en) * | 2006-11-09 | 2008-05-15 | Idemitsu Kosan Co., Ltd. | Organic el material-containing solution, method for forming thin film of organic el material, thin film of organic el material, and organic el device |
| WO2008081823A1 (en) * | 2006-12-29 | 2008-07-10 | Idemitsu Kosan Co., Ltd. | Solution containing organic el material, method for synthesis of organic el material, compound synthesized by the synthesis method, method for formation of thin film of organic el material, thin film of organic el material, organic el element |
| US8790792B2 (en) | 2007-03-27 | 2014-07-29 | Seiko Epson Corporation | Organic electroluminescent device |
| US8410476B2 (en) | 2007-09-28 | 2013-04-02 | Sharp Kabushiki Kaisha | Organic electroluminescent display device and production method thereof |
| JP2016156016A (en) * | 2009-12-23 | 2016-09-01 | メルク パテント ゲーエムベーハー | Composition containing polymer binder |
| JP2013516053A (en) * | 2009-12-23 | 2013-05-09 | メルク パテント ゲーエムベーハー | Composition comprising a polymeric binder |
| US9178156B2 (en) | 2009-12-23 | 2015-11-03 | Merck Patent Gmbh | Compositions comprising polymeric binders |
| CN102845133A (en) * | 2010-03-26 | 2012-12-26 | 住友化学株式会社 | Method for manufacturing light-emitting device |
| WO2011118654A1 (en) * | 2010-03-26 | 2011-09-29 | 住友化学株式会社 | Method for manufacturing light-emitting device |
| JP2011243583A (en) * | 2011-08-05 | 2011-12-01 | Semiconductor Energy Lab Co Ltd | Light-emitting device and manufacturing method thereof |
| JP2015173113A (en) * | 2015-03-27 | 2015-10-01 | 株式会社半導体エネルギー研究所 | Method of manufacturing light-emitting device |
| JP2020516034A (en) * | 2017-03-31 | 2020-05-28 | メルク パテント ゲーエムベーハー | Printing method for organic light emitting diode (OLED) |
| JP7123967B2 (en) | 2017-03-31 | 2022-08-23 | メルク パテント ゲーエムベーハー | Printing method for organic light emitting diodes (OLEDs) |
| WO2019078085A1 (en) | 2017-10-19 | 2019-04-25 | 住友化学株式会社 | Organic electronic device manufacturing method |
| KR20200072494A (en) | 2017-10-19 | 2020-06-22 | 스미또모 가가꾸 가부시키가이샤 | Manufacturing method of organic electronic device |
| US11527743B2 (en) | 2017-10-19 | 2022-12-13 | Sumitomo Chemical Company, Limited | Organic electronic device manufacturing method |
| JP2020111647A (en) * | 2019-01-09 | 2020-07-27 | 信越ポリマー株式会社 | Conductive polymer aqueous dispersion, method for producing conductive polymer composite, method for producing conductive polymer-containing solution and method for producing conductive film |
| JP7190357B2 (en) | 2019-01-09 | 2022-12-15 | 信越ポリマー株式会社 | Method for producing conductive polymer composite, method for producing liquid containing conductive polymer, and method for producing conductive film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2000323276A (en) | Manufacture of organic el element, organic el element, and ink composition | |
| JP3900724B2 (en) | Organic EL element manufacturing method and organic EL display device | |
| KR100554338B1 (en) | Method of producing organic el element | |
| JP3941169B2 (en) | Manufacturing method of organic EL element | |
| US6825061B2 (en) | Method of manufacturing organic EL device and ink composition for organic EL device | |
| JP3911775B2 (en) | Manufacturing method of organic EL element | |
| JP4731629B2 (en) | Manufacturing method of organic EL device | |
| JP4226159B2 (en) | Manufacturing method of organic LED display | |
| US8430706B2 (en) | Organic electroluminescent device and method of manufacturing organic electroluminescent device | |
| JP3649125B2 (en) | ELECTROLUMINESCENT ELEMENT MANUFACTURING METHOD AND ELECTROLUMINESCENT ELEMENT | |
| JP2002231447A (en) | Method of manufacturing organic electroluminescence device and organic electroluminescence device and electronic equipment | |
| WO1998024271A1 (en) | Method of producing organic el elements, organic el elements and organic el display device | |
| JP2000106278A (en) | Manufacture of organic el element and the organic el element | |
| EP1372195B1 (en) | Manufacturing process for an organic electroluminescent element | |
| WO2005022959A2 (en) | Electroluminescent devices and methods | |
| JP2001291587A (en) | Manufacturing method of organic light emission device and organic light emission device manufactured by the method | |
| JP2009064642A (en) | Manufacturing method of organic electroluminescent display device, and manufacturing apparatus | |
| JP4513800B2 (en) | Manufacturing method of organic EL element | |
| JP4765857B2 (en) | Organic EL light emitting material and method for manufacturing organic EL device | |
| JP2004140004A (en) | Manufacturing method of organic electroluminescent device, and organic electroluminescent device and electronic device | |
| JP3807621B2 (en) | Manufacturing method of organic EL element | |
| JP2003142260A (en) | Manufacturing method and manufacturing device of organic el element | |
| JP2005056855A (en) | Electroluminescent element and manufacturing method of the same | |
| JP2005322437A (en) | Manufacturing method of organic el element, organic el element, and electronic equipment | |
| JP3685188B2 (en) | Organic EL device and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060613 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060809 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20061010 |
|
| A761 | Written withdrawal of application |
Free format text: JAPANESE INTERMEDIATE CODE: A761 Effective date: 20061211 |