JP2002313565A - Method of manufacturing luminescent display element - Google Patents
Method of manufacturing luminescent display elementInfo
- Publication number
- JP2002313565A JP2002313565A JP2001118460A JP2001118460A JP2002313565A JP 2002313565 A JP2002313565 A JP 2002313565A JP 2001118460 A JP2001118460 A JP 2001118460A JP 2001118460 A JP2001118460 A JP 2001118460A JP 2002313565 A JP2002313565 A JP 2002313565A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- electrode
- transport layer
- light emitting
- forming
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 91
- 239000000758 substrate Substances 0.000 claims abstract description 78
- 238000002347 injection Methods 0.000 claims abstract description 63
- 239000007924 injection Substances 0.000 claims abstract description 63
- 239000007864 aqueous solution Substances 0.000 claims abstract description 40
- 125000000524 functional group Chemical group 0.000 claims abstract description 12
- 238000004070 electrodeposition Methods 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 55
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 52
- 229910052697 platinum Inorganic materials 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 22
- -1 polyparaphenylene vinylene Polymers 0.000 claims description 19
- 238000000151 deposition Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 238000001652 electrophoretic deposition Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 3
- 229920002518 Polyallylamine hydrochloride Polymers 0.000 claims description 3
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 3
- 229920002098 polyfluorene Polymers 0.000 claims description 3
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 3
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 claims description 2
- 229920001287 Chondroitin sulfate Polymers 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 108010039918 Polylysine Proteins 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229940059329 chondroitin sulfate Drugs 0.000 claims description 2
- 229920000547 conjugated polymer Polymers 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 2
- 229920000548 poly(silane) polymer Polymers 0.000 claims description 2
- 229920001197 polyacetylene Polymers 0.000 claims description 2
- 229920000656 polylysine Polymers 0.000 claims description 2
- 229920001444 polymaleic acid Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 238000001962 electrophoresis Methods 0.000 claims 2
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims 1
- 229960000633 dextran sulfate Drugs 0.000 claims 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims 1
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 18
- 238000013508 migration Methods 0.000 abstract 1
- 230000005012 migration Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 154
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000010408 film Substances 0.000 description 16
- 239000010409 thin film Substances 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 12
- 238000000059 patterning Methods 0.000 description 10
- 239000000872 buffer Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 6
- 229960002796 polystyrene sulfonate Drugs 0.000 description 6
- 239000011970 polystyrene sulfonate Substances 0.000 description 6
- 238000007740 vapor deposition Methods 0.000 description 6
- 238000007654 immersion Methods 0.000 description 5
- 229920000083 poly(allylamine) Polymers 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000001771 vacuum deposition Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000004375 Dextrin Substances 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 239000002094 self assembled monolayer Substances 0.000 description 2
- 239000013545 self-assembled monolayer Substances 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- WKZNAWCDMVRAFO-UHFFFAOYSA-N PCOP Chemical compound PCOP WKZNAWCDMVRAFO-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NJSVDVPGINTNGX-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethanamine Chemical compound CCC[Si](OC)(OC)OCN NJSVDVPGINTNGX-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- OHAPIZYOVBUCCX-UHFFFAOYSA-N amino(methoxy)silicon Chemical compound CO[Si]N OHAPIZYOVBUCCX-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- CFNHVUGPXZUTRR-UHFFFAOYSA-N n'-propylethane-1,2-diamine Chemical compound CCCNCCN CFNHVUGPXZUTRR-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、発光表示素子の製
造方法に関する。更に詳しくは、本発明は、発光層、正
孔注入輸送層及び電子注入輸送層の内の少なくとも１層
の形成に泳動電着を利用した発光表示素子の製造方法に
関する。特に、本発明は、フルカラー発光素子の製造に
好適に使用できる。[0001] The present invention relates to a method for manufacturing a light emitting display device. More specifically, the present invention relates to a method for manufacturing a light emitting display device using electrophoretic deposition for forming at least one of a light emitting layer, a hole injection transport layer and an electron injection transport layer. In particular, the present invention can be suitably used for manufacturing a full color light emitting device.
【０００２】[0002]
【従来の技術】ＥＬ表示素子（発光表示素子）は、蛍光
性の無機及び有機化合物を含む薄膜を、陰極と陽極とで
挟んだ構成を有し、前記薄膜に電子及び正孔（ホール）
を注入して再結合させることにより励起子（エキシト
ン）を生成させ、このエキシトンが失活する際の光の放
出（蛍光・燐光）を利用して発光させる素子である。2. Description of the Related Art An EL display device (light-emitting display device) has a structure in which a thin film containing a fluorescent inorganic or organic compound is sandwiched between a cathode and an anode, and electrons and holes are formed in the thin film.
Are injected and recombined to generate excitons (excitons), and emit light using light emission (fluorescence / phosphorescence) when the excitons are deactivated.
【０００３】ＥＬ表示素子の特徴は、１０Ｖ以下の低電
圧で１００〜１０００００ｃｄ／ｍ 2程度の高輝度の面
発光が可能であることと、蛍光物質の種類を選択するこ
とにより青色から赤色までの発光が可能なことである。
ＥＬ表示素子は、安価な大面積フルカラー表示素子を実
現するものとして注目を集めている（電子情報通信学会
技術報告、第８９巻、Ｎｏ．１０６、４９頁、１９８９
年）。この報告では、強い蛍光を発する色素を発光層に
使用し、青、緑、赤の明るい発光を得ている。成膜は、
真空蒸着法による。更に、薄膜状で強い蛍光を発し、ま
た蒸着においてピンホール欠陥ができないような有機色
素を用いることで、高輝度なフルカラー表示実現の可能
性が示唆されている。[0003] EL display elements are characterized by a low voltage of 10 V or less.
100-100,000 cd / m in pressure TwoHigh brightness surface
Be able to emit light and select the type of fluorescent material.
Thus, light emission from blue to red is possible.
EL display elements are inexpensive large-area full-color display elements.
Is attracting attention as a manifestation (The Institute of Electronics, Information and Communication Engineers)
Technical Report, Vol. 106, 49, 1989
Year). In this report, a dye that emits strong fluorescence is added to the light-emitting layer.
Used and has obtained bright luminescence of blue, green and red. Film formation
By a vacuum evaporation method. Furthermore, it emits strong fluorescence in the form of a thin film,
Organic color that does not allow pinhole defects in wet deposition
High-brightness full-color display can be realized by using
Sex is suggested.
【０００４】更に、特開平５−７８６５５号公報では、
正孔注入輸送材料と発光材料の混合物からなる発光層を
真空蒸着法により設けることで、濃度消光を防止して発
光材料の選択幅を広げる技術が記載され、この技術は高
輝度なフルカラー素子へ応用できるとされている。[0004] Further, in Japanese Patent Application Laid-Open No. 5-78655,
A technology has been described in which a light emitting layer composed of a mixture of a hole injection transport material and a light emitting material is provided by a vacuum evaporation method to prevent concentration quenching and expand the range of selection of light emitting materials. It is said that it can be applied.
【０００５】フルカラー化の方式については、現在まで
に、さまざまな方式が提案されている。[0005] As for the full color system, various systems have been proposed so far.
【０００６】低分子材料系では、表示電極が表面に形成
された基板上に突出しかつ上部に基板と平行方向に突出
するオーバーハング部を有する絶縁性隔壁を形成し、そ
の上に三原色に対応する発光層を金属マスクを用いて順
次真空蒸着法によりパターニングする方法で並べるとい
う方式が、最も発光効率のロスが少ない方法であるとし
て、特開平８−３１５９８１号公報に記載されている。In the low-molecular material system, an insulating partition having a display electrode protruding above a substrate formed on the surface thereof and having an overhang portion protruding in a direction parallel to the substrate is formed on the display electrode, and a display electrode corresponding to the three primary colors is formed thereon. Japanese Patent Application Laid-Open No. 8-315981 describes that a method of arranging the light-emitting layers sequentially by a patterning method using a metal mask by a vacuum deposition method is a method with the least loss of luminous efficiency.
【０００７】また、特開平９−２０４９８３号公報で
は、陽極中、薄膜を蒸着したい部分以外の部分を加熱す
ることによって、該蒸着を所望しない陽極の部分上に蒸
着されるのを防ぎ、薄膜を蒸着したい陽極上にのみ蒸着
する方法が提案されている。In Japanese Patent Application Laid-Open No. Hei 9-209833, by heating a portion of the anode other than the portion where the thin film is to be deposited, it is prevented from being deposited on the portion of the anode where the deposition is not desired. A method of depositing only on the anode to be deposited has been proposed.
【０００８】一方、湿式での薄膜のパターン形成法の１
つにミセル電解法がある。これは、水に難溶性あるいは
不溶性の微粒子を、電気的な酸化反応を受けて陽電荷を
帯びるようなフェロセン系ノニオン系界面活性剤を用い
て水溶液にミセル化分散した後、このミセル水溶液中に
電極付きの基板及び対向電極を浸漬し、それぞれに正電
荷、負電荷をかけて電極上でミセル水溶液を電解し、こ
れにより、電極上で界面活性剤が陽電荷を帯びて微粒子
表面から脱離し、界面活性剤の吸着が解かれた微粒子が
電極上に物理吸着により堆積することで薄膜を形成する
方法である。薄膜形成を行う場所にあらかじめ電極パタ
ーンを形成しておき、そこだけ電圧を印加すれば電極パ
ターンにならって所望の形状の薄膜を形成することがで
き、これによりフルカラー表示に求められる微細なパタ
ーニングができることが特開平１１−８７０５４号公報
で報告されている。On the other hand, one of the wet thin film pattern forming methods
One is micellar electrolysis. This is because fine particles that are hardly soluble or insoluble in water are micellized and dispersed in an aqueous solution using a ferrocene-based nonionic surfactant that is positively charged by undergoing an electrical oxidation reaction, and then dispersed in the aqueous micelle solution. A substrate with electrodes and a counter electrode are immersed, a positive charge and a negative charge are applied to each, and the micelle aqueous solution is electrolyzed on the electrodes, whereby the surfactant is positively charged on the electrodes and detaches from the fine particle surface. In this method, fine particles from which a surfactant has been adsorbed are deposited on an electrode by physical adsorption to form a thin film. An electrode pattern is formed in advance at the place where the thin film is to be formed, and if a voltage is applied only there, a thin film of a desired shape can be formed following the electrode pattern, thereby achieving the fine patterning required for full color display. What is possible is reported in JP-A-11-87054.
【０００９】更に、特開平２−２６７２９８号公報に記
載があるように、印加電圧及び印加時間をコントロール
すれば、容易に任意の膜厚を形成することができる。Further, as described in JP-A-2-267298, an arbitrary film thickness can be easily formed by controlling the applied voltage and the applied time.
【００１０】一方、ポリマー系の有機ＥＬ素子に関して
は、予めパターニングが施された凸版上に、適当な有機
溶剤中に溶かした発光性ポリマーを塗布した後、基板上
に転写する印刷法が知られている。また、大型のインク
ジェットプリンターのインクとして発光性ポリマーを混
ぜたインクを使い、かつ基板上に微細な撥水処理を施す
ことで、サブピクセルサイズが約７０μｍのカラーＥＬ
パネルを作製した例が木口らの応用物理学会有機バイオ
エレクトロニクス研究会Ｖｏｌ．１１、Ｎｏ．１、７８
−８５頁（２０００）で報告されている。On the other hand, with respect to polymer-based organic EL devices, there is known a printing method in which a luminescent polymer dissolved in an appropriate organic solvent is applied onto a relief pattern that has been patterned in advance, and then transferred onto a substrate. ing. In addition, by using an ink mixed with a luminescent polymer as the ink for a large-sized inkjet printer and performing a fine water-repellent treatment on the substrate, a color EL having a sub-pixel size of about 70 μm is used.
An example of a panel was prepared by Kiguchi et al. 11, No. 1,78
-85 (2000).
【００１１】更に、低分子発光材料にアルコキシシリル
基を付加した材料を使用し、ゾル・ゲル溶液を作製し、
その溶液をＩＴＯ電極を備えた基板上に１．５μｍ厚に
なるようにスピンコート及びフォトマスクによりＵＶラ
ンプを用いて発光層をパターニングしつつ形成して４５
μｍ×４５μｍピクセルのＥＬ素子を試作した例がＬａ
ｓｅｒ Ｆｏｃｕｓ Ｗｏｒｌｄ Ｖｏｌ．３５（１
１）、Ｎｏｖｅｍｂｅｒ（１９９９）に記載されてい
る。Further, a sol-gel solution is prepared by using a material obtained by adding an alkoxysilyl group to a low molecular light emitting material,
The solution is formed on a substrate provided with an ITO electrode to a thickness of 1.5 μm by spin coating and using a photomask while patterning a light emitting layer using a UV lamp.
An example of a prototype of an EL element of μm × 45 μm pixel is La
ser Focus World Vol. 35 (1
1), November (1999).
【００１２】[0012]
【発明が解決しようとする課題】しかしながら、上記従
来の技術の内、真空蒸着法では、赤、緑、青の発光層を
微細にパターニングすることは技術的に非常に困難であ
り、フルカラー表示パネルの構成や製造方法については
ある程度までは実証されているものの試作段階の域を超
えず、信頼性・再現性が乏しい。つまり、電子注入輸送
層、正孔注入輸送層及び発光層を蒸着時にマスクでパタ
ーニングしたり、あるいは蒸着後、通常のフォトリソグ
ラフィーで発光層等をパターン加工したりすることは非
常に困難であるという問題点を有していた。更に、ＥＬ
素子は、発光色毎に発光輝度や発光効率が異なるのが通
常である。効率は正孔注入輸送層及び発光層の膜厚に多
大な影響を受ける。真空蒸着法による素子形成の場合、
各画素毎に異なる膜厚の正孔注入輸送層をパターニング
したり、正孔注入輸送層の膜厚を赤、緑及び青の発光層
にあわせて調整したり、更に発光層の膜厚をそのパター
ニングと併せて制御することは困難であるという問題点
を有していた。However, among the above-mentioned conventional techniques, it is technically very difficult to finely pattern the red, green, and blue light-emitting layers by the vacuum deposition method. Although the configuration and manufacturing method have been proven to some extent, they do not go beyond the prototype stage and have poor reliability and reproducibility. In other words, it is very difficult to pattern the electron injection / transport layer, the hole injection / transport layer, and the light emitting layer with a mask at the time of vapor deposition, or to pattern the light emitting layer or the like by ordinary photolithography after vapor deposition. Had problems. Furthermore, EL
The elements usually have different emission luminance and emission efficiency for each emission color. Efficiency is greatly affected by the thickness of the hole injection transport layer and the light emitting layer. In the case of element formation by vacuum evaporation method,
A hole injection transport layer having a different thickness is patterned for each pixel, the thickness of the hole injection transport layer is adjusted according to the red, green, and blue light emitting layers, and the thickness of the light emitting layer is further adjusted. There was a problem that it was difficult to control it together with patterning.
【００１３】また、ゾル・ゲル法では、従来のフォトリ
ソグラフィー技術を利用して発光層をパターニングでき
る利点を有するものの、ゾル・ゲル法に適した材料を合
成しなければないという問題点を有している。例えば、
上記公報のように既存の低分子色素材料にアルコキシシ
リル基を付加させるには複雑な合成過程を経なければな
らない。Although the sol-gel method has an advantage that the light emitting layer can be patterned by using the conventional photolithography technique, it has a problem that a material suitable for the sol-gel method must be synthesized. ing. For example,
In order to add an alkoxysilyl group to an existing low-molecular dye material as described in the above publication, a complicated synthesis process must be performed.
【００１４】更に、ミセル電解法は、発光層等を直接に
微細パターニングし、しかも任意に膜厚をコントロール
できる優れた薄膜形成法である。しかしながら、材料粒
子を所定の界面活性剤を用いて純水に分散させる必要が
ある。したがって、材料の表面は界面活性剤の疎水部と
強く相互作用するものが有効である。ミセル電解法の原
材料であるミセル化分散水溶液の分散安定性は、薄膜の
均一性確保をはじめ、溶液のポットライフが向上すると
いう点で非常に重要である。しかし、このようなミセル
化分散水のポットライフは２４時間程度と短く、かつ所
望の界面活性剤が材料表面に吸着しやすいように陽極を
修飾したり疎水化したりしなければならないという煩雑
な工程を必要とするため、新たな材料表面の設計が必要
であるという問題点を有していた。Further, the micellar electrolysis method is an excellent thin film forming method capable of directly finely patterning a light emitting layer and the like and controlling the film thickness arbitrarily. However, it is necessary to disperse the material particles in pure water using a predetermined surfactant. Therefore, it is effective that the surface of the material strongly interacts with the hydrophobic part of the surfactant. The dispersion stability of the micellar dispersion aqueous solution, which is a raw material of the micellar electrolysis method, is very important in terms of ensuring uniformity of the thin film and improving the pot life of the solution. However, the pot life of such micellar dispersion water is as short as about 24 hours, and a complicated process of modifying or hydrophobizing the anode so that the desired surfactant can be easily adsorbed on the material surface. Therefore, there is a problem that a new material surface design is required.
【００１５】[0015]
【課題を解決するための手段】本発明の発明者は、鋭意
研究を行った結果、少なくとも発光層を含む活性層の形
成用材料である水溶性ポリマーが純水中で安定に存在す
ること、電圧を基板に形成された電極に印加することで
水溶液中の水溶性ポリマーがその電極上に選択的に吸着
すること、与えた電圧の制御によって水溶性ポリマーの
吸着速度を制御できることを見出し本発明に至った。Means for Solving the Problems As a result of diligent research, the present inventors have found that a water-soluble polymer, which is a material for forming at least an active layer including a light emitting layer, is stably present in pure water. The present invention has been found that the water-soluble polymer in the aqueous solution is selectively adsorbed on the electrode by applying a voltage to the electrode formed on the substrate, and that the adsorption rate of the water-soluble polymer can be controlled by controlling the applied voltage. Reached.
【００１６】更に、上記の方法と、例えば米国特許第
５，５１８，７６７号に記載されている交互吸着法とを
利用することで、発光表示素子の活性層である正孔注入
輸送層、発光層及び電子注入輸送層の各層の材料及び厚
さを、それぞれの層の下の電極に与える電圧を制御する
ことにより、同一基板上に独立に制御して積層できるこ
とも見出した。更にこの方法によれば、発光効率の高
い、色バランスに優れたフルカラーＥＬ素子を提供でき
ることも見出した。Further, by utilizing the above-mentioned method and the alternate adsorption method described in, for example, US Pat. No. 5,518,767, a hole injection / transport layer, which is an active layer of a light emitting display element, is used. It has also been found that the material and thickness of each layer of the layer and the electron injecting and transporting layer can be independently controlled and laminated on the same substrate by controlling the voltage applied to the electrode below each layer. Furthermore, it has been found that this method can provide a full-color EL device having high luminous efficiency and excellent color balance.
【００１７】かくして本発明によれば、第１電極を備え
た基板を、正又は負の極性に帯電しうる官能基を有する
発光層、電子注入輸送層又は正孔注入輸送層の形成用材
料の水溶液中に浸漬し、泳動電着により形成用材料を第
１電極上に積層することで発光層、電子注入輸送層又は
正孔注入輸送層を形成することを特徴とする発光表示素
子の製造方法が提供される。Thus, according to the present invention, the substrate provided with the first electrode can be used as a material for forming a light emitting layer, an electron injection transport layer or a hole injection transport layer having a functional group capable of being charged to positive or negative polarity. A method for manufacturing a light-emitting display element, wherein a light-emitting layer, an electron injection transport layer or a hole injection transport layer is formed by immersing in an aqueous solution and laminating a forming material on the first electrode by electrophoretic deposition. Is provided.
【００１８】[0018]
【発明の実施の形態】本発明では、正孔注入輸送層、発
光層及び電子注入輸送層からなる活性層の少なくとも１
層を泳動電着で形成することを特徴の１つとしている。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, at least one active layer composed of a hole injection / transport layer, a light emitting layer and an electron injection / transport layer is provided.
One of the features is that the layer is formed by electrophoretic deposition.
【００１９】上記泳動電着において、基板上の電極に電
圧を印加することで、分子レベルの膜厚の制御性で層を
形成することができる。更に、複数の活性層を形成する
ための複数種の形成用材料を用いて、各層の膜厚を任意
の厚さで制御して所望の膜構造を有した薄膜（超格子薄
膜）を選択的に形成することができる。従って、任意の
電極上に赤、緑、青の発光層をそれぞれ選択して成膜す
ることが可能となり、また、任意の膜厚を形成すること
ができるため、発光効率が高く、各発光色毎に発光輝度
をそろえた色バランスに優れたフルカラーＥＬ表示素子
を安価に作製できる。In the above-described electrophoretic deposition, by applying a voltage to the electrode on the substrate, a layer can be formed with controllability of the film thickness at the molecular level. Further, a thin film (superlattice thin film) having a desired film structure is selectively formed by controlling the film thickness of each layer to an arbitrary thickness using a plurality of kinds of forming materials for forming a plurality of active layers. Can be formed. Therefore, it is possible to selectively form red, green, and blue light emitting layers on an arbitrary electrode, and to form an arbitrary film thickness. A full-color EL display element excellent in color balance with uniform emission luminance can be manufactured at low cost.
【００２０】本発明において、所望の電極上に活性層の
少なくとも１層を形成できるのは、以下のような原理に
基づいている。正又は負（例えば、負）の極性に帯電し
うる官能基を備えた該層の形成用材料のうち、基板上に
従来法により形成した所定パターンの第１電極の内の吸
着させるべき特定の電極Ａに所定の電圧を印加して基板
表面を帯電（例えば正電圧を印加）させる。また、当該
材料を吸着させたくない電極Ｂ上には、当該材料と同じ
極性（この場合は負）の所定の電圧を印加して基板表面
を帯電させる。これらの帯電分布した基板を形成用材料
を含む水溶液（この場合はアニオン性の材料）に浸漬す
ると、クーロン相互作用によって材料と同極性に帯電し
た電極Ｂ上にはクーロン斥力により材料が吸着せず、一
方、材料と逆極性に帯電した電極Ａ上にはクーロン引力
により当該材料が吸着する。この原理により、所望の第
１電極上に活性層の少なくとも１層を形成することがで
きる。In the present invention, at least one active layer can be formed on a desired electrode based on the following principle. Among the materials for forming the layer having a functional group capable of being charged to a positive or negative (for example, negative) polarity, a specific material to be adsorbed in a first electrode of a predetermined pattern formed on a substrate by a conventional method. A predetermined voltage is applied to the electrode A to charge the substrate surface (for example, apply a positive voltage). Further, a predetermined voltage having the same polarity (in this case, negative) as that of the material is applied to the electrode B on which the material is not desired to be adsorbed, thereby charging the substrate surface. When these charged substrates are immersed in an aqueous solution containing a forming material (in this case, an anionic material), the material is not adsorbed on the electrode B charged to the same polarity as the material by Coulomb interaction due to Coulomb repulsion. On the other hand, the material is adsorbed on the electrode A charged to the opposite polarity to the material by Coulomb attraction. By this principle, at least one active layer can be formed on a desired first electrode.
【００２１】これにより、活性層のパターニング化が可
能となり、加えて各層の特性（例えば、正孔注入量、電
子注入量等）を色別に制御することができるので、発光
効率が高く各発光色毎に発光輝度をそろえた色バランス
に優れたフルカラーＥＬ表示素子の製造が可能となる。As a result, the active layer can be patterned, and in addition, the characteristics of each layer (eg, the amount of injected holes, the amount of injected electrons, etc.) can be controlled for each color. It becomes possible to manufacture a full-color EL display element having excellent color balance with uniform emission luminance every time.
【００２２】更に、その際に、電極Ａは表面上の帯電が
材料の吸着により中和するのみならず、過剰に材料が吸
着されるため、その表面には新たな帯電（この場合は負
の帯電）が現れる。次に、この基板に印加していた電圧
を切った後、先に用いた材料と反対の帯電をもつ形成用
材料を含む溶液（この場合はカチオン溶液）に基板を浸
漬する。これにより、前記材料が吸着した電極Ａにのみ
カチオン溶液中の材料がクーロン引力により吸着する。
この過程を繰り返すことによって、電極Ａにのみアニオ
ン性とカチオン性の形成用材料の交互吸着を実質上無限
に繰り返すことができる。Further, at this time, the electrode A not only neutralizes the charge on the surface due to the adsorption of the material but also absorbs the material excessively, so that the surface of the electrode A has a new charge (in this case, a negative charge). Charging) appears. Next, after the voltage applied to the substrate is cut off, the substrate is immersed in a solution containing a forming material having the opposite charge to the previously used material (in this case, a cation solution). As a result, the material in the cation solution is adsorbed by Coulomb attraction only to the electrode A on which the material is adsorbed.
By repeating this process, the alternate adsorption of the anionic and cationic forming materials only on the electrode A can be repeated substantially indefinitely.
【００２３】このように、吸着させようとする材料の極
性とは逆の極性の電極表面にのみ交互に所望の層を選択
成膜させることが可能となる。これは、同一基板上の異
なる電極部位に異なる材料からなる層を容易に分けて形
成できることを意味し、それゆえ、フルカラー発光表示
素子を容易に形成することができることとなる。As described above, it is possible to selectively form a desired layer alternately only on the electrode surface having the polarity opposite to the polarity of the material to be adsorbed. This means that layers made of different materials can be easily formed at different electrode sites on the same substrate, and therefore, a full-color light-emitting display element can be easily formed.
【００２４】また、本発明の方法では、浸漬の各ステッ
プ毎に電圧を任意に変化させることで成膜速度と膜厚を
制御することができるので、層厚の制御性を維持しなが
ら各層の膜厚をÅオーダーから数十ｎｍ程度まで自由に
制御することができる。しかも、本発明の方法は電圧を
印加した電極を備える基板を形成用材料の水溶液に浸漬
するだけという、きわめて簡便な手法で行うことができ
る。In the method of the present invention, the film forming rate and the film thickness can be controlled by arbitrarily changing the voltage at each step of immersion. The film thickness can be freely controlled from the order of Å to several tens nm. In addition, the method of the present invention can be performed by an extremely simple method of merely immersing a substrate provided with a voltage-applied electrode in an aqueous solution of a forming material.
【００２５】つまり、本発明の方法において複数層を積
層する場合には各形成用材料の溶液を準備するだけでよ
いということである。これに対して、例えば、マスク蒸
着法によりフルカラー有機ＥＬディスプレイを作製する
場合、赤、緑、青の３色の発光層を塗り分けるために基
板上に載せた金属マスクを少しずつずらしながら各発光
層を蒸着法により成膜する必要がある。この場合、大が
かりな真空装置を用いかつμｍの位置精度で金属マスク
をアライメントする必要があるため、高度な技術と莫大
な費用を要する。更に、発光層の形成用材料は大変高価
であり、マスク蒸着法では蒸着された材料の殆どが真空
槽内部に付着してしまい、材料の利用効率が極めて悪
い。これに対して、本発明の方法は基板上の特定の電極
にのみ選択的に有機分子を吸着させるので、何度でも溶
液を使用することができ形成用材料を１００％近く使用
することができる。That is, in the case of laminating a plurality of layers in the method of the present invention, it is only necessary to prepare a solution of each forming material. On the other hand, for example, when a full-color organic EL display is manufactured by a mask vapor deposition method, each light emission is performed while shifting the metal mask placed on the substrate little by little in order to separately apply the red, green, and blue light-emitting layers. The layers need to be deposited by vapor deposition. In this case, since it is necessary to use a large-scale vacuum apparatus and align the metal mask with a positional accuracy of μm, high technology and enormous cost are required. Further, the material for forming the light emitting layer is very expensive, and most of the vapor deposited material adheres to the inside of the vacuum chamber by the mask vapor deposition method, so that the utilization efficiency of the material is extremely low. On the other hand, the method of the present invention selectively adsorbs organic molecules only to a specific electrode on a substrate, so that a solution can be used as many times as possible and nearly 100% of a forming material can be used. .
【００２６】また、インクジェット法では、材料の利用
効率は本発明の方法と同様１００％に近いが、プリンタ
ヘッドを用いて一カ所ずつインクを塗布しなければなら
ず基板の面積が大きくなればなるほど装置自体が大がか
りとなり、かつ製造時間もかかり効率的ではない。ま
た、インクを塗布する位置精度も精々±２５μｍであ
り、本発明より精度が劣るという問題点もある。Further, in the ink-jet method, the utilization efficiency of the material is close to 100% as in the method of the present invention, but the ink has to be applied one place at a time using a printer head, and the larger the area of the substrate, the larger the area. The apparatus itself becomes large-scale, requires a long manufacturing time, and is not efficient. In addition, the positional accuracy of applying the ink is at most ± 25 μm, which is inferior to that of the present invention.
【００２７】更に、ゾル・ゲル法はパターン精度がマス
ク蒸着法と同様マスクの精度で決定される。しかしなが
ら、本発明の方法では、赤、緑及び青３色の発光層の塗
り分け精度は電極パターンで決まるので、前記方法に比
べて高精度に塗り分けが可能となる。Further, in the sol-gel method, the pattern accuracy is determined by the accuracy of the mask as in the mask evaporation method. However, according to the method of the present invention, since the coloring accuracy of the three light emitting layers of red, green and blue is determined by the electrode pattern, the coloring can be performed with higher precision than the above method.
【００２８】更に詳しく本発明を説明する。The present invention will be described in more detail.
【００２９】本発明で使用する形成用材料は、水溶性ポ
リマーに限られず、正又は負の極性に帯電しうる官能基
を備えた有機又は無機の材料である。本発明では、有機
材料を使用することより好ましい。官能基とは、例え
ば、ニトロ基、水酸基、スルホン酸基、カルボキシル基
等の正に帯電しうる基、チオフェニル基、４級アンモニ
ウム基、アミノ基等の負に帯電しうる基が挙げられる。The forming material used in the present invention is not limited to a water-soluble polymer, and is an organic or inorganic material having a functional group capable of being charged to a positive or negative polarity. In the present invention, it is more preferable to use an organic material. Examples of the functional group include a positively chargeable group such as a nitro group, a hydroxyl group, a sulfonic acid group, and a carboxyl group, and a negatively chargeable group such as a thiophenyl group, a quaternary ammonium group, and an amino group.
【００３０】より具体的には、発光層を形成するための
材料としては、ルテニウム、エルビウム、ユーロピウ
ム、イリジウム、白金等の有機錯体イオン、ポリフルオ
レン誘導体、ポリパラフェニレンビニレンの前駆体とそ
の誘導体、ポリチオフェン誘導体、ポリパラフェニレン
誘導体、ポリシラン誘導体、ポリアセチレン誘導体、ポ
リビニルカルバゾール誘導体及びポリピロール誘導体等
を構成する共役高分子に、上記官能基を付与した材料を
挙げることができる。More specifically, materials for forming the light emitting layer include organic complex ions such as ruthenium, erbium, europium, iridium and platinum, polyfluorene derivatives, precursors of polyparaphenylene vinylene and derivatives thereof, A material in which the above functional group is added to a conjugated polymer constituting a polythiophene derivative, a polyparaphenylene derivative, a polysilane derivative, a polyacetylene derivative, a polyvinylcarbazole derivative, a polypyrrole derivative, or the like can be given.
【００３１】更に、活性層は任意に、正孔注入輸送層、
電子注入輸送層を備えていてもよく、これら層も本発明
の方法により形成することができる。Further, the active layer may optionally include a hole injection transport layer,
An electron injection / transport layer may be provided, and these layers can also be formed by the method of the present invention.
【００３２】本発明の方法が使用可能な正孔注入輸送層
の形成用材料としては、ポリスチレンスルホン酸（ＰＳ
Ｓ）、ポリビニル硫酸（ＰＶＳ）、デキストラン酸、コ
ンドロイチン硫酸、ポリアクリル酸（ＰＡＡ）、ポリメ
タクリル酸（ＰＭＡ）、ポリマレイン酸、ポリフマル酸
等が挙げられるが、上記材料に限らず発光材料より大き
く透明電極より小さい仕事関数を有する材料であればよ
い。Polystyrene sulfonic acid (PS) is used as a material for forming the hole injection transport layer in which the method of the present invention can be used.
S), polyvinyl sulfate (PVS), dextran acid, chondroitin sulfate, polyacrylic acid (PAA), polymethacrylic acid (PMA), polymaleic acid, polyfumaric acid, etc. Any material having a work function smaller than that of the electrode may be used.
【００３３】一方、本発明の方法が使用可能な正孔注入
輸送層の形成用材料としては、ポリエチレンイミン（Ｐ
ＥＩ）、ポリアリルアミン塩酸塩（ＰＡＨ）、ポリアリ
ルジメチルアンモニウムクロリド（ＰＤＤＡ）、ポリビ
ニルピリジン（ＰＶＰ）、ポリリジン等が挙げられる
が、上記材料に限らず発光材料より大きく陰極よりも小
さい電子親和力を有する材料であればよい。On the other hand, as a material for forming the hole injection transport layer in which the method of the present invention can be used, polyethyleneimine (P
EI), polyallylamine hydrochloride (PAH), polyallyldimethylammonium chloride (PDDA), polyvinylpyridine (PVP), polylysine, and the like, but are not limited to the above materials and have a larger electron affinity than the light emitting material and smaller than the cathode. Any material may be used.
【００３４】上記層以外にもバッファ層（例えば、フラ
ーレン誘導体、ポリアニリン誘導体、フタロシアニン誘
導体）等を備えていてもよい。In addition to the above layers, a buffer layer (for example, a fullerene derivative, a polyaniline derivative, a phthalocyanine derivative) or the like may be provided.
【００３５】上記によれば、活性層を構成する層のパタ
ーニング化が可能となり、また、任意の膜厚を形成する
ことができるため、各層の特性（例えば、正孔注入量、
電子注入量等）を色別に制御することができるので、発
光効率が高く、各発光色毎に発光輝度をそろえた色バラ
ンスに優れたフルカラーＥＬ表示素子の製造が可能とな
る。According to the above, the layers constituting the active layer can be patterned and an arbitrary film thickness can be formed, so that the characteristics of each layer (for example, the amount of hole injection,
Since the amount of injected electrons can be controlled for each color, it is possible to manufacture a full-color EL display element with high luminous efficiency and excellent luminous luminance for each luminescent color and excellent in color balance.
【００３６】なお、上記形成用材料は、いずれも水ある
いは水と有機溶媒との混合液に可溶なものが通常使用さ
れる。The above-mentioned materials for formation are usually soluble in water or a mixture of water and an organic solvent.
【００３７】基板としては、ガラス基板、石英、ポリマ
ーフィルムや、Ｓｉ、ＧａＡｓ、ＧａＮ等の未ドープの
絶縁性の半導体基板等の絶縁性基板が挙げられる。Examples of the substrate include a glass substrate, quartz, a polymer film, and an insulating substrate such as an undoped insulating semiconductor substrate such as Si, GaAs, and GaN.
【００３８】更に、第１電極としては、上記絶縁性基板
上に、蒸着法等により成膜した銀、金、アルミニウム等
の金属層や、ドーピングによって導電性を持たせたＩＴ
Ｏ（Ｉｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ）、ＺｎＯ、Ｔ
ｉＯ2等の酸化物薄膜を従来法によりパターニングした
ものを用いることができる。なお、これら例に限られ
ず、導電性を有する部分が絶縁性基板表面にパターン化
され露出しているものであればどのようなものでも用い
ることができる。Further, as the first electrode, a metal layer of silver, gold, aluminum or the like formed on the insulating substrate by a vapor deposition method or the like, or an IT which is made conductive by doping.
O (Indium Tin Oxide), ZnO, T
A material obtained by patterning an oxide thin film such as iO 2 by a conventional method can be used. It should be noted that the present invention is not limited to these examples, and any conductive material may be used as long as it is patterned and exposed on the surface of the insulating substrate.
【００３９】形成用材料の溶解用の溶媒には、基本的に
水を使用するが、溶解性に応じて有機溶媒を混合しても
よい。溶液濃度は形成用材料の溶解性に依存するが、吸
着過程が基板表面の荷電の中和及び再飽和に基づいてい
るので、特に厳密な濃度設定は必要としない。標準的な
濃度例としては、０．００１ｍＭ〜１Ｍの範囲で調製さ
れ、より好ましくは１ｍＭ〜０．１Ｍの範囲である。ま
た、第１電極に印加する電圧としては、用いる溶液の種
類、溶液濃度、ｐＨ等に依存して調整しなければならな
いが、１ｍＶ〜５０Ｖが好ましく、更に好ましくは、
０．１Ｖ〜１０Ｖ程度である。Water is basically used as a solvent for dissolving the forming material, but an organic solvent may be mixed according to the solubility. Although the solution concentration depends on the solubility of the forming material, no particular strict concentration setting is required since the adsorption process is based on neutralization and resaturation of the charge on the substrate surface. As a standard concentration example, it is prepared in the range of 0.001 mM to 1 M, and more preferably in the range of 1 mM to 0.1 M. Also, the voltage applied to the first electrode must be adjusted depending on the type of solution used, the solution concentration, the pH, etc., but is preferably 1 mV to 50 V, more preferably
It is about 0.1V to 10V.
【００４０】また、溶液中のｐＨ値を変化させることに
より形成用材料の吸着速度を制御することができる。こ
れにより各層の成膜速度を制御することができるので、
発光効率が高く各発光色毎に発光輝度をそろえた色バラ
ンスに優れたフルカラーＥＬ表示素子の製造の効率化を
図ることが可能となる。Further, by changing the pH value in the solution, the adsorption speed of the forming material can be controlled. This makes it possible to control the deposition rate of each layer,
It is possible to increase the efficiency of manufacturing a full-color EL display element having high luminous efficiency and excellent luminous luminance for each luminescent color and excellent in color balance.
【００４１】本発明の方法をその操作順に説明する。The method of the present invention will be described in the order of operation.
【００４２】まず、全ての工程に先立って、第１電極を
備えた基板を洗浄することが好ましい。具体的には、有
機溶媒により洗浄・乾燥する方法及び／又は表面を紫外
線照射することによりオゾン洗浄を施す方法が挙げられ
る。First, prior to all the steps, it is preferable to wash the substrate provided with the first electrode. Specific examples include a method of washing and drying with an organic solvent and / or a method of performing ozone washing by irradiating the surface with ultraviolet rays.
【００４３】次に、形成用材料の吸着性を向上させるた
めに、電極の表面を以下のように処理することが好まし
い。すなわち、オゾン洗浄を施した場合、水酸基で修飾
されるため第１電極は負に帯電することとなるから、特
に処理の必要はない。一方、第１電極表面にまず負に帯
電する形成用材料を吸着させたい場合は、表面をアミノ
トリクロロシリル誘導体、アミノトリエトキチシリル誘
導体あるいはアミノトリメトキシシリル誘導体等の自己
組織化単分子膜を形成し、表面を正の極性に変成するこ
とが好ましい。Next, in order to improve the adsorptivity of the forming material, the surface of the electrode is preferably treated as follows. That is, when ozone cleaning is performed, the first electrode is negatively charged because it is modified with a hydroxyl group, so that no special treatment is required. On the other hand, if it is desired to first adsorb a negatively charged forming material on the surface of the first electrode, a self-assembled monolayer such as an aminotrichlorosilyl derivative, an aminotriethoxysilyl derivative or an aminotrimethoxysilyl derivative is formed on the surface. However, it is preferable that the surface be transformed to a positive polarity.
【００４４】次に、例えば対向電極を白金電極とし、吸
着させたい電極には用いる形成用材料の極性とは反対の
極性の電圧を印加し、吸着させたくない電極には同極性
の電圧を印加する。電圧の印加により、形成用材料が反
対の極性の電圧が印加された電極にのみに選択的にクー
ロン相互作用により引き寄せられ吸着することで所定の
層を形成することができる。Next, for example, the opposite electrode is a platinum electrode, and a voltage having a polarity opposite to the polarity of the forming material used is applied to the electrode to be adsorbed, and a voltage of the same polarity is applied to the electrode not to be adsorbed. I do. By applying a voltage, a predetermined layer can be formed by selectively attracting and attracting the forming material only to the electrode to which a voltage of the opposite polarity is applied by Coulomb interaction.
【００４５】得られた層は純水により洗浄することが好
ましい。The obtained layer is preferably washed with pure water.
【００４６】続けて、上記層上に更に層を形成してもよ
い。この場合、先に用いた形成用材料とは反対の極性を
有する形成用材料の溶液に浸漬することが好ましい。そ
うすると、上述の処理により先の形成用材料が吸着しな
かった電極表面は後の形成用材料と同極性となっており
後の形成用材料は吸着せず、一方、先の形成用材料が吸
着した電極表面にはクーロン引力により後の形成用材料
が選択的に吸着し過飽和状態となる。所定の膜厚の有機
膜が得られたら水による洗浄を行うことが好ましい。Subsequently, another layer may be formed on the above layer. In this case, it is preferable to immerse in a solution of the forming material having the opposite polarity to the previously used forming material. Then, the electrode surface on which the former forming material was not adsorbed by the above-described processing has the same polarity as the later forming material, and the latter forming material does not adsorb, while the former forming material does not adsorb. The subsequent forming material is selectively adsorbed on the surface of the electrode by Coulomb attraction, and becomes a supersaturated state. When an organic film having a predetermined thickness is obtained, it is preferable to perform washing with water.
【００４７】負及び正の形成用材料を適当に選び、上記
一連の操作を順次行うことによって、所望の構造を持っ
た有機超格子構造を特定の電極にのみ選択的に形成する
ことができる。なお、形成用材料は、複数種の混合材料
であってもよい。また、電圧を印加して形成用材料を電
極上に選択吸着させる場合、透析法を併用することによ
り、溶液中に存在する吸着を妨害するイオンを除去する
ことが好ましい。An organic superlattice structure having a desired structure can be selectively formed only on a specific electrode by appropriately selecting the negative and positive forming materials and sequentially performing the above series of operations. Note that the forming material may be a mixed material of a plurality of types. In addition, when a voltage is applied to selectively adsorb the forming material on the electrode, it is preferable to use a dialysis method in combination to remove ions present in the solution that interfere with the adsorption.
【００４８】なお、本発明の方法では、活性層の少なく
とも１層が上記方法で形成されていれば、それ以外の層
は、公知の方法で形成してもよい。しかしながら、活性
層全てを本発明の方法で形成することがより効果を奏す
るので好ましい。In the method of the present invention, as long as at least one of the active layers is formed by the above method, the other layers may be formed by a known method. However, it is preferable to form all the active layers by the method of the present invention, because the effect is more exhibited.
【００４９】更に、活性層上の第２電極は、特に限定さ
れず、公知の材料で、公知の方法により形成することが
できる。また、発光表示素子が、基板側から発光を取出
すタイプの場合（第１電極が陽極、第２電極が陰極とな
る）、少なくとも基板と第１電極が透明であり、第２電
極側から発光を取出すタイプの場合は、第２電極が透明
であればよい。Further, the second electrode on the active layer is not particularly limited, and can be formed of a known material by a known method. When the light-emitting display element is of a type that emits light from the substrate side (the first electrode is an anode and the second electrode is a cathode), at least the substrate and the first electrode are transparent, and light is emitted from the second electrode side. In the case of the extraction type, the second electrode may be transparent.
【００５０】[0050]
【実施例】以下、本発明を実施例を図面に基づいて説明
する。Embodiments of the present invention will be described below with reference to the drawings.
【００５１】（実施例１）図1は、ストライプ状にピッ
チ１００μｍのＩＴＯ透明画素電極（第１電極）をパタ
ーン形成したガラスからなる透明基板上に、ＥＬ素子を
形成するプロセスを示す図である。Example 1 FIG. 1 is a view showing a process of forming an EL element on a transparent substrate made of glass on which ITO transparent pixel electrodes (first electrodes) having a pitch of 100 μm are formed in a stripe pattern. .
【００５２】そのプロセスを説明すると、透明基板１０
４上に真空スパッタ法により、厚さ１５０ｎｍの透明な
ＩＴＯ電極を形成し、フォトリソグラフィー法にてパタ
ーニングする。これにより赤色発光域のＩＴＯ電極１０
１、緑色発光域のＩＴＯ電極１０２、青色発光域のＩＴ
Ｏ電極１０３を得る（図１（Ａ）参照）。The process will be described.
A transparent ITO electrode having a thickness of 150 nm is formed on the substrate 4 by a vacuum sputtering method, and is patterned by a photolithography method. As a result, the ITO electrode 10 in the red emission region
1. ITO electrode 102 in the green light emitting region, IT in the blue light emitting region
An O electrode 103 is obtained (see FIG. 1A).
【００５３】上記基板表面を大気中１７２ｎｍの波長の
エキシマランプにより１０ｍＷ／ｃｍ2の１５分間照射
を行い、基板表面を親水化処理した。得られた表面の水
の接触角を接触角計にて調べたところ３゜以下となり、
基板表面は極めて清浄であり超親水性を呈することが分
った。The substrate surface was irradiated with 10 mW / cm 2 for 15 minutes in the atmosphere by an excimer lamp having a wavelength of 172 nm, thereby hydrophilizing the substrate surface. When the contact angle of water on the obtained surface was examined with a contact angle meter, it was 3 ° or less.
It was found that the substrate surface was extremely clean and exhibited superhydrophilicity.
【００５４】次に、図２に示す装置を用いて活性層を形
成する。図２中、２０１は直流電源、２０２は白金電
極、２０３は容器、２０４は活性層形成用材料の溶液、
２０５は透明基板、２０６はＩＴＯ電極、２０７は水晶
振動子を意味する。具体的には以下のように行う。Next, an active layer is formed using the apparatus shown in FIG. In FIG. 2, 201 is a DC power supply, 202 is a platinum electrode, 203 is a container, 204 is a solution of a material for forming an active layer,
Reference numeral 205 denotes a transparent substrate, 206 denotes an ITO electrode, and 207 denotes a quartz oscillator. Specifically, this is performed as follows.
【００５５】まず、ＩＴＯ電極のうち対向する白金電極
に対してＩＴＯ電極１０１に−３Ｖ、ＩＴＯ電極１０２
及びＩＴＯ電極１０３に＋１Ｖの電圧を印加した状態
で、０．０１Ｍのポリフェニレンビニレン前駆体水溶液
中に２０分浸漬し、ＩＴＯ電極１０１にのみ選択的にポ
リフェニレンビニレン前駆体(ｐｒｅ−ＰＰＶ)を１５ｎ
ｍ吸着させ、赤色発光用正孔注入輸送層１０５形成用の
前駆体層が形成された。基板を水溶液中から取出し、純
水で３回リンスした。First, -3 V is applied to the ITO electrode 101 with respect to the opposing platinum electrode among the ITO electrodes,
Then, while applying a voltage of +1 V to the ITO electrode 103, the substrate was immersed in a 0.01M aqueous solution of a polyphenylenevinylene precursor for 20 minutes, and the polyphenylenevinylene precursor (pre-PPV) was selectively applied only to the ITO electrode 101 for 15n.
Thus, a precursor layer for forming the hole injection / transport layer 105 for red light emission was formed. The substrate was taken out of the aqueous solution and rinsed three times with pure water.
【００５６】次に、白金に対するＩＴＯ電極１０１、Ｉ
ＴＯ電極１０２及びＩＴＯ電極１０３の電圧を０Ｖに
し、１Ｍの１，４−（２，７−カルボキヘプタオキシ）
−５−エトキシフェニレン）ビニレン（ＣＨＥＯＰＰ
Ｖ）水溶液中に基板を２０分浸漬し、ＩＴＯ電極１０１
にのみ厚さ１０ｎｍの赤色発光用の発光層１０６を吸着
させた。上記の操作を５回繰り返すことにより、ｐｒｅ
−ＰＰＶ（１５ｎｍ）／ＣＨＥＯＰＰＶ（１０ｎｍ）を
単位とする層がＩＴＯ電極１０１にのみ選択的に５層形
成された。Next, the ITO electrodes 101, I
The voltage of the TO electrode 102 and the ITO electrode 103 is set to 0 V, and 1M 1,4- (2,7-carboxyheptaoxy)
-5-ethoxyphenylene) vinylene (CHEOPP)
V) The substrate was immersed in the aqueous solution for 20 minutes,
The red light-emitting layer 106 having a thickness of 10 nm was adsorbed only on the substrate. By repeating the above operation 5 times, pre
Five layers with units of -PPV (15 nm) / CHEOPPV (10 nm) were selectively formed only on the ITO electrode 101.
【００５７】その後、基板１０４を窒素雰囲気中で２０
０℃で１２時間アニールし、ｐｒｅ−ＰＰＶからなる前
駆体層をＰＰＶからなる正孔注入輸送層１０５に変成し
た。パターニングは、図３に示すように、基板３０４上
に形成された各色毎のＩＴＯ電極３０１〜３０３に選択
的に導電性ゴム３０５を圧着して直流電源３０６により
通電することでなされる。対向電極は白金電極３０７と
し、膜厚の設定は通電時間によりなされ、長いほど膜は
厚くなる（図１（Ｂ）参照）。なお、３０１は赤色発光
領域、３０２は緑色発光領域、３０３は青色発光領域の
ＩＴＯ電極を表す。Thereafter, the substrate 104 is placed in a nitrogen atmosphere for 20 minutes.
Annealing was performed at 0 ° C. for 12 hours to transform the precursor layer made of pre-PPV into the hole injection / transport layer 105 made of PPV. As shown in FIG. 3, the patterning is performed by selectively pressing conductive rubber 305 onto ITO electrodes 301 to 303 for each color formed on the substrate 304 and applying a current from a DC power supply 306. The counter electrode is a platinum electrode 307, and the thickness is set by the energization time. The longer the film, the thicker the film (see FIG. 1B). Reference numeral 301 denotes a red light emitting region, 302 denotes a green light emitting region, and 303 denotes an ITO electrode in a blue light emitting region.
【００５８】次に、ＩＴＯ電極のうち対向する白金電極
に対してＩＴＯ電極１０２に−３Ｖ、ＩＴＯ電極１０１
及びＩＴＯ電極１０３に＋１Ｖの電圧を印加した状態
で、１Ｍのポリフェニレンビニレン前駆体水溶液中に２
０分浸漬し、ＩＴＯ電極１０２にのみ選択的にポリフェ
ニレンビニレン前駆体（ｐｒｅ−ＰＰＶ）を３０ｎｍ吸
着させ、緑色発光用の発光層１０９の前駆体層が形成さ
れた。基板を水溶液中から取出し、純水で３回リンスし
た。次に、白金電極に対するＩＴＯ電極１０１、ＩＴＯ
電極１０２及びＩＴＯ電極１０３の電圧を０Ｖにし、
０．１Ｍのポリスチレンスルフォネート（ＰＳＳ）水溶
液中に基板を２０分浸漬し、ＩＴＯ電極１０２にのみ厚
さ４ｎｍの緑発色用バッファ層を吸着させた。上記の操
作を７回繰り返すことにより、ｐｒｅ−ＰＰＶ（３０ｎ
ｍ）／ＰＳＳ（４ｎｍ）を単位とする層がＩＴＯ電極１
０２にのみ選択的に７層形成された。その後、基板１０
４を窒素雰囲気中で２００℃で１２時間アニールし、ｐ
ｒｅ−ＰＰＶからなる前駆体層をＰＰＶからなる発光層
１０９に変成した（図１（Ｃ）参照）。Next, -3 V is applied to the ITO electrode 102 with respect to the platinum electrode facing the ITO electrode,
Then, while applying a voltage of +1 V to the ITO electrode 103, 2M was added to the 1M aqueous solution of polyphenylenevinylene precursor.
After immersion for 0 minutes, the polyphenylene vinylene precursor (pre-PPV) was selectively adsorbed on the ITO electrode 102 only by 30 nm to form a precursor layer of the light emitting layer 109 for green light emission. The substrate was taken out of the aqueous solution and rinsed three times with pure water. Next, the ITO electrode 101 with respect to the platinum electrode,
The voltage of the electrode 102 and the ITO electrode 103 is set to 0 V,
The substrate was immersed in a 0.1 M polystyrene sulfonate (PSS) aqueous solution for 20 minutes, and a 4 nm-thick green color buffer layer was adsorbed only on the ITO electrode 102. By repeating the above operation seven times, pre-PPV (30 n
m) / PSS (4 nm) unit is ITO electrode 1
Only 02 was selectively formed in seven layers. Then, the substrate 10
4 was annealed at 200 ° C. for 12 hours in a nitrogen atmosphere,
The precursor layer made of re-PPV was transformed into a light emitting layer 109 made of PPV (see FIG. 1C).
【００５９】ＩＴＯ電極のうち対向する白金電極に対し
てＩＴＯ電極１０３に−３Ｖ、ＩＴＯ電極１０１及びＩ
ＴＯ電極１０２に＋１Ｖの電圧を印加した状態で、０．
０５Ｍのポリアリルアミン（ＰＡＡ）水溶液中に２０分
浸漬し、ＩＴＯ電極１０３にのみ選択的にＰＡＡを４ｎ
ｍ吸着させ、青色発光用の正孔注入輸送層１１１が形成
された。基板を水溶液中から取出し、純水で３回リンス
した。次に、白金電極に対するＩＴＯ電極１０１、ＩＴ
Ｏ電極１０２及びＩＴＯ電極１０３の電圧を０Ｖにし、
１Ｍのスルホン化ポリパラフェニレン（ＳＰＰＰ）水溶
液中に基板を２０分浸漬し、ＩＴＯ電極１０３にのみ厚
さ４ｎｍの青色発光用の発光層１１２を吸着させた。上
記の操作を１０回繰り返すことにより、ＰＡＡ（４ｎ
ｍ）／ＳＰＰＰ（４ｎｍ）を単位とする層がＩＴＯ電極
１０３にのみ選択的に１０層形成された。その後、基板
１０４を窒素雰囲気中で１００℃で４時間アニールし乾
燥させた（図１（Ｄ）参照）。Of the ITO electrodes, -3 V was applied to the ITO electrode 103 with respect to the opposing platinum electrode, and the ITO electrodes 101 and I
In a state where a voltage of +1 V is applied to the TO electrode 102, the voltage of.
Immerse in a 05M polyallylamine (PAA) aqueous solution for 20 minutes, and selectively apply 4n of PAA only to the ITO electrode 103.
m, and the hole injection / transport layer 111 for blue light emission was formed. The substrate was taken out of the aqueous solution and rinsed three times with pure water. Next, the ITO electrode 101 with respect to the platinum electrode, IT
The voltage of the O electrode 102 and the ITO electrode 103 is set to 0 V,
The substrate was immersed in a 1 M aqueous solution of sulfonated polyparaphenylene (SPPP) for 20 minutes, and only a 4 nm-thick blue light emitting layer 112 was adsorbed to the ITO electrode 103. By repeating the above operation 10 times, PAA (4n
m) Ten layers having units of / SPPP (4 nm) were selectively formed only on the ITO electrode 103. After that, the substrate 104 was annealed at 100 ° C. for 4 hours in a nitrogen atmosphere and dried (see FIG. 1D).
【００６０】最後に、抵抗加熱蒸着法にてＣａ陰極（第
２電極）１１４を２００ｎｍ及びＡｇを１００ｎｍをＩ
ＴＯパターンと直交するように幅３００μｍにパターン
形成する。こうして、単純マトリックス駆動のフルカラ
ーＥＬ表示素子を得ることができる（図１（Ｅ）参
照）。Finally, 200 nm of Ca cathode (second electrode) 114 and 100 nm of Ag were
A pattern having a width of 300 μm is formed so as to be orthogonal to the TO pattern. Thus, a full-color EL display element driven by a simple matrix can be obtained (see FIG. 1E).
【００６１】なお、図１中、電子注入輸送層（赤色発光
用）１０７、正孔注入輸送層（緑色発光用）１０８、電
子注入輸送層（緑色発光用）１１０、電子注入輸送層
（青色発光用）１１３は実施例１では形成していない。In FIG. 1, an electron injection / transport layer (for red light emission) 107, a hole injection / transport layer (for green light emission) 108, an electron injection / transport layer (for green light emission) 110, and an electron injection / transport layer (blue light emission) For example, 113 is not formed in the first embodiment.
【００６２】（実施例２）実施例１と同様に準備した基
板表面を大気中１７２ｎｍの波長のエキシマランプによ
り１０ｍＷ／ｃｍ2の１５分間照射を行い、基板表面を
親水化処理した。得られた表面の水の接触角を接触角計
にて調べたところ２゜以下となり、基板表面は極めて清
浄であり超親水性を呈することが分った。そして、ＩＴ
Ｏ電極表面をカチオン化するために１ｍＭの酢酸を混ぜ
たメターノル：純水：Ｎ−［３−トリメトキシシリル）
プロピル］エチレンジアミン(ＡＰＴＭＳ)の混合溶液
（容積比４４：５：１）に２０分浸漬後、エタノールで
リンスし、大気中１２０℃１時間アニールを行いＡＰＴ
ＭＳのメトキシシリル基を電極表面と結合させた。接触
角計により水の接触角を調べたところ、約２６゜であ
り、アミノメトシキシランの自己組織化単分子膜が電極
表面上に形成されていることが分った。次に、ＩＴＯ電
極のうち対向する白金電極に対してＩＴＯ電極１０１に
＋３Ｖ、ＩＴＯ電極１０２及びＩＴＯ電極１０３に−１
Ｖの電圧を印加した状態で、１Ｍの１，４−（２，９−
カルボキノナオキシ）−５−メトキシフェニレンビニレ
ン（ＣＮＭＯＰＰＶ）水溶液中に２０分浸漬し、ＩＴＯ
電極１０１にのみ選択的にＣＮＭＯＰＰＶを２０ｎｍ吸
着させ、発光層１０６が形成された。基板を水溶液中か
ら取出し、純水で３回リンスした。次に、白金電極に対
するＩＴＯ電極１０１、ＩＴＯ電極１０２及びＩＴＯ電
極１０３の電圧を０Ｖにし、０．０１Ｍのポリフェニレ
ンビニレン前駆体水溶液中に基板を２０分浸漬し、ＩＴ
Ｏ電極１０１にのみ厚さ４ｎｍの赤発光バッファ層の前
駆体層を吸着させた。上記の操作を４回繰り返すことに
より、ＣＮＭＯＰＰＶ（２０ｎｍ）／ｐｒｅ−ＰＰＶ
（４ｎｍ）を単位とする層がＩＴＯ電極１０１にのみ選
択的に４層形成された。更に、ＩＴＯ電極のうち対向す
る白金電極に対してＩＴＯ電極１０１に＋３Ｖ、ＩＴＯ
電極１０２及びＩＴＯ電極１０３に−１Ｖの電圧を印加
した状態で、０．０１Ｍのデキストリン硫酸水溶液に３
０分浸漬し、デキストリン硫酸を約１０ｎｍ吸着させ、
赤色発光用の電子注入輸送層１０７を形成した（図１
（Ｂ）参照）。(Example 2) The surface of the substrate prepared in the same manner as in Example 1 was irradiated with 10 mW / cm 2 for 15 minutes by an excimer lamp having a wavelength of 172 nm in the air to hydrophilize the substrate surface. When the contact angle of water on the obtained surface was examined with a contact angle meter, it was found to be 2 ° or less, indicating that the substrate surface was extremely clean and exhibited superhydrophilicity. And IT
Methanol mixed with 1 mM acetic acid to cationize the O electrode surface: pure water: N- [3-trimethoxysilyl)
[Propyl] ethylenediamine (APTMS), immersed in a mixed solution (volume ratio: 44: 5: 1) for 20 minutes, rinsed with ethanol, and annealed in air at 120 ° C. for 1 hour to perform APT.
The methoxysilyl group of MS was bound to the electrode surface. When the contact angle of water was examined by a contact angle meter, it was about 26 °, and it was found that a self-assembled monolayer of aminomethoxysilane was formed on the electrode surface. Next, +3 V is applied to the ITO electrode 101 with respect to the platinum electrode facing the ITO electrode, and -1 is applied to the ITO electrode 102 and the ITO electrode 103.
With a voltage of V applied, 1M 1,4- (2,9-
Carboquinonaoxy) -5-methoxyphenylenevinylene (CNMOPPV) aqueous solution for 20 minutes, ITO
The light emitting layer 106 was formed by selectively adsorbing CNMOPPV to the electrode 101 only by 20 nm. The substrate was taken out of the aqueous solution and rinsed three times with pure water. Next, the voltage of the ITO electrode 101, the ITO electrode 102, and the ITO electrode 103 with respect to the platinum electrode was set to 0 V, and the substrate was immersed in a 0.01 M aqueous solution of a polyphenylenevinylene precursor for 20 minutes.
A precursor layer of a red emission buffer layer having a thickness of 4 nm was adsorbed only to the O electrode 101. By repeating the above operation four times, CNMOPPV (20 nm) / pre-PPV
(4 nm) were selectively formed only on the ITO electrode 101 in four layers. Further, +3 V is applied to the ITO electrode 101 with respect to the platinum electrode facing the ITO electrode,
While a voltage of -1 V is applied to the electrode 102 and the ITO electrode 103, a 3M aqueous solution of dextrin sulfuric acid is
Immersion for 0 minutes, adsorb dextrin sulfate about 10nm,
An electron injection transport layer 107 for emitting red light was formed (FIG. 1).
(B)).
【００６３】次にＩＴＯ電極のうち対向する白金電極に
対してＩＴＯ電極１０２に＋４Ｖ、ＩＴＯ電極１０１及
びＩＴＯ電極１０３に−１Ｖの電圧を印加した状態で、
０．１Ｍのスルホン化ポリアニリン（ＳＰＡｎ）水溶液
中に５分浸漬し、ＩＴＯ電極１０２にのみ選択的にＳＰ
Ａｎを４ｎｍ吸着させ、緑色発光用の正孔注入輸送層１
０８が形成された。基板を水溶液中から取出し、純水で
３回リンスした。次に、白金電極に対するＩＴＯ電極１
０１、ＩＴＯ電極１０２及びＩＴＯ電極１０３の電圧を
０Ｖにし、１Ｍのポリフェニレンビニレン前駆体（ｐｒ
ｅ−ＰＰＶ）水溶液中に基板を５分浸漬し、ＩＴＯ電極
１０２にのみ厚さ４ｎｍの発光層１０９の前駆体層を吸
着させた。上記の操作を１０回繰り返すことにより、Ｓ
ＰＡｎ（４ｎｍ）／ｐｒｅ−ＰＰＶ（４ｎｍ）を単位と
する層がＩＴＯ電極１０２にのみ選択的に１０層形成さ
れた。更に、ＩＴＯ電極のうち対向する白金電極に対し
てＩＴＯ電極１０１に＋３Ｖ、ＩＴＯ電極１０２及びＩ
ＴＯ電極１０３に−１Ｖの電圧を印加した状態で、０．
１Ｍのポリ１，４−（２−ヘキシル−３，５−カルボキ
ペンタオキシ）フェニレン水溶液に３０分浸漬し、ポリ
１，４−（２−ヘキシル−３，５−カルボキペンタオキ
シ）フェニレンを約５ｎｍ吸着させ、緑色発光用の電子
注入輸送層１１０を形成した（図１（Ｃ）参照）。Next, with a voltage of +4 V applied to the ITO electrode 102 and a voltage of -1 V applied to the ITO electrode 101 and the ITO electrode 103 with respect to the opposing platinum electrode among the ITO electrodes,
Immersion in a 0.1 M aqueous solution of sulfonated polyaniline (SPAn) for 5 minutes to selectively apply SP only to the ITO electrode 102
An hole-injecting / transporting layer 1 for emitting green light by adsorbing 4 nm of An
08 was formed. The substrate was taken out of the aqueous solution and rinsed three times with pure water. Next, the ITO electrode 1 with respect to the platinum electrode
01, the voltage of the ITO electrode 102 and the ITO electrode 103 was set to 0 V, and the 1 M polyphenylenevinylene precursor (pr
The substrate was immersed in an e-PPV) aqueous solution for 5 minutes to adsorb the 4 nm-thick precursor layer of the light emitting layer 109 only on the ITO electrode 102. By repeating the above operation 10 times, S
Ten layers having a unit of PAn (4 nm) / pre-PPV (4 nm) were selectively formed only on the ITO electrode 102. Further, +3 V is applied to the ITO electrode 101 with respect to the opposing platinum electrode among the ITO electrodes, and the ITO electrode 102 and the I
In a state where a voltage of -1 V is applied to the TO electrode 103, a voltage of 0.1 V is applied.
It is immersed in a 1 M aqueous solution of poly 1,4- (2-hexyl-3,5-carboxypentaoxy) phenylene for 30 minutes, and the poly-1,4- (2-hexyl-3,5-carboxypentaoxy) phenylene is immersed in about 5 nm. The light was absorbed to form an electron injection / transport layer 110 for emitting green light (see FIG. 1C).
【００６４】ＩＴＯ電極のうち対向する白金電極に対し
てＩＴＯ電極１０３に＋４Ｖ、ＩＴＯ電極１０１及びＩ
ＴＯ電極１０２に−１Ｖの電圧を印加した状態で、１Ｍ
のスルホン化ポリフルオレン（ＳＰＦ）水溶液中に１０
分浸漬し、ＩＴＯ電極１０３にのみ選択的にＳＰＦを４
ｎｍ吸着させ、発光層１１２が形成された。基板を水溶
液中から取出し、純水で３回リンスした。次に、白金電
極に対するＩＴＯ電極１０１、ＩＴＯ電極１０２及びＩ
ＴＯ電極１０３の電圧を０Ｖにし、０．５Ｍのポリエチ
レンイミン（ＰＥＩ）水溶液中に基板を２０分浸漬し、
ＩＴＯ電極１０３にのみ厚さ４ｎｍの青色バッファ層を
吸着させた。上記の操作を２０回繰り返すことにより、
ＳＰＦ（４ｎｍ）／ＰＥＩ（４ｎｍ）を単位とする層が
ＩＴＯ電極１０３にのみ選択的に２０層形成された。更
に、ＩＴＯ電極のうち対向する白金電極に対してＩＴＯ
電極１０１に＋３Ｖ、ＩＴＯ電極１０２及びＩＴＯ電極
１０３に−１Ｖの電圧を印加した状態で、０．１Ｍのポ
リ１，４−（２−ヘキシル−３，５−カルボキペンタオ
キシ）フェニレン水溶液に３０分浸漬し、ポリ１，４−
（２−ヘキシル−３，５−カルボキペンタオキシ）フェ
ニレンを約５ｎｍ吸着させ、青色発光用の電子注入輸送
層１１３を形成した。その後、透明基板１０４を１×１
０-6Ｔｏｒｒ以下の真空中にて２００℃で１２時間アニ
ールし、ｐｒｅ−ＰＰＶからなる前駆体層がＰＰＶから
なる赤色発光バッファ層及び発光層１０９に変成すると
共に、全ての層中に存在する水分を除去した（図１
（Ｄ）参照）。+4 V is applied to the ITO electrode 103 with respect to the opposing platinum electrode, and the ITO electrodes 101 and I
With a voltage of -1 V applied to the TO electrode 102, 1M
In aqueous solution of sulfonated polyfluorene (SPF)
Immersion for 4 minutes and selectively applying SPF to the ITO electrode 103 only for 4 minutes.
Then, the light emitting layer 112 was formed. The substrate was taken out of the aqueous solution and rinsed three times with pure water. Next, the ITO electrode 101, the ITO electrode 102 and the I
The voltage of the TO electrode 103 was set to 0 V, and the substrate was immersed in an aqueous solution of 0.5 M polyethyleneimine (PEI) for 20 minutes.
A 4 nm-thick blue buffer layer was adsorbed only on the ITO electrode 103. By repeating the above operation 20 times,
Twenty layers having units of SPF (4 nm) / PEI (4 nm) were selectively formed only on the ITO electrode 103. Furthermore, the ITO electrode is opposed to the platinum electrode facing the ITO electrode.
A voltage of +3 V is applied to the electrode 101 and a voltage of -1 V is applied to the ITO electrode 102 and the ITO electrode 103, and the resultant is applied to a 0.1 M aqueous solution of poly 1,4- (2-hexyl-3,5-carboxypentaoxy) phenylene for 30 minutes. Dipped, poly 1,4-
(2-hexyl-3,5-carboxypentaoxy) phenylene was adsorbed by about 5 nm to form an electron injection / transport layer 113 for blue light emission. After that, the transparent substrate 104 is 1 × 1
Annealed at 200 ° C. for 12 hours in a vacuum of 0 −6 Torr or less, the precursor layer composed of pre-PPV is transformed into the red light-emitting buffer layer composed of PPV and the light-emitting layer 109 and is present in all the layers. Water was removed (Fig. 1
(D)).
【００６５】最後に、抵抗加熱蒸着法にてＣａ陰極１１
４を２００ｎｍ及びＡｇを１００ｎｍに，ＩＴＯパター
ンと直交するように幅３００μｍにパターン形成する
（図１（Ｅ）参照）。Finally, the Ca cathode 11 was formed by a resistance heating evaporation method.
4 is formed to have a width of 200 nm, Ag is formed to have a thickness of 100 nm, and a pattern having a width of 300 μm is formed so as to be orthogonal to the ITO pattern (see FIG. 1E).
【００６６】こうして、単純マトリックス駆動のフルカ
ラーＥＬ表示素子を得ることができる。Thus, a full-color EL display element driven by a simple matrix can be obtained.
【００６７】なお、図１中、正孔注入輸送層（赤色発光
用）１０５、正孔注入輸送層（青色発光用）１１１は、
実施例２では形成していない。In FIG. 1, the hole injection / transport layer (for red light emission) 105 and the hole injection / transport layer (for blue light emission) 111
It is not formed in the second embodiment.
【００６８】（実施例３）実施例１と同様に準備した基
板表面を大気中１７２ｎｍの波長のエキシマランプによ
り１０ｍＷ／ｃｍ2の１５分間照射を行い、基板表面を
親水化処理した。得られた表面の水の接触角を接触角計
にて調べたところ２゜以下となり、基板表面は極めて清
浄であり超親水性を呈することが分った。次に、ＩＴＯ
電極のうち対向する白金電極に対してＩＴＯ電極１０１
に−３Ｖ、ＩＴＯ電極１０２及びＩＴＯ電極１０３に＋
１Ｖの電圧を印加した状態で、０．０１Ｍのポリフェニ
レンビニレン前駆体水溶液中に２０分浸漬し、ＩＴＯ電
極１０１にのみ選択的にポリフェニレンビニレン前駆体
（ｐｒｅ−ＰＰＶ）を１５ｎｍ吸着させ、正孔注入輸送
層１０５形成用の前駆体層が形成された。基板を水溶液
中から取出し、純水で３回リンスした。次に、白金電極
に対するＩＴＯ電極１０１に＋４Ｖ、ＩＴＯ電極１０２
及びＩＴＯ電極１０３に−１Ｖの電圧を印加し、０．０
０１Ｍのスルホン化トリス（２，２’−ビピリジル)ル
テニウム錯体を混ぜた０．１Ｍのポリ１，４−（３，５
−カルボキシペンチルオキシ）チオフェン（ＰＣＯＰ
Ｔ）水溶液中に基板を２０分浸漬し、ＩＴＯ電極１０１
にのみ厚さ４０ｎｍの発光層１０６を吸着させた。上記
の操作を３回繰り返すことにより、ｐｒｅ−ＰＰＶ（１
５ｎｍ）／ＰＣＯＰＴ（４０ｎｍ）を単位とする層がＩ
ＴＯ電極１０１にのみ選択的に３層形成された。その
後、基板１０４を窒素雰囲気中で２００℃で１２時間ア
ニールし、ｐｒｅ−ＰＰＶからなる前駆体層をＰＰＶか
らなる正孔注入輸送層１０５に変成させた（図１（Ｂ）
参照）。(Example 3) The surface of the substrate prepared in the same manner as in Example 1 was irradiated with 10 mW / cm 2 for 15 minutes in the atmosphere by an excimer lamp having a wavelength of 172 nm, thereby hydrophilizing the substrate surface. When the contact angle of water on the obtained surface was examined with a contact angle meter, it was found to be 2 ° or less, indicating that the substrate surface was extremely clean and exhibited superhydrophilicity. Next, ITO
ITO electrode 101 with respect to the opposing platinum electrode of the electrodes
-3V, and + to the ITO electrode 102 and the ITO electrode 103
With a voltage of 1 V applied, the electrode was immersed in a 0.01 M aqueous solution of polyphenylenevinylene precursor for 20 minutes to selectively adsorb the polyphenylenevinylene precursor (pre-PPV) at a thickness of 15 nm only on the ITO electrode 101 and inject holes. A precursor layer for forming the transport layer 105 was formed. The substrate was taken out of the aqueous solution and rinsed three times with pure water. Next, +4 V is applied to the ITO electrode 101 with respect to the platinum electrode,
And a voltage of -1 V is applied to the ITO electrode 103,
0.1M poly-1,4- (3,5) mixed with 01M sulfonated tris (2,2'-bipyridyl) ruthenium complex
-Carboxypentyloxy) thiophene (PCOP)
T) Immerse the substrate in an aqueous solution for 20 minutes,
The light emitting layer 106 having a thickness of 40 nm was adsorbed only on the substrate. By repeating the above operation three times, pre-PPV (1
5 nm) / PCOPT (40 nm) as a unit
Three layers were selectively formed only on the TO electrode 101. Thereafter, the substrate 104 was annealed in a nitrogen atmosphere at 200 ° C. for 12 hours to transform the precursor layer made of pre-PPV into the hole injection / transport layer 105 made of PPV (FIG. 1B).
reference).
【００６９】次にＩＴＯ電極のうち対向する白金電極に
対してＩＴＯ電極１０２に−４Ｖ、ＩＴＯ電極１０１及
びＩＴＯ電極１０３に＋１Ｖの電圧を印加した状態で、
１Ｍの水溶液中に２０分浸漬し、ＩＴＯ電極１０２にの
み選択的にポリフェニレンビニレン前駆体（ｐｒｅ−Ｐ
ＰＶ）を３０ｎｍ吸着させ、発光層１０９形成用の前駆
体層が形成された。基板を水溶液中から取出し、純水で
３回リンスした。次に、白金電極に対するＩＴＯ電極１
０２に＋３Ｖ、ＩＴＯ電極１０１及びＩＴＯ電極１０３
に−１Ｖの電圧を印加し、０．１Ｍのポリスチレンスル
フォネート（ＰＳＳ）水溶液中に基板を５分浸漬し、Ｉ
ＴＯ電極１０２にのみ厚さ４ｎｍの緑発色用バッファ層
を吸着させた。上記の操作を７回繰り返すことにより、
ｐｒｅ−ＰＰＶ（３０ｎｍ）／ＰＳＳ（４ｎｍ）を単位
とする層がＩＴＯ電極１０２にのみ選択的に７層形成さ
れた。その後、基板１０４を窒素雰囲気中で２００℃で
１２時間アニールし、ｐｒｅ−ＰＰＶからなる前駆体層
をＰＰＶからなる発光層１０９に変成した（図１（Ｃ）
参照）。Next, with a voltage of -4 V applied to the ITO electrode 102 and a voltage of +1 V applied to the ITO electrode 101 and the ITO electrode 103 with respect to the opposing platinum electrode among the ITO electrodes,
It was immersed in a 1M aqueous solution for 20 minutes, and was selectively applied only to the ITO electrode 102. The polyphenylenevinylene precursor (pre-P
PV) was absorbed by 30 nm to form a precursor layer for forming the light-emitting layer 109. The substrate was taken out of the aqueous solution and rinsed three times with pure water. Next, the ITO electrode 1 with respect to the platinum electrode
02 + 3V, ITO electrode 101 and ITO electrode 103
A voltage of -1 V was applied to the substrate, and the substrate was immersed in a 0.1 M aqueous solution of polystyrene sulfonate (PSS) for 5 minutes.
A buffer layer for green color development having a thickness of 4 nm was adsorbed only to the TO electrode 102. By repeating the above operation seven times,
Seven layers having a unit of pre-PPV (30 nm) / PSS (4 nm) were selectively formed only on the ITO electrode 102. Thereafter, the substrate 104 was annealed at 200 ° C. for 12 hours in a nitrogen atmosphere to transform the precursor layer made of pre-PPV into the light emitting layer 109 made of PPV (FIG. 1C).
reference).
【００７０】ＩＴＯ電極のうち対向する白金電極に対し
てＩＴＯ電極１０３に−３Ｖ、ＩＴＯ電極１０１及びＩ
ＴＯ電極１０２に＋１Ｖの電圧を印加した状態で、０．
１Ｍのポリ１，４−パラ−（３−アミノ）フェニレン
（ＰＰＡＰ）水溶液中に２０分浸漬し、ＩＴＯ電極１０
３にのみ選択的にＰＰＡＰを４０ｎｍ吸着させ、発光層
１１２が形成された。基板を水溶液中から取出し、純水
で３回リンスした。次に、白金電極に対するＩＴＯ電極
１０３に＋４Ｖ、ＩＴＯ電極１０１及びＩＴＯ電極１０
２に−１Ｖの電圧を印加し、０．１Ｍのポリビニル硫酸
（ＰＶＳ）水溶液中に基板を５分浸漬し、ＩＴＯ電極１
０３にのみ厚さ４ｎｍの青色バッファ層を吸着させた。
上記の操作を８回繰り返すことにより、ＰＡＡ（４ｎ
ｍ）／ＳＰＰＰ（４ｎｍ）を単位とする層がＩＴＯ電極
１０３にのみ選択的に３層形成された。その後、基板１
０４を窒素雰囲気中で１００℃で１時間アニールし乾燥
させた（図１（Ｄ）参照）。The ITO electrode 103 has a voltage of -3 V with respect to the opposing platinum electrode among the ITO electrodes.
In a state where a voltage of +1 V is applied to the TO electrode 102, the voltage of.
The electrode was immersed in a 1 M aqueous solution of poly 1,4-para- (3-amino) phenylene (PPAP) for 20 minutes to form an ITO electrode 10
The light-emitting layer 112 was formed by selectively adsorbing PPAP to 40 nm only on No.3. The substrate was taken out of the aqueous solution and rinsed three times with pure water. Next, +4 V is applied to the ITO electrode 103 with respect to the platinum electrode, and the ITO electrode 101 and the ITO electrode 10
2 was applied with a voltage of -1 V, and the substrate was immersed in a 0.1 M aqueous solution of polyvinyl sulfate (PVS) for 5 minutes.
Only on 03, a blue buffer layer having a thickness of 4 nm was adsorbed.
By repeating the above operation eight times, PAA (4n
m) Three layers having units of / SPPP (4 nm) were selectively formed only on the ITO electrode 103. Then, the substrate 1
04 was annealed at 100 ° C. for 1 hour in a nitrogen atmosphere and dried (see FIG. 1D).
【００７１】最後に、抵抗加熱蒸着法にてＣａ陰極１１
４を２００ｎｍ及びＡｇを１００ｎｍをＩＴＯパターン
と直交するように幅３００μｍにパターン形成する（図
１（Ｅ）参照）。Finally, the Ca cathode 11 was formed by resistance heating evaporation.
4 is formed to have a width of 300 μm so that 200 nm and Ag are 100 nm perpendicular to the ITO pattern (see FIG. 1E).
【００７２】こうして、単純マトリックス駆動のフルカ
ラーＥＬ表示素子を 得ることができる。Thus, a full-color EL display element driven by a simple matrix can be obtained.
【００７３】なお、図１中、電子注入輸送層（赤色発光
用）１０７、正孔注入輸送層（緑色発光用）１０８、電
子注入輸送層（緑色発光用）１１０、正孔注入輸送層
（青色発光用）１１１、電子注入輸送層（青色発光用）
１１３は、実施例３では形成していない。In FIG. 1, an electron injection / transport layer (for red light emission) 107, a hole injection / transport layer (for green light emission) 108, an electron injection / transport layer (for green light emission) 110, and a hole injection / transport layer (blue) (For light emission) 111, electron injection transport layer (for blue light emission)
113 is not formed in the third embodiment.
【００７４】[0074]
【発明の効果】以上詳しく説明したように、本発明によ
れば、発光表示素子中の活性層の少なくとも１層のパタ
ーンニングが容易であり、及び任意の膜厚に形成するこ
とができる。更に、本発明においては、従来、パターニ
ングができないとされた正孔注入輸送層及び発光層を電
界泳動交互吸着方式により膜厚をコントロールしながら
形成及び配列することでパターニングが可能となり、発
光効率及び色バランスに優れたフルカラーの発光表示素
子を実現できる。また、交互吸着法を用いるため成膜均
一性の確保ができ、安価で大画面のフルカラー表示体が
歩留まり良く製造可能となり、効果はきわめて大きい。As described in detail above, according to the present invention, patterning of at least one active layer in a light emitting display element is easy, and the active layer can be formed to an arbitrary thickness. Furthermore, in the present invention, patterning is possible by forming and arranging the hole injecting and transporting layer and the light emitting layer, which are conventionally considered to be unpatternable, while controlling the film thickness by the electrophoretic alternating adsorption method, thereby enabling luminous efficiency and A full-color light-emitting display device with excellent color balance can be realized. Further, since the alternate adsorption method is used, uniformity of film formation can be ensured, and an inexpensive and large-screen full-color display can be manufactured with high yield, and the effect is extremely large.
【図１】本発明の実施例１〜３の発光表示素子の概略製
造工程図である。FIG. 1 is a schematic manufacturing process diagram of a light emitting display element of Examples 1 to 3 of the present invention.
【図２】本発明の実施例１〜３の発光表示素子に使用す
る電解泳動交互吸着法の装置の概略構成図である。FIG. 2 is a schematic configuration diagram of an apparatus for an electrophoretic alternate adsorption method used for the light emitting display elements of Examples 1 to 3 of the present invention.
【図３】本発明の実施例１〜３の電解泳動交互吸着法に
よる 正孔注入輸送層、発光層及び電子注入輸送層のパ
ターニング時の電極への選択的電圧印加用の概略回路構
成図である。FIG. 3 is a schematic circuit configuration diagram for selectively applying a voltage to an electrode during patterning of a hole injection / transport layer, a light emitting layer, and an electron injection / transport layer by the electrophoretic alternating adsorption method according to Examples 1 to 3 of the present invention. is there.
１０１…ＩＴＯ電極（赤色発光域） １０２…ＩＴＯ電極（緑色発光域） １０３…ＩＴＯ電極（青色発光域） １０４…基板 １０５…正孔注入輸送層（赤色発光用） １０６…発光層（赤色発光用） １０７…電子注入輸送層（赤色発光用） １０８…正孔注入輸送層（緑色発光用） １０９…発光層（緑色発光用） １１０…電子注入輸送層（緑色発光用） １１１…正孔注入輸送層（青色発光用） １１２…発光層（青色発光用） １１３…電子注入輸送層（青色発光用） １１４…陰極 ２０１…直流電源 ２０２…白金電極 ２０３…容器 ２０４…形成用材料の溶液 ２０５…基板 ２０６…ＩＴＯ電極 ２０７…水晶振動子 ３０１…ＩＴＯ電極（赤色発光領域） ３０２…ＩＴＯ電極（緑色発光領域） ３０３…ＩＴＯ電極（青色発光領域） ３０４…基板 ３０５…導電性ゴム ３０６…直流電源 ３０７…白金電極 101: ITO electrode (red emission area) 102: ITO electrode (green emission area) 103: ITO electrode (blue emission area) 104: substrate 105: hole injection / transport layer (for red emission) 106: emission layer (for red emission) 107 ... Electron injection / transport layer (for red light emission) 108 ... Hole injection / transport layer (for green light emission) 109 ... Emission layer (for green light emission) 110 ... Electron injection / transport layer (for green light emission) 111 ... Hole injection / transport Layer (for blue light emission) 112 ... Light emitting layer (for blue light emission) 113 ... Electron injection / transport layer (for blue light emission) 114 ... Cathode 201 ... DC power supply 202 ... Platinum electrode 203 ... Container 204 ... Solution of forming material 205 ... Substrate 206: ITO electrode 207: quartz oscillator 301: ITO electrode (red light emitting region) 302: ITO electrode (green light emitting region) 303: ITO electrode (blue light emitting region) 304: substrate 305: conductive rubber 306: DC power supply 307: platinum electrode
Claims (7)
性に帯電しうる官能基を有する発光層、電子注入輸送層
又は正孔注入輸送層の形成用材料の水溶液中に浸漬し、
泳動電着により形成用材料を第１電極上に積層すること
で発光層、電子注入輸送層又は正孔注入輸送層を形成す
ることを特徴とする発光表示素子の製造方法。A substrate provided with a first electrode is immersed in an aqueous solution of a material for forming a light emitting layer, an electron injection transport layer or a hole injection transport layer having a functional group capable of being charged to a positive or negative polarity. ,
A method for manufacturing a light-emitting display element, comprising forming a light-emitting layer, an electron injection transport layer or a hole injection transport layer by laminating a forming material on a first electrode by electrophoretic deposition.
送層の形成用材料が、ルテニウム、エルビウム、ユーロ
ピウム、イリジウム又は白金を含む有機錯体、ポリフル
オレン誘導体、ポリパラフェニレンビニレンの前駆体と
その誘導体、ポリチオフェン誘導体、ポリパラフェニレ
ン誘導体、ポリシラン誘導体、ポリアセチレン誘導体、
ポリビニルカルバゾール誘導体及びポリピロール誘導体
を構成する共役高分子に正又は負の極性に帯電しうる官
能基を付加させた材料、ポリスチレンスルホン酸、ポリ
ビニル硫酸、デキストラン硫酸、コンドロイチン硫酸、
ポリアクリル酸、ポリメタクリル酸、ポリマレイン酸、
ポリフマル酸、ポリエチレンイミン、ポリアリルアミン
塩酸塩、ポリジアリルジメチルアンモニウムクロリド、
ポリビニルピリジン、ポリリジンから選択される請求項
１に記載の製造方法。2. A material for forming a light emitting layer, an electron injection transport layer or a hole injection transport layer, comprising a precursor of an organic complex containing ruthenium, erbium, europium, iridium or platinum, a polyfluorene derivative, or a polyparaphenylene vinylene. Its derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives,
A material obtained by adding a functional group capable of being charged to positive or negative polarity to a conjugated polymer constituting a polyvinyl carbazole derivative and a polypyrrole derivative, polystyrene sulfonic acid, polyvinyl sulfate, dextran sulfate, chondroitin sulfate,
Polyacrylic acid, polymethacrylic acid, polymaleic acid,
Polyfumaric acid, polyethyleneimine, polyallylamine hydrochloride, polydiallyldimethylammonium chloride,
The production method according to claim 1, wherein the production method is selected from polyvinylpyridine and polylysine.
酸基及びカルボキシル基からなる負に帯電しうる基、チ
オフェニル基、４級アンモニウム基、アミノ基からなる
正に帯電しうる基から選択される請求項２に記載の製造
方法。3. The functional group is selected from a negatively chargeable group comprising a nitro group, a hydroxyl group, a sulfonic acid group and a carboxyl group, a thiophenyl group, a quaternary ammonium group and a positively chargeable group comprising an amino group. The production method according to claim 2.
送層を第１電極上に泳動電着するに際して、第１電極が
複数設けられ、その上に発光層、電子注入輸送層又は正
孔注入輸送層の形成を所望しない第１電極に、発光層、
電子注入輸送層又は正孔注入輸送層の形成用材料の極性
と逆の極性の電圧を印加することで、所望の第１電極上
に発光層、電子注入輸送層又は正孔注入輸送層を形成す
る請求項１〜３のいずれか１つに記載の製造方法。4. When a light emitting layer, an electron injecting and transporting layer or a hole injecting and transporting layer is electrophoretically deposited on the first electrode, a plurality of first electrodes are provided, on which a light emitting layer, an electron injecting and transporting layer or a positive electrode is transported. A light emitting layer, a first electrode for which formation of a hole injection transport layer is not desired,
A light emitting layer, an electron injection / transport layer or a hole injection / transport layer is formed on a desired first electrode by applying a voltage having a polarity opposite to the polarity of the material for forming the electron injection / transport layer or the hole injection / transport layer. The production method according to any one of claims 1 to 3.
ことで、発光層、電子注入輸送層又は正孔注入輸送層の
形成速度を所望の値に設定した条件下で行われる請求項
１〜４のいずれか１つに記載の製造方法。5. The electrophoretic electrodeposition is performed under the condition that the formation rate of the light emitting layer, the electron injection transport layer or the hole injection transport layer is set to a desired value by changing the pH of the aqueous solution. 5. The method according to any one of items 1 to 4.
注入輸送層とが電気泳動により形成され、一方の層を該
層の形成用材料を泳動電着することにより形成し、他方
の層を一方の層の形成用材料と逆の極性に帯電しうる官
能基を備えた形成用材料を泳動電着することにより形成
する請求項１〜５のいずれか１つに記載の製造方法。6. A light emitting layer and an electron injecting and transporting layer, and a light emitting layer and a hole injecting and transporting layer are formed by electrophoresis. One layer is formed by electrophoretically depositing a material for forming the layer, and the other is formed. The method according to any one of claims 1 to 5, wherein the layer is formed by electrophoretically depositing a forming material having a functional group capable of being charged to a polarity opposite to that of the forming material of one layer. .
層が電気泳動により形成され、一層目の層を該層の形成
用材料を泳動電着することにより形成し、二層目の層を
一層目の層の形成用材料と逆の極性に帯電しうる官能基
を備えた形成用材料を泳動電着することにより形成し、
三層目の層を二層目の層の形成用材料と逆の極性に帯電
しうる官能基を備えた形成用材料を泳動電着することに
より形成する請求項１〜５のいずれか１つに記載の製造
方法。7. An electron injecting and transporting layer, a light emitting layer and a hole injecting and transporting layer are formed by electrophoresis, a first layer is formed by electrophoretically depositing a material for forming the layer, and a second layer is formed. The layer is formed by electrophoretically depositing a forming material having a functional group capable of being charged to the opposite polarity to the forming material of the first layer,
The third layer is formed by electrophoretically depositing a forming material having a functional group capable of being charged to a polarity opposite to that of the forming material of the second layer. The production method described in 1.
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|---|---|---|---|
| JP2001118460A JP2002313565A (en) | 2001-04-17 | 2001-04-17 | Method of manufacturing luminescent display element |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001118460A JP2002313565A (en) | 2001-04-17 | 2001-04-17 | Method of manufacturing luminescent display element |
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|---|---|
| JP2002313565A true JP2002313565A (en) | 2002-10-25 |
Family
ID=18968846
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|---|---|---|---|
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| WO2004068912A1 (en) * | 2003-01-30 | 2004-08-12 | Fujitsu Limited | Material for hole injection layer, organic el element and organic el display |
| WO2006137462A1 (en) * | 2005-06-22 | 2006-12-28 | Seiko Epson Corporation | Method for manufacturing substrate for electronic device, substrate for electronic device, electronic device and electronic instrument |
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